Silane compound and composition comprising same

Abstract

The present invention relates to a polymer latex composition, to a process for preparing such a polymer latex composition, to the use of said polymer latex composition, to a compound latex composition comprising said polymer latex composition, to a process for preparing a dip-molded article, to a process for preparing an elastomeric film and article, a method of repairing or reforming an elastomeric film or article, and an article prepared by using the polymer latex composition.

Description

[0001] The present invention relates to a polymer latex composition, a method for preparing such a polymer latex composition, the use of the polymer latex composition, a compounded latex composition comprising the polymer latex composition, a method for preparing an impregnated molded article, a method for preparing an elastomeric film and article, a method for repairing or rehabilitating an elastomeric film or article, and an article prepared by using the polymer latex composition. Background Art

[0002] In the field of preparing articles based on polymer latexes, it is generally desirable to achieve a high tensile strength and at the same time a high elongation at break of the film forming the article, in order to provide the article with high mechanical strength and a desired softness. This is particularly important for gloves such as surgical gloves. In addition, it has recently been found that an increasing number of people show allergic reactions to latex-based products. For example, natural rubber latex, which was previously commonly used to manufacture latex products such as dipped molded products, contains up to 5% non-rubber components such as proteins, lipids, and trace elements. Users of natural rubber latex products have developed type I hypersensitivity reactions, which are caused by residual extractable latex proteins present in natural rubber products.

[0003] Natural as well as synthetic polymer latexes are generally crosslinked using a sulfur vulcanization system including sulfur and sulfur-containing accelerators. The use of these sulfur vulcanization systems in rubber glove manufacturing can cause delayed type IV hypersensitivity reactions such as allergic contact dermatitis.

[0004] Accordingly, it is desirable to avoid sulfur vulcanization systems, and in particular to provide a polymer latex that can be used to manufacture impregnated molded articles, which does not require a standard sulfur vulcanization system including sulfur-containing accelerators previously used therein to obtain the desired mechanical properties of the final product.

[0005] Other commonly known crosslinking agents can provide the desired mechanical properties, but generally result in a shorter shelf life of the composition, which can be remedied by using large amounts of these crosslinking agents. However, this results in higher costs and may even lead to a reduction in the tensile and durability properties of the final product derived from the polymer latex composition.

[0006] Accordingly, an object of the present invention is to provide a hydrolytically stable polymer latex composition having an increased shelf life while maintaining favorable mechanical properties of the final product, such as good force at break (FAB), tensile strength (TS), and elongation at break (EB), and providing high durability properties even after 6 months. Summary of the Invention

[0007] The following clauses summarize some aspects of the present invention.

[0008] According to a first aspect, the present invention relates to a polymer latex composition for preparing an elastomeric film, comprising:

[0009] (a) latex polymer particles obtained by free radical emulsion polymerization of a composition comprising ethylenically unsaturated monomers, said latex polymer comprising a functional group (A); and

[0010] (b) a silane compound selected from compounds of formula I, II, oligomers thereof or any combination of the foregoing:

[0011]

[0012] wherein

[0013] X is a functional group capable of forming a bond with the functional group (A) of the latex polymer (a);

[0014] R 1 is a linking group between the functional group X and the silicon atom or R 1 is a bond;

[0015] R 2 is independently a hydrolysable or non-hydrolysable group;

[0016] wherein at least one of R 2 is a hydrolysable group, and at least one of R 2 is a non-hydrolysable group;

[0017]

[0018] wherein Y is O, S, NH or NR 3 ; wherein R 3 is a straight-chain or branched-chain, substituted or unsubstituted alkyl or alkenyl;

[0019] R 1 is a linking group between the functional group Y and the silicon atom;

[0020] R 2 is independently a hydrolysable or non-hydrolysable group;

[0021] wherein at least one of R 2 is a non-hydrolysable group.

[0022] The Si-Y bond can be hydrolysable to form Si-OH groups and Y-H groups, wherein the Y-H groups are functional groups capable of forming a bond with the functional group (A) of the latex polymer (a).

[0023] The polymer latex composition may contain 0.10 - 4.00 parts by weight; preferably 0.20 to 2.00 parts by weight, more preferably 0.20 to 1.80 parts by weight, even more preferably 0.20 to 1.50 parts by weight; most preferably 0.40 - 1.50 parts by weight of the silane compound (b); based on 100 parts by weight of the latex polymer (a).

[0024] Preferably, each non-hydrolyzable R 2 is independently a straight-chain C1-C 20 alkyl group, a straight-chain C2-C 20 alkenyl group, a branched or cyclic C3-C 20 alkyl group or alkenyl group or aryl group, more preferably a straight-chain C1-C 20 alkyl group.

[0025] Preferably, each hydrolyzable R 2 is independently -H, -OR', -OC(O)CH3, -OCH2OCH3, -SR', -NHR', -NR'2, halogen, where R' is a straight-chain C1-C6 alkyl group, a branched C3-C6 alkyl group or alkenyl group, or an aryl group; more preferably each hydrolyzable R 2 is independently -OR' or -halogen, where R' is a straight-chain C1-C6 alkyl group, a branched C3-C6 alkyl group or alkenyl group, or an aryl group.

[0026] The linking group R between the functional group X and the silicon atom 1 may be a straight-chain C1-C 20 alkanediyl group, a branched C2-C 20 alkanediyl group, a cyclic C3-C 20 alkanediyl group or alkenediyl group, or an arylenediyl group; preferably a straight-chain C1-C 20 alkanediyl group, where optionally one or more methylene groups in each of the above alkanediyl groups, alkenediyl groups and arylenediyl groups are replaced by heteroatoms, provided that no heteroatom is directly bonded to another heteroatom and no heteroatom is directly bonded to Si, where the heteroatom is preferably oxygen, sulfur or nitrogen, more preferably oxygen.

[0027] The linking group R between the functional group Y and the silicon atom 1 may be a straight-chain or branched C3-C 20 alkanediyl group; preferably a straight-chain or branched C3-C 10 alkanediyl group, where optionally one or more methylene groups in each of the above alkanediyl groups are replaced by heteroatoms, provided that no heteroatom is directly bonded to another heteroatom and no heteroatom is directly bonded to Si, where the heteroatom is preferably oxygen, sulfur or nitrogen, more preferably oxygen.

[0028] The functional group X may be selected from a carbon-carbon double bond, (meth)acryloyloxy, a halogen functional group, an epoxy group, a glycidyl group, a thiol, a hydroxyl group, a hydroxylamine, a primary amino group, a secondary amino group, isocyanato, an oxazoline group, an aziridinyl group, an imino group, a carbodiimide group, a diol, an ester, an acetoxy group, an acetoacetoxy group, a carboxylic acid, a dioxolanone, a hydrazide group, an aldehyde, a boric acid, an alkoxysilyl group, and a ketone; preferably selected from a carbon-carbon double bond, (meth)acryloyloxy, a halogen functional group, a glycidyl group, an epoxy group, a thiol, a hydroxyl group, a primary amino group, a secondary amino group, and isocyanato; more preferably selected from a glycidyl group, an epoxy group, a thiol, a hydroxyl group, a primary amino group, and a secondary amino group.

[0029] The silane compound (b) may be selected from (3-glycidoxypropyl)methyldiethoxysilane, (3-glycidoxypropyl)dimethyl ethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane, 3-aminopropyldimethylmethoxysilane, 3-aminopropyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldiisopropylethoxysilane, 4-amino-3,3-dimethylbutylmethyldimethoxysilane, (1-aminopropan-2-yl)ethoxydimethylsilane, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminoisobutyldimethylmethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminoisobutylmethyldimethoxysilane, (N-cyclohexylaminomethyl)methyldiethoxysilane, N-methylaminopropylmethyldimethoxysilane, (phenylaminomethyl)methyldimethoxysilane, 3-(N,N-dimethylaminopropyl)aminopropylmethyldimethoxysilane, (3-acryloxypropyl)methyldiethoxysilane, (3-acryloxypropyl)methyldimethoxysilane, (3-acryloxypropyl)dimethylmethoxysilane, (methacryloxymethyl)methyldiethoxysilane, (methacryloxymethyl)methyldimethoxysilane, (methacryloxymethyl)dimethylethoxysilane, (methacryloxypropyl)dimethylmethoxysilane, allylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldimethoxysilane, vinyldimethylethoxysilane, (5-bicyclo[2.2.1]hept-2-enyl)methyldiethoxysilane, (5-bicyclo[2.2.1]hept-2-enyl)dimethylethoxysilane, (5-bicyclo[2.2.1) (hept-2-enyl)methyldichlorosilane, (mercaptomethyl)methyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, chloromethyldimethylethoxysilane, ((chloromethyl)phenyl ethyl)methyldimethoxysilane, 3-chloropropyldimethylethoxysilane, 3-chloropropyldimethylmethoxysilane, 3-chloroisobutyldimethylmethoxysilane, chloromethyldimethylethoxysilane, 3-chloropropylmethyldiisopropoxysilane, (3-iodopropyl)methyldiisopropoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 1,1-dimethyl-1-sila-2-oxacyclohexane, 2,2,4-trimethyl-1-oxa-4-aza-2-silacyclohexane, 1-decyl-1-methyl-1-sila-2-oxacyclohexane, 2,2,4-trimethyl-1-thia-2-silacyclopentane, N-(2-aminoethyl)-2,2,4-trimethyl-1-aza-2-silacyclopentane, N-(3-aminopropyldimethylsilyl)-aza-2,2-dimethyl-2-silacyclopentane, (N,N-dimethylaminopropyl)-aza-2-methyl-2-methoxysilacyclopentane, and combinations thereof.

[0030] The functional group (A) of the latex polymer (a) can be selected from carbon-carbon double bonds, carboxylic acids, hydroxyl groups, epoxy groups, glycidyl groups, acetoacetoxy groups, primary or secondary amino groups, acetoxy groups, isocyanato groups, alkoxysilyl groups, alkoxy groups, dioxolanones, halogen functional groups, thiols, hydroxylamines, oxazolinyl groups, aziridinyl groups, imino groups, carbodiimide groups, diols, esters, hydrazide groups, aldehydes, ketones, and combinations thereof; preferably selected from carbon-carbon double bonds, carboxylic acids, halogen functional groups, epoxy groups, glycidyl groups, thiols, hydroxyl groups, primary or secondary amino groups, isocyanato groups, and combinations thereof; more preferably selected from carboxylic acids.

[0031] The bond formed between the functional group (A) of the latex polymer (a) and the functional group X of the silane compound (b) can be selected from disulfides, tetrasulfides, carbonates, ureas, thioureas, esters, β-hydroxy esters, thioesters, β-hydroxyamines, β-hydroxy thioethers, amides, urethanes, enamines, imines, hemiacetals, acetals, hemiketals, ketals, borate esters, siloxanes, oximes, acylhydrazones, aldols, thiuram disulfides, and trithiocarbonates.

[0032] The bond formed between the functional group (A) of the latex polymer (a) and the functional group Y-H of the silane compound (b) can be selected from disulfides, tetrasulfides, carbonates, ureas, thioureas, esters, β-hydroxy esters, thioesters, amides, urethanes, enamines, imines, hemiacetals, acetals, hemiketals, ketals, and borate esters.

[0033] The polymer latex composition may further comprise a silane compound (c) different from the silane compound (b), wherein the silane compound (c) is selected from compounds of Formula III, IV, oligomers thereof, or any combination of the foregoing substances:

[0034]

[0035] wherein

[0036] Z is a functional group capable of forming a bond with the functional group (A) of the latex polymer (a);

[0037] R a is a linking group between the functional group Z and the silicon atom or R a is a bond;

[0038] R b is a hydrolysable group;

[0039]

[0040] wherein

[0041] Z' is O, S, NH or NR 3 ; where R 3 is a straight-chain or branched-chain, substituted or unsubstituted alkyl or alkenyl;

[0042] R a is a linking group between the functional group Z' and the silicon atom;

[0043] R b is a hydrolysable group.

[0044] The Si-Z' bond may be hydrolysable to form Si-OH groups and Z'-H groups, where the Z'-H groups are functional groups capable of forming a bond with the functional group (A) of the latex polymer (a).

[0045] Preferably, each hydrolysable R b is independently -H, -OR', -OC(O)Me, -OCH2OCH3, -SR', -NHR', -NR'2, -halogen, where R' is a straight-chain C1-C6 alkyl, branched-chain C3-C6 alkyl or alkenyl, or aryl; more preferably each hydrolysable R b is independently -OR' or -halogen, where R' is a straight-chain C1-C6 alkyl, branched-chain C3-C6 alkyl or alkenyl, or aryl.

[0046] The linking group R a between the functional group Z and the silicon atom may be a straight-chain C1-C 20 alkanediyl, branched-chain C2-C 20 alkanediyl, cyclic C3-C 20an alkylene or alkenylene, or arylene diyl group; preferably a straight-chain C1-C 20 alkylene group; wherein optionally one or more methylene groups in each of the above alkylene, alkenylene and arylene diyl groups are replaced by heteroatoms, provided that no heteroatoms are directly bonded to another heteroatom and no heteroatoms are directly bonded to Si, wherein the heteroatoms are preferably oxygen, sulfur or nitrogen, more preferably oxygen.

[0047] Preferably, the linking group R between the functional group Z' and the silicon atom a is a straight-chain or branched C3-C 20 alkylene group; more preferably a straight-chain or branched C3-C 10 alkylene group; wherein optionally one or more methylene groups in each of the above alkylene, alkenylene and arylene diyl groups are replaced by heteroatoms, provided that no heteroatoms are directly bonded to another heteroatom and no heteroatoms are directly bonded to Si, wherein the heteroatoms are preferably oxygen, sulfur or nitrogen, more preferably oxygen.

[0048] The functional group Z may be selected from a carbon-carbon double bond, (meth)acryloyloxy, a halogen functional group, an epoxy group, a glycidyl group, a thiol, a hydroxyl group, a hydroxylamine, a primary amino group, a secondary amino group, isocyanato, oxazolinyl, aziridinyl, imino, carbodiimide, diol, ester, acetyloxy, acetoacetyloxy, carboxylic acid, dioxolanone, hydrazide, aldehyde, boric acid, alkoxysilyl and ketone; preferably selected from a carbon-carbon double bond, (meth)acryloyloxy, a halogen functional group, an epoxy group, a glycidyl group, a thiol, a hydroxyl group, a primary amino group, a secondary amino group and isocyanato; more preferably selected from a glycidyl group, an epoxy group, a thiol, a hydroxyl group, a primary amino group and a secondary amino group.

[0049] When the silane compound (c) is present, the mass ratio of the silane compound (c) to the silane compound (b) may be 1:40 - 40:1, preferably 1:20 - 2:1.

[0050] The polymer latex composition may contain a total of 0.10 to 5.00 parts by weight; preferably 0.20 to 5.00 parts by weight; more preferably 0.20 to 4.50 parts by weight; even more preferably 0.20 to 4.00 parts by weight of the silane compound (b) and the silane compound (c); based on 100 parts by weight of the latex polymer (a).

[0051] The monomer composition for obtaining the latex polymer (a) particles may contain:

[0052] (i) 15 to 99% by weight of a conjugated diene;

[0053] (ii) 1 to 80% by weight of a monomer selected from ethylenically unsaturated nitrile compounds;

[0054] (iii) 0 to 10% by weight of an ethylenically unsaturated compound containing a functional group (A) different from (i) and (ii);

[0055] (iv) 0 to 80% by weight of a vinyl aromatic monomer; and

[0056] (v) 0 to 65% by weight of an alkyl ester of an ethylenically unsaturated acid;

[0057] The weight percentages are based on the total weight of the ethylenically unsaturated monomers in the monomer composition.

[0058] It is contemplated that:

[0059] (i) The conjugated diene may be selected from 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, 3,7,11-trimethyl-1,3,6,10-dodecatetraene, 7,11-dimethyl-3-methylene-1,6,10-dodecatriene, 7-methyl-3-methylene-1,6-octadiene, and combinations thereof;

[0060] (ii) The ethylenically unsaturated nitrile compound may be selected from (meth)acrylonitrile, α-cyanoethyl acrylonitrile, fumaronitrile, α-chloronitrile, and combinations thereof;

[0061] (iii) The ethylenically unsaturated compound containing a functional group (A) different from (i) and (ii) may be selected from

[0062] (iii 1) An ethylenically unsaturated compound having at least two different ethylenically unsaturated groups, preferably selected from allyl (meth)acrylate, vinyl (meth)acrylate, and combinations thereof;

[0063] (iii2) An ethylenically unsaturated acid and its salts, preferably selected from (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, ethylenically unsaturated sulfonic acid, ethylenically unsaturated phosphoric acid-containing acid, polycarboxylic anhydride, polycarboxylic partial ester monomer, carboxyalkyl ester of an ethylenically unsaturated acid, and combinations thereof;

[0064] (iii 3) A hydroxy-functional ethylenically unsaturated compound, preferably selected from allyl alcohol, vinyl alcohol, N-methylolacrylamide, 1-penten-3-ol, hydroxyalkyl ester of an ethylenically unsaturated acid, and combinations thereof;

[0065] (iii4) Epoxy-functionalized ethylenically unsaturated compounds, preferably selected from vinyl cyclohexene oxide, limonene oxide, 2-ethyl (3',4'-epoxyheptyl) (meth)acrylate, (6',7'-epoxyheptyl) (meth)acrylate, allyl 3,4-epoxyheptyl ether, 6,7-epoxyheptyl allyl ether, vinyl 3,4-epoxyheptyl ether, 3,4-epoxyheptyl vinyl ether, 6,7-epoxyheptyl vinyl ether, 3-vinyl cyclohexene oxide, 2-(3,4-epoxycyclohexyl)methyl (meth)acrylate, 3,4-epoxy-1-butene, 1,2-epoxy-5-hexene, 4-vinyl-1-cyclohexene 1,2-epoxide, 2-methyl-2-vinyl oxirane, 3,4-epoxy-1-cyclohexene, and combinations thereof,

[0066] (iii 5) Glycidyl-functionalized ethylenically unsaturated compounds, preferably selected from glycidyl (meth)acrylate, allyl glycidyl ether, vinyl glycidyl ether, 2-ethyl glycidyl (meth)acrylate, 2-(n-propyl) glycidyl (meth)acrylate, 2-(n-butyl) glycidyl (meth)acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl glycidyl methacrylate, glycidyl propargyl ether, and combinations thereof;

[0067] (iii 6) Acetoacetoxy-functionalized ethylenically unsaturated compounds, preferably selected from 2-ethyl acetoacetoxy (meth)acrylate, 3-ethyl acetoacetoxy (meth)acrylate, allyl acetoacetate, 4-ethyl acetoacetoxy (meth)acrylate, 2,3-bis(acetoacetoxy)propyl (meth)acrylate, acetoacetoxy (methyl)ethyl (meth)acrylate, acetoacetamidoethyl (meth)acrylate, 3-(methacryloyloxy)-2,2-dimethylpropyl 3-oxobutyrate, 3-(methacryloyloxy)-2,2,4,4-tetramethylcyclobutyl 3-oxobutyrate, 3-(methacryloyloxy)-2,2,4-trimethylpentyl 3-oxobutyrate, 1-(methacryloyloxy)-2,2,4-trimethylpent-3-yl 3-oxobutyrate, (4-(methacryloxymethyl)cyclohexyl)methyl 3-oxobutyrate, and combinations thereof;

[0068] (iii 7) An ethylenically unsaturated compound having a primary or secondary amino group, preferably selected from (meth)acrylamide, 2-aminoethyl (meth)acrylate hydrochloride, 2-aminoethyl (meth)acrylamide hydrochloride, N-ethyl (meth)acrylamide, N-(3-aminopropyl)(meth)acrylamide hydrochloride, N-hydroxyethyl (meth)acrylamide, N-3-(dimethylamino)propyl (meth)acrylamide, [3-(methacryloylamino)propyl]trimethylammonium, N-[tris(hydroxymethyl)methyl](meth)acrylamide, N-phenylacrylamide, alkylacrylamide, methacrylamide poly(ethylene glycol)amine hydrochloride, and combinations thereof;

