Polymer Latex Composition

Abstract

The present invention relates to a polymer latex composition, a method for preparing such a polymer latex composition, the use of said polymer latex composition for the manufacture of elastomeric articles, a formulated latex composition comprising said polymer latex composition, a method for the manufacture of a dip molded article, a method for the manufacture of an elastomeric article, and an article manufactured using said polymer latex composition.

Description

[Technical field]

[0001] The present invention relates to a polymer latex composition, a method for preparing such a polymer latex composition, the use of said polymer latex composition for the manufacture of elastomeric articles, a formulated latex composition comprising said polymer latex composition, a method for the manufacture of a dip molded article, a method for the manufacture of an elastomeric article, and an article manufactured using said polymer latex composition. [Background technology]

[0002] In the art of manufacturing articles based on polymer latex, it is generally desirable to achieve high tensile strength and, at the same time, high elongation of the film forming the article to provide the article with high mechanical strength and the desired flexibility. This is particularly important for gloves, such as surgical gloves. Furthermore, in recent years, it has been discovered that an increasing number of people are experiencing allergic reactions to natural rubber latex, which has been commonly used in the past in the manufacture of latex-based articles, such as latex products, e.g., dip-molded products, which contain up to 5% non-rubber components, such as proteins, lipids and trace elements. Users of natural rubber latex products have developed type I hypersensitivity caused by leachable latex proteins remaining in the natural rubber products.

[0003] Natural and synthetically produced polymer latexes are generally crosslinked using sulfur vulcanization systems that contain sulfur and sulfur-containing accelerators. The use of these sulfur vulcanization systems in rubber glove manufacturing can cause IV type hypersensitivity stagnation, such as allergic contact dermatitis.

[0004] As a result, it is desirable to avoid sulfur vulcanization systems, and in particular to provide polymer latexes that can be used to produce dip molded articles that do not require the standard sulfur vulcanization systems containing previously used sulfur-containing accelerators to obtain the desired mechanical properties of the final article.

[0005] It is a further object of the present invention to provide a polymer latex composition that results in a softer film while maintaining the advantageous properties of the polymer latex, such as good tensile properties.

[0006] Another object is to provide a polymer latex composition having an increased pot life while maintaining the advantageous properties of the polymer latex to simultaneously achieve high tensile strength and high elongation in the film forming article.

[0007] It is a further object of the present invention to provide good durability of the polymer latex. Summary of the Invention

[0008] The following section summarizes certain aspects of the invention.

[0009] According to a first aspect, the present invention relates to a polymer latex composition for the preparation of an elastomeric film, comprising the following components: (I) particles of a latex polymer obtained by free radical emulsion polymerization of a composition comprising an ethylenically unsaturated monomer, the particles of the latex polymer comprising functional groups (Ia); and (II) a silane compound containing at least two terminal silane functional groups (II-a) and a thermally reversible bond (II-b); or (III) a silane compound comprising one terminal silane functional group (III-a) and at least one additional functional group (III-b) capable of forming a thermally reversible bond (III-c) with the functional group (Ia) of the latex polymer (I).

[0010] The polymer latex composition may have thermally reversible bonds (II-b) or (III-c) that can be cleaved and rearranged at temperatures below 200°C.

[0011] The thermally reversible bond (II-b) or (III-c) may be selected from the group consisting of disulfides, tetrasulfides, carbonates, ureas, thioureas, esters, β-hydroxyesters, thioesters, β-hydroxyamines, β-hydroxythioethers, amides, urethanes, enamines, imines, hemiacetals, acetals, hemiketals, ketals, boronate esters, siloxanes, oximes, acylhydrazones, aldols, thiuram disulfides, and trithiocarbonates.

[0012] Preferably, the silane compound (II) has the structure of the following formula: [ka] During the ceremony, X is a thermally reversible bond (II-b), preferably selected from the group comprising disulfides, tetrasulfides, carbonates, ureas, thioureas, esters, β-hydroxyesters, thioesters, β-hydroxyamines, β-hydroxythioethers, amides, urethanes, enamines, imines, hemiacetals, acetals, hemiketals, ketals, boronate esters, siloxanes, oximes, acylhydrazones, aldols, thiuram disulfides and trithiocarbonates; R is independently selected from hydrogen, halogen, hydroxy, alkoxy, hydrocarbyl, silane, or combinations thereof; R 1 are independently linear or branched C1-C 20 Alkanediyl, cyclic C3-C 20 alkyl or alkenyl, or arylenediyl, preferably linear C1-C 20 It is an alkanediyl.

[0013] Additionally, the silane compound (II) may be formed in situ from a first silane compound (IV) that includes one terminal silane functional group (IV-a) and at least one additional functional group (IV-b) capable of forming a thermally reversible bond (IV-c) with an additional functional group (IV-b) of a second silane compound (IV).

[0014] At least one additional functional group (III-b) of the silane compound (III) or at least one additional functional group (IV-b) of the first silane compound (IV) and / or at least one additional functional group (IV-b) of the second silane compound (IV) may be protected.

[0015] The silane compound (II) is preferably bis[3-(trialkoxysilylpropyl)] disulfide, bis[3-(trialkoxysilyl)propyl] tetrasulfide bis[3-(trialkoxysilyl)propyl] carbonate, N,N'-bis[3-(trialkoxysilyl)propyl] urea, N,N'-bis[3-(trialkoxysilyl)propyl] thiourea, 2-hydroxy-3-[3-(trialkoxysilyl)propoxy]propyl-3-(trihydroxysilyl)propanoate, 2-hydroxy-7-(trialkoxysilyl)heptyl-3-(trihydroxysilyl)propanoate, 9,9-dialkoxy-1,1,1-trihydroxy-10-oxa-5-thia-1,9-disilado decan-4-one, N-[3-(trialkoxysilyl)propyl]-3-(trihydroxysilyl)propenamide, (trialkoxysilyl)methyl N-[3-(trialkoxysilyl)propyl]carbamate, (7E)-4,4,12,12-tetraalkoxy-3,13-dioxa-8-aza-4,12-disilapentadec-7-ene, 4,4,11,11-tetraalkoxy-3,6,12-trioxa-4,11-disilatetradecan-7-ol, 4,4,10,10-tetraalkoxy-7-[3-(trialkoxysilyl)propyl]-3,6,8,11-tetraoxa-4,10-disilatridecane, oligomeric siloxanes, and combinations thereof.

[0016] The silane compound (III) or the silane compound (IV) may have the structure of the following formula: [ka] During the ceremony, R2 is independently selected from hydrogen, halogen, hydroxy, alkoxy, hydrocarbyl, or combinations thereof; R 3 is a linear or branched C1-C 20 Alkanediyl, cyclic C3-C 20 alkyl or alkenyl, or arylenediyl, preferably linear C1-C 20 It is an alkanediyl; Y is a functional group (III-b) or (IV-b), preferably selected from the group consisting of epoxy, thiol, hydroxy, hydroxylamine, primary or secondary amino, isocyanato, oxazolino, aziridino, imino, carbodiimide, glycol, ester, acetoxy, carboxylic acid, dioxolanone, hydrazide, aldehyde, ketone, and combinations thereof.

[0017] The silane compound (III) or the silane compound (IV) may be, for example, (3-glycidyloxypropyl)trialkoxysilane, β-(3,4-epoxycyclohexylethyltrialkoxysilane), dialkoxy(3-glycidyloxypropyl)alkylsilane, 3-glycidoxypropyldialkylalkoxysilane, 5,6-epoxyhexyltrialkoxysilane, aminopropyltrialkoxysilane, hydroxymethyltrialkoxysilane, 3-mercaptopropyltrialkoxysilane, 3-chloropropyltrialkoxysilane, vinyltrialkoxysilane, methyl ... The alkoxysilane may be selected from the group consisting of alkoxysilane, 3-(trialkoxysilyl)furan, norbornenyltrialkoxysilane, carboxyethylsilanetriol, 3-isocyanatopropyltrialkoxysilane, tris[3-(trialkoxysilyl)propyl]isocyanurate, trialkoxysilylbutyraldehyde, ureidopropyltrialkoxysilane, cyanomethyl[3-(trialkoxysilyl)propyl]trithiocarbonate, S-(octanoyl)mercaptopropyltrialkoxysilane, and combinations thereof.

[0018] Preferably, the particles of latex polymer (I) can be present in an amount of 80-99.9% by weight, preferably 85-99.9% by weight, more preferably 90-99.9% by weight, even more preferably 92-99.8% by weight, and most preferably 95-99.8% by weight, and the silane compound (II) can be present in an amount of 0.1-20% by weight, preferably 0.1-15% by weight, more preferably 0.1-10% by weight, even more preferably 0.2-8% by weight, and most preferably 0.2-5% by weight; Alternatively, the silane compound (III) may be present in an amount of 0.1 to 20% by weight, preferably 0.1 to 18% by weight, more preferably 0.1 to 15% by weight, even more preferably 0.1 to 12% by weight, and most preferably 0.1 to 10% by weight; These are based on the total weight of the particles of latex polymer (I) and silane compound (II) or silane compound (III).

[0019] The functional groups (Ia) of the particles of the latex polymer (I) may be selected from the group consisting of carbon-carbon double bonds, carboxylic acids, hydroxy, epoxy, acetoacetyl, primary or secondary amino, acetoxy, isocyanato, alkoxy, dioxolanone, halide functional groups, thiol, hydroxylamine, oxazolino, aziridino, imino, carbodiimide, glycol, ester, hydrazide, aldehyde, ketone, and combinations thereof.

[0020] The polymer latex composition comprising silane compound (II) may further comprise silane compound (V), which comprises one terminal silane functional group (Va) and at least one additional functional group (Vb) reactive with the functional group (Ia) of the latex polymer (I).

[0021] The functional group (Vb) of the silane compound (V) may preferably be selected from the group consisting of a carbon-carbon double bond, a halide functional group, an epoxy, a thiol, a hydroxy, a hydroxylamine, a primary or secondary amino, an isocyanato, an oxazolino, an aziridino, an imino, a carbodiimide, a glycol, an ester, an acetoxy, a carboxylic acid, a dioxolanone, a hydrazide, an aldehyde, a ketone, and combinations thereof.

[0022] The silane compound (V) can have the structure: [ka] During the ceremony, R 4 is independently selected from hydrogen, halogen, hydroxy, alkoxy, hydrocarbyl, or combinations thereof; R 5 is a linear or branched C1-C 20 Alkanediyl, cyclic C3-C 20 alkyl or alkenyl, or arylenediyl, preferably linear C1-C 20 It is an alkanediyl; Z is a functional group (Vb) reactive with the functional group (Ia) of the particles of the latex polymer (I), where the functional group (Vb) may preferably be selected from the group consisting of carbon-carbon double bonds, halide functional groups, epoxy, thiol, hydroxy, hydroxylamine, primary or secondary amino, isocyanato, oxazolino, aziridino, imino, carbodiimide, glycol, ester, acetoxy, carboxylic acid, dioxolanone, hydrazide, aldehyde, ketone, and combinations thereof.

[0023] Preferably, the silane compound (V) may be selected from the group consisting of (3-glycidyloxypropyl)trialkoxysilane, β-(3,4-epoxycyclohexylethyltrialkoxysilane), dialkoxy(3-glycidyloxypropyl)alkylsilane, 3-glycidoxypropyldialkylalkoxysilane, 5,6-epoxyhexyltrialkoxysilane, aminopropyltrialkoxysilane, hydroxymethyltrialkoxysilane, 3-mercaptopropyltrialkoxysilane, 3-chloropropyltrialkoxysilane, vinyltrialkoxysilane, 3-(trialkoxysilyl)furan, norbornenyltrialkoxysilane, carboxyethylsilanetriol, 3-isocyanatopropyltrialkoxysilane, tris[3-(trialkoxysilyl)propyl]isocyanurate, trialkoxysilylbutyraldehyde, ureidopropyltrialkoxysilane, cyanomethyl[3-(trialkoxysilyl)propyl]trithiocarbonate, S-(octanoyl)mercaptopropyltrialkoxysilane, and combinations thereof.

[0024] The particles of latex polymer (I) can be present in an amount of 80 to 99.8% by weight, preferably 85 to 99.8% by weight, more preferably 90 to 99.5% by weight, even more preferably 92 to 99.5% by weight, and most preferably 95 to 99.2% by weight, the silane compound (II) can be present in an amount of 0.1 to 20% by weight, preferably 0.1 to 15% by weight, more preferably 0.1 to 10% by weight, even more preferably 0.2 to 8% by weight, and most preferably 0.2 to 5% by weight, and the silane compound (V) can be present in an amount of 0.1 to 20% by weight, preferably 0.1 to 15% by weight, more preferably 0.1 to 10% by weight, even more preferably 0.2 to 8% by weight, and most preferably 0.2 to 5% by weight, which are based on the total weight of the particles of latex polymer (I), the silane compound (II) and the silane compound (V).

[0025] Preferably, the mass ratio of silane compound (II) to silane compound (V) may be 100:1 to 1:100, preferably 80:1 to 1:80, more preferably 50:1 to 1:50, even more preferably 20:1 to 1:20, and most preferably 10:1 to 1:10.

[0026] The monomer composition for obtaining the particles of latex polymer (I) comprises the following components: (i) 15 to 99 weight percent 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 different from (i) and (ii) containing a functional group (a); (iv) 0 to 80 weight percent vinyl aromatic monomer; and (v) 0 to 65 weight percent of an alkyl ester of an ethylenically unsaturated acid; The weight percentages are based on the total weight of monomers in the monomer composition.

