CA1231490A - Thermoplastic resin composition - Google Patents
Thermoplastic resin compositionInfo
- Publication number
- CA1231490A CA1231490A CA000489326A CA489326A CA1231490A CA 1231490 A CA1231490 A CA 1231490A CA 000489326 A CA000489326 A CA 000489326A CA 489326 A CA489326 A CA 489326A CA 1231490 A CA1231490 A CA 1231490A
- Authority
- CA
- Canada
- Prior art keywords
- resin composition
- polypropylene
- thermoplastic resin
- copolymer
- composition according
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
Abstract
Abstract THERMOPLASTIC RESIN COMPOSITION
A novel thermoplastic resin composition is provided. It has excellent balance in the physical properties and is usable as shaped articles, sheets and films having excellent appearance in uniformity and smoothness. The thermoplastic resin composition is a blend of a resin composition (D) with a copolymer (C) containing an epoxy group, said resin composition (D) being composed of polypropylene graft-modified (A) with an unsaturated carboxylic acid or anhydride thereof, with or without unmodified polypropylene, and a saturated polyester resin (B). The copolymer (C) is composed of an unsaturated epoxy compound and ethylene, with or without an ethylenically unsaturated compound other than ethylene.
A novel thermoplastic resin composition is provided. It has excellent balance in the physical properties and is usable as shaped articles, sheets and films having excellent appearance in uniformity and smoothness. The thermoplastic resin composition is a blend of a resin composition (D) with a copolymer (C) containing an epoxy group, said resin composition (D) being composed of polypropylene graft-modified (A) with an unsaturated carboxylic acid or anhydride thereof, with or without unmodified polypropylene, and a saturated polyester resin (B). The copolymer (C) is composed of an unsaturated epoxy compound and ethylene, with or without an ethylenically unsaturated compound other than ethylene.
Description
Al TIER PLASTIC RESIN COMPOSITION
This invention relates to a novel thermoplastic resin composition usable as shaped articles, sheets and films by injection molding, extrusion molding and the like. More particularly, it relates to a novel thermos plastic resin composition excellent in balance among physical properties and appearance, which is composed of polypropylene resin, a saturated polyester resin and a co-polymer containing an epoxy group.
Polypropylene possesses excellent properties in processability,toughness, water resistance, gasoline resistance and chemical resistance. It has small specie lie gravity and is inexpensive. It has been hence conventionally used widely for various shaped articles, films and sheets.
However, polypropylene possesses shortcomings or difficulties to be improved in heat resistance, rigidity, impact resistance, paintability, adhesion and printability. These problems arrest the new development in commercial applications. In order to improve paint-ability, adhesion and printability, a process had been proposed wherein at least a part of polypropylene is modified by having such unsaturated carboxylic acid or android thereof as malefic android grafted thereon (Japanese Examined Patent Publication No. 47413J1983;
Japanese Unexamined Patent Publication No. 49736/1983).
However, the modification is not satisfactory yet in order to have impact resistance, heat resistance, rigid-try or other properties substantially improved On the other hand, saturated polyester resins are widely used for automotive parts, and electric and electronic parts as an engineering resin having outstanding ,:
I
features in heat resistance, rigidity, strength and oil resistance. Further improvements are still expected, however, in process ability, impact resistance (notched, water resistance and chemical resistance. Besides, it has essential difficulties, i.e., greater specific gravity than polyolefin, and is expensive.
From the viewpoint above, the possibility of novel wider applications will be expected when a thermoplastic resin appears which possesses both features of pulpier-pylon resin and saturated polyester resin, by blending polypropylene resin selected from modified polypropylene with or without unmodified polypropylene and saturated polyester resin. However, it is known that polypropylene resin is hardly compatible with a saturated polyester resin. Blending simply causes too much damages to a mixture product: (1) since Bars effect of molten polyp men is extreme, stable intake of extruded strand is next to impossible, and processabilit~ is very poor;
This invention relates to a novel thermoplastic resin composition usable as shaped articles, sheets and films by injection molding, extrusion molding and the like. More particularly, it relates to a novel thermos plastic resin composition excellent in balance among physical properties and appearance, which is composed of polypropylene resin, a saturated polyester resin and a co-polymer containing an epoxy group.
Polypropylene possesses excellent properties in processability,toughness, water resistance, gasoline resistance and chemical resistance. It has small specie lie gravity and is inexpensive. It has been hence conventionally used widely for various shaped articles, films and sheets.
However, polypropylene possesses shortcomings or difficulties to be improved in heat resistance, rigidity, impact resistance, paintability, adhesion and printability. These problems arrest the new development in commercial applications. In order to improve paint-ability, adhesion and printability, a process had been proposed wherein at least a part of polypropylene is modified by having such unsaturated carboxylic acid or android thereof as malefic android grafted thereon (Japanese Examined Patent Publication No. 47413J1983;
Japanese Unexamined Patent Publication No. 49736/1983).
However, the modification is not satisfactory yet in order to have impact resistance, heat resistance, rigid-try or other properties substantially improved On the other hand, saturated polyester resins are widely used for automotive parts, and electric and electronic parts as an engineering resin having outstanding ,:
I
features in heat resistance, rigidity, strength and oil resistance. Further improvements are still expected, however, in process ability, impact resistance (notched, water resistance and chemical resistance. Besides, it has essential difficulties, i.e., greater specific gravity than polyolefin, and is expensive.
From the viewpoint above, the possibility of novel wider applications will be expected when a thermoplastic resin appears which possesses both features of pulpier-pylon resin and saturated polyester resin, by blending polypropylene resin selected from modified polypropylene with or without unmodified polypropylene and saturated polyester resin. However, it is known that polypropylene resin is hardly compatible with a saturated polyester resin. Blending simply causes too much damages to a mixture product: (1) since Bars effect of molten polyp men is extreme, stable intake of extruded strand is next to impossible, and processabilit~ is very poor;
(2) the injection molded articles are extremely ununiform and are poor in appearance because of flow marks, and cannot he applicable practically for use in automotive parts or electronic and electric parts; and I the mechanical properties, in particular t impact resistance and tensile elongation of moldings are lower than those expected from the properties of the individual resins.
It is an object of this invention to provide a novel thermoplastic resin composition possessing an extremely satisfactory balance in properties including process ability, rigidity, heat resistance, impact resistance, scratch resistance, paintability, oil nests-lance, chemical resistance and water resistance, and excelling in appearance in uniformity and smoothness.
The present invention resides in a thermoplastic resin composition comprising 100 parts by weight of a resin composition (Do defined below and 2 to 30 parts by weight of copolymer (C) which is a copolymer of (a) ethylene and an unsaturated epoxy compound having one of the formulas If 2 / 2 and R-X-CH2-CH\-~H2 wherein R is a hydrocarbon group with 2 - 18 carbon atoms having an ethylenically unsaturated bond and X is -SHEA-or O-, or (b) ethylene, the unsaturated epoxy compound defined above and vinyl esters of saturated carboxylic acids having 2 to 6 carbon atoms, esters of a saturated alcohol component having 1 to B carbon atoms with acrylic or methacrylic acid, halogenated vinyl compounds or vinyl ethers, said resin composition (D) being composed of 50 to 90 White of polypropylene-resin (A) which is a grafted-copolymer of a polypropylene with 0.05 to 20 wt. 3 of an unsaturated carboxylic acid or android thereof or said grafted-copolymer and polypropylene and 50 to 10 wt. %
of saturated polyester resin (so composed or a dicarboxylic acid moiety, at least 40 mow % of thy dicarboxylic moiety being from terephthalic acid, and a dill moiety.
The polypropylene resin (A is modified polyp propylene with or without unmodified polypropylene. Here, polypropylene refers to crystalline polypropylene. It includes, besides homopolymers of propylene, lock or random copolymers of propylene copolymerized with, for example elan buttonhole or other olefins~ The modified polypropylene is a product of graft modification , I
pa -of such homopolymer or copolymer of propylene with an us-saturated carboxylic acid or its android in the range of 0.05 to 20 wt. %, or preferably 0.1 to 10 wt. I. The melt index of this polypropylene resin IAN may be in the 5 range of 0.1 to 100, preferably 0.5 to 40.
The homopolymer and block or random copolymers of propylene may be obtained by the reaction in the presence of a combined catalyst system of, for example, titanium trichloride and an alkylaluminum compound which is familiar as the Ziegler-Natta type catalyst.
The modified polypropylene is one which is graft-modified with an unsaturated carboxylic acid or its android. Examples of monomers to be grafted include acrylic acid, methacrylic acid, malefic acid, itaconic acid, malefic android and itaconic android.
Particularly, malefic android is preferable.
Grating the monomers onto polypropylene may be effected by various known methods. For example, polypropylene, a grafting monomer and a radical initiator are mixed, and kneaded in the molten state in an extrude.
Alternatively, polypropylene is dissolved in an organic solvent such as ~ylene, and a radical initiator is added thereto under nitrogen atmosphere, then, the mixture is allowed to react under heat, cooled after the reaction, washed, filtered and dried. Furthermore, polypropylene may be irradiated with ultraviolet rays or radial rays, or brought into contact with oxygen or ozone in the presence of the grafting monomers.
Saturated polyester resin (B) is composed of a dicarboxylic acid moiety and a dill moiety. At least 40 mol.% of the wormer dicarboxylic acid moiety is terephthalic acid. The remaining acid, if any, is at least one of aliphatic dicarbo~ylic acids hazing 2 - 20 carbon atoms such as adipic acid, sebacic acid, dodecane-dicarboxylic acid, etc., aromatic dicarboxylic acids such as isophthalic acid, naphthalenedicarboxylic acid, etc., and alicyclic dicarboxylic acids such as cycle-hexanedicarbo~ylic acid, etc. eye dill moiety is at least one of aliphatic glycol and alicyclic glycol, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1.6-hexanediol, 1,10-decanediol, 1,4-cyclohe~anediol.
Polybutylene terephthalate and polyethylene terephthalate are most preferable. The saturated polyp ester resins (B) should have intrinsic viscosity of within the range of 0.5 - 3.0 (in o-chlorophenol~ 25C~.
No product is obtained which has desirable mechanical properties, as long as saturated polyester resin (B) does not satisfy the intrinsic viscosity defined above.
The copolymer (C) containing an epoxy group is a I, 5 I
copolymer of an unsaturated epoxy compound and an ethyl-Nikolai unsaturated compound. The composition ratio of the copolymer (C) containing an epoxy resin is not part-ocularly limited, but the unsaturated epoxy compound may be present in an am~lnt of 0.1 to 50 wt.%, preferably l to 30 White The unsaturated epoxy compound possesses an unsaturated group which is copolymerizable with an ethylenically unsaturated compound, and an epoxy group.
For example, unsaturated glycidyl esters or unsaturated glycidyl ethers having the formula (1) or (2) below may be used.
R-ll--CH2-C\-/H2 (1) O O
where R is a hydrocarbon group with 2 to 18 carbon atoms having an ethylenically unsaturated bond;
R-X-CH2-CH-CH2 (2) where R is the same as defined above and X is -SHEA- or -O-.
Examples thereof are glycidyl acrylate, glycidyl methacrylate, glycidyl itaconate, ally glycidyl ether, 2-methylallyl glycidyl ether, stroll glycidyl ether and the like.
The ethylenically unsaturated compound may be olefins, vinyl esters of saturated carboxylic acids having 2 to 6 carbon atoms, esters of a saturated alcohol component having 1 to 8 carbon atoms with acrylic or methacrylic acid, Maltese, methacrylates, fumarates, halogenated vinyl compounds, styrenes, nitrites, vinyl ethers and acrylamides~ Examples are ethylene, propylene, button, vinyl acetate, methyl acrylate, ethyl acrylate, methyl methacrylate, deathly Malta, deathly fumaràte, vinyl chloride, vinylidene chloride, styrenes acrylonitrile, ., I
isobutyl vinyl ether, acrylamide and the like. Above all, ethylene is particularly preferable.
The copolymer I containing an epoxy group may be prepared by various methods. One of the methods is a random copolymeri~ation method in which an unsaturated epoxy compound is introduced into the trunk chain of the copolymer. Alternatively, a graft copolymerization method is effected in which an unsaturated epoxy compound is introduced as the side chain of the copolymer. Specific gaily, for instance, an unsaturated epoxy compound and ethylene are copolymerized in the presence of a radical initiator at 500 to 4,000 atmospheric pressures and 100 to 300C, with or without a proper solvent or a chain transfer agent. Alternatively, an unsaturated epoxy compound and a radical initiator are mixed with pulpier pylon, and the mixture is molten in an extrude for graft copolymerization; or an unsaturated epoxy compound and an ethylenically unsaturated compound are copolymeri~ed in the presence of a radical initiator in an inert solvent such as an organic solvent or water.
In the thermoplastic resin composition according to this invention, the polypropylene resin PA) as the first component is present in an amount of 50 to 90 wt. %, preferably 60 to 80 woo or on the basis of PA) plus By If the amount of polypropylene resin PA) is less than 50 wt.%, process ability toughness, water resistance and chemical resistance are not satisfactory, while if the amount thereof is more than 90 White, favorable properties are not obtainable in the heat resistance, strength and rigidity. When modified polypropylene is used with unmodified polypropylene it is necessary that the amount of modified polypropylene should be 5 wt.% or more in the mixture. If the amount of modified one is less than S wt.
I, toughness and impact resistance obtained are not satisfactory and no substantial improvement is expected in paintability, adhesion and printability, I`
It is an object of this invention to provide a novel thermoplastic resin composition possessing an extremely satisfactory balance in properties including process ability, rigidity, heat resistance, impact resistance, scratch resistance, paintability, oil nests-lance, chemical resistance and water resistance, and excelling in appearance in uniformity and smoothness.
The present invention resides in a thermoplastic resin composition comprising 100 parts by weight of a resin composition (Do defined below and 2 to 30 parts by weight of copolymer (C) which is a copolymer of (a) ethylene and an unsaturated epoxy compound having one of the formulas If 2 / 2 and R-X-CH2-CH\-~H2 wherein R is a hydrocarbon group with 2 - 18 carbon atoms having an ethylenically unsaturated bond and X is -SHEA-or O-, or (b) ethylene, the unsaturated epoxy compound defined above and vinyl esters of saturated carboxylic acids having 2 to 6 carbon atoms, esters of a saturated alcohol component having 1 to B carbon atoms with acrylic or methacrylic acid, halogenated vinyl compounds or vinyl ethers, said resin composition (D) being composed of 50 to 90 White of polypropylene-resin (A) which is a grafted-copolymer of a polypropylene with 0.05 to 20 wt. 3 of an unsaturated carboxylic acid or android thereof or said grafted-copolymer and polypropylene and 50 to 10 wt. %
of saturated polyester resin (so composed or a dicarboxylic acid moiety, at least 40 mow % of thy dicarboxylic moiety being from terephthalic acid, and a dill moiety.
The polypropylene resin (A is modified polyp propylene with or without unmodified polypropylene. Here, polypropylene refers to crystalline polypropylene. It includes, besides homopolymers of propylene, lock or random copolymers of propylene copolymerized with, for example elan buttonhole or other olefins~ The modified polypropylene is a product of graft modification , I
pa -of such homopolymer or copolymer of propylene with an us-saturated carboxylic acid or its android in the range of 0.05 to 20 wt. %, or preferably 0.1 to 10 wt. I. The melt index of this polypropylene resin IAN may be in the 5 range of 0.1 to 100, preferably 0.5 to 40.
The homopolymer and block or random copolymers of propylene may be obtained by the reaction in the presence of a combined catalyst system of, for example, titanium trichloride and an alkylaluminum compound which is familiar as the Ziegler-Natta type catalyst.
The modified polypropylene is one which is graft-modified with an unsaturated carboxylic acid or its android. Examples of monomers to be grafted include acrylic acid, methacrylic acid, malefic acid, itaconic acid, malefic android and itaconic android.
Particularly, malefic android is preferable.
Grating the monomers onto polypropylene may be effected by various known methods. For example, polypropylene, a grafting monomer and a radical initiator are mixed, and kneaded in the molten state in an extrude.
Alternatively, polypropylene is dissolved in an organic solvent such as ~ylene, and a radical initiator is added thereto under nitrogen atmosphere, then, the mixture is allowed to react under heat, cooled after the reaction, washed, filtered and dried. Furthermore, polypropylene may be irradiated with ultraviolet rays or radial rays, or brought into contact with oxygen or ozone in the presence of the grafting monomers.
Saturated polyester resin (B) is composed of a dicarboxylic acid moiety and a dill moiety. At least 40 mol.% of the wormer dicarboxylic acid moiety is terephthalic acid. The remaining acid, if any, is at least one of aliphatic dicarbo~ylic acids hazing 2 - 20 carbon atoms such as adipic acid, sebacic acid, dodecane-dicarboxylic acid, etc., aromatic dicarboxylic acids such as isophthalic acid, naphthalenedicarboxylic acid, etc., and alicyclic dicarboxylic acids such as cycle-hexanedicarbo~ylic acid, etc. eye dill moiety is at least one of aliphatic glycol and alicyclic glycol, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1.6-hexanediol, 1,10-decanediol, 1,4-cyclohe~anediol.
Polybutylene terephthalate and polyethylene terephthalate are most preferable. The saturated polyp ester resins (B) should have intrinsic viscosity of within the range of 0.5 - 3.0 (in o-chlorophenol~ 25C~.
No product is obtained which has desirable mechanical properties, as long as saturated polyester resin (B) does not satisfy the intrinsic viscosity defined above.
The copolymer (C) containing an epoxy group is a I, 5 I
copolymer of an unsaturated epoxy compound and an ethyl-Nikolai unsaturated compound. The composition ratio of the copolymer (C) containing an epoxy resin is not part-ocularly limited, but the unsaturated epoxy compound may be present in an am~lnt of 0.1 to 50 wt.%, preferably l to 30 White The unsaturated epoxy compound possesses an unsaturated group which is copolymerizable with an ethylenically unsaturated compound, and an epoxy group.
For example, unsaturated glycidyl esters or unsaturated glycidyl ethers having the formula (1) or (2) below may be used.
R-ll--CH2-C\-/H2 (1) O O
where R is a hydrocarbon group with 2 to 18 carbon atoms having an ethylenically unsaturated bond;
R-X-CH2-CH-CH2 (2) where R is the same as defined above and X is -SHEA- or -O-.
Examples thereof are glycidyl acrylate, glycidyl methacrylate, glycidyl itaconate, ally glycidyl ether, 2-methylallyl glycidyl ether, stroll glycidyl ether and the like.
The ethylenically unsaturated compound may be olefins, vinyl esters of saturated carboxylic acids having 2 to 6 carbon atoms, esters of a saturated alcohol component having 1 to 8 carbon atoms with acrylic or methacrylic acid, Maltese, methacrylates, fumarates, halogenated vinyl compounds, styrenes, nitrites, vinyl ethers and acrylamides~ Examples are ethylene, propylene, button, vinyl acetate, methyl acrylate, ethyl acrylate, methyl methacrylate, deathly Malta, deathly fumaràte, vinyl chloride, vinylidene chloride, styrenes acrylonitrile, ., I
isobutyl vinyl ether, acrylamide and the like. Above all, ethylene is particularly preferable.
The copolymer I containing an epoxy group may be prepared by various methods. One of the methods is a random copolymeri~ation method in which an unsaturated epoxy compound is introduced into the trunk chain of the copolymer. Alternatively, a graft copolymerization method is effected in which an unsaturated epoxy compound is introduced as the side chain of the copolymer. Specific gaily, for instance, an unsaturated epoxy compound and ethylene are copolymerized in the presence of a radical initiator at 500 to 4,000 atmospheric pressures and 100 to 300C, with or without a proper solvent or a chain transfer agent. Alternatively, an unsaturated epoxy compound and a radical initiator are mixed with pulpier pylon, and the mixture is molten in an extrude for graft copolymerization; or an unsaturated epoxy compound and an ethylenically unsaturated compound are copolymeri~ed in the presence of a radical initiator in an inert solvent such as an organic solvent or water.
In the thermoplastic resin composition according to this invention, the polypropylene resin PA) as the first component is present in an amount of 50 to 90 wt. %, preferably 60 to 80 woo or on the basis of PA) plus By If the amount of polypropylene resin PA) is less than 50 wt.%, process ability toughness, water resistance and chemical resistance are not satisfactory, while if the amount thereof is more than 90 White, favorable properties are not obtainable in the heat resistance, strength and rigidity. When modified polypropylene is used with unmodified polypropylene it is necessary that the amount of modified polypropylene should be 5 wt.% or more in the mixture. If the amount of modified one is less than S wt.
I, toughness and impact resistance obtained are not satisfactory and no substantial improvement is expected in paintability, adhesion and printability, I`
3 I
since difficulty is encountered in compatible dispersion in the present resin composition.
The amount of saturated polyester resin (B) as the second component is 50 to 10 White, preferably 40 to 20 wt. I, on the basis of [A) plus (s). If it is less than 10%, the heat resistance 9 rigidity and strength obtained are not sufficient, while if it exceeds 50 wt. I, processabili~y, toughness, water resistance and chemical resistance obtained are not satisfactory. Besides, there are such drawbacks as higher specific gravity and increase in cost The copolymer (C) containing an epoxy group is blended by 2 to 30 parts by weight, preferably 3 to 20 parts by weight, relative to the sum of 100 parts by weight of the polypropylene resin (A) and the saturated polyester resin (By. If the amount of copolymer I is less than 2 parts by weight, toughness and impact resistance are not sufficient, flow marks appear on the shaped articles to deteriorate the appearance and the extrusion stability is not good, since compatible dispersion of the resin composition is not satisfactory. If the amount of copolymer I exceeds 30 parts by weight, favorable results are not obtained because layer peeling occurs on the molded articles, and rigidity toughness and impact resistance are greatly damaged.
The present composition may be used as it is.
Alternatively, it may be in composite forms incorporating therein at least one of glass fibers, carbon fibers, polyamide fibers, metal whiskers or other reinforcing fiber materials, and silica, alumina, calcium carbonate, talc, mica, carbon black, Shea, no, Sb~03 or other inorganic fillers and flame retarding alps, lubricants, nucleating agents, plasticizers, distaffs r pigments, antistatic agents, antioxidant, weather Abe aids or the like.
.
` :' I
The resin composition of this invention is prepared by any of publicly known methods. Most preferred from a commercial point of view is to knead the in molten state, although it is effective to blend the components in a solution and evaporate the solvent or precipitate in a non-solvent. A Danbury mixer, extrudes, rolls, kneaders and other ordinary machines may be used for the kneading in molten state. In the kneading, it is preferable to uniformly premix the resin components in powder or pellet form by means of tumblers, Herschel mixers or the like.
It is possible, if necessary, to feed them quantitatively in separate ways into a kneading machine, without the premixing step.
The kneaded resin composition may be shaped by any of injection molding or extrusion molding. Alterna-lively, directly kneading in the melting and processing operation by blendincJ in dry state at the time of inject lion molding or extrusion molding may be effected without the pro kneading. In this invention, the kneading order is not particularly specified. That is, for example, the components I (B) and (C) may be kneaded altogether, or first (A) and (B) may be pre-kneaded before (C) is added.
Any other kneading orders may be possible, except that of first kneading PA) and (C), before adding I since a gel may sometimes be formed and a favorable resin composition is not obtained.
Hereinafter this invention will be described in conjunction with the working examples, wherein they are merely illustrative ones, and this invention is not limited to them. In these examples, the tensile test is conducted according to JIG K 7113, the bending test JIG K 7203 (thickness 3.2 on) and the Idea impact strength (thickness 3,2 my JIG K 7110.
. "
Jo I
The modified polypropylene and copolymers containing epoxy group, used in the examples and reference examples were prepared in the following prescriptions.
As the polypropylene and the saturated polyester resin, commercial products were used.
(1) Modified polypropylene It was prepared by referring to the method disclosed in the Japanese Examined Patent Publication No.
9925/1981.
Polypropylene, malefic android and tertiary butylperoxy laureate were premixed. An extrude with a screw diameter of 30 mm and Lid ratio of 28 was set at a barrel temperature of 230C, and the above mixture was fed in from a hopper, and the machine was operated at a screw rotating speed of 60 rum to promote the reaction. The modified polypropylene-molten strand discharged from the die of the extrude was cooled in water and then poulticed.
(2) Polypropylene propylene homopolymer: Symptom Noble Wow"
manufactured by Symptom Chemical Co., Ltd.
oPropylene-ethylene propylene block copolymer:
Sumitomo"Noblen AW564"2anufactured by Symptom Chemical Co., Ltd.
(3) Saturated polyester resins oPolybutylene terephthalate: "Tough pet PUT N1000"
by Mitsubishi Rayon Co., Ltd.
Polyethylene terephthalate: "Mob Unitika Co., Ltd.
l. Trademark 2. Trademark 3. Trademark ~;~; 4. Trademark - 1 o
since difficulty is encountered in compatible dispersion in the present resin composition.
The amount of saturated polyester resin (B) as the second component is 50 to 10 White, preferably 40 to 20 wt. I, on the basis of [A) plus (s). If it is less than 10%, the heat resistance 9 rigidity and strength obtained are not sufficient, while if it exceeds 50 wt. I, processabili~y, toughness, water resistance and chemical resistance obtained are not satisfactory. Besides, there are such drawbacks as higher specific gravity and increase in cost The copolymer (C) containing an epoxy group is blended by 2 to 30 parts by weight, preferably 3 to 20 parts by weight, relative to the sum of 100 parts by weight of the polypropylene resin (A) and the saturated polyester resin (By. If the amount of copolymer I is less than 2 parts by weight, toughness and impact resistance are not sufficient, flow marks appear on the shaped articles to deteriorate the appearance and the extrusion stability is not good, since compatible dispersion of the resin composition is not satisfactory. If the amount of copolymer I exceeds 30 parts by weight, favorable results are not obtained because layer peeling occurs on the molded articles, and rigidity toughness and impact resistance are greatly damaged.
The present composition may be used as it is.
Alternatively, it may be in composite forms incorporating therein at least one of glass fibers, carbon fibers, polyamide fibers, metal whiskers or other reinforcing fiber materials, and silica, alumina, calcium carbonate, talc, mica, carbon black, Shea, no, Sb~03 or other inorganic fillers and flame retarding alps, lubricants, nucleating agents, plasticizers, distaffs r pigments, antistatic agents, antioxidant, weather Abe aids or the like.
.
` :' I
The resin composition of this invention is prepared by any of publicly known methods. Most preferred from a commercial point of view is to knead the in molten state, although it is effective to blend the components in a solution and evaporate the solvent or precipitate in a non-solvent. A Danbury mixer, extrudes, rolls, kneaders and other ordinary machines may be used for the kneading in molten state. In the kneading, it is preferable to uniformly premix the resin components in powder or pellet form by means of tumblers, Herschel mixers or the like.
It is possible, if necessary, to feed them quantitatively in separate ways into a kneading machine, without the premixing step.
The kneaded resin composition may be shaped by any of injection molding or extrusion molding. Alterna-lively, directly kneading in the melting and processing operation by blendincJ in dry state at the time of inject lion molding or extrusion molding may be effected without the pro kneading. In this invention, the kneading order is not particularly specified. That is, for example, the components I (B) and (C) may be kneaded altogether, or first (A) and (B) may be pre-kneaded before (C) is added.
Any other kneading orders may be possible, except that of first kneading PA) and (C), before adding I since a gel may sometimes be formed and a favorable resin composition is not obtained.
Hereinafter this invention will be described in conjunction with the working examples, wherein they are merely illustrative ones, and this invention is not limited to them. In these examples, the tensile test is conducted according to JIG K 7113, the bending test JIG K 7203 (thickness 3.2 on) and the Idea impact strength (thickness 3,2 my JIG K 7110.
. "
Jo I
The modified polypropylene and copolymers containing epoxy group, used in the examples and reference examples were prepared in the following prescriptions.
As the polypropylene and the saturated polyester resin, commercial products were used.
(1) Modified polypropylene It was prepared by referring to the method disclosed in the Japanese Examined Patent Publication No.
9925/1981.
Polypropylene, malefic android and tertiary butylperoxy laureate were premixed. An extrude with a screw diameter of 30 mm and Lid ratio of 28 was set at a barrel temperature of 230C, and the above mixture was fed in from a hopper, and the machine was operated at a screw rotating speed of 60 rum to promote the reaction. The modified polypropylene-molten strand discharged from the die of the extrude was cooled in water and then poulticed.
(2) Polypropylene propylene homopolymer: Symptom Noble Wow"
manufactured by Symptom Chemical Co., Ltd.
oPropylene-ethylene propylene block copolymer:
Sumitomo"Noblen AW564"2anufactured by Symptom Chemical Co., Ltd.
(3) Saturated polyester resins oPolybutylene terephthalate: "Tough pet PUT N1000"
by Mitsubishi Rayon Co., Ltd.
Polyethylene terephthalate: "Mob Unitika Co., Ltd.
l. Trademark 2. Trademark 3. Trademark ~;~; 4. Trademark - 1 o
(4) Copolymers containing an epoxy group oGlyc.idyl methacrylate-ethylene copolymer and glycidyl methacrylate-ethylene-vinyl acetate copolymer The copolymers were prepared by referring to the methods disclosed in the Japanese Unexamined Patent Publication No. 23490/1972 and Japanese Unexamined Patent Publication No. 11388/1973.
To a temperature-controllable 40-liter stainless steel reaction vessel equipped with proper feeding inlets, takeout Outlet and an agitating device, were continuously supplied and agitated glycidyl methacryla-te, ethylene, vinyl acetate, a radical initiator agent and a chain-transfer agent, and copolymerization was effected at 1,400 to 1,600 atmospheric pressures and 180 to 200C.
oGlycidyl methacrylate-grafted ethylene-vinyl acetate copolymer I
It was manufactured by referring to the Japanese Examined Patent Publication No. 12449Jl~0.
Glycidyl. methacrylate having dicumyl peroxide dissolved preliminarily was mixed with ethylene-vinyl acetate copolymer pellets, and the mixture was allowed to diffuse and penetrate at room temperature. The pellets impregnating glycidyl metnacrylate jury extruded at -the terminal temperature of 170~C by an extrude with 65 my vent, and graft-copolymerized copolymer pellets containing an epoxy group were obtained.
Example 1 Preparation of mod eloper no *
~omopolymer ISumitomo Noble FS10t2 manufactured by Symptom Chemical Co., It'd.) as the base resin was * Trademark ,.,, } I
modified with malefic android to obtain modified polyp propylene having malefic android grafted by 0.11 White.
This modified polypropylene, polybutylene terephthalate, and glycidyl methacrylate-ethylene-vinyl acetate copolymer (ratio by weight: 10-85-5) were blended at the rate mentioned in Table 1-1. They were preliminary-lye admixed for 20 minutes in a tumbler and charged into an extrude with 65 my vent (manufactured by Ikegai Iron Works, Ltd.). The blend was molten and kneaded at 240C, and a poulticed resin composition was obtained. After having been dried for 5 hours at 140C, this composition was molded in a 10-ounce injection molding machine (model IS150E-V manufactured by Toshiba Corporation) at a molding 15 temperature of 240C and a mold temperature of 70C, and test pieces for measurement of the properties were obtained.
The test results of the obtained test pieces were as shown in Table 1-2.
The resin composition of this invention was good in stability of strand pulling in kneading by an extrude and excellent in the appearance ox an injection molded piece. Besides, the balance of properties was excellent.
In particular, the tensile elongation and Issued impact strength were extremely high. This substantiates the fact that the compatible dispersion of this resin compost-lion is extremely good Examples 2~3 The modified polypropylene manufactured in Example 1, propylene homopolymer, polybutylene terephtha-late and glycidyl methacrylate-ethylene-vinyl acetate copolymer (ratio by weight: 10-85-5) or glvcidyl Matthew-crylate~ethylene copol~mer ratio TV weight: 6-94) were blended at the rate mentioned in Table lo TV were mixed, kneaded and injection-molded in the same manner as in En to 1 I\
... . .
to prepare test pieces for measurement of the properties.
The test results are shown in Table 1-2.
The resin composition of this invention was good in stability of strand pulling in kneading by an extrude and excellent in the appearance ox an injection molded piece. Besides, the balance of properties was excellent.
In particular, the tensile elongation and Issued impact strength were extremely high. This exhibits that the compatible dispersion of this resin composition is extreme-lye good.
Reference Example 1 The modified polypropylene manufactured in Example 1 and polyb-1tylene terephthalate were blended at the rate mentioned in Table 1-1. They were mixed, kneaded and in-section molded in the same manner as in Example 1 to prepare test pieces for measurement of the properties. The test results are shown in Tale 1-2.
When the copolymer containing an epoxy group was not blended, the stability in strand pulling in kneading by an extrude was inferior -to the present composition, and flow marks were observed on the injection molded pieces and the appearance was extremely poor. Besides, since the compatible dispersion was insufficient, the tensile elongation and Issued impact strength were particularly inferior to those of the present composition.
Reference Example 2 The modified polypropylene manufactured in example 1, propylene homopolymer and polybutylene terephthalate were blended at the rate mentioned in Table 1-1. They were mixed, kneaded and injection molded in the same manner as in Example 1 to obtain test pieces for measurement of the properties. The test results are shown in Table 1-2.
"
Reference Example 3 Propylene homopolymer, polybutylene tereph~halate and glycidyl methacrylate-ethylene-vinyl acetate copolymer (ratio by weight: 10-85-51 were blended at the rate mentioned in Table 1-1. They were mixed, kneaded and injection molded in the same manner as in example 1 to prepare test pieces for measurement of the properties. The test results are shown in Table 1-2.
When a copolymer containing an epoxy group was blended, the stability in strand pulling in kneading by an extrude and appearance of injection molded piece were improved.
However, since modified polypropylene was not blended, the compatible dispersion was not sufficient, and the tensile elongation and Issued impact strength were particularly in-fervor to those of the present composition.
Table 1-1 twenty: White) _ Reference Examples Examples Resin composition 1 2 3 1 2 3 - - 5) _ Modified polypropylene lowboys 66 25 24 70 26 25P~lypropylene 4) polymer - 41 39 - 44 66 Saturated polyester resin PBT1) 29 29 27 30 30 29 Copolymer containing epoxy group GAME 5 5 - _ - 5 30GMA-E ) _ - 10 _ _ _ Notes 1) Polybutylene terephthalate 2) Glycidyl methacrylate-ethylene-vinyl acetate copolymer Katie by weight: 10-85-5) 3) Glycidyl methacrylate-ethylene copolymer Jo (ratio by weight: 6-34) I, 3) Glycidyl methacrylate-ethylene copol~rner (ratio by weight: 6-9~) I) Polypropylene Melt Index (230C, 2.16 kg) 8.0
To a temperature-controllable 40-liter stainless steel reaction vessel equipped with proper feeding inlets, takeout Outlet and an agitating device, were continuously supplied and agitated glycidyl methacryla-te, ethylene, vinyl acetate, a radical initiator agent and a chain-transfer agent, and copolymerization was effected at 1,400 to 1,600 atmospheric pressures and 180 to 200C.
oGlycidyl methacrylate-grafted ethylene-vinyl acetate copolymer I
It was manufactured by referring to the Japanese Examined Patent Publication No. 12449Jl~0.
Glycidyl. methacrylate having dicumyl peroxide dissolved preliminarily was mixed with ethylene-vinyl acetate copolymer pellets, and the mixture was allowed to diffuse and penetrate at room temperature. The pellets impregnating glycidyl metnacrylate jury extruded at -the terminal temperature of 170~C by an extrude with 65 my vent, and graft-copolymerized copolymer pellets containing an epoxy group were obtained.
Example 1 Preparation of mod eloper no *
~omopolymer ISumitomo Noble FS10t2 manufactured by Symptom Chemical Co., It'd.) as the base resin was * Trademark ,.,, } I
modified with malefic android to obtain modified polyp propylene having malefic android grafted by 0.11 White.
This modified polypropylene, polybutylene terephthalate, and glycidyl methacrylate-ethylene-vinyl acetate copolymer (ratio by weight: 10-85-5) were blended at the rate mentioned in Table 1-1. They were preliminary-lye admixed for 20 minutes in a tumbler and charged into an extrude with 65 my vent (manufactured by Ikegai Iron Works, Ltd.). The blend was molten and kneaded at 240C, and a poulticed resin composition was obtained. After having been dried for 5 hours at 140C, this composition was molded in a 10-ounce injection molding machine (model IS150E-V manufactured by Toshiba Corporation) at a molding 15 temperature of 240C and a mold temperature of 70C, and test pieces for measurement of the properties were obtained.
The test results of the obtained test pieces were as shown in Table 1-2.
The resin composition of this invention was good in stability of strand pulling in kneading by an extrude and excellent in the appearance ox an injection molded piece. Besides, the balance of properties was excellent.
In particular, the tensile elongation and Issued impact strength were extremely high. This substantiates the fact that the compatible dispersion of this resin compost-lion is extremely good Examples 2~3 The modified polypropylene manufactured in Example 1, propylene homopolymer, polybutylene terephtha-late and glycidyl methacrylate-ethylene-vinyl acetate copolymer (ratio by weight: 10-85-5) or glvcidyl Matthew-crylate~ethylene copol~mer ratio TV weight: 6-94) were blended at the rate mentioned in Table lo TV were mixed, kneaded and injection-molded in the same manner as in En to 1 I\
... . .
to prepare test pieces for measurement of the properties.
The test results are shown in Table 1-2.
The resin composition of this invention was good in stability of strand pulling in kneading by an extrude and excellent in the appearance ox an injection molded piece. Besides, the balance of properties was excellent.
In particular, the tensile elongation and Issued impact strength were extremely high. This exhibits that the compatible dispersion of this resin composition is extreme-lye good.
Reference Example 1 The modified polypropylene manufactured in Example 1 and polyb-1tylene terephthalate were blended at the rate mentioned in Table 1-1. They were mixed, kneaded and in-section molded in the same manner as in Example 1 to prepare test pieces for measurement of the properties. The test results are shown in Tale 1-2.
When the copolymer containing an epoxy group was not blended, the stability in strand pulling in kneading by an extrude was inferior -to the present composition, and flow marks were observed on the injection molded pieces and the appearance was extremely poor. Besides, since the compatible dispersion was insufficient, the tensile elongation and Issued impact strength were particularly inferior to those of the present composition.
Reference Example 2 The modified polypropylene manufactured in example 1, propylene homopolymer and polybutylene terephthalate were blended at the rate mentioned in Table 1-1. They were mixed, kneaded and injection molded in the same manner as in Example 1 to obtain test pieces for measurement of the properties. The test results are shown in Table 1-2.
"
Reference Example 3 Propylene homopolymer, polybutylene tereph~halate and glycidyl methacrylate-ethylene-vinyl acetate copolymer (ratio by weight: 10-85-51 were blended at the rate mentioned in Table 1-1. They were mixed, kneaded and injection molded in the same manner as in example 1 to prepare test pieces for measurement of the properties. The test results are shown in Table 1-2.
When a copolymer containing an epoxy group was blended, the stability in strand pulling in kneading by an extrude and appearance of injection molded piece were improved.
However, since modified polypropylene was not blended, the compatible dispersion was not sufficient, and the tensile elongation and Issued impact strength were particularly in-fervor to those of the present composition.
Table 1-1 twenty: White) _ Reference Examples Examples Resin composition 1 2 3 1 2 3 - - 5) _ Modified polypropylene lowboys 66 25 24 70 26 25P~lypropylene 4) polymer - 41 39 - 44 66 Saturated polyester resin PBT1) 29 29 27 30 30 29 Copolymer containing epoxy group GAME 5 5 - _ - 5 30GMA-E ) _ - 10 _ _ _ Notes 1) Polybutylene terephthalate 2) Glycidyl methacrylate-ethylene-vinyl acetate copolymer Katie by weight: 10-85-5) 3) Glycidyl methacrylate-ethylene copolymer Jo (ratio by weight: 6-34) I, 3) Glycidyl methacrylate-ethylene copol~rner (ratio by weight: 6-9~) I) Polypropylene Melt Index (230C, 2.16 kg) 8.0
5) Modified polypropylene Melt Index (230C,2.16 kg) Table 1-2 10 `==~ I_ Examples Examples Test results \ 1 2 3 1 2 3 Extrusion stability Excel- Excel- Excel-Poor Poor Swahili-lent lent lent lent 15 Tensile strength 2 310 320 300 320 340 280 Tensile elongation I 220 230 330 10 11 12 Issued impact strength (kg cm/cm) Notched 7.0 5.5 6.8 2.2 2.3 2.9 notched 104 l12 Nbroken 24 28 40 1 Bendirlg strenlkgth/ 2) 490 500 470 550 570 460 Bending Zulus of elasticity Ikg/cm2) 16500 1660016500 185t)0 18800 1S000 Appearance Excel- Excel-l~cel-Good Good Excel-lent lent lent lent Example 4 The modified polypropylene manufactured in Example 1, polybutylene terephthalate and glycidyl methacrylate-30 ethylene copolymer (ratio by weight: 12-88) were blended at the rate mentioned in Table 2-l. They were mixed, kneaded and injection molded in the same manner as in Example 1 to obtain -test pieces for measurement of the properties. The results are shown in Table 2-2.
Examples 5 - 7 The modified polypropylene manufactured in Example 1, propylene homopolymer, polybutylene terephtha-late and a glycidyl methacrylate-ethylene ratio by weight: 12-88) were blended. They were mixed, kneaded and injection molded in the same manner as in Example 1 to prepare test pieces for measurement of the properties.
The test results are shown in Table 2-2.
reference Example 4 The modified polypropylene manufactured in Example 1, propylene homopolymer and polybutylene lore-phthalate were blended at the rate mentioned on Table I hey were mixed, kneaded and injection molded in the same manner as in Example 1 to obtain test pieces for measure-mint of the properties. The results are shown in Table 2-2.
Reference Exhume 5 The modified polypropylene manufactured in example 1, propylene homopolymer, polybutylene terephtha-late and glycidyl methacrylate-ethylene copolymer (ratio by weight: 12-88) were blended at the Nate mentioned in Table 2-1.
They were mixed, kneaded and injection molded in the same manner as in Example l to prepare test pieces for measure-mint of the properties. The test results are shown in Table 2-2.
When 1 part by weight of the copolymer contain-in epoxy group was blended with 100 parts by weight of the resin composition comprising the polypropylene resin and the saturated polyester resin, the compatible dispel-soon was not sufficient yet, while the stability in strand pulling in kneading by an extrude and appearance of injection molded piece were somewhat improved, bolt were not sufficient. The properties are also inferior to those I
of the present composition Table 2-1 unit: w-t.%) -I _ .
~~--__ Reference o. Examples Examples Resin composition 4 5 6 7 4 5 . 4 Modified polypropylene ) 52 19 18 18 21 21 Homobase Polypropylene) - 33 31 29 34 34 Homopolymer Saturated polyester resin PUT )43 43 41 38 45 44 Copolymer containing epoxy group MA En) 5 5 10 15 _ _ Notes 1) Polyb~ltylene terephthalate 2) Glycidyl methacryla-te-ethylene copolymer (ratio by weight: 12-83) 3) Polypropylene Melt Index (230C, 2.16 kg) 8.0 4) Modified polypropylene Melt Index l230C, 2.1~ kg) 30 _ 17 -_ _ l I a) o Lo I Lo o o Lo O Lo O I}
4oJ X
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I
a, o Lo Lo o o corn o Lo . ,_ a) I o co O o r-l ED a) O cry O I) En o n o r- C r- o o .-Lo a) co o o Jo Lo LO cud I 0 0 ED Lo O O I
or I` Lo o Jo o a) n -------I
1.1 Jo , I
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a) 11 Llrn m pa pa ,1 a Jo Al u, r. o Jo 1/ a X a.) to N ~1 I, .¢
Jo '}I
Exam 8 Preparation of modified polypropylene Propylene-ethylene-propylene block copolymer (Symptom Noble AYE manufactured by Symptom Chemical Co., Ltd.) as the base resin was modified with malefic android to obtain a modified polypropylene hazing malefic acid grafted by 0.22 White.
The above modified polypropylene, propylene-ethylene-propylene block copolymer, polybutylene lore-phthalate and glycidyl methacrylate-ethylene-vinyl acetate copolymer (ratio by weight: 10-85-5) were blended at the rate in Table 3-1. They were mixed, kneaded and injection molded in the same manner as in Example 1 to obtain test pieces for measurement of the properties. The results are shown in Table 3-2.
Example 9 The modified polypropylene manufactured in Example 1, propylene homopolymer, polyethylene terephtha-late and glycidyl methacrylate-ethylene copolymer (ratio by weight: 6-94) were blended at the rate mentioned in Table 3-1. They were premixed for 20 minutes in a tumbler and kneaded in the molten state at 270~C in an extrude with 65 my vent manufactured by Ikegai Iron Work, Ltd.) to be poulticed, thus, a resin composition was obtained.
After having been dried at 140C for 5 hours, this come position was molded into test pieces for measurement of the properties at molding temperature at 240C and mold temperature of 70C by a 10-ounce injection molding machine (model IS150-E-V manufactured by Toshiba Corporation).
The test results were as shown in Table 3-2.
The resin composition of this invention was Good in stability of strand pulling in kneading by an extrude, and excellent in the appearance ox injection molded * Trademark pieces. Besides, the balance of properties was excellent.
In particular, the tensile elongation and Issued impact strength were extremely high. This substantiates that the compatible dispersion of this resin composition is extremely good Reference Example 6 The modified polypropylene manufactured in Example 1, propylene homopolymer and polyethylene lore-phthalate were blended at the rate mentioned in Table I Herr mixed, kneaded and injection molded in the same manner as in Example 9 to prepare test pieces for measure-mint of the properties. The test results are shown in Table 3-2.
The stability in strand pulling in kneading by an extrude and the appearance of injection molded piece were inferior to that of the present composition. Come partible dispersion were not sufficient yet, and the tensile elongation and Issued impact strength were particularly inferior to those of this invention.
Example 10 Preparation of modified polypropylene A propylene-ethylene random copolymer (Symptom Heublein Foe manufactured by Symptom Chemical Co., lid.) as the base resin was modified with malefic android to obtain modified polypropylene having malefic anhydrlde grafted by 0.14 White.
The above modified polypropylene, propylene homopolymer, polybutylene terephthalate and glycidyl methacrylate-grafted ethylene-vinyl acetate (containing MA by 4 White) were blended at the rate in Table 3-1.
They were mixed, kneaded and injection molded in the same manner as in Example 1 to obtain test pieces for * Trademark Jo -- Jo --measurement of the properties. The results are shown in Table 3-2.
Table 3-1 unwept: -~[ I) Examples ¦ once amp _ _ _ E ply Resin composition 8 9 10 Modified polypropylene Homobase8) - I - 26 Block base) 25 - _ Random basely) _ _ 7 Polypropylene Homopolymer ) - 42 59 44 Block copolymer ) 41 - -Saturated polyester resin Copolymer containing ego GUAVA 5 - _ GAME ) - 5 -GMA-~-EVA ) __ _ _ _ . __ ____~ Jo 25 N _ _ 1) Polybutylene terephthalate 2) Polyethylene terephthala-te I Glycidyl methacrylate-ethylene-vinyl acetate copolymer (ratio by White: 10-85-4) I Glvcidyl methacrylate~ethylene copolymer (ratio by ticket: 6-94) 5) Glyci.dyl me-thacrylate-cJrafted ethylene-vinyl acetate copolymer (containing cJlyciclyl moth-acrylate by 4 to
Examples 5 - 7 The modified polypropylene manufactured in Example 1, propylene homopolymer, polybutylene terephtha-late and a glycidyl methacrylate-ethylene ratio by weight: 12-88) were blended. They were mixed, kneaded and injection molded in the same manner as in Example 1 to prepare test pieces for measurement of the properties.
The test results are shown in Table 2-2.
reference Example 4 The modified polypropylene manufactured in Example 1, propylene homopolymer and polybutylene lore-phthalate were blended at the rate mentioned on Table I hey were mixed, kneaded and injection molded in the same manner as in Example 1 to obtain test pieces for measure-mint of the properties. The results are shown in Table 2-2.
Reference Exhume 5 The modified polypropylene manufactured in example 1, propylene homopolymer, polybutylene terephtha-late and glycidyl methacrylate-ethylene copolymer (ratio by weight: 12-88) were blended at the Nate mentioned in Table 2-1.
They were mixed, kneaded and injection molded in the same manner as in Example l to prepare test pieces for measure-mint of the properties. The test results are shown in Table 2-2.
When 1 part by weight of the copolymer contain-in epoxy group was blended with 100 parts by weight of the resin composition comprising the polypropylene resin and the saturated polyester resin, the compatible dispel-soon was not sufficient yet, while the stability in strand pulling in kneading by an extrude and appearance of injection molded piece were somewhat improved, bolt were not sufficient. The properties are also inferior to those I
of the present composition Table 2-1 unit: w-t.%) -I _ .
~~--__ Reference o. Examples Examples Resin composition 4 5 6 7 4 5 . 4 Modified polypropylene ) 52 19 18 18 21 21 Homobase Polypropylene) - 33 31 29 34 34 Homopolymer Saturated polyester resin PUT )43 43 41 38 45 44 Copolymer containing epoxy group MA En) 5 5 10 15 _ _ Notes 1) Polyb~ltylene terephthalate 2) Glycidyl methacryla-te-ethylene copolymer (ratio by weight: 12-83) 3) Polypropylene Melt Index (230C, 2.16 kg) 8.0 4) Modified polypropylene Melt Index l230C, 2.1~ kg) 30 _ 17 -_ _ l I a) o Lo I Lo o o Lo O Lo O I}
4oJ X
o Lo co I o o or O or o D on .
I
a, o Lo Lo o o corn o Lo . ,_ a) I o co O o r-l ED a) O cry O I) En o n o r- C r- o o .-Lo a) co o o Jo Lo LO cud I 0 0 ED Lo O O I
or I` Lo o Jo o a) n -------I
1.1 Jo , I
I O / I
I z / t ) ^ o a) o 1 I I owe pa I
I / C X
I Do / t) O -- I
I I/ C -ill)-- C7 r on_ I I So I I m a I I toll O I L
I I I, mu I o O a I I r (n a) on En x I / on O
I I a) I I I Lo (n I r r. or I I
a) 11 Llrn m pa pa ,1 a Jo Al u, r. o Jo 1/ a X a.) to N ~1 I, .¢
Jo '}I
Exam 8 Preparation of modified polypropylene Propylene-ethylene-propylene block copolymer (Symptom Noble AYE manufactured by Symptom Chemical Co., Ltd.) as the base resin was modified with malefic android to obtain a modified polypropylene hazing malefic acid grafted by 0.22 White.
The above modified polypropylene, propylene-ethylene-propylene block copolymer, polybutylene lore-phthalate and glycidyl methacrylate-ethylene-vinyl acetate copolymer (ratio by weight: 10-85-5) were blended at the rate in Table 3-1. They were mixed, kneaded and injection molded in the same manner as in Example 1 to obtain test pieces for measurement of the properties. The results are shown in Table 3-2.
Example 9 The modified polypropylene manufactured in Example 1, propylene homopolymer, polyethylene terephtha-late and glycidyl methacrylate-ethylene copolymer (ratio by weight: 6-94) were blended at the rate mentioned in Table 3-1. They were premixed for 20 minutes in a tumbler and kneaded in the molten state at 270~C in an extrude with 65 my vent manufactured by Ikegai Iron Work, Ltd.) to be poulticed, thus, a resin composition was obtained.
After having been dried at 140C for 5 hours, this come position was molded into test pieces for measurement of the properties at molding temperature at 240C and mold temperature of 70C by a 10-ounce injection molding machine (model IS150-E-V manufactured by Toshiba Corporation).
The test results were as shown in Table 3-2.
The resin composition of this invention was Good in stability of strand pulling in kneading by an extrude, and excellent in the appearance ox injection molded * Trademark pieces. Besides, the balance of properties was excellent.
In particular, the tensile elongation and Issued impact strength were extremely high. This substantiates that the compatible dispersion of this resin composition is extremely good Reference Example 6 The modified polypropylene manufactured in Example 1, propylene homopolymer and polyethylene lore-phthalate were blended at the rate mentioned in Table I Herr mixed, kneaded and injection molded in the same manner as in Example 9 to prepare test pieces for measure-mint of the properties. The test results are shown in Table 3-2.
The stability in strand pulling in kneading by an extrude and the appearance of injection molded piece were inferior to that of the present composition. Come partible dispersion were not sufficient yet, and the tensile elongation and Issued impact strength were particularly inferior to those of this invention.
Example 10 Preparation of modified polypropylene A propylene-ethylene random copolymer (Symptom Heublein Foe manufactured by Symptom Chemical Co., lid.) as the base resin was modified with malefic android to obtain modified polypropylene having malefic anhydrlde grafted by 0.14 White.
The above modified polypropylene, propylene homopolymer, polybutylene terephthalate and glycidyl methacrylate-grafted ethylene-vinyl acetate (containing MA by 4 White) were blended at the rate in Table 3-1.
They were mixed, kneaded and injection molded in the same manner as in Example 1 to obtain test pieces for * Trademark Jo -- Jo --measurement of the properties. The results are shown in Table 3-2.
Table 3-1 unwept: -~[ I) Examples ¦ once amp _ _ _ E ply Resin composition 8 9 10 Modified polypropylene Homobase8) - I - 26 Block base) 25 - _ Random basely) _ _ 7 Polypropylene Homopolymer ) - 42 59 44 Block copolymer ) 41 - -Saturated polyester resin Copolymer containing ego GUAVA 5 - _ GAME ) - 5 -GMA-~-EVA ) __ _ _ _ . __ ____~ Jo 25 N _ _ 1) Polybutylene terephthalate 2) Polyethylene terephthala-te I Glycidyl methacrylate-ethylene-vinyl acetate copolymer (ratio by White: 10-85-4) I Glvcidyl methacrylate~ethylene copolymer (ratio by ticket: 6-94) 5) Glyci.dyl me-thacrylate-cJrafted ethylene-vinyl acetate copolymer (containing cJlyciclyl moth-acrylate by 4 to
6) Polypropylene E~omopolymer i~telt Index 1230C, 2.16 kc~) 8.0 I 1~J~3
7) Polypropylene Block copolymer Melt Index (230C, 2.16 kg) 2.0
8) Modified polypropylene Homobase Melt Index (230C, 2.16 kg) 30
9) Modified polypropylene Block base Melt Index ~230C, 2.16 I 30
10) Modified polypropylene Random base Melt Index (230C, 2.16 kg) 10 10 Table 3-2 Examples Refer SUE _ Example Taoist results 8 10 6 Extrusion stability Excellent Excellent Excellen-Good Tensile strength (kg/cm ) 250 330 300 370 Tensile elongation (Q~)81 43 210 11 Issued impact strength (kg cm/cm) Notched 6~1 4.0 6.7 2.3 Unwished 91 60 108 31 Bending strength (k~/cm2) 380 'Go '170 540 Bending n~xlulus of east clout 1280018400 15300 20000 Appearance excellent Excellent Easily t Cod __ _ _ Excuse 11 -to 13 The modified polypropylene (16.5 White) manufac-lured in Example 1, propylene homopolymer ~27.6 wt.%), 30 polybutylene terephthala-te ~18.~ wits glyciclyl methacry-late-etnylene-vinyl acetate copolymer (ratio by weight:
10-85-S) (7 wt.%) and various reinforcing agents (30 White;) shown in Table were blended. They were mixed, kneaded and injection molded in the same procedure as in Example 1 35 to prepare test pieces. The test results are shown in Table 4.
I I
- I -Table 4 Examples pie Test results 7 8 9 Reinforcing agent Glass fiber Talc Mica Extrusion stability Excellent Excellent Excellent Tensile strength (kg/cm )1050 420 470 Tensile elongation (%) 10 17 15 Issued impact strength (kg.cm/cm) Notched 14 6.2 5.6 Unwished 94 79 57 Bending strength (kg/cm2)1380 680 760 Bending modulus of else 32300 42300 Taoist (kg/cm ) Appearance - Excellent excellent Glass fiber: RES06-TP37 made by Japan Glass Fiber Co.
(Eyebrow Dow microns, length 3 mm) 0 Talc: JR-2 made by Whoosh Chemical Co. (mean particle size 3 microns) Mica: 325 HO made by Queerer lid (mean particle size 40 microns) The thermoplastic resin composition of this invention is excellent not only in process ability, but also in various proper-ties of the molded articles which are by far better -than those of the individual components of the composition.
Moreover, -the thermoplastic resin composition of this invention is easily able to be shaped into molded articles, films or sheets by any of working processes for thermoplastic resins familiar to the swilled, such as injection molding and extrusion molding The shaped products are extremely balanced in rigidity, heat nests--lance, impact resistance, scratch resistance, paintability, oil resistance, chemical resistance and water resistance, and also have excellent appearance in uniformity and smoothness.
10-85-S) (7 wt.%) and various reinforcing agents (30 White;) shown in Table were blended. They were mixed, kneaded and injection molded in the same procedure as in Example 1 35 to prepare test pieces. The test results are shown in Table 4.
I I
- I -Table 4 Examples pie Test results 7 8 9 Reinforcing agent Glass fiber Talc Mica Extrusion stability Excellent Excellent Excellent Tensile strength (kg/cm )1050 420 470 Tensile elongation (%) 10 17 15 Issued impact strength (kg.cm/cm) Notched 14 6.2 5.6 Unwished 94 79 57 Bending strength (kg/cm2)1380 680 760 Bending modulus of else 32300 42300 Taoist (kg/cm ) Appearance - Excellent excellent Glass fiber: RES06-TP37 made by Japan Glass Fiber Co.
(Eyebrow Dow microns, length 3 mm) 0 Talc: JR-2 made by Whoosh Chemical Co. (mean particle size 3 microns) Mica: 325 HO made by Queerer lid (mean particle size 40 microns) The thermoplastic resin composition of this invention is excellent not only in process ability, but also in various proper-ties of the molded articles which are by far better -than those of the individual components of the composition.
Moreover, -the thermoplastic resin composition of this invention is easily able to be shaped into molded articles, films or sheets by any of working processes for thermoplastic resins familiar to the swilled, such as injection molding and extrusion molding The shaped products are extremely balanced in rigidity, heat nests--lance, impact resistance, scratch resistance, paintability, oil resistance, chemical resistance and water resistance, and also have excellent appearance in uniformity and smoothness.
Claims (11)
1. A thermoplastic resin composition comprising 100 parts by weight of a resin composition (D) defined below and 2 to 30 parts by weight of copolymer (C) which is a copolymer of (a) ethylene and an unsaturated epoxy compound having one of the formulas and wherein R is a hydrocarbon group with 2 - 18 carbon atoms having an ethylenically unsaturated bond and X is -CH2O-or O-, or (b) ethylene, the unsaturated epoxy compound defined above and vinyl esters of saturated carboxylic acids having 2 to 6 carbon atoms, esters of a saturated alcohol component having 1 to 8 carbon atoms with acrylic or methacrylic acid, halogenated vinyl compounds or vinyl ethers, said resin composition (D) being composed of 50 to 90 wt. % of polypropylene-resin (A) which is a grafted-copolymer of a polypropylene with 0.05 to 20 wt.% of an unsaturated carboxylic acid or anhydride thereof or said grafted-copolymer and a polypropylene, and 50 to 10 wt. %
of saturated polyester resin (B) composed of a dicarboxylic acid moiety, at least 40 mol % of the dicarboxylic moiety being from terephthalic acid, and a diol moiety.
of saturated polyester resin (B) composed of a dicarboxylic acid moiety, at least 40 mol % of the dicarboxylic moiety being from terephthalic acid, and a diol moiety.
2. A thermoplastic resin composition according to claim 1 wherein (A) is present in an amount of 60 - 80 wt.%, (B) is present in an amount of 40 - 20 wt.% and (C) is present in an amount of 3 - 20 parts by weight.
3. A thermoplastic resin composition according to claim 1 wherein the polypropylene is a crystalline copolymer of propylene and at least one other .alpha.-olefin.
4. A thermoplastic resin composition according to claim 1 wherein the carboxylic acid or anhydride thereof is present in an amount of 0.1 - 10 wt.%.
5. A thermoplastic resin composition according to claim 1 wherein the unsaturated carboxylic acid or anhydride in the polypropylene-resin (A) is maleic anhydride.
6. A thermoplastic resin composition according to claim 1 wherein the grafted-copolymer is present in an amount of 5 wt.% or more on the basis of polypropylene-resin (A) when it is used with a polypropylene.
7. A thermoplastic resin composition according to claim 1 wherein the resin (B) has an intrinsic viscosity of 0.5 to 3.0 in o-chlorophenol at 25°C.
8. A thermoplastic resin composition according to claim 1 wherein the resin (B) is polybutylene terephthalate or polyethylene terephthalate.
9. A thermoplastic resin composition according to claim 1 wherein the unsaturated epoxy compound in (C) is present in an amount of 0.1 - 50 wt. %.
10. A thermoplastic resin composition according to claim 9 wherein the amount of unsaturated epoxy compound in (C) is 1 - 30 wt.%.
11. A thermoplastic resin composition according to claim 1 wherein R is ethylene.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59183250A JPS6160746A (en) | 1984-08-31 | 1984-08-31 | Thermoplastic resin composition |
| JP183250/84 | 1984-08-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1231490A true CA1231490A (en) | 1988-01-12 |
Family
ID=16132391
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000489326A Expired CA1231490A (en) | 1984-08-31 | 1985-08-23 | Thermoplastic resin composition |
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| Country | Link |
|---|---|
| US (1) | US5004782A (en) |
| EP (1) | EP0177151B1 (en) |
| JP (1) | JPS6160746A (en) |
| CA (1) | CA1231490A (en) |
| DE (1) | DE3584214D1 (en) |
Families Citing this family (34)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0726008B2 (en) * | 1987-03-31 | 1995-03-22 | 住友化学工業株式会社 | Method for producing thermoplastic resin composition |
| DE3851800T2 (en) * | 1987-07-16 | 1995-05-11 | Showa Denko Kk | Propylene copolymer composition. |
| DE3852738T2 (en) * | 1987-09-09 | 1995-08-31 | Nippon Petrochemicals Co Ltd | Thermoplastic composition and process for its manufacture. |
| JPH0214231A (en) * | 1988-03-31 | 1990-01-18 | Sumitomo Chem Co Ltd | Polypropylene composition |
| US5095063A (en) * | 1988-03-31 | 1992-03-10 | Sumitomo Chemical Company, Limited | Polypropylene composition |
| US4981896A (en) * | 1988-03-31 | 1991-01-01 | Sumitomo Chemical Company | Thermoplastic resin composition |
| CA1329435C (en) * | 1988-03-31 | 1994-05-10 | Takayuki Okada | Modified polypropylene resin composition |
| AU627176B2 (en) * | 1988-05-13 | 1992-08-20 | E.I. Du Pont De Nemours And Company | Thermoplastic elastomeric compositions |
| JP2722697B2 (en) * | 1988-08-17 | 1998-03-04 | 住友化学工業株式会社 | Thermoplastic propylene resin composition |
| GB8926632D0 (en) * | 1989-11-24 | 1990-01-17 | Ici Plc | Polymer blend composition |
| EP0443736A3 (en) * | 1990-02-02 | 1992-04-22 | Tonen Corporation | Thermoplastic resin composition |
| EP0459766B1 (en) * | 1990-05-29 | 1996-09-25 | Tonen Corporation | Modified polyolefincontaining thermoplastic resin composition |
| JP2792205B2 (en) * | 1990-06-14 | 1998-09-03 | 住友化学工業株式会社 | Thermoplastic resin composition |
| CA2035827A1 (en) * | 1991-02-06 | 1992-08-07 | Masashi Yamamoto | Thermoplastic resin composition |
| US5548013A (en) * | 1991-02-27 | 1996-08-20 | Sumitomo Chemical Company, Limited | Thermoplastic resin composition |
| EP0518447B1 (en) * | 1991-06-12 | 1996-11-13 | Tonen Corporation | Thermoplastic resin composition |
| JP2528341Y2 (en) * | 1991-08-07 | 1997-03-12 | 住友重機械工業株式会社 | Roller apron for beam blank and rectangular slab in continuous casting equipment |
| US5280066A (en) * | 1991-09-18 | 1994-01-18 | Globe-Union Inc. | Polyester-polyolefin blends containing a functionalized elastomer |
| US5296550A (en) * | 1991-11-01 | 1994-03-22 | Enichem S.P.A. | Impact modified polyester blends with improved polymer compatibility |
| US5290856A (en) * | 1992-04-16 | 1994-03-01 | Himont Incorporated | Engineering resin-propylene polymer graft composition |
| JPH0632951A (en) * | 1992-07-15 | 1994-02-08 | Sumitomo Chem Co Ltd | Thermoplastic resin composition and its injection-molded product |
| US5502098A (en) * | 1993-06-28 | 1996-03-26 | Cosmo Research Institute | Polymer composition for electrical part material |
| US5502160A (en) * | 1994-08-03 | 1996-03-26 | Hercules Incorporated | Polyolefin-polyarylate alloy fibers and their use in hot-mix compositions for making and repairing geoways |
| US5618881A (en) * | 1995-01-09 | 1997-04-08 | Du Pont Canada Inc. | Compatibilizer composition |
| US6166143A (en) * | 1996-11-06 | 2000-12-26 | The Yokohama Rubber Co., Ltd. | Thermoplastic elastomer composition, hose comprising thermoplastic elastomer composition and process of production thereof |
| US6020432A (en) * | 1998-07-02 | 2000-02-01 | Hna Holdings, Inc. | High density polyester composition |
| JP4050480B2 (en) * | 2001-04-10 | 2008-02-20 | 矢崎総業株式会社 | Insulated wire |
| JP2003021275A (en) * | 2001-07-06 | 2003-01-24 | Toyoda Gosei Co Ltd | Resin pipe and manufacturing method therefor |
| US6986864B2 (en) * | 2002-04-30 | 2006-01-17 | David Scott Porter | Polyester compositions |
| US7275543B2 (en) * | 2002-09-20 | 2007-10-02 | Baxter International Inc. | Coupler member for joining dissimilar materials |
| DE102007050903A1 (en) * | 2007-10-23 | 2009-04-30 | A. Schulman Gmbh | Polymer blend, useful as head-lamp housing or molded part for illumination device, comprises polypropylene, polyester, compatibilizing system and laser radiation absorbing pigment |
| ITPI20110090A1 (en) * | 2011-08-17 | 2013-02-18 | Auserpolimeri S R L | SHOCKPROOF THERMOPLASTIC MATERIAL BASED ON POLYCONDENSATION POLYMERS AND ITS PRODUCTION METHOD |
| CN107987378A (en) * | 2017-11-24 | 2018-05-04 | 广东威林工程塑料股份有限公司 | One kind is used for high comfortable feel non-woven fabrics modified polypropylene material and preparation method thereof |
| CN111073145A (en) * | 2019-12-26 | 2020-04-28 | 苏州润佳高分子材料有限公司 | Fabric-touch-like polypropylene composite material for automobile |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE609226A (en) * | 1960-10-19 | 1900-01-01 | ||
| US4054549A (en) * | 1972-11-27 | 1977-10-18 | Imperial Chemical Industries Limited | Polymer composition |
| US4172859A (en) * | 1975-05-23 | 1979-10-30 | E. I. Du Pont De Nemours And Company | Tough thermoplastic polyester compositions |
| JPS5674168A (en) * | 1979-11-24 | 1981-06-19 | Toyo Alum Kk | Adhesive composition |
| JPS57105448A (en) * | 1980-12-23 | 1982-06-30 | Toray Ind Inc | Wire coating resin composition |
| JPS5847419A (en) * | 1981-09-18 | 1983-03-19 | 梶山 朔二 | Fishing net by float control |
| NL8204966A (en) * | 1981-12-28 | 1983-07-18 | Mitsubishi Rayon Co | POLYOLEFINE RESIN MIXTURE. |
| JPS5989346A (en) * | 1982-11-12 | 1984-05-23 | Sumitomo Naugatuck Co Ltd | Thermoplastic resin composition |
| JPS59115352A (en) * | 1982-12-22 | 1984-07-03 | Unitika Ltd | Resin composition |
| JPS59149944A (en) * | 1983-02-15 | 1984-08-28 | Toyo Seikan Kaisha Ltd | Hot-melt adhesive |
-
1984
- 1984-08-31 JP JP59183250A patent/JPS6160746A/en active Granted
-
1985
- 1985-08-20 DE DE8585305927T patent/DE3584214D1/en not_active Expired - Fee Related
- 1985-08-20 EP EP85305927A patent/EP0177151B1/en not_active Expired
- 1985-08-23 CA CA000489326A patent/CA1231490A/en not_active Expired
-
1989
- 1989-09-29 US US07/414,574 patent/US5004782A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| US5004782A (en) | 1991-04-02 |
| JPH0588265B2 (en) | 1993-12-21 |
| EP0177151A2 (en) | 1986-04-09 |
| EP0177151B1 (en) | 1991-09-25 |
| DE3584214D1 (en) | 1991-10-31 |
| EP0177151A3 (en) | 1988-03-09 |
| JPS6160746A (en) | 1986-03-28 |
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Legal Events
| Date | Code | Title | Description |
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| MKEX | Expiry |