[0069] (iii 8) An acetoxy-functional ethylenically unsaturated compound, preferably selected from 1-acetoxy-1,3-butadiene, diacetone acrylamide, and combinations thereof;

[0070] (iii 9) An isocyanato-functional ethylenically unsaturated compound, preferably selected from 2-isocyanatoethyl (meth)acrylate, allyl isocyanate, vinyl isocyanate, 3-isopropenyl-α,α-dimethylbenzyl isocyanate, and combinations thereof;

[0071] (iii 10) An alkoxysilyl-functional ethylenically unsaturated compound, preferably selected from allyltrimethoxysilane, allyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-butenyltriethoxysilane, 3-(trimethoxysilyl)propyl (meth)acrylate, 5-hexenyltriethoxysilane, styrylethyltrimethoxysilane, trimethoxy(7-octen-1-yl)silane, 11-allyloxydodecyltrimethoxysilane, allylphenylpropyltriethoxysilane, [(5-bicyclo[2.2.1]hept-2-enyl)ethyl]trimethoxysilane, (5-bicyclo[2.2.1]hept-2-enyl)triethoxysilane, n-allyl-aza-2,2-dimethoxysilacyclopentane, norbornenyltriethoxysilane, [2-(3-cyclohexenyl)ethyl]triethoxysilane, and combinations thereof;

[0072] (iii 11) An alkoxy-functional ethylenically unsaturated compound, preferably selected from 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, methyl-3-methoxy(meth)acrylate, and combinations thereof;

[0073] (iii 12) A dioxolanone-functional ethylenically unsaturated compound, preferably selected from glycerol carbonate (meth)acrylate, 4-vinyl-1,3-dioxolan-2-one, and combinations thereof;

[0074] (iii 13) Halogen-functionalized ethylenically unsaturated compounds, preferably selected from vinyl chloride, allyl chloride, 2-chloro-1,3-butadiene, 2-chloroethyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, methyl 2-(chloromethyl)acrylate, 2,3-dichloropropyl (meth)acrylate, 2,3-dibromopropyl (meth)acrylate, and combinations thereof;

[0075] (iii 14) Thiol-functionalized ethylenically unsaturated compounds, preferably selected from allyl mercaptan, N-acryloyl-cysteamine, and combinations thereof;

[0076] (iii 15) Hydroxyamine-functionalized ethylenically unsaturated compounds, preferably selected from acrylohydroxamic acid;

[0077] (iii 16) Oxazolinyl-functionalized ethylenically unsaturated compounds, preferably selected from oxazoline-substituted acrylates;

[0078] (iii 17) Aziridinyl-functionalized ethylenically unsaturated compounds, preferably selected from 2-(aziridin-1-yl)ethyl acrylate;

[0079] (iii 18) Imino-functionalized ethylenically unsaturated compounds, preferably selected from 2-[(2-methylprop-2-enoyl)oxy]ethyl (3E)-3-(alkylimino)butanoate;

[0080] (iii 19) Carbodiimido-functionalized ethylenically unsaturated compounds, preferably selected from N-α,α'-dimethylisopropenylbenzyl-N'-cyclohexylcarbodiimide, N-α,α'-dimethylisopropenylbenzyl-N'-butylcarbodiimide, and combinations thereof;

[0081] (iii20) Diol-functionalized ethylenically unsaturated compounds, preferably selected from ethylene glycol methyl ether (meth)acrylate, ethylene glycol phenyl ether (meth)acrylate, di(ethylene glycol) methyl ether (meth)acrylate, tri(ethylene glycol) methyl ether (meth)acrylate, poly(ethylene glycol) methyl ether (meth)acrylate, poly(ethylene glycol) phenyl ether acrylate, poly(ethylene glycol) (meth)acrylate, poly(propylene glycol) (meth)acrylate, poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (meth)acrylate, polyglycol partial ester monomers, and combinations thereof;

[0082] (iii21) Hydrazide-functionalized ethylenically unsaturated compounds, preferably selected from 2-acryloylhydrazide or (meth)acryloylhydrazide, and combinations thereof;

[0083] (iii22) Aldehyde-functionalized ethylenically unsaturated compounds, preferably selected from (meth)acrolein, 2-ethylacrolein, 3-methyl-2-butenal, tiglic aldehyde, crotonaldehyde, 3-methylcrotonaldehyde, 2-pentenal, 2-methyl-2-pentenal, 4-pentenal, 2,2-dimethyl-4-pentenal, 2,4-heptadienal, and combinations thereof;

[0084] (iii23) Ketone-functionalized ethylenically unsaturated compounds, preferably selected from 1-penten-3-one, 3-buten-2-one, 4-methoxy-3-buten-2-one, 3-penten-2-one, 2-cyclopenten-1-one, 2-cyclohexen-1-one, and combinations thereof;

[0085] And combinations thereof;

[0086] (iv) Vinyl aromatic monomers may be selected from styrene, α-methylstyrene, and combinations thereof;

[0087] (v) Alkyl esters of ethylenically unsaturated acids may be selected from methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and combinations thereof;

[0088] And combinations thereof.

[0089] It is contemplated that:

[0090] - The functional group (A) of the latex polymer (a) may be selected from groups having a carbon-carbon double bond, and the functional group of the silane compound (b) may be selected from groups having a carbon-carbon double bond, (meth)acryloxy groups, and thiols;

[0091] - The functional group (A) of the latex polymer (a) may be selected from carboxylic acid functional groups, and the functional group of the silane compound (b) may be selected from epoxy groups, glycidyl groups, thiols, hydroxyl groups, primary or secondary amino groups, isocyanato groups, oxazolinyl groups, aziridinyl groups, imino groups, carbodiimido groups, diol groups, ester groups, and acetoxy groups;

[0092] - The functional group (A) of the latex polymer (a) may be selected from hydroxyl groups, and the functional group of the silane compound (b) may be selected from carboxylic acid functional groups, isocyanato groups, primary or secondary amino groups, aldehydes, boric acids, and ester groups;

[0093] - The functional group (A) of the latex polymer (a) may be selected from epoxy groups, and the functional group of the silane compound (b) may be selected from carboxylic acid functional groups, hydroxyl groups, and ester groups;

[0094] - The functional group (A) of the latex polymer (a) may be selected from glycidyl groups, and the functional group of the silane compound (b) may be selected from carboxylic acid functional groups, hydroxyl groups, and ester groups;

[0095] - The functional group (A) of the latex polymer (a) can be selected from acetoacetoxy, and the functional group of the silane compound (b) can be selected from groups having a carbon-carbon double bond, (meth)acryloxy, isocyanato, aldehyde, hydrazine, acylhydrazide, and primary or secondary amino groups;

[0096] - The functional group (A) of the latex polymer (a) can be selected from primary or secondary amino groups, and the functional group of the silane compound (b) can be selected from carboxylic acid functional groups, epoxy groups, glycidyl groups, ester groups, and dioxolanone groups;

[0097] - The functional group (A) of the latex polymer (a) can be selected from acetoxy, and the functional group of the silane compound (b) can be selected from acylhydrazide groups and primary or secondary amino groups;

[0098] - The functional group (A) of the latex polymer (a) can be selected from isocyanato, and the functional group of the silane compound (b) can be selected from carboxylic acid functional groups, hydroxyl groups, primary or secondary amino groups, and thiols;

[0099] - The functional group (A) of the latex polymer (a) can be selected from alkoxysilyl, and the functional group of the silane compound (b) can be selected from hydroxyl groups and alkoxysilyl;

[0100] - The functional group (A) of the latex polymer (a) can be selected from alkoxy, and the functional group of the silane compound (b) can be selected from ester groups;

[0101] - The functional group (A) of the latex polymer (a) can be selected from ester groups, and the functional group of the silane compound (b) can be selected from hydroxyl groups, carboxylic acid groups, and ester groups;

[0102] - The functional group (A) of the latex polymer (a) can be selected from dioxolanone groups, and the functional group of the silane compound (b) can be selected from primary or secondary amino groups;

[0103] - The functional group (A) of the latex polymer (a) can be selected from halogen functional groups, and the functional group of the silane compound (b) can be selected from carboxylic acids;

[0104] - The functional group (A) of the latex polymer (a) can be selected from thiol functional groups, and the functional group of the silane compound (b) can be selected from carbon-carbon double bonds, (meth)acryloxy, carboxylic acid functional groups, or isocyanato;

[0105] - The functional group (A) of the latex polymer (a) can be selected from hydroxylamine, and the functional group of the silane compound (b) can be selected from aldehydes;

[0106] - The functional group (A) of the latex polymer (a) can be selected from oxazolinyl, and the functional group of the silane compound (b) can be selected from carboxylic acids;

[0107] - The functional group (A) of the latex polymer (a) can be selected from aziridinyl, and the functional group of the silane compound (b) can be selected from carboxylic acids or hydroxyl groups;

[0108] - The functional group (A) of the latex polymer (a) may be selected from imino groups, and the functional group of the silane compound (b) may be selected from carboxylic acids;

[0109] - The functional group (A) of the latex polymer (a) may be selected from carbodiimide groups, and the functional group of the silane compound (b) may be selected from carboxylic acids;

[0110] - The functional group (A) of the latex polymer (a) may be selected from diol groups, and the functional group of the silane compound (b) may be selected from carboxylic acid functional groups;

[0111] - The functional group (A) of the latex polymer (a) may be selected from hydrazide groups, and the functional group of the silane compound (b) may be selected from aldehydes;

[0112] - The functional group (A) of the latex polymer (a) may be selected from aldehydes, and the functional group of the silane compound (b) may be selected from hydroxyl groups, acetoacetoxy groups, hydroxylamine groups or hydrazide groups; or

[0113] - The functional group (A) of the latex polymer (a) may be selected from ketones, and the functional group of the silane compound (b) may be selected from hydroxyl groups.

[0114] Another aspect of the present invention relates to a method for preparing a polymer latex composition, the method comprising:

[0115] (i) polymerizing a monomer composition containing ethylenically unsaturated monomers used for the latex polymer (a) in an emulsion polymerization method, the ethylenically unsaturated monomers containing at least one monomer that generates a functional group (A) after polymerization, to obtain a latex containing latex polymer (a) particles, the latex polymer containing the functional group (A); and

[0116] (ii) adding a silane compound (b) selected from compounds of formula I, II, oligomers thereof or any combination of the foregoing:

[0117]

[0118] wherein

[0119] X is a functional group capable of forming a bond with the functional group (A) of the latex polymer (a);

[0120] R 1 is a linking group between the functional group X and the silicon atom or R 1 is a bond;

[0121] R 2 is independently a hydrolysable group or a non-hydrolysable group;

[0122] wherein at least one of R 2 is a hydrolysable group, and R 2At least one of them is a non-hydrolyzable group;

[0123]

[0124] wherein

[0125] Y is O, S, NH or NR 3 ; wherein R 3 is a linear or branched, substituted or unsubstituted alkyl or alkenyl;

[0126] R 1 is a linking group between the functional group Y and the silicon atom;

[0127] R 2 is independently a hydrolyzable group or a non-hydrolyzable group;

[0128] wherein at least one of R 2 is a non-hydrolyzable group; and

[0129] (iii) Optionally, a silane compound (c) different from the silane compound (b) is added, wherein the silane compound (c) is selected from compounds of formula III, IV, oligomers thereof or any combination of the foregoing:

[0130]

[0131] wherein

[0132] Z is a functional group capable of forming a bond with the functional group (A) of the latex polymer (a);

[0133] wherein R a is a linking group between the functional group Z and the silicon atom or R a is a bond;

[0134] R b is a hydrolyzable group;

[0135]

[0136] wherein

[0137] Z' is O, S, NH or NR 3 ; wherein R 3 is a linear or branched, substituted or unsubstituted alkyl or alkenyl;

[0138] R a is a linking group between the functional group Z' and the silicon atom;

[0139] R b is a hydrolyzable group.

[0140] Monomer composition for obtaining latex polymer (a) particles; functional group (A) of polymer latex (a); functional group (X) of silane compound (b); functional group (Z) of silane compound (c); hydrolyzable group R 2 and R b ; non-hydrolyzable group R 2 , linking group R 1 and R a ; the amount of silane compound (b) and / or (c); and the weight ratio of silane compounds (b) and (c) can be as described above.

[0141] According to another aspect, the present invention relates to the use of a polymer latex composition as described above or prepared by the method as described above for the production of dipped molded articles, elastomeric films, self-supporting elastomeric films or articles or for coating or impregnating a substrate, preferably a textile substrate.

[0142] Furthermore, according to another aspect, the present invention relates to a compounded polymer latex composition suitable for the production of dipped molded articles, which comprises a polymer latex composition as described above or prepared by the above method and optionally auxiliaries selected from sulfur vulcanizing agents, vulcanization accelerators, free radical initiators, pigments and combinations thereof, preferably free of sulfur vulcanizing agents and accelerators for sulfur vulcanization, and optionally comprises polyvalent cations and / or silica-based fillers.

[0143] Another aspect of the present invention relates to a method for producing a dipped molded article, which is carried out by the following steps:

[0144] (a) Providing the above compounded latex composition;

[0145] (b) Immersing a mold having the desired shape of the final article in a coagulant bath containing a metal salt solution;

[0146] (c) Removing the mold from the coagulant bath and optionally drying the mold;

[0147] (d) Immersing the mold treated in steps b) and c) in the compounded latex composition of step a);

[0148] (e) Coagulating the latex film on the surface of the mold;

[0149] (f) Removing the latex-coated mold from the compounded latex composition and optionally immersing the latex-coated mold in a water bath;

[0150] (g) Optionally drying the latex-coated mold;

[0151] (h) Heat-treating the latex-coated mold obtained in step e) or f) at 40 °C to 180 °C; and / or exposing the latex-coated mold obtained in step e) or f) to UV radiation;

[0152] (i) Remove the latex product from the mold.

[0153] Furthermore, according to another aspect, the present invention relates to a method for producing a continuous elastomeric film, comprising:

[0154] (A) Providing a polymer latex composition as defined or prepared as described above;

[0155] (B) Forming a continuous polymer film from the aqueous polymer latex composition;

[0156] (C) Optionally drying the continuous polymer film obtained in step (B);

[0157] (D) Heat-treating the continuous polymer film obtained in step (B) or (C) at a temperature of 40 °C to 180 °C, preferably for 20 minutes or less, to form a continuous elastomeric film; and / or UV treatment, and

[0158] (E) Optionally rolling up the continuous elastomeric film obtained in step (D) into a roll.

[0159] Another aspect of the present invention relates to a method for preparing an elastomeric article, which is carried out by the following steps:

[0160] - Aligning two separate continuous elastomeric films obtained as described above;

[0161] - Cutting the aligned continuous elastomeric films into a preselected shape to obtain two superimposed layers of elastomeric films of the preselected shape; and

[0162] - Joining the superimposed layers of elastomeric films together at at least a preselected portion of the periphery of the superimposed layers to form an elastomeric article.

[0163] The joining together can be carried out by using thermal measures, preferably selected from heat sealing and welding or by gluing.

[0164] The cutting can be carried out by a heatable template cutting device or a laser cutting machine, providing the preselected shape, and the cutting device can be heated in the portion in contact with the elastomeric film, where the films are joined together, so as to simultaneously cut the elastomeric film into the preselected shape and heat seal a preselected portion of the periphery of the superimposed elastomeric films.

[0165] The present invention also relates to a method for repairing or reforming an elastomeric film or an article comprising the elastomeric film, which method comprises:

[0166] a) Providing a film or article comprising one or more elastomeric films, the one or more elastomeric films having at least two surfaces to be reconnected,

[0167] (b) Rejoin the at least two surfaces of the one or more elastomeric membranes and heat or anneal the one or more elastomeric membranes while maintaining the rejoined surfaces of the damaged membranes in close contact at a temperature of 40 to 200 °C, preferably 60 to 175 °C, more preferably 95 to 135 °C, wherein

[0168] (c) The elastomeric membrane is made of a polymer latex composition as defined or prepared as described above.

[0169] Furthermore, another aspect of the present invention relates to an article prepared by using a polymer latex composition as defined or prepared as described above.

[0170] The article may be selected from surgical gloves, examination gloves, industrial gloves, household gloves, disposable gloves, textile-supported gloves, catheters, elastomeric sleeves, condoms, balloons, tubes, dental dams, aprons, and preformed gaskets. DETAILED DESCRIPTION OF THE INVENTION

[0172] The present invention relates to a polymer latex composition comprising:

[0173] (a) latex polymer particles obtained by free radical emulsion polymerization of a composition comprising ethylenically unsaturated monomers, the latex polymer comprising a functional group (A); and (b) a silane compound selected from compounds of formula I, II, oligomers thereof, or any combination of the foregoing:

[0174]

[0175] wherein X is a functional group capable of forming a bond with the functional group (A) of the latex polymer (a); R 1 is a linking group between the functional group X and the silicon atom or R 1 is a bond; R 2 is independently a hydrolysable group or a non-hydrolysable group; wherein at least one of R 2 is a hydrolysable group, and at least one of R 2 is a non-hydrolysable group;

[0176]

[0177] wherein Y is O, S, NH or NR 3 ; wherein R 3 is a straight-chain or branched-chain, substituted or unsubstituted alkyl or alkenyl; R 1 is a linking group between the functional group Y and the silicon atom; R 2 is independently a hydrolysable group or a non-hydrolysable group; wherein at least one of R 2 is a non-hydrolysable group. The polymer latex composition of the present invention is suitable for preparing elastomeric membranes.

[0178] The Si-Y bond of formula II can be hydrolyzable to form Si-OH groups and Y-H groups. When formed, the Y-H groups are functional groups capable of forming bonds with the functional group (A) of the latex polymer (a).

[0179] The latex polymer (a) containing the functional group (A)

[0180] The latex polymer (a) used in the present invention can be prepared by any suitable free radical emulsion polymerization method known in the art. Suitable process parameters are those that will be discussed below.

[0181] The unsaturated monomers used to prepare the latex polymer (a) and their relative amounts are not particularly critical, as long as the monomer mixture contains at least one ethylenically unsaturated monomer that provides the functional group (A) on the latex polymer (a). A monomer composition containing a conjugated diene and an ethylenically unsaturated nitrile compound is particularly suitable for, for example, dip molding applications.

[0182] Suitable functional groups (A) of the latex polymer (a) particles can be selected from carbon-carbon double bonds, carboxylic acids, hydroxyl groups, epoxy groups, glycidyl groups, acetoacetoxy groups, primary or secondary amino groups, acetoxy groups, isocyanato groups, alkoxysilyl groups, alkoxy groups, dioxolanones, halogen functional groups, thiols, hydroxylamines, oxazolinyl groups, aziridinyl groups, imino groups, carbodiimide groups, diols, esters, hydrazide groups, aldehydes, ketones and combinations thereof. Preferably, the functional group (A) of the latex polymer (a) particles is selected from carbon-carbon double bonds, carboxylic acids, halogen functional groups, epoxy groups, glycidyl groups, thiols, hydroxyl groups, primary or secondary amino groups, isocyanato groups and combinations thereof; more preferably selected from carboxylic acids.

[0183] According to the present invention, the monomer composition for obtaining the latex polymer (a) particles may comprise:

[0184] (i) 15 to 99% by weight of a conjugated diene;

[0185] (ii) 1 to 80% by weight of a monomer selected from ethylenically unsaturated nitrile compounds;

[0186] (iii) 0 to 10% by weight of an ethylenically unsaturated compound containing a functional group (A) different from (i) and (ii);

[0187] (iv) 0 to 80% by weight of a vinyl aromatic monomer; and

[0188] (v) 0 to 65% by weight of an alkyl ester of an ethylenically unsaturated acid; the weight percentages are based on the total weight of the ethylenically unsaturated monomers in the monomer composition.