[0027] It is assumed that: (i) the conjugated diene of the polymer latex composition may be selected from butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, and combinations thereof; (ii) the ethylenically unsaturated nitrile compound of the polymer latex composition may be selected from (meth)acrylonitrile, α-cyanoethyl acrylonitrile, fumaronitrile, α-chloronitrile, and combinations thereof; (iii) The ethylenically unsaturated compound containing functional group (a) of the polymer latex composition, different from (i) and (ii), may be selected from: (iii1) 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) ethylenically unsaturated acids and their salts, preferably selected from (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, ethylenically unsaturated sulfonic acids, ethylenically unsaturated phosphorus-containing acids and their salts, polycarboxylic acid anhydrides, polycarboxylic acid partial ester monomers, carboxyalkyl esters of ethylenically unsaturated acids, and combinations thereof; (iii3) hydroxy-functional ethylenically unsaturated compounds, preferably selected from allyl alcohol, vinyl alcohol, N-methylol acrylamide, 1-penten-3-ol, hydroxyalkyl esters of ethylenically unsaturated acids, and combinations thereof; (iii4) Oxirane-functional ethylenically unsaturated compounds, preferably glycidyl methacrylate, allyl glycidyl ether, vinyl glycidyl ether, vinylcyclohexene oxide, limonene oxide, 2-ethyl glycidyl (meth)acrylate, 2-(n-propyl)glycidyl (meth)acrylate, 2-(n-butyl)glycidyl (meth)acrylate, glycidyl (meth)acrylate, (3',4'epoxyheptyl)-2-ethyl (meth)acrylate, (6',7'-epoxyheptyl) (meth)acrylate, allyl-3,4-epoxyheptyl ether, 6,7-epoxyheptyl allyl ether, vinyl-3,4-epoxyheptyl ether, ether, 3,4-epoxyheptyl vinyl ether, 6,7-epoxyheptyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3-vinylcyclohexene oxide, α-methylglycidyl methacrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3,4-epoxy-1-butene, 1,2-epoxy-5-hexene, 4-vinyl-1-cyclohexene 1,2-epoxide, 2-methyl-2-vinyloxirane, 3,4-epoxy-1-cyclohexene, glycidyl propargyl ether, and combinations thereof; (iii5) Acetoacetyl-functional ethylenically unsaturated compounds, preferably acetoacetoxyethyl (meth)acrylate, acetoacetoxypropyl (meth)acrylate, allyl acetoacetate, acetoacetoxybutyl (meth)acrylate, 2,3-di(acetoacetoxy)propyl (meth)acrylate, acetoacetoxy(methyl)ethyl (meth)acrylate, acetoacetamidoethyl (meth)acrylate, 3-(methacryloyloxy)-2,2-dimethyl (meth)acrylate, ethylpropyl 3-oxobutanoate, 3-(methacryloyloxy)-2,2,4,4-tetramethylcyclobutyl 3-oxobutanoate, 3-(methacryloyloxy)-2,2,4-trimethylpentyl 3-oxobutanoate, l-(methacryloyloxy)-2,2,4-trimethylpentan-3-yl 3-oxobutanoate, (4-(methacryloyloxymethyl)cyclohexyl)methyl 3-oxobutanoate, or combinations thereof; (iii6) ethylenically unsaturated compounds 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, alkylacrylamides, methacrylamide poly(ethylene glycol)amine hydrochloride, and combinations thereof; (iii7) acetoxy-functional ethylenically unsaturated compounds, preferably 1-acetoxy-1,3-butadiene, diacetone acrylamide, or combinations thereof; (iii8) isocyanato-functional ethylenically unsaturated compounds, preferably 2-isocyanatoethyl (meth)acrylate, allyl isocyanate, 3-isopropenyl-α,α-dimethylbenzyl isocyanate, or combinations thereof; (iii9) alkoxysilyl-functional ethylenically unsaturated compounds, preferably 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-dimethoxysilacyclopentanenorbornenyltriethoxysilane, [2-(3-cyclohexenyl)ethyl]triethoxysilane, or combinations thereof; (iii10) alkoxy-functional ethylenically unsaturated compounds, preferably 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, methyl-3-methoxy (meth)acrylate, or combinations thereof; (iii11) dioxolanone-functional ethylenically unsaturated compounds, preferably glycerol carbonate methacrylate, 4-vinyl-1,3-dioxolan-2-one, or combinations thereof; (iii12) halide-functional ethylenically unsaturated compounds, preferably 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, or combinations thereof; (iii13) a thiol-functional ethylenically unsaturated compound, preferably allyl mercaptan, N-acryloyl-cysteamine, or a combination thereof; (iii14) hydroxylamine-functional ethylenically unsaturated compounds, preferably acrylohydroxamic acid; (iii15) oxazolino-functional ethylenically unsaturated compounds, preferably oxazoline-substituted acrylic esters; (iii16) aziridino-functional ethylenically unsaturated compounds, preferably 2-(aziridin-1-yl)ethyl acrylate; (iii17) imino-functional ethylenically unsaturated compounds, preferably 2-[(2-methylprop-2-enoyl)oxy]ethyl(3E)-3-(alkylimino)butanoate; (iii18) carbodiimino-functional ethylenically unsaturated compounds, preferably N-α,α'-dimethylisopropenylbenzyl-N'-cyclohexylcarbodiimide, N-α,α'-dimethylisopropenylbenzyl-N'-butylcarbodiimide, or combinations thereof; (iii19) glycol-functional ethylenically unsaturated compounds, preferably 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, or combinations thereof; (iii20) a hydrazide-functional ethylenically unsaturated compound, preferably 2-propenoic acid hydrazide, methacryloyl hydrazide, or a combination thereof; (iii21) aldehyde-functional ethylenically unsaturated compounds, preferably (meth)acrolein, 2-ethylacrolein, 3-methyl-2-butenal, tiglinaldehyde, crotonaldehyde, 3-methylcrotonaldehyde, 2-pentenal, 2-methyl-2-pentenal, 4-pentenal, 2,2-dimethyl-4-pentenal, 2,4-heptadienal, or combinations thereof; (iii22) ketone-functional ethylenically unsaturated compounds, preferably 1-penten-3-one, 3-buten-2-one, 4-methoxy-3-buten-2-one, 3-penten-2-one, 2-cyclopent-1-one, 2-cyclohexen-1-one, or combinations thereof; as well as combinations thereof; (iv) the vinyl aromatic monomer of the polymer latex composition may be selected from styrene, α-methylstyrene, and combinations thereof; (v) the alkyl ester of an ethylenically unsaturated acid of the polymer latex composition may be selected from methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and combinations thereof; as well as combinations thereof; The mixture of ethylenically unsaturated monomers for the latex polymer (I) may optionally include ethylenically unsaturated monomers selected from the following: (vi) vinyl carboxylates, preferably vinyl acetate; (vii) monomers having at least two identical ethylenically unsaturated groups, preferably selected from divinylbenzene, ethylene glycol dimethacrylate, glycerol dimethacrylate, 1,4-butanediol di(meth)acrylate, and combinations thereof; and combinations thereof.

[0028] It is assumed that: - the functional group (Ia) can be chosen from groups having a carbon-carbon double bond and the functional group (Vb) can be chosen from groups having a carbon-carbon double bond and thiols; or - the functional group (Ia) may be chosen from carboxylic acid functional groups and the functional group (Vb) may be chosen from epoxy, thiol, hydroxy, primary or secondary amino, isocyanato, oxazolino, aziridino, imino, carbodiimide, glycol groups, ester groups and acetoxy; or - the functional group (Ia) may be chosen from hydroxy and the functional group (Vb) may be chosen from alkoxysilyl, carboxylic acid functional groups; isocyanato, primary or secondary amino, aldehyde, boronic acid and ester groups; or - the functional group (Ia) may be chosen from epoxy and the functional group (Vb) may be chosen from carboxylic acid functional groups, hydroxy groups and ester groups; or - the functional group (Ia) may be selected from acetoacetyl and the functional group (Vb) may be selected from groups having a carbon-carbon double bond, isocyanato, aldehyde, hydrazide, hydrazine and primary or secondary amino; or - the functional group (Ia) may be chosen from primary or secondary amino and the functional group (Vb) may be chosen from carboxylic acid functional groups, epoxy groups, ester groups and dioxolanone groups; or - functional group (Ia) may be selected from acetoxy and functional group (Vb) may be selected from hydrazide and primary or secondary amino; or - the functional group (Ia) may be chosen from isocyanato and the functional group (Vb) may be chosen from carboxylic acid functional groups, hydroxy, primary or secondary amino and thiol; or - the functional group (Ia) may be chosen from alkoxysilyl and the functional group (Vb) may be chosen from hydroxy and alkoxysilyl; or - the functional group (Ia) may be chosen from alkoxy and the functional group (Vb) may be chosen from ester groups; or - the functional group (Ia) may be selected from ester groups and the functional group (Vb) may be selected from hydroxy groups, carboxylic acid groups and ester groups; - functional group (Ia) may be chosen from dioxolanone groups and functional group (Vb) may be chosen from primary or secondary amino; - functional group (Ia) may be selected from halide functional groups and functional group (Vb) may be selected from carboxylic acids; - the functional group (Ia) may be chosen from thiol functional groups and the functional group (Vb) may be chosen from carbon-carbon double bonds, carboxylic acid functional groups and isocyanato; - functional group (Ia) may be selected from hydroxylamines and functional group (Vb) may be selected from aldehydes; - functional group (Ia) may be selected from oxazolino and functional group (Vb) may be selected from carboxylic acid; - the functional group (Ia) may be selected from aziridino and the functional group (Vb) may be selected from carboxylic acid and hydroxy; - functional group (Ia) may be selected from imino and functional group (Vb) may be selected from carboxylic acid; - functional group (Ia) may be selected from carbodiimino and functional group (Vb) may be selected from carboxylic acid; - the functional group (Ia) may be selected from glycol groups and the functional group (Vb) may be selected from carboxylic acid functional groups; - functional group (Ia) may be selected from hydrazides and functional group (Vb) may be selected from aldehydes; - the functional group (Ia) may be selected from aldehydes and the functional group (Vb) may be selected from hydroxy, acetoacetyl, hydroxylamine and hydrazide; The functional group (Ia) may be selected from ketones and the functional group (Vb) may be selected from hydroxy.

[0029] Preferably, the bond formed by reaction of functional group (Ia) with functional group (Vb) is thermoreversible.

[0030] A further aspect of the present invention relates to a method for preparing a polymer latex composition comprising the steps of: (A) polymerizing, in an emulsion polymerization process, a composition comprising ethylenically unsaturated monomers for a latex polymer (I) comprising at least one monomer that provides a functional group (Ia) after polymerization to obtain a latex comprising particles of the latex polymer (I) comprising the functional group (Ia); and (B1) adding a silane compound (II) containing at least two terminal silane functional groups (II-a) and a thermally reversible bond (II-b); or (B2) adding a silane compound (III) containing one terminal silane functional group (III-a) and at least one additional functional group (III-b) capable of forming a thermally reversible bond (III-c) with the functional group (Ia) of the latex polymer (I).

[0031] Preferably, the method for preparing the polymer latex composition comprises the following steps: (B1) adding a compound (II) containing at least two terminal silane functional groups (II-a) and a thermally reversible bond (II-b); and (C) optionally adding a compound (V) containing one terminal silane functional group (Va) and at least one additional functional group (Vb) that is reactive with the functional group (Ia) of the particles of the latex polymer (I).

[0032] Yet another aspect of the present invention relates to the use of the polymer latex composition for the manufacture of elastomeric articles or for coating or impregnating a substrate.

[0033] Further, according to a further aspect, the present invention relates to a formulated polymer latex composition suitable for making dip molded articles comprising the above-mentioned polymer latex composition and optionally comprising an adjuvant selected from a sulfur vulcanizing agent, a vulcanization accelerator, a free radical initiator, a pigment, and combinations thereof.

[0034] Preferably, the compounded latex composition is free of sulfur vulcanizing agents and accelerators for sulfur vulcanization, and may optionally include multivalent cations and / or silica-based fillers.

[0035] The formulated latex composition may include multivalent cations present in an amount of up to 20% by weight, based on the total weight of the particles of latex polymer (I), silane compound (II) or silane compound (III) and optional silane compound (V).

[0036] Another aspect of the invention relates to a method for producing a dip-molded article by the following steps: (a) providing a compounded latex composition as described above; (b) immersing a form having the desired shape of the final article into a coagulant bath containing a solution of metal salts; (c) removing the form from the coagulant bath and optionally drying the form; (d) immersing the former treated in steps (b) and (c) into the compounded latex composition of step (a); (e) solidifying a latex film onto the surface of the mold; (f) removing the latex coated former from the formulated latex composition and optionally immersing the latex coated former in a water bath; (g) optionally drying the latex coated former; (h) heat treating the latex coated form obtained from step (e) or (f) at a temperature between 40°C and 180°C and / or exposing the latex coated form obtained from step (e) or (f) to UV radiation; (i) Removing the latex article from the mold.

[0037] Furthermore, according to another aspect, the present invention relates to a method for producing an elastomeric article, the method comprising the steps of: (a) obtaining a continuous elastomeric film from the polymer latex composition described above; (b) optionally, heat treating the continuous elastomeric film and / or exposing the continuous elastomeric film to UV radiation; (c) overlapping and aligning two separate continuous elastomeric films; (d) cutting or punching the overlapping continuous elastomeric film into a preselected shape to obtain two overlapping layers of elastomeric film of the preselected shape; (e) bonding the superimposed layers together about at least a preselected portion of the periphery to form an elastomeric article.

[0038] The joining together can be done by using thermal means, preferably selected from heat sealing and welding, or by adhesion, or by a combination of thermal means and adhesion.

[0039] Another aspect of the present invention relates to articles manufactured by using the above-described polymer latex composition.

