CA1039886A - Block copolymer of polyamide and polyether, and its preparation and use - Google Patents
Block copolymer of polyamide and polyether, and its preparation and useInfo
- Publication number
- CA1039886A CA1039886A CA191,942A CA191942A CA1039886A CA 1039886 A CA1039886 A CA 1039886A CA 191942 A CA191942 A CA 191942A CA 1039886 A CA1039886 A CA 1039886A
- Authority
- CA
- Canada
- Prior art keywords
- block copolymer
- polyether
- film
- polyamide
- per cent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/40—Polyamides containing oxygen in the form of ether groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/2964—Artificial fiber or filament
- Y10T428/2967—Synthetic resin or polymer
- Y10T428/2969—Polyamide, polyimide or polyester
Abstract
BLOCK COPOLYMER OF POLYAMIDE AND POLYETHER, AND ITS PREPARATION AND USE
ABSTRACT OF THE DISCLOSURE:
A block copolymer of at least one polyamide and at least one polyether, the content of the polyether being about 0.2 to 10% by weight based on the block copolymer, having a scattering index of not less than about 1 wherein the particles of the polyether are agglomerated in a maximum size of not more than about 10 µ and dispersed in the block copolymer, the polyamide consisting of a diamine constituent containing 100 to 50 mol % of m-xylylenediamine or its mixture with p-xylylenediamine and the dicarboxylic acid constituent containing 100 to 50 mol % of at least one aliphatic dicarboxylic acid having 6 to 12 carbon atoms and the polyether having an amino group or a carboxyl group at least one terminal position and a molecular weight of about 2,000 to 20,000. The new polymer is useful for making shaped products such as films, having improved bonding strength, puncture resistance and low temperature impact resistance.
ABSTRACT OF THE DISCLOSURE:
A block copolymer of at least one polyamide and at least one polyether, the content of the polyether being about 0.2 to 10% by weight based on the block copolymer, having a scattering index of not less than about 1 wherein the particles of the polyether are agglomerated in a maximum size of not more than about 10 µ and dispersed in the block copolymer, the polyamide consisting of a diamine constituent containing 100 to 50 mol % of m-xylylenediamine or its mixture with p-xylylenediamine and the dicarboxylic acid constituent containing 100 to 50 mol % of at least one aliphatic dicarboxylic acid having 6 to 12 carbon atoms and the polyether having an amino group or a carboxyl group at least one terminal position and a molecular weight of about 2,000 to 20,000. The new polymer is useful for making shaped products such as films, having improved bonding strength, puncture resistance and low temperature impact resistance.
Description
1~39886 The present invention relates to a block copolymer - of polyamide and polyether, and its preparation and use. More particularly, it relates to a block copolymer of polyamide and polyether and its shaped products such as films, and their preparations.
In general, shaped products made Of xylylene group containing polyamides are excellent in a variety of physical and mechanical properties such as Young modulus, break strength, tear strength, gloss, transparency, chemical resistance and gas barrier property. In addition, they can be melt molded to make various useful shaped articles such as films, sheets, vessels, bristles and filaments.
As commonly seen in condensation polymers, however, xylylene group-containing polyamides unfavorably contain a certain amount (e.g. about 2%) of cyclic oligomers. Different from oligomers as contained in aliphatic polyamides such as polycapramide and polyhexamethyleneadipamide which are readily soluble in water, those contained in aromatic poly-amides such as xylylene group-containing polyamides are hardly soluble in water. Because of this difference, the oligomers present in aliphatic polyamides can be easily eliminated by washing the chips or any shaped article made of such polymers with water, while those in aromatic polyamides are not.
When, for instance, any shaped article made of xylylene group-containing polyamides is contacted with hot water or steam, a trace amount of the oligomers therein is separated out on the surface but such stains can not be eliminated with water.
Besides, shaped articles made of xylylene group-containing polyamides such as films have high break strength and tear strength but are inferior in bending strength, puncture
In general, shaped products made Of xylylene group containing polyamides are excellent in a variety of physical and mechanical properties such as Young modulus, break strength, tear strength, gloss, transparency, chemical resistance and gas barrier property. In addition, they can be melt molded to make various useful shaped articles such as films, sheets, vessels, bristles and filaments.
As commonly seen in condensation polymers, however, xylylene group-containing polyamides unfavorably contain a certain amount (e.g. about 2%) of cyclic oligomers. Different from oligomers as contained in aliphatic polyamides such as polycapramide and polyhexamethyleneadipamide which are readily soluble in water, those contained in aromatic poly-amides such as xylylene group-containing polyamides are hardly soluble in water. Because of this difference, the oligomers present in aliphatic polyamides can be easily eliminated by washing the chips or any shaped article made of such polymers with water, while those in aromatic polyamides are not.
When, for instance, any shaped article made of xylylene group-containing polyamides is contacted with hot water or steam, a trace amount of the oligomers therein is separated out on the surface but such stains can not be eliminated with water.
Besides, shaped articles made of xylylene group-containing polyamides such as films have high break strength and tear strength but are inferior in bending strength, puncture
- 2 -.. .. . .
~039886 resistance ancl low tem~erature impact resistance.
As the result of an extensive study, it has been found that a block copolymer comprising a polyamide segment and a polyether segment wherein the polyether ~;
segment is dispersed within the polyamide segment in the form of agglomerates of a size of not more than 10 ~, the scattering index (N) of the block copolymer being not less than 1, can overcome the said drawbacks as seen in conventional xylylene group-containing polyamides while retaining their advantageous properties.
According to the present invention, there is provided a block copolymer consisting of segments of at least one polyamide and segments of at least one polyether, .
said polyether and polyamide being chemically bonded to -each other but the polyether segments being distributed in the block copolymer in an agglomerated state to form islands of maximum size no~ more than 10 ~, the content of the polyamide being 99.8 to 90 per cent and that of the polyether being 0.2 to 10 per cent, by weight based on the block copolymer, the block copolymer having a scattering index of not less than 1, the polyamide comprising a diamine constituent containin~ 100 to 50 mol percent of m-xylylene-diamine or its mixture with p-xylylene~diamine and 0 to 50 mol per cent of another amine component and the dicarboxylic acid constituent comprising lOO to 50 mol per cent of at least one aliphatic dicarboxylic acid having 6 to 12 carbon atoms and 0 to 50 mol per cent of -~
another carboxylic acid component and the polyether having a molecular weight of 2,000 to 20,000 and being represented by the formula:
X ( OY) OXI (A) ~ _3_ 1~)3~886 wherein x and X' are each hydrogen a hydrocarbon group having 1 to 20 carbon atoms or a group having 1 to 6 carbon atoms and bearing an amino, carboxyl and/or esterified carboxyl group, at least one of X and X' being a group having 1 to 6 carbon atoms and bearing an amino, carboxyl,esterified carboxyl group, Y is alkylene or cycloalkylene having not more than 6 carbon atoms and n is a number which can set the molecular weight of the compound (A) within a range of 2,000 to 20,000-The term "scattering index (N)" as hereinabove used is intended to indicate the value calculated accord-ing to the following equation:
N = (E400 ~ E )/D
wherein E400 and E800 are respectively the absorbances measured on am amorphous film prepared by melt extruding the said block copolymer at b~oO m~ and 800 m~ and D is the thickness (mm) of the Q
~.. . . .
amorphous film.
Hitherto, there are ~nown a number of block - copolymers of polyamides and polyethers, which are used for improvement of the antistatic pxoperty of nylon fibers and also for manufacture of elastic filaments [Japanese Patent Publications Nos. 15912/1960, 23349/1963, 10380/
1973; U.S. Patent 3,044,989, etc.]. Such advantageous properties are based on the utiliza~ion of the hydrophilic property and the low Young modulus of the polyether components therein. However, the technical effects attained by the present invention such as the prevention of the separation of the oligomers, the high folding endurance and the excellent low temperature impact strength have been neither realized nor suggested by the conventional techniques as above. It is particularly notable that the use of only a small amount of polyethers to be block polymerized is sufficient to achieve a remarkable effect.
The polyamide segment in the block copolymer of this invention may comprise a constituent consisting of m-xylylenediamine or its mixture with p-xyxlylenediamine and at least one aliphatic dicarboxylic acid having 6 to 12 carbon atoms in a content of 100 to 50 mol %, preferably of 100 to 70 mol %. In addition to such essential constituent, there may be included any optional constituent having an amine component other than the said diamine and/or a carboxylic acid component other than the said dicarboxylic acid in a content of 0 to 50 m~l %, preferably of 0 to 30 mol %. Specific examples of the essential constituent are poly-m-xylyleneadipamide, poly-m-xylylene-suberamide, poly-m-xylylenesebacamide, poly-m-xylylenedecanamide, poly-m~
xylylene/p-xylyleneadipamide, poly-m-xylylene/p-xylylene-: - . . : .
.: . . .
pimelamide, poly-m-xylylene~p-xylylenesuberamide, poly-m-xylylene/p-xylylenesebacamide, poly-m-xylylene/p-xylylene-decanamide, etc. As the amine component for the optional constituent, there may be exemplified aliphatic diamines (e.g. hexamethylenediamine, tri-methylhexamethylenediamine, dodecamethylenediamine), alicyclic daimines (e.g. N-amino-ethylpiperazine, N,N'-bisaminopropylpiperazine, 1,3-biasaminomethylcyclohexane, bis-p aminocyclohexylmethane), aromatic diamines (e.g. p-bis(2-aminoethyl)benzene), etc.
As the carboxylic acid component for the optional constituent, there may be exemplified aromatic dicarboxylic acids (e.g.
terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,1,3-trimethyl-3-p-carboxyphenylindane-5-carboxylic acid). There may be also used as the amine or carboxylic acid component ~-aminocarboxylic acids (e.g. ~-aminocaproic acid, 7-aminoheptanoic acid, 12-aminododecanoic acid, p-aminocyclohexylcarboxylic acid) and their lactams. The content of p-xylylenediamine in the xylylenediamine component is favored to be from 0 to 30 % by weight from the viewpoints of the coloring and the processability of the resulting block copolymer. Usually, the molecular weight of the block copol-ymer is desirable to be the one as shPwing a relative viscosity of 1.8 to 4Ø
In the block copolymer, the polyether segment is dispersed in an island state, i.e. in an agglomerated form of not more than 10 ~ in particle size. The polyether seyment has a molecular weight of 2,000 to 20,000 and is representable by the following formula:
X~OY)noX' (A) wherein X and X' are each hydrogen, a hydrocarbon group having 1 to 20 carbon atoms or a group having 1 to 6 carbon _ 5 `':' ~ - . .: ' ' ~039~86 atoms and bearing amino, carboxyl and/or esterified carboxyl, with the proviso that at least one of X and X' is said group having 1 to 6 carbon atoms, Y is allcylene or cycloalkylene having not more than 6 carbon atoms and n is a number which can set the molecular weight of the compound (A) within a range of 2,000 to 20,000. Specific examples of the group having amino, carboxyl and/or esterified carboxyl represented by the symbol X or X' are amino-containing groups such as 2 aminoethyl, 3-aminopropyl, 2-hydroxy-3-aminopropyl or 2-hydroxy-N-butyl-3-aminopropyl, carboxyl-containing groups such as carboxymethyl~ carboxyethyl, 2-carboxypropyl, 4-carboxybutyl, 5-carboxypentyl or carboxyphenyl, esterified carboxyl-containing groups such as methoxycarbonylmethyl, ethoxycarbonylmethyl, ethoxycarbonylethyl, 2-ethoxycarbony-lpropyl, 4-methoxycarbonyl-butyl or 5-butoxycarbonylpentyl, etc. As the group represented by the symbol Y, there may be exemplified -CH2, -CH2-CH- (Rl:
12 Rl H or CH3), -CH2-C-CH2- (R2: H or CH3; R3: H or CH ) -cH2cH2cH2cH2-~ -CH\ ~CH , etc.
The pol~ether segment is required to have such a large molecular weight as can be bound to the polyamide segment and dispersed in an island state in the latter.
The molecular weight of the polyether segment capable of being dispersed in an island state is somewhat varied with the content of the polyether segment, and a molecular weight of not less than 2,000 is usually necessary in case of the content being from 0.2 to 10 % by weight. When the molecular weight is less than 2,000, the polyether segment . .
is dissolved in the poly ~e9s8e~gm6ent and can not attain the technical effect which is aimed at in the present invention.
~ In addition, the physical and mechanical properties of the shaped products made of the resulting block copolymer such as gas barrier property and resistance to hot water are much decreased. For making easy the dispersibility of the polyether segment of not more than lO ~ in particle size into the polyamide segment, however, a too large molecular weight of the polyether segment is not favorable. Thus, the molecular weight of the polyether segment is required to be not more than 20,000.
In order to attain the purpose of this invention, the amount of the polyether segment in the block copolymer is desired not less than 0.2~ by weight. In case of the content exceeding to 10~ by weight, however, the amount of the island structure formed by the polyether segment becomes too much so that the transparency of the block copolymer is much lowered with deterioration of various physical property. The most preferred content is 1 to 5 by weight.
One of the objects of this invention is to improve disadvantageous properties inherent to polyamides such as the separation of oligomers leading to whitening, the inferior folding endurance, the poor puncture resistance and the small low temperature impact strength without deteriorating advantageous properties inherent thereto such as high Young modulus, breaking strength, burst strength and gas barrier property by the use of a relatively small amount of polyethers to be block polymerized. For attaining such object, it is desired to copolymerize a polyether component having at least one functional group such as amino or carboxyl at the termi~a~ 3e9 ~ position and a molecular weight of 2,000 to 20,000 in a proportion of 0.2 to 10 %
by weight on the block copolymer. The effect is, however, much associated with the conditions under which the block copolymer is manufactured, even if the composition is the same.