[0189] The conjugated diene monomers suitable for preparing the latex polymer (a) of the present invention may include conjugated diene monomers selected from the following: 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene, 1,3-octadiene, 2-methyl-1,3-pentadiene, 2,3-dimethyl-1,3-pentadiene, 3,4-dimethyl-1,3-hexadiene, 2,3-diethyl-1,3-butadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, 3,7-dimethyl-1,3,6-octatriene, 2-methyl-6-methylene-1,7-octadiene, 7-methyl-3-methylene-1,6-octadiene, 1,3,7-octatriene, 2-ethyl-1,3-butadiene, 2-pentyl-1,3-butadiene, 3,7-dimethyl-1,3,7-octatriene, 3,7-dimethyl-1,3,6-octatriene, 3,7,11-trimethyl-1,3,6,10-dodecatetraene, 7,11-dimethyl-3-methylene-1,6,10-dodecatriene, 2,6-dimethyl-2,4,6-octatriene, 2-phenyl-1,3-butadiene, 2-methyl-3-isopropyl-1,3-butadiene, 1,3-cyclohexadiene, and combinations thereof, preferably 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, 3,7,11-trimethyl-1,3,6,10-dodecatetraene, 7,11-dimethyl-3-methylene-1,6,10-dodecatriene, 7-methyl-3-methylene-1,6-octadiene, and combinations thereof. 1,3-Butadiene, isoprene, and combinations thereof are more preferred conjugated dienes. 1,3-Butadiene is the most preferred conjugated diene.

[0190] Generally, the amount of the conjugated diene monomer is 15 to 99% by weight, preferably 20 to 95% by weight, more preferably 30 to 75% by weight, and most preferably 40 to 70% by weight, based on the total weight of the ethylenically unsaturated monomers in the monomer composition. Thus, based on the total weight of the ethylenically unsaturated monomers in the monomer composition, the conjugated diene can be present in an amount of at least 15% by weight, at least 20% by weight, at least 22% by weight, at least 24% by weight, at least 26% by weight, at least 28% by weight, at least 30% by weight, at least 32% by weight, at least 34% by weight, at least 36% by weight, at least 38% by weight, or at least 40% by weight. Thus, the conjugated diene monomer can be used in an amount of at most 99% by weight, at most 95% by weight, at most 90% by weight, at most 85% by weight, at most 80% by weight, at most 78% by weight, at most 76% by weight, at most 74% by weight, at most 72% by weight, at most 70% by weight, at most 68% by weight, at most 66% by weight, at most 64% by weight, at most 62% by weight, at most 60% by weight, at most 58% by weight, or at most 56% by weight, based on the total weight of the ethylenically unsaturated monomers in the monomer composition. Those skilled in the art will appreciate that any range between any explicitly disclosed lower and upper limits is disclosed herein.

[0191] The ethylenically unsaturated nitrile monomers useful in the present invention can include polymerizable unsaturated aliphatic nitrile monomers, which preferably contain 2 to 4 carbon atoms in a straight-chain or branched-chain arrangement and which can be substituted with an acetyl group or another nitrile group. The ethylenically unsaturated nitrile compounds used to prepare the latex polymer (a) of the present invention can be selected from (meth)acrylonitrile, α-cyanoethyl acrylonitrile, fumaronitrile, α-chloronitrile, and combinations thereof, with acrylonitrile being most preferred.

[0192] Based on the total weight of the ethylenically unsaturated monomers in the monomer composition, the content of these nitrile monomers can be from 1% to 80% by weight, preferably from 10% to 70% by weight, or from 1% to 60% by weight, more preferably from 15% to 50% by weight, even more preferably from 20% to 50% by weight, and most preferably from 23% to 43% by weight. Thus, the unsaturated nitrile can be present in an amount of at least 1%, at least 5%, at least 10%, at least 12%, at least 14%, at least 16%, at least 18%, at least 20%, at least 22%, at least 24%, at least 26%, at least 28%, at least 30%, at least 32%, at least 34%, at least 36%, at least 38%, or at least 40% by weight. Thus, the unsaturated nitrile monomers can be used in an amount of at most 80%, at most 75%, at most 73%, at most 70%, at most 68%, at most 66%, at most 64%, at most 62%, at most 60%, at most 58%, at most 56%, at most 54%, at most 52%, at most 50%, at most 48%, at most 46%, or at most 44% by weight. Based on the total weight of the ethylenically unsaturated monomers in the monomer composition. Those skilled in the art will understand that any range between any explicitly disclosed lower and upper limits is disclosed herein.

[0193] The ethylenically unsaturated compounds containing a functional group (A) different from (i) and (ii) and suitable for preparing the latex polymer (a) of the present invention may be selected from:

[0194] (iii 1) ethylenically unsaturated compounds having at least two different ethylenically unsaturated groups;

[0195] (iii2) ethylenically unsaturated acids and their salts;

[0196] (iii 3) hydroxy-functional ethylenically unsaturated compounds;

[0197] (iii4) epoxy-functional ethylenically unsaturated compounds;

[0198] (iii 5) glycidyl-functional ethylenically unsaturated compounds;

[0199] (iii 6) acetoacetoxy-functional ethylenically unsaturated compounds;

[0200] (iii 7) ethylenically unsaturated compounds with a primary or secondary amino group;

[0201] (iii 8) acetoxy-functional ethylenically unsaturated compounds;

[0202] (iii 9) Isocyanate-functional ethylenically unsaturated compounds;

[0203] (iii 10) Alkoxysilyl-functional ethylenically unsaturated compounds;

[0204] (iii 11) Alkoxy-functional ethylenically unsaturated compounds;

[0205] (iii 12) Dioxolanone-functional ethylenically unsaturated compounds;

[0206] (iii 13) Halogen-functional ethylenically unsaturated compounds;

[0207] (iii 14) Mercapto-functional ethylenically unsaturated compounds;

[0208] (iii 15) Hydroxyamine-functional ethylenically unsaturated compounds;

[0209] (iii 16) Oxazolinyl-functional ethylenically unsaturated compounds;

[0210] (iii 17) Aziridinyl-functional ethylenically unsaturated compounds;

[0211] (iii 18) Imino-functional ethylenically unsaturated compounds;

[0212] (iii 19) Carbodiimido-functional ethylenically unsaturated compounds;

[0213] (iii 20) Diol-functional ethylenically unsaturated compounds;

[0214] (iii 21) Hydrazide-functional ethylenically unsaturated compounds;

[0215] (iii 22) Aldehyde-functional ethylenically unsaturated compounds;

[0216] (iii 23) Ketone-functional ethylenically unsaturated compounds;

[0217] And combinations thereof.

[0218] Suitable ethylenically unsaturated compounds (iii 1) having at least two different ethylenically unsaturated groups may be selected from allyl (meth)acrylate, vinyl (meth)acrylate, and combinations thereof.

[0219] Suitable ethylenically unsaturated acids and their salts (iii2) may be selected from ethylenically unsaturated carboxylic acid monomers and their anhydrides, ethylenically unsaturated sulfonic acid monomers, and ethylenically unsaturated phosphoric acid-containing monomers. The ethylenically unsaturated carboxylic acid monomers and their anhydrides applicable to the present invention include monocarboxylic acid monomers such as (meth)acrylic acid, crotonic acid, and vinylacetic acid; dicarboxylic acid monomers such as fumaric acid, itaconic acid, maleic acid, and maleic anhydride; monoesters of dicarboxylic acids; carboxyalkyl esters of ethylenically unsaturated acids such as 2-carboxyethyl (meth)acrylate, polycarboxylic acids and their anhydrides, and polycarboxylic acid partial ester monomers. Examples of ethylenically unsaturated sulfonic acid monomers include vinylsulfonic acid, sodium 4-vinylbenzenesulfonate, 2-methyl-2-propene-1-sulfonic acid, 4-styrenesulfonic acid, 3-allyloxy-2-hydroxy-1-propane sulfonic acid, 2-acrylamido-2-methyl-1-propane sulfonic acid, and their salts. Examples of ethylenically unsaturated phosphoric acid-containing monomers include vinylphosphonic acid, dimethyl vinylphosphonate, diethyl vinylphosphonate, diethyl allylphosphonate, allylphosphonic acid, and their salts.

[0220] Preferably, the ethylenically unsaturated acids and their salts (iii2) are selected from (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, ethylenically unsaturated sulfonic acids, ethylenically unsaturated phosphoric acids, polycarboxylic anhydrides, polycarboxylic acid partial ester monomers, carboxyalkyl esters of ethylenically unsaturated acids, and combinations thereof.

[0221] Suitable hydroxyl-functional ethylenically unsaturated compounds (iii 3) may be selected from allyl alcohol, vinyl alcohol, N-methylolacrylamide, 1-penten-3-ol, hydroxyalkyl esters of ethylenically unsaturated acids, and combinations thereof. Hydroxyalkyl esters of ethylenically unsaturated acids include hydroxyalkyl (meth)acrylate monomers such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, glycerol (meth)acrylate, 2-hydroxypropyl maleate, and glycerol undecylenate.

[0222] Suitable epoxy-functional ethylenically unsaturated compounds (iii4) may be selected from vinylcyclohexene oxide, limonene oxide, 2-ethyl (3',4'-epoxyheptyl) (meth)acrylate, (6',7'-epoxyheptyl) (meth)acrylate, allyl 3,4-epoxyheptyl ether, 6,7-epoxyheptyl allyl ether, vinyl 3,4-epoxyheptyl ether, 3,4-epoxyheptyl vinyl ether, 6,7-epoxyheptyl vinyl ether, 3-vinylcyclohexene oxide, 2-(3,4-epoxycyclohexyl)methyl (meth)acrylate, 3,4-epoxy-1-butene, 1,2-epoxy-5-hexene, 4-vinyl-1-cyclohexene 1,2-epoxide, 2-methyl-2-vinyl oxirane, 3,4-epoxy-1-cyclohexene, and combinations thereof.

[0223] Suitable glycidyl-functional ethylenically unsaturated compounds (iii 5) may be selected from glycidyl (meth)acrylate, allyl glycidyl ether, vinyl glycidyl ether, 2-ethyl glycidyl (meth)acrylate, 2-(n-propyl) glycidyl (meth)acrylate, 2-(n-butyl) glycidyl (meth)acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl glycidyl methacrylate, glycidyl propargyl ether, and combinations thereof.

[0224] Suitable acetoacetoxy-functional ethylenically unsaturated compounds (iii 6) may be selected from acetoacetoxyethyl (meth)acrylate, acetoacetoxypropyl (meth)acrylate, allyl acetoacetate, acetoacetoxybutyl (meth)acrylate, 2,3-bis(acetoacetoxy)propyl (meth)acrylate, (meth)acetoacetoxy(meth)ethyl acrylate, acetoacetamido-ethyl (meth)acrylate, 3-(methacryloyloxy)-2,2-dimethylpropyl 3-oxobutyrate, 3-(methacryloyloxy)-2,2,4,4-tetramethylcyclobutyl 3-oxobutyrate, 3-(methacryloyloxy)-2,2,4-trimethylpentyl 3-oxobutyrate, 1-(methacryloyloxy)-2,2,4-trimethylpent-3-yl 3-oxobutyrate, (4-(methacryloxymethyl)cyclohexyl)methyl 3-oxobutyrate, and combinations thereof.

[0225] Ethylenically unsaturated compounds with primary or secondary amino groups (iii 7) suitable for preparing the latex polymer (a) of the present invention may be selected from (meth)acrylamide, 2-aminoethyl (meth)acrylate hydrochloride, 2-aminoethyl (meth)acrylamide hydrochloride, N-ethyl (meth)acrylamide, N-(3-aminopropyl)(meth)acrylamide hydrochloride, N-hydroxyethyl (meth)acrylamide, N-3-(dimethylamino)propyl (meth)acrylamide, [3-(methacrylamido)propyl]trimethylammonium, N-[tris(hydroxymethyl)methyl](meth)acrylamide, N-phenylacrylamide, alkylacrylamide, methacrylamide polyethylene glycol amine hydrochloride, and combinations thereof.

[0226] Suitable acetoxy-functional ethylenically unsaturated compounds (iii 8) may be selected from 1-acetoxy-1,3-butadiene, diacetone acrylamide, and combinations thereof.

[0227] Suitable isocyanato-functional ethylenically unsaturated compounds (iii 9) may be selected from 2-isocyanatoethyl (meth)acrylate, allyl isocyanate, vinyl isocyanate, 3-isopropenyl-α,α-dimethylbenzyl isocyanate, and combinations thereof.

[0228] Suitable alkoxysilyl-functionalized ethylenically unsaturated compounds (iii 10) may be selected from allyltrimethoxysilane, allyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-butenyltriethoxysilane, 3-(trimethoxysilyl)propyl (meth)acrylate, 5-hexenyltriethoxysilane, styrylethyltrimethoxysilane, trimethoxy(7-octen-1-yl)silane, 11-allyloxoundecyltrimethoxysilane, allylphenylpropyltriethoxysilane, [(5-bicyclo[2.2.1]hept-2-enyl)ethyl]trimethoxysilane, (5-bicyclo[2.2.1]hept-2-enyl)triethoxysilane, n-allyl-aza-2,2-dimethoxysilacyclopentane, norbornenyltriethoxysilane, [2-(3-cyclohexenyl)ethyl]triethoxysilane, and combinations thereof.

[0229] Suitable alkoxy-functionalized ethylenically unsaturated compounds (iii 11) may be selected from N-methoxymethyl-(meth)acrylamide, N-n-butoxy-methyl-(meth)acrylamide, N-isobutoxy-methyl-(meth)acrylamide, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, methoxyethoxyethyl acrylate, methyl-3-methoxy (meth)acrylate, and combinations thereof. Preferred alkoxy-functionalized ethylenically unsaturated compounds are 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, methyl-3-methoxy (meth)acrylate, and combinations thereof.

[0230] Suitable dioxolanone-functionalized ethylenically unsaturated compounds (iii 12) may be selected from glycerol (meth)acrylate carbonate, 4-vinyl-1,3-dioxolan-2-one, and combinations thereof.

[0231] Suitable halogen-functionalized ethylenically unsaturated compounds (iii 13) may be selected from vinyl chloride, allyl chloride, 2-chloro-1,3-butadiene, 2-chloroethyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, methyl 2-(chloromethyl) (meth)acrylate, 2,3-dichloropropyl (meth)acrylate, 2,3-dibromopropyl (meth)acrylate, and combinations thereof.

[0232] Suitable thiol-functionalized ethylenically unsaturated compounds (iii 14) may be selected from allyl mercaptan, N-acryloyl-cysteamine, and combinations thereof.

[0233] Suitable hydroxyamine-functionalized ethylenically unsaturated compounds (iii 15) may be selected from acryloxyoxime acid.

[0234] Suitable oxazolinyl-functionalized ethylenically unsaturated compounds (iii 16) may be selected from oxazoline-substituted acrylates. Suitable oxazoline-substituted acrylates and their synthesis are disclosed in US 6,063,885.

[0235] Suitable aziridinyl-functionalized ethylenically unsaturated compounds (iii 17) may be selected from 2-(aziridin-1-yl)ethyl acrylate.

[0236] Suitable imino-functionalized ethylenically unsaturated compounds (iii 18) may be selected from 2-[(2-methylprop-2-enoyl)oxy]ethyl (3E)-3-(alkylimino)butanoate. The imino-functionalized ethylenically unsaturated compounds (iii 18) can be prepared by the reaction of a primary or secondary amine with acetylacetoxyethyl (meth)acrylate, as described in Esser, R.J., Devona, J.E., Setzke, D.E. and Wagemans L. Prog. Org. Coat., 1999, 36(1-2) 45-52 & Yu, Z., Alessso, S., Pears, D., Worthington, P.A., Luke, R.W.A., Bradley, M., Tetrahedron Lett., 2000, 41(46) 8963-8967.

[0237] Suitable carbodiimido-functionalized ethylenically unsaturated compounds (iii 19) may be selected from N-α,α'-dimethylisopropenylbenzyl-N'-cyclohexylcarbodiimide, N-α,α'-dimethylisopropenylbenzyl-N'-butylcarbodiimide, and combinations thereof. The synthesis of the carbodiimido-functionalized ethylenically unsaturated compounds is disclosed in Pham, H.H. and Winnik, M.A., J Polym Sci A Polym Chem, 2000, 38, 855-869.

[0238] Suitable diol-functionalized ethylenically unsaturated compounds (iii 20) may be selected from ethylene glycol methyl ether (meth)acrylate, ethylene glycol phenyl ether (meth)acrylate, di(ethylene glycol) methyl ether (meth)acrylate, tri(ethylene glycol) methyl ether (meth)acrylate, poly(ethylene glycol) methyl ether (meth)acrylate, poly(ethylene glycol) phenyl ether acrylate, poly(ethylene glycol) (meth)acrylate, poly(propylene glycol) (meth)acrylate, poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (meth)acrylate, polyglycol partial ester monomers, and combinations thereof.

[0239] Suitable hydrazide-functionalized ethylenically unsaturated compounds (iii 21) may be selected from 2-acryloylhydrazide, methacryloylhydrazide, and combinations thereof.

[0240] Suitable aldehyde-functionalized ethylenically unsaturated compounds (iii22) may be selected from (meth)acrolein, 2-ethylacrolein, 3-methyl-2-butenal, tiglic aldehyde, crotonaldehyde, 3-methylcrotonaldehyde, 2-pentenal, 2-methyl-2-pentenal, 4-pentenal, 2,2-dimethyl-4-pentenal, 2,4-heptadienal, and combinations thereof.

[0241] Suitable ketone-functionalized ethylenically unsaturated compounds (iii23) may be selected from 1-penten-3-one, 3-buten-2-one, 4-methoxy-3-buten-2-one, 3-penten-2-one, 2-cyclopenten-1-one, 2-cyclohexen-1-one, and combinations thereof.

[0242] In addition to the conjugated diene (i) that can provide a carbon-carbon double bond as the functional group (A), the compound (iii) can provide the functional group (A). Based on the total weight of the ethylenically unsaturated monomers in the monomer composition, the content of the ethylenically unsaturated compound (iii) having a functional group (A) different from (i) and (ii) can be 0-10% by weight, preferably 0.05-10% by weight, particularly 0.1-10% by weight or 0.5-7% by weight, more preferably 0.7-8% by weight, even more preferably 1.0-7% by weight, and most preferably 2.0-7% by weight. Thus, the ethylenically unsaturated compound (iii) can be present in an amount of at least 0.01% by weight, at least 0.05% by weight, at least 0.1% by weight, at least 0.3% by weight, at least 0.5% by weight, at least 0.7% by weight, at least 0.9% by weight, at least 1.0% by weight, at least 1.2% by weight, at least 1.4% by weight, at least 1.6% by weight, at least 1.8% by weight, at least 2.0% by weight, at least 2.5% by weight, or at least 3.0% by weight, based on the total weight of the ethylenically unsaturated monomers in the monomer composition. Similarly, based on the total weight of the ethylenically unsaturated monomers in the monomer composition, the ethylenically unsaturated compound (iii) can be present in an amount of at most 10% by weight, at most 9.5% by weight, at most 9% by weight, at most 8.5% by weight, at most 8% by weight, at most 7.5% by weight, at most 7% by weight, at most 6.5% by weight, at most 6% by weight, at most 5.5% by weight, or at most 5% by weight. Those skilled in the art will understand that any range defined by the explicitly disclosed lower limit and the explicitly disclosed upper limit is disclosed herein.

[0243] Suitable examples of the vinyl aromatic monomer (iv) may be selected from styrene, α-methylstyrene, vinyltoluene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 2,4-dimethylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-tert-butylstyrene, 5-tert-butyl-2-methylstyrene, vinylnaphthalene, vinyltoluene, vinyldimethylbenzene, 2-vinylpyridine, 4-vinylpyridine, 1,1-diphenylethylene, 1,2-diphenylethylene, and combinations thereof. Preferably, the vinyl aromatic monomer (iv) is selected from styrene, α-methylstyrene, and combinations thereof.