[0040] The article may be selected from surgical gloves, examination gloves, condoms, catheters, industrial gloves, cloth-supported gloves, household gloves, balloons, tubing, dental dams, aprons, and preformed gaskets. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0041] Detailed description of the invention: The present invention relates to a polymer latex composition, comprising: (I) particles of a latex polymer obtained by free radical emulsion polymerization of a composition comprising an ethylenically unsaturated monomer, the particles of the latex polymer comprising functional groups (Ia); and (II) a silane compound containing at least two terminal silane functional groups (II-a) and a thermally reversible bond (II-b); or (III) a silane compound comprising one terminal silane functional group (III-a) and at least one additional functional group (III-b) capable of forming a thermally reversible bond (III-c) with the functional group (Ia) of the latex polymer (I).

[0042] The polymer latex composition is suitable for preparing an elastomeric film. As used herein, the term "thermally reversible bond" refers to a chemical bond between two functional groups resulting from a chemical reaction based on a temperature-dependent equilibrium, where the chemical bond is formed at a low temperature, but is reversibly induced 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 less, preferably 180°C or less, more preferably 160°C or less. Typically, the thermoreversible bond can be formed in a temperature range of 25 to 200°C. According to the present invention, the thermoreversible bond can be broken and rearranged to form a thermoreversible bond at a temperature of 200°C or less, preferably 190°C or less, more preferably 180°C or less. Typically, the thermoreversible bond can be broken and rearranged in a temperature range of 25 to 200°C.

[0043] Latex polymer (I) containing functional group (Ia) The latex polymer (I) used according to the present invention can be prepared by any suitable free radical emulsion polymerization process known in the art. Suitable process parameters are as described below.

[0044] The unsaturated monomers and their relative amounts used in preparing the latex polymer (I) are not particularly critical, so long as the monomer mixture contains at least one ethylenically unsaturated monomer that provides a functional group (Ia) on the latex polymer (I). Monomer compositions containing conjugated dienes and ethylenically unsaturated nitrile compounds are particularly useful, for example, in dip molding applications.

[0045] Suitable functional groups (Ia) of the particles of the latex polymer (I) may be selected from the group consisting of carbon-carbon double bonds, carboxylic acids, hydroxy, epoxy, acetoacetyl, primary or secondary amino, acetoxy, isocyanato, alkoxy, dioxolanone, halide functional groups, thiol, hydroxylamine, oxazolino, aziridino, imino, carbodiimide, glycol, ester, hydrazide, aldehyde, ketone, and combinations thereof.

[0046] According to the invention, the monomer composition for obtaining particles of latex polymer (I) comprises: (i) 15 to 99 weight percent 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 different from (i) and (ii) containing a functional group (a); (iv) 0 to 80 weight percent vinyl aromatic monomer; and (v) 0 to 65 weight percent of an alkyl ester of an ethylenically unsaturated acid; The weight percentages are based on the total weight of monomers in the monomer composition.

[0047] Conjugated diene monomers suitable for preparing the latex polymer (I) according to the present invention include 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-octadiene Conjugated diene monomers selected from 1,3-butadiene, 2-ethyl-1,3-butadiene, 2-amyl-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, and combinations thereof. 1,3-butadiene, isoprene and combinations thereof are more preferred conjugated dienes. 1,3-butadiene is the most preferred diene. Typically the amount of conjugated diene monomer ranges from 15 to 99% by weight, preferably from 20 to 95% by weight, more preferably from 30 to 75% by weight, and most preferably from 40 to 70% by weight, based on the total weight of monomers.Thus, the conjugated diene may 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 based on the total weight of the ethylenically unsaturated monomers of the latex polymer (I). Thus, the conjugated diene monomer may be used in an amount of 99% by weight or less, 95% by weight or less, 90% by weight or less, 85% by weight or less, 80% by weight or less, 78% by weight or less, 76% by weight or less, 74% by weight or less, 72% by weight or less, 70% by weight or less, 68% by weight or less, 66% by weight or less, 64% by weight or less, 62% by weight or less, 60% by weight or less, 58% by weight or less, or 56% by weight or less. One of ordinary skill in the art would understand that any range between any of the explicitly disclosed lower and upper limits is disclosed herein.

[0048] The unsaturated nitrile monomers that can be used in the present invention may include polymerizable unsaturated aliphatic nitrile monomers containing 2 to 4 carbon atoms in a linear or branched arrangement, which may be substituted by either an acetyl group or an additional nitrile group. The ethylenically unsaturated nitrile compounds for the preparation of the latex polymer (I) according to the present invention may be selected from acrylonitrile, methacrylonitrile, α-cyanoethyl acrylonitrile, fumaronitrile, α-chloronitrile and combinations thereof, with acrylonitrile being the most preferred. These nitrile monomers may be included in an amount of 1 to 80% by weight, preferably 10 to 70% by weight or 1 to 60% by weight, more preferably 15 to 50% by weight, even more preferably 20 to 50% by weight, and most preferably 23 to 43% by weight, based on the total weight of the ethylenically unsaturated monomers of the latex polymer (I).

[0049] Thus, the unsaturated nitrile may be present in an amount of at least 1 weight percent, at least 5 weight percent, at least 10 weight percent, at least 12 weight percent, at least 14 weight percent, at least 16 weight percent, at least 18 weight percent, at least 20 weight percent, at least 22 weight percent, at least 24 weight percent, at least 26 weight percent, at least 28 weight percent, at least 30 weight percent, at least 32 weight percent, at least 34 weight percent, at least 36 weight percent, at least 38 weight percent, or at least 40 weight percent based on the total weight of the ethylenically unsaturated monomers of the latex polymer (I). Thus, the unsaturated nitrile monomer can be used in amounts of 80% or less, 75% or less, 73% or less, 70% or less, 68% or less, 66% or less, 64% or less, 62% or less, 60% or less, 58% or less, 56% or less, 54% or less, 52% or less, 50% or less, 48% or less, 46% or less, or 44% or less by weight. One of ordinary skill in the art would understand that any range between any of the explicitly disclosed lower and upper limits is disclosed herein.

[0050] The ethylenically unsaturated compounds different from (i) and (ii) containing functional group (a) suitable for the preparation of the latex polymer (I) according to the present invention may be selected from: (iii1) an ethylenically unsaturated compound having at least two different ethylenically unsaturated groups; (iii2) Ethylenically unsaturated acids and their salts; (iii3) Hydroxy-functional ethylenically unsaturated compounds; (iii4) oxirane-functional ethylenically unsaturated compounds; (iii5) Acetoacetyl-functional ethylenically unsaturated compounds; (iii6) Ethylenically unsaturated compounds containing primary or secondary amino groups; (iii7) Acetoxy-functional ethylenically unsaturated compounds; (iii8) Isocyanato-functional ethylenically unsaturated compounds; (iii9) alkoxysilyl-functional ethylenically unsaturated compounds; (iii10) Alkoxy-functional ethylenically unsaturated compounds; (iii11) Dioxolanone-functional ethylenically unsaturated compounds; (iii12) Halide-functional ethylenically unsaturated compounds; (iii13) Thiol-functional ethylenically unsaturated compounds; (iii14) Hydroxylamine-functional ethylenically unsaturated compounds; (iii15) oxazolino-functional ethylenically unsaturated compounds; (iii16) aziridino-functional ethylenically unsaturated compounds; (iii17) imino-functional ethylenically unsaturated compounds; (iii18) carbodiimino-functional ethylenically unsaturated compounds; (iii19) Glycol-functional ethylenically unsaturated compounds; (iii20) hydrazide-functional ethylenically unsaturated compounds; (iii21) Aldehyde-functional ethylenically unsaturated compounds; (iii22) Ketone-functional ethylenically unsaturated compounds; and combinations thereof.

[0051] Suitable ethylenically unsaturated compounds (iii1) having at least two different ethylenically unsaturated groups may be selected from allyl (meth)acrylates, vinyl (meth)acrylates, and combinations thereof.

[0052] Suitable ethylenically unsaturated acids and their salts (iii2) may be selected from ethylenically unsaturated carboxylic acid monomers, ethylenically unsaturated sulfonic acid monomers, ethylenically unsaturated phosphorus-containing acid monomers. Ethylenically unsaturated carboxylic acid monomers suitable for use in the present invention include mono- and dicarboxylic acid monomers, monoesters of dicarboxylic acids, and carboxyalkyl esters of ethylenically unsaturated acids such as 2-carboxyethyl (meth)acrylate. In carrying out the present invention, it is preferred to use ethylenically unsaturated aliphatic mono- or dicarboxylic acids or anhydrides containing 3 to 5 carbon atoms. Examples of monocarboxylic acid monomers include (meth)acrylic acid, crotonic acid, and examples of dicarboxylic acid monomers include fumaric acid, itaconic acid, maleic acid, and maleic anhydride. Examples of other suitable ethylenically unsaturated acids include vinyl acetate, vinyl lactate, vinyl sulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrene sulfonic acid, acrylamidomethylpropane sulfonic acid, and salts thereof. Particularly preferred are (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, ethylenically unsaturated sulfonic acids, ethylenically unsaturated phosphorus-containing acids and their salts, polycarboxylic acid anhydrides, polycarboxylic acid partial ester monomers, carboxyalkyl esters of ethylenically unsaturated acids, and combinations thereof.

[0053] Examples of ethylenically unsaturated sulfonic acid monomers include vinyl sulfonic acid, phenyl vinyl sulfonate, sodium 4-vinylbenzenesulfonate, 2-methyl-2-propene-1-sulfonic acid, 4-styrenesulfonic acid, 3-allyloxy-2-hydroxy-1-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, and salts thereof.

[0054] Examples of ethylenically unsaturated phosphorus-containing acid monomers include vinyl phosphonic acid, dimethyl vinyl phosphonate, diethyl vinyl phosphonate, diethyl allyl phosphonate, allyl phosphonic acid, and salts thereof.

[0055] Suitable hydroxy-functional ethylenically unsaturated compounds (iii3) 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 undecenoate.

[0056] Suitable oxirane-functional ethylenically unsaturated monomers (iii4) are glycidyl (meth)acrylate, allyl glycidyl ether, vinyl glycidyl ether, vinylcyclohexene oxide, limonene oxide, 2-ethyl glycidyl (meth)acrylate, 2-(n-propyl)glycidyl (meth)acrylate, 2-(n-butyl)glycidyl (meth)acrylate, glycidyl (meth)acrylate, (3',4'-epoxyheptyl)-2-ethyl acrylate, (3',4'-epoxyheptyl)-2-ethyl (meth)acrylate, (6',7'-epoxyheptyl) (meth)acrylate, allyl-3,4-epoxyheptyl ether, 6,7-epoxyheptyl allyl ether. The epoxy group may be selected from the group consisting of vinyl-3,4-epoxyheptyl ether, 3,4-epoxyheptyl vinyl ether, 6,7-epoxyheptyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3-vinylcyclohexene oxide, α-methylglycidyl methacrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-4-epoxy-1-butene, 1,2-epoxy-5-hexene, 4-vinyl-1-cyclohexene 1,2-epoxide, 2-methyl-2-vinyloxirane, 3,4-epoxy-1-cyclohexene, glycidyl propargyl ether, and combinations thereof. Glycidyl (meth)acrylate is particularly preferred.

[0057] Suitable acetoacetyl-functional ethylenically unsaturated compounds (iii5) are acetoacetoxyethyl (meth)acrylate, acetoacetoxypropyl (meth)acrylate, allyl acetoacetate, acetoacetoxybutyl (meth)acrylate, 2,3-di(acetoacetoxy)propyl (meth)acrylate, acetoacetoxy(methyl)ethyl (meth)acrylate, acetoacetamido-ethyl (methyl)acrylate, (2-acetoacetamido-2-methylpropyl) (meth)acrylate, 3-(methacryloyl)-2-propanol, 2 ...

[0043] The acryloyloxymethyl)cyclohexyl group may be selected from 3-(methacryloyloxy)-2,2-dimethylpropyl 3-oxobutanoate, 3-(methacryloyloxy)-2,2,4,4-tetramethylcyclobutyl 3-oxobutanoate, 3-(methacryloyloxy)-2,2,4-trimethylpentyl 3-oxobutanoate, I-((meth)acryloyloxy)-2,2,4-trimethylpentan-3-yl 3-oxobutanoate, (4-((meth)acryloyloxymethyl)cyclohexyl)methyl 3-oxobutanoate, and combinations thereof.

[0058] The ethylenically unsaturated compound (iii6) having a primary or secondary amino group suitable for preparing the latex polymer (I) according to the present invention may be selected from (meth)acrylamide, alkyl(meth)acrylamides such as N-ethyl(meth)acrylamide, N-tert-butyl(meth)acrylamide, N-phenyl(meth)acrylamide, N-(isobutoxymethyl)(meth)acrylamide, N-propyl(meth)acrylamide, aminoalkyl esters of ethylenically unsaturated acids such as 2-aminoethyl(meth)acrylate hydrochloride, N-(3-aminopropyl)(meth)acrylamide hydrochloride, 2-aminoethyl(meth)acrylamide hydrochloride, (2-(N-tert-butoxycarbonylamino)ethyl(meth)acrylate, and N-3-(dimethylamino)propyl(meth)acrylamide. The ethylenically unsaturated compound having a primary or secondary amino group may be selected from (meth)acrylamide, alkyl(meth)acrylamides such as N-ethyl(meth)acrylamide, N-tert-butyl(meth)acrylamide, N-phenyl(meth)acrylamide, N-(isobutoxymethyl)(meth)acrylamide, N-propyl(meth)acrylamide, aminoalkyl esters of ethylenically unsaturated acids such as 2-aminoethyl(meth)acrylate hydrochloride, N-(3-aminopropyl)(meth)acrylamide hydrochloride, 2-aminoethyl(meth)acrylamide hydrochloride, (2-(N-tert-butoxycarbonylamino)ethyl(meth)acrylate, and N-3-(dimethylamino)propyl(meth)acrylamide. The saturated compound (iii6) may preferably 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-(methacryloylamino)propyl] trimethylammonium, N-[tris(hydroxymethyl)methyl] (meth)acrylamide, N-phenylacrylamide, alkylacrylamides, methacrylamide poly(ethylene glycol)amine hydrochloride, and combinations thereof. The suitable acetoxy-functional ethylenically unsaturated compound (iii7) may be selected from 1-acetoxy-1,3-butadiene, diacetone acrylamide, and combinations thereof.