When a polyether component having an appropriate functional group is copolymerized on a polyamide component by heating, the incorporation oE the polyether component may be effected at any of the initial, intermediary and late stages of polymerization, but it is preferred that such incorporation is carried out at the initial to intermediary stage of pressurized polymerization in view of the solubility of the polyether component into the polyamide component or water and the reactivity among them. The most preferred condition is to effect the water-pressurized polymerization under a gauge pressure of 5 to 15 kg/cm2 with sufficient stirring to produce a polymer havins a low degree of polymerization, e.g. corresponding to a relative viscosity of about 1.~ to 1.5 and, after releasing the pressure to atmospheric pressure, increasing the degree of polymerization by continuing the polymerization at a temperature higher than the melting point of the polymer. When the evaporation of water is effected under a lower pressure (e.g. 4kg/cm gauge pressure) and then the temperature is elevated above ~-the melting point of the polvmer while keeping the said pressure, the polyether component in the obtained polymer is dispersed in an island state of more than 10 ~ even if incorporated at the initial stage. Thus, the physical properties of the produced block copolymer are not favourable.
- 8 ~
''''' ' "' ~039886 The favourable gauge pressure ran~e may be 7 to 1.3 kg/cm2.
In case of the pressure being above 15 kg/cm2, the polyether component is not agglomeratively dispersed into the polyamide component and makes a uniform phase so that the folding endurance, the low temperature impact strength, the gas barrier property and the like are considerably lowered.
In addition to the polymerization conditions, the concentration of the nylon salt aqueous solution, the rate of water evaporation and the like may be appropriately sel~cted for obtaining favorable properties of the block copolymer.
The characteristic properties of the block copoly-mer prepared as above can be evaluated by melting a piece of the block copolymer on a hot plate under nitrogen atmosphere; pressing the melt to a constant thickness, followed by immediate cooling to make an amorphous film;
and measuring the light absorption spectrum of the film and observing the film by a microscope. Namely, such amorphous film shows a mildly scattering absorption which decreases hyperboloidally and regularly from the ultraviolet region to the visible region, and the absorption is particularly strong in the region of short wave length. The block copolymer having a scattering index within the following range exhibits generally favorable physical properties:
N = (E400 - E800)/D > 1. Particularly preferred is the one which shows N > 2.
On the microscopic observation of the island state in the amorphous, undrawn film as above, the preferred one shows the maximum particle size of not more than 10 ~. The more preferred is the one having a maximum particle size of not more than 6 ~ and an average particle size of not more than g _ 1~39886
~039886 resistance ancl low tem~erature impact resistance.
As the result of an extensive study, it has been found that a block copolymer comprising a polyamide segment and a polyether segment wherein the polyether ~;
segment is dispersed within the polyamide segment in the form of agglomerates of a size of not more than 10 ~, the scattering index (N) of the block copolymer being not less than 1, can overcome the said drawbacks as seen in conventional xylylene group-containing polyamides while retaining their advantageous properties.
According to the present invention, there is provided a block copolymer consisting of segments of at least one polyamide and segments of at least one polyether, .
said polyether and polyamide being chemically bonded to -each other but the polyether segments being distributed in the block copolymer in an agglomerated state to form islands of maximum size no~ more than 10 ~, the content of the polyamide being 99.8 to 90 per cent and that of the polyether being 0.2 to 10 per cent, by weight based on the block copolymer, the block copolymer having a scattering index of not less than 1, the polyamide comprising a diamine constituent containin~ 100 to 50 mol percent of m-xylylene-diamine or its mixture with p-xylylene~diamine and 0 to 50 mol per cent of another amine component and the dicarboxylic acid constituent comprising lOO to 50 mol per cent of at least one aliphatic dicarboxylic acid having 6 to 12 carbon atoms and 0 to 50 mol per cent of -~
another carboxylic acid component and the polyether having a molecular weight of 2,000 to 20,000 and being represented by the formula:
X ( OY) OXI (A) ~ _3_ 1~)3~886 wherein x and X' are each hydrogen a hydrocarbon group having 1 to 20 carbon atoms or a group having 1 to 6 carbon atoms and bearing an amino, carboxyl and/or esterified carboxyl group, at least one of X and X' being a group having 1 to 6 carbon atoms and bearing an amino, carboxyl,esterified carboxyl group, Y is alkylene or cycloalkylene having not more than 6 carbon atoms and n is a number which can set the molecular weight of the compound (A) within a range of 2,000 to 20,000-The term "scattering index (N)" as hereinabove used is intended to indicate the value calculated accord-ing to the following equation:
N = (E400 ~ E )/D
wherein E400 and E800 are respectively the absorbances measured on am amorphous film prepared by melt extruding the said block copolymer at b~oO m~ and 800 m~ and D is the thickness (mm) of the Q
~.. . . .
amorphous film.
Hitherto, there are ~nown a number of block - copolymers of polyamides and polyethers, which are used for improvement of the antistatic pxoperty of nylon fibers and also for manufacture of elastic filaments [Japanese Patent Publications Nos. 15912/1960, 23349/1963, 10380/
1973; U.S. Patent 3,044,989, etc.]. Such advantageous properties are based on the utiliza~ion of the hydrophilic property and the low Young modulus of the polyether components therein. However, the technical effects attained by the present invention such as the prevention of the separation of the oligomers, the high folding endurance and the excellent low temperature impact strength have been neither realized nor suggested by the conventional techniques as above. It is particularly notable that the use of only a small amount of polyethers to be block polymerized is sufficient to achieve a remarkable effect.
The polyamide segment in the block copolymer of this invention may comprise a constituent consisting of m-xylylenediamine or its mixture with p-xyxlylenediamine and at least one aliphatic dicarboxylic acid having 6 to 12 carbon atoms in a content of 100 to 50 mol %, preferably of 100 to 70 mol %. In addition to such essential constituent, there may be included any optional constituent having an amine component other than the said diamine and/or a carboxylic acid component other than the said dicarboxylic acid in a content of 0 to 50 m~l %, preferably of 0 to 30 mol %. Specific examples of the essential constituent are poly-m-xylyleneadipamide, poly-m-xylylene-suberamide, poly-m-xylylenesebacamide, poly-m-xylylenedecanamide, poly-m~
xylylene/p-xylyleneadipamide, poly-m-xylylene/p-xylylene-: - . . : .
.: . . .
pimelamide, poly-m-xylylene~p-xylylenesuberamide, poly-m-xylylene/p-xylylenesebacamide, poly-m-xylylene/p-xylylene-decanamide, etc. As the amine component for the optional constituent, there may be exemplified aliphatic diamines (e.g. hexamethylenediamine, tri-methylhexamethylenediamine, dodecamethylenediamine), alicyclic daimines (e.g. N-amino-ethylpiperazine, N,N'-bisaminopropylpiperazine, 1,3-biasaminomethylcyclohexane, bis-p aminocyclohexylmethane), aromatic diamines (e.g. p-bis(2-aminoethyl)benzene), etc.
As the carboxylic acid component for the optional constituent, there may be exemplified aromatic dicarboxylic acids (e.g.
terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,1,3-trimethyl-3-p-carboxyphenylindane-5-carboxylic acid). There may be also used as the amine or carboxylic acid component ~-aminocarboxylic acids (e.g. ~-aminocaproic acid, 7-aminoheptanoic acid, 12-aminododecanoic acid, p-aminocyclohexylcarboxylic acid) and their lactams. The content of p-xylylenediamine in the xylylenediamine component is favored to be from 0 to 30 % by weight from the viewpoints of the coloring and the processability of the resulting block copolymer. Usually, the molecular weight of the block copol-ymer is desirable to be the one as shPwing a relative viscosity of 1.8 to 4Ø
In the block copolymer, the polyether segment is dispersed in an island state, i.e. in an agglomerated form of not more than 10 ~ in particle size. The polyether seyment has a molecular weight of 2,000 to 20,000 and is representable by the following formula:
X~OY)noX' (A) wherein X and X' are each hydrogen, a hydrocarbon group having 1 to 20 carbon atoms or a group having 1 to 6 carbon _ 5 `':' ~ - . .: ' ' ~039~86 atoms and bearing amino, carboxyl and/or esterified carboxyl, with the proviso that at least one of X and X' is said group having 1 to 6 carbon atoms, Y is allcylene or cycloalkylene having not more than 6 carbon atoms and n is a number which can set the molecular weight of the compound (A) within a range of 2,000 to 20,000. Specific examples of the group having amino, carboxyl and/or esterified carboxyl represented by the symbol X or X' are amino-containing groups such as 2 aminoethyl, 3-aminopropyl, 2-hydroxy-3-aminopropyl or 2-hydroxy-N-butyl-3-aminopropyl, carboxyl-containing groups such as carboxymethyl~ carboxyethyl, 2-carboxypropyl, 4-carboxybutyl, 5-carboxypentyl or carboxyphenyl, esterified carboxyl-containing groups such as methoxycarbonylmethyl, ethoxycarbonylmethyl, ethoxycarbonylethyl, 2-ethoxycarbony-lpropyl, 4-methoxycarbonyl-butyl or 5-butoxycarbonylpentyl, etc. As the group represented by the symbol Y, there may be exemplified -CH2, -CH2-CH- (Rl:
12 Rl H or CH3), -CH2-C-CH2- (R2: H or CH3; R3: H or CH ) -cH2cH2cH2cH2-~ -CH\ ~CH , etc.
The pol~ether segment is required to have such a large molecular weight as can be bound to the polyamide segment and dispersed in an island state in the latter.
The molecular weight of the polyether segment capable of being dispersed in an island state is somewhat varied with the content of the polyether segment, and a molecular weight of not less than 2,000 is usually necessary in case of the content being from 0.2 to 10 % by weight. When the molecular weight is less than 2,000, the polyether segment . .
is dissolved in the poly ~e9s8e~gm6ent and can not attain the technical effect which is aimed at in the present invention.
~ In addition, the physical and mechanical properties of the shaped products made of the resulting block copolymer such as gas barrier property and resistance to hot water are much decreased. For making easy the dispersibility of the polyether segment of not more than lO ~ in particle size into the polyamide segment, however, a too large molecular weight of the polyether segment is not favorable. Thus, the molecular weight of the polyether segment is required to be not more than 20,000.
In order to attain the purpose of this invention, the amount of the polyether segment in the block copolymer is desired not less than 0.2~ by weight. In case of the content exceeding to 10~ by weight, however, the amount of the island structure formed by the polyether segment becomes too much so that the transparency of the block copolymer is much lowered with deterioration of various physical property. The most preferred content is 1 to 5 by weight.
One of the objects of this invention is to improve disadvantageous properties inherent to polyamides such as the separation of oligomers leading to whitening, the inferior folding endurance, the poor puncture resistance and the small low temperature impact strength without deteriorating advantageous properties inherent thereto such as high Young modulus, breaking strength, burst strength and gas barrier property by the use of a relatively small amount of polyethers to be block polymerized. For attaining such object, it is desired to copolymerize a polyether component having at least one functional group such as amino or carboxyl at the termi~a~ 3e9 ~ position and a molecular weight of 2,000 to 20,000 in a proportion of 0.2 to 10 %
by weight on the block copolymer. The effect is, however, much associated with the conditions under which the block copolymer is manufactured, even if the composition is the same.
When a polyether component having an appropriate functional group is copolymerized on a polyamide component by heating, the incorporation oE the polyether component may be effected at any of the initial, intermediary and late stages of polymerization, but it is preferred that such incorporation is carried out at the initial to intermediary stage of pressurized polymerization in view of the solubility of the polyether component into the polyamide component or water and the reactivity among them. The most preferred condition is to effect the water-pressurized polymerization under a gauge pressure of 5 to 15 kg/cm2 with sufficient stirring to produce a polymer havins a low degree of polymerization, e.g. corresponding to a relative viscosity of about 1.~ to 1.5 and, after releasing the pressure to atmospheric pressure, increasing the degree of polymerization by continuing the polymerization at a temperature higher than the melting point of the polymer. When the evaporation of water is effected under a lower pressure (e.g. 4kg/cm gauge pressure) and then the temperature is elevated above ~-the melting point of the polvmer while keeping the said pressure, the polyether component in the obtained polymer is dispersed in an island state of more than 10 ~ even if incorporated at the initial stage. Thus, the physical properties of the produced block copolymer are not favourable.
- 8 ~
''''' ' "' ~039886 The favourable gauge pressure ran~e may be 7 to 1.3 kg/cm2.
In case of the pressure being above 15 kg/cm2, the polyether component is not agglomeratively dispersed into the polyamide component and makes a uniform phase so that the folding endurance, the low temperature impact strength, the gas barrier property and the like are considerably lowered.
In addition to the polymerization conditions, the concentration of the nylon salt aqueous solution, the rate of water evaporation and the like may be appropriately sel~cted for obtaining favorable properties of the block copolymer.
The characteristic properties of the block copoly-mer prepared as above can be evaluated by melting a piece of the block copolymer on a hot plate under nitrogen atmosphere; pressing the melt to a constant thickness, followed by immediate cooling to make an amorphous film;
and measuring the light absorption spectrum of the film and observing the film by a microscope. Namely, such amorphous film shows a mildly scattering absorption which decreases hyperboloidally and regularly from the ultraviolet region to the visible region, and the absorption is particularly strong in the region of short wave length. The block copolymer having a scattering index within the following range exhibits generally favorable physical properties:
N = (E400 - E800)/D > 1. Particularly preferred is the one which shows N > 2.