[0244] The vinyl aromatic compound (vi) can be used in an amount in the range of 0 to 80% by weight, or 0 to 70% by weight, or 0 to 50% by weight, preferably 0 to 40% by weight, more preferably 0 to 25% by weight, even more preferably 0 to 15% by weight, and most preferably 0 to 10% by weight, based on the total weight of the ethylenically unsaturated monomers in the monomer composition. Thus, the vinyl aromatic compound (iv) can be present in an amount of up to 80% by weight, up to 75% by weight, up to 60% by weight, up to 50% by weight, up to 40% by weight, up to 35% by weight, up to 30% by weight, up to 25% by weight, up to 20% by weight, up to 18% by weight, up to 16% by weight, up to 14% by weight, up to 12% by weight, up to 10% by weight, up to 8% by weight, up to 6% by weight, up to 4% by weight, up to 2% by weight, or up to 1% by weight, based on the total weight of the ethylenically unsaturated monomers in the monomer composition. The vinyl aromatic compound (iv) can also be completely absent in the monomer composition used to obtain the latex polymer (a) particles.

[0245] Suitable examples of the alkyl esters of ethylenically unsaturated acids (v) may be selected from the n-alkyl esters, isoalkyl esters, or tert-alkyl esters of (meth)acrylic acid, wherein the alkyl group has 1 to 20 carbon atoms, and the reaction products of methacrylic acid with glycidyl esters of neoacids such as versatic acid, neodecanoic acid, or pivalic acid.

[0246] Generally, preferred alkyl esters of (meth)acrylic acid may be selected from C1-C 10Alkyl esters, preferably C1-C8 alkyl (meth)acrylates. Examples of such (meth)acrylate monomers include n-butyl acrylate, sec-butyl acrylate, ethyl acrylate, hexyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, 4-methyl-2-pentyl acrylate, 2-methylbutyl acrylate, methyl methacrylate, tert-butyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, ethyl methacrylate, isopropyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, and cetyl methacrylate. (Meth)methyl acrylate, (meth)ethyl acrylate, (meth)propyl acrylate, (meth)butyl acrylate, (meth)2-ethylhexyl acrylate, and combinations thereof are preferred.

[0247] Generally, the alkyl esters (v) of ethylenically unsaturated acids can be present in an amount of up to 65% by weight, up to 60% by weight, up to 55% by weight, up to 50% by weight, up to 45% by weight, up to 40% by weight, up to 35% by weight, up to 30% by weight, up to 25% by weight, up to 20% by weight, up to 18% by weight, up to 16% by weight, up to 14% by weight, up to 12% by weight, up to 10% by weight, up to 8% by weight, up to 6% by weight, up to 4% by weight, up to 2% by weight, or up to 1% by weight, based on the total weight of the ethylenically unsaturated monomers in the monomer composition.

[0248] According to the present invention, the monomer composition for obtaining the latex polymer (a) particles may comprise:

[0249] (i) 30 to 75% by weight of a conjugated diene;

[0250] (ii) 15 to 50% by weight of a monomer selected from ethylenically unsaturated nitrile compounds;

[0251] (iii) 0.1 to 10% by weight of an ethylenically unsaturated compound containing a functional group (A) different from (i) and (ii);

[0252] (iv) 0 to 40% by weight of a vinyl aromatic monomer; and

[0253] (v) 0 to 30% by weight of an alkyl ester of an ethylenically unsaturated acid; the weight percentages are based on the total weight of the ethylenically unsaturated monomers in the monomer composition.

[0254] In addition, the mixture of ethylenically unsaturated monomers for the latex polymer (a) may comprise additional ethylenically unsaturated monomers different from the above monomers. These monomers may be selected from vinyl acetate (vi) and / or monomers (vii) having two identical ethylenically unsaturated groups.

[0255] The vinyl ester monomers (vi) that can be used according to the present invention include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl 2-ethylhexanoate, vinyl stearate, and vinyl versatate. The most preferred vinyl ester monomer for use in the present invention is vinyl acetate. Generally, based on the total weight of the ethylenically unsaturated monomers in the monomer mixture, the vinyl ester monomer can be present in an amount of up to 18% by weight, up to 16% by weight, up to 14% by weight, up to 12% by weight, up to 10% by weight, up to 8% by weight, up to 6% by weight, up to 4% by weight, up to 2% by weight, or up to 1% by weight.

[0256] In addition, monomers (vii) having at least two identical ethylenically unsaturated groups can be present in the monomer mixture for preparing the polymer latex of the present invention in an amount of 0 to 6.0% by weight, preferably 0.1 to 3.5% by weight, based on the total weight of the ethylenically unsaturated monomers in the monomer mixture. Generally, these monomers can be present in an amount of up to 6% by weight, up to 4% by weight, up to 2% by weight, up to 1% by weight, based on the total weight of the ethylenically unsaturated monomers in the monomer mixture. Suitable difunctional monomers (vii) (referred to as polyfunctional monomers in this application) capable of providing internal crosslinking and branching in the polymer are selected from divinylbenzene and diacrylates and di(meth)acrylates. Examples are ethylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and dipropylene glycol di(meth)acrylate. Monomers (vii) having at least two ethylenically unsaturated groups are preferably selected from divinylbenzene, 1,2-ethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate and combinations thereof.

[0257] According to the present invention, the amounts of the above monomers for preparing the latex polymer (a) can total 100% by weight.

[0258] Method for preparing the polymer latex (a) of the present invention:

[0259] The latex polymer (a) of the present invention can be prepared by any emulsion polymerization method known to those skilled in the art. Particularly suitable is the method disclosed in EP792891A.

[0260] In the emulsion polymerization for preparing the latex polymer (a) of the present invention, seed latex can be used. Any seed particles known to those skilled in the art can be used.

[0261] Based on 100 parts by weight of the total ethylenically unsaturated monomers in the monomer mixture, the seed latex particles are preferably present in an amount of from 0.01 to 10 parts by weight, preferably from 1 to 5 parts by weight. Thus, the lower limit of the amount of the seed latex particles can be 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4 or 2.5 parts by weight, based on 100 parts by weight of the total ethylenically unsaturated monomers in the monomer mixture. The upper limit of the amount can be 10, 9, 8, 7, 6, 5.5, 5, 4.5, 4, 3.8, 3.6, 3.4, 3.3, 3.2, 3.1 or 3 parts by weight, based on 100 parts by weight of the total ethylenically unsaturated monomers in the monomer mixture. Those skilled in the art will understand that any range formed by any explicitly disclosed lower and upper limits is clearly encompassed in this specification.

[0262] The process for preparing the above polymer latex can be carried out in the absence or presence of one or more emulsifiers, in the absence or presence of one or more colloids and one or more initiators at a temperature of from 0 to 130 °C, preferably from 0 to 100 °C, particularly preferably from 5 to 70 °C, very particularly preferably from 5 to 60 °C. The temperature includes all values and sub - values therebetween, in particular including 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120 and 125 °C.

[0263] The initiators that can be used when carrying out the present invention include water - soluble and / or oil - soluble initiators effective for the purpose of polymerization. Representative initiators are well - known in the art and include, for example: azo compounds (such as AIBN, AMBN and cyanovaleric acid) and inorganic peroxides, such as hydrogen peroxide, sodium persulfate, potassium persulfate and ammonium persulfate, sodium percarbonate, potassium percarbonate and ammonium percarbonate, sodium perborate, potassium perborate and ammonium perborate, and organic peroxides, such as alkyl hydroperoxides, dialkyl peroxides, acyl hydroperoxides and diacyl peroxides, and esters, such as tert - butyl perbenzoate, and combinations of inorganic and organic initiators.

[0264] Use an adequate amount of an initiator to initiate the polymerization reaction at a desired rate. Generally, an amount of initiator of from 0.01% to 5% by weight, preferably from 0.1% to 4% by weight, based on the total weight of the monomers in the monomer mixture, is sufficient. Most preferably, the amount of initiator is from 0.01 to 2% by weight, based on the total weight of the monomers in the monomer mixture. The amount of initiator includes all values and sub-values therebetween, particularly including 0.01, 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 4 and 4.5% by weight, based on the total weight of the monomers in the monomer mixture.

[0265] As is well known in the art, the above-mentioned inorganic and organic peroxides can also be used alone or in combination with one or more suitable reducing agents. Examples of such reducing agents can include sulfur dioxide, alkali metal metabisulfites, alkali metal bisulfites and ammonium bisulfite, thiosulfates, dithionites and formaldehyde sulfoxylates, as well as hydroxylamine hydrochloride, hydrazine sulfate, iron(II) sulfate, copper naphthenate, glucose, sulfonic acid compounds such as sodium methanesulfonate, amine compounds such as dimethylaniline and ascorbic acid. The amount of the reducing agent is preferably from 0.03 to 10 parts by weight per part by weight of the polymerization initiator.

[0266] Surfactants or emulsifiers suitable for stabilizing the latex particles include those conventional surfactants used in polymerization processes. One or more surfactants can be added to the aqueous phase and / or the monomer phase. The effective amount of surfactant in the seeded method is the amount selected to support the stabilization of the particles as a colloid, minimize the contact between the particles and prevent coagulation. In the non-seeded method, the effective amount of surfactant is the amount selected to affect the particle size.

[0267] Representative surfactants include saturated and olefinically unsaturated sulfonic acids or their salts, including, for example, unsaturated hydrocarbon sulfonic acids such as vinylsulfonic acid, allylsulfonic acid and methallylsulfonic acid and their salts; aromatic hydrocarbon acids such as p-styrenesulfonic acid, isopropenylbenzenesulfonic acid and vinyloxybenzenesulfonic acid and their salts; sulfoalkyl esters of (meth)acrylic acid such as 2-sulfoethyl methacrylate and 3-sulfopropyl methacrylate and their salts, and 2-acrylamido-2-methylpropanesulfonic acid and its salts; alkylated diphenyl ether disulfonates, sodium dodecylbenzenesulfonate and dihexyl sulfosuccinate, sodium alkyl esters of sulfonic acids, ethoxylated alkylphenols and ethoxylated alcohols; fatty alcohol (poly)ether sulfates.

[0268] The type and amount of surfactant are usually determined by the number of particles, their size and their composition. Generally, based on the total weight of the monomers in the monomer mixture, the amount of surfactant used is from 0 to 20% by weight, preferably from 0 to 10% by weight, more preferably from 0 to 5% by weight. The amount of surfactant includes all values and sub-values therebetween, in particular including 0, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 and 19% by weight, based on the total weight of the monomers in the monomer mixture. Polymerization can be carried out without using a surfactant.

[0269] It is also possible to use various protective colloids instead of or in addition to the above-mentioned surfactants. Suitable colloids include polyhydroxy compounds such as partially acetylated polyvinyl alcohol, casein, hydroxyethyl starch, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polysaccharides and degraded polysaccharides, polyethylene glycol and gum arabic. Preferred protective colloids are carboxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose. Generally, based on the total weight of the monomers in the monomer mixture, these protective colloids are used in an amount of from 0 to 10 parts by weight, preferably from 0 to 5 parts by weight, more preferably from 0 to 2 parts by weight. The amount of protective colloid includes all values and sub-values therebetween, particularly including 1, 2, 3, 4, 5, 6, 7, 8 and 9% by weight, based on the total weight of the monomers in the monomer mixture.

[0270] Those skilled in the art will understand that the type and amount of monomers, surfactants and protective colloids with polar functional groups are to be selected such that the polymer latexes according to the invention are suitable for dip molding applications. Thus, it is preferred that the polymer latex composition of the invention has a certain maximum electrolyte stability, which is determined as the critical coagulation concentration of less than 30 mmol / l of CaCl2, preferably less than 25 mmol / l, more preferably less than 20 mmol / l, most preferably less than 10 mmol / l (measured at pH 10 and 23 °C for a total solids content of 0.1% of the composition).

[0271] It is generally advisable to carry out the emulsion polymerization additionally in the presence of buffer substances and chelating agents. Suitable substances are, for example, alkali metal phosphates and pyrophosphates (buffer substances) and the alkali metal salts of ethylenediaminetetraacetic acid (EDTA) or hydroxy-2-ethylenediaminetriacetic acid (HEEDTA) as chelating agents. Based on the total weight of the monomers in the monomer mixture, the amount of buffer substance and chelating agent is generally from 0.001% by weight to 1.0% by weight.

[0272] Furthermore, it may be advantageous to use a chain transfer agent (modifier) in the emulsion polymerization. Typical reagents are, for example, organic sulfur compounds such as thioesters, 2-mercaptoethanol, 3-mercaptopropionic acid and C1-C 12Alkyl mercaptans, preferably n-dodecyl mercaptan and tert-dodecyl mercaptan. If present, the amount of the chain transfer agent is usually 0.05 - 3.0% by weight, preferably 0.2 - 2.0% by weight, based on the total weight of the monomers in the monomer mixture.

[0273] In addition, it may be beneficial to introduce partial neutralization during the polymerization process. Those skilled in the art will understand that the necessary control can be achieved by appropriately selecting this parameter.

[0274] Various other additives and ingredients can be added to prepare the latex composition of the present invention. Such additives include, for example: defoamers, wetting agents, thickeners, plasticizers, fillers, pigments, dispersants, optical brighteners, crosslinking agents, accelerators, antioxidants, biocides, and metal chelating agents. Known defoamers include silicone oils and acetylene glycols. Commonly known wetting agents include alkylphenol ethoxylates, alkali metal dialkyl sulfosuccinates, acetylene glycols, and alkali metal alkyl sulfates. Typical thickeners include polyacrylate (salts), polyacrylamides, xanthan gum, modified celluloses, or particulate thickeners such as silica and clay. Typical plasticizers include mineral oil, liquid polybutene, liquid polyacrylate, and lanolin. Zinc oxide is a suitable crosslinking agent. Titanium dioxide (TiO2), calcium carbonate, and clay are commonly used fillers. Known accelerators and co-accelerators include dithiocarbamates such as zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, zinc dibenzyldithiocarbamate, zinc pentamethylenedithiocarbamate (ZPD), xanthates, thiurams such as tetramethylthiuram monosulfide (TMTM), tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), dipentamethylenethiuram hexasulfide (DPTT), and amines such as diphenylguanidine (DPG), di-o-tolylguanidine (DOTG), and o-tolylbiguanide (OTBG).

[0275] Silane compound (b)

[0276] The polymer latex composition comprises a silane compound (b) selected from the compounds of formula I, II, their oligomers, or any combination of the foregoing.

[0277] As used herein, the term "its oligomer" refers to a polysiloxane oligomer comprising at least two repeating units and formed by hydrolysis and condensation of a silane compound (b), i.e., selected from Formula I, II, and combinations thereof. The polysiloxane oligomer can be prepared by hydrolyzing the silane compound (b) to form silanols and condensing the silanols by removing water. Hydrolysis of the silane compound can be carried out in the presence of water, such as 2 to 15 moles of water per mole of silane; and optionally reacting in the presence of a hydrolysis catalyst to provide an intermediate containing silanols. The hydrolysis can be carried out at a temperature of 10 to 100 °C. Suitable examples of hydrolysis catalysts include metal salts, alkylammonium salts, ion exchange resins, carboxylic acids, inorganic acids, or metal chelates, preferably carboxylic acids. The amount of catalyst used can be 1 ppm to 1 wt% based on the total weight of the silane compound. It is further advantageous to remove hydrolysis by-products such as alcohols by distillation. Condensation of the silanols to form oligomeric polysiloxanes can be achieved by removing water (e.g., by distillation). The distillation for removing water can be carried out at a temperature of 10 to 100 °C and preferably at a pressure of 0.01 kPa to 200 kPa. Removal of water and condensation of the silanols generally require 1 to 200 hours, more specifically 2 to 24 hours. Removal of water and condensation of the silanols can be assisted by sparging the reaction mixture with an inert gas such as nitrogen. Suitable methods for preparing such oligomers are disclosed in more detail in US2013 / 0158159A1, specifically in paragraphs

[0046] to

[0072] and paragraphs

[0117] to

[0146] .

[0278] The silane compound (b) can be selected from Formula I, its oligomers, or a combination of any of the foregoing:

[0279]

[0280] wherein X is a functional group capable of forming a bond with the functional group (A) of the latex polymer (a); R 1 is a linking group between the functional group X and the silicon atom or R 1 is a bond; R 2 are independently hydrolysable groups or non-hydrolysable groups; wherein at least one of R 2 is a hydrolysable group, and at least one of R 2 is a non-hydrolysable group. The silane compound (b) can be selected from Formula I.

[0281] As used in this application, the term "non-hydrolysable group" refers to a group that cannot be cleaved by hydrolysis. Each non-hydrolysable R 2 can independently be a straight-chain C1 to C 20 alkyl, straight-chain C2-C 20 alkyl, branched or cyclic C3-C 20 alkyl or alkenyl or aryl. Preferably, each non-hydrolysable R 2Independently is a straight-chain C1-C 20 alkyl group.

[0282] As used in this application, the term "hydrolyzable group" refers to a group that can be cleaved by hydrolysis and is capable of forming a Si-OH group upon cleavage. Each hydrolyzable R 2 is independently -H, -OR', -OC(O)CH3, OCH2OCH3, -SR', -NHR', -NR'2 or -halogen, where R' is a straight-chain C1-C6 alkyl group, a branched C3-C6 alkyl group or an alkenyl group, or an aryl group. Preferably, each hydrolyzable R 2 is independently -OR' or -halogen, where R' is a straight-chain C1-C6 alkyl group, a branched C3-C6 alkyl group or an alkenyl group, or an aryl group.

[0283] R 1 can be a linking group between the functional group X and the silicon atom. The linking group R 1 between the functional group X and the silicon atom can be a straight-chain C1-C 20 alkanediyl group, a branched C2-C 20 alkanediyl group, a cyclic C3-C 20 alkanediyl group or an alkenediyl group, or an arylenediyl group. Preferably, the linking group R 1 between the functional group X and the silicon atom is a straight-chain C1-C 20 alkanediyl group. Optionally, one or more methylene groups in each of the above alkanediyl groups, alkenediyl groups and arylenediyl groups are replaced by heteroatoms, provided that no heteroatoms are directly bonded to another heteroatom, and no heteroatoms are directly bonded to Si. Preferably, no heteroatoms are directly bonded to the functional group X, except when X is a glycidyl group. The heteroatoms are preferably oxygen, sulfur or nitrogen, more preferably oxygen.

[0284] R 1 can be a bond between the functional group X and the silicon atom, preferably only when the functional group X is a carbon-carbon double bond.

[0285] According to the present invention, the functional group X can be selected from a carbon-carbon double bond, (meth)acryloyloxy, a halogen functional group, an epoxy group, a glycidyl group, a thiol, a hydroxyl group, a hydroxylamine, a primary amino group, a secondary amino group, isocyanato, an oxazolinyl group, an aziridinyl group, an imino group, a carbodiimide group, a diol, an ester, an acetoxy group, an acetoacetoxy group, a carboxylic acid, a dioxolanone, a hydrazide group, an aldehyde, a boric acid, an alkoxysilyl group and a ketone. Preferably, the functional group X can be selected from a carbon-carbon double bond, (meth)acryloyloxy, a halogen functional group, a glycidyl group, an epoxy group, a thiol, a hydroxyl group, a primary amino group, a secondary amino group and isocyanato. The functional group X can be selected from a glycidyl group, an epoxy group, a thiol, a hydroxyl group, a primary amino group and a secondary amino group.

[0286] The silane compound (b) can be selected from Formula II, its oligomers, or any combination of the foregoing substances:

[0287]

[0288] wherein Y is O, S, NH, or NR 3 ; wherein R 3 is a straight-chain or branched, substituted or unsubstituted alkyl or alkenyl; R 1 is a linking group between the functional group Y and the silicon atom; R 2 is independently a hydrolysable group or a non-hydrolysable group; wherein at least one of R 2 is a non-hydrolysable group. The silane compound (b) can be selected from Formula II.

[0289] Each non-hydrolysable R 2 can independently be a straight-chain C1-C 20 alkyl, straight-chain C2-C 20 alkenyl, branched or cyclic C3-C 20 alkyl or alkenyl, or aryl. Preferably, each non-hydrolysable R 2 is independently a straight-chain C1-C 20 alkyl.