[0059] Suitable isocyanato-functional ethylenically unsaturated compounds (iii8) may be selected from 2-isocyanatoethyl (meth)acrylate, allyl isocyanate, vinyl isocyanate, 3-isopropenyl-α,α-dimethylbenzyl isocyanate, and combinations thereof.

[0060] Suitable alkoxysilyl-functional ethylenically unsaturated compounds (iii9) are allyltrimethoxysilane, allyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-butenyltriethoxysilane, 3-(trimethoxysilyl)propyl(meth)acrylate, 5-hexenyltriethoxysilane, styrylethyltrimethoxysilane, trimethoxy(7-octen-1-yl)silane, 11-allyloxyundecyloxysilane, 12-allyloxyundecyloxy ...

[0043] The silane may be selected from the group consisting of n-allyltrimethoxysilane, 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.

[0061] Suitable alkoxy-functional ethylenically unsaturated compounds (iii10) may be selected from N-methoxymethyl-(meth)acrylamide, Nn-butoxymethyl-(meth)acrylamide, N-isobutoxymethyl-(meth)acrylamide, 2-methoxyethyl(meth)acrylate, 2-ethoxyethyl(meth)acrylate, 2-butoxyethyl(meth)acrylate, methoxyethoxyethylacrylate, methyl-3-methoxy(meth)acrylate, and combinations thereof. Preferred alkoxy-functional ethylenically unsaturated compounds are 2-methoxyethyl(meth)acrylate, 2-ethoxyethyl(meth)acrylate, methyl-3-methoxy(meth)acrylate, and combinations thereof.

[0062] Suitable dioxolanone-functional ethylenically unsaturated compounds (iii11) may be selected from glycerol carbonate (meth)acrylate, 4-vinyl-1,3-dioxolan-2-one, and combinations thereof.

[0063] Suitable halide-functional ethylenically unsaturated compounds (iii12) 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.

[0064] Suitable thiol-functional ethylenically unsaturated compounds (iii13) may be selected from allyl mercaptan, N-acryloyl-cysteamine, and combinations thereof.

[0065] Suitable hydroxylamine functional ethylenically unsaturated compounds (iii14) may be selected from acrylohydroxamic acids.

[0066] Suitable oxazolino-functional ethylenically unsaturated compounds (iii15) can be selected from oxazoline-substituted acrylic acid esters. Suitable oxazoline-substituted acrylic acid esters and their synthesis are described in US 6,063,885.

[0067] A suitable aziridino-functional ethylenically unsaturated compound (iii16) may be selected from 2-(aziridin-1-yl)ethyl acrylate.

[0068] Suitable imino-functional ethylenically unsaturated compounds (iii17) can be selected from 2-[(2-methylprop-2-enoyl)oxy]ethyl(3E)-3-(alkylimino)butanoate. Imino-functional ethylenically unsaturated compounds (iii17) can be prepared by reacting primary or secondary amines with acetoacetoxyethyl (meth)acrylate, as described in Esser, RJ, Devona, JE, Setzke, DE and Wagemans L., Prog.Org.Coat., 1999, 36(1-2)45-52 and Yu, Z., Alesso, S., Pears, D., Worthington, PA, Luke, RWA, Bradley, M., Tetrahedron Lett, 2000, 41(46)8963-8967.

[0069] Suitable carbodiimino-functional ethylenically unsaturated compounds (iii18) may be selected from N-α,α'-dimethylisopropenylbenzyl-N'-cyclohexylcarbodiimide, N-α,α'-dimethylisopropenylbenzyl-N'-butylcarbodiimide, and combinations thereof. The synthesis of the carbodiimino-functional ethylenically unsaturated compounds is described in Pham, HH and Winnik, MA, J Polym Sci A Polym Chem, 2000, 38, 855-869.

[0070] Suitable glycol functional ethylenically unsaturated compounds (iii19) 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.

[0071] Suitable hydrazide-functional ethylenically unsaturated compounds (iii20) may be selected from 2-propenoic acid hydrazide, methacryloyl hydrazide, and combinations thereof.

[0072] Suitable aldehyde-functional ethylenically unsaturated compounds (iii21) may be selected from (meth)acrolein, 2-ethylacrolein, 3-methyl-2-butenal, tiglinaldehyde, crotonaldehyde, 3-methylcrotonaldehyde, 2-pentenal, 2-methyl-2-pentenal, 4-pentenal, 2,2-dimethyl-4-pentenal, 2,4-heptadienal, and combinations thereof.

[0073] Suitable ketone functional ethylenically unsaturated compounds (iii22) 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.

[0074] Monomers (iii) provide functional groups (Ia) that are reactive with functional groups (III-b) of silane compounds (III) or functional groups (Vb) of silane compounds (V) according to the invention. Moreover, due to their polarity, they can affect the properties of the polymer dispersion. This determines the type and amount of these monomers. Typically, such amounts are 0.05 to 10% by weight, in particular 0.1 to 10% by weight, or 0.5 to 7% by weight, preferably 0.1 to 9% by weight, more preferably 0.1 to 8% by weight, even more preferably 1 to 7% by weight, most preferably 2 to 7% by weight, based on the total weight of the ethylenically unsaturated monomers for the latex polymer (I). Thus, the ethylenically unsaturated compound (iii) may be present in an amount of at least 0.01 wt%, at least 0.05 wt%, at least 0.1 wt%, at least 0.3 wt%, at least 0.5 wt%, at least 0.7 wt%, at least 0.9 wt%, at least 1 wt%, at least 1.2 wt%, at least 1.4 wt%, at least 1.6 wt%, at least 1.8 wt%, at least 2 wt%, at least 2.5 wt%, or at least 3 wt%. Similarly, the ethylenically unsaturated compound (iii) may be present in an amount of 10 wt% or less, 9.5 wt% or less, 9 wt% or less, 8.5 wt% or less, 8 wt% or less, 7.5 wt% or less, 7 wt% or less, 6.5 wt% or less, 6 wt% or less, 5.5 wt% or less, or 5 wt% or less, based on the total weight of the ethylenically unsaturated monomers for the latex polymer (I). One of ordinary skill in the art would understand that any range defined by an explicitly disclosed lower limit and an explicitly disclosed upper limit is disclosed herein.

[0075] Representative examples of vinyl aromatic monomers include, for example, 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, vinylxylene, 2-vinylpyridine, 4-vinylpyridine, 1,1-diphenylethylene, and 1,2-diphenylethene. Mixtures of one or more vinyl aromatic compounds (vi) can also be used. Preferably, vinyl aromatic monomer (iv) is selected from styrene, α-methylstyrene, and combinations thereof. The vinyl aromatic compound (vi) can be used in the range of 0-80 wt%, 0-70 wt%, 0-50 wt%, preferably 0-40 wt%, more preferably 0-25 wt%, even more preferably 0-15 wt%, and most preferably 0-10 wt%, based on the total weight of the ethylenically unsaturated monomers of the latex polymer (I). Thus, the vinyl aromatic compound (iv) can be present in an amount of 80 wt% or less, 75 wt% or less, 60 wt% or less, 50 wt% or less, 40 wt% or less, 35 wt% or less, 30 wt% or less, 25 wt% or less, 20 wt% or less, 18 wt% or less, 16 wt% or less, 14 wt% or less, 12 wt% or less, 10 wt% or less, 8 wt% or less, 6 wt% or less, 4 wt% or less, 2 wt% or less, or 1 wt% or less, based on the total weight of the ethylenically unsaturated monomers of the latex polymer (I). The vinyl aromatic compound (iv) may also be completely absent.

[0076] Suitable alkyl esters of ethylenically unsaturated acids (v) may be selected from n-, iso- or tert-alkyl esters of (meth)acrylic acid, in which the alkyl group has 1 to 20 carbon atoms, and reaction products of methacrylic acid with glycidyl esters of neo acids, such as versatic acid, neodecanoic acid or pivalic acid.

[0077] Generally, preferred alkyl esters of (meth)acrylic acid are C1-C 10 It can be selected from alkyl (meth)acrylate, preferably C1-C8-alkyl (meth)acrylate.Examples of such (meth)acrylate monomer include n-butyl acrylate, secondary butyl acrylate, ethyl acrylate, hexyl acrylate, tert-butyl acrylate, 2-ethyl-hexyl 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.Methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and their combinations are preferred.

[0078] Typically, the alkyl ester of an ethylenically unsaturated acid (v) can be present in an amount of 65% or less, 60% or less, 55% or less, 50% or less, 45% or less, 40% or less, 35% or less, 30% or less, 25% or less, 20% or less, 18% or less, 16% or less, 14% or less, 12% or less, 10% or less, 8% or less, 6% or less, 4% or less, 2% or less, or 1% or less by weight, based on the total weight of the ethylenically unsaturated monomers in the latex polymer (I).

[0079] Furthermore, the mixture of ethylenically unsaturated monomers for the latex polymer (I) according to the present invention can contain additional ethylenically unsaturated monomers different from the above-defined monomers, which can be selected from vinyl carboxylates (vi) and / or monomers (vii) having two identical ethylenically unsaturated groups.

[0080] The vinyl carboxylate monomer (vi) that can be used according to the present invention includes vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl-2-ethylhexanoate, vinyl stearate, and vinyl ester of Versatic acid. The most preferred vinyl ester monomer for use in the present invention is vinyl acetate. Typically, the vinyl ester monomer can be present in an amount of 18% by weight or less, 16% by weight or less, 14% by weight or less, 12% by weight or less, 10% by weight or less, 8% by weight or less, 6% by weight or less, 4% by weight or less, 2% by weight or less, or 1% by weight or less based on the total weight of the ethylenically unsaturated monomers for the latex polymer (I).

[0081] Additionally, monomers (vii) having at least two identical ethylenically unsaturated groups can be present in the monomer mixture for the preparation of 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 for the latex polymer (I). Typically, these monomers can be present in an amount of 6% by weight or less, 4% by weight or less, 2% by weight or less, 1% by weight or less, based on the total weight of the ethylenically unsaturated monomers for the latex polymer (I). Suitable difunctional monomers (vii) capable of providing internal crosslinking and branching in the polymer (known herein as multifunctional monomers) can be selected from divinylbenzene, diacrylates and di(meth)acrylates. Examples include 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. The monomer (vii) having at least two ethylenically unsaturated groups is 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.

[0082] According to the present invention, the amounts of the above mentioned monomers for the preparation of the latex polymer (I) can total 100% by weight.

[0083] Method for preparing the polymer latex of the present invention: The latex polymer (I) according to the present invention can be prepared by any emulsion polymerization process known to those skilled in the art, provided that the monomer mixtures defined herein are used.The process described in EP-A-792891 is particularly suitable.

[0084] A seed latex may be employed in the emulsion polymerization to prepare the latex polymer (I) of the present invention. Any seed particles known to those skilled in the art may be used.

[0085] The seed latex particles are preferably present in an amount of 0.01 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the total ethylenically unsaturated monomers used in the polymer. Thus, the lower limit of the amount of 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. The upper limit of said 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. One of ordinary skill in the art will understand that any range formed by any of the explicitly disclosed lower and upper limits is expressly encompassed herein.

[0086] The above-mentioned process for the preparation of the polymer latex can be carried out in the presence or absence of one or more emulsifiers, in the presence or absence of one or more colloids and in the presence of one or more initiators at temperatures of 0 to 130° C., preferably 0 to 100° C., particularly preferably 5 to 70° C. and very particularly preferably 5 to 60° C., including all values ​​and subvalues ​​therebetween, in particular 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.

[0087] The initiator that can be used in carrying out the present invention includes water-soluble and / or oil-soluble initiators that are effective for polymerization purposes.Representative initiators are well known in the art, and include, for example, azo compounds (such as AIBN, AMBN, and cyanovaleric acid), inorganic peroxy compounds (such as hydrogen peroxide, sodium peroxydisulfate, potassium peroxydisulfate, and ammonium peroxydisulfate, peroxycarbonates, and peroxyborates), organic peroxy compounds (such as alkyl hydroperoxides, dialkyl peroxides, acyl hydroperoxides, and diacyl peroxides), esters (such as tertiary butyl perbenzoate), and combinations of inorganic and organic initiators.

[0088] The initiator is used in an amount sufficient to initiate the polymerization reaction at the desired rate. Generally, an amount of initiator of 0.01 to 5 weight percent, preferably 0.1 to 4 weight percent, based on the total weight of the monomers in the monomer composition, is sufficient. The amount of initiator is most preferably 0.01 to 2 weight percent, based on the total weight of the monomers in the monomer composition. The amount of initiator includes all values ​​and subvalues ​​therebetween, particularly including 0.01, 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 4 and 4.5 weight percent, based on the total weight of the monomers in the monomer composition.

[0089] The above inorganic and organic peroxy compounds may also be used alone or in combination with one or more suitable reducing agents, as is well known in the art. Examples of such reducing agents include sulfur dioxide, alkali metal disulfites, alkali metal and ammonium hydrogen sulfites, thiosulfates, dithionite and formaldehyde sulfoxylate, 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 reducing agent is preferably 0.03 to 10 parts by weight per part by weight of the polymerization initiator.