On the microscopic observation of the island state in the amorphous, undrawn film as above, the preferred one shows the maximum particle size of not more than 10 ~. The more preferred is the one having a maximum particle size of not more than 6 ~ and an average particle size of not more than g _ 1~39886
3 ~. When the particle size is more than 10 ~, the improvement of the puncture resistance and the folding endurance in the shaped products made of the block copolymer is not seen, and the physical and mechanical properties are rather lowered. The once produced dispersion state is not changed even when melted again.
When any additive (e.g. weathering agent, anti-oxidizing agent, anti-coloring agent, heat stabilizer, whitening agent, lubricant, nucleating agent, pigment, filler) in the block copolymer affords an influence on the absorbence in the above evaluation, deduction or compensation is as a matter of course needed.
Into the block copolymer, the incorporation of a phenolic oxidation inhibitor, an organic or inorganic oxyphosphorus compound or its alkali metal salt or ester, or the like is practically favored.
Melt extrusion of the block copolymer as above -can afford a transparent, undrawn film. The undrawn film may be as such used as a deep drawing material. Alternatively, it may be drawn to give an oriented or shrink film having excellent properties. Further, it may be co-extruded with any other polymer to make a laminated film. In the form of such film, the characteristic properties of the block -copolymer of the invention are particularly exhibited. The provision of such film is also one of the objects of this invention. ;
By the present invention, the block copolymer is melt extruded to yive a film of 10 to 1,000 ~ in thickness, of which the scattering index is not less than 1 and in which the polyether segment is dispersed in an island state of not more than 10 ~ in maximum particle size. Such film .:
103~8~36 is excellent in folding endurance, puncture resistance low temperature impact s-trength and gas barrier property.
For the preparation of the film, the block copolymer may be dried to a water content of 0.01 to 0.1~ by weight, heated at a temperature higher than the melting point (preferably from about 250 to 280~C~, extruded through a T die in a film form and cooled on a roll or in atmosphere, for instance, of 30 to 70C to a temperature below the secondary transition point, whereby a transparent, undrawn film is obtained. When the cooling is effected at a temperature higher than the secondary transition point of the block copolymer, a flat film is hardly obtained and creases are apt to be produced so as to make difficult the uniform drawing in the subsequent drawing step. `~
When desired, the above prepared undrawn film may be uniaxially or biaxially drawn to produce favorable properties as not -seen in the undrawn film. In case of the biaxial drawing, it may be carried out simultaneously or stepwise. The temperature for drawing (TC) may be appropriately controlled depending on the water content (W %) and the drawing rate ~ %/min) of the undrawn film.
The preferred condition is representable by the following formula:
g 1000 12W > T > Tg - 6W
wherein Tg is the secondary transition point. The water content of the undrawn film is varied with the environment under which the drawing is carried out and can be appropria-tely regulated. From the practical viewpoint, the water content is controlled normally below 5 % by weight, 3Q preferably below 3% by weight. The drawing rate may be ~ .
... . . .
~)3988~;
varied within a broad range depending on the thickness o~
the film, the physical properties, the drawing apparatus and the economy. Practically, it may be from 500 to 50,000 %/min, preferably 1,000 to 10,000 ~/min. Accordingly, the preferred drawing temperature for obtaining a uniformly drawn film may be from about 60 to 110C. When the drawing temperature is too low, a high tension is required for drawing, thereby the film being broken at the initial stage of drawing in most cases. When it is too high, the drawing at a high draw ratio produces necking and uneven thickness as well as breakage at the rate stage of drawing. The draw ratio may be 2 to 6, preferably 2.5 to 4.5 in one direction.
In case of biaxial drawing, the draw ratio in a machine direction may be same as or different from that in a trans-verse direction. The same draw ratio in machine and trans-~erse directions results in the same drawing rate in both directions. When the draw ratio in a machine direction is different from that in a transverse direction, the drawing rates in both directions may be different from each other in accordance therewith.
The thus produced drawn film can show good ~
physical and mechanical properties as such, except that `~ -the shrinking property is positively utilized as in the ;`
case of shrink films. However, it is usually subjected to heat treatment so as to impart a size stability. The heat treatment may be carried out at a temperature not less than 5C above the higher temperature of the said drawing temperatures and lower than the melting point of the block copolymer, usually from 120 to 210C, for a period of not more than 5 minutes, preferably from 15 to 60 seconds. When .,, - . .
:. .- ~....................... . -:
~39886 the temperature for heat treatment is too high, the film tends to be broken, the orientation produced by drawing becomes uneven, the film thickness is made uneven and the physical properties are deteriorated. Even in the said preferred range of temperature, heat treatment for a too long period of time causes disadvantageously various unfavorable phenomena such as oxidation, heat deterioration and cleavage of the molecular chain. During the heat treatment, the film is maintained under a tensioned or relaxed state. As the result of the heat treatment or heat fixing treatment as above, the crystallinity of the film is increased, the strain produced in the course of drawing is eliminated and the mechanical property, particularly the size property of the film are improved.
The thus obtained film has an excellent crystallinity and an orientation balanced both in machine and transverse directions. Such ~ilm also has various excellent properties as seen in the undrawn film such as a high low temperature impact strength (e.g. more than 6 kg.cm/25 ~ at -40C), a 20 good oxygen permeability coefficient (e.g. 2 x 10 12 ml.cm/
cm2.sec.cmHg) and the like. It also has many good properties as a biaxially drawn film such as breaking strength (MD, TD) of more than 10 kg/mm , breaking elongation of 20 to 120 %, burst strength of more than 30 kg/mm2, initial Young modulus of more than 300 kg/mm2, end tearing strength of more than 15 kg/25 ~, folding endurance of more than 150,000 times, puncture resistance of more than 200 times, transparence ~haze) of less than 10 and transparence after treatment with boiling water (haze~ of less than 15.
Illustrating the relationship between the above properties and the polyether component used in this invention, ~39813~;
any ~ilm satisfactory in folding endurance, low temperature impact strength and transparence after treatment with boiling water can not be obtained when the polyether com-ponent as specified above is not used or not present in the dispersion state as specified above. In order to obtain a film to be satisfied in the above respects, the amount of the polyether component must be not less than 0.2 % by weight. The increase of the amount of the polyether component can improve remarkably the folding endurance, the low tem-perature impact strength and the transparence after treatment with boiling water without lowering the breaking strength, the breaking elongation, the burst strength and the oxygen `
permeability coefficient inherent to a film of the poly- -amide component. When, however, the amount of the polyether component exceeds 10 ~ by weight, the exertion of a more excellent effect can not be expected and the mechanical properties are rather lowered. ;
Hereupon, in case of the molecular weight of the polyether component being less than 2,000, the incorporation in a large amount results in the increase of the folding endurance but the low temperature impact strength and the transparence after treatment with boiling water become unsatisfactory. In case of the molecular weight being more than 20,000, the transparence is much decreased.
Particularly favorable film properties are seen in a film having a scattering index (N) of not less than 2 and an island structure of not more than lO ~ in maximum particle si7e. Such film is particularly excellent in puncture resistance, low temperature impact strength and gas barrier property. Since the biaxially drawn one is provided with various advantageous properties required in processing ~ - 14 -... . ........................... .
. . .
~ 1039886 and circulation markets such as breaking strength, hotwater resistance~ burst strength, size stability, suitability for printing, laminate adhesion and the like, it is quite suitable as ~ packaging material for transportation and storage of various foods. It is also suitable for the use as an electrical material or a magnetic recording material.
~he film of this invention may be used in the form of a simple film or of a coated or laminated film. Examples of the latter are as follows:
Film/Heat seal layer;
Film/Metallic foil/Heat seal layer;
Film/Printing layer/Heat seal lay~r;
Film/Film suitable for printing/Printing layer/Heat seal layer;
Film/Printing layer/Metallic foil/Heat seal layer;
Printing layer/Film/Heat seal layer;
Surface protecting layer/Printing layer/
Film/Heat seal layer; etc.
Wherein the heat seal layer is an easily heat sealable coating or laminating layer having a lower melting point than that of the film of the invention, e.g., low ~ -density polyethylene, high density polyethylene, non-orientated polypropylene, polyvinyl chloride, polyvinylidene chloride, chlorinated polypropylene, and ethylene copolymers such as Surlyn A, trademark of ~u Pont. -~
- 14a -, , ,, ~:
10.~98~6 Practical and presently preferred embodiments of the present invention are illustratively shown in the following Examp~es wherein parts and ~D are by weight.
The physical constants are determined as follows:
(1) Relative viscosity (~r):-The relative viscosity is measured on a solutionof the polymer (1 g) in m-cresol (100 ml) at 25C. by the use of an Ostwald (Trademark) viscosimeter.
(2) Scattering index:- ;
A piece of the polymer is melted on a hot plate in nitrogen atmosphere, pressed to make a uniform thickness of less than 100 ~ and cooled rapidly to give an amorphous film. The absorbance of the film at 360 to 900~m by a spectrometer ("Hitachi Model 124" trademark o~ Hitachi, Ltd. ) is measured, and the values at 400~m (E400) and at 800~m (E800) are read off. On the other hand, the exact and precise thickness (D, mm) of the film is measured by a microgauge. According to the following equation, the scattering index (N) is calculated:
N = E400 E800 D
when the film contains any additive which affords any influence on the absorbance in the said range of wave length~ deduction is made separately.
(3) Breaking strength, breaking elongation and Young Modulus:-~ -As described in ASTM ( American Society of Testing for Material ) D-882, measurement is made by elongating a specimen of 50 mm long and 10 mm wide in machine and tran-verse directions at a rate of pulling of 100 mm/min under the condition of a temperature of 20C. and a relative humidity '~
3~88~i of 65% by the use of a load elongation tester ("Tensilon UTM-3" trademark of Toyo Sokki K.K.). From the initial gradient of the stress-strain curve, Young modulus is calculated.
When any additive (e.g. weathering agent, anti-oxidizing agent, anti-coloring agent, heat stabilizer, whitening agent, lubricant, nucleating agent, pigment, filler) in the block copolymer affords an influence on the absorbence in the above evaluation, deduction or compensation is as a matter of course needed.
Into the block copolymer, the incorporation of a phenolic oxidation inhibitor, an organic or inorganic oxyphosphorus compound or its alkali metal salt or ester, or the like is practically favored.
Melt extrusion of the block copolymer as above -can afford a transparent, undrawn film. The undrawn film may be as such used as a deep drawing material. Alternatively, it may be drawn to give an oriented or shrink film having excellent properties. Further, it may be co-extruded with any other polymer to make a laminated film. In the form of such film, the characteristic properties of the block -copolymer of the invention are particularly exhibited. The provision of such film is also one of the objects of this invention. ;
By the present invention, the block copolymer is melt extruded to yive a film of 10 to 1,000 ~ in thickness, of which the scattering index is not less than 1 and in which the polyether segment is dispersed in an island state of not more than 10 ~ in maximum particle size. Such film .:
103~8~36 is excellent in folding endurance, puncture resistance low temperature impact s-trength and gas barrier property.
For the preparation of the film, the block copolymer may be dried to a water content of 0.01 to 0.1~ by weight, heated at a temperature higher than the melting point (preferably from about 250 to 280~C~, extruded through a T die in a film form and cooled on a roll or in atmosphere, for instance, of 30 to 70C to a temperature below the secondary transition point, whereby a transparent, undrawn film is obtained. When the cooling is effected at a temperature higher than the secondary transition point of the block copolymer, a flat film is hardly obtained and creases are apt to be produced so as to make difficult the uniform drawing in the subsequent drawing step. `~
When desired, the above prepared undrawn film may be uniaxially or biaxially drawn to produce favorable properties as not -seen in the undrawn film. In case of the biaxial drawing, it may be carried out simultaneously or stepwise. The temperature for drawing (TC) may be appropriately controlled depending on the water content (W %) and the drawing rate ~ %/min) of the undrawn film.
The preferred condition is representable by the following formula:
g 1000 12W > T > Tg - 6W
wherein Tg is the secondary transition point. The water content of the undrawn film is varied with the environment under which the drawing is carried out and can be appropria-tely regulated. From the practical viewpoint, the water content is controlled normally below 5 % by weight, 3Q preferably below 3% by weight. The drawing rate may be ~ .
... . . .
~)3988~;
varied within a broad range depending on the thickness o~
the film, the physical properties, the drawing apparatus and the economy. Practically, it may be from 500 to 50,000 %/min, preferably 1,000 to 10,000 ~/min. Accordingly, the preferred drawing temperature for obtaining a uniformly drawn film may be from about 60 to 110C. When the drawing temperature is too low, a high tension is required for drawing, thereby the film being broken at the initial stage of drawing in most cases. When it is too high, the drawing at a high draw ratio produces necking and uneven thickness as well as breakage at the rate stage of drawing. The draw ratio may be 2 to 6, preferably 2.5 to 4.5 in one direction.
In case of biaxial drawing, the draw ratio in a machine direction may be same as or different from that in a trans-verse direction. The same draw ratio in machine and trans-~erse directions results in the same drawing rate in both directions. When the draw ratio in a machine direction is different from that in a transverse direction, the drawing rates in both directions may be different from each other in accordance therewith.
The thus produced drawn film can show good ~
physical and mechanical properties as such, except that `~ -the shrinking property is positively utilized as in the ;`
case of shrink films. However, it is usually subjected to heat treatment so as to impart a size stability. The heat treatment may be carried out at a temperature not less than 5C above the higher temperature of the said drawing temperatures and lower than the melting point of the block copolymer, usually from 120 to 210C, for a period of not more than 5 minutes, preferably from 15 to 60 seconds. When .,, - . .
:. .- ~....................... . -:
~39886 the temperature for heat treatment is too high, the film tends to be broken, the orientation produced by drawing becomes uneven, the film thickness is made uneven and the physical properties are deteriorated. Even in the said preferred range of temperature, heat treatment for a too long period of time causes disadvantageously various unfavorable phenomena such as oxidation, heat deterioration and cleavage of the molecular chain. During the heat treatment, the film is maintained under a tensioned or relaxed state. As the result of the heat treatment or heat fixing treatment as above, the crystallinity of the film is increased, the strain produced in the course of drawing is eliminated and the mechanical property, particularly the size property of the film are improved.
The thus obtained film has an excellent crystallinity and an orientation balanced both in machine and transverse directions. Such ~ilm also has various excellent properties as seen in the undrawn film such as a high low temperature impact strength (e.g. more than 6 kg.cm/25 ~ at -40C), a 20 good oxygen permeability coefficient (e.g. 2 x 10 12 ml.cm/
cm2.sec.cmHg) and the like. It also has many good properties as a biaxially drawn film such as breaking strength (MD, TD) of more than 10 kg/mm , breaking elongation of 20 to 120 %, burst strength of more than 30 kg/mm2, initial Young modulus of more than 300 kg/mm2, end tearing strength of more than 15 kg/25 ~, folding endurance of more than 150,000 times, puncture resistance of more than 200 times, transparence ~haze) of less than 10 and transparence after treatment with boiling water (haze~ of less than 15.
Illustrating the relationship between the above properties and the polyether component used in this invention, ~39813~;
any ~ilm satisfactory in folding endurance, low temperature impact strength and transparence after treatment with boiling water can not be obtained when the polyether com-ponent as specified above is not used or not present in the dispersion state as specified above. In order to obtain a film to be satisfied in the above respects, the amount of the polyether component must be not less than 0.2 % by weight. The increase of the amount of the polyether component can improve remarkably the folding endurance, the low tem-perature impact strength and the transparence after treatment with boiling water without lowering the breaking strength, the breaking elongation, the burst strength and the oxygen `
permeability coefficient inherent to a film of the poly- -amide component. When, however, the amount of the polyether component exceeds 10 ~ by weight, the exertion of a more excellent effect can not be expected and the mechanical properties are rather lowered. ;
Hereupon, in case of the molecular weight of the polyether component being less than 2,000, the incorporation in a large amount results in the increase of the folding endurance but the low temperature impact strength and the transparence after treatment with boiling water become unsatisfactory. In case of the molecular weight being more than 20,000, the transparence is much decreased.
Particularly favorable film properties are seen in a film having a scattering index (N) of not less than 2 and an island structure of not more than lO ~ in maximum particle si7e. Such film is particularly excellent in puncture resistance, low temperature impact strength and gas barrier property. Since the biaxially drawn one is provided with various advantageous properties required in processing ~ - 14 -... . ........................... .
. . .
~ 1039886 and circulation markets such as breaking strength, hotwater resistance~ burst strength, size stability, suitability for printing, laminate adhesion and the like, it is quite suitable as ~ packaging material for transportation and storage of various foods. It is also suitable for the use as an electrical material or a magnetic recording material.
~he film of this invention may be used in the form of a simple film or of a coated or laminated film. Examples of the latter are as follows:
Film/Heat seal layer;
Film/Metallic foil/Heat seal layer;
Film/Printing layer/Heat seal lay~r;
Film/Film suitable for printing/Printing layer/Heat seal layer;
Film/Printing layer/Metallic foil/Heat seal layer;
Printing layer/Film/Heat seal layer;
Surface protecting layer/Printing layer/
Film/Heat seal layer; etc.
Wherein the heat seal layer is an easily heat sealable coating or laminating layer having a lower melting point than that of the film of the invention, e.g., low ~ -density polyethylene, high density polyethylene, non-orientated polypropylene, polyvinyl chloride, polyvinylidene chloride, chlorinated polypropylene, and ethylene copolymers such as Surlyn A, trademark of ~u Pont. -~
- 14a -, , ,, ~:
10.~98~6 Practical and presently preferred embodiments of the present invention are illustratively shown in the following Examp~es wherein parts and ~D are by weight.
The physical constants are determined as follows:
(1) Relative viscosity (~r):-The relative viscosity is measured on a solutionof the polymer (1 g) in m-cresol (100 ml) at 25C. by the use of an Ostwald (Trademark) viscosimeter.
(2) Scattering index:- ;
A piece of the polymer is melted on a hot plate in nitrogen atmosphere, pressed to make a uniform thickness of less than 100 ~ and cooled rapidly to give an amorphous film. The absorbance of the film at 360 to 900~m by a spectrometer ("Hitachi Model 124" trademark o~ Hitachi, Ltd. ) is measured, and the values at 400~m (E400) and at 800~m (E800) are read off. On the other hand, the exact and precise thickness (D, mm) of the film is measured by a microgauge. According to the following equation, the scattering index (N) is calculated:
N = E400 E800 D
when the film contains any additive which affords any influence on the absorbance in the said range of wave length~ deduction is made separately.
(3) Breaking strength, breaking elongation and Young Modulus:-~ -As described in ASTM ( American Society of Testing for Material ) D-882, measurement is made by elongating a specimen of 50 mm long and 10 mm wide in machine and tran-verse directions at a rate of pulling of 100 mm/min under the condition of a temperature of 20C. and a relative humidity '~
3~88~i of 65% by the use of a load elongation tester ("Tensilon UTM-3" trademark of Toyo Sokki K.K.). From the initial gradient of the stress-strain curve, Young modulus is calculated.
(4) Burst strength:-A specimen of 80 mm in diameter is fixed on a load cell of 45 mm in inner diameter and pushed by a rod type load having a semi-spherical top of 38 mm in diameter at a rate of 50 mm/min. The burst load is measured under the conditions of a temperature of 20C and a relative humidity of 65% by the use of a load elongation tester "Tensilon UTM- 3 " .
(5) Low temperature impact strength:~
Measurement is made at a temperature of -40C by the use of a film impact tester.
Measurement is made at a temperature of -40C by the use of a film impact tester.
(6) End tear strength:-As described in JIS (Japanese Industrial~Standard) -C2318, a specimen of 20 mm wide is placed on the end of a M
~ .
type metal plate having an opening angle of 150C, and the ~0 tensile burst strength is measured at 20C by the aid of a ~
load elongation tester "Tensilon UTM-3" with a rate of 200 -mm/min.
~ .
type metal plate having an opening angle of 150C, and the ~0 tensile burst strength is measured at 20C by the aid of a ~
load elongation tester "Tensilon UTM-3" with a rate of 200 -mm/min.
(7) Folding endurance:-As described in JIS P8115, a film of 15 mm wide is pinched by a chuck in a folding endurance tester and, under the conditions of a temperature of 20C and a relative humidity of 65%, ~olded repeatedly with an angle of -135 repeatedly at a rate of 175 times/min by charging a load of 1 kg. The folding times up to breaking are counted.
(8~ Puncture Resistance:-A square film of 15 cm long and 15 cm wide having `
~-. .:, - -- -: -, . ~ , . ,, ,: -a certain thickness is ~ ~a~ ~fi end of a Y shaped glass pipe and expanded to make a swollen bag. Two other ends of the pipe are connected respectively to a vacuum line and a pressure air line of 0.2 kg/cm gauge pressure intervening switch valves. The switch valves are alternately and inter-mittently operated in automatically so as to subject the atmosphere in the bag under the reduced and elevated pressure conditions whereby a flexing stress is repeatedly gi~en. The times of repetition up to the production vf pinholes in the 10 bag due to the flexing stress which causes the depression ~ "
in the extent of vacuum are counted under the conditions of a temperature of 23C and a relative humidity of 65~.
(9) Oxygen permeability coefficient:-As described in ASTM D-1434, measurement is made on the basis of the change in pressure at 30C using a gas permeability measuring apparatus.
(10) Haze and transparence:-As described in JIS K6714, these are calculated ;~
according to the following equations based on the values measured at 20C by a haze tester:
T
Transparence: Tt = ~2 x 100 T4 - T3(T2/T1) Td = ~ - x 100 Td Haze: H = Tt - x 100 (%) wherein Tl is the amount of incident light, T2 is the total amount of transmitted light, T3 is the amount of scattered light due to the apparatus and T4 is the amount of scattered light due to the apparatus and the specimen.
(11) Plane orientation index and degree of balance:~
The refractive indexes of a specimen in the machine direction (x), the transverse direction (y) and the vertical.
direction ~z) are measured by the use of an Abbe's refracto-meter, and calculations are made according to the following equations:
Plane orientation index = ~ - z Degree of balance = x - y (12) Peel strength:-Using a laminated film of 1 cm wide and 10 cm long having a non-adhered zone of 5 cm in one side as a specimen, -the stress required for peeling off the polyamide film layer `~
from the polyolefin layer at a peel angle of 180C with a rate of 200 mm/min is measured by a load elongation tester : ~.
"Tensilon UTN-3".
(13) Heat seal strength~
Two films are heat bonded at 180C under a pressure ;:
of 2 kg/cm2 for 1 second, and the stress required for peeling off the bonded films from each other at a rate of 200 mm/min ~-is measured by a load elongation tester "Tensilon UTM-3".
Example 1 Polyethylene glycol having a number average . ;
molecular weight of 20,000, 8,300, 4,080, 2,000, 1,000 or 600 is subjected to cyanoethylation in toluene in the presence of sodium methoxide as a catalyst and then to hydrogenation using Raney nickel as a catalyst to give bis-aminopropyl ~ ;~
(polyethylene oxide) (hereinafter referred to as "PEG-DA") in an amination degree of 82 to g7%. To demineralized water (2,000 parts), the nylon salt of xylylene-diamine ;~
consisting of 27% of p-xylylenediamine (hereinafter referred 103g886 to as "PXD") and 73% of m~xylylenediamine (hereinafter referred to as "MXD") with adipic acid (1,000 parts) and the above prepared PEG-DA ~30 parts) are added, and an equivalent amount of adipic acid to the said PEG~DA is added thereto. In a 4 liter volume autoclave, the resultant mixture is subjected to polymerization at 280C under an autogenic pressure, and the produced polymer is extruded to make chips. The melting point of the polymer is 262~C. The relative viscoslty is as follows: 2.51, ~.~8, 2.53, 2.56, 2.45, 2.47.
After drying, the chips of the polymer are extruded at 280~C to make a film o~ about 200 11 in thickness, and the film is drawn at 102C at a draw ratio of 3.2 in a machine direction and at a draw ratio of 3.5 in a transverse direction -and set at 180C to make a transparent film.
On the microscopic observation, a matrix of island structure of 1 to 10 11 in particle size is recognized in the film made of the polymer containing PEG-DA of 2,000 or more in molecular weight.
Twenty pieces of the said transparent film and of a transparent film made of a polymer but containing no PEG-DA
in the same manner as above (for control), each piece having a size of 10 cm long and 10 cm wide, are extracted with boiling water and then dried. From the change in the weight - of the film before and after the extraction, the extracted amount is determined. Further, the polymer before making in a transparent film is subjected to measurement of the absorbence, and the scattering index is determined. The results are shown in Table 1.
- 19 - .
TAaLE 1 Decreased weigh-t Haze Molecular on extraction (%) (96~ Scatt-weight of _ ~ _ -- ering polyethyl- 10 30 1 2 5 0 30 5 index No. ene glycol min. min. hr. hrs. hrs. mln. mln. hrs. N
1 20,000 0.88 0.92 0.96 1.01 1.06 5.3 7.8 7.3 2.1 2 =0 0.82 0.87 0.91 0.97 1.1)4 4.7 5.9 5.2 8.8 3 4tO80 0.90 0.96 1.02 1.04 1.09 3.2 4.5 3.7 7.9 _ _ ___ _ _ 4 2,0001.07 1.14 1,21 1 26 1.33 2.1 6.9 5.8 1.2 ;, ' ,;
1,0001.32 1.42 1.52 1.59 1.66 2.0 ll.S 8.8 0.3 __ _ . __ __ ._ '' ', 6 6001.46 1.58 1.67 1.75 1.89 1.8 13.6 9.2 0.1 ,' ._ ...... _ _ _ __ _ 7 Control1.62 1.87 1.99 2.10 2.15 2.8 14.1 9.8 0.1 From the above results, it is understood that, in case of PEG-DA of 2,000 or more in molecular weight being copolymerized and the resulting polymer having a scattering index of not less than 1, the extracted amount is apparently ;~
decreased. Although the dissolving can be not completely , 20 blocked, the whitening may be considered not to occur, because only the oligomers having a large solubility are extracted.
Example 2 Polyethylene glycol having a number average molecular weight of 4,080 is subjected to cyanoethylation in dioxane in ,'-' the presence of sodium hydroxide as a catalyst, followed by neutralization with,an acid and evaporation of the solvent.
The residue is dissolved in methanol, and hydrogenation is - carried out in the presence of Raney nickel as a catalyst to give PEG-DA in an aminatioll degree of 9096. To demineralized 30 water (2,000 parts), the nylon salt of MXD with adipic acid -- 20 ~
. . .
. . :
~0398~6 (1,000 parts) and the above prepared PEG-DA (25 parts~ are ~-added, and an equivalent amount (i.e. O.O9~part) of adipic acid to the said PEG-DA is added thereto. The resulting mixture is charged in a 4 liter volume autoclave, the atmos-phere is replaced by nitrogen and the temperature is elevated with the agitation rate and the water evaporation pressure as shown in Table 2. Then, the pressure is brought to atmospheric pressure while elevating the temperature, and the polymerization under atmospheric pressure is continued at 260C for 2 hours. The produced polymer is extruded to make chips. The polymer shows a melting point of 239C and a relative viscosity of 2.30 (when determined in 1~ m~cresol solution at 25C). The scattering index of the polymer as well as the maximum particle size of the islands dispersed in the polymer (by the microscopic observation) are examined.
The results are shown in Table 2.
, :
Water Evapora- Agitation Scattering Maximum part-tion pressure rate index icIe size of No. (kg/cm2 gauge)(r/m) N island (~) _ 1 4 0 0.7 14 2 4 50 0.9 11 3 4 100 1.5 9 4 8 0 0.9 6
(8~ Puncture Resistance:-A square film of 15 cm long and 15 cm wide having `
~-. .:, - -- -: -, . ~ , . ,, ,: -a certain thickness is ~ ~a~ ~fi end of a Y shaped glass pipe and expanded to make a swollen bag. Two other ends of the pipe are connected respectively to a vacuum line and a pressure air line of 0.2 kg/cm gauge pressure intervening switch valves. The switch valves are alternately and inter-mittently operated in automatically so as to subject the atmosphere in the bag under the reduced and elevated pressure conditions whereby a flexing stress is repeatedly gi~en. The times of repetition up to the production vf pinholes in the 10 bag due to the flexing stress which causes the depression ~ "
in the extent of vacuum are counted under the conditions of a temperature of 23C and a relative humidity of 65~.
(9) Oxygen permeability coefficient:-As described in ASTM D-1434, measurement is made on the basis of the change in pressure at 30C using a gas permeability measuring apparatus.
(10) Haze and transparence:-As described in JIS K6714, these are calculated ;~
according to the following equations based on the values measured at 20C by a haze tester:
T
Transparence: Tt = ~2 x 100 T4 - T3(T2/T1) Td = ~ - x 100 Td Haze: H = Tt - x 100 (%) wherein Tl is the amount of incident light, T2 is the total amount of transmitted light, T3 is the amount of scattered light due to the apparatus and T4 is the amount of scattered light due to the apparatus and the specimen.
(11) Plane orientation index and degree of balance:~
The refractive indexes of a specimen in the machine direction (x), the transverse direction (y) and the vertical.
direction ~z) are measured by the use of an Abbe's refracto-meter, and calculations are made according to the following equations:
Plane orientation index = ~ - z Degree of balance = x - y (12) Peel strength:-Using a laminated film of 1 cm wide and 10 cm long having a non-adhered zone of 5 cm in one side as a specimen, -the stress required for peeling off the polyamide film layer `~
from the polyolefin layer at a peel angle of 180C with a rate of 200 mm/min is measured by a load elongation tester : ~.
"Tensilon UTN-3".
(13) Heat seal strength~
Two films are heat bonded at 180C under a pressure ;:
of 2 kg/cm2 for 1 second, and the stress required for peeling off the bonded films from each other at a rate of 200 mm/min ~-is measured by a load elongation tester "Tensilon UTM-3".
Example 1 Polyethylene glycol having a number average . ;
molecular weight of 20,000, 8,300, 4,080, 2,000, 1,000 or 600 is subjected to cyanoethylation in toluene in the presence of sodium methoxide as a catalyst and then to hydrogenation using Raney nickel as a catalyst to give bis-aminopropyl ~ ;~
(polyethylene oxide) (hereinafter referred to as "PEG-DA") in an amination degree of 82 to g7%. To demineralized water (2,000 parts), the nylon salt of xylylene-diamine ;~
consisting of 27% of p-xylylenediamine (hereinafter referred 103g886 to as "PXD") and 73% of m~xylylenediamine (hereinafter referred to as "MXD") with adipic acid (1,000 parts) and the above prepared PEG-DA ~30 parts) are added, and an equivalent amount of adipic acid to the said PEG~DA is added thereto. In a 4 liter volume autoclave, the resultant mixture is subjected to polymerization at 280C under an autogenic pressure, and the produced polymer is extruded to make chips. The melting point of the polymer is 262~C. The relative viscoslty is as follows: 2.51, ~.~8, 2.53, 2.56, 2.45, 2.47.
After drying, the chips of the polymer are extruded at 280~C to make a film o~ about 200 11 in thickness, and the film is drawn at 102C at a draw ratio of 3.2 in a machine direction and at a draw ratio of 3.5 in a transverse direction -and set at 180C to make a transparent film.
On the microscopic observation, a matrix of island structure of 1 to 10 11 in particle size is recognized in the film made of the polymer containing PEG-DA of 2,000 or more in molecular weight.
Twenty pieces of the said transparent film and of a transparent film made of a polymer but containing no PEG-DA
in the same manner as above (for control), each piece having a size of 10 cm long and 10 cm wide, are extracted with boiling water and then dried. From the change in the weight - of the film before and after the extraction, the extracted amount is determined. Further, the polymer before making in a transparent film is subjected to measurement of the absorbence, and the scattering index is determined. The results are shown in Table 1.
- 19 - .
TAaLE 1 Decreased weigh-t Haze Molecular on extraction (%) (96~ Scatt-weight of _ ~ _ -- ering polyethyl- 10 30 1 2 5 0 30 5 index No. ene glycol min. min. hr. hrs. hrs. mln. mln. hrs. N
1 20,000 0.88 0.92 0.96 1.01 1.06 5.3 7.8 7.3 2.1 2 =0 0.82 0.87 0.91 0.97 1.1)4 4.7 5.9 5.2 8.8 3 4tO80 0.90 0.96 1.02 1.04 1.09 3.2 4.5 3.7 7.9 _ _ ___ _ _ 4 2,0001.07 1.14 1,21 1 26 1.33 2.1 6.9 5.8 1.2 ;, ' ,;
1,0001.32 1.42 1.52 1.59 1.66 2.0 ll.S 8.8 0.3 __ _ . __ __ ._ '' ', 6 6001.46 1.58 1.67 1.75 1.89 1.8 13.6 9.2 0.1 ,' ._ ...... _ _ _ __ _ 7 Control1.62 1.87 1.99 2.10 2.15 2.8 14.1 9.8 0.1 From the above results, it is understood that, in case of PEG-DA of 2,000 or more in molecular weight being copolymerized and the resulting polymer having a scattering index of not less than 1, the extracted amount is apparently ;~
decreased. Although the dissolving can be not completely , 20 blocked, the whitening may be considered not to occur, because only the oligomers having a large solubility are extracted.
Example 2 Polyethylene glycol having a number average molecular weight of 4,080 is subjected to cyanoethylation in dioxane in ,'-' the presence of sodium hydroxide as a catalyst, followed by neutralization with,an acid and evaporation of the solvent.
The residue is dissolved in methanol, and hydrogenation is - carried out in the presence of Raney nickel as a catalyst to give PEG-DA in an aminatioll degree of 9096. To demineralized 30 water (2,000 parts), the nylon salt of MXD with adipic acid -- 20 ~
. . .
. . :
~0398~6 (1,000 parts) and the above prepared PEG-DA (25 parts~ are ~-added, and an equivalent amount (i.e. O.O9~part) of adipic acid to the said PEG-DA is added thereto. The resulting mixture is charged in a 4 liter volume autoclave, the atmos-phere is replaced by nitrogen and the temperature is elevated with the agitation rate and the water evaporation pressure as shown in Table 2. Then, the pressure is brought to atmospheric pressure while elevating the temperature, and the polymerization under atmospheric pressure is continued at 260C for 2 hours. The produced polymer is extruded to make chips. The polymer shows a melting point of 239C and a relative viscosity of 2.30 (when determined in 1~ m~cresol solution at 25C). The scattering index of the polymer as well as the maximum particle size of the islands dispersed in the polymer (by the microscopic observation) are examined.
The results are shown in Table 2.
, :
Water Evapora- Agitation Scattering Maximum part-tion pressure rate index icIe size of No. (kg/cm2 gauge)(r/m) N island (~) _ 1 4 0 0.7 14 2 4 50 0.9 11 3 4 100 1.5 9 4 8 0 0.9 6
8 50 6.8 3 6 8 100 7.7 < 1 7 15 0 2.1 < 1 8 , 15 50 0.6 < 1
9 15 100 0.4 < 1 _ .
-~L039~3~36 Example 3 Polyethylene glycol having a number average molecu-lar weight of 3,400 is treated with metallic sodium in dioxane to convert into the sodium alcoholate and then treated with ethyl monochloroacetate to give polyethylene glycol-bis-acetyl ethylate. This product (25 parts) is admixed with the nylon salt of MXD with adipic acid (1,000 parts) in water, and the polymerization is carried out as in Example 2. The thus produced polymer shows a melting point of 239C, a relative viscosity of 2.23 and a scattering index of 3.8. On the microscopic observation, the island structure of not more than 2 ~ in particle size is recognized.
Example 4 The dried chips of the polymer obtained in Example 2, No. 5 or Example 3 are extruded at 260C by the use of a T die to make a film of about 200 ~ in thickness, which is then drawn at 95C at a draw ratio of 3.5 in both of the machine and transverse directions and heat set to give a transparent film.
In the same manner as above, there are prepared transparent films made of a polymer manufactured by the same amount of polyethylene glycol but not aminated at the end and made of a polymer not including any polyethylene glycol.
The transparent films prepared as above are treated with steam for 20 minutes, and the transparence and the haze are measured. The results are shown in Table 3 wherein the value after water washing indicates the one measured on the film after treatment with steam and ~ashing sufficiently with water at 30C in a washing machine.
- ?
~ ~
. _ . .
Tra Isparen e (%) ] laze ~% _ sefore After Aftex sefore After After Film treat- treat- water treat- treat- water No. materials ment ment washing ment menk washing _ . ...
1 PEG~DA 88.8 88.4 88.6 3.0 5.2 3.6 PEG DC
2 containing 88.5 88.1 88.4 3.0 4.8 3.7 3 MoxnDta6ining 87.6 86.8 87.2 4.5 7.8 7.5 ;
4 MXD-6 89.2 78.8 86.7l 2.8 34 6 7.6 ~xample 5 A 40~ aqueous solution containing the nylon salt -of xylylenediamine consisting of 1~ of PXD and 99% of MXD
with adipic acid (1,200 parts) and a 10% aqueous solution of the salt of PEG-DA (PEG number average molecular weight, 8,300; amination percent, 90%) (12 parts) with an equivalent amount of adipic acid thereto are charged in an autoclavP, the atmosphere is replaced by nitrogen and the temperature is ele~ated under a pressure of 10 kg/cm2 to evaporate water. Then, the polymerization under atmospheric pressure is carried out at 260C, and the produced polymer is extruded to make chips, which are dried at 100C under reduced pressure. M.P., 239C, nr. 2.37. Water con~entj 0.05%.
The dried chips are melted at 260C in an extruder and extruded through a T die on a chill roll to make a film of 240 ~ in thickness. The film is drawn at 100C first in a machine direction at draw ratio of 3.8 and then in a ~)398~3S ::
transverse direction at a draw ratio of 4.0, the drawingrate being 5~000 %/min, followed by heat setting at 200C
for 30 seconds to make a transparent, elastic film.
Example 6 As in Example 5, the salt containing 1~ of PEG-DA
(PEG number average molecular weight, 610, 1,006, 2,030, 4,000 or 20,000; amino value percent, 80 to 90~) is subjected to polvmerization, the produced polymer is extruded to form a film and the film is drawn and heat set to give a trans- ;
lO parent film. The physical properties of the transparent film obtained in this Example as well as those of the transparent film obtained in Examle 1 are shown in Table 4.
, ~ ~.' . .
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::1039~136 _ _ N ___ a . N Ul V
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_ n ~' co ~D ~ _ E~ o~ ~ o~ ~D
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NN ~ ~ ' r~ N
. ~ ~ O ~1 :' O N N ~D ~ N .
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~r I ~r ON CO ~ ' ~n O . o Cl:~ N ~ O
~1 E~U~ r~ o . _ ~ E~ N I~ ~D ~
N ~) ~1 N L~'~ - 0:~ ~9 N O
. ~ , . . .
~(~398~36 ~ r, ~ O r~l N O
t-~ t- ~r co X o o ,_ ~:r oo ~ o l _ ..... _ .. _ __ _.
l ~ ~
CO O O~ ~1 O 07 O W
,_1 1~ a~ N ~D X O O V
t~l . _ _ __ .- ', O ~ ~D l n ~o ~r . . . o ~) ~-1 ~~1 a~ ~ ~ ~X o o v : ~
O O 0~ -`~ , _ ~ ~` 0~ 10 ~ ~ ~
C~ . . . ~ O O
u~ ~ O ,1 ~r X v ~1 ~ r-~ ~0 O ~. .3~ .
~ ,~ ~
_ .
~ ~. ~
00 ~D ~ O O~ O
~r ~ ~ ,i u~ ~X ~o o ~ ~
CO, ~1 11~ O 1- V
_ ~1 . '.' O 00 O 10 ~) O .
LO ~ r~i ~9 ~X O O l CO ~) ~ O O ~ , ~ l _ \ ~, _ -'~
c~ oo ~ l r~ o~
t~ In . . ~r o t~ o ~) 0~ N X O O
N O O
.. ___ a) ~ ~ ~ ~1 ~`
~: _ ~o~ ~ O
~Jo\O td- 'Q ~. la ~:
rl ~ J.J ~ ~a ~ ~J ~ N
P~ ~ ~1 ~ ~ ~ . Il)~1 'tn 0~1 _ ~ 3 ~,a) E~ O O a~
. S~ ~ ~P ~ ~ ~ ~ ~ : ~ ' .~ Z ~ 1~ _ '~ ~ ~ ~ E3 ~U a) o ~ ~ a~ a) ~ ~ ~ I ~ ~ ~
O ~ ~;Il] N N ~ rl~ a) ~ la b- ~1 r~ ~ ~ E~ ~C ~ ~x o ~ a --~ 26 --., - . .
1~39886 From the above resul-ts, it ls seen that, in case of the molecular weight of polyethylene glycol being not more than 2,000, the folding endurance is strengthened more than 3 times, the burst strength, the low temperature impact strength and the end tearing strength are much improved, and the haze after treatment with boiliny water is remarkably increased.
Example 7 _ As in Example 5, a 35~ aqueous solution containing the nylon salt of MXD with adipic acid, which also contains 2.5, 5.0 or 10% of PEG-DA (PEG number average molecular weight 4,000), is charged in an autoclave, a phenolic oxida-tion inhibitor ("Irganox 1010" trademark of Ciba-Geigy A.G.) ~:
is added thereto to make a concentration of 0.05%, and poly-merization is carried out at 260C to give a polymer. The polymer is extruded at 255C through a T die to make a film of about 230 ~ in thickness, and the film is drawn at 98C
first in a machine direction at a draw ratio of 3.8 and then in a transverse direction at a draw ratio of 4.0 with a rate 20 of 5,000 %/min, followed by heat setting at 200C for 30 -seconds. The physical properties of the film thus obtained are shown in Table 5.
: - : - . . . . .: :. . . .
.... . .
~039886 TAsLE 5 Run No. 10 .. _ . _ . ._ .. __ Content of polyethylene glycol (~) 2.5 5 10 :
. . _ _ _ . _ Relative viscosity (~r) 2.24 2.27 2.31 ThicXness t~) 18 17 18 E4 -E _ _ -.
Scattering Index ( ---D - : 11.3 17.8 25.1 . .. ._ _ Puncture Resistance (time) 762 801 2310 : :
_ _ _. _ . _ .... _ ':
2 MD TD MD TD MD TD i Breaking strength (kg/mm )17 8 18.5 16.6 19.8 15.3 18.4 Breaking elongation (%) 44 30 46 35 64 37 ~:
. __ .__ __ . , '~: ' Initial2Young modulus :
(kg/mm ) 423 458 405 422 337 358 :~
_ _ _ .. ' Burst strength (kg~25 ~) 49 4 4 .. _ .
End tearing strength :-(kg/25 ~) 25 23 20 _ _ _ _ - i -FGlding endurance (time) 1457002 2008572 2019005 :
._ Low temperature impact strength (kg-cm/25 ~)8.5 8.3 7.5 , . _ ~
Transparence (%) 88.5 86.8 85.1 . .. ._ _ .
Haze (%) 3.7 6.8 8.5 _ Haze after treatment with boiling water (%) 4.6 8.3 10.2 ... _ ._ .. _ Oxygen permeability -13 -13 -13 coefficient 1.6x10 3.8x10 5.6x10 (CC-cm/cm2.sec.cmHg) . __ __ Plane orientation index 0.038 0.036 0.033 .
Degree of balance -0.023 -0.027 -0.013 _ I .
Particle size of islands (~' . - - : - - - .... . .
, ~03988~i Example 8 Polyxylyleneadipamide containing 2.5~ of PEG-DA
(PEG number average molecular weight, 8,300) in the condensate of MXD/PXD (73/23 in molar ratio) with adipic acid (No. 12), polyxylyleneadipamide containing 2.5% of PEG-DA (PEG number average molecular weight, 4,000) in the said condensate (No. 13), polyxylyleneadipamide containing 2.5% of PEG-DA
(PEG number average molecular weight, 2,980; amination per-cent, 91%) in the said condensate (No. 14), polyxylyleneadi- .
pamide containing 2.5% of polyethylene glycol/polypropylene glycol block copolymer (weight ratio~ 50 : 50; PEG number average molecular weight, 3,500; amination percent, 100~) in the said condensate (No. 15) and polyxylyleneadipamide not containing any polyether (No. 11) are each extruded as in Example 1 to make a film of about 250 ~ in thickness, which is then drawn and heat set. The physical properties of the film are shown in Table 6.
.:' - ` .' . . - -. :~
- ~
.: . . ::
~L039886 ~ l ~ ~ ~ T ~ ~
~ ~ O t~ O O N ~D r'l ~ ~ O t~
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~ 1 . , . ~
~` 30 ~
. . . ~ . .
, . . . . . - .
~0398~
~1 ~ co ~ ~r ~X ~. ~ Vll, _ _ ~ .......................................................
.' ~ o ~ co ~r 1,l O O ~
r~ ~ ~ ~ X o ol v~l ~7 1~ u~ ~ a~ l In ~ : .
r--I ~ CO N ~ X O O V 11 _ _ _ ~ ___ N N ~D (J~ X N O V ¦¦
.1 o:l ~11 o o~ ~ rl ~1 _ ,.
~1 ~) ~ N ~1 X O O l :~
_ _ . _ _ ~`.' E 3 X ::
u oP E^ E O o u~ ~ ~ ~ ~ (d R ,~ ~
. ~ o~ô h 3 U ~ O O a) ;:
a c c N N 1 X O ~) 11 O
.. . ..
.:;: ~ . . . , ; .
~. . . . . ..
~3g886 Example 9 -As in Example 5, a 40~ aqueous solution containing the nylon salt of MXD with adipic acid, which also contains 3~ of PEG-DA (PEG number average molecular weight, 4,000), is charged in an autoclave, and polymerization is carxied out at 260C to give a polymer. The polymer is extruded to make chips. The polymer shows a melting point of 239C, a relative viscosity of 2.41 and a water content of 0.08%.
The dried chips of the polymer obtained as above
-~L039~3~36 Example 3 Polyethylene glycol having a number average molecu-lar weight of 3,400 is treated with metallic sodium in dioxane to convert into the sodium alcoholate and then treated with ethyl monochloroacetate to give polyethylene glycol-bis-acetyl ethylate. This product (25 parts) is admixed with the nylon salt of MXD with adipic acid (1,000 parts) in water, and the polymerization is carried out as in Example 2. The thus produced polymer shows a melting point of 239C, a relative viscosity of 2.23 and a scattering index of 3.8. On the microscopic observation, the island structure of not more than 2 ~ in particle size is recognized.
Example 4 The dried chips of the polymer obtained in Example 2, No. 5 or Example 3 are extruded at 260C by the use of a T die to make a film of about 200 ~ in thickness, which is then drawn at 95C at a draw ratio of 3.5 in both of the machine and transverse directions and heat set to give a transparent film.
In the same manner as above, there are prepared transparent films made of a polymer manufactured by the same amount of polyethylene glycol but not aminated at the end and made of a polymer not including any polyethylene glycol.
The transparent films prepared as above are treated with steam for 20 minutes, and the transparence and the haze are measured. The results are shown in Table 3 wherein the value after water washing indicates the one measured on the film after treatment with steam and ~ashing sufficiently with water at 30C in a washing machine.
- ?
~ ~
. _ . .
Tra Isparen e (%) ] laze ~% _ sefore After Aftex sefore After After Film treat- treat- water treat- treat- water No. materials ment ment washing ment menk washing _ . ...
1 PEG~DA 88.8 88.4 88.6 3.0 5.2 3.6 PEG DC
2 containing 88.5 88.1 88.4 3.0 4.8 3.7 3 MoxnDta6ining 87.6 86.8 87.2 4.5 7.8 7.5 ;
4 MXD-6 89.2 78.8 86.7l 2.8 34 6 7.6 ~xample 5 A 40~ aqueous solution containing the nylon salt -of xylylenediamine consisting of 1~ of PXD and 99% of MXD
with adipic acid (1,200 parts) and a 10% aqueous solution of the salt of PEG-DA (PEG number average molecular weight, 8,300; amination percent, 90%) (12 parts) with an equivalent amount of adipic acid thereto are charged in an autoclavP, the atmosphere is replaced by nitrogen and the temperature is ele~ated under a pressure of 10 kg/cm2 to evaporate water. Then, the polymerization under atmospheric pressure is carried out at 260C, and the produced polymer is extruded to make chips, which are dried at 100C under reduced pressure. M.P., 239C, nr. 2.37. Water con~entj 0.05%.
The dried chips are melted at 260C in an extruder and extruded through a T die on a chill roll to make a film of 240 ~ in thickness. The film is drawn at 100C first in a machine direction at draw ratio of 3.8 and then in a ~)398~3S ::
transverse direction at a draw ratio of 4.0, the drawingrate being 5~000 %/min, followed by heat setting at 200C
for 30 seconds to make a transparent, elastic film.
Example 6 As in Example 5, the salt containing 1~ of PEG-DA
(PEG number average molecular weight, 610, 1,006, 2,030, 4,000 or 20,000; amino value percent, 80 to 90~) is subjected to polvmerization, the produced polymer is extruded to form a film and the film is drawn and heat set to give a trans- ;
lO parent film. The physical properties of the transparent film obtained in this Example as well as those of the transparent film obtained in Examle 1 are shown in Table 4.
, ~ ~.' . .
, : ' .. .
~ 24 -, . . . . . . .
... . . . .. ..
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::1039~136 _ _ N ___ a . N Ul V
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_ n ~' co ~D ~ _ E~ o~ ~ o~ ~D
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NN ~ ~ ' r~ N
. ~ ~ O ~1 :' O N N ~D ~ N .
U~ ~) U )CO _ Lrl ~ N O ~r N N ,_1 ~ O O ~r N N 1`
C~ ~ ~r ~c, _ ._ ~
N t~ ~r) O
~r I ~r ON CO ~ ' ~n O . o Cl:~ N ~ O
~1 E~U~ r~ o . _ ~ E~ N I~ ~D ~
N ~) ~1 N L~'~ - 0:~ ~9 N O
. ~ , . . .
~(~398~36 ~ r, ~ O r~l N O
t-~ t- ~r co X o o ,_ ~:r oo ~ o l _ ..... _ .. _ __ _.
l ~ ~
CO O O~ ~1 O 07 O W
,_1 1~ a~ N ~D X O O V
t~l . _ _ __ .- ', O ~ ~D l n ~o ~r . . . o ~) ~-1 ~~1 a~ ~ ~ ~X o o v : ~
O O 0~ -`~ , _ ~ ~` 0~ 10 ~ ~ ~
C~ . . . ~ O O
u~ ~ O ,1 ~r X v ~1 ~ r-~ ~0 O ~. .3~ .
~ ,~ ~
_ .
~ ~. ~
00 ~D ~ O O~ O
~r ~ ~ ,i u~ ~X ~o o ~ ~
CO, ~1 11~ O 1- V
_ ~1 . '.' O 00 O 10 ~) O .
LO ~ r~i ~9 ~X O O l CO ~) ~ O O ~ , ~ l _ \ ~, _ -'~
c~ oo ~ l r~ o~
t~ In . . ~r o t~ o ~) 0~ N X O O
N O O
.. ___ a) ~ ~ ~ ~1 ~`
~: _ ~o~ ~ O
~Jo\O td- 'Q ~. la ~:
rl ~ J.J ~ ~a ~ ~J ~ N
P~ ~ ~1 ~ ~ ~ . Il)~1 'tn 0~1 _ ~ 3 ~,a) E~ O O a~
. S~ ~ ~P ~ ~ ~ ~ ~ : ~ ' .~ Z ~ 1~ _ '~ ~ ~ ~ E3 ~U a) o ~ ~ a~ a) ~ ~ ~ I ~ ~ ~
O ~ ~;Il] N N ~ rl~ a) ~ la b- ~1 r~ ~ ~ E~ ~C ~ ~x o ~ a --~ 26 --., - . .
1~39886 From the above resul-ts, it ls seen that, in case of the molecular weight of polyethylene glycol being not more than 2,000, the folding endurance is strengthened more than 3 times, the burst strength, the low temperature impact strength and the end tearing strength are much improved, and the haze after treatment with boiliny water is remarkably increased.
Example 7 _ As in Example 5, a 35~ aqueous solution containing the nylon salt of MXD with adipic acid, which also contains 2.5, 5.0 or 10% of PEG-DA (PEG number average molecular weight 4,000), is charged in an autoclave, a phenolic oxida-tion inhibitor ("Irganox 1010" trademark of Ciba-Geigy A.G.) ~:
is added thereto to make a concentration of 0.05%, and poly-merization is carried out at 260C to give a polymer. The polymer is extruded at 255C through a T die to make a film of about 230 ~ in thickness, and the film is drawn at 98C
first in a machine direction at a draw ratio of 3.8 and then in a transverse direction at a draw ratio of 4.0 with a rate 20 of 5,000 %/min, followed by heat setting at 200C for 30 -seconds. The physical properties of the film thus obtained are shown in Table 5.
: - : - . . . . .: :. . . .
.... . .
~039886 TAsLE 5 Run No. 10 .. _ . _ . ._ .. __ Content of polyethylene glycol (~) 2.5 5 10 :
. . _ _ _ . _ Relative viscosity (~r) 2.24 2.27 2.31 ThicXness t~) 18 17 18 E4 -E _ _ -.
Scattering Index ( ---D - : 11.3 17.8 25.1 . .. ._ _ Puncture Resistance (time) 762 801 2310 : :
_ _ _. _ . _ .... _ ':
2 MD TD MD TD MD TD i Breaking strength (kg/mm )17 8 18.5 16.6 19.8 15.3 18.4 Breaking elongation (%) 44 30 46 35 64 37 ~:
. __ .__ __ . , '~: ' Initial2Young modulus :
(kg/mm ) 423 458 405 422 337 358 :~
_ _ _ .. ' Burst strength (kg~25 ~) 49 4 4 .. _ .
End tearing strength :-(kg/25 ~) 25 23 20 _ _ _ _ - i -FGlding endurance (time) 1457002 2008572 2019005 :
._ Low temperature impact strength (kg-cm/25 ~)8.5 8.3 7.5 , . _ ~
Transparence (%) 88.5 86.8 85.1 . .. ._ _ .
Haze (%) 3.7 6.8 8.5 _ Haze after treatment with boiling water (%) 4.6 8.3 10.2 ... _ ._ .. _ Oxygen permeability -13 -13 -13 coefficient 1.6x10 3.8x10 5.6x10 (CC-cm/cm2.sec.cmHg) . __ __ Plane orientation index 0.038 0.036 0.033 .
Degree of balance -0.023 -0.027 -0.013 _ I .
Particle size of islands (~' . - - : - - - .... . .
, ~03988~i Example 8 Polyxylyleneadipamide containing 2.5~ of PEG-DA
(PEG number average molecular weight, 8,300) in the condensate of MXD/PXD (73/23 in molar ratio) with adipic acid (No. 12), polyxylyleneadipamide containing 2.5% of PEG-DA (PEG number average molecular weight, 4,000) in the said condensate (No. 13), polyxylyleneadipamide containing 2.5% of PEG-DA
(PEG number average molecular weight, 2,980; amination per-cent, 91%) in the said condensate (No. 14), polyxylyleneadi- .
pamide containing 2.5% of polyethylene glycol/polypropylene glycol block copolymer (weight ratio~ 50 : 50; PEG number average molecular weight, 3,500; amination percent, 100~) in the said condensate (No. 15) and polyxylyleneadipamide not containing any polyether (No. 11) are each extruded as in Example 1 to make a film of about 250 ~ in thickness, which is then drawn and heat set. The physical properties of the film are shown in Table 6.
.:' - ` .' . . - -. :~
- ~
.: . . ::
~L039886 ~ l ~ ~ ~ T ~ ~
~ ~ O t~ O O N ~D r'l ~ ~ O t~
~ ~ O ~ _ ~0, Ir~ ~r _ _ v __ ~ t~
~ 1 . , . ~
~` 30 ~
. . . ~ . .
, . . . . . - .
~0398~
~1 ~ co ~ ~r ~X ~. ~ Vll, _ _ ~ .......................................................
.' ~ o ~ co ~r 1,l O O ~
r~ ~ ~ ~ X o ol v~l ~7 1~ u~ ~ a~ l In ~ : .
r--I ~ CO N ~ X O O V 11 _ _ _ ~ ___ N N ~D (J~ X N O V ¦¦
.1 o:l ~11 o o~ ~ rl ~1 _ ,.
~1 ~) ~ N ~1 X O O l :~
_ _ . _ _ ~`.' E 3 X ::
u oP E^ E O o u~ ~ ~ ~ ~ (d R ,~ ~
. ~ o~ô h 3 U ~ O O a) ;:
a c c N N 1 X O ~) 11 O
.. . ..
.:;: ~ . . . , ; .
~. . . . . ..
~3g886 Example 9 -As in Example 5, a 40~ aqueous solution containing the nylon salt of MXD with adipic acid, which also contains 3~ of PEG-DA (PEG number average molecular weight, 4,000), is charged in an autoclave, and polymerization is carxied out at 260C to give a polymer. The polymer is extruded to make chips. The polymer shows a melting point of 239C, a relative viscosity of 2.41 and a water content of 0.08%.
The dried chips of the polymer obtained as above
10 is extruded at 275C through a T die on a chill roll of 75C
to make a film of 170 ~ in thickness. The film is sent to rolls which are heated at 90C and different each other in the circumferential speed and drawn in a machine direction at a draw ratio of 3.5 with a circumferential speed of 2 m/
min at the low speed roll. The resulting uniaxially drawn film is then sent to a tenter heated at 110C and drawn in a transverse direction at a draw ratio of 4.5 with a rate of deformation of 5,000 ~/min. The resultant biaxially drawn film is passed through a zone for heat treatment at 20 200C for 20 seconds with a relaxation of 3~. The physical properties of the thus obtained heat set film are shown in Table 7.
- 32 - ~
...... . ,, , , '-~(~398~3~
. _ MD TD
-_ . _ . _. . "~,~,.
Thickness (~) 12 ... _ 2 . _. .
Breaking strength (kg/mm ) 19.8 26.9 _~
Breaking elongation (%) 43 32 ~--- 2 ~-~ - ~~-~~ -Initial Young modulus (kg/mm )410 454 ..._ ..
Burst strength (kg/25 ~) 6 ...__ .. _ . _ .__ End tearing strength (kg/25 ~) 26 Polding endurance (time) 1.56 x 10 Puncture Resistance (time) 620 . ._ Low temperature impact strength (kg-cm/25 ~) (-40C) 7.8 . . _ Transparence (%) 88.0 Haze (~) 3.5 ..__ , Haze after treatment with boiling water (%) 46 .. _ __ Oxygen permeability coefficient -13 (CC-cm/cm2.sec.cmHg) 2.2 x l0 Plane orientation index 0.042 Degree of balance 0.018 :
.~, - - - .
16~398~6 ~xample 10 .... .
A mixture of the nylon salt of xylylenediamine consisting of 1~ of PXD and 99% of MXD with adipic acid and the nylon salt of PEG-DA wlth adipic acid (PEG number average molecular weight, 8,300) in a weight ratio of 99 : 1 is subjected to polycondensation. The dried chips of the resulting polymer (M.P., 239C; relative viscosity, 2.37) are melted at 270C and extruded through a T die on a chill roll to make a film of about 210 ~ in thickness. The film is drawn in a machine direction at a draw ratio of 3.86 with a roll heated at 87C and then drawn in a transverse direction at a draw ratio of 4.35 in a tenter kept at 110C, followed by heat setting at 200C for 15 seconds to give a biaxially drawn film of 12 ~ in thickness.
An anchor coating agent (concentration, 4%) is applied on the surface of the above obtained biaxially drawn film according to the lami-roll method and, after drying -with hot wind of 110C in a drying apparatus of 2 m long, polyethylene ("Petrosen 205" trademark of Mitsui Polychemical Co., Ltd.) is melt extruded at 350C thereon with a rate of 60 m/min to make a layer of 40 ~I. The thus ohtained laminated film is subjected to heat bonding at 180C under 2 kg/cm2 for 1 second and then the pee] strength is measured. The results are sho~n in Table 8.
:
34 ;
. . .
:. : . ~ , , . -. ~
~039886 ._ _ . . . ~ .
Heat seal strength ~kg/15 mm) __ .
Before Af-ter Peel treatment treatment Anchor strength with boiling with boiling coating agent (g/20 mm) water water*) . _ .__ _ _ Nipporan 3002/
Coronet L -(trademark of Not Nippon Poly- peeled 3.6 3.4 urethane Co., Ltd.) ~ . ~ _ .
2319 (trademark Mot of Toyo Ink K.K.) peeled 3.4 3.2 _._ ..
(trademark of Not Dainippon Ink & peeled 3.6 3.5 Chemicals Inc.) _ .. .... __ (trademark of Dainippon Ink & Not Chemicals Inc.) Peeled 3.3 3.2 . . ~
None 180 3.0 1.8 . _ v' Note: *) Measured after treatment with boiling water for 30 minutes.
From the above results, it is understood that the adhesive strength between the polyamide film and a polyethylene film without any anchor coating agent is considerably low and the heat seal strength in such case ;
is much lowered by treatment with boiling water. Thus, the use of an anchor coating agent is recommendable.
Still, the laminated film as prepared in this Example can afford a bag o~ sufficient strength, when 103~886 manufactured by the use of an automatic bag making machine `. which is provided with a hot plate set at 220 to 230C andoperated at a speed capable of manufacturing 60 bags per minute.
.;
, ~
.'' ;' ;" .
, . . -~' ' ~ ' :
.- ~ '' '.
"', -''~ ' :, '`' ' ' - . '',,.,- ;'~ ,''., ` ~ ' :' - ~
- i-:. - : - . - . . . - . - ~. . .. .. .
-., , . . ~.. .. -,,; : . . . :, .
to make a film of 170 ~ in thickness. The film is sent to rolls which are heated at 90C and different each other in the circumferential speed and drawn in a machine direction at a draw ratio of 3.5 with a circumferential speed of 2 m/
min at the low speed roll. The resulting uniaxially drawn film is then sent to a tenter heated at 110C and drawn in a transverse direction at a draw ratio of 4.5 with a rate of deformation of 5,000 ~/min. The resultant biaxially drawn film is passed through a zone for heat treatment at 20 200C for 20 seconds with a relaxation of 3~. The physical properties of the thus obtained heat set film are shown in Table 7.
- 32 - ~
...... . ,, , , '-~(~398~3~
. _ MD TD
-_ . _ . _. . "~,~,.
Thickness (~) 12 ... _ 2 . _. .
Breaking strength (kg/mm ) 19.8 26.9 _~
Breaking elongation (%) 43 32 ~--- 2 ~-~ - ~~-~~ -Initial Young modulus (kg/mm )410 454 ..._ ..
Burst strength (kg/25 ~) 6 ...__ .. _ . _ .__ End tearing strength (kg/25 ~) 26 Polding endurance (time) 1.56 x 10 Puncture Resistance (time) 620 . ._ Low temperature impact strength (kg-cm/25 ~) (-40C) 7.8 . . _ Transparence (%) 88.0 Haze (~) 3.5 ..__ , Haze after treatment with boiling water (%) 46 .. _ __ Oxygen permeability coefficient -13 (CC-cm/cm2.sec.cmHg) 2.2 x l0 Plane orientation index 0.042 Degree of balance 0.018 :
.~, - - - .
16~398~6 ~xample 10 .... .
A mixture of the nylon salt of xylylenediamine consisting of 1~ of PXD and 99% of MXD with adipic acid and the nylon salt of PEG-DA wlth adipic acid (PEG number average molecular weight, 8,300) in a weight ratio of 99 : 1 is subjected to polycondensation. The dried chips of the resulting polymer (M.P., 239C; relative viscosity, 2.37) are melted at 270C and extruded through a T die on a chill roll to make a film of about 210 ~ in thickness. The film is drawn in a machine direction at a draw ratio of 3.86 with a roll heated at 87C and then drawn in a transverse direction at a draw ratio of 4.35 in a tenter kept at 110C, followed by heat setting at 200C for 15 seconds to give a biaxially drawn film of 12 ~ in thickness.
An anchor coating agent (concentration, 4%) is applied on the surface of the above obtained biaxially drawn film according to the lami-roll method and, after drying -with hot wind of 110C in a drying apparatus of 2 m long, polyethylene ("Petrosen 205" trademark of Mitsui Polychemical Co., Ltd.) is melt extruded at 350C thereon with a rate of 60 m/min to make a layer of 40 ~I. The thus ohtained laminated film is subjected to heat bonding at 180C under 2 kg/cm2 for 1 second and then the pee] strength is measured. The results are sho~n in Table 8.
:
34 ;
. . .
:. : . ~ , , . -. ~
~039886 ._ _ . . . ~ .
Heat seal strength ~kg/15 mm) __ .
Before Af-ter Peel treatment treatment Anchor strength with boiling with boiling coating agent (g/20 mm) water water*) . _ .__ _ _ Nipporan 3002/
Coronet L -(trademark of Not Nippon Poly- peeled 3.6 3.4 urethane Co., Ltd.) ~ . ~ _ .
2319 (trademark Mot of Toyo Ink K.K.) peeled 3.4 3.2 _._ ..
(trademark of Not Dainippon Ink & peeled 3.6 3.5 Chemicals Inc.) _ .. .... __ (trademark of Dainippon Ink & Not Chemicals Inc.) Peeled 3.3 3.2 . . ~
None 180 3.0 1.8 . _ v' Note: *) Measured after treatment with boiling water for 30 minutes.
From the above results, it is understood that the adhesive strength between the polyamide film and a polyethylene film without any anchor coating agent is considerably low and the heat seal strength in such case ;
is much lowered by treatment with boiling water. Thus, the use of an anchor coating agent is recommendable.
Still, the laminated film as prepared in this Example can afford a bag o~ sufficient strength, when 103~886 manufactured by the use of an automatic bag making machine `. which is provided with a hot plate set at 220 to 230C andoperated at a speed capable of manufacturing 60 bags per minute.
.;
, ~
.'' ;' ;" .
, . . -~' ' ~ ' :
.- ~ '' '.
"', -''~ ' :, '`' ' ' - . '',,.,- ;'~ ,''., ` ~ ' :' - ~
- i-:. - : - . - . . . - . - ~. . .. .. .
-., , . . ~.. .. -,,; : . . . :, .
Claims (13)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A block copolymer consisting of segments of at least one polyamide and segments of at least one polyether, said polyether and polyamide being chemically bonded to each other but the polyether segments being distributed in the block copolymer in an agglomerated state to form islands of maximum size not more than 10 µ, the content of the polyamide being 99.8 to 90 per cent and that of the polyether being 0.2 to 10 per cent, by weight based on the block copolymer, the block copolymer having a scattering index of not less than 1, the polyamide comprising a diamine constituent containing 100 to 50 mol per cent of m-xylylene-diamine or its mixture with p-xylylenediamine and 0 to 50 mol per cent of another amine component and the dicarboxylic acid constituent comprising 100 to 50 mol per cent of at least one aliphatic dicarboxylic acid having 6 to 12 carbon atoms and 0 to 50 mol per cent of another carboxylic acid component and the polyether having a molecular weight of 2,000 to 20,000 and being represented by the formula:
(A) wherein X and X' are each hydrogen, a hydrocarbon group having 1 to 20 carbon atoms or a group having 1 to 6 carbon atoms and bearing an amino , carboxyl and/or esterified carboxyl group, at least one of X and X' being a group having 1 to 6 carbon atoms and bearing an amino, carboxyl, esterified carboxyl group, Y is alkylene or cycloalkylene having not more than 6 carbon atoms and n is a number which can set the molecular weight of the compound (A) within a range of 2,000 to 20,000.
(A) wherein X and X' are each hydrogen, a hydrocarbon group having 1 to 20 carbon atoms or a group having 1 to 6 carbon atoms and bearing an amino , carboxyl and/or esterified carboxyl group, at least one of X and X' being a group having 1 to 6 carbon atoms and bearing an amino, carboxyl, esterified carboxyl group, Y is alkylene or cycloalkylene having not more than 6 carbon atoms and n is a number which can set the molecular weight of the compound (A) within a range of 2,000 to 20,000.
2. The block copolymer according to claim 1, wherein the diamine constituent contains 100 to 70 mol % of m-xylylene-diamine or its mixture with p-xylylene-diamine.
3. The block copolymer according to claim 1, wherein the dicarboxylic acid constituent contains 100 to 70 mol % of at least one aliphatic dicarboxylic acid having 6 to 12 carbon atoms.
4. The block copolymer according to claim 1, wherein the diamine constituent contains 100 to 70 mol %
of a mixture of m-xylylenediamine and p-xylylenediamine, the content of p-xylylenediamine being not more than about 30% by weight based on the mixture, and the dicarboxylic acid constituent contains 100 to 70 mol % of at least one aliphatic dicarboxylic acid having 6 to 12 carbon atoms.
of a mixture of m-xylylenediamine and p-xylylenediamine, the content of p-xylylenediamine being not more than about 30% by weight based on the mixture, and the dicarboxylic acid constituent contains 100 to 70 mol % of at least one aliphatic dicarboxylic acid having 6 to 12 carbon atoms.
5. The block copolymer according to claim 1, wherein the polyether agglomerates have a maximum size of not more than about 6 µ and an average size of not more than about 3 µ.
6. The block copolymer according to claim 1, wherein the polyamide is m-xylylenedipamide and the polyether is bis-aminopropyl(polyethylene oxide).
7. The block copolymer according to claim 1, wherein the polyamide is m-xylylene/p-xylylene/adipamide and the polyether is bis-aminopropyl (polyethylene oxide).
8. The block copolymer according to claim 1, wherein the polyamide is the reaction product of m-xylylene-diamine/hexamethylenediamine/adipic acid and the polyether is bis-aminopropyl (polyethylene oxide).
9. The block copolymer according to claim 1, in the form of a film.
10. The block copolymer according to claim 9 wherein the film has an initial Young modulus (at 20°C) of not less than 200 kg/mm2 , folding endurance of not less than 5,000 and oxygen permeability coefficient (at 30°C) of not more than 2 x 10-12 ml?cm/cm2?sec cm Hg.
11. The block copolymer according to claim 9 in the form of a biaxially drawn film having a breaking strength in machine and transverse directions of not less than 10 kg/mm2, breaking elongation of 20 to 120 %, folding endurance of not less than 150,000 and low temperature impact strength (at 40°C) of not less than 6 kg-cm/25 µ.
12. The block copolymer film according to claim 9 in the form of a laminate and including at least one layer selected from a heat seal layer, metallic foil, printing layer and a film suitable for printing or surface protecting layer on at least one surface of said film.
13. A process for preparing a block copolymer as claimed in Claim 1 which comprises subjecting an aqueous slurry comprising at least one diamine component containing 100 to 50 mol per cent of m-xylylenediamine or its mixture with p-xylylenediamine, and 0 to 50 mol per cent of another amine component and at least one dicarboxylic acid component containing 100 to 50 mol per cent of at least one aliphatic dicarboxylic acid having 6 to 12 carbon atoms and 0 to 50 mol per cent of another carboxylic acid component, to heat polymerization in the presence of at least one polyether having a molecular weight of 2,000 to 20,000 and an amino or carboxyl group in at least one terminal position, under steam pressurized conditions within a gauge pressure range of 5 to 15 kg/cm2 up to the production of polymer of low degree of polymerization corresponding to a relative viscosity of 1.2 to 1.5, releasing steam so as to make pressure atmospheric and then continuing polymerization to produce a higher degree of polymerization.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1531873A JPS5519948B2 (en) | 1973-02-06 | 1973-02-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1039886A true CA1039886A (en) | 1978-10-03 |
Family
ID=11885413
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA191,942A Expired CA1039886A (en) | 1973-02-06 | 1974-02-06 | Block copolymer of polyamide and polyether, and its preparation and use |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US3946089A (en) |
| JP (1) | JPS5519948B2 (en) |
| CA (1) | CA1039886A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2930343A1 (en) * | 1979-07-26 | 1981-02-19 | Huels Chemische Werke Ag | MOLDS FROM A HIGH MOLECULAR LINEAR POLYESTER |
| JPS56117211U (en) * | 1980-02-09 | 1981-09-08 | ||
| US4346200A (en) * | 1980-12-29 | 1982-08-24 | Monsanto Company | Thermoplastic polyamide compositions |
| JPS58206628A (en) | 1982-05-27 | 1983-12-01 | Toray Ind Inc | Preparation of polyether ester amide |
| JPS60174629A (en) * | 1984-02-20 | 1985-09-07 | Mitsubishi Monsanto Chem Co | Manufacture of biaxially oriented polyamide film |
| DE3425318A1 (en) * | 1984-07-10 | 1986-01-16 | Bayer Ag, 5090 Leverkusen | BRANCHED, THERMOPLASTICALLY PROCESSABLE, IMPACT TOE POLYAMIDE |
| JPH0442105Y2 (en) * | 1986-07-25 | 1992-10-05 | ||
| US4923742A (en) * | 1986-10-15 | 1990-05-08 | Kimberly-Clark Corporation | Elastomeric polyether block amide nonwoven web |
| US4820572A (en) * | 1986-10-15 | 1989-04-11 | Kimberly-Clark Corporation | Composite elastomeric polyether block amide nonwoven web |
| US4724184A (en) * | 1986-10-15 | 1988-02-09 | Kimberly-Clark Corporation | Elastomeric polyether block amide nonwoven web |
| US4919997A (en) * | 1987-11-06 | 1990-04-24 | Allied-Signal Inc. | Melt-blown water-absorbing tissues and matts |
| EP0540293B1 (en) * | 1991-10-28 | 1996-07-24 | Idemitsu Petrochemical Co. Ltd. | Oriented film easy to split and method of producing the same |
| DE69631449T2 (en) * | 1995-04-11 | 2004-09-16 | Atofina | Packaging made of polymers with polyamide and polyether blocks to keep products fresh |
| US6110411A (en) * | 1997-03-18 | 2000-08-29 | Clausen; Christian Henning | Laser sinterable thermoplastic powder |
| US6162857A (en) | 1997-07-21 | 2000-12-19 | Eastman Chemical Company | Process for making polyester/platelet particle compositions displaying improved dispersion |
| US6010971A (en) * | 1997-11-21 | 2000-01-04 | Kimberly-Clark Worldwide, Inc. | Polyethylene oxide thermoplastic composition |
| US6110849A (en) * | 1997-12-19 | 2000-08-29 | Kimberly-Clark Worlwide, Inc. | Thermoplastic composition including polyethylene oxide |
| US6486252B1 (en) | 1997-12-22 | 2002-11-26 | Eastman Chemical Company | Nanocomposites for high barrier applications |
| US6239233B1 (en) | 1998-10-09 | 2001-05-29 | Eastman Chemical Company | Polyester/polyamide blends with improved color |
| JP2002531666A (en) * | 1998-12-07 | 2002-09-24 | イーストマン ケミカル カンパニー | High I.D. developed using oligomer resin precursor V. Method for producing polymer nanocomposites and articles made therefrom |
| US6384121B1 (en) | 1998-12-07 | 2002-05-07 | Eastman Chemical Company | Polymeter/clay nanocomposite comprising a functionalized polymer or oligomer and a process for preparing same |
| US6552114B2 (en) | 1998-12-07 | 2003-04-22 | University Of South Carolina Research Foundation | Process for preparing a high barrier amorphous polyamide-clay nanocomposite |
| WO2000034375A1 (en) * | 1998-12-07 | 2000-06-15 | Eastman Chemical Company | A polymer/clay nanocomposite comprising a clay mixture and a process for making same |
| US6548587B1 (en) | 1998-12-07 | 2003-04-15 | University Of South Carolina Research Foundation | Polyamide composition comprising a layered clay material modified with an alkoxylated onium compound |
| AU758470B2 (en) * | 1998-12-07 | 2003-03-20 | University Of South Carolina Research Foundation | Polymer/clay nanocomposite and process for making same |
| BR9916039A (en) | 1998-12-07 | 2001-12-04 | Eastman Chem Co | Polymer-clay nanocomposite, article, composition, and process for the preparation of a polymer-clay nanocomposite |
| US6610772B1 (en) | 1999-08-10 | 2003-08-26 | Eastman Chemical Company | Platelet particle polymer composite with oxygen scavenging organic cations |
| US6777479B1 (en) | 1999-08-10 | 2004-08-17 | Eastman Chemical Company | Polyamide nanocomposites with oxygen scavenging capability |
| US6486253B1 (en) | 1999-12-01 | 2002-11-26 | University Of South Carolina Research Foundation | Polymer/clay nanocomposite having improved gas barrier comprising a clay material with a mixture of two or more organic cations and a process for preparing same |
| CA2393015A1 (en) | 1999-12-01 | 2001-06-07 | Gary Wayne Connell | A polymer-clay nanocomposite comprising an amorphous oligomer |
| US6737464B1 (en) | 2000-05-30 | 2004-05-18 | University Of South Carolina Research Foundation | Polymer nanocomposite comprising a matrix polymer and a layered clay material having a low quartz content |
| JP2003535204A (en) * | 2000-05-30 | 2003-11-25 | ユニバーシティ オブ サウスカロライナ リサーチ ファウンデーション | Polymer nanocomposites containing matrix polymers and layered clay materials with improved levels of extractables |
| US6962670B1 (en) | 2000-08-16 | 2005-11-08 | Eastman Chemical Company | Determination of layer thickness or non-uniformity of layer thickness based on fluorophore additives |
| US20050159526A1 (en) * | 2004-01-15 | 2005-07-21 | Bernard Linda G. | Polymamide nanocomposites with oxygen scavenging capability |
| DE102005031491A1 (en) * | 2005-07-04 | 2007-01-11 | Degussa Ag | Use of a polyamide molding composition having high melt stiffness for coextrusion with a refractory polymer |
| JP5383496B2 (en) * | 2006-11-09 | 2014-01-08 | ヴァルスパー・ソーシング・インコーポレーテッド | Powder composition and method for producing articles therefrom |
| US8247492B2 (en) | 2006-11-09 | 2012-08-21 | Valspar Sourcing, Inc. | Polyester powder compositions, methods and articles |
| WO2009078240A1 (en) * | 2007-12-17 | 2009-06-25 | Kureha Corporation | Thermally shrinkable laminate film for deep drawing, packaged article, and method for packaging of cheese |
| WO2012111636A1 (en) * | 2011-02-14 | 2012-08-23 | 三菱瓦斯化学株式会社 | Polyether polyamide elastomer |
| WO2012111635A1 (en) * | 2011-02-14 | 2012-08-23 | 三菱瓦斯化学株式会社 | Polyether polyamide elastomer |
| US8993677B2 (en) * | 2011-06-10 | 2015-03-31 | Mitsubishi Gas Chemical Company, Inc. | Reactive polyamide resins and polyamide resin compositions |
| KR20150043305A (en) * | 2012-08-14 | 2015-04-22 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Polyether-polyamide composition |
| WO2014027649A1 (en) * | 2012-08-14 | 2014-02-20 | 三菱瓦斯化学株式会社 | Polyether polyamide resin composition |
| KR20150044884A (en) * | 2012-08-14 | 2015-04-27 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Polyether polyamide composition |
| JP6094342B2 (en) * | 2013-04-09 | 2017-03-15 | 三菱瓦斯化学株式会社 | Inner liner for pneumatic tires |
| US20160046836A1 (en) * | 2013-04-09 | 2016-02-18 | Mitsubishi Gas Chemical Company, Inc. | Metal-coating material |
| TW201821477A (en) | 2016-08-09 | 2018-06-16 | 英商英威達紡織〈英國〉有限公司 | Nylon polymer |
| US20240042677A1 (en) | 2021-04-19 | 2024-02-08 | Jabil Inc. | Elastomeric additive manufacturing composition |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1129657A (en) * | 1964-12-02 | 1968-10-09 | Asahi Chemical Ind | Method for preparing copolymers |
| GB1180403A (en) * | 1966-02-11 | 1970-02-04 | Toyo Rayon Co Ltd | Polyamide Resin Composition |
| FR1550292A (en) * | 1966-11-01 | 1968-12-20 | ||
| US3514498A (en) * | 1966-11-01 | 1970-05-26 | Toray Industries | Antistatic synthetic resin composition containing a polyether - polyamide block copolymer wherein an ionic functional group is made to coexist |
| US3594266A (en) * | 1967-06-03 | 1971-07-20 | Toyo Rayon Co Ltd | Composite filament |
| US3522329A (en) * | 1968-02-06 | 1970-07-28 | Kaoru Okazaki | Composition comprising polyester and polyether-polyamide blockcopolymer |
-
1973
- 1973-02-06 JP JP1531873A patent/JPS5519948B2/ja not_active Expired
-
1974
- 1974-02-06 CA CA191,942A patent/CA1039886A/en not_active Expired
- 1974-02-06 US US05/439,987 patent/US3946089A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5519948B2 (en) | 1980-05-29 |
| JPS49105850A (en) | 1974-10-07 |
| US3946089A (en) | 1976-03-23 |
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