CA1112387A - Heteropolymer acrylic latices and textiles treated therewith - Google Patents
Heteropolymer acrylic latices and textiles treated therewithInfo
- Publication number
- CA1112387A CA1112387A CA279,849A CA279849A CA1112387A CA 1112387 A CA1112387 A CA 1112387A CA 279849 A CA279849 A CA 279849A CA 1112387 A CA1112387 A CA 1112387A
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- Canada
- Prior art keywords
- monomer
- weight
- composition
- core
- shell
- 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
Links
Classifications
-
- 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
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- 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
- B32B27/065—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 of foam
-
- 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
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/022—Non-woven fabric
-
- 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
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/024—Woven fabric
-
- 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
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/026—Knitted fabric
-
- 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
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/245—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it being a foam layer
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
- D06M15/233—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
- D06M15/29—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides containing a N-methylol group or an etherified N-methylol group; containing a N-aminomethylene group; containing a N-sulfidomethylene group
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06N3/042—Acrylic polymers
-
- 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
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B2038/0052—Other operations not otherwise provided for
- B32B2038/0076—Curing, vulcanising, cross-linking
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
Abstract
ABSTRACT OF THE DISCLOSURE
Low temperature properties of resin-treated textiles are improved by using as the resin an acrylic emulsion polymer wherein the latex particles have a core-shell structure. The monomers forming the core are selected to provide a Tg in the core of -20° C. or lower and the monomer composition forming the shell is selected to provide a Tg in the shell of about 60° C. to about -10° C.
The core monomer composition contains a latent crosslinker together with an active crosslinker or a graftlinker, and the shell monomer composition contains a latent crosslinker.
Low temperature properties of resin-treated textiles are improved by using as the resin an acrylic emulsion polymer wherein the latex particles have a core-shell structure. The monomers forming the core are selected to provide a Tg in the core of -20° C. or lower and the monomer composition forming the shell is selected to provide a Tg in the shell of about 60° C. to about -10° C.
The core monomer composition contains a latent crosslinker together with an active crosslinker or a graftlinker, and the shell monomer composition contains a latent crosslinker.
Description
RACKGROUND OF THE INVENI'ION
This in~ention relates to latex compositions and to their use with textile materials to improve the low temperature properties thereof.
Although a great variety of resin latices have been developed which are useful as finish coats, binders, adhesives, back-coatings, transfer films and interlayers for a wide variety of textile applications, there is lacking a textile resin of the acrylic latex type which provides, alone or in cooperation with other materials used in textiles, resistance to cracking at the low ~emperatures often encountered. For example, wearing apparel, such as clothing and shoe uppers, and particularly upholstery for automobiles, must be supple and drape well, must be impact and abrasion-resistant, and must be free from surface tack and blocking tendencies not only at room temperatures and the highest use temperatures, but also at low temperatures sometimes encountered during use, trans-~~port or storage, of the order of about -20C. and especially ~30C. and lower. Textile resins are available which satisfy these requirements. However, the resins are of the plastisol or solution polymer type and are becoming less desirable due to hazards accompanying their application to fabrics ~such as fire hazards due to the use of organic solvents~ or upon burning of textiles containing such resins (such as dense smoke and noxious fumes).
' ~ ' ' ' Acrylic polymer latices have outstanding advantages over plastisol and solution polymer resin systems as textile resins. Their all-aqueous nature permits excellent handling ease. They provide good hand, strength, durability, low hazard and low cost without external plasticizers.
Moreover, they are compatible with a variety of additives, colorants and o~her textile coating materials.
Nevertheless, an ability to impart low temperature properties to textiles!has not been achieved. One measure of significant low temperature acceptability is a "cold crack"
temperature of -30C. or lower. Cold crack measurements reflect the ability of a textile material treated with a textile resin to withstand cracking upon impact or folding at low temperatures. However, it will be appreciated that even if a resin imparts good cold crack to a textile material, the resulting treated textile must also be acceptable from several other standpoints, particularly low surface tack, impact and abrasion resistance, and good flexibility at all use temperatures. The achievement of a suitable balance among all of these properties is largely empirical and is not predictable on the basis of , achievement of any one or even several of the properties.
SUMMARY OF THE INVENTION
In general ~erms, superior cold crack is aahleved ln~combination wlth other properties required in resin-treated textiles by treating a textile material with a thermosetting~acrylic latex compositlon wherein the :
~ 30~
:~: :
!
~1 , ~ . .
...... . :....... . : .. ,.,.. ..... .. , . . .- : . i . .. . .. : . . . . .
.;, .. . . . . ... ...... . . . . . .. ... ... ... . . . . .
latex particles comprise about 30-60~, preferably 45-55%
by weight of a polymeric core and about 70 40%, preferably 55~45~, by weight of a polymeric shell. The core is ormed by emulsion polymerization of a first monomer composition consisting essentially of a) a major amount of a principal monomer system consisting essentially of at: least one Cl-C8 straight or branched chain alkyl acrylate and from 0-20%
by weight ~ based on said alkyl acrylate, of another monoethylenically unsaturated monomer which is copolymerizable with said alkyl acrylate, said other monoethylenically unsaturated monomer being non-crosslinking with respect to the alkyl acrylate; and b) a minor amount of a crosslinking monomer system comprising (1) from about 0.5~ to 6%:by weight on the total monomer composition of a gxaftlinking monomer which is a polyfunctional monomer which has at least two copolymerizable ethylenically unsaturated bonds which react at substantially different rates thereby resulting in a portion of the functionality entering into formation of the coxe and capable of reacting with suitable functionality of-the shell (or second) monomer composition as defined hereinafter; to graft :~ the shell upon the core; or a polyfunctional monomer which crosslinks a polymer composition during the initial formation thereof, and containing at least two addition polymerizable vinylidene groups, and (2) from about ~% to 10~ by weight, based on the total first monomer composition, o a latent crosslinking monomer which is a polyfunctional monomer wherein a portion of -the functionality enters into the copolymerization with other monomers in the monomer composition, the residual functionality causing crosslinking of the polymeric core or shell upon subsequent complete drying of the latex particles on a textile substrate material; the shell is formed on the core by emulsion polymerization of a second monomer composition ~ ,;, J
, . . . ..... . . .. .
ln the presence of the core polymer, the second monomer composition consisting essentially of a) a major amount of a principal monomer system as hereinbefore deined; and b) from about 2% to 10~ ~y weight, based on the total second monomer composition, of a latent crosslinking monomer system as hereinbefore defined. The monomers of the first monomer composition are selected in a known manner to provide a glass trasition temperature (Tg) in the core of -20C. or lower, and the monomers of the second monomer composition are selected in a known manner to provide a T in the shell of about 60C. to about -10C.
The textile material so treated is characterized by having good flexibility and impact resistance at low - ;
temperatures (good "cold crack" properties), as well as low - surface tack and good impact resistance, abrasion resistance, and flexibility at all use temperatures.
Textiles of all types are beneficially treated ~` with the acrylic polymer latices in accordance with the invention. Application techniques include direct coating, transfer film application, lamination or any other technique known in the art.
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30 ~ ~
4a -: ~ : J `!~ ` :
., ~, ~1 :: :
.
': : ' ~ ,. : ' : , . . . . : ' : ' , : ' .
'7 In this speci~ication the term "acrylic" is used in a genexal sense to describe polymers wherein at least one of the monomers is of the acrylic or methacrylic type, including acids, estexs, amides and substit:uted derivatives thereo~.
DETAILED DESCRIPTION
The monomers forming the polymeric core of the heteropolymer are selected to provide a glass transition temperature ~Tg) in the core o~ -30C. or lower. It is believed that the resulting rubbery character of the core in cooperation with the crosslinking character of core and shell results in the cracking resistance and ~lexibility at room temperature and low temperature as well as the impact resistance provided by the finished polymer.
The core polymer is formed by emulsion polymerization of a first monomer composition comprising a ma~or amount of a principal monomer system and a minor amount of a crosslinking monomer system. The principal monomer system typically contains a Cl-C8 alkyl acrylate wherein the alkyl group is straight or branched chain, such as ethyl acrylate, butyl acr~late, 2-ethylhexyl acrylate, and mixtures thereof.
Part of the alkyl acrylatel up to a maximum of about 20~ by weight, may be replaced with a non-crosslinking (with respect to the alkyl acrylate) mono~ethyleni~ally unsaturat~d monomer having alpha, beta-unsaturation.
Examples of such other monomers are vinylidene chloride, vinyl chloride, acrylonitrile, vinyl esters such as vinyl ~ormate, vinyl acetate and vinyl propionate, and mixtures ~ of ethylene and such vinyl esters, al~yl methacrylic esters, ;~ 30 acryllc and methacrylic acid esters of alcohol-ethers such as diethylene glycol monoethyl or monobutyl ether, styrene, ring-alkyl styrenes such as ortho- r meta and paramethyl ;
.
,:
., . :
styrenes, alpha-alkyl styrenes such as alpha-methyl st~rene and the like, mixtures of ethylene with other alpha olefins such as propyleneJ butylene, pentene and the like, and combinations of ethylene with vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, vinyl 2-methoxylethyl ether, vinyl 2-chloroethyl ether and the like.
Of the foregoing monomers, butyl acrylate is particularly preferred alone or in combination with minor amounts of methyl methacrylate, of the order of about 70-95~ by weight of butyl acrylate and about 1-15~ by weight of methyl methacrylate, based on the total weight of the monomers in the monomer composition forming the core polymer.
Careful selection of the crosslinking monomer system both in the core monomer composition and in the shell monomer composition is important for obtaining the proper balance of properties in fabrics treated with the hetero-polymer. The crosslinking monomer system in the monomer composition forming the core comprises:
1~ At least about 0.5% (for example, 1-6%) on total monomer composition weight of a graftlinking monomer or an active cross-linking monomer, and
This in~ention relates to latex compositions and to their use with textile materials to improve the low temperature properties thereof.
Although a great variety of resin latices have been developed which are useful as finish coats, binders, adhesives, back-coatings, transfer films and interlayers for a wide variety of textile applications, there is lacking a textile resin of the acrylic latex type which provides, alone or in cooperation with other materials used in textiles, resistance to cracking at the low ~emperatures often encountered. For example, wearing apparel, such as clothing and shoe uppers, and particularly upholstery for automobiles, must be supple and drape well, must be impact and abrasion-resistant, and must be free from surface tack and blocking tendencies not only at room temperatures and the highest use temperatures, but also at low temperatures sometimes encountered during use, trans-~~port or storage, of the order of about -20C. and especially ~30C. and lower. Textile resins are available which satisfy these requirements. However, the resins are of the plastisol or solution polymer type and are becoming less desirable due to hazards accompanying their application to fabrics ~such as fire hazards due to the use of organic solvents~ or upon burning of textiles containing such resins (such as dense smoke and noxious fumes).
' ~ ' ' ' Acrylic polymer latices have outstanding advantages over plastisol and solution polymer resin systems as textile resins. Their all-aqueous nature permits excellent handling ease. They provide good hand, strength, durability, low hazard and low cost without external plasticizers.
Moreover, they are compatible with a variety of additives, colorants and o~her textile coating materials.
Nevertheless, an ability to impart low temperature properties to textiles!has not been achieved. One measure of significant low temperature acceptability is a "cold crack"
temperature of -30C. or lower. Cold crack measurements reflect the ability of a textile material treated with a textile resin to withstand cracking upon impact or folding at low temperatures. However, it will be appreciated that even if a resin imparts good cold crack to a textile material, the resulting treated textile must also be acceptable from several other standpoints, particularly low surface tack, impact and abrasion resistance, and good flexibility at all use temperatures. The achievement of a suitable balance among all of these properties is largely empirical and is not predictable on the basis of , achievement of any one or even several of the properties.
SUMMARY OF THE INVENTION
In general ~erms, superior cold crack is aahleved ln~combination wlth other properties required in resin-treated textiles by treating a textile material with a thermosetting~acrylic latex compositlon wherein the :
~ 30~
:~: :
!