[0090] Suitable surfactants or emulsifiers for stabilizing latex particles include conventional surfactants for polymerization processes. Surfactants can be added to the aqueous phase and / or the monomer phase. In a seeded process, an effective amount of surfactant is an amount selected to support colloidal stabilization of the particles, minimizing interparticle contact and preventing agglomeration. In a non-seeded process, an effective amount of surfactant is an amount selected to affect particle size.

[0091] Representative surfactants include, for example, saturated and ethylenically unsaturated sulfonic acids or their salts, such as unsaturated hydrocarbon sulfonic acids and their salts, such as vinyl sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, etc.; aromatic hydrocarbon acids and their salts, such as p-styrene sulfonic acid, isopropenyl benzene sulfonic acid, vinyloxybenzene sulfonic acid, etc.; sulfoalkyl esters of acrylic acid and methacrylic acid, such as sulfoethyl methacrylate and sulfopropyl methacrylate and their salts, and 2-acrylamido-2-methylpropane sulfonic acid and its salts; alkylated diphenyloxide disulfonates, sodium dodecylbenzene sulfonate, dihexyl ester of sodium sulfosuccinate, sodium alkyl esters of sulfonic acid, ethoxylated alkylphenols, and ethoxylated alcohols; and fatty alcohol (poly)ether sulfates.

[0092] The type and amount of surfactant typically depends on the number of particles, their size and their composition. Typically, surfactants are used in an amount of 0-20% by weight, preferably 0-10% by weight, more preferably 0-5% by weight, based on the total weight of monomers in the monomer composition. The amount of surfactant includes all values ​​and subvalues ​​therebetween, including in particular 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 monomers in the monomer composition. The polymerization can be carried out without surfactants.

[0093] Instead of or in addition to the above surfactants, various protective colloids can also be used. Suitable colloids include polyhydroxy compounds such as partially acetylated polyvinyl alcohol, casein, hydroxyethyl starch, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polysaccharides and decomposed polysaccharides, polyethylene glycols and gum arabic. Preferred protective colloids are carboxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose. Generally, these protective colloids are used in a content of 0 to 10 parts by weight, preferably 0 to 5 parts by weight, more preferably 0 to 2 parts by weight, based on the total weight of the monomers. The amount of protective colloid includes all values ​​and subvalues ​​therebetween, in particular 1, 2, 3, 4, 5, 6, 7, 8 and 9% by weight, based on the total weight of the monomers.

[0094] Those skilled in the art will understand that the type and amount of polar functional monomer, surfactant and protective colloid are selected to make the polymer latex according to the present invention suitable for dip molding applications. Therefore, it is preferred that the polymer latex composition of the present invention has a certain maximum electrolyte stability (measured at pH 10 and 23°C for 0.1% total solids of the composition) determined as a critical coagulation concentration in CaCl2 of less than 30 mmol / l, preferably less than 25 mmol / l, more preferably less than 20 mmol / l, and most preferably less than 10 mmol / l.

[0095] If the electrolyte is too stable, it will be difficult to coagulate the polymer latex in the dip molding process, resulting in either no continuous film of polymer latex being formed on the dip mold or the resulting product having an uneven thickness.

[0096] It is within the routine of a person skilled in the art to properly adjust the electrolyte stability of the polymer latex.The electrolyte stability depends on certain different factors, such as the amount and selection of monomers (especially those containing polar functional groups) used to prepare the polymer latex, and the selection and amount of stabilizing system (e.g., emulsion polymerization process for preparing the polymer latex).The stabilizing system can contain surfactants and / or protective colloids.

[0097] Depending on the monomers selected and their relative amounts for making the polymer latex of the present invention, one skilled in the art will be able to tailor the stabilization system to achieve electrolyte stability according to the present invention.

[0098] It is often recommended that the emulsion polymerization is further carried out in the presence of buffer substances and chelating agents. Suitable substances are, for example, alkali metal phosphates and pyrophosphates (buffer substances) and alkali metal salts of ethylenediaminetetraacetic acid (EDTA) or hydroxy-2-ethylenediaminetriacetic acid (HEEDTA) as chelating agents. The amounts of buffer substances and chelating agents are usually 0.001-1.0% by weight, based on the total amount of monomers.

[0099] In addition, it may be advantageous to use chain transfer agents (regulators) in the emulsion polymerization. Typical agents are, for example, thioesters, 2-mercaptoethanol, 3-mercaptopropionic acid and C1-C 12 The chain transfer agent is an organic sulfur compound such as an alkyl mercaptan, with n-dodecyl mercaptan and t-dodecyl mercaptan being preferred. The amount of chain transfer agent, if present, is usually 0.05-3.0% by weight, preferably 0.2-2.0% by weight, based on the total weight of the monomers used.

[0100] Additionally, it may be beneficial to introduce partial neutralization into the polymerization process. Those skilled in the art will appreciate that by appropriate selection of this parameter the necessary control may be achieved.

[0101] 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, crosslinkers, 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 polyacrylates, polyacrylamides, xanthan gum, modified cellulose, or granular thickeners (e.g., silica and clay). Typical plasticizers include mineral oils, liquid polybutenes, liquid polyacrylates, and lanolin. Zinc oxide is a preferred crosslinker. Titanium dioxide (TiO2), calcium carbonate, and clay are typically used fillers. Known accelerators and secondary accelerators include dithiocarbamates (e.g., zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, zinc dibenzyldithiocarbamate, zinc pentamethylenedithiocarbamate (ZPD)), xanthates, thiurams (e.g., tetramethylthiuram monosulfide (TMTM), tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), dipentamethylenethiuram hexasulfide (DPTT)), and amines (e.g., diphenylguanidine (DPG), di-o-tolylguanidine (DOTG), o-tolylbiguanidine (OTBG)).

[0102] A silane compound (II) comprising at least two terminal silane functional groups (II-a) and a thermally reversible bond (II-b): According to the present invention, any silane compound (II) containing at least two terminal silane functional groups (II-a) and a thermoreversible bond (II-b) can be used. The silane compound (II) can ensure that the elastomeric film of the final dip-molded article exhibits the desired mechanical properties even if sulfur vulcanization is not used.

[0103] The thermally reversible bond (II-b) may be selected from the group consisting of disulfides, tetrasulfides, carbonates, ureas, thioureas, esters, β-hydroxyesters, thioesters, β-hydroxyamines, β-hydroxythioethers, amides, urethanes, enamines, imines, hemiacetals, acetals, hemiketals, ketals, boronate esters, siloxanes, oximes, acylhydrazones, aldols, thiuram disulfides, and trithiocarbonates.

[0104] According to the present invention, the silane compound (II) may have the structure of the following formula: [ka] During the ceremony, X is a thermally reversible bond (II-b), preferably selected from the group comprising disulfides, tetrasulfides, carbonates, ureas, thioureas, esters, β-hydroxyesters, thioesters, β-hydroxyamines, β-hydroxythioethers, amides, urethanes, enamines, imines, hemiacetals, acetals, hemiketals, ketals, boronate esters, siloxanes, oximes, acylhydrazones, aldols, thiuram disulfides and trithiocarbonates; R is independently selected from hydrogen, halogen, hydroxy, alkoxy, hydrocarbyl, silane, or combinations thereof; R 1 are independently linear or branched C1-C 20 Alkanediyl, cyclic C3-C 20 alkyl or alkenyl, or arylenediyl, preferably linear C1-C 20 It is an alkanediyl.

[0105] Suitable silane compounds (II) are bis[3-(trialkoxysilylpropyl)] disulfide, bis[3-(trialkoxysilyl)propyl] tetrasulfide bis[3-(trialkoxysilyl)propyl] carbonate, N,N'-bis[3-(trialkoxysilyl)propyl] urea, N,N'-bis[3-(trialkoxysilyl)propyl] thiourea, 2-hydroxy-3-[3-(trialkoxysilyl)propoxy]propyl-3-(trihydroxysilyl)propanoate, 2-hydroxy-7-(trialkoxysilyl)heptyl-3-(trihydroxysilyl)propanoate, 9,9-dialkoxy-1,1,1-trihydroxy-10-oxa-5-thia-1,9-di It may be selected from siladodecan-4-one, N-[3-(trialkoxysilyl)propyl]-3-(trihydroxysilyl)propenamide, (trialkoxysilyl)methyl N-[3-(trialkoxysilyl)propyl]carbamate, (7E)-4,4,12,12-tetraalkoxy-3,13-dioxa-8-aza-4,12-disilapentadec-7-ene, 4,4,11,11-tetraalkoxy-3,6,12-trioxa-4,11-disilatetradecane-7-ol, 4,4,10,10-tetraalkoxy-7-[3-(trialkoxysilyl)propyl]-3,6,8,11-tetraoxa-4,10-disilatridecane, oligomeric siloxane, and combinations thereof.Preferably, the alkoxy group is selected from methoxy and ethoxy groups, more preferably from ethoxy groups. As used herein, the term "oligomeric siloxane" refers to a siloxane having a weight average molecular weight (Mw) in the range of 200 to 2,000 Da, determined according to GPC using polystyrene as the standard, as described in US 8,728,345 B2. Suitable examples of oligomeric siloxanes include CoatOSil MP-200, CoatOSil T-Cure, and Silquest VX-225 (all commercially available from Momentive Performance Materials, Inc., USA).

[0106] Preferably, the silane compound (II) is selected from the group consisting of bis[3-(triethoxysilylpropyl)] disulfide, bis[3-(triethoxysilyl)propyl] tetrasulfide, bis[3-(triethoxysilyl)propyl] carbonate, N,N'-bis[3-(triethoxysilyl)propyl] urea, N,N'-bis[3-(triethoxysilyl)propyl] thiourea, 2-hydroxy-3-[3-(triethoxysilyl)propoxy]propyl 3-(trihydroxysilyl)propanoate, 2-hydroxy-7-(triethoxysilyl)heptyl 3-(trihydroxysilyl)propanoate, 9,9-diethoxy-1,1,1-trihydroxy-10-oxa-5-thia-1,9- It may be selected from disiladodecan-4-one, N-[3-(triethoxysilyl)propyl]-3-(trihydroxysilyl)propenamide, (triethoxysilyl)methyl N-[3-(triethoxysilyl)propyl]carbamate, (7E)-4,4,12,12-tetraethoxy-3,13-dioxa-8-aza-4,12-disilapentadec-7-ene, 4,4,11,11-tetraethoxy-3,6,12-trioxa-4,11-disilatetradecan-7-ol, 4,4,10,10-tetraethoxy-7-[3-(triethoxysilyl)propyl]-3,6,8,11-tetraoxa-4,10-disilatridecane, oligomeric siloxanes, and combinations thereof.

[0107] Alternatively, the silane compound (II) of the present invention can be formed in situ from a first silane compound (IV) that includes one terminal silane functional group (IV-a) and at least one additional functional group (IV-b) that can form a thermally reversible bond (IV-c) with the additional functional group (IV-b) of the second silane compound (IV). According to the present invention, the first silane compound can be the same as the second silane compound, or the first silane compound can be different from the second silane compound. Those skilled in the art will understand that the additional functional group (IV-b) of the first silane compound must be capable of forming a thermally reversible bond (IV-c) with the additional functional group of the second silane compound.

[0108] At least one additional functional group (IV-b) of the first silane compound (IV) and / or at least one additional functional group (IV-b) of the second silane compound (IV) may be protected. As used herein, the term "protected" refers to an adduct derived from the reaction of a functional group of the compound with a protecting agent, whereby the adduct is thermally unstable and dissociates (deprotects) at elevated temperatures, such as temperatures above 40°C. Examples of suitable protecting agents include materials that deprotect during thermal treatment of the polymer latex composition, for example, at temperatures ranging from 40 to 120°C, 60 to 120°C. One skilled in the art will appreciate that the appropriate protection depends on the respective functional group. For example, amino and hydroxy functionalities can be protected with tert-butylcarbonyl. Thiol functionalities can be protected with (C5 to C9) alkyl carboxylic acids. The isocyanato functional group can be protected with aliphatic alcohols having 1 to 6 carbon atoms, such as methanol and n-butanol, alicyclic alcohols, such as cyclohexanol, and phenolic compounds, such as phenol. Suitable protected silane compounds include S-(octanoyl)mercaptopropyltrialkoxysilanes, such as S-(octanoyl)mercaptopropyltriethoxysilane.

[0109] According to the present invention, the silane compound (IV) may have the structure of the following formula: [ka] During the ceremony, R 2 is independently selected from hydrogen, halogen, hydroxy, alkoxy, hydrocarbyl, or combinations thereof; R 3 is a linear or branched C1-C 20 Alkanediyl, cyclic C3-C 20 alkyl or alkenyl, or arylenediyl, preferably linear C1-C 20 It is an alkanediyl; Y is a functional group (IV-b).

[0110] The functional group (IV-b) may preferably be selected from the group consisting of epoxy, thiol, hydroxy, hydroxylamine, primary or secondary amino, isocyanato, oxazolino, aziridino, imino, carbodiimide, glycol, ester, acetoxy, carboxylic acid, dioxolanone, hydrazide, aldehyde, ketone, and combinations thereof.