[0290] Each hydrolysable R 2 is independently -H, -OR', -OC(O)CH3, OCH2OCH3, -SR', -NHR', -NR'2, or -halogen, where R' is a straight-chain C1-C6 alkyl; branched C3-C6 alkyl or alkenyl, or aryl. Preferably, each hydrolysable R 2 is independently -OR' or -halogen, where R' is a straight-chain C1-C6 alkyl; branched C3-C6 alkyl or alkenyl, or aryl.

[0291] The linking group R 1 between the functional group Y and the silicon atom can be a straight-chain or branched C3-C 20 alkanediyl. Preferably, the linking group R 1 between the functional group Y and the silicon atom can be a straight-chain or branched C3-C 10 alkanediyl. Optionally, one or more methylenes in each of the above alkanediyl, alkenediyl, and arylenediyl are replaced by heteroatoms, provided that no heteroatom is directly bonded to another heteroatom, and no heteroatom is directly bonded to Si. Preferably, no heteroatom is directly bonded to the functional group Y. The heteroatom is preferably oxygen, sulfur, or nitrogen, more preferably oxygen.

[0292] The Si-Y bond can be hydrolyzable to form Si-OH groups and Y-H groups, where the Y-H group is a functional group capable of forming a bond with the functional group (A) of the latex polymer (a). The functional group Y-H can be -OH, -SH, NH2 or NHR 3 ; where R 3 is a straight-chain or branched, substituted or unsubstituted alkyl or alkenyl group. Hydrolysis of the Si-Y bond can be achieved in the presence of water and optionally in the presence of a hydrolysis catalyst as described above. The hydrolysis can be carried out at a temperature of 10 to 100 °C, preferably 30 to 80 °C, most preferably 25 to 70 °C.

[0293] The polymer latex composition of the present invention may contain from 0.10 to 4.00 parts by weight, preferably from 0.20 to 2.00 parts by weight, more preferably from 0.20 to 1.80 parts by weight, even more preferably from 0.20 to 1.50 parts by weight; most preferably from 0.40 to 1.50 parts by weight of the silane compound (b); based on 100 parts by weight of the latex polymer (a). Thus, the silane compound (b) can be present in an amount of at least 0.05 part by weight, at least 0.10 part by weight, at least 0.15 part by weight, at least 0.20 part by weight, at least 0.25 part by weight, at least 0.30 part by weight, at least 0.35 part by weight, at least 0.40 part by weight, at least 0.45 part by weight, at least 0.50 part by weight, at least 0.55 part by weight, at least 0.60 part by weight, based on 100 parts by weight of the latex polymer (a). Similarly, the silane compound (b) can be present in an amount of at most 4.50 parts by weight, at most 4.00 parts by weight, at most 3.80 parts by weight, at most 3.50 parts by weight, at most 3.20 parts by weight, at most 3.00 parts by weight, at most 2.80 parts by weight, at most 2.50 parts by weight, at most 2.2 parts by weight, at most 2.00 parts by weight, at most 1.80 parts by weight, at most 1.50 parts by weight, based on 100 parts by weight of the latex polymer (a). Those skilled in the art will understand that any range can be used. Ranges defined by a clearly disclosed lower limit and a clearly disclosed upper limit are disclosed herein.

[0294] The silane compound (b) may be selected from compounds of formula I, II or a combination of any of the foregoing compounds. Suitable silane compounds (b) may be selected from (3-glycidoxypropyl)methyldiethoxysilane, (3-glycidoxypropyl)dimethyl ethoxysilane, (3-glycidoxypropyl)methyl dimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane, 3-aminopropyldimethylmethoxysilane, 3-aminopropyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldiisopropylethoxysilane, 4-amino-3,3-dimethylbutylmethyldimethoxysilane, (1-aminopropan-2-yl)ethoxydimethylsilane, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminoisobutyldimethylmethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminoisobutylmethyldimethoxysilane, (N-cyclohexylaminomethyl)methyldiethoxysilane, N-methylaminopropylmethyldimethoxysilane, (phenylaminomethyl)methyldimethoxysilane, 3-(N,N-dimethylaminopropyl)aminopropylmethyldimethoxysilane, (3-acryloxypropyl)methyldiethoxysilane, (3-acryloxypropyl)methyldimethoxysilane, (3-acryloxypropyl)dimethylmethoxysilane, (methacryloxymethyl)methyldiethoxysilane, (methacryloxymethyl)methyldimethoxysilane, (methacryloxymethyl)dimethylethoxysilane, (methacryloxypropyl)dimethylmethoxysilane, allylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldimethoxysilane, vinyldimethylethoxysilane, (5-bicyclo[2.2.1]hept-2-enyl)methyldiethoxysilane, (5-bicyclo[2.2.1]hept-2-enyl)dimethylethoxysilane, (5-bicyclo[2.2.1) (hept-2-enyl)methyldichlorosilane, (mercaptomethyl)methyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, chloromethyldimethylethoxysilane, ((chloromethyl)phenyl ethyl)methyldimethoxysilane, 3-chloropropyldimethylethoxysilane, 3-chloropropyldimethylmethoxysilane, 3-chloroisobutyldimethylmethoxysilane, chloromethyldimethylethoxysilane, 3-chloropropylmethyldiisopropoxysilane, (3-iodopropyl)methyldiisopropoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 1,1-dimethyl-1-sila-2-oxacyclohexane, 2,2,4-trimethyl-1-oxa-4-aza-2-silacyclohexane, 1-decyl-1-methyl-1-sila-2-oxacyclohexane, 2,2,4-trimethyl-1-thia-2-silacyclopentane, N-(2-aminoethyl)-2,2,4-trimethyl-1-aza-2-silacyclopentane, N-(3-aminopropyldimethylsilyl)aza-2,2-dimethyl-2-silacyclopentane, (N,N-dimethylaminopropyl)-aza-2-methyl-2-methoxysilacyclopentane and combinations thereof.

[0295] Preferably, the silane compound (b) is selected from (3-glycidoxypropyl)methyldiethoxysilane, (3-glycidoxypropyl)dimethyl ethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane, 3-aminopropyldimethylmethoxysilane, 3-aminopropyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldiisopropylethoxysilane, 4-amino-3,3-dimethylbutylmethyldimethoxysilane, (1-aminopropan-2-yl)ethoxydimethylsilane, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminoisobutyldimethylmethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminoisobutylmethyldimethoxysilane, (N-cyclohexylaminomethyl)methyldiethoxysilane, N-methylaminopropylmethyldimethoxysilane, (phenylaminomethyl)methyldimethoxysilane, 3-(N,N-dimethylaminopropyl)aminopropylmethyldimethoxysilane, (mercaptomethyl)methyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 1,1-dimethyl-1-sila-2-oxacyclohexane, 2,2,4-trimethyl-1-oxa-4-aza-2-silacyclohexane, 1-decyl-1-methyl-1-sila-2-oxacyclohexane, 2,2,4-trimethyl-1-thia-2-silacyclopentane, N-(2-aminoethyl)-2,2,4-trimethyl-1-aza-2-silacyclopentane, N-(3-aminopropyldimethylsilyl)aza-2,2-dimethyl-2-silacyclopentane, (N,N-dimethylaminopropyl)-aza-2-methyl-2-methoxysilacyclopentane, and combinations thereof.

[0296] According to the present invention, the bond formed between the functional group (A) of the latex polymer (a) and the functional group X of the silane compound (b) can be selected from disulfide, tetrasulfide, carbonate, urea, thiourea, ester, β-hydroxy ester, thioester, β-hydroxy amine, β-hydroxy thioether, amide, carbamate, enamine, imine, hemiacetal, acetal, hemiketal, ketal, borate, siloxane, oxime, acylhydrazone, aldol, thiuram disulfide, and trithiocarbonate. Preferably, the bond formed between the functional group (A) of the latex polymer (a) and the functional group X of the silane compound (b) is selected from ester, β-hydroxy ester, thioester, amide, enamine, and imine.

[0297] According to the present invention, the bond formed between the functional group (A) of the latex polymer (a) and the functional group Y-H of the silane compound (b) can be selected from disulfide, tetrasulfide, carbonate, urea, thiourea, ester, β-hydroxy ester, thioester, amide, carbamate, enamine, imine, hemiacetal, acetal, hemiketal, ketal, and borate ester. Preferably, the bond formed between the functional group (A) of the latex polymer (a) and the functional group Y-H of the silane compound (b) is selected from ester, β-hydroxy ester, thioester, amide, enamine, and imine.

[0298] The bond formed between the functional group (A) of the latex polymer (a) and the functional group X and / or Y-H of the silane compound (b) can be a thermoreversible bond. As used in this application, the term "thermoreversible bond" refers to a chemical linkage between two functional groups produced by a temperature-dependent equilibrium-based chemical reaction, where the chemical linkage is formed at low temperature but is reversibly driven to break and rearrange as the temperature increases. According to the present invention, the thermoreversible bond can be formed at a temperature of 200 °C or below 200 °C, preferably 180 °C or below 180 °C, more preferably 160 °C or below 160 °C. Generally, the thermoreversible bond can be formed in the temperature range of 25 to 200 °C. According to the present invention, the thermoreversible bond is capable of breaking and rearranging at a temperature equal to or less than 200 °C, preferably equal to or less than 190 °C, more preferably equal to or less than 180 °C to form a thermoreversible bond. Generally, the thermoreversible bond is capable of breaking and rearranging in the temperature range of 25 to 200 °C.

[0299] The functional group (A) of the latex polymer (a) and the functional group of the silane compound (b) used to form the bond can be selected to provide the following combinations:

[0300] - The functional group (A) of the latex polymer (a) can be selected from groups having a carbon-carbon double bond, and the functional group of the silane compound (b) can be selected from groups having a carbon-carbon double bond, (meth)acryloyloxy, and thiol;

[0301] - The functional group (A) of the latex polymer (a) can be selected from carboxylic acid functional groups, and the functional group of the silane compound (b) can be selected from epoxy group, glycidyl group, thiol, hydroxyl group, primary or secondary amino group, isocyanate group, oxazolinyl group, aziridinyl group, imino group, carbodiimide group, diol group, ester group, and acetoxy group;

[0302] - The functional group (A) of the latex polymer (a) can be selected from hydroxyl groups, and the functional group of the silane compound (b) can be selected from carboxylic acid functional groups, isocyanate group, primary or secondary amino group, aldehyde, boric acid, and ester group;

[0303] - The functional group (A) of the latex polymer (a) can be selected from epoxy groups, and the functional group of the silane compound (b) can be selected from carboxylic acid functional groups, hydroxyl groups, and ester groups;

[0304] - The functional group (A) of the latex polymer (a) can be selected from glycidyl, and the functional group of the silane compound (b) can be selected from carboxylic acid functional groups, hydroxyl groups, and ester groups;

[0305] - The functional group (A) of the latex polymer (a) can be selected from acetoacetoxy, and the functional group of the silane compound (b) can be selected from groups having a carbon-carbon double bond, (meth)acryloyloxy, isocyanato, aldehyde, hydrazine, acylhydrazide, and primary or secondary amino groups;

[0306] - The functional group (A) of the latex polymer (a) can be selected from primary or secondary amino groups, and the functional group of the silane compound (b) can be selected from carboxylic acid functional groups, epoxy groups, glycidyl groups, ester groups, and dioxolanone groups;

[0307] - The functional group (A) of the latex polymer (a) can be selected from acetoxy, and the functional group of the silane compound (b) can be selected from acylhydrazide groups and primary or secondary amino groups;

[0308] - The functional group (A) of the latex polymer (a) can be selected from isocyanato, and the functional group of the silane compound (b) can be selected from carboxylic acid functional groups, hydroxyl groups, primary or secondary amino groups, and thiols;

[0309] - The functional group (A) of the latex polymer (a) can be selected from alkoxysilyl, and the functional group of the silane compound (b) can be selected from hydroxyl groups and alkoxysilyl;

[0310] - The functional group (A) of the latex polymer (a) can be selected from alkoxy, and the functional group of the silane compound (b) can be selected from ester groups;

[0311] - The functional group (A) of the latex polymer (a) can be selected from ester groups, and the functional group of the silane compound (b) can be selected from hydroxyl groups, carboxylic acid groups, and ester groups;

[0312] - The functional group (A) of the latex polymer (a) can be selected from dioxolanone groups, and the functional group of the silane compound (b) can be selected from primary or secondary amino groups;

[0313] - The functional group (A) of the latex polymer (a) can be selected from halogen functional groups, and the functional group of the silane compound (b) can be selected from carboxylic acids;

[0314] - The functional group (A) of the latex polymer (a) can be selected from thiol functional groups, and the functional group of the silane compound (b) can be selected from carbon-carbon double bonds, (meth)acryloyloxy, carboxylic acid functional groups, or isocyanato;

[0315] - The functional group (A) of the latex polymer (a) can be selected from hydroxylamine, and the functional group of the silane compound (b) can be selected from aldehydes;

[0316] - The functional group (A) of the latex polymer (a) can be selected from oxazolinyl, and the functional group of the silane compound (b) can be selected from carboxylic acid;

[0317] - The functional group (A) of the latex polymer (a) can be selected from aziridinyl, and the functional group of the silane compound (b) can be selected from carboxylic acid or hydroxyl;

[0318] - The functional group (A) of the latex polymer (a) can be selected from imino, and the functional group of the silane compound (b) can be selected from carboxylic acid;

[0319] - The functional group (A) of the latex polymer (a) can be selected from carbodiimino, and the functional group of the silane compound (b) can be selected from carboxylic acid;

[0320] - The functional group (A) of the latex polymer (a) can be selected from diol group, and the functional group of the silane compound (b) can be selected from carboxylic acid functional group;

[0321] - The functional group (A) of the latex polymer (a) can be selected from hydrazide group, and the functional group of the silane compound (b) can be selected from aldehyde;

[0322] - The functional group (A) of the latex polymer (a) can be selected from aldehyde, and the functional group of the silane compound (b) can be selected from hydroxyl, acetoacetoxy, hydroxylamine or hydrazide group; or

[0323] - The functional group (A) of the latex polymer (a) can be selected from ketone, and the functional group of the silane compound (b) can be selected from hydroxyl.

[0324] A silane compound (c) different from the silane compound (b)

[0325] The polymer latex composition of the present invention may further comprise a silane compound (c) different from the silane compound (b). The silane compound (c) can be selected from compounds of formula III, IV, their oligomers or any combination of the foregoing substances:

[0326]

[0327] wherein Z is a functional group capable of forming a bond with the functional group (A) of the latex polymer (a); R a is a linking group between the functional group Z and the silicon atom or R a is a bond; wherein R b is a hydrolysable group;

[0328]

[0329] wherein Z' is O, S, NH or NR 3 ; wherein R 3 is a straight-chain or branched-chain, substituted or unsubstituted alkyl or alkenyl; R ais a linking group between the functional group Z' and the silicon atom; R b is a hydrolysable group.

[0330] The oligomers of the silane compound (c) can be obtained as described above. Another suitable method for preparing such oligomers is more specifically disclosed in EP3628700A1, specifically in paragraphs

[0026] to

[0030] and

[0048] . Suitable examples of the oligomers of the compounds of formulas III and IV include CoatOSil MP-200 and CoatOSil T-Cure, both of which are commercially available from Momentive Performance Materials Inc. (USA); and Dynsylan VPS4721 and Dynasylan 6490, both of which are commercially available from Evonik Industries AG (Germany).

[0331] The Si-Z' bond can be hydrolysable to form Si-OH groups and Z'-H groups, where the Z'-H group is a functional group capable of forming a bond with the functional group (A) of the latex polymer (a). The functional group Z'-H group can be -OH, -SH, NH2 or NHR 3 ; where R 3 is a straight-chain or branched, substituted or unsubstituted alkyl or alkenyl. The hydrolysis of the Si-Z' bond can be achieved in the presence of water and optionally in the presence of a hydrolysis catalyst as described above. The hydrolysis can be carried out at a temperature of 10 - 100 °C, preferably 15 - 80 °C, most preferably 25 - 70 °C.

[0332] Each hydrolysable R b is independently -H, -OR', -OC(O)CH3, -OCH2OCH3, -SR', -NHR', -NR'2 or -halogen, where R' is a straight-chain C1-C6 alkyl; a branched C3-C6 alkyl or alkenyl, or an aryl. Preferably, each hydrolysable R b is independently -OR' or -halogen, where R' is a straight-chain C1-C6 alkyl; a branched C3-C6 alkyl or alkenyl, or an aryl.

[0333] R a can be a linking group between the functional group Z and the silicon atom. The linking group R a between the functional group Z and the silicon atom can be a straight-chain C1-C 20 alkanediyl, a branched C2-C 20 alkanediyl, a cyclic C3-C 20 alkanediyl or an alkenediyl, or an arylenediyl. Preferably, the linking group R a between the functional group Z and the silicon atom is a straight-chain C1-C 20Alkylene group. Optionally, one or more methylene groups in each of the above alkylene group, alkenylene group and arylenediyl group are replaced by heteroatoms, provided that no heteroatoms are directly bonded to another heteroatom, and no heteroatoms are directly bonded to Si. Preferably, except when Z is a glycidyl group, no heteroatoms are directly bonded to the functional group Z. The heteroatom is preferably oxygen, sulfur or nitrogen, more preferably oxygen.

[0334] R a can be a bond between the functional group Z and the silicon atom, preferably only when the functional group Z is a carbon-carbon double bond.

[0335] According to the present invention, the functional group Z is selected from a carbon-carbon double bond, (meth)acryloxy group, halogen functional group, epoxy group, glycidyl group, mercapto group, hydroxyl group, hydroxylamine group, primary amino group, secondary amino group, isocyanato group, oxazolinyl group, aziridinyl group, imino group, carbodiimide group, diol, ester, acetyloxy group, acetoacetyloxy group, carboxylic acid, dioxolanone group, hydrazide group, aldehyde, boric acid, alkoxysilyl group and ketone. Preferably, the functional group Z is selected from a carbon-carbon double bond, (meth)acryloxy group, halogen functional group, glycidyl group, epoxy group, mercapto group, hydroxyl group, primary amino group, secondary amino group and isocyanato group; more preferably selected from glycidyl group, epoxy group, mercapto group, hydroxyl group, primary amino group and secondary amino group.

[0336] The linking group R between the functional group Z' and the silicon atom a can be a straight-chain or branched C3-C 20 alkylene group. Preferably, the linking group R between the functional group Z' and the silicon atom a can be a straight-chain or branched C3-C 10 alkylene group. Optionally, one or more methylene groups in each of the above alkylene group, alkenylene group and arylenediyl group are replaced by heteroatoms, provided that no heteroatoms are directly bonded to another heteroatom, and no heteroatoms are directly bonded to Si. Preferably, no heteroatoms are directly bonded to the functional group Z'. The heteroatom is preferably oxygen, sulfur or nitrogen, more preferably oxygen.

[0337] Suitable examples of the silane compound (c) may be selected from (3-glycidoxypropyl)trialkoxysilane, β-(3,4-epoxycyclohexylethyltrialkoxysilane), dialkoxy(3-glycidoxypropyl)alkylsilane, 3-glycidoxypropyl dialkylalkoxysilane, 5,6-epoxyhexyltrialkoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrialkoxysilane, (meth)acryloylpropyltrialkoxysilane, (meth)acryloylmethyltrialkoxysilane, 3-aminopropyltrialkoxysilane, 4-aminobutyltrialkoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane, 11-aminoundecyltrialkoxysilane, aminophenyltrialkoxysilane, aminophenoxytrialkoxysilane, N-alkylaminopropyltrialkoxysilane, N-(2-aminoethyl)-3-aminopropyltrialkoxysilane, N-(6-aminohexyl)aminomethyltrialkoxysilane, N-(2-aminoethyl)-11-aminoundecyltrialkoxysilane, N-3-[(amino(polypropyleneglycoloxy)]aminopropyltrialkoxysilane, (3-trialkoxysilylpropyl)diethylenetriamine, 3-(N-allylamino)propyltrialkoxysilane, N-butylaminopropyltrialkoxysilane, tert-butylaminopropyltrialkoxysilane, (N-cyclohexylaminomethyl)trialkoxysilane, (N-cyclohexylaminopropyl)trialkoxysilane, (3-(N-ethylamino)isobutyl)trialkoxysilane, N-methylaminopropyltrialkoxysilane, N-phenylaminomethyltrialkoxysilane, N-phenylaminopropyltrialkoxysilane, N-(2-N-benzylaminoethyl)-3-aminopropyltrialkoxysilane, hydroxymethyltrialkoxysilane, N,N-bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, 3-mercaptopropyltrialkoxysilane, 11-mercaptoundecyltrialkoxysilane, 2,2-dialkoxy-1-thia-2-silacyclopentane, chloromethyltrialkoxysilane, 3-chloropropyltrialkoxysilane, 3-chloroisobutyltrialkoxysilane, 11-chloroundecyltrialkoxysilane, ((chloromethyl)phenethyl)trialkoxysilane, 2-(chloromethyl)allyltrimethoxysilane, 3-bromopropyltrialkoxysilane, 4-bromobutyltrialkoxysilane, 5-bromopentyltrialkoxysilane, 7-bromoheptyltrialkoxysilane, 11-bromoundecyltrialkoxysilane, 3-iodopropyltrialkoxysilane, allyltrialkoxysilane, vinyltrialkoxysilane, 11-allyloxyundecyltrialkoxysilane, allylphenylpropyltrialkoxysilane, 3-butenyltriethoxysilane, 5-hexenyltrialkoxysilane, 7-octenyltrialkoxysilane, styrylethyltrialkoxysilane, 10-undecenyltrialkoxysilane, [(5-bicyclo[2.2.1]hept-2-enyl)ethyl]trialkoxysilane, (5-bicyclo[2.2.1] (hept-2-enyl)trialkoxysilane, [2-(3-cyclohexenyl)ethyl]trialkoxysilane, [2-(3-cyclohexenyl)ethyl]trialkoxysilane, docosenyltrialkoxysilane, 3-(trialkoxysilyl)furan, norbornenyltrialkoxysilane, 3-isocyanatopropyltrialkoxysilane, tris[3-(trialkoxysilyl)propyl]isocyanurate, trialkoxysilylbutyraldehyde, trialkoxysilylundecanal, ureidopropyltrialkoxysilane, cyanomethyl [3-(trialkoxysilyl)propyl]trithiocarbonate, S-(octanoyl)mercapto propyltrialkoxysilane, N-allyl-aza-2,2-dimethoxysilacyclopentane, N-N-butyl-aza-2,2-dimethoxysilacyclopentane, 2,2-dimethoxy-1,6-diaza-2-silacyclooctane, 1-ethyl-2,2-dimethoxy-4-methyl-1-aza-2-silacyclopentane, methacryloxypropyl tris(methoxyethoxy)silane, vinyltriacetoxysilane, vinyltriisopropenoxysilane, and combinations thereof. The alkoxy groups in the corresponding examples of the silane compound (c) are preferably selected from methoxy, ethoxy, propoxy, butoxy, and combinations thereof, more preferably selected from methoxy, ethoxy, and combinations thereof.

[0338] When the silane compound (c) is present in the polymer latex composition of the present invention, the mass ratio of the silane compound (c) to the silane compound (b) can be 1:40 - 40:1, preferably 1:30 - 30:1, more preferably 1:20 - 20:1, even more preferably 1:20 - 10:1, and most preferably 1:20 - 2:1.

[0339] The polymer latex composition of the present invention may contain up to 4.00 parts by weight, preferably up to 3.00 parts by weight, more preferably up to 2.00 parts by weight, even more preferably up to 1.50 parts by weight; most preferably up to 1.00 part by weight of the silane compound (c); based on 100 parts by weight of the latex polymer (a). The silane compound (c) may be present in an amount of up to 4.00 parts by weight, up to 3.50 parts by weight, up to 3.00 parts by weight, up to 2.00 parts by weight, up to 1.50 parts by weight, up to 1.00 part by weight, up to 0.80 part by weight, up to 0.5 part by weight, based on 100 parts by weight of the latex polymer (a).

[0340] The polymer latex composition of the present invention may comprise a total amount of 0.10 to 5.00 parts by weight of a silane compound (b) and a silane compound (c); preferably 0.20 to 5.00 parts by weight; more preferably 0.20 to 4.50 parts by weight; even more preferably 0.20 to 4.00 parts by weight; based on 100 parts by weight of the latex polymer (a). Thus, the total amount in which the silane compound (b) and the silane compound (c) may be present is at least 0.05 part by weight, at least 0.10 part by weight, at least 0.15 part by weight, at least 0.20 part by weight, at least 0.25 part by weight, at least 0.30 part by weight, at least 0.35 part by weight, at least 0.40 part by weight, at least 0.45 part by weight, at least 0.50 part by weight, at least 0.55 part by weight, at least 0.60 part by weight, based on 100 parts by weight of the latex polymer (a). Similarly, the total amount in which the silane compound (b) and the silane compound (c) may be present is at most 5.00 parts by weight, at most 4.50 parts by weight, at most 4.00 parts by weight, 3.80 parts by weight, at most 3.50 parts by weight, at most 3.20 parts by weight, at most 3.00 parts by weight, at most 2.80 parts by weight, at most 2.50 parts by weight, at most 2.2 parts by weight, at most 2.00 parts by weight, at most 1.80 parts by weight, at most 1.50 parts by weight, based on 100 parts by weight of the latex polymer (a). Those skilled in the art will understand that any range defined by the explicitly disclosed lower limit and the explicitly disclosed upper limit is disclosed herein.

[0341] Preparation of the latex composition

[0342] The present invention also relates to a method for preparing the polymer latex composition of the present invention. The method comprises: (i) polymerizing a monomer composition comprising an ethylenically unsaturated monomer used for the latex polymer (a) in an emulsion polymerization method, the ethylenically unsaturated monomer comprising at least one monomer that generates a functional group (A) after polymerization, to obtain a latex comprising latex polymer (a) particles, the latex polymer comprising the functional group (A); and (ii) adding a silane compound (b) selected from the compounds of formula I, II, oligomers thereof or any combination of the foregoing:

[0343]

[0344] wherein X is a functional group capable of forming a bond with the functional group (A) of the latex polymer (a); R 1 is a linking group between the functional group X and the silicon atom or R 1 is a bond; R 2 is independently a hydrolysable group or a non-hydrolysable group; wherein at least one of R 2 is a hydrolysable group, and at least one of R 2 is a non-hydrolysable group;

[0345]

[0346] wherein Y is O, S, NH or NR 3 ; wherein R 3 is a straight-chain or branched-chain, substituted or unsubstituted alkyl or alkenyl; R 1 is a linking group between the functional group Y and the silicon atom; R 2 is independently a hydrolysable group or a non-hydrolysable group; wherein at least one of R 2 is a non-hydrolysable group.

[0347] Optionally, the method includes (iii) adding a silane compound (c) different from the silane compound (b), wherein the silane compound (c) is selected from compounds of formulae III, IV, oligomers thereof or any combination of the foregoing:

[0348]

[0349] wherein Z is a functional group capable of forming a bond with the functional group (A) of the latex polymer (a); R a is a linking group between the functional group Z and the silicon atom or R a is a bond; R b is a hydrolysable group;

[0350]

[0351] wherein Z' is O, S, NH or NR 3 ; wherein R 3 is a straight-chain or branched-chain, substituted or unsubstituted alkyl or alkenyl; R a is a linking group between the functional group Z' and the silicon atom; R b is a hydrolysable group. The silane compound (c) can be added before, during or after the addition of the silane compound (b).

[0352] The monomer composition for obtaining the latex polymer (a) particles as described above can be used; the functional group (A) of the polymer latex (a); the functional group X of the silane compound (b); the functional group Z of the silane compound (c); the hydrolysable groups R 2 and R b ; the non-hydrolysable groups R 2 , the linking groups R 1 and R a , the relative amounts of the silane compounds (b) and (c); and all variations in the mass ratio of the silane compounds (b) and (c).

[0353] Compounding latex compositions and methods for preparing dipped molded articles and elastomeric films

[0354] The present invention also relates to the use of the polymer latex composition of the present invention or the polymer latex composition prepared by the method of the present invention for the preparation of dipped molded articles, elastomeric films, self-supporting elastomeric films or articles, or for coating or impregnating substrates. Preferably, the substrate is a textile substrate.

[0355] Furthermore, the present invention relates to a compounded polymer latex composition suitable for the production of dipped molded articles. The compounded latex composition of the present invention comprises the polymer latex composition of the present invention or the polymer latex composition prepared by the method of the present invention.

[0356] In order to obtain reproducible and good physical film properties, it is recommended to adjust the pH of the compounded polymer latex composition to a range of pH 7 to 11, preferably 8 to 10, more preferably 9 to 10, using a pH regulator, for dipping to produce thin disposable gloves. For the production of reusable gloves, with or without a carrier, it is recommended to adjust the pH of the compounded polymer latex composition to a range of pH 8.0 to 12.0, preferably 9.0 to 11.5. The pH value of the compounded polymer latex composition can be adjusted using a pH regulator selected from sodium hydroxide, potassium hydroxide and ammonia solution. Preferably, potassium hydroxide can be used to adjust the pH value of the polymer latex composition.

[0357] Optionally, the compounded polymer latex composition comprises adjuvants selected from sulfur vulcanizing agents, vulcanization accelerators, free radical initiators, pigments and combinations thereof. The compounded latex composition may further comprise polyvalent cations and / or silica-based fillers. Suitable silica-based fillers include pyrogenic silica and precipitated silica.

[0358] A conventional vulcanization system can be added to the compounded polymer latex composition for the dipping molding method according to the present invention, for example, sulfur combined with accelerators (such as thiurams, urethanes and zinc oxide) to make it curable. Alternatively or additionally, a crosslinking agent component can be added, such as a polyvalent cation or other polyfunctional organic compound suitable for reacting with the functional groups on the latex particles to achieve chemical crosslinking. Preferably, polyvalent cations and / or silica-based fillers can be added to the latex composition of the present invention. Suitable polyvalent cations include metal oxides, preferably zinc oxide, magnesium oxide, iron oxide.

[0359] However, a particular advantage of the present invention is that the compounded latex composition of the present invention can be free of sulfur vulcanizing agents and accelerators for sulfur vulcanization, and the polymer latex compound of the present invention can still be cured to provide an impregnated molded article having desired tensile properties. A polyvalent cation such as ZnO is preferably used as an additional crosslinking agent component to appropriately adjust the mechanical properties of a very thin elastomeric film having a film thickness of at most 0.1 mm, preferably 0.01 to 0.1 mm, more preferably 0.03 to 0.08 mm.

[0360] Suitably, based on the total weight of the latex polymer (a) particles, the silane compound (b) and the silane compound (c) if present, the polyvalent cation can be present in an amount of up to 20% by weight.

[0361] In certain heavy-duty applications such as industrial gloves, in addition to the self-crosslinking nature of the polymer latex of the present invention, it may be advantageous to use a conventional sulfur vulcanization system as described above in order to further increase the mechanical strength of the impregnated molded article.

[0362] The present invention relates to a method for manufacturing an impregnated molded article. The method comprises (a) providing a compounded latex composition according to the present invention. The method further comprises (b) immersing a mold having the desired shape of the final article into a coagulant bath containing a metal salt solution. The coagulant is typically used as a solution in water, an alcohol or a mixture thereof. As specific examples of the coagulant, the metal salt can be a metal halide such as calcium chloride, magnesium chloride, barium chloride, zinc chloride and aluminum chloride; a metal nitrate such as calcium nitrate, barium nitrate and zinc nitrate; a metal sulfate such as calcium sulfate, magnesium sulfate and aluminum sulfate; and an acetate such as calcium acetate, barium acetate and zinc acetate. Calcium chloride and calcium nitrate are most preferred. The coagulant solution may contain additives to improve the wetting behavior of the mold.

[0363] The method for preparing an impregnated molded article further comprises (c) removing the mold from the coagulant bath and optionally drying the mold; (d) immersing the mold treated in steps (b) and (c) into the compounded latex composition of step (a); and (e) coagulating the latex film on the surface of the mold. The latex film can be obtained by multiple dipping steps, particularly two sequential dipping steps.

[0364] Thereafter, the method for preparing an impregnated molded article further comprises (f) removing the latex-coated mold from the compounded latex composition and optionally immersing the latex-coated mold into a water bath. The latex-coated mold can be immersed into the water bath in order to extract, for example, polar components from the composition and to wash the coagulated latex film.

[0365] Subsequently, the latex-coated mold (g) is optionally dried, preferably at a temperature below 80°C. Finally, the method for preparing an impregnated molded article includes (h) heat-treating the latex-coated mold obtained from step (e) or (f) at a temperature of 40°C to 180°C, such as at a temperature of 40°C to 160°C, or 40°C to 150°C, or 40°C to 130°C; and / or exposing the latex-coated mold obtained from step (e) or (f) to UV radiation. Then, the final latex film (i) is removed from the mold. The duration of the heat treatment will depend on the temperature and is typically between 1 minute and 60 minutes. The higher the temperature, the shorter the required treatment time.

[0366] The present invention also relates to a method for producing a continuous elastomeric film. The method includes (A) providing a polymer latex composition according to the present invention or a polymer latex composition prepared by the method according to the present invention; (B) forming a continuous polymer film from the aqueous polymer latex composition, for example, by a casting method. The method for producing a continuous elastomeric film further includes (C) optionally drying the continuous polymer film obtained in step (B); and (D) heat-treating the continuous polymer film obtained in step (B) or (C) at a temperature of 40°C to 180°C, preferably for 20 minutes or less, to form a continuous elastomeric film; and / or UV treatment. Optionally, the method for producing a continuous elastomeric film further includes (E) winding the continuous elastomeric film obtained in step (D) into a roll.

[0367] As an alternative, a cutting and sealing process can be used. The present invention relates to a method for manufacturing an elastomeric article, which is carried out by the following steps: aligning two separate continuous elastomeric films obtained by the method for producing a continuous elastomeric film as described above; cutting the aligned continuous elastomeric films into a preselected shape to obtain two superimposed layers of elastomeric films in the preselected shape; and joining the superimposed layers of elastomeric films together at at least a preselected portion of the periphery of the superimposed layers to form an elastomeric article.

[0368] The joining together can be carried out by using thermal measures, preferably selected from heat sealing and welding or by gluing or a combination of heating and gluing. The cutting can be carried out by a heatable template cutting device or a laser cutting machine, thereby providing the preselected shape, and the cutting device can be heated in the portion in contact with the elastomeric film, where the films are joined together, so as to simultaneously cut the elastomeric film into the preselected shape and heat-seal the preselected portion of the periphery of the superimposed elastomeric films.

[0369] In addition, the present invention also relates to a method for repairing or reconditioning an elastomeric film or an article comprising the elastomeric film, the method being carried out by the following steps: a) providing a film or an article comprising one or more elastomeric films, the one or more elastomeric films having at least two surfaces to be reconnected, b) rejoining the at least two surfaces of the one or more elastomeric films and heating or annealing the one or more elastomeric films while maintaining the rejoined surfaces of the damaged film in close contact at a temperature of 40 to 200 °C, preferably 60 to 175 °C, more preferably 95 to 135 °C, wherein c) the elastomeric film is made of a polymer latex composition according to the present invention or prepared by the method according to the present invention.

[0370] The present invention relates to an article prepared by using the polymer latex composition of the present invention or a polymer latex composition prepared by the method of the present invention or the compounded latex composition of the present invention. The article may be selected from surgical gloves, examination gloves, industrial gloves, household gloves, disposable gloves, textile-supported gloves, catheters, elastomeric sleeves, condoms, balloons, tubes, dental dams, aprons and preformed gaskets.

[0371] The present invention will be further illustrated with reference to the following examples. Examples

[0372] In the examples, a carboxylated nitrile rubber (XNBR) grade latex commercially available from Synthomer Sdn. Bhd (Malaysia) was used.

[0373] Crosslinking agent 1 [3-(2,3-epoxypropoxy)-propyl]-trimethoxysilane

[0374] Crosslinking agent 2 [3-(2,3-epoxypropoxy)-propyl]-methyldiethoxysilane

[0375] Preparation of latex composition for cured film

[0376] Latex composition preparation A (pot life) - latex without accelerator

[0377] Under stirring, compounding materials zinc oxide (ZnO) and titanium dioxide (TiO2) and crosslinking agent 1 or crosslinking agent 2 were added to the latex polymer. The zinc oxide and titanium dioxide used were dispersions. The composition was stirred and the pH was adjusted to pH 9.5 - 10.0 by adding 5% aqueous potassium hydroxide solution, diluted to a total solids content of 18%, and cured by continuous stirring at 25 (±2) °C for at least 16 hours. A compounded latex from latex composition preparation A was obtained. Then, in the next step, immediately before model dipping, the compounded latex was used (after 0 months) or stored at 25 °C (±2) for 33 days (after 1 month). A long elapsed time of more than 1 month was selected to demonstrate the robustness of the crosslinking agent used.

[0378] Preparation B of latex composition (shelf life) - latex without accelerator

[0379] Preparation B of latex composition is exactly similar to Preparation A of latex composition, except that crosslinking agent 1 and crosslinking agent 2 are pre-added before adding the compounding materials to the corresponding latex. The latex with pre-added crosslinking agent 1 and 2 (after 0 months) is used immediately or stored at 25 (±2) °C for 89 days (after 3 months) and 186 days (after 6 months). After a period of time, the compounding materials are added and cured in the usual manner. The compounded latex from Preparation B of latex composition is obtained. The long elapsed times of 3 months and 6 months are selected to demonstrate the robustness of the pre-added crosslinking agents in the latex.

[0380] Preparation C of latex composition (sulfur-accelerator nitrile latex) - sulfur-vulcanized latex

[0381] Preparation C of latex composition is exactly similar to Preparation A of latex composition, except that crosslinking agent 1 and crosslinking agent 2 are not used. Instead, a sulfur-vulcanization system containing an accelerator and sulfur is used. A sulfur dispersion and an accelerator dispersion, zinc diethyldithiocarbamate (ZDEC), are added to the latex, and the latex is prepared and used immediately.

[0382] The compositions of Preparations A, B, and C of latex composition are summarized as Examples (Ex.) and Comparative Examples (CE) in Table 1, in parts per hundred rubber (phr).

[0383] Table 1: Composition of latex used in compounding

[0384]

[0385]

[0386] Model dipping

[0387] Impregnation is carried out manually or using an automatic film, spatula and glove dipping machine (commercially available from Kendek Products Sdn Bhd., Malaysia). The lining gloves are mounted onto a model, and the model is conditioned in an air-circulation oven at 70 °C and then immersed in a coagulant solution containing an aqueous solution (containing 18 - 20 wt% calcium nitrate and 2 - 3 wt% calcium carbonate) at 60 °C for 1 second. The model is then placed in an oven set at 75 - 85 °C for a certain time and then immersed in the corresponding latex composition A, B or C at a model temperature of 60 - 65 °C for a set time, taken out and kept rotating to avoid the formation of droplets, thereby obtaining a latex-impregnated model. The latex-impregnated model is then gelled in an oven at 100 °C for 1 minute to form film-beaded and rinsed in a deionized water rinsing tank at 50 - 60 °C for 1 minute, and then cured in an oven at 95 °C or 120 °C for 20 minutes. Finally, the cured latex gloves are manually peeled off the model. Before other physical tests, the gloves are conditioned in a climate chamber at 23 (±2) °C and 50% (±5) relative humidity for at least 16 hours.

[0388] Determination of tensile properties (ASTM D6319 and EN 455)

[0389] The tensile properties of the final gloves or films are tested according to the American Society for Testing and Materials (ASTM) and European Standards (EN) as specified in the test procedures ASTM D6319 and EN455. Dumbbell-shaped samples are cut from the palm area of the gloves or films prepared from each latex mixture. Before testing on an extensometer, the unaged and aged samples ( "aged" means specimens placed in an oven at 100 °C for 22 hours before testing tensile properties) are conditioned at 23 ± 2 °C and 50 ± 5% relative humidity for 24 hours. The film thickness (mm) is measured, where typical film thickness values are between 0.055 - 0.075 mm. The reported tensile strength (TS) corresponds to the maximum tensile stress determined when the sample is stretched to break. The elongation at break (EB) corresponds to the elongation at which break occurs. While the moduli 100, 300 and 500 correspond to the tensile stresses determined when the sample is stretched at 100, 300 and 500% elongation. The reported TS, EB, moduli 100, 300 and 500 are measured according to the ASTM D6319 test procedure. Finally, the breaking force (FAB) corresponding to the force at which break occurs is measured according to EN455.

[0390] The prepared latex compositions A, B or C are used immediately or stored for a period of elapsed time and cured at 95 °C or 120 °C, having a tensile strength (TS) of 20 MPa or higher, an elongation at break (EB) of 500 - 750%, and a 100% modulus (M100) of 3 - 10 MPa.

[0391] Determination of fatigue durability

[0392] Use scissors to cut the test model dipped glove in a straight line from the crotch between the index finger and middle finger to the cuff line below the thumb. Keep the cut of the thumb and finger samples along the outer edge to the point at the tip of the thumb. Open the sample and connect the tip of the index finger to the top jaws of the automatic stress and relaxation device, and close the clamp. Connect the lower area of the sample between the jaws at the lower clamp and close the clamp. Attach the free "wing" of the sample to the side bar of the test device by using masking tape. Place the test device in a beaker containing deionized water adjusted to pH 4 with a 5% citric acid solution such that the crotch between the thumb and index finger is completely immersed in the acidic aqueous solution. Set the test device to zero (0) and start the test. The test is carried out at 25 °C. The measurement automatically stops when the sample breaks, and the number of cycles required to reach the break point is recorded. Repeat the test 5 times to calculate the average value, where each test uses fresh citric acid solution. The reported durability (in minutes) corresponds to the average number of cycles (the average number of cycles required to cause the sample to fail) divided by 267 (the total number of cycles per hour). Stop the test after 5 hours or until failure.

[0393] Determination of the applicable period and shelf life according to fatigue durability

[0394] The applicable period and shelf life refer to the available time period during which the obtained cured film can meet specific criteria, i.e., where the fatigue durability is preferably 60 minutes or longer. The specific criteria will be further described below.

[0395] Specifically, the applicable period refers to the available period of the compounded latex, i.e., from latex compounding and curing to the production of the cured film for latex composition preparation (A); where the fatigue durability is 60 min or longer. After latex compounding and curing at 0 days (not stored and used immediately) and 33 days (1 month), the fatigue durability of the composition preparation (A) is compared.

[0396] Specifically, the shelf life refers to the available period of the latex containing pre-added crosslinking agent 1 or 2, i.e., from the pre-addition of crosslinking agent 1 or 2 to the production of the cured film for latex composition preparation (B); where the fatigue durability is 60 min or longer. After 0 days (no storage and used immediately), 89 days (3 months), and 186 days (6 months) of pre-adding crosslinking agent 1 or 2, the fatigue durability of the composition preparation (B) is compared.

[0397] Measure and summarize the tensile data of the examples and comparative examples prepared as described above in Tables 2 to 11.

[0398]

[0399]

[0400]

[0401]

[0402] In Tables 2 to 5, a comparison between Crosslinking Agent 1 and different contents of Crosslinking Agent 2 for the curing of the latex composition at 70, 95, and 120 °C for 20 minutes is shown.

[0403] Tables 2 and 3 show the tensile property results of the compounded latex after 0 months, and it can be seen that using Crosslinking Agent 2 is comparable to Crosslinking Agent 1 from low to high curing temperatures (70 - 120 °C). The amount of Crosslinking Agent 2 can be as low as 0.2 phr or as high as 4.0 phr without significant deterioration of the tensile properties.

[0404] Tables 4 and 5 show the tensile property results of the compounded latex after 1 month, and it can be seen that even after 1 month, a trend similar to that of the compounded latex after 0 months is observed.

[0405]

[0406]

[0407]

[0408] In Tables 6 to 11, a comparison between the sulfur-vulcanized polymer latex composition and the polymer latex composition using pre-added Crosslinking Agent 1 or Crosslinking Agent 2 (pre-added for 0 to 6 months) is shown, which is cured at 95 °C and 120 °C for 20 minutes. It can be seen that using Crosslinking Agent 1 and Crosslinking Agent 2 has slightly lower TS but higher EB than the sulfur-vulcanized polymer latex at low (95 °C) and high (120 °C) curing temperatures.

[0409] Surprisingly, the tensile properties of the polymer latexes without accelerators (CE2 and Ex.2) improve after aging. Compared with the sulfur-vulcanized polymer latex, both polymer latexes without accelerators improve in terms of TS and EB, where the aged TS value is comparable to that of the sulfur-vulcanized polymer latex.

[0410] Nevertheless, in the case of the latex without accelerators, the polymer latex cured with Crosslinking Agent 2 at 0.6 phr is comparable to that cured with Crosslinking Agent 1.

[0411] Table 12: Durability results of the compounded latex compositions of Ex.1 - 4 and CE2 after 0 months and 1 month.

[0412]

[0413] Table 13: Durability results of Composition CE1, Composition Ex.2, and CE2; after 0 months, 3 months, and 6 months, with crosslinker 1 or 2 pre-added

[0414]

[0415] In Table 12, the durability fatigue results of Example CE2 with crosslinker 1 (0.6 phr) and Examples 1 to 4 with an increased crosslinker 2 content (0.2 - 4.0 phr) are shown. Surprisingly, after 1 month, cured at 70 °C and 95 °C for 20 minutes, all examples met the preferred fatigue durability of 1 hour or longer, except for Example 4 with 4.0 phr crosslinker 2. It can be seen that high fatigue durability was maintained even after 1 month. Therefore, the pot life of the selective composition containing crosslinker 1 or crosslinker 2 can be up to 1 month, where the content of crosslinker 2 can be as low as 0.2 parts.

[0416] In Table 13, the durability fatigue results of Examples CE1, CE2, and Ex.2 are shown. CE1 is a sulfur-vulcanized polymer latex composition that is compounded and used immediately without pre-addition. CE2 and Ex.2 are polymer latex compositions without accelerator with crosslinker 1 or crosslinker 2 pre-added (0 - 6 months), and then compounded and used. For CE1, the sulfur-vulcanized polymer latex composition requires a high curing temperature of 120 °C to achieve high durability. For CE2 and the polymer latex composition Ex.2 without accelerator, a significant reduction in the fatigue durability of CE2 using crosslinker 1 was observed. For CE2, after pre-adding for 3 months and curing at a low temperature of 95 °C, the preferred fatigue durability of 1 hour or longer could not be achieved. In contrast, Ex.2 using only crosslinker 2 could maintain its high fatigue durability for up to 6 months, cured at 95 °C or 120 °C for 20 minutes.

Claims

1. A polymer latex composition for preparing an elastomeric film, comprising: (a) latex polymer particles obtained by free radical emulsion polymerization of a composition comprising ethylenically unsaturated monomers, the latex polymer comprising a functional group (A); and (b) a silane compound selected from compounds of formula I, II, their oligomers or any combination of the foregoing: Wherein X is a functional group capable of forming a bond with the functional group (A) of the latex polymer (a); R 1 is a linking group between the functional group X and the silicon atom or R 1 is a bond; R 2 is independently a hydrolysable group or a non-hydrolysable group; wherein at least one of R 2 is a hydrolyzable group, and at least one of R 2 is a non-hydrolyzable group; Wherein Y is O, S, NH or NR 3 ; wherein R 3 is a straight-chain or branched-chain, substituted or unsubstituted alkyl or alkenyl; R 1 is a linking group between the functional group Y and the silicon atom; R 2 is independently a hydrolysable group or a non-hydrolysable group; wherein at least one of R 2 is a non-hydrolyzable group.

2. The polymer latex composition according to claim 1, wherein the Si-Y bond is hydrolyzable to form Si-OH groups and Y-H groups, wherein the Y-H group is a functional group capable of forming a bond with the functional group (A) of the latex polymer (a).

3. The polymer latex composition according to any one of the preceding claims, comprising from 0.10 to 4.00 parts by weight; preferably from 0.20 to 2.00 parts by weight, more preferably from 0.20 to 1.80 parts by weight, even more preferably from 0.20 to 1.50 parts by weight; most preferably from 0.40 to 1.50 parts by weight of the silane compound (b); based on 100 parts by weight of the latex polymer (a).

4. The polymer latex composition according to any one of the preceding claims, wherein each non-hydrolyzable R 2 is independently a linear C1-C 20 alkyl group, a linear C2-C 20 alkenyl group, a branched or cyclic C3-C 20 alkyl or alkenyl or aryl group, preferably a linear C1-C 20 alkyl group.

5. The polymer latex composition according to any one of the preceding claims, wherein each hydrolysable R 2 is independently -H, -OR', -OC(O)CH3, -OCH2OCH3, -SR', -NHR', -NR'2, or halogen, where R' is a straight-chain C1-C6 alkyl, branched C3-C6 alkyl or alkenyl, or aryl; Preferably, each hydrolyzable R 2 is independently —OR′ or —halogen, where R′ is a straight-chain C1-C6 alkyl, branched C3-C6 alkyl or alkenyl, or aryl.

6. The polymer latex composition according to any one of the preceding claims, wherein the linking group R between the functional group X and the silicon atom 1 is a linear C1-C 20 alkanediyl, a branched C2-C 20 alkanediyl, a cyclic C3-C 20 alkanediyl or an alkenediyl, or an arylenediyl; preferably a linear C1-C 20 alkanediyl, Wherein optionally one or more methylene groups in each of the above alkylene diyl, alkenylene diyl and arylene diyl are replaced by heteroatoms, provided that no heteroatoms are directly bonded to another heteroatom and no heteroatoms are directly bonded to Si, wherein the heteroatoms are preferably oxygen, sulfur or nitrogen, more preferably oxygen.

7. The polymer latex composition according to any one of the preceding claims, wherein the linking group R between the functional group Y and the silicon atom 1 is a straight-chain or branched C3-C 20 alkanediyl; preferably a straight-chain or branched C3-C 10 alkanediyl, wherein optionally one or more methylene groups in each of the above alkanediyls are replaced by heteroatoms, provided that no heteroatoms are directly bonded to another heteroatom and no heteroatoms are directly bonded to Si, wherein the heteroatom is preferably oxygen, sulfur or nitrogen, more preferably oxygen.

8. The polymer latex composition according to any one of the preceding claims, wherein the functional group X is selected from carbon-carbon double bonds, (meth)acryloxy groups, halogen functional groups, epoxy groups, glycidyl groups, thiols, hydroxyl groups, hydroxylamines, primary amino groups, secondary amino groups, isocyanato groups, oxazolinyl groups, aziridinyl groups, imino groups, carbodiimide groups, diols, esters, acetoxy groups, acetoacetoxy groups, carboxylic acids, dioxolane ketones, hydrazide groups, aldehydes, boric acids, alkoxysilyl groups and ketones; preferably selected from carbon-carbon double bonds, (meth)acryloxy groups, halogen functional groups, glycidyl groups, epoxy groups, thiols, hydroxyl groups, primary amino groups, secondary amino groups and isocyanato groups; more preferably selected from glycidyl groups, epoxy groups, thiols, hydroxyl groups, primary amino groups and secondary amino groups.

9. The polymer latex composition according to any one of the preceding claims, wherein the silane compound (b) is selected from (3-glycidoxypropyl)methyldiethoxysilane, (3-glycidoxypropyl)dimethyl ethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane, 3-aminopropyldimethylmethoxysilane, 3-aminopropyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldiisopropylethoxysilane, 4-amino-3,3-dimethylbutylmethyldimethoxysilane, (1-aminopropan-2-yl)ethoxydimethylsilane, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminoisobutyldimethylmethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminoisobutylmethyldimethoxysilane, (N-cyclohexylaminomethyl)methyldiethoxysilane, N-methylaminopropylmethyldimethoxysilane, (phenylaminomethyl)methyldimethoxysilane, 3-(N,N-dimethylaminopropyl)aminopropylmethyldimethoxysilane, (3-acryloxypropyl)methyldiethoxysilane, (3-acryloxypropyl)methyldimethoxysilane, (3-acryloxypropyl)dimethylmethoxysilane, (methacryloxymethyl)methyldiethoxysilane, (methacryloxymethyl)methyldimethoxysilane, (methacryloxymethyl)dimethylethoxysilane, (methacryloxypropyl)dimethylmethoxysilane, allylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldimethoxysilane, vinyldimethylethoxysilane, (5-bicyclo[2.2.1]hept-2-enyl)methyldiethoxysilane, (5-bicyclo[2.2.1]hept-2-enyl)dimethylethoxysilane, (5-bicyclo[2.2.1) (hept-2-enyl)methyldichlorosilane, (mercaptomethyl)methyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, chloromethyldimethylethoxysilane, ((chloromethyl)phenyl ethyl)methyldimethoxysilane, 3-chloropropyldimethylethoxysilane, 3-chloropropyldimethylmethoxysilane, 3-chloro-isobutyldimethylmethoxysilane, chloromethyldimethylethoxysilane, 3-chloropropylmethyldiisopropoxysilane, (3-iodopropyl)methyldiisopropoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 1,1-dimethyl-1-sila-2-oxacyclohexane, 2,2,4-trimethyl-1-oxa-4-aza-2-silacyclohexane, 1-decyl-1-methyl-1-sila-2-oxacyclohexane, 2,2,4-trimethyl-1-thia-2-silacyclopentane, N-(2-aminoethyl)-2,2,4-trimethyl-1-aza-2-silacyclopentane, N-(3-aminopropyldimethylsilyl)-aza-2,2-dimethyl-2-silacyclopentane, (N,N-dimethylaminopropyl)-aza-2-methyl-2-methoxysilacyclopentane, and combinations thereof.

10. The polymer latex composition according to any one of the preceding claims, wherein the functional group (A) of the latex polymer (a) is selected from carbon-carbon double bonds, carboxylic acids, hydroxyl groups, epoxy groups, glycidyl groups, acetoacetoxy groups, primary or secondary amino groups, acetoxy groups, isocyanato groups, alkoxysilyl groups, alkoxys, dioxolane ketones, halogen functional groups, thiols, hydroxylamines, oxazolinyl groups, aziridinyl groups, imino groups, carbodiimide groups, diols, esters, hydrazide groups, aldehydes, ketones and combinations thereof; preferably selected from carbon-carbon double bonds, carboxylic acids, halogen functional groups, epoxy groups, glycidyl groups, thiols, hydroxyl groups, primary or secondary amino groups, isocyanato groups and combinations thereof; more preferably selected from carboxylic acids.

11. The polymer latex composition according to any one of the preceding claims, wherein the bond formed between the functional group (A) of the latex polymer (a) and the functional group X of the silane compound (b) is selected from disulfide, tetrasulfide, carbonate, urea, thiourea, ester, β-hydroxy ester, thioester, β-hydroxy amine, β-hydroxy thioether, amide, carbamate, enamine, imine, hemiacetal, acetal, hemiketal, ketal, borate, siloxane, oxime, acylhydrazone, aldol, thiuram disulfide and trithiocarbonate, preferably ester, β-hydroxy ester, thioester, amide, enamine and imine.

12. The polymer latex composition according to any one of the preceding claims, wherein the bond formed between the functional group (A) of the latex polymer (a) and the functional group Y-H of the silane compound (b) is selected from disulfide, tetrasulfide, carbonate, urea, thiourea, ester, β-hydroxy ester, thioester, amide, carbamate, enamine, imine, hemiacetal, acetal, hemiketal, ketal and borate, preferably ester, β-hydroxy ester, thioester, amide, enamine and imine.

13. The polymer latex composition according to any one of the preceding claims, further comprising a silane compound (c) different from the silane compound (b), wherein the silane compound (c) is selected from compounds of formula III, IV, their oligomers or any combination of the foregoing: wherein Z is a functional group capable of forming a bond with the functional group (A) of the latex polymer (a); R a is a linking group between the functional group Z and the silicon atom or R a is a bond; R b is a hydrolysable group; wherein Z' is O, S, NH or NR 3 ; wherein R 3 is a straight-chain or branched-chain, substituted or unsubstituted alkyl or alkenyl; R a is a linking group between the functional group Z' and the silicon atom; R b is a hydrolyzable group.

14. The polymer latex composition according to claim 13, wherein the Si-Z' bond is hydrolyzable to form an Si-OH group and a Z'-H group, wherein the Z'-H group is a functional group capable of forming a bond with the functional group (A) of the latex polymer (a).

15. The polymer latex composition according to claim 13 or 14, wherein each hydrolysable R b is independently -H, -OR', -OC(O)Me, -OCH2OCH3, -SR', -NHR', -NR'2, -halogen, where R' is a straight-chain C1-C6 alkyl, branched C3-C6 alkyl or alkenyl, or aryl; wherein preferably each hydrolysable R b is independently -OR' or -halogen, where R' is a straight-chain C1-C6 alkyl, branched C3-C6 alkyl or alkenyl, or aryl; wherein the linking group R between the functional group Z and the silicon atom a is a linear C1-C 20 alkanediyl, a branched C2-C 20 alkanediyl, a cyclic C3-C 20 alkanediyl or an alkenediyl, or an arylenediyl; preferably a linear C1-C 20 alkanediyl; wherein optionally one or more methylene groups in each of the above alkanediyl, alkenediyl and arylenediyl are replaced by heteroatoms, provided that no heteroatoms are directly bonded to another heteroatom and no heteroatoms are directly bonded to Si, wherein the heteroatom is preferably oxygen, sulfur or nitrogen, more preferably oxygen; wherein the linking group R between the functional group Z' and the silicon atom a is a straight-chain or branched C3-C 20 alkanediyl; preferably a straight-chain or branched C3-C 10 alkanediyl; wherein optionally one or more methylene groups in each of the above alkanediyl, alkenediyl and arylenediyl groups are replaced by heteroatoms, provided that no heteroatoms are directly bonded to another heteroatom and no heteroatoms are directly bonded to Si, wherein the heteroatoms are preferably oxygen, sulfur or nitrogen, more preferably oxygen; and wherein the functional group Z is selected from carbon-carbon double bond, (meth)acryloyloxy, halogen functional group, epoxy group, glycidyl group, thiol, hydroxyl group, hydroxyl amine, primary amino group, secondary amino group, isocyanato, oxazolinyl, aziridinyl, imino, carbodiimide group, diol, ester, acetoxy, acetoacetoxy, carboxylic acid, dioxolanone, hydrazide group, aldehyde, boric acid, alkoxysilyl and ketone; preferably selected from carbon-carbon double bond, (meth)acryloyloxy, halogen functional group, epoxy group, glycidyl group, thiol, hydroxyl group, primary amino group, secondary amino group and isocyanato; more preferably selected from glycidyl group, epoxy group, thiol, hydroxyl group, primary amino group and secondary amino group.

16. The polymer latex composition according to any one of claims 13 to 15, wherein the mass ratio of the silane compound (c) to the silane compound (b) is 1:40 to 40:1, preferably 1:20 to 2:

1.

17. The polymer latex composition according to any one of claims 13 to 16, which comprises a total of 0.10 to 5.00 parts by weight; preferably 0.20 to 5.00 parts by weight; more preferably 0.20 to 4.50 parts by weight, even more preferably 0.20 to 4.00 parts by weight of the silane compound (b) and the silane compound (c); based on 100 parts by weight of the latex polymer (a).

18. The polymer latex composition according to any one of the preceding claims, wherein the monomer composition for obtaining the latex polymer (a) particles comprises: (i) 15 to 99% by weight of a conjugated diene; (ii) 1 to 80% by weight of a monomer selected from ethylenically unsaturated nitrile compounds; (iii) 0 to 10% by weight of an ethylenically unsaturated compound containing a functional group (A) different from (i) and (ii); (iv) 0 to 80% by weight of a vinyl aromatic monomer; and (v) 0 to 65% by weight of an alkyl ester of an ethylenically unsaturated acid; the weight percentages being based on the total weight of the ethylenically unsaturated monomers in the monomer composition.

19. The polymer latex composition according to claim 18, wherein (i) the conjugated diene is selected from 1,3 - butadiene, isoprene, 2,3 - dimethyl - 1,3 - butadiene, 2 - ethyl - 1,3 - butadiene, 1,3 - pentadiene, 3,7,11 - trimethyl - 1,3,6,10 - dodecatetraene, 7,11 - dimethyl - 3 - methylene - 1,6,10 - dodecatriene, 7 - methyl - 3 - methylene - 1,6 - octadiene and combinations thereof; (ii) the ethylenically unsaturated nitrile compound is selected from (meth)acrylonitrile, α - cyanoethyl acrylonitrile, fumaronitrile, α - chloronitrile and combinations thereof; (iii) the ethylenically unsaturated compound containing a functional group (A) different from (i) and (ii) may be selected from (iii 1) an ethylenically unsaturated compound having at least two different ethylenically unsaturated groups, preferably selected from allyl (meth)acrylate, vinyl (meth)acrylate and combinations thereof; (iii2) an ethylenically unsaturated acid and its salts, preferably selected from (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, ethylenically unsaturated sulfonic acid, ethylenically unsaturated phosphoric acid, polycarboxylic anhydride, polycarboxylic partial ester monomer, carboxyalkyl ester of an ethylenically unsaturated acid and combinations thereof; (iii 3) a hydroxyl - functional ethylenically unsaturated compound, preferably selected from allyl alcohol, vinyl alcohol, N - hydroxymethyl acrylamide, 1 - penten - 3 - ol, hydroxyalkyl ester of an ethylenically unsaturated acid and combinations thereof; (iii4) an epoxy - functional ethylenically unsaturated compound, preferably selected from vinyl cyclohexene oxide, limonene oxide, 2 - ethyl (3',4' - epoxyheptyl) (meth)acrylate, (6',7' - epoxyheptyl) (meth)acrylate, allyl 3,4 - epoxyheptyl ether, 6,7 - epoxyheptyl allyl ether, vinyl 3,4 - epoxyheptyl ether, 3,4 - epoxyheptyl vinyl ether, 6,7 - epoxyheptyl vinyl ether, 3 - vinyl cyclohexene oxide, 2 - (3,4 - epoxycyclohexyl) methyl (meth)acrylate, 3,4 - epoxy - 1 - butene, 1,2 - epoxy - 5 - hexene, 4 - vinyl - 1 - cyclohexene 1,2 - epoxide, 2 - methyl - 2 - vinyl oxirane, 3,4 - epoxy - 1 - cyclohexene and combinations thereof, (iii 5) glycidyl-functionalized ethylenically unsaturated compounds, preferably selected from glycidyl (meth)acrylate, allyl glycidyl ether, vinyl glycidyl ether, 2-ethyl glycidyl (meth)acrylate, 2-(n-propyl) glycidyl (meth)acrylate, 2-(n-butyl) glycidyl (meth)acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl glycidyl methacrylate, glycidyl propargyl ether and combinations thereof; (iii 6) acetoacetoxy-functionalized ethylenically unsaturated compounds, preferably selected from ethyl acetoacetoxy (meth)acrylate, propyl acetoacetoxy (meth)acrylate, allyl acetoacetate, butyl acetoacetoxy (meth)acrylate, 2,3-bis(acetoacetoxy)propyl (meth)acrylate, acetoacetoxy(methyl)ethyl (meth)acrylate, aminoethyl acetoacetoxy (meth)acrylate, 3-(methacryloyloxy)-2,2-dimethylpropyl 3-oxobutyrate, 3-(methacryloyloxy)-2,2,4,4-tetramethylcyclobutyl 3-oxobutyrate, 3-(methacryloyloxy)-2,2,4-trimethylpentyl 3-oxobutyrate, 1-(methacryloyloxy)-2,2,4-trimethylpent-3-yl 3-oxobutyrate, (4-(methacryloxymethyl)cyclohexyl)methyl 3-oxobutyrate and combinations thereof; (iii 7) ethylenically unsaturated compounds with primary or secondary amino groups, preferably selected from (meth)acrylamide, 2-aminoethyl (meth)acrylate hydrochloride, 2-aminoethyl (meth)acrylamide hydrochloride, N-ethyl (meth)acrylamide, N-(3-aminopropyl)(meth)acrylamide hydrochloride, N-hydroxyethyl (meth)acrylamide, N-3-(dimethylamino)propyl (meth)acrylamide, [3-(methacrylamido)propyl]trimethylammonium, N-[tris(hydroxymethyl)methyl](meth)acrylamide, N-phenylacrylamide, alkylacrylamide, methacrylamide poly(ethylene glycol) amine hydrochloride and combinations thereof; (iii 8) acetoxy-functionalized ethylenically unsaturated compounds, preferably selected from 1-acetoxy-1,3-butadiene, diacetone acrylamide and combinations thereof; (iii 9) isocyanato-functionalized ethylenically unsaturated compounds, preferably selected from 2-isocyanatoethyl (meth)acrylate, allyl isocyanate, vinyl isocyanate, 3-isopropenyl-α,α-dimethylbenzyl isocyanate and combinations thereof; (iii 10) Alkoxysilyl-functionalized ethylenically unsaturated compounds, preferably selected from allyltrimethoxysilane, allyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-butenyltriethoxysilane, 3-(trimethoxysilyl)propyl (meth)acrylate, 5-hexenyltriethoxysilane, styrylethyltrimethoxysilane, trimethoxy(7-octen-1-yl)silane, 11-allyloxyundecyltrimethoxysilane, allylphenylpropyltriethoxysilane, [(5-bicyclo[2.2.1]hept-2-enyl)ethyl]trimethoxysilane, (5-bicyclo[2.2.1]hept-2-enyl)triethoxysilane, n-allyl-aza-2,2-dimethoxysilacyclopentane, norbornenyltriethoxysilane, [2-(3-cyclohexenyl)ethyl]triethoxysilane, and combinations thereof; (iii 11) Alkoxy-functionalized ethylenically unsaturated compounds, preferably selected from 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, methyl 3-methoxy(meth)acrylate, and combinations thereof; (iii 12) Dioxolanone-functionalized ethylenically unsaturated compounds, preferably selected from glycerol carbonate (meth)acrylate, 4-vinyl-1,3-dioxolan-2-one, and combinations thereof; (iii 13) Halogen-functionalized ethylenically unsaturated compounds, preferably selected from vinyl chloride, allyl chloride, 2-chloro-1,3-butadiene, 2-chloroethyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, methyl 2-(chloromethyl) (meth)acrylate, 2,3-dichloropropyl (meth)acrylate, 2,3-dibromopropyl (meth)acrylate, and combinations thereof; (iii 14) Thiol-functionalized ethylenically unsaturated compounds, preferably selected from allyl mercaptan, N-acryloyl-cysteamine, and combinations thereof; (iii 15) Hydroxyamine-functionalized ethylenically unsaturated compounds, preferably selected from acryloxyoxime acid; (iii 16) Oxazolinyl-functionalized ethylenically unsaturated compounds, preferably selected from oxazoline-substituted acrylates; (iii 17) Aziridinyl-functionalized ethylenically unsaturated compounds, preferably selected from 2-(aziridin-1-yl)ethyl acrylate; (iii 18) Imino-functionalized ethylenically unsaturated compounds, preferably selected from 2-[(2-methylprop-2-enoyl)oxy]ethyl (3E)-3-(alkylimino)butanoate; (iii 19) Carbodiimido-functionalized ethylenically unsaturated compounds, preferably selected from N-α,α'-dimethylisopropenylbenzyl-N'-cyclohexylcarbodiimide, N-α,α'-dimethylisopropenylbenzyl-N'-butylcarbodiimide, and combinations thereof; (iii20) A diol-functional ethylenically unsaturated compound, preferably selected from ethylene glycol methyl ether (meth)acrylate, ethylene glycol phenyl ether (meth)acrylate, di(ethylene glycol) methyl ether (meth)acrylate, tri(ethylene glycol) methyl ether (meth)acrylate, poly(ethylene glycol) methyl ether (meth)acrylate, poly(ethylene glycol) phenyl ether acrylate, poly(ethylene glycol) (meth)acrylate, poly(propylene glycol) (meth)acrylate, poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (meth)acrylate, polyglycol partial ester monomers, and combinations thereof; (iii21) A hydrazide-functional ethylenically unsaturated compound, preferably selected from 2-acryloyl hydrazide or (meth)acryloyl hydrazide, and combinations thereof; (iii22) An aldehyde-functional ethylenically unsaturated compound, preferably selected from (meth)acrolein, 2-ethylacrolein, 3-methyl-2-butenal, tiglic aldehyde, crotonaldehyde, 3-methylcrotonaldehyde, 2-pentenal, 2-methyl-2-pentenal, 4-pentenal, 2,2-dimethyl-4-pentenal, 2,4-heptadienal, and combinations thereof; (iii23) A ketone-functional ethylenically unsaturated compound, preferably selected from 1-penten-3-one, 3-buten-2-one, 4-methoxy-3-buten-2-one, 3-penten-2-one, 2-cyclopenten-1-one, 2-cyclohexen-1-one, and combinations thereof; and combinations thereof; (iv) Vinyl aromatic monomers are selected from styrene, α-methylstyrene, and combinations thereof; (v) Alkyl esters of ethylenically unsaturated acids are selected from methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and combinations thereof; and combinations thereof.

20. The polymer latex composition according to claim 18 or 19, wherein - the functional group (A) of the latex polymer (a) is selected from groups having a carbon-carbon double bond and the functional group of the silane compound (b) is selected from groups having a carbon-carbon double bond, (meth)acryloxy group, and thiol group; - the functional group (A) of the latex polymer (a) is selected from carboxylic acid functional groups and the functional group of the silane compound (b) is selected from epoxy group, glycidyl group, thiol group, hydroxyl group, primary or secondary amino group, isocyanate group, oxazolinyl group, aziridinyl group, imino group, carbodiimide group, diol group, ester group, and acetoxy group; - the functional group (A) of the latex polymer (a) is selected from hydroxyl groups and the functional group of the silane compound (b) is selected from carboxylic acid functional groups, isocyanate group, primary or secondary amino group, aldehyde group, boric acid, and ester group; - the functional group (A) of the latex polymer (a) is selected from epoxy groups and the functional group of the silane compound (b) is selected from carboxylic acid functional groups, hydroxyl groups, and ester groups; - the functional group (A) of the latex polymer (a) is selected from glycidyl groups and the functional group of the silane compound (b) is selected from carboxylic acid functional groups, hydroxyl groups, and ester groups; - The functional group (A) of the latex polymer (a) is selected from acetoacetoxy groups, and the functional group of the silane compound (b) is selected from groups having a carbon-carbon double bond, (meth)acryloxy groups, isocyanato groups, aldehyde groups, hydrazine groups, hydrazide groups, and primary or secondary amino groups; - The functional group (A) of the latex polymer (a) is selected from primary or secondary amino groups, and the functional group of the silane compound (b) is selected from carboxylic acid functional groups, epoxy groups, glycidyl groups, ester groups, and dioxolanone groups; - The functional group (A) of the latex polymer (a) is selected from acetoxy groups, and the functional group of the silane compound (b) is selected from hydrazide groups and primary or secondary amino groups; - The functional group (A) of the latex polymer (a) is selected from isocyanato groups, and the functional group of the silane compound (b) is selected from carboxylic acid functional groups, hydroxyl groups, primary or secondary amino groups, and thiols; - The functional group (A) of the latex polymer (a) is selected from alkoxysilyl groups, and the functional group of the silane compound (b) is selected from hydroxyl groups and alkoxysilyl groups; - The functional group (A) of the latex polymer (a) is selected from alkoxy groups, and the functional group of the silane compound (b) is selected from ester groups; - The functional group (A) of the latex polymer (a) is selected from ester groups, and the functional group of the silane compound (b) is selected from hydroxyl groups, carboxylic acid groups, and ester groups; - The functional group (A) of the latex polymer (a) is selected from dioxolanone groups, and the functional group of the silane compound (b) is selected from primary or secondary amino groups; - The functional group (A) of the latex polymer (a) is selected from halogen functional groups, and the functional group of the silane compound (b) is selected from carboxylic acids; - The functional group (A) of the latex polymer (a) is selected from thiol functional groups, and the functional group of the silane compound (b) is selected from carbon-carbon double bonds, (meth)acryloxy groups, carboxylic acid functional groups, or isocyanato groups; - The functional group (A) of the latex polymer (a) is selected from hydroxylamine groups, and the functional group of the silane compound (b) is selected from aldehyde groups; - The functional group (A) of the latex polymer (a) is selected from oxazoline groups, and the functional group of the silane compound (b) is selected from carboxylic acids; - The functional group (A) of the latex polymer (a) is selected from aziridine groups, and the functional group of the silane compound (b) is selected from carboxylic acids or hydroxyl groups; - The functional group (A) of the latex polymer (a) is selected from imino groups, and the functional group of the silane compound (b) is selected from carboxylic acids; - The functional group (A) of the latex polymer (a) is selected from carbodiimide groups, and the functional group of the silane compound (b) is selected from carboxylic acids; - The functional group (A) of the latex polymer (a) is selected from diol groups, and the functional group of the silane compound (b) is selected from carboxylic acid functional groups; - The functional group (A) of the latex polymer (a) is selected from hydrazide groups, and the functional group of the silane compound (b) is selected from aldehyde groups; - The functional group (A) of the latex polymer (a) is selected from aldehyde groups, and the functional group of the silane compound (b) is selected from hydroxyl groups, acetoacetoxy groups, hydroxylamine groups, or hydrazide groups; or - The functional group (A) of the latex polymer (a) is selected from ketone groups, and the functional group of the silane compound (b) is selected from hydroxyl groups.

21. A method for preparing a polymer latex composition, comprising: (i) In a method of emulsion polymerization, polymerize a monomer composition comprising an ethylenically unsaturated monomer for a latex polymer (a), the ethylenically unsaturated monomer comprising at least one monomer that generates a functional group (A) after polymerization, to obtain a latex comprising latex polymer (a) particles, the latex polymer comprising functional group (A); and (ii) Add a silane compound (b) selected from compounds of formula I, II, oligomers thereof, or any combination of the foregoing: wherein X is a functional group capable of forming a bond with the functional group (A) of the latex polymer (a); R 1 is a linking group between the functional group X and the silicon atom or R 1 is a bond; R 2 is independently a hydrolysable group or a non-hydrolysable group; wherein at least one of R 2 is a hydrolysable group, and at least one of R 2 is a non-hydrolysable group; wherein Y is O, S, NH or NR 3 ; wherein R 3 is a straight-chain or branched-chain, substituted or unsubstituted alkyl or alkenyl; R 1 is a linking group between the functional group Y and the silicon atom; R 2 is independently a hydrolysable group or a non-hydrolysable group; wherein at least one of R 2 is a non-hydrolyzable group; and (iii) Optionally add a silane compound (c) different from the silane compound (b), wherein the silane compound (c) is selected from compounds of formula III, IV, oligomers thereof, or any combination of the foregoing: wherein Z is a functional group capable of forming a bond with the functional group (A) of the latex polymer (a); R a is a linking group between the functional group Z and the silicon atom or R a is a bond; R b is a hydrolysable group; wherein Z' is O, S, NH or NR 3 ; wherein R 3 is a straight-chain or branched-chain, substituted or unsubstituted alkyl or alkenyl; R a is a linking group between the functional group Z' and the silicon atom; R b is a hydrolysable group.

22. The method for preparing a polymer latex composition according to claim 21, wherein at least one, more than one, or all of the following: - The monomer composition for obtaining the latex polymer (a) particles; - The functional group (A) of the polymer latex (a); - The functional group (X) of the silane compound (b); - The functional group (Z) of the silane compound (c); - Hydrolyzable group R 2 and R b ; - Non-hydrolyzable group R 2 - linking group R 1 and R a - The amounts of the silane compounds (b) and (c); - The weight ratio of the silane compounds (b) and (c), as described in any one of claims 2 to 20.

23. Use of the polymer latex composition according to any one of claims 1 to 20 or the polymer latex composition prepared by the method according to claim 21 or 22 for the production of dip-molded articles, elastomeric films, self-supporting elastomeric films or articles, or for coating or impregnating a substrate, preferably a textile substrate.

24. A compounded polymer latex composition suitable for the production of dip-molded articles, comprising the polymer latex composition according to any one of claims 1 to 20 or the polymer latex composition prepared by the method according to claim 21 or 22 and optionally additives selected from self-vulcanizing agents, vulcanization accelerators, free radical initiators, pigments, and combinations thereof, preferably free of self-vulcanizing agents and accelerators for sulfur vulcanization, and optionally comprising polyvalent cations and / or silica-based fillers.

25. A method for preparing a dip-molded article, the method comprising the following steps: (a) Provide the compounded latex composition according to claim 24; (b) Immerse a mold having the desired shape of the final article in a coagulant bath containing a metal salt solution; (c) Remove the mold from the coagulant bath and optionally dry the mold; (d) Immerse the mold treated in steps b) and c) in the compounded latex composition of step a); (e) Coagulate the latex film on the surface of the mold; (f) Remove the latex-coated mold from the compounded latex composition and optionally immerse the latex-coated mold in a water bath; (g) Optionally dry the latex-coated mold; (h) Heat-treat the latex-coated mold obtained from step e) or f) at a temperature of 40 °C to 180 °C, and / or expose the latex-coated mold obtained from step e) or f) to UV radiation; (i) Remove the elastomeric article from the mold.

26. A method for producing a continuous elastomeric film, comprising: (A) Providing a polymer latex composition defined or prepared according to any one of claims 1 to 22; (B) Forming a continuous polymer film from the aqueous polymer latex composition; (C) Optionally drying the continuous polymer film obtained in step B); (D) Heat-treating the continuous polymer film obtained in step B) or C) at a temperature of 40 °C to 180 °C, preferably for 20 minutes or less, to form a continuous elastomeric film; and / or UV treatment, and (E) Optionally winding the continuous elastomeric film obtained in step D) into a roll.

27. A method for preparing an elastomeric article, the method comprising the steps of: - Aligning two separate continuous elastomeric films obtained according to claim 26; - Cutting the aligned continuous elastomeric films into a preselected shape to obtain two superimposed layers of elastomeric films of the preselected shape; And - Joining the superimposed layers of elastomeric films together at at least a preselected portion of the periphery of the superimposed layers to form an elastomeric article.

28. The method according to claim 27, wherein the joining together is carried out by using thermal measures, the thermal measures being preferably selected from heat sealing and welding or by gluing.

29. The method according to any one of claims 27 or 28, wherein the cutting is carried out by a heatable template cutting device or a laser cutter so as to provide the preselected shape, and the cutting device is heated in the portion where the film joined together contacts the elastomeric film, so as to simultaneously cut the elastomeric film into the preselected shape and heat seal a preselected portion of the periphery of the superimposed elastomeric films.

30. A method for repairing or reforming an elastomeric film or an article comprising the elastomeric film, the method comprising the steps of: a) Providing a film or article comprising one or more elastomeric films, the one or more elastomeric films having at least two surfaces to be reconnected; b) Rejoining the at least two surfaces of the one or more elastomeric films and heating or annealing the one or more elastomeric films while maintaining the surfaces of the damaged film to be rejoined in close contact at a temperature of 40 to 200 °C, preferably 60 to 175 °C, more preferably 95 to 135 °C, wherein c) The elastomeric film is made of a polymer latex composition defined or prepared according to any one of claims 1 to 22.

31. An article prepared by using a polymer latex composition defined or prepared according to any one of claims 1 to 22.

32. The article according to claim 31, which is selected from surgical gloves, examination gloves, industrial gloves, household gloves, disposable gloves, textile-supported gloves, catheters, elastomeric sleeves, condoms, balloons, tubes, dental dams, aprons and preformed gaskets.

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