~1 , ~ . .
...... . :....... . : .. ,.,.. ..... .. , . . .- : . i . .. . .. : . . . . .
.;, .. . . . . ... ...... . . . . . .. ... ... ... . . . . .
latex particles comprise about 30-60~, preferably 45-55%
by weight of a polymeric core and about 70 40%, preferably 55~45~, by weight of a polymeric shell. The core is ormed by emulsion polymerization of a first monomer composition consisting essentially of a) a major amount of a principal monomer system consisting essentially of at: least one Cl-C8 straight or branched chain alkyl acrylate and from 0-20%
by weight ~ based on said alkyl acrylate, of another monoethylenically unsaturated monomer which is copolymerizable with said alkyl acrylate, said other monoethylenically unsaturated monomer being non-crosslinking with respect to the alkyl acrylate; and b) a minor amount of a crosslinking monomer system comprising (1) from about 0.5~ to 6%:by weight on the total monomer composition of a gxaftlinking monomer which is a polyfunctional monomer which has at least two copolymerizable ethylenically unsaturated bonds which react at substantially different rates thereby resulting in a portion of the functionality entering into formation of the coxe and capable of reacting with suitable functionality of-the shell (or second) monomer composition as defined hereinafter; to graft :~ the shell upon the core; or a polyfunctional monomer which crosslinks a polymer composition during the initial formation thereof, and containing at least two addition polymerizable vinylidene groups, and (2) from about ~% to 10~ by weight, based on the total first monomer composition, o a latent crosslinking monomer which is a polyfunctional monomer wherein a portion of -the functionality enters into the copolymerization with other monomers in the monomer composition, the residual functionality causing crosslinking of the polymeric core or shell upon subsequent complete drying of the latex particles on a textile substrate material; the shell is formed on the core by emulsion polymerization of a second monomer composition ~ ,;, J
, . . . ..... . . .. .
ln the presence of the core polymer, the second monomer composition consisting essentially of a) a major amount of a principal monomer system as hereinbefore deined; and b) from about 2% to 10~ ~y weight, based on the total second monomer composition, of a latent crosslinking monomer system as hereinbefore defined. The monomers of the first monomer composition are selected in a known manner to provide a glass trasition temperature (Tg) in the core of -20C. or lower, and the monomers of the second monomer composition are selected in a known manner to provide a T in the shell of about 60C. to about -10C.
The textile material so treated is characterized by having good flexibility and impact resistance at low - ;
temperatures (good "cold crack" properties), as well as low - surface tack and good impact resistance, abrasion resistance, and flexibility at all use temperatures.
Textiles of all types are beneficially treated ~` with the acrylic polymer latices in accordance with the invention. Application techniques include direct coating, transfer film application, lamination or any other technique known in the art.
::
; . :
' .
:
. ~ :
30 ~ ~
4a -: ~ : J `!~ ` :
., ~, ~1 :: :
.
': : ' ~ ,. : ' : , . . . . : ' : ' , : ' .
'7 In this speci~ication the term "acrylic" is used in a genexal sense to describe polymers wherein at least one of the monomers is of the acrylic or methacrylic type, including acids, estexs, amides and substit:uted derivatives thereo~.
DETAILED DESCRIPTION
The monomers forming the polymeric core of the heteropolymer are selected to provide a glass transition temperature ~Tg) in the core o~ -30C. or lower. It is believed that the resulting rubbery character of the core in cooperation with the crosslinking character of core and shell results in the cracking resistance and ~lexibility at room temperature and low temperature as well as the impact resistance provided by the finished polymer.
The core polymer is formed by emulsion polymerization of a first monomer composition comprising a ma~or amount of a principal monomer system and a minor amount of a crosslinking monomer system. The principal monomer system typically contains a Cl-C8 alkyl acrylate wherein the alkyl group is straight or branched chain, such as ethyl acrylate, butyl acr~late, 2-ethylhexyl acrylate, and mixtures thereof.
Part of the alkyl acrylatel up to a maximum of about 20~ by weight, may be replaced with a non-crosslinking (with respect to the alkyl acrylate) mono~ethyleni~ally unsaturat~d monomer having alpha, beta-unsaturation.
Examples of such other monomers are vinylidene chloride, vinyl chloride, acrylonitrile, vinyl esters such as vinyl ~ormate, vinyl acetate and vinyl propionate, and mixtures ~ of ethylene and such vinyl esters, al~yl methacrylic esters, ;~ 30 acryllc and methacrylic acid esters of alcohol-ethers such as diethylene glycol monoethyl or monobutyl ether, styrene, ring-alkyl styrenes such as ortho- r meta and paramethyl ;
.
,:
., . :
styrenes, alpha-alkyl styrenes such as alpha-methyl st~rene and the like, mixtures of ethylene with other alpha olefins such as propyleneJ butylene, pentene and the like, and combinations of ethylene with vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, vinyl 2-methoxylethyl ether, vinyl 2-chloroethyl ether and the like.
Of the foregoing monomers, butyl acrylate is particularly preferred alone or in combination with minor amounts of methyl methacrylate, of the order of about 70-95~ by weight of butyl acrylate and about 1-15~ by weight of methyl methacrylate, based on the total weight of the monomers in the monomer composition forming the core polymer.
Careful selection of the crosslinking monomer system both in the core monomer composition and in the shell monomer composition is important for obtaining the proper balance of properties in fabrics treated with the hetero-polymer. The crosslinking monomer system in the monomer composition forming the core comprises:
1~ At least about 0.5% (for example, 1-6%) on total monomer composition weight of a graftlinking monomer or an active cross-linking monomer, and
2. At least about 4~ (for example, 4~10%) on total monomer composition weight of a latent crosslinking monomer~
~ Generally, thP amount of graftlinking or active ;; crosslinking monomer in the core monomer composition should be that which will provide sufficient mutual insolubility of the Gore and shell polymer compositions or formatlon of a true heteropolymer and which will not unduly reduce the elongation properties of the heteropolymer. This will depend, of course, on other monomers in the monomer ~r ' ' ' . . :.
compositions of both core and shell, and may be varied accordingly.
The shell monomer composition requires only a latent crosslinker. Upon polymerization of the shell monomer S composition in the presence of ~he core polymer, the shell polymer composition becomes intimately associated with the core, i~ not actually graftlinked, through ~he condensation reactions possi~le with the latent crosslinking monomers present in the core and shell polymer composition~. It appears that the shell contributes significantly to the good abrasion-resistance, dryness (little or no tack) solvent resistance and launderability of the textiles treated with the heteropolymer by virtue either of gra~tlinking of the shell polymer onto the core polymer or of tight formation o~
the shell over th~ core short of actual graftlinking.
For the purposes of th.is description, the term "latent crosslinkin~ monomer" means a polyfunctional monomer wherein a portion of the functionality enters into the co- -.
polymerization with o~her monomers in the monomer composition ~0 forming the core or the shell, the residual :Eunctionality causing cxosslinking of the polymeric core or shell upon s~sequent complete drying of the latex particles on a textile substrate material treated therewith~ Generally, such latent crosslinking monomers are amides or N-alkylolamides of alpha;
beta-ethylenically unsaturated carboxylic acids having 4-10 carbons, such as acrylamide, methacrylamide, N-methylol acrylamide~ N-ethanol acrylamide, N-propanol acrylamide, N-methylol methacrylamide, N-ethanol methacrylamide, N-methylol : maleimide, N-methylol maleamide, N-methylol maleamic acid, N-methylol maleamic acid esters, th N-alkylol amides of the vinyl aromatic acids such as N methylol-p-vinyl benzam:ide and the like, and others. The pre~erred monomers of the N-alkylol ?~'~
amide type, because of their ready availability and relative low cost, are the N-alkylol amides of alpha, beta-monoolefinically unsaturated monocarboxylic acids, such as N-methylol acrylamide and N-methylol methacrylamide. Other preferred latent cross-linking monomer systems are mixtures such as equimolar mixturesof acrylamide and N-methylol acrylamide or of methacrylamide and N-methylol methacrylamide. The latent crosslinking monomers are known to impart self-curing c~aracteristics to compositions containing them. The cure may be enhanced by reaction with an active hydrogen containins resin added to coating formulations containing the core or shell monomer compositions or the hetero-polymers, such as the triazine-formaldehyde and urea-formaldehyde resins. In either case, full cure occurs upon complete drying of the compositions on the textile substrates treated therewith.
By the term '1active crosslinking monomer" is meant a polyfunctional monomer which crosslinks a polymer composition during the initial formation thereof. Subsequent drying or other curing techniques are not required. Monomers of this -- type are well-known and comprise monomers wherein the function-ality is of substantially equivalent reactivity so that uniform crossLinking occurs. Typically, such monomers contain at least two addition polymerizable vinylidene groups and are alpha, i beta~ethylenically unsaturated monocarboxylic acid esters of polyhydric alcohols containing 2-6 ester groups. Suitable ; ;25~ ~preferred active crosslinking monomers include alkylene glycol diacrylates and dimethacryIatés such as ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate propylene~glycol diacrylate, triethylene glycol dimethacrylate, etc.; 1,3-glycerol dimethacrylate, 1~ trimethylol propane ~dimethacrylate, 1,1,1-trimethylol ethane diacrylate, penta-erythritol trimethacrylate, lg2,~-hexane triacrylate, sorbitol pentamethacrylate,~ etc. Other useful crosslinkers include methylene bisacrylamide, methylene bismethacrylamide, divinyl benzene, vinyl methacrylate, vinyl crotonate, vinyl acrylate, vinyl acetylene, trivinyl benzene, trially:L cyanurate, divinyl acetylene, divinyl ethane, divinyl sulfide, divinyl ether, divinyl sulone, hexatriene, diallyl cyanamide, ethylene glycol divinyl ether, diallyl phthalate, divinyl dimethyl silane, glycerol trivinyl ether, divinyl adipate, etc.
By "graftlinking monomer" is meant a polyfunctional monomer wherein the functionality has different reactivity.
This results in a portion of the functionality entering into - the formation of the core polymer and the remaining function-ality being pendant From the core polymer and capable of reacting with suitable functionality of the shell monomer composition to graft the shell upon the core polymer. Typically, the gratlinking monomers have at least two copolymerizable ethylenically unsaturated bonds which react at substantially different rates and comprise allyl esters of alpha, beta unsaturated mono- and dicarboxylic acids having termlnal ~ ethylenic unsaturation. Typical usefu] esters include allyl 20- methacryIate, allyl acrylate, diallylmaleate, diallyl fumarate and diallyl itaconate.
The monomers of the composition forming the shell polymer may be the same as the monomers of the core polymer composition or may be di~ferent, provided the glass transition temperature in the shell is about 60C. to about -10C., preferably about 25C. to ~bout -10C. A Tg in the shell higher than this range makes the heteropolymer unsuitable for ~ use in the treatment of textiles due to stiff or papery hand - and pcor flexibility. A Tg in the 25C. to 60C. range, although somewhat harder than necessary for many applications or locations, may he tolerable in warmer or continuously hot climates.
~9~ : ~
~,.
~ Generally, thP amount of graftlinking or active ;; crosslinking monomer in the core monomer composition should be that which will provide sufficient mutual insolubility of the Gore and shell polymer compositions or formatlon of a true heteropolymer and which will not unduly reduce the elongation properties of the heteropolymer. This will depend, of course, on other monomers in the monomer ~r ' ' ' . . :.
compositions of both core and shell, and may be varied accordingly.
The shell monomer composition requires only a latent crosslinker. Upon polymerization of the shell monomer S composition in the presence of ~he core polymer, the shell polymer composition becomes intimately associated with the core, i~ not actually graftlinked, through ~he condensation reactions possi~le with the latent crosslinking monomers present in the core and shell polymer composition~. It appears that the shell contributes significantly to the good abrasion-resistance, dryness (little or no tack) solvent resistance and launderability of the textiles treated with the heteropolymer by virtue either of gra~tlinking of the shell polymer onto the core polymer or of tight formation o~
the shell over th~ core short of actual graftlinking.
For the purposes of th.is description, the term "latent crosslinkin~ monomer" means a polyfunctional monomer wherein a portion of the functionality enters into the co- -.
polymerization with o~her monomers in the monomer composition ~0 forming the core or the shell, the residual :Eunctionality causing cxosslinking of the polymeric core or shell upon s~sequent complete drying of the latex particles on a textile substrate material treated therewith~ Generally, such latent crosslinking monomers are amides or N-alkylolamides of alpha;
beta-ethylenically unsaturated carboxylic acids having 4-10 carbons, such as acrylamide, methacrylamide, N-methylol acrylamide~ N-ethanol acrylamide, N-propanol acrylamide, N-methylol methacrylamide, N-ethanol methacrylamide, N-methylol : maleimide, N-methylol maleamide, N-methylol maleamic acid, N-methylol maleamic acid esters, th N-alkylol amides of the vinyl aromatic acids such as N methylol-p-vinyl benzam:ide and the like, and others. The pre~erred monomers of the N-alkylol ?~'~
amide type, because of their ready availability and relative low cost, are the N-alkylol amides of alpha, beta-monoolefinically unsaturated monocarboxylic acids, such as N-methylol acrylamide and N-methylol methacrylamide. Other preferred latent cross-linking monomer systems are mixtures such as equimolar mixturesof acrylamide and N-methylol acrylamide or of methacrylamide and N-methylol methacrylamide. The latent crosslinking monomers are known to impart self-curing c~aracteristics to compositions containing them. The cure may be enhanced by reaction with an active hydrogen containins resin added to coating formulations containing the core or shell monomer compositions or the hetero-polymers, such as the triazine-formaldehyde and urea-formaldehyde resins. In either case, full cure occurs upon complete drying of the compositions on the textile substrates treated therewith.
By the term '1active crosslinking monomer" is meant a polyfunctional monomer which crosslinks a polymer composition during the initial formation thereof. Subsequent drying or other curing techniques are not required. Monomers of this -- type are well-known and comprise monomers wherein the function-ality is of substantially equivalent reactivity so that uniform crossLinking occurs. Typically, such monomers contain at least two addition polymerizable vinylidene groups and are alpha, i beta~ethylenically unsaturated monocarboxylic acid esters of polyhydric alcohols containing 2-6 ester groups. Suitable ; ;25~ ~preferred active crosslinking monomers include alkylene glycol diacrylates and dimethacryIatés such as ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate propylene~glycol diacrylate, triethylene glycol dimethacrylate, etc.; 1,3-glycerol dimethacrylate, 1~ trimethylol propane ~dimethacrylate, 1,1,1-trimethylol ethane diacrylate, penta-erythritol trimethacrylate, lg2,~-hexane triacrylate, sorbitol pentamethacrylate,~ etc. Other useful crosslinkers include methylene bisacrylamide, methylene bismethacrylamide, divinyl benzene, vinyl methacrylate, vinyl crotonate, vinyl acrylate, vinyl acetylene, trivinyl benzene, trially:L cyanurate, divinyl acetylene, divinyl ethane, divinyl sulfide, divinyl ether, divinyl sulone, hexatriene, diallyl cyanamide, ethylene glycol divinyl ether, diallyl phthalate, divinyl dimethyl silane, glycerol trivinyl ether, divinyl adipate, etc.
By "graftlinking monomer" is meant a polyfunctional monomer wherein the functionality has different reactivity.
This results in a portion of the functionality entering into - the formation of the core polymer and the remaining function-ality being pendant From the core polymer and capable of reacting with suitable functionality of the shell monomer composition to graft the shell upon the core polymer. Typically, the gratlinking monomers have at least two copolymerizable ethylenically unsaturated bonds which react at substantially different rates and comprise allyl esters of alpha, beta unsaturated mono- and dicarboxylic acids having termlnal ~ ethylenic unsaturation. Typical usefu] esters include allyl 20- methacryIate, allyl acrylate, diallylmaleate, diallyl fumarate and diallyl itaconate.
The monomers of the composition forming the shell polymer may be the same as the monomers of the core polymer composition or may be di~ferent, provided the glass transition temperature in the shell is about 60C. to about -10C., preferably about 25C. to ~bout -10C. A Tg in the shell higher than this range makes the heteropolymer unsuitable for ~ use in the treatment of textiles due to stiff or papery hand - and pcor flexibility. A Tg in the 25C. to 60C. range, although somewhat harder than necessary for many applications or locations, may he tolerable in warmer or continuously hot climates.
~9~ : ~
~,.
3~
The amour.. G!C: latent crosslinking monomer or monomers of the second shell monomer composition is at least about 2~ by weight, based on the total weight of the second monomer composition. A useful range is ~-10~, preferably 5-8%.
The Tg of the core polymer composition and shell polymer composition are determinable in a known manner either experimentally or by calculation. The method of calculating the Tg based upon the Tg of homopolymers of individual monomers is described by Fox, B~l . Am. Physics Soc. 1, 3, page 123 tl956). Examples of the Tg of the :
homopolymers which permit such calculations are the following:
NOMOPOL MER OF T ;
n-octyl acrylate -80C. ..
n-decyl methacrylate -60C.
: 2-ethylhexyl acrylate -70C.
octyl methacrylate -20C. ~
n-tetradecyl methacr~late 9C. - ~:
methyl acrylate 9C.
2 n-tetradecyl acrylate 20C.
methyl methacrylate 105C.
acrylic acid 106C.
Monomers may be selected to obtain the app.ropriate .
: Tg through use of the "Rohm and Eaas Acrylic Glass Temperature :;~ 25 Analyzer'l, publication CM-24L/cb of Rohm and Haas Company, :
Philadelphia, Pennsylvania.
~ ~ The heteropolymer compositions are prepared by -~ emulsion polymerization techniques based on a two-stage polymerization and gradual a~dition of the monom~r emulsion ~30 ~in each of the two stages. While it is advantageous to ~: ~ initiate and catalyæe the reaction in each stage in a .
conventional manner, wherein the initiator is activated . :. :
S'$~`3 7 either thermally or hy a redox reaction, thermal initiation is preferred from the standpoint of better storage stabilit~
o the resulting polymer emulsion and balance o~ properties as a textile treating resin. The latex particle size should be relatively small, o the order of about 300 nm or less, preferably about 150-200 nm. As is well-known, given the same polymer backbone, particle size is controlled primarily by the type and level of emulsifier used in each stage of the emulsion polymerization. Molecular weight of the heteropolymers generally is of the order of about 70,000 to 2,000,000, preferably about 250,000 to 1,000,000.
The foregoing and other aspects of two-stage heteropolymer emulsion polymerization are well-known as described, for example, in U.S. Patents 3,812,205t 3,895,082, 3,461,188 and 3,457,209 except for the cri~ical monomer selection described herein.
Among the great variety of principal monomer compositions useful ~or forming the core polymer are the following compositions where the monomers total 91%:
76-91 BA/0-15 MM~
76-91 BA/0-15 St 74~91 BA/0-17 EMA
74~91 BAjO-17 HEMA
56-86 BA/0-~5 EA/O~10 MMA
46-91 BA/0~45 VC12 58 Bd/33 St ~ - .
,, ~ he crosslinking rnonomer s~stems ~or use with any oS the foregoing monomer s~stems include the following where the monomers total 9 ~:
The amour.. G!C: latent crosslinking monomer or monomers of the second shell monomer composition is at least about 2~ by weight, based on the total weight of the second monomer composition. A useful range is ~-10~, preferably 5-8%.
The Tg of the core polymer composition and shell polymer composition are determinable in a known manner either experimentally or by calculation. The method of calculating the Tg based upon the Tg of homopolymers of individual monomers is described by Fox, B~l . Am. Physics Soc. 1, 3, page 123 tl956). Examples of the Tg of the :
homopolymers which permit such calculations are the following:
NOMOPOL MER OF T ;
n-octyl acrylate -80C. ..
n-decyl methacrylate -60C.
: 2-ethylhexyl acrylate -70C.
octyl methacrylate -20C. ~
n-tetradecyl methacr~late 9C. - ~:
methyl acrylate 9C.
2 n-tetradecyl acrylate 20C.
methyl methacrylate 105C.
acrylic acid 106C.
Monomers may be selected to obtain the app.ropriate .
: Tg through use of the "Rohm and Eaas Acrylic Glass Temperature :;~ 25 Analyzer'l, publication CM-24L/cb of Rohm and Haas Company, :
Philadelphia, Pennsylvania.
~ ~ The heteropolymer compositions are prepared by -~ emulsion polymerization techniques based on a two-stage polymerization and gradual a~dition of the monom~r emulsion ~30 ~in each of the two stages. While it is advantageous to ~: ~ initiate and catalyæe the reaction in each stage in a .
conventional manner, wherein the initiator is activated . :. :
S'$~`3 7 either thermally or hy a redox reaction, thermal initiation is preferred from the standpoint of better storage stabilit~
o the resulting polymer emulsion and balance o~ properties as a textile treating resin. The latex particle size should be relatively small, o the order of about 300 nm or less, preferably about 150-200 nm. As is well-known, given the same polymer backbone, particle size is controlled primarily by the type and level of emulsifier used in each stage of the emulsion polymerization. Molecular weight of the heteropolymers generally is of the order of about 70,000 to 2,000,000, preferably about 250,000 to 1,000,000.
The foregoing and other aspects of two-stage heteropolymer emulsion polymerization are well-known as described, for example, in U.S. Patents 3,812,205t 3,895,082, 3,461,188 and 3,457,209 except for the cri~ical monomer selection described herein.
Among the great variety of principal monomer compositions useful ~or forming the core polymer are the following compositions where the monomers total 91%:
76-91 BA/0-15 MM~
76-91 BA/0-15 St 74~91 BA/0-17 EMA
74~91 BAjO-17 HEMA
56-86 BA/0-~5 EA/O~10 MMA
46-91 BA/0~45 VC12 58 Bd/33 St ~ - .
,, ~ he crosslinking rnonomer s~stems ~or use with any oS the foregoing monomer s~stems include the following where the monomers total 9 ~:
4-8 MAM/1-4 AlNA/0-2 IA
4-8 NlMAM/1-4 AlMA/0-2 IA
4-8 MlMAM/1-4 EGD~/0-2 IA
4-8 MlAM/1-4 EGDMA/0-2 IA
4-8 Ml~AM/1-4 BDM/0 2 IA ~ -4-8 MlAM/1-4 BDM/0-2 IA
Principal monomer s~stems for prepara~ion of the ~::
shell polymer include the followiny where the monomers total 92%: ~:
47-67 BA/25-45 ~N
47-67 BA/25-45 St 70-91 EA~1-22 MMA
40-65 BA/27-52 HPM~
32-50 EHA/41~60 AN
15 E/77 ~A
S0 EA~42 VC~2 40 Bd/52 St ~ Cross1inking monomer sys~ems for use within the ~:
; ~ shell monomer composition includP the following monom~rs (total 6-~%)~ ~
6-8 MlMAM/0-2 IA ~:
6-~ MlAM/0-2 IA
, ~ 2-6 MlMAM/6~2 MAM/0-2 IA
:-2-6 MlAM/6-2 AM/02 IA
` ~ -12-:: :
The above monomer abbreviations have the following meanings:
BA bùtyl acrylate MMA methyl methacrylate St styrene EMA ethyl methacrylate VA vinyl acetate HEMA hydroxyethyl methacrylate E ethylene EHA 2-ethylhexyl acrylate Bd butadiene ~PMA hydroxypropyl methacrylate IA i~aconic acid VC12 vinylidene chloride AM acrylamide BDM butylene dimethacry:Late ~N acrylonitrile AlMA allyl methacrylate EA ethyl acrylate EGDMA ethylene glycol di~
methacrylate MlMAM N-methylol metha~
crylamide MAM methacrylamide - ~ :
MlAM N-methylol acrylamide A preferred heteropolymer is prepared from a ~irst monomer composition comprisi~g:
70-95% by weight of a Cl-C8 alkyl acrylate, 0-15~ by weight of a Cl-C8 alkyl methacrylate, 4-10~ by weiyht of acrylamide or methacrylamide, I-5% by weight of allyl methacrylate, and 0-2% by weight of itaconic acid;
and a second monomer composition comprising:
40~70~ by wei~ht oE a Cl-C8 alkyl acrylate, ~:
20-50~ by weight of a Cl~C8 alkyl methacrylate 2-10~ by weight o N-methylol acrylamide, N-methylol methacxylamide, or a mixture of acrylamide and N-methylol acrylamide, or a ~:
mixture of methacrylamide and N-methylol ::
methacrylamide, and .:
0-2% by weight o~ itaconic acid.
The heteropolymer latices o the invention may be applied to any form of textile fabric to obtain a wide variety .
: ~ 13 3~~
of useful textile articles. In one end-use applicationr the heteropolymer is used as a cast transfer film which is laminated with an adhesive to a suitable fabric substrate in the manufacture of upholstery materials. The adhesive in such case may be a known adhesive useful for adhering acrylic films to fabrics or, prefer~bly, it is a foam which is applied to the fabric substrate in the form of a foamed acrylic latex.
One such foam is a latently crosslinkable acrylic polymer latex based on monomers providing a suitable Tg so that the form will not unduly stiffen the fabric. The acrylic polymer latex may be mechanically frothed or the foam may be generated by the addition of a foaming agentO The foam preferably also contains a foam stabilizer and is applied to the fabric at a wet foc~m thickness of about 10-150 mils and dried but without causing crosslinking. During drying the foam may shrink up to about 30~ or more, depending on its wet density. The foam is then crushed to a thickness o~ about 5-25 of its dry thickness or crushing may be pos~poned until after application of the heteropolymer top film.
Such top film normally is formed by depositing the thermosettable heteropolymer latex onto release paper, drying the composition without thermosetting, positioning the film while still on the release paper over the foamr and then laminating the fabric, foam and top film together at a suitable ~25 pressure and temperature to cause crushîng, consolidation and thermoset-ting of;the materials together. Preferably the release paper is removed beore lamination. The heteropolymer film thus provides a highly effective wear layer over the crushed f~am. A;top film thickness of the order of about 0.1-5 mils, preferably about 1.5-2.5 mils, is suitable for this purpose.
The foregoing and other details o laminatecl textil2 ;
:,i., .: :
fabrics, where a heteropolymer of this invention may be used as a top film over a crushed foam, are set forth in U.S. Reissue Patent 28,682 to Hoey/ reissued January 13, 1976.
Cast heteropolymer films of the invention may also be adhered to suitable ~abric substrates by other types of adhesives, foamed or non-foamed. Such adhesives are well-known in the art and include various other acrylic polymers such as acrylonitrile and non-acrylics such as styrene/butadiene, polyvinyl chloride, polyvinyl acetate, vinyl chloride/ethylene copolymers, various urethane type polymers, and the like.
~oamed adhesives are generally preferred, and of these the water-based types are particularly preferred, due to less penetration of the fabric substrate, which penetration might result in undue stifening of the fabric.
The heteropolymer latices of the invention are also useful ~or direct application in a foamed or non-foamed state to various types of fabric substrates including wovens, non-wovens and knitted ~abrics. The latex may be applied to the fabrics in any suitable manner, such as by spraying, dipping, roll transfer/ knife coating or the likeO
In the case of treatment o non-wovens, similar techniques known in the art may be employed, such as the procedures, f~brics and devices d~scribed in U~S. Patenk 3,157,562.
A concentration of polymer in the latex of ahout 10-70% by wei~ht, preferably about 40-60~, is suitable.
U.S. Patents 3,607,341 and 3,713,~68 urthex illustrate applications of foamed acrylic latex compositions ~ -for textile treatment wherein substitution therefor of the . .
heteropolymers of the present invention will provide impro~ed low temperature properties.
The heteropolymer latices of the invention are also useful as finish coats for leather or leather-like fabric substrates by direct application of the latices to the substrates or by use over a crushed foam in the manner of U.S. Patent 3,919,451. The heteropolymer i.n ~he latter case may also constitute the polymer of the foam interlayer.
Whether used as an interlayer or as a toplayer, the heteropolymers of the invention may be topcoated with various materials for urther improvements such as elimination o any residual tack or tendency to grab or ~o soil. Such topcoats are well-known, particularly in the leather ~inishing art, and generally comprise polymeric materials of relatively ~ :
hard character. The topcoat resins may be latices or organic solvent based topcoats of any of the known types, including acrylics, urethanes, polyvinyl chlorides, cellulose acetate butyrates, and combinations thereof.
The heteropolymer dispersions may contain any additives useful for improving various properties, such as ultraviolet light stabilizers, silicone release acids, de-.
foamers, pigments, leveling agents, thickening agents, ~ preservatives, heat or foam stabilizers~ and the like.
The following examples further illustrate the invention. All parts and pexcentages are by weight, unless otherwise indicated~
.
-~6-3~
PREPARATION OF ~ETE~OPOLYMER E~ULSION
__ rrhe ollowing monomer emulsions I and II are prepared:
Monomer Emulsion I II
Sodium lauryl sulfate (28~) 36.9 g. 36.9 g.
Water 498.0 ml. 269.0 ml.
Methacrylamide (MAM3 76.16 g. -M-methylol methacrylamide (25%) (MlM~M) _ 304.64 g.
Itaconic Acid (IA) 13.88 g. 10.88 g.
Bu~yl acrylate (BA) 935.68 g. 620.16 g~
Methyl methacrylate (MMA) 54.4 g. 380.80 g.
Allyl methacrylate (AlMA) 10.88 g.
To a suitable reaction vessel is added 3.885 g.
sodium lauryl sulfate (28%) and 625 ml. water. ~he mixture is heated to 80C. with a nitrogen 1ush. ~ gentle nitrogen blanket is maintained during the entire ollowing polymerization.
To th~ mixture is then added a catalyst solution of 3.81 g. sodium persulfate in 26 ml. water. Polymeri~ation begins and the temperature rises about 5C. About 5-10 minutes later/ monomer emulsion I and 122 ml. of a catalyst solution of 3.81 g. sodium persulfate in 244 ml. water are gradually added over 1-1/2 hours at 80-86C. After the addition the batch ls held at 80-85C.
~or~one hour~ Monomer emulsion II is then added togethex with the balance of the catalyst solution over 1-1/2 hours at 80-86C.
$he reaction is held 30 minutes at 80-86C. followed by cooling to 55C. and the addition of a ~irst chaser catalyst solution containing 10 ml of 0O15~ FeSO4 7 H2O, 1.0 g. t-butyl hydro-peroxide in 7 ml. water and 0.~7 g. sodium formaldehyde sul-foxylate in 17 ml. water. About a 1C. exotherm occurs. 15 minutes later, a second chaser catalyst solution ( same as first chaser except for absence of FeSO~ 7 ~2 solutioll~ is acLded. A
17 ~ :
third chaser catalyst solution (same as second chaser~ is added 15 minutes later and the reaction mixture is held for 15 minutes, cooled and filtered.
The resulting heteropolymer latex is characterized as follows:
Composition:
Core polymer: BA/MMA/MAM/AIMA/IA, 86/5/7/1/1 ~wt.%~
Shell polymer: BA/MMA/MlMAM/IA, 57/35/7/1 (wt.%) Core/Shell weight ratio: 50/50 Solids: 48.8%
Polymer emulsions were prepared having the following compositions (Table 1) where the monomer abbreviations are as identified in Example 1 and EGDMA is ethylene glycol dimethacrylate. Preparation was substantially as described in Example 1 above (thermal) except for Example 3 which was a redox process.
TAB~E 1 CORE/
EX. PO~YMER COMPOSITION ~ SHELL
NO. (CQRE//S~ELL) _ SOLIDS RATIO(%) 2 85 BA/3 MMA/4 EDGMA/7 MlMAM/
1 IA//57 BA/35 MMA/7 Ml~AM/
1 IA 48.9 50/50 3 86 BA/5 MMA/l AlMA/7 MAM/
1 IA//57 BA/35 MMA/7 MlMAM/
1 IA 5~.0 40/60 EX~MPLE 4 A. PREPAR~ION OE FABRIC SAMPLES
The polymer emulsions of Examples 1 3 are each applied to a textile fabric in the following manner:
The acrylic polymer emulsio~ is adjusted to 50~ solids, cast onto a silicone-coated release paper and dried for 2 minutes at 180 F.~to give a dry film 2 mils in thickness.
An acrylic polymer emulsion of the composition 96 butyl acryl~te, 2 acrylamide and 2 N-methylol acrylamide is ~ .
,.
2J3~
prepared and compounded in the following formulation having a total solids content of 46.8~:
INGREDIENTSOLIDS
-Polymer emulsion 200 92 Titanium dioxide 25 25 Melamine-formaldehyde resin ("Aerotex MW", American Cyanamid Co.) 4.6 3.7 Ammonium Stearate 14 4.6 Water 20 10 Ammonium hydroxide (28%) 4 267.6 125.3 Foams are prepared from the foregoing formulation by whipping air into the formulation using a "Kitchen-Aid"
Mixer (Model C) to a wet density of 0.15 g/cm3. The foam i5 then cast onto a cotton twill fabric to a 60 mils wet .
thickness and dried 5 minutes at 250F. The 2 mil precast film on release paper is then placed film side down onto the .....
dried foam, and the entire assembly is crushed and laminated -- between embossing plates for 3 seconds at 180F. and under a pressure of 30 tons. The release paper is then peeled off and the composite curea for 5 minutes at 300F. The result is a crushed foam coated textile fabric.having as a top film a heteropolymer emulsion polymer of Examples 1-3 B. PROPERTIES OF FABRIC SAMPLES
The fabric samples prepared as above each had the hand, drape and impact resistance required or textile use and were particularly suited for use in transportation (upholstery) fabrics due to the following combination of properties:
, : .
*Trademark ~ .
$'~
FABRIC POLYMER SURFACE BALLY TABER COLD
SAM2LE EX. NO. TACK~l) FLEX(2) ABRASION(3) CRACK(4) ,, ~
A 1 2 ~100,000 Excellent -35 C.
B 2 2 ~100,000 Excellent -35 C.
C 3 1 ~100,000 Excellent -35 C.
Tes-t Procedures (1) Tack: A 5" by 5" sample is folded face to face and diagonally to form a triangle. A weight which produces a force of 1 psi is placed on the sample and let in a 140F. oven for 16 hours. The sample is then taken from the oven, the weight is removed and the sample is allowed to cool for 30 minutes. The sample is gripped by one corner and rated as follows wherein values of 0, 1 and 2 i~dicate acceptability:
0 = no tack, sample unfolds under own weight.
1 = sample unfolds with a shake 2 - sample easily pulled apart 3 = moderate sticking 4 - heavy sticking
4-8 NlMAM/1-4 AlMA/0-2 IA
4-8 MlMAM/1-4 EGD~/0-2 IA
4-8 MlAM/1-4 EGDMA/0-2 IA
4-8 Ml~AM/1-4 BDM/0 2 IA ~ -4-8 MlAM/1-4 BDM/0-2 IA
Principal monomer s~stems for prepara~ion of the ~::
shell polymer include the followiny where the monomers total 92%: ~:
47-67 BA/25-45 ~N
47-67 BA/25-45 St 70-91 EA~1-22 MMA
40-65 BA/27-52 HPM~
32-50 EHA/41~60 AN
15 E/77 ~A
S0 EA~42 VC~2 40 Bd/52 St ~ Cross1inking monomer sys~ems for use within the ~:
; ~ shell monomer composition includP the following monom~rs (total 6-~%)~ ~
6-8 MlMAM/0-2 IA ~:
6-~ MlAM/0-2 IA
, ~ 2-6 MlMAM/6~2 MAM/0-2 IA
:-2-6 MlAM/6-2 AM/02 IA
` ~ -12-:: :
The above monomer abbreviations have the following meanings:
BA bùtyl acrylate MMA methyl methacrylate St styrene EMA ethyl methacrylate VA vinyl acetate HEMA hydroxyethyl methacrylate E ethylene EHA 2-ethylhexyl acrylate Bd butadiene ~PMA hydroxypropyl methacrylate IA i~aconic acid VC12 vinylidene chloride AM acrylamide BDM butylene dimethacry:Late ~N acrylonitrile AlMA allyl methacrylate EA ethyl acrylate EGDMA ethylene glycol di~
methacrylate MlMAM N-methylol metha~
crylamide MAM methacrylamide - ~ :
MlAM N-methylol acrylamide A preferred heteropolymer is prepared from a ~irst monomer composition comprisi~g:
70-95% by weight of a Cl-C8 alkyl acrylate, 0-15~ by weight of a Cl-C8 alkyl methacrylate, 4-10~ by weiyht of acrylamide or methacrylamide, I-5% by weight of allyl methacrylate, and 0-2% by weight of itaconic acid;
and a second monomer composition comprising:
40~70~ by wei~ht oE a Cl-C8 alkyl acrylate, ~:
20-50~ by weight of a Cl~C8 alkyl methacrylate 2-10~ by weight o N-methylol acrylamide, N-methylol methacxylamide, or a mixture of acrylamide and N-methylol acrylamide, or a ~:
mixture of methacrylamide and N-methylol ::
methacrylamide, and .:
0-2% by weight o~ itaconic acid.
The heteropolymer latices o the invention may be applied to any form of textile fabric to obtain a wide variety .
: ~ 13 3~~
of useful textile articles. In one end-use applicationr the heteropolymer is used as a cast transfer film which is laminated with an adhesive to a suitable fabric substrate in the manufacture of upholstery materials. The adhesive in such case may be a known adhesive useful for adhering acrylic films to fabrics or, prefer~bly, it is a foam which is applied to the fabric substrate in the form of a foamed acrylic latex.
One such foam is a latently crosslinkable acrylic polymer latex based on monomers providing a suitable Tg so that the form will not unduly stiffen the fabric. The acrylic polymer latex may be mechanically frothed or the foam may be generated by the addition of a foaming agentO The foam preferably also contains a foam stabilizer and is applied to the fabric at a wet foc~m thickness of about 10-150 mils and dried but without causing crosslinking. During drying the foam may shrink up to about 30~ or more, depending on its wet density. The foam is then crushed to a thickness o~ about 5-25 of its dry thickness or crushing may be pos~poned until after application of the heteropolymer top film.
Such top film normally is formed by depositing the thermosettable heteropolymer latex onto release paper, drying the composition without thermosetting, positioning the film while still on the release paper over the foamr and then laminating the fabric, foam and top film together at a suitable ~25 pressure and temperature to cause crushîng, consolidation and thermoset-ting of;the materials together. Preferably the release paper is removed beore lamination. The heteropolymer film thus provides a highly effective wear layer over the crushed f~am. A;top film thickness of the order of about 0.1-5 mils, preferably about 1.5-2.5 mils, is suitable for this purpose.
The foregoing and other details o laminatecl textil2 ;
:,i., .: :
fabrics, where a heteropolymer of this invention may be used as a top film over a crushed foam, are set forth in U.S. Reissue Patent 28,682 to Hoey/ reissued January 13, 1976.
Cast heteropolymer films of the invention may also be adhered to suitable ~abric substrates by other types of adhesives, foamed or non-foamed. Such adhesives are well-known in the art and include various other acrylic polymers such as acrylonitrile and non-acrylics such as styrene/butadiene, polyvinyl chloride, polyvinyl acetate, vinyl chloride/ethylene copolymers, various urethane type polymers, and the like.
~oamed adhesives are generally preferred, and of these the water-based types are particularly preferred, due to less penetration of the fabric substrate, which penetration might result in undue stifening of the fabric.
The heteropolymer latices of the invention are also useful ~or direct application in a foamed or non-foamed state to various types of fabric substrates including wovens, non-wovens and knitted ~abrics. The latex may be applied to the fabrics in any suitable manner, such as by spraying, dipping, roll transfer/ knife coating or the likeO
In the case of treatment o non-wovens, similar techniques known in the art may be employed, such as the procedures, f~brics and devices d~scribed in U~S. Patenk 3,157,562.
A concentration of polymer in the latex of ahout 10-70% by wei~ht, preferably about 40-60~, is suitable.
U.S. Patents 3,607,341 and 3,713,~68 urthex illustrate applications of foamed acrylic latex compositions ~ -for textile treatment wherein substitution therefor of the . .
heteropolymers of the present invention will provide impro~ed low temperature properties.
The heteropolymer latices of the invention are also useful as finish coats for leather or leather-like fabric substrates by direct application of the latices to the substrates or by use over a crushed foam in the manner of U.S. Patent 3,919,451. The heteropolymer i.n ~he latter case may also constitute the polymer of the foam interlayer.
Whether used as an interlayer or as a toplayer, the heteropolymers of the invention may be topcoated with various materials for urther improvements such as elimination o any residual tack or tendency to grab or ~o soil. Such topcoats are well-known, particularly in the leather ~inishing art, and generally comprise polymeric materials of relatively ~ :
hard character. The topcoat resins may be latices or organic solvent based topcoats of any of the known types, including acrylics, urethanes, polyvinyl chlorides, cellulose acetate butyrates, and combinations thereof.
The heteropolymer dispersions may contain any additives useful for improving various properties, such as ultraviolet light stabilizers, silicone release acids, de-.
foamers, pigments, leveling agents, thickening agents, ~ preservatives, heat or foam stabilizers~ and the like.
The following examples further illustrate the invention. All parts and pexcentages are by weight, unless otherwise indicated~
.
-~6-3~
PREPARATION OF ~ETE~OPOLYMER E~ULSION
__ rrhe ollowing monomer emulsions I and II are prepared:
Monomer Emulsion I II
Sodium lauryl sulfate (28~) 36.9 g. 36.9 g.
Water 498.0 ml. 269.0 ml.
Methacrylamide (MAM3 76.16 g. -M-methylol methacrylamide (25%) (MlM~M) _ 304.64 g.
Itaconic Acid (IA) 13.88 g. 10.88 g.
Bu~yl acrylate (BA) 935.68 g. 620.16 g~
Methyl methacrylate (MMA) 54.4 g. 380.80 g.
Allyl methacrylate (AlMA) 10.88 g.
To a suitable reaction vessel is added 3.885 g.
sodium lauryl sulfate (28%) and 625 ml. water. ~he mixture is heated to 80C. with a nitrogen 1ush. ~ gentle nitrogen blanket is maintained during the entire ollowing polymerization.
To th~ mixture is then added a catalyst solution of 3.81 g. sodium persulfate in 26 ml. water. Polymeri~ation begins and the temperature rises about 5C. About 5-10 minutes later/ monomer emulsion I and 122 ml. of a catalyst solution of 3.81 g. sodium persulfate in 244 ml. water are gradually added over 1-1/2 hours at 80-86C. After the addition the batch ls held at 80-85C.
~or~one hour~ Monomer emulsion II is then added togethex with the balance of the catalyst solution over 1-1/2 hours at 80-86C.
$he reaction is held 30 minutes at 80-86C. followed by cooling to 55C. and the addition of a ~irst chaser catalyst solution containing 10 ml of 0O15~ FeSO4 7 H2O, 1.0 g. t-butyl hydro-peroxide in 7 ml. water and 0.~7 g. sodium formaldehyde sul-foxylate in 17 ml. water. About a 1C. exotherm occurs. 15 minutes later, a second chaser catalyst solution ( same as first chaser except for absence of FeSO~ 7 ~2 solutioll~ is acLded. A
17 ~ :
third chaser catalyst solution (same as second chaser~ is added 15 minutes later and the reaction mixture is held for 15 minutes, cooled and filtered.
The resulting heteropolymer latex is characterized as follows:
Composition:
Core polymer: BA/MMA/MAM/AIMA/IA, 86/5/7/1/1 ~wt.%~
Shell polymer: BA/MMA/MlMAM/IA, 57/35/7/1 (wt.%) Core/Shell weight ratio: 50/50 Solids: 48.8%
Polymer emulsions were prepared having the following compositions (Table 1) where the monomer abbreviations are as identified in Example 1 and EGDMA is ethylene glycol dimethacrylate. Preparation was substantially as described in Example 1 above (thermal) except for Example 3 which was a redox process.
TAB~E 1 CORE/
EX. PO~YMER COMPOSITION ~ SHELL
NO. (CQRE//S~ELL) _ SOLIDS RATIO(%) 2 85 BA/3 MMA/4 EDGMA/7 MlMAM/
1 IA//57 BA/35 MMA/7 Ml~AM/
1 IA 48.9 50/50 3 86 BA/5 MMA/l AlMA/7 MAM/
1 IA//57 BA/35 MMA/7 MlMAM/
1 IA 5~.0 40/60 EX~MPLE 4 A. PREPAR~ION OE FABRIC SAMPLES
The polymer emulsions of Examples 1 3 are each applied to a textile fabric in the following manner:
The acrylic polymer emulsio~ is adjusted to 50~ solids, cast onto a silicone-coated release paper and dried for 2 minutes at 180 F.~to give a dry film 2 mils in thickness.
An acrylic polymer emulsion of the composition 96 butyl acryl~te, 2 acrylamide and 2 N-methylol acrylamide is ~ .
,.
2J3~
prepared and compounded in the following formulation having a total solids content of 46.8~:
INGREDIENTSOLIDS
-Polymer emulsion 200 92 Titanium dioxide 25 25 Melamine-formaldehyde resin ("Aerotex MW", American Cyanamid Co.) 4.6 3.7 Ammonium Stearate 14 4.6 Water 20 10 Ammonium hydroxide (28%) 4 267.6 125.3 Foams are prepared from the foregoing formulation by whipping air into the formulation using a "Kitchen-Aid"
Mixer (Model C) to a wet density of 0.15 g/cm3. The foam i5 then cast onto a cotton twill fabric to a 60 mils wet .
thickness and dried 5 minutes at 250F. The 2 mil precast film on release paper is then placed film side down onto the .....
dried foam, and the entire assembly is crushed and laminated -- between embossing plates for 3 seconds at 180F. and under a pressure of 30 tons. The release paper is then peeled off and the composite curea for 5 minutes at 300F. The result is a crushed foam coated textile fabric.having as a top film a heteropolymer emulsion polymer of Examples 1-3 B. PROPERTIES OF FABRIC SAMPLES
The fabric samples prepared as above each had the hand, drape and impact resistance required or textile use and were particularly suited for use in transportation (upholstery) fabrics due to the following combination of properties:
, : .
*Trademark ~ .
$'~
FABRIC POLYMER SURFACE BALLY TABER COLD
SAM2LE EX. NO. TACK~l) FLEX(2) ABRASION(3) CRACK(4) ,, ~
A 1 2 ~100,000 Excellent -35 C.
B 2 2 ~100,000 Excellent -35 C.
C 3 1 ~100,000 Excellent -35 C.
Tes-t Procedures (1) Tack: A 5" by 5" sample is folded face to face and diagonally to form a triangle. A weight which produces a force of 1 psi is placed on the sample and let in a 140F. oven for 16 hours. The sample is then taken from the oven, the weight is removed and the sample is allowed to cool for 30 minutes. The sample is gripped by one corner and rated as follows wherein values of 0, 1 and 2 i~dicate acceptability:
0 = no tack, sample unfolds under own weight.
1 = sample unfolds with a shake 2 - sample easily pulled apart 3 = moderate sticking 4 - heavy sticking
5 .- severe sticXing - sample damaged (2~ Bally Flex: A room temperature flexibility test as described in Society of Leather Technologists and Chemists, Method SLP-14. The data represents the number of cycles survived by the sample. 100,000 or more cycles indicates :
excellent performance.
(3) Taber Abrasion: ASTM D-1175-71, using an H-18 wheel 500 gm. weight, 1000 cycles. A loss o~ 200 mg. or less in .
apparel and upholstery uses is acceptable. A loss of 100 mg. or less in shoe uppers is acceptable.
(4) Cold Crack: ASTM D-17g0 62 modified as follows: A
1" x 3" sample is placed in a cold box and allowed to come to equilibrium at 30Fq A 1QP is fo~m~d with the hetero-:, . : , polymer film side facing out, and a 4 lb. weight .is dropped 9 inches onto the edge of the loop. The sample is examined ~or cracks. The temperature is lowered in 10F.
increments until failure occurs. The lowest temperature at which the sample passes is reco.rded as the cold crack temperature.
DIRECT COATIMG OF CRUSHED FOAM COATED FABRIC
A fabric sample is prepared as described in Part Aof Example 5 except for absence of the pre-cast heteropolymer top film. However, the acrylic polymer foam (about 45 mils wet thickness) is dried and crushed to a thickness of about 8 mils. A heteropolymer emulsion ~uch as described in Example 1 is then thickened with "Acrysol ASE-60" acrylic thickener to a viscosi~y of about 3000 cps., and a 5 mil wet coating of the emulsion is applied ~ .
to the crushed foam. The coating is dried 5 minutes at 240 F.
and cured for 5 minutes at 300F. The resulting product is useful as furniture upholstery or other synthetiG textile applisation.
TRANSFER COATING OF FABRIC WITHOUT CRUSHED FOAM : .
A silicone-coated release paper is knife-coated over ~ -a roll with a polymer emulsion such as described in Examples 1-3 to a wet thickness of 4-5 mils. The coating is dried to a B stage and ilm thickness of about 2 mils in a three zone oven with temperatures set as follows: Zone 1, 170 F.;
Zone 2, 190F.; and Zone 3, 24Q F~ Using a thr~e roll reverse roll coater, an acrylic polymeric emulsion (."Rhoplex TR-93q" polymer emulsion thickened to a viscosity of 10,000 cps) is applied to the dried film as an adhesive.
A napped and sheared abric is then placed on the wet adhesive ~I'radema~k -21-nap side down, and the composite is laminated at 60-80 psi pressure. The composite is then dried and cured in a second, three zone oven using the following temperatures: Zone l, 220 F.;
Zone 2, 280 F.; and Zone 31 330 F. The release paper is thereafter stripped away and the composite rolled up. The resulting coated ~abric is suitable for upholstery, handbag and other simulated leather uses and exhibits a cold-crack of -20 F.
l~ LEATHER COATING
A corrected grain upholstery leather stock is treated with a standard, commercially available basecoat formulation and dried for one hour at 120F. A polymer emulsion such as described in Examples 1-3 is formulated as follows:
Polymer Emulsion 80 par~s Water 16 **
"Leveller MA-65" 2 "Leveller MK~
Ammonium hydroxide (28~
Silicone Emulsion 8 The compounded emulsion is then applied to the base-coated leather by spraying twice and is dried for l hour at l20~ F. ater each spraying. A total coating weight of about 2 g,/ft~2 solids is obtained. The coa~ed leather sample is then embossed with a hair cell print at 500 psi pressure1 250 F. and 3 seconds dwell time.
EX~MPLE 9 NON-WOVEN BINDER APPLICATION
__ A polymex emulsion such as described in Examples 1-3 is diluted to 15~ solids content and 0~5% ammonium nitrate **~rademark ***Trademar~ -22-'~ X ' , .. . .
catalyst is added. The latex is applied to a carded, non-woven rayon web, prebonded with a small quantity of polyvinyl alcohol and weighing about 0.5 g./yd.2/ by paclding (saturation~
on a "Birch Brothers Padder" operating at 30 pSiCJ and about 7 yds./min. Wet pick up of the emulsion is about 150~.
After drying at room temperature the fabric is cured at 300 F.
for 2 minutes. The resulting product is suitable for use as an interliner. If the add-ons of emulsion solids are lower ~<100%), the product is suitable for applications such as diaper cover stock and sanitary napkins.
*Trademark
excellent performance.
(3) Taber Abrasion: ASTM D-1175-71, using an H-18 wheel 500 gm. weight, 1000 cycles. A loss o~ 200 mg. or less in .
apparel and upholstery uses is acceptable. A loss of 100 mg. or less in shoe uppers is acceptable.
(4) Cold Crack: ASTM D-17g0 62 modified as follows: A
1" x 3" sample is placed in a cold box and allowed to come to equilibrium at 30Fq A 1QP is fo~m~d with the hetero-:, . : , polymer film side facing out, and a 4 lb. weight .is dropped 9 inches onto the edge of the loop. The sample is examined ~or cracks. The temperature is lowered in 10F.
increments until failure occurs. The lowest temperature at which the sample passes is reco.rded as the cold crack temperature.
DIRECT COATIMG OF CRUSHED FOAM COATED FABRIC
A fabric sample is prepared as described in Part Aof Example 5 except for absence of the pre-cast heteropolymer top film. However, the acrylic polymer foam (about 45 mils wet thickness) is dried and crushed to a thickness of about 8 mils. A heteropolymer emulsion ~uch as described in Example 1 is then thickened with "Acrysol ASE-60" acrylic thickener to a viscosi~y of about 3000 cps., and a 5 mil wet coating of the emulsion is applied ~ .
to the crushed foam. The coating is dried 5 minutes at 240 F.
and cured for 5 minutes at 300F. The resulting product is useful as furniture upholstery or other synthetiG textile applisation.
TRANSFER COATING OF FABRIC WITHOUT CRUSHED FOAM : .
A silicone-coated release paper is knife-coated over ~ -a roll with a polymer emulsion such as described in Examples 1-3 to a wet thickness of 4-5 mils. The coating is dried to a B stage and ilm thickness of about 2 mils in a three zone oven with temperatures set as follows: Zone 1, 170 F.;
Zone 2, 190F.; and Zone 3, 24Q F~ Using a thr~e roll reverse roll coater, an acrylic polymeric emulsion (."Rhoplex TR-93q" polymer emulsion thickened to a viscosity of 10,000 cps) is applied to the dried film as an adhesive.
A napped and sheared abric is then placed on the wet adhesive ~I'radema~k -21-nap side down, and the composite is laminated at 60-80 psi pressure. The composite is then dried and cured in a second, three zone oven using the following temperatures: Zone l, 220 F.;
Zone 2, 280 F.; and Zone 31 330 F. The release paper is thereafter stripped away and the composite rolled up. The resulting coated ~abric is suitable for upholstery, handbag and other simulated leather uses and exhibits a cold-crack of -20 F.
l~ LEATHER COATING
A corrected grain upholstery leather stock is treated with a standard, commercially available basecoat formulation and dried for one hour at 120F. A polymer emulsion such as described in Examples 1-3 is formulated as follows:
Polymer Emulsion 80 par~s Water 16 **
"Leveller MA-65" 2 "Leveller MK~
Ammonium hydroxide (28~
Silicone Emulsion 8 The compounded emulsion is then applied to the base-coated leather by spraying twice and is dried for l hour at l20~ F. ater each spraying. A total coating weight of about 2 g,/ft~2 solids is obtained. The coa~ed leather sample is then embossed with a hair cell print at 500 psi pressure1 250 F. and 3 seconds dwell time.
EX~MPLE 9 NON-WOVEN BINDER APPLICATION
__ A polymex emulsion such as described in Examples 1-3 is diluted to 15~ solids content and 0~5% ammonium nitrate **~rademark ***Trademar~ -22-'~ X ' , .. . .
catalyst is added. The latex is applied to a carded, non-woven rayon web, prebonded with a small quantity of polyvinyl alcohol and weighing about 0.5 g./yd.2/ by paclding (saturation~
on a "Birch Brothers Padder" operating at 30 pSiCJ and about 7 yds./min. Wet pick up of the emulsion is about 150~.
After drying at room temperature the fabric is cured at 300 F.
for 2 minutes. The resulting product is suitable for use as an interliner. If the add-ons of emulsion solids are lower ~<100%), the product is suitable for applications such as diaper cover stock and sanitary napkins.
*Trademark
Claims (24)
1. A textile treating composition consisting essentially of an acrylic latex, the particles of which comprise about 30-60% by weight of a polymeric core and about 70-40% by weight of a polymeric shell, wherein said core is formed by emulsion polymerization of a first monomer composition consisting essentially of:
(a) a major amount of principal monomer system consisting essentially of at least one C1-C8 straight or branched chain alkyl acrylate and from 0-20% by weight, based on said alkyl acrylate, of another monoethylenically unsaturated monomer which is copolymerizable with said alkyl acrylate, said other monoethylenically unsaturated monomer being non-crosslinking with respect to the alkyl acrylate; and (b) a minor amount of a crosslinking monomer system comprising:
(i) from about 0.5% to 6% by weight, based on the total first monomer composition, of a graftlinking monomer which is a poly-funtional monomer which has at least two copolymerizable ethylenically unsaturated bonds which react at substantially different rates thereby resulting in a portion of the functionality entering into formation of the core and the remaining functionality being pendant from the core and capable of reacting with suitable functionality of the shell (or second) monomer composition as defined hereinafter, to graft the shell upon the core; or a polyfunctional monomer which crosslinks a polymer composition during the initial formation thereof, and containing at least two addition polymerizable vinylidene groups, and (ii) from about 4% to 10% by weight, based on the total first monomer composition, of a latent crosslinking monomer which is a polyfunctional monomer wherein a portion of the functionality enters into the copolymerization with other monomers in the monomer composition, the residual functionality causing crosslinking of the polymeric core or shell upon subsequent complete drying of the latex particles on a textile substrate material;
and wherein said shell is formed on said core by emulsion polymerization of a second monomer composition in the presence of said core, said second monomer composition consisting essentially of:
(a) a major amount of a principal monomer system as hereinbefore defined; and (b) from about 2% to 10% by weight, based on the total second monomer composition of a latent crosslinking monomer as hereinbefore defined; the monomers of said first monomer composition being selected to provide a Tg in said core of -20°C. or lower, and the monomers of said second monomer composition being selected to provide a Tg in said shell of about 60°C. to about -10°C;
said composition providing good flexibility and impact resistance (good "cold crack" properties) at low temperatures as well as low surface tack and good impact resistance, abrasion resistance and flexibility at all use temperatures, to the treated textile.
(a) a major amount of principal monomer system consisting essentially of at least one C1-C8 straight or branched chain alkyl acrylate and from 0-20% by weight, based on said alkyl acrylate, of another monoethylenically unsaturated monomer which is copolymerizable with said alkyl acrylate, said other monoethylenically unsaturated monomer being non-crosslinking with respect to the alkyl acrylate; and (b) a minor amount of a crosslinking monomer system comprising:
(i) from about 0.5% to 6% by weight, based on the total first monomer composition, of a graftlinking monomer which is a poly-funtional monomer which has at least two copolymerizable ethylenically unsaturated bonds which react at substantially different rates thereby resulting in a portion of the functionality entering into formation of the core and the remaining functionality being pendant from the core and capable of reacting with suitable functionality of the shell (or second) monomer composition as defined hereinafter, to graft the shell upon the core; or a polyfunctional monomer which crosslinks a polymer composition during the initial formation thereof, and containing at least two addition polymerizable vinylidene groups, and (ii) from about 4% to 10% by weight, based on the total first monomer composition, of a latent crosslinking monomer which is a polyfunctional monomer wherein a portion of the functionality enters into the copolymerization with other monomers in the monomer composition, the residual functionality causing crosslinking of the polymeric core or shell upon subsequent complete drying of the latex particles on a textile substrate material;
and wherein said shell is formed on said core by emulsion polymerization of a second monomer composition in the presence of said core, said second monomer composition consisting essentially of:
(a) a major amount of a principal monomer system as hereinbefore defined; and (b) from about 2% to 10% by weight, based on the total second monomer composition of a latent crosslinking monomer as hereinbefore defined; the monomers of said first monomer composition being selected to provide a Tg in said core of -20°C. or lower, and the monomers of said second monomer composition being selected to provide a Tg in said shell of about 60°C. to about -10°C;
said composition providing good flexibility and impact resistance (good "cold crack" properties) at low temperatures as well as low surface tack and good impact resistance, abrasion resistance and flexibility at all use temperatures, to the treated textile.
2. The textile treating composition of claim 1 wherein said latent crosslinking monomer is acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, or any mixture of two or more thereof.
3. The textile treating composition of claim 1 wherein said graftlinking monomer is an allyl, methallyl or crotyl ester of an alpha, beta-ethylenically unsaturated carboxylic acid.
4. The textile treating composition of claim 1 wherein said active crosslinking monomer is an alpha, beta-ethylenically unsaturated monocarboxylic acid ester of a polyhydric alcohol.
5. The textile treating composition of claim 1 wherein the principal monomer system of the core comprises about 70-95% by weight of butyl acrylate and about 1-15%
by weight of methyl methacrylate, based on total monomer weight.
by weight of methyl methacrylate, based on total monomer weight.
6. The textile treating composition of claim 1 wherein said first monomer composition consists essentially of:
70-95% by weight of a C1-C8 alkyl acrylate, 0-15% by weight of a C1-C8 alkyl methacrylate, 4-10% by weight of acrylamide or methacrylamide, 1-5% by weight of allyl methacrylate, and 0-2% by weight of itaconic acid;
and wherein said second monomer composition consists essentially of:
40-70% by weight of a C1-C8 alkyl acrylate, 20-50% by weight of a C1-C8 alkyl methacrylate, 2-10% by weight of N-methylol acrylamide N-methylol methacrylamide, or a mixture of acrylamide and N-methylol acrylamide, or a mixture of methacrylamide and N-methylol methacrylamide, and 0-2% by weight of itaconic acid.
70-95% by weight of a C1-C8 alkyl acrylate, 0-15% by weight of a C1-C8 alkyl methacrylate, 4-10% by weight of acrylamide or methacrylamide, 1-5% by weight of allyl methacrylate, and 0-2% by weight of itaconic acid;
and wherein said second monomer composition consists essentially of:
40-70% by weight of a C1-C8 alkyl acrylate, 20-50% by weight of a C1-C8 alkyl methacrylate, 2-10% by weight of N-methylol acrylamide N-methylol methacrylamide, or a mixture of acrylamide and N-methylol acrylamide, or a mixture of methacrylamide and N-methylol methacrylamide, and 0-2% by weight of itaconic acid.
7. An article of manufacture comprising a textile material treated with a polymeric composition formed from acrylic latex particles, said latex particles comprising about 30-60% by weight of a polymeric core and about 70-40%
by weight of a polymeric shell, wherein said core is formed by emulsion polymerization of a first monomer composition consisting essentially of:
(a) a major amount of a principal monomer system consisting essentially of at least one C1 - C8 straight or branched chain alkyl acrylate and from 0-20% by weight, based on said alkyl acrylate, of another monoethylenicallly unsaturated monomer which is copolymeriable with said acrylate, said other monoethylenically unsaturated monomer being non-crosslinking with respect to the alkyl acrylate; and (b) a minor amount of a crosslinking monomer system comprising:
(i) from about 0.5% to 6% by weight based on the total monomer composition, of a graftlinking monomer which is a polyfunctional monomer which has a-t least two copolymerizable ethylenically unsaturated bonds which react: at substantially different rates thereby resulting in a portion of the functionality entering into formation of -the core and the remaining functionality being pendant from the core and capable of reacting with suitable functionality of the shell (or second) monomer composition as defined hereinafter, to graft the shell upon the core; or a polyfunctional monomer which crosslinks a polymer composition during the initial formation thereof, and containing at least two addition polymerizable vinylidene groups, and (ii) from about 4% to 10% by weight, based on the total monomer composition, of a latent crosslinking monomer which is a polyfunctional monomer wherein a portion of the functionality enters into the copolymerization with other monomers in the monomer composition, the residual functionality causing crosslinking of the polymeric core or shell upon subsequent complete drying of the latex particles on a textile substrate material;
and wherein said shell is formed on said core by emulsion polymerization of a second monomer composition in the presence of said core, said second monomer composition consisting essentially of:
(a) a major amount of a principal monomer system as hereinbefore defined; and (b) from about 2% to 10% based on the total second monomer composition, of a latent crosslinking monomer as hereinbefore defined;
the monomers of said first monomer composition being selected to provide a Tg in said core of -20°C. or lower, and the monomers of said second monomer composition being selected to provide a Tg in said shell of about 60°C. to about -10°C; said article being characterized by having good flexibility and impact resistance at low temperatures (good "cold crack" properties), as well as low surface tack and good impact resistance, abrasion resistance, and flexibility at all use temperatures.
by weight of a polymeric shell, wherein said core is formed by emulsion polymerization of a first monomer composition consisting essentially of:
(a) a major amount of a principal monomer system consisting essentially of at least one C1 - C8 straight or branched chain alkyl acrylate and from 0-20% by weight, based on said alkyl acrylate, of another monoethylenicallly unsaturated monomer which is copolymeriable with said acrylate, said other monoethylenically unsaturated monomer being non-crosslinking with respect to the alkyl acrylate; and (b) a minor amount of a crosslinking monomer system comprising:
(i) from about 0.5% to 6% by weight based on the total monomer composition, of a graftlinking monomer which is a polyfunctional monomer which has a-t least two copolymerizable ethylenically unsaturated bonds which react: at substantially different rates thereby resulting in a portion of the functionality entering into formation of -the core and the remaining functionality being pendant from the core and capable of reacting with suitable functionality of the shell (or second) monomer composition as defined hereinafter, to graft the shell upon the core; or a polyfunctional monomer which crosslinks a polymer composition during the initial formation thereof, and containing at least two addition polymerizable vinylidene groups, and (ii) from about 4% to 10% by weight, based on the total monomer composition, of a latent crosslinking monomer which is a polyfunctional monomer wherein a portion of the functionality enters into the copolymerization with other monomers in the monomer composition, the residual functionality causing crosslinking of the polymeric core or shell upon subsequent complete drying of the latex particles on a textile substrate material;
and wherein said shell is formed on said core by emulsion polymerization of a second monomer composition in the presence of said core, said second monomer composition consisting essentially of:
(a) a major amount of a principal monomer system as hereinbefore defined; and (b) from about 2% to 10% based on the total second monomer composition, of a latent crosslinking monomer as hereinbefore defined;
the monomers of said first monomer composition being selected to provide a Tg in said core of -20°C. or lower, and the monomers of said second monomer composition being selected to provide a Tg in said shell of about 60°C. to about -10°C; said article being characterized by having good flexibility and impact resistance at low temperatures (good "cold crack" properties), as well as low surface tack and good impact resistance, abrasion resistance, and flexibility at all use temperatures.
8. The article of claim 7 wherein said latent crosslinking monomer is acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, or any mixture of two or more thereof.
9. The article of claim 7 wherein said graft-linking monomer is an allyl, methallyl or crotyl ester of an alpha, beta-ethylenically unsaturated carboxylic acid.
10. The article of claim 7 wherein said active crosslinking monomer is an alpha, beta-ethylenically unsaturated monocarboxylic acid ester of a polyhydric alcohol.
11. The article of claim 7 wherein the principal monomer system of the core comprises about 70-95% by weight of butyl acrylate and about 1-15% by weight of methyl methacrylate, based on total monomer weight.
12. The article of claim 7 wherein said first monomer composition consists essentially of:
70-95% by weight of a C1-C8 alkyl acrylate, 0-15% by weight of a C1-C8 alkyl methacrylate, 4-10% by weight of acrylamide or methacryl-amide, 1-5% by weight of allyl methacrylate, and 0-2% by weight of itaconic acid;
and wherein said second monomer composition consists essentially of:
40-70% by weight of a C1- C8 alkyl acrylate, 20-50% by weight of a C1-C8 alkyl methacry-late, 2-10% by weight of N-methylol acrylamide, N-methylol methacrylamide, or a mixture of acrylamide and N-methylol acrylamide, or a mixture of methacrylamide and N-methylol methacrylamide, and 0-2% by weight of itaconic acid.
70-95% by weight of a C1-C8 alkyl acrylate, 0-15% by weight of a C1-C8 alkyl methacrylate, 4-10% by weight of acrylamide or methacryl-amide, 1-5% by weight of allyl methacrylate, and 0-2% by weight of itaconic acid;
and wherein said second monomer composition consists essentially of:
40-70% by weight of a C1- C8 alkyl acrylate, 20-50% by weight of a C1-C8 alkyl methacry-late, 2-10% by weight of N-methylol acrylamide, N-methylol methacrylamide, or a mixture of acrylamide and N-methylol acrylamide, or a mixture of methacrylamide and N-methylol methacrylamide, and 0-2% by weight of itaconic acid.
13. An article as in Claim 7 wherein said textile material is leather or a leather substitute and said polymeric composition is a direct or transfer coating.
14. An article as in Claim 13 further including a crushed foam layer between said textile material and said coating.
15. An article as in Claim 7 wherein said textile material is a woven, knitted or non-woven fabric and said polymeric composition is a direct or transfer coating.
16. An article as in Claim 15 further includ-ing a crushed foam layer between said fabric and said coating.
17. A process which comprises treating a tex-tile material with the composition of Claim 1, and dry-ing and curing the latex on said material.
18. A process which comprises covering a tex-tile material with a crushed foam prepared from a polymer emulsion, covering said crushed foam covered material with the composition of Claim 1, and drying and curing said acrylic latex thereon.
19. A process which comprises covering a tex-tile material with a foamed polymer emulsion, drying said foamed emulsion short of curing, applying a dry film pre-pared from the composition of Claim 1, and laminating said foamed polymer emulsion and said film to said textile material.
20. An article as in Claim 7 further including a crushed foam layer between said textile material and said coating, and wherein said coating is a transfer coating.
21. An article of manufacture comprising a sheet of release material having a dried film of the composition of Claim 1 thereon.
22. An article of manufacture comprising a sheet of release material having a dried film of thecomposition of Claim 6 thereon,
23. The article of Claim 21 wherein said sheet of release material is silicone-treated release paper.
24. The article of Claim 22 wherein said sheet of release material is silicone-treated release paper.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/697,171 US4107120A (en) | 1976-06-17 | 1976-06-17 | Heteropolymer acrylic latices and textiles treated therewith |
| US697,171 | 1976-06-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1112387A true CA1112387A (en) | 1981-11-10 |
Family
ID=24800094
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA279,849A Expired CA1112387A (en) | 1976-06-17 | 1977-06-03 | Heteropolymer acrylic latices and textiles treated therewith |
Country Status (16)
| Country | Link |
|---|---|
| US (1) | US4107120A (en) |
| JP (1) | JPS532590A (en) |
| AU (1) | AU511706B2 (en) |
| BE (1) | BE855743A (en) |
| BR (1) | BR7703801A (en) |
| CA (1) | CA1112387A (en) |
| DE (1) | DE2726806A1 (en) |
| ES (1) | ES459886A1 (en) |
| FR (1) | FR2355038A1 (en) |
| GB (1) | GB1583671A (en) |
| IT (1) | IT1083434B (en) |
| NL (1) | NL7706667A (en) |
| NZ (1) | NZ184347A (en) |
| PH (1) | PH12788A (en) |
| SE (1) | SE7707021L (en) |
| ZA (1) | ZA773463B (en) |
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|---|---|---|---|---|
| US4181769A (en) * | 1976-06-17 | 1980-01-01 | Rohm And Haas Company | Heteropolymer acrylic latices and textiles treated therewith |
| US4277384A (en) * | 1978-09-25 | 1981-07-07 | Rohm And Haas Company | Heteropolymer acrylic latices and textiles treated therewith |
| US4351875A (en) * | 1978-09-25 | 1982-09-28 | Rohm And Haas Company | Heteropolymer acrylic latices and textiles treated therewith |
| US4256809A (en) * | 1979-02-02 | 1981-03-17 | Rohm And Haas Company | Ambient or low-temperature curable coatings for leather and other flexible substrates |
| DE2906118C2 (en) * | 1979-02-17 | 1981-06-19 | Wolff Walsrode Ag, 3030 Walsrode | Aqueous polymer mixture, process for its production and its use as a substrate-anchoring, block-resistant single-layer sealing lacquer on flat structures |
| US4337185A (en) * | 1980-06-23 | 1982-06-29 | The Dow Chemical Company | Process for making cationic structured particle latexes using reactive polymeric surfactants |
| US4289823A (en) * | 1980-09-30 | 1981-09-15 | Rohm And Haas Company | Calenderable acrylic polymers and textiles treated therewith |
| DE3116995A1 (en) * | 1981-04-29 | 1982-11-25 | Röhm GmbH, 6100 Darmstadt | LATEX FOR IMMOBILIZING BIOLOGICALLY EFFECTIVE SUBSTANCES |
| US4413068A (en) * | 1981-07-02 | 1983-11-01 | Polysar International S.A. | Hard shell soft core latex |
| US4474927A (en) * | 1981-12-16 | 1984-10-02 | E. I. Du Pont De Nemours And Company | Polyamide compositions toughened with crosslinked acrylic rubber |
| FI832883A (en) * | 1982-08-12 | 1984-02-13 | Scm Corp | SUSTAINABLE POLYMER BEARING |
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| US4617230A (en) * | 1983-12-27 | 1986-10-14 | The B. F. Goodrich Company | Latex containing odor inhibitor |
| GB8507221D0 (en) * | 1985-03-20 | 1985-04-24 | Courtaulds Plc | Polymer compositions |
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| DE3700534A1 (en) * | 1987-01-10 | 1988-07-21 | Basf Ag | AQUEOUS POLYMER DISPERSIONS FOR WOOD COATING |
| GB8718036D0 (en) * | 1987-07-30 | 1987-09-03 | Tioxide Group Plc | Polymeric particles |
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| GB8729399D0 (en) * | 1987-12-17 | 1988-02-03 | Tioxide Group Plc | Polymeric particles & their preparation |
| US4880842A (en) * | 1988-05-20 | 1989-11-14 | Rohm & Haas Company | Multi-stage opacifying polymer particles containing non-polymeric acid absorbed therein |
| US4970241A (en) * | 1988-05-20 | 1990-11-13 | Rohm And Haas Company | Multi-stage opacifying polymer particles containing non-polymeric acid absorbed therein |
| DE3902103A1 (en) * | 1989-01-25 | 1990-08-02 | Roehm Gmbh | BINDER FOR WAESSED GLOSSY COLORS |
| US5185387A (en) * | 1989-03-16 | 1993-02-09 | Rohm Gmbh | Aqueous synthetic resin dispersion |
| US5063091A (en) * | 1989-10-06 | 1991-11-05 | Rohm And Haas Company | Method for use of aqueous elastomeric coatings |
| GB9007199D0 (en) * | 1990-03-30 | 1990-05-30 | Tioxide Group Plc | Preparation of polymeric particles |
| US5182179A (en) * | 1990-12-07 | 1993-01-26 | Rohm And Haas Company | Fiber binder |
| CA2071756A1 (en) * | 1991-07-03 | 1993-01-04 | Rohm And Haas Company | Multi-staged binder for use in elastomeric coatings, caulks, and sealants |
| DE9110054U1 (en) * | 1991-08-14 | 1991-10-10 | Roehm Gmbh, 6100 Darmstadt, De | |
| ATE127549T1 (en) * | 1991-12-17 | 1995-09-15 | Kufner Textilwerke Gmbh | COATED SURFACE. |
| DE4141760A1 (en) * | 1991-12-18 | 1993-06-24 | Basf Ag | AQUEOUS POLYMER DISPERSION |
| GB9209438D0 (en) * | 1992-05-01 | 1992-06-17 | Amtico Co | Floor coverings |
| US6004676A (en) * | 1992-06-17 | 1999-12-21 | Ppg Industries, Inc. | Optical fiber cable assembly |
| US5827612A (en) * | 1992-06-17 | 1998-10-27 | Ppg Industries, Inc. | Aqueous coating compositions for glass fibers, fiber strands coated with such compositions and optical fiber cable assemblies including such fiber strands |
| US6379794B1 (en) | 1992-06-17 | 2002-04-30 | Ppg Industries Ohio, Inc. | Acrylic impregnant for fibers |
| US5674933A (en) * | 1993-04-05 | 1997-10-07 | The Goodyear Tire & Rubber Company | Low fogging rubbery polymer |
| US5461125A (en) * | 1993-04-30 | 1995-10-24 | Minnesota Mining And Manufacturing Company | Waterborne core-shell latex polymers |
| DE4338374A1 (en) * | 1993-11-10 | 1995-05-11 | Wacker Chemie Gmbh | Use of aqueous dispersions of biphasic emulsion graft copolymers as binders for stiffening materials in the textile and leather industry |
| FR2712293B1 (en) * | 1993-11-10 | 1996-01-19 | Cray Valley Sa | Structured particle latex for solvent-free paints. |
| DE4344149A1 (en) | 1993-12-23 | 1995-06-29 | Basf Ag | Aqueous resin dispersions free of formaldehyde |
| US5723182A (en) * | 1996-08-27 | 1998-03-03 | Rohm And Haas Company | Method for coating leather |
| DE19811314A1 (en) * | 1998-03-16 | 1999-09-23 | Basf Ag | Aqueous, pigment containing composition useful for production of dispersion dyes |
| US6869996B1 (en) * | 1999-06-08 | 2005-03-22 | The Sherwin-Williams Company | Waterborne coating having improved chemical resistance |
| ATE355526T1 (en) * | 2000-10-31 | 2006-03-15 | Micronas Gmbh | PATTERNED POLYMER SURFACES SUITABLE FOR BIOCONJUGATIONS AND PROCESSES FOR THEIR PRODUCTION |
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| US9394464B2 (en) * | 2010-04-28 | 2016-07-19 | Gcp Applied Technologies Inc. | Waterproofing membrane |
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| CN102382239B (en) * | 2011-08-18 | 2013-12-25 | 山东圣光化工集团有限公司 | Hollow polymer emulsion and preparation method thereof |
| TWI713498B (en) | 2015-03-24 | 2020-12-21 | 美商羅門哈斯公司 | Core-shell aqueous latex |
| CN111454402B (en) * | 2020-06-02 | 2023-03-14 | 上海金狮化工有限公司 | Acrylate emulsion leather finishing agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3461188A (en) * | 1965-08-23 | 1969-08-12 | Monsanto Co | Polyblends prepared by polymerizing vinyl monomers in the presence of cross-linked rubber |
| US3502745A (en) * | 1965-10-07 | 1970-03-24 | Rohm & Haas | Acrylic elastomeric materials and process therefor |
| US3457209A (en) * | 1966-12-30 | 1969-07-22 | Goodrich Co B F | Alkyl acrylate latices |
| US3745196A (en) * | 1969-05-26 | 1973-07-10 | Rohm & Haas | Low-temperature and oil-resistant core-shell acrylic polymers |
| US3607341A (en) * | 1969-11-28 | 1971-09-21 | Gaf Corp | Process for producing a coated substrate |
| FR2090483A5 (en) * | 1970-04-13 | 1972-01-14 | Roehm & Haas Gmbh | |
| US3812205A (en) * | 1970-04-13 | 1974-05-21 | Rohm & Haas | Process for preparing graftlinked heteropolymer film |
| US3714078A (en) * | 1970-09-16 | 1973-01-30 | Gen Latex And Chem Corp | Foamable acrylic latex composition and method of preparation |
| US3992486A (en) * | 1971-02-09 | 1976-11-16 | Rohm And Haas Company | Process for altering appearance of polymer by incorporating therein crosslinked particulate polymers prepared by endopolymerization |
| US3895082A (en) * | 1971-05-27 | 1975-07-15 | Du Pont | Polymer composition |
| US3793402A (en) * | 1971-11-05 | 1974-02-19 | F Owens | Low haze impact resistant compositions containing a multi-stage,sequentially produced polymer |
| US3843753A (en) * | 1972-02-09 | 1974-10-22 | Rohm & Haas | Composite interpolymer and low haze impact resistant thermoplastic compositions thereof |
| USRE28682E (en) | 1972-05-10 | 1976-01-13 | Rohm & Haas Company | Decorative laminate |
| US3787522A (en) * | 1972-11-01 | 1974-01-22 | Ford Motor Co | Acrylate polymer particles comprising a core,an outer shell,and an intermediate layer |
| US3919451A (en) * | 1973-07-09 | 1975-11-11 | Rohm & Haas | Method for finishing leather and leather substitutes |
| DE2343294C3 (en) * | 1973-08-28 | 1980-03-20 | Bayer Ag, 5090 Leverkusen | Composite materials and processes for their manufacture |
| JPS5094064A (en) * | 1973-11-22 | 1975-07-26 | ||
| JPS5226535B2 (en) * | 1973-12-05 | 1977-07-14 | ||
| US3985703A (en) * | 1975-06-24 | 1976-10-12 | Rohm And Haas Company | Process for manufacture of acrylic core/shell polymers |
-
1976
- 1976-06-17 US US05/697,171 patent/US4107120A/en not_active Expired - Lifetime
-
1977
- 1977-06-03 CA CA279,849A patent/CA1112387A/en not_active Expired
- 1977-06-07 PH PH19854A patent/PH12788A/en unknown
- 1977-06-08 ZA ZA00773463A patent/ZA773463B/en unknown
- 1977-06-09 NZ NZ184347A patent/NZ184347A/en unknown
- 1977-06-10 GB GB24352/77A patent/GB1583671A/en not_active Expired
- 1977-06-13 BR BR7703801A patent/BR7703801A/en unknown
- 1977-06-14 DE DE19772726806 patent/DE2726806A1/en not_active Withdrawn
- 1977-06-16 BE BE178487A patent/BE855743A/en unknown
- 1977-06-16 AU AU26170/77A patent/AU511706B2/en not_active Expired
- 1977-06-16 NL NL7706667A patent/NL7706667A/en not_active Application Discontinuation
- 1977-06-16 JP JP7158477A patent/JPS532590A/en active Granted
- 1977-06-16 IT IT68400/77A patent/IT1083434B/en active
- 1977-06-16 SE SE7707021A patent/SE7707021L/en not_active Application Discontinuation
- 1977-06-16 FR FR7718571A patent/FR2355038A1/en active Granted
- 1977-06-17 ES ES459886A patent/ES459886A1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB1583671A (en) | 1981-01-28 |
| AU511706B2 (en) | 1980-09-04 |
| SE7707021L (en) | 1977-12-18 |
| FR2355038B1 (en) | 1980-04-25 |
| PH12788A (en) | 1979-08-17 |
| AU2617077A (en) | 1978-12-21 |
| ZA773463B (en) | 1978-07-26 |
| BR7703801A (en) | 1978-05-09 |
| BE855743A (en) | 1977-12-16 |
| JPS5546645B2 (en) | 1980-11-25 |
| ES459886A1 (en) | 1978-04-16 |
| JPS532590A (en) | 1978-01-11 |
| DE2726806A1 (en) | 1977-12-29 |
| US4107120A (en) | 1978-08-15 |
| FR2355038A1 (en) | 1978-01-13 |
| NL7706667A (en) | 1977-12-20 |
| NZ184347A (en) | 1979-10-25 |
| IT1083434B (en) | 1985-05-21 |
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| MKEX | Expiry |