[0111] Suitable silane compounds (IV) may be selected from (3-glycidyloxypropyl)trialkoxysilane, β-(3,4-epoxycyclohexylethyltrialkoxysilane), dialkoxy(3-glycidyloxypropyl)alkylsilane, 3-glycidoxypropyldialkylalkoxysilane, 5,6-epoxyhexyltrialkoxysilane, aminopropyltrialkoxysilane, hydroxymethyltrialkoxysilane, 3-mercaptopropyltrialkoxysilane, 3-chloropropyltrialkoxysilane, vinyltrialkoxysilane, 3-(trialkoxysilyl)furan, norbornenyltrialkoxysilane, carboxyethylsilanetriol, 3-isocyanatopropyltrialkoxysilane, tris[3-(trialkoxysilyl)propyl]isocyanurate, trialkoxysilylbutyraldehyde, ureidopropyltrialkoxysilane, cyanomethyl[3-(trialkoxysilyl)propyl]trithiocarbonate, S-(octanoyl)mercaptopropyltrialkoxysilane and combinations thereof. Preferably, the alkoxy groups are selected from methoxy and ethoxy groups, more preferably ethoxy groups.

[0112] Preferably, the silane compound (IV) is (3-glycidyloxypropyl)trimethoxysilane, (3-glycidyloxypropyl)triethoxysilane, β-(3,4-epoxycyclohexylethyltrimethoxysilane), diethoxy(3-glycidyloxypropyl)methylsilane, 3-glycidoxypropyldimethylethoxysilane, 5,6-epoxyhexyltriethoxysilane, aminopropyltriethoxysilane, hydroxymethyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxy ... The silane may be selected from the group consisting of mercaptopropyltriethoxysilane, vinyltriethoxysilane, 3-(triethoxysilyl)furan, norbornenyltriethoxysilane, carboxyethylsilanetriol, 3-isocyanatopropyltriethoxysilane, tris[3-(trimethoxysilyl)propyl]isocyanurate, triethoxysilylbutyraldehyde, ureidopropyltrimethoxysilane, cyanomethyl[3-(trimethoxysilyl)propyl]trithiocarbonate, S-(octanoyl)mercaptopropyltriethoxysilane, and combinations thereof.

[0113] The polymer latex composition of the present invention may comprise 80-99.9 wt%, preferably 85-99.9 wt%, more preferably 90-99.9 wt%, even more preferably 92-99.8 wt%, and most preferably 95-99.8 wt% of latex polymer (I) based on the total weight of the particles of latex polymer (I) and the silane compound described herein. Thus, the lower limit of the amount of particles of latex polymer (I) may be 80 wt%, 82 wt%, 85 wt%, 86 wt%, 88 wt%, 90 wt%, 92 wt%, 94 wt%, or 95 wt%, based on the total weight of the particles of latex polymer (I) and the silane compound of the present invention described herein. The upper limit of the amount of the particles of the latex polymer (I) can be 99.9 wt%, 99.8 wt%, 99.5 wt%, 99.2 wt%, 99 wt%, 98 wt%, 97 wt%, or 96 wt% based on the total weight of the particles of the latex polymer (I) of the present invention and the silane compound described herein. The polymer latex composition of the present invention can contain 0.1 to 20 wt%, preferably 0.1 to 15 wt%, more preferably 0.1 to 10 wt%, even more preferably 0.2 to 8 wt%, and most preferably 0.2 to 5 wt% of the silane compound (II) based on the total weight of the particles of the latex polymer (I) of the present invention and the silane compound described herein. The lower limit of the amount of silane compound (II) can be 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.8 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, or 3 wt%, based on the total weight of the particles of the latex polymer (I) of the present invention and the silane compound described herein. The upper limit of the amount of silane compound (II) can be 20 wt%, 18 wt%, 15 wt%, 14 wt%, 12 wt%, 10 wt%, 9 wt%, 8 wt%, or 5 wt%, based on the total weight of the particles of the latex polymer (I) of the present invention and the silane compound described herein. Those skilled in the art will understand that any range formed by any of the explicitly disclosed lower and upper limits is explicitly disclosed herein.

[0114] The polymer latex composition of the present invention comprising silane compound (II) may further comprise silane compound (V), which comprises one terminal silane functional group (Va) and at least one additional functional group (Vb) reactive with the functional group (Ia) of the latex polymer (I). The combination of silane compound (II) and silane compound (V) surprisingly improves the elongation at break (EB) of the final dip molded article.

[0115] Depending on the type of functional group (Ia) on the latex polymer (I), the functional group (Vb) of the silane compound (V) may be selected from carbon-carbon double bonds, halide functional groups, epoxy, thiol, hydroxy, hydroxylamine, primary or secondary amino, isocyanato, oxazolino, aziridino, imino, carbodiimide, glycol, ester, acetoxy, carboxylic acid, dioxolanone, hydrazide, aldehyde, ketone, and combinations thereof.

[0116] According to the present invention, the silane compound (V) has the structure of the following formula: [ka] During the ceremony, R 4 is independently selected from hydrogen, halogen, hydroxy, alkoxy, hydrocarbyl, or combinations thereof; R 5 is a linear or branched C1-C 20 Alkanediyl, cyclic C3-C 20 alkyl or alkenyl, or arylenediyl, preferably linear C1-C 20 It is an alkanediyl; Z is a functional group (Vb) reactive with the functional group (Ia) of the particles of the latex polymer (I).Preferably, the functional group (Vb) can be selected from carbon-carbon double bonds, halide functional groups, epoxy, thiol, hydroxy, hydroxylamine, primary or secondary amino, isocyanato, oxazolino, aziridino, imino, carbodiimide, glycol, ester, acetoxy, carboxylic acid, dioxolanone, hydrazide, aldehyde, ketone and combinations thereof.The functional group (Vb) of the silane compound (V) may be protected as described above.

[0117] Suitable silane compounds (V) may be selected from (3-glycidyloxypropyl)trialkoxysilane, β-(3,4-epoxycyclohexylethyltrialkoxysilane), dialkoxy(3-glycidyloxypropyl)alkylsilane, 3-glycidoxypropyldialkylalkoxysilane, 5,6-epoxyhexyltrialkoxysilane, aminopropyltrialkoxysilane, hydroxymethyltrialkoxysilane, 3-mercaptopropyltrialkoxysilane, 3-chloropropyltrialkoxysilane, vinyltrialkoxysilane, 3-(trialkoxysilyl)furan, norbornenyltrialkoxysilane, carboxyethylsilanetriol, 3-isocyanatopropyltrialkoxysilane, tris[3-(trialkoxysilyl)propyl]isocyanurate, trialkoxysilylbutyraldehyde, ureidopropyltrialkoxysilane, cyanomethyl[3-(trialkoxysilyl)propyl]trithiocarbonate, S-(octanoyl)mercaptopropyltrialkoxysilane and combinations thereof. Preferably, the alkoxy groups are selected from methoxy and ethoxy groups, more preferably ethoxy groups.

[0118] Preferably, the silane compound (V) is selected from the group consisting of (3-glycidyloxypropyl)trimethoxysilane, (3-glycidyloxypropyl)triethoxysilane, β-(3,4-epoxycyclohexylethyltrimethoxysilane), diethoxy(3-glycidyloxypropyl)methylsilane, 3-glycidoxypropyldimethylethoxysilane, 5,6-epoxyhexyltriethoxysilane, aminopropyltriethoxysilane, hydroxymethyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3-chloropropyltrimethysilane, 3-chloropropyltriethoxy ... The silane may be selected from dimethylsilane, vinyltriethoxysilane, 3-(triethoxysilyl)furan, norbornenyltriethoxysilane, carboxyethylsilanetriol, 3-isocyanatopropyltriethoxysilane, tris[3-(trimethoxysilyl)propyl]isocyanurate, triethoxysilylbutyraldehyde, ureidopropyltrimethoxysilane, cyanomethyl[3-(trimethoxysilyl)propyl]trithiocarbonate, S-(octanoyl)mercaptopropyltriethoxysilane, and combinations thereof.

[0119] The polymer latex composition of the present invention may comprise 80-99.8% by weight, preferably 85-99.8% by weight, more preferably 90-99.5% by weight, even more preferably 92-99.5% by weight, and most preferably 95-99.2% by weight of latex polymer (I) based on the total weight of the particles of latex polymer (I) of the present invention and the silane compound described herein. Thus, the lower limit of the amount of particles of latex polymer (I) may be 80% by weight, 82% by weight, 85% by weight, 86% by weight, 88% by weight, 90% by weight, or 92% by weight based on the total weight of the particles of latex polymer (I) of the present invention and the silane compound described herein. The upper limit of the amount of particles of latex polymer (I) can be 99.8 wt%, 99.5 wt%, 99.2 wt%, 99 wt%, 98 wt%, 97 wt%, 96 wt%, 95 wt%, 94 wt%, or 93 wt% based on the total weight of particles of latex polymer (I) of the present invention and silane compound described herein. The polymer latex composition of the present invention can contain 0.1 to 20 wt%, preferably 0.1 to 15 wt%, more preferably 0.1 to 10 wt%, even more preferably 0.2 to 8 wt%, and most preferably 0.2 to 5 wt% of silane compound (II) based on the total weight of particles of latex polymer (I) of the present invention and silane compound described herein. The lower limit of the amount of silane compound (II) may be 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.8 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, or 3 wt%, based on the total weight of the particles of the latex polymer (I) of the present invention and the silane compound described herein. The upper limit of the amount of silane compound (II) may be 20 wt%, 18 wt%, 15 wt%, 14 wt%, 12 wt%, 10 wt%, 9 wt%, 8 wt%, or 5 wt%, based on the total weight of the particles of the latex polymer (I) of the present invention and the silane compound described herein.The polymer latex composition of the present invention may contain 0.1 to 20% by weight, preferably 0.1 to 15% by weight, more preferably 0.1 to 10% by weight, even more preferably 0.2 to 8% by weight, and most preferably 0.2 to 5% by weight of silane compound (V) based on the total weight of the particles of the latex polymer (I) of the present invention and the silane compound described herein. The lower limit of the amount of silane compound (V) may be 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4% by weight, 0.5% by weight, 0.6% by weight, 0.8% by weight, 1% by weight, 1.5% by weight, 2% by weight, 2.5% by weight, or 3% by weight based on the total weight of the particles of the latex polymer (I) of the present invention and the silane compound described herein. The upper limit of the amount of silane compound (V) can be 20%, 18%, 15%, 14%, 12%, 10%, 9%, 8%, or 5% by weight based on the total weight of the particles of the inventive latex polymer (I) and the silane compound described herein. One of ordinary skill in the art will understand that any range formed by any of the explicitly disclosed lower and upper limits is expressly disclosed herein.

[0120] The mass ratio of silane compound (II) to silane compound (V) may be from 100:1 to 1:100, preferably from 80:1 to 1:80, more preferably from 50:1 to 1:50, even more preferably from 20:1 to 1:20, and most preferably from 10:1 to 1:10.

[0121] The functional group (Ia) on the latex polymer (I) and the functional group (Vb) of the silane compound (V) can be selected to provide the following combination: - the functional group (Ia) is selected from groups having a carbon-carbon double bond and the functional group (Vb) is selected from groups having a carbon-carbon double bond and thiols; - the functional group (Ia) is selected from carboxylic acid functional groups and the functional group (Vb) is selected from epoxy, thiol, hydroxy, primary or secondary amino, isocyanato, oxazolino, aziridino, imino, carbodiimide, glycol groups, ester groups and acetoxy; - the functional group (Ia) is selected from hydroxy and the functional group (Vb) is selected from alkoxysilyl, carboxylic acid functional groups, isocyanato, primary or secondary amino, aldehyde, boronic acid and ester groups; - the functional group (Ia) is selected from epoxy and the functional group (Vb) is selected from carboxylic acid functional groups, hydroxy and ester groups; - the functional group (Ia) is selected from acetoacetyl and the functional group (Vb) is selected from groups having a carbon-carbon double bond, isocyanato, aldehyde, hydrazine, hydrazide and primary or secondary amino; - the functional group (Ia) is selected from primary or secondary amino and the functional group (Vb) is selected from carboxylic acid functional groups, epoxy, ester groups and dioxolanone groups; - functional group (Ia) is selected from acetoxy and functional group (Vb) is selected from hydrazide and primary or secondary amino; - the functional group (Ia) is selected from isocyanato and the functional group (Vb) is selected from carboxylic acid functional groups, hydroxy, primary or secondary amino and thiol; - the functional group (Ia) is selected from alkoxysilyl and the functional group (Vb) is selected from hydroxy and alkoxysilyl; - functional group (Ia) is selected from alkoxy and functional group (Vb) is selected from ester groups; - the functional group (Ia) is selected from ester groups and the functional group (Vb) is selected from hydroxy, carboxylic acid and ester groups; - functional group (Ia) is selected from dioxolanone groups and functional group (Vb) is selected from primary or secondary amino; - functional group (Ia) is selected from halide functional groups and functional group (Vb) is selected from carboxylic acids; - the functional group (Ia) is selected from thiol functional groups and the functional group (Vb) is selected from a carbon-carbon double bond, a carboxylic acid functional group and an isocyanato; - functional group (Ia) is selected from hydroxylamines and functional group (Vb) is selected from aldehydes; - functional group (Ia) is selected from oxazolino and functional group (Vb) is selected from carboxylic acid; - the functional group (Ia) is selected from aziridino and the functional group (Vb) is selected from carboxylic acid and hydroxy; - functional group (Ia) is selected from imino and functional group (Vb) is selected from carboxylic acid; - the functional group (Ia) is selected from carbodiimino and the functional group (Vb) is selected from carboxylic acids; - the functional group (Ia) is selected from glycol groups and the functional group (Vb) is selected from carboxylic acid functional groups; - functional group (Ia) is selected from hydrazides and functional group (Vb) is selected from aldehydes; - the functional group (Ia) is selected from aldehydes and the functional group (Vb) is selected from hydroxy, acetoacetyl, hydroxylamine and hydrazide; the functional group (Ia) is selected from ketones and the functional group (Vb) is selected from hydroxy.

[0122] Preferably, the bond formed by the reaction of the functional group (ia) on the latex polymer (I) with the functional group (Vb) of the silane compound (V) is thermoreversible.

[0123] A silane compound (III) comprising one terminal silane functional group (III-a) and at least one additional functional group (III-b): According to the present invention, any silane compound (III) can be used that contains one terminal silane functional group (III-a) and at least one additional functional group (III-b) capable of forming a thermoreversible bond (III-c) with the functional group (Ia) of the latex polymer (I). The silane compound (III) can ensure that the elastomeric film of the final dip-molded article exhibits the desired mechanical properties, even if sulfur vulcanization is not used.

[0124] The thermally reversible bond (III-c) may be selected from the group consisting of disulfides, tetrasulfides, carbonates, ureas, thioureas, esters, β-hydroxyesters, thioesters, β-hydroxyamines, β-hydroxythioethers, amides, urethanes, enamines, imines, hemiacetals, acetals, hemiketals, ketals, boronate esters, siloxanes, oximes, acylhydrazones, aldols, thiuram disulfides, and trithiocarbonates.

[0125] According to the present invention, the silane compound (III) may have the structure of the following formula: [ka] During the ceremony, R 2 is independently selected from hydrogen, halogen, hydroxy, alkoxy, hydrocarbyl, and combinations thereof; R 3 is a linear or branched C1-C 20 Alkanediyl, cyclic C3-C 20 alkyl or alkenyl, or arylenediyl, preferably linear C1-C 20 It is an alkanediyl; Y is a functional group (III-b).

[0126] The functional group (III-b) may be preferably selected from the group consisting of epoxy, thiol, hydroxy, hydroxylamine, primary or secondary amino, isocyanato, oxazolino, aziridino, imino, carbodiimide, glycol, ester, acetoxy, carboxylic acid, dioxolanone, hydrazide, aldehyde, ketone and combinations thereof. The functional group (III-b) of the silane compound (III) may be protected as described above.

[0127] Suitable silane compounds (III) may be selected from (3-glycidyloxypropyl)trialkoxysilane, β-(3,4-epoxycyclohexylethyltrialkoxysilane), dialkoxy(3-glycidyloxypropyl)alkylsilane, 3-glycidoxypropyldialkylalkoxysilane, 5,6-epoxyhexyltrialkoxysilane, aminopropyltrialkoxysilane, hydroxymethyltrialkoxysilane, 3-mercaptopropyltrialkoxysilane, 3-chloropropyltrialkoxysilane, vinyltrialkoxysilane, 3-(trialkoxysilyl)furan, norbornenyltrialkoxysilane, carboxyethylsilanetriol, 3-isocyanatopropyltrialkoxysilane, tris[3-(trialkoxysilyl)propyl]isocyanurate, trialkoxysilylbutyraldehyde, ureidopropyltrialkoxysilane, cyanomethyl[3-(trialkoxysilyl)propyl]trithiocarbonate, S-(octanoyl)mercaptopropyltrialkoxysilane and combinations thereof. Preferably, the alkoxy groups are selected from methoxy and ethoxy groups, more preferably ethoxy groups.

[0128] Preferably, the silane compound (III) is selected from the group consisting of (3-glycidyloxypropyl)trimethoxysilane, (3-glycidyloxypropyl)triethoxysilane, β-(3,4-epoxycyclohexylethyltrimethoxysilane), diethoxy(3-glycidyloxypropyl)methylsilane, 3-glycidoxypropyldimethylethoxysilane, 5,6-epoxyhexyltriethoxysilane, aminopropyltriethoxysilane, hydroxymethyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxy ... The silane may be selected from the group consisting of mercaptopropyltriethoxysilane, vinyltriethoxysilane, 3-(triethoxysilyl)furan, norbornenyltriethoxysilane, carboxyethylsilanetriol, 3-isocyanatopropyltriethoxysilane, tris[3-(trimethoxysilyl)propyl]isocyanurate, triethoxysilylbutyraldehyde, ureidopropyltrimethoxysilane, cyanomethyl[3-(trimethoxysilyl)propyl]trithiocarbonate, S-(octanoyl)mercaptopropyltriethoxysilane, and combinations thereof.

[0129] The polymer latex composition of the present invention may comprise 80-99.9 wt%, preferably 85-99.9 wt%, more preferably 90-99.9 wt%, even more preferably 92-99.8 wt%, and most preferably 95-99.8 wt% of latex polymer (I) based on the total weight of the particles of the latex polymer (I) of the present invention and the silane compound described herein. Thus, the lower limit of the amount of particles of the latex polymer (I) may be 80 wt%, 82 wt%, 85 wt%, 86 wt%, 88 wt%, 90 wt%, 92 wt%, 94 wt%, or 95 wt% based on the total weight of the particles of the latex polymer (I) of the present invention and the silane compound described herein. The upper limit of the amount of the particles of the latex polymer (I) can be 99.9 wt%, 99.8 wt%, 99.5 wt%, 99.2 wt%, 99 wt%, 98 wt%, 97 wt%, or 96 wt% based on the total weight of the particles of the latex polymer (I) of the present invention and the silane compound described herein. The polymer latex composition of the present invention can contain 0.1 to 20 wt%, preferably 0.1 to 18 wt%, more preferably 0.1 to 15 wt%, even more preferably 0.1 to 12 wt%, and most preferably 0.1 to 10 wt% of the silane compound (III) based on the total weight of the particles of the latex polymer (I) of the present invention and the silane compound described herein. The lower limit of the amount of silane compound (III) can be 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.8 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, or 3 wt%, based on the total weight of the particles of the latex polymer (I) of the present invention and the silane compound described herein. The upper limit of the amount of silane compound (III) can be 20 wt%, 18 wt%, 15 wt%, 14 wt%, 12 wt%, 10 wt%, 9 wt%, 8 wt%, or 5 wt%, based on the total weight of the particles of the latex polymer (I) of the present invention and the silane compound described herein. Those skilled in the art will understand that any range formed by any of the lower and upper limits explicitly disclosed is explicitly disclosed herein.

[0130] According to the present invention, the latex polymer (I) is prepared by aqueous emulsion polymerization as described above. The silane compound (II) or the silane compound (III) is added to the obtained polymer latex containing particles of the latex polymer (I) at any suitable stage, for example, before forming an article containing an elastomeric film from the polymer latex of the present invention. For example, the silane compound (II) or the silane compound (III) can be added to the polymer latex containing the latex polymer (I) before or after it is formulated into a dip molding composition. The same applies to the silane compound (V). The silane compound (V) can be added to the obtained polymer latex containing particles of the latex polymer at any suitable stage, for example, before forming an article containing an elastomeric film from the polymer latex of the present invention, and before or after adding the silane compound (II).

[0131] The functional group (Ia) on the latex polymer (I) and the functional group (III-b) of the silane compound (III) can be selected to provide the combinations described above for the combinations of functional group (Ia) on the latex polymer (I) and functional group (Vb) of the silane compound (V).

[0132] The polymer latex composition of the present invention may further comprise a multivalent cation. Suitable multivalent cations may be metal oxides such as zinc oxide, magnesium oxide, or iron oxide.

[0133] Preparation of the Latex Composition The present invention further relates to a method for preparing the polymer latex composition of the present invention, which comprises: polymerizing, in an emulsion polymerization process, a composition comprising ethylenically unsaturated monomers for a latex polymer (I), comprising at least one monomer that provides a functional group (Ia) after polymerization, to obtain a latex comprising particles of the latex polymer (I) comprising functional group (Ia); and adding a silane compound (II) comprising at least two terminal silane functional groups (II-a) and a thermoreversible bond (II-b), or adding a silane compound (III) comprising one terminal silane functional group (III-a) and at least one additional functional group (III-b) capable of forming a thermoreversible bond (III-c) with the functional group (Ia) of the latex polymer (I);

[0134] Optionally, a compound (V) containing one terminal silane functional group (Va) and at least one additional functional group (Vb) reactive with the functional group (Ia) of the particles of the latex polymer (I) can be added before, during or after the addition of the silane compound (II). All variations on the latex polymer (I), silane compound (II), silane compound (III), silane compound (IV), silane compound (V) and their relative amounts as described above can be used.

[0135] Formulated latex composition for the production of dip-molded articles: The polymer latex composition of the present invention is particularly suitable for dip molding processes. Thus, according to one aspect of the present invention, the polymer latex composition is formulated to produce a curable polymer latex formulation that can be directly used in a dip molding process. For dipping to produce thin disposable gloves, it is desirable to adjust the pH of the formulated polymer latex composition by a pH adjuster to a range of pH 7-11, preferably 8-10, more preferably 9-10, in order to obtain reproducible good physical film properties. For dipping to produce unsupported and / or supported reusable gloves, it is desirable to adjust the pH of the formulated polymer latex composition by a pH adjuster to a range of pH 8-10, preferably 8.5-9.5. The formulated polymer latex composition comprises the polymer latex composition of the present invention, optionally comprising a pH adjuster, preferably ammonia or an alkali hydroxide, and further optionally comprising the usual additives used in these compositions selected from antioxidants, pigments, TiO2, fillers such as silica-based fillers, and dispersants. Suitable silica-based fillers include fumed silica and precipitated silica.

[0136] Alternatively, instead of preparing the polymer latex composition of the present invention, a polymer latex comprising a latex polymer (I) as defined above can be prepared in the same manner as defined above, during or after the preparation step as defined above, and a silane compound (II) as defined above and a silane compound (III) as defined above can be added to provide the prepared latex composition of the present invention. Furthermore, a silane compound (V) as defined above can be added during or after the preparation of the latex polymer composition comprising the polymer latex (I) and the silane compound (II). Of course, all the variations on the latex polymer (I), silane compound (II), silane compound (III), silane compound (IV), silane compound (V) and their relative amounts as described above can be used.

[0137] The compounded polymer latex composition according to the present invention can be added with a conventional vulcanization system to be used in the dip molding process, for example, sulfur can be added in combination with accelerators such as thiurams and carbamates and zinc oxide to make it curable. Alternatively or in addition, crosslinker components, such as polyvalent cations or other polyfunctional organic compounds, suitable for reacting with functional groups on the latex particles to achieve chemical crosslinking, can be added. Preferably, polyvalent cations and / or silica-based fillers can be added to the latex composition according to the present invention. Suitable polyvalent cations include metal oxides, preferably zinc oxide, magnesium oxide, and iron oxide.

[0138] However, it is a particular advantage of the present invention that the compounded latex composition of the present invention can be free of sulfur vulcanizing agents and sulfur vulcanization accelerators and the polymeric latex compound of the present invention can still be cured to provide a dip molded article having the required tensile properties. It is preferred to use a multivalent cation, such as ZnO, as an additional crosslinker component to properly adjust the mechanical properties of very thin elastomeric films, especially those having a film thickness of 0.1 mm or less, preferably 0.01-0.1 mm, more preferably 0.03-0.08 mm.

[0139] Suitably, the polyvalent cation may be present in an amount of up to 20% by weight, based on the total weight of the particles of latex polymer (I), silane compound (II) or silane compound (III) and, if present, silane compound (V).

[0140] In certain heavy duty applications such as industrial gloves, in addition to the self-crosslinking properties of the polymer latex of the present invention, it may be advantageous to use a conventional sulfur vulcanization system as described above to further increase the mechanical strength of the dip molded article.

[0141] Manufacturing method of dip moulded products: In a suitable method for producing a dip-molded latex article, a mold having the desired shape of the final article is first immersed in a coagulant bath containing a solution of a metal salt. The coagulant is usually used as a solution in water, alcohol or a mixture thereof. As specific examples of coagulants, the metal salts can be metal halides such as calcium chloride, magnesium chloride, barium chloride, zinc chloride and aluminum chloride; metal nitrates such as calcium nitrate, barium nitrate and zinc nitrate; metal sulfates such as calcium sulfate, magnesium sulfate and aluminum sulfate; and acetates such as calcium acetate, barium acetate and zinc acetate. Most preferred are calcium chloride and calcium nitrate. The coagulant solution may also contain additives to improve the wetting behavior of the mold.

[0142] The mold is then removed from the bath and optionally dried. The treated mold is then immersed in a formulated latex composition according to the invention, which causes a thin film of latex to solidify on the mold surface. Alternatively, the latex film can be obtained by performing multiple immersion steps, in particular two immersion steps, in sequence.

[0143] The former is then removed from the latex composition and optionally immersed in a water bath to extract, for example, polar components from the composition and to wash the coagulated latex film.

[0144] The latex coated former is then optionally dried, preferably at a temperature below 80°C.

[0145] Finally, the latex coated mold is heat treated at a temperature between 40 and 180°C, e.g., 40-160°C, 40-150°C, or 40-130°C, and / or exposed to UV radiation to obtain the desired mechanical properties for the final film product. The final latex film is then removed from the mold. The duration of the heat treatment depends on the temperature and is typically between 1 and 60 minutes. The higher the temperature, the shorter the treatment time required.

[0146] Alternatively, a cutting and sealing process may be used. In a first step, a continuous elastomeric film of polymer latex is produced, for example, by a casting process and optional curing by heating and / or UV curing. In a next step, two separate continuous elastomeric films are superimposed, and then the superimposed continuous elastomeric film is cut or punched into a preselected shape to obtain two superimposed layers of elastomeric film of a preselected shape. The superimposed layers of elastomeric film are bonded to each other at least in a preselected portion of the periphery of the superimposed layers to form an elastomeric article. The bonding together can be done by using thermal means, preferably selected from heat sealing and welding, or by gluing, or by a combination of heating and gluing.

[0147] The present invention relates to articles made using the polymer latex composition of the present invention or the compounded latex composition of the present invention.

[0148] The present invention is particularly applicable to latex articles selected from healthcare devices such as surgical gloves, examination gloves, condoms, catheters, balloons, tubing, dental dams and aprons, or all different kinds of industrial and household gloves.

[0149] Furthermore, the polymer latex of the present invention can also be used to coat and impregnate substrates, preferably fabric substrates, whereby suitable products include fabric-supported gloves and preformed gaskets.

[0150] The invention will now be further described with reference to the following examples. EXAMPLES

[0151] The following abbreviations are used in the examples: MAA = methacrylic acid Bd = butadiene ACN = acrylonitrile GMA = glycidyl methacrylate tDDM = tert-dodecyl mercaptan Na4EDTA = tetrasodium salt of ethylenediaminetetraacetic acid ZnO = zinc oxide TiO2 = Titanium dioxide TS = Tensile strength EB = Elongation at break FAB = force at break

[0152] Below, all parts and percentages are by weight unless otherwise stated.

[0153] Example 1: Preparation of Latex A A nitrogen purged autoclave was charged with 2 parts by weight (based on monomer solids) of oxirane free seed latex (average particle size 36 nm) and 80 parts by weight water (based on 100 parts by weight monomer with seed latex) and heated to 30°C. Then 0.01 parts by weight Na4EDTA and 0.005 parts by weight Bruggolite FF6 dissolved in 2 parts by weight water were added, followed by 0.08 parts by weight sodium persulfate dissolved in 2 parts by weight water. Monomers (35 parts by weight ACN, 58 parts by weight Bd, 5 parts by weight MAA) were then added over 4 hours along with 0.6 parts by weight tDDM. Over 10 hours, 2.2 parts by weight sodium dodecylbenzenesulfonate, 0.2 parts by weight tetrasodium pyrophosphate and 22 parts by weight water were added. A coactivator feed of 0.13 parts by weight Bruggolite FF6 in 8 parts by weight water was added over 9 hours. The temperature was maintained at 30°C until 95% conversion and 45% total solids. The polymerization was briefly stopped by the addition of 0.08 parts by weight of a 5% aqueous solution of diethylhydroxylamine. The pH was adjusted to pH 7.0 with potassium hydroxide (5% aqueous solution) and residual monomer was removed by vacuum distillation at 60°C. 0.5 parts by weight of Wingstay L type antioxidant (60% dispersion in water) was added to the raw latex and the pH was adjusted to 8.0 by the addition of a 5% aqueous solution of potassium hydroxide.

[0154] Example 2: Preparation of Latex B A nitrogen purged autoclave was charged with 2.0 parts by weight of diphenyl oxide disulfonate dissolved in 185 parts by weight of water per 100 parts by weight of monomer and heated to a temperature of 70° C. 0.1 parts by weight of tDDM and 0.05 parts by weight of Na4EDTA were added to the initial charge in aliquot additions along with 0.7 parts by weight of ammonium peroxodisulfate (12% aqueous solution). Next, a solution of 45.4 parts by weight of Bd, 14.6 parts by weight of ACN, and 5.0 parts by weight of diphenyl oxide disulfonate dissolved in 50 parts by weight of water was added over 6.5 hours. The addition of 40 parts by weight of GMA was started after 1 hour and added over 6.5 hours. After the addition of the monomers, the temperature was maintained at 70° C. The polymerization was maintained to 99% conversion. The reaction mixture was cooled to room temperature and sieved through a filter screen (90 μm).

[0155] Preparation of dip latex examples Latex preparation and maturation XNBR grade latex available from Sintomer (Malaysia) was used throughout the dipping examples. The latex compound was prepared by adding to the latex according to Tables 1 and 2 in parts per hundred rubber (phr) under continuous stirring. The accelerator used is zinc diethyldithiocarbamate. Additive A1 is (3-glycidyloxypropyl)trimethoxysilane, Additive A2 is bis[3-(triethoxysilyl)propyl]disulfide, and Additive A3 is bis[3-(triethoxysilyl)propyl]tetrasulfide. The prepared latex under stirring was then adjusted to pH 10.0 by adding 5% aqueous potassium hydroxide solution, diluted to 18% total solids, and aged at 25°C for at least 16 hours under continuous stirring.

[0156] Spade dipping Spade dipping was performed manually or using an automatic dipping machine. The dipped plate molds were conditioned in an air-circulating oven at 70°C and dipped in a coagulant solution containing 18-20% by weight of calcium nitrate aqueous solution and 2-3% by weight of calcium carbonate at 60°C for 1 second. The dipped plate molds were then placed in an oven set at 75-85°C for a certain period of time, after which the dipped plate molds were dipped in each latex at a temperature of 60-65°C for a certain period of time to obtain latex-dipped plate molds. The latex-dipped plate molds were then gelled in an oven at 100°C for 1 minute, leached in a deionized water leaching tank at 50-60°C for 1 minute, and subsequently cured in an oven at 120°C for 20 minutes. Finally, the cured latex was manually peeled off the plate molds. The cured latex was conditioned in a climate chamber at 23°C (±2) and 50% relative humidity (±5) for at least 16 hours before other physical tests.

[0157] Former immersion Dipping was performed manually or using an automatic dipping machine. The liner glove was placed on the former, the former was conditioned in an air-circulating oven at 70°C, and dipped in a coagulant solution containing 18-20% by weight of calcium nitrate aqueous solution and 2-3% by weight of calcium carbonate at 60°C for 1 second. The former was then placed in an oven set at 75-85°C for a certain period of time, and the former was dipped in each latex at a temperature of 60-65°C for a certain period of time, pulled out, and left rotating to prevent droplets from forming, resulting in a latex-dipped former. The latex-dipped former was then gelled in an oven at 100°C for 1 minute, film-beaded, leached in a deionized water leaching tank at 50-60°C for 1 minute, and subsequently cured in an oven at 120°C for 20 minutes. Finally, the cured latex glove was manually peeled off from the former. The gloves were conditioned in a climate chamber at 23° C. (±2) and 50% relative humidity (±5) for at least 16 hours prior to any other physical testing.

[0158] Tensile property measurements (ASTM D6319 and EN 455) Tensile properties of the final gloves or films were tested according to ASTM D6319 and EN455 test methods. Dumbbell specimens were cut from the palm area of ​​gloves or films prepared from each latex compound. Unaged and aged specimens ("aged" refers to specimens placed in an oven at 100°C for 22 hours before testing for tensile properties) were conditioned at 23±2°C and 50±5% relative humidity for 24 hours before testing on the extensometer. Film thickness (mm) was measured with typical film thickness values ​​between 0.060 and 0.070 mm. The reported tensile strength (TS) corresponds to the maximum tensile stress measured when stretching the specimen to break. The elongation at break (EB) corresponds to the elongation at which break occurs. The force at break (FAB) corresponds to the force at which break occurs. Meanwhile, modulus of elasticity 100, 300 and 500 correspond to the tensile stress measured when stretching the specimen at 100, 300 and 500% elongation.

[0159] Stress relaxation time Stress relaxation time experiments were performed under strain control at specific temperatures (115°C, 135°C and 155°C) in tension mode using a DMA Q800 instrument. Measuring film samples of approximately 20mm x 6mm x 0.06mm were mounted on tensile clamps with a static force of less than 0.01N. The axial force was then adjusted to 0N and the instrument chamber was heated to at least 95% of the target temperature within 3 minutes and allowed to equilibrate at the target temperature for approximately 5 minutes. Each sample was then subjected to an instantaneous 2% strain. The stress decay was monitored for at least 20 minutes while maintaining a constant strain. The period required for the stress decay to reach 1 / e of the initial value is the stress relaxation time.

[0160] Measuring durability The dipped gloves of the former to be tested were cut with scissors in a straight line from the crotch between the index and middle fingers to the cuff line under the thumb. The specimen cuts of the thumb and fingers were maintained along the outer edge to a point at the tip of the thumb. The specimen was opened and the tip of the index finger was attached to the top jaw of the automatic stress relief apparatus and the clamp was closed. The lower area of ​​the specimen was attached between the jaws of the lower clamp and the clamp was closed. The free "wings" of the specimen were attached to the side bars of the test apparatus using masking tape. The test apparatus was placed in a beaker containing an aqueous citric acid solution at pH 4 and the crotch between the thumb and index finger was completely immersed in the acid solution. The test apparatus was set to zero (0) and the test was started. The test was performed at 25°C. The measurement was automatically stopped when the specimen broke and the number of cycles required to reach the breaking point was recorded. The test was repeated five times to calculate the average and a new aqueous citric acid solution was used for each test. The reported durability (in minutes) corresponds to the mean number of cycles (average number of cycles required to cause specimen failure) divided by 267 (total number of cycles per hour) multiplied by 60. Tests were stopped after 300 minutes or at break. Fatigue durability is preferably 60 minutes or greater. Performance levels can be classified as "fail" for less than 60 minutes, "poor" for 60-120 minutes, "medium" for 120-240 minutes, and "good" for more than 240 minutes.

[0161] Table 1 (Examples 1-9 and Comparative Example CE1) shows the latex compounding formulations and ageing for spade dipping.

[0162] Table 1: Latex formulations and ageing for spade dipping [Table 1]

[0163] Table 2 (Examples 10 to 15 and Comparative Example 2) shows the latex compounding formulations and aging for former immersion.

[0164] Table 2: Latex formulations and ageing for former dipping [Table 2]

[0165] The tensile data of the above as-prepared films were measured and summarized in Tables 3-6.

[0166] Table 3: Non-aging results for Examples 1-9 and Comparative Example 1 [Table 3]

[0167] Table 4: Aging results for Examples 1 to 9 and Comparative Example 1 [Table 4]

[0168] The comparative example (Comparative Example 1) is a latex cured with conventional sulfur and accelerator. As shown in Table 3 (non-aged samples), the tensile properties of all samples containing silane (Examples 1-9) are comparable to Comparative Example 1. For the aged samples shown in Table 4, all samples containing silane (Examples 1-9) are softer, i.e., have a lower modulus 500 (M500), higher tensile strength (TS) and higher elongation at break (EB) compared to Comparative Example 1.

[0169] Examples 1 and 8 show the use of Additive A1 alone, while Examples 2 and 7 show the use of Additive A2 alone. When both silanes were used at increasing phr, they showed tensile properties comparable to Comparative Example 1.

[0170] As shown in Examples 3 and 9, when Additive 1 was used in combination with Additive 2 or Additive 3 in a 1:1 ratio, both examples showed comparable TS and showed improvements in terms of EB and lower M500.

[0171] Table 5: Non-aging results for Examples 10 to 15 and Comparative Example 2 [Table 5]

[0172] Table 6: Aging results for Examples 10 to 14 and Comparative Example 2 [Table 6]

[0173] Comparative Example 2 uses a latex formulation that does not contain an accelerator. As shown in Table 5 (non-aged samples), the tensile properties of all samples containing silane (Examples 10-15) are comparable to Comparative Example 2. As shown in Table 6, a similar behavior is observed for the aged samples, with all samples containing silane (Examples 10-15) being softer and having higher EB. The use of compound (II) alone, shown in Example 11, had comparable tensile strength but provided the highest EB and softest characteristics.

[0174] The relaxation time (τ * ) were measured and are summarized in Table 7.

[0175] Table 7: Stress relaxation times of samples from spade immersion [Table 7]

[0176] Stress relaxation time (τ * ) is the time required for a latex polymer to relax its stress under a constant strain at a given temperature. * indicates less stability of crosslinked and entangled polymer network. As shown in Table 7, the stress relaxation times of Examples 1-4 and Examples 7-9 are all faster than Comparative Example 1. At the same time, the tensile performance of Examples 1-4 and Examples 7-9 is maintained. The samples containing Additive A1 in combination with Additive A2 or Additive A3 show the fastest stress relaxation times.

[0177] The durability results of the above as-prepared films were measured and are summarized in Table 8.

[0178] Table 8: Durability results for Examples 10 to 15 and Comparative Example 2 [Table 8]

[0179] From the durability results shown in Table 8, for Examples 10, 13 and 14, the addition of 0.7 phr of Additive A1 provided good durability. The use of Additive A2 does not reduce durability performance. When Additive A1 is used alone or in combination with Additive A2, similar performance is achieved as the latex formulation without accelerator (Comparative Example 2). Surprisingly, the use of Additive A2 when used alone (Example 11) has a moderate level of durability performance. The use of Additive A3 alone provides low but longer than the preferred 60 minute durability time.

Claims

1. Polymer latex compositions for the preparation of elastomer films, including the following: (I) Latex polymer particles obtained by free radical emulsion polymerization of a composition containing an ethylenically unsaturated monomer, wherein the latex polymer particles contain a functional group (I-a); and (II) Silane compounds comprising at least two terminal silane functional groups (II-a) and a thermoreversible bond (II-b); Here, the polymer latex composition does not contain sulfur vulcanizing agents or vulcanization accelerators.

2. The thermoreversible bond (II-b) can be broken and rearranged at temperatures below 200°C; and / or The thermoreversible bond (II-b) is selected from the group consisting of disulfides, tetrasulfides, carbonates, ureas, thioureas, esters, β-hydroxyesters, thioesters, β-hydroxyamines, β-hydroxythioethers, amides, urethanes, enamines, imines, hemiacetals, acetals, hemiketals, ketals, boronate esters, siloxanes, oximes, acylhydrazones, aldols, thiuram disulfide, and trithiocarbonates; and / or The polymer latex composition according to claim 1, wherein the functional group (I-a) of the particles of the latex polymer (I) is selected from the group consisting of carbon-carbon double bond, carboxylic acid, hydroxy, epoxy, acetoacetyl, primary or secondary amino, acetoxy, isocyanate, alkoxy, dioxolanone, halide functional group, thiol, hydroxylamine, oxazolino, azilidino, imino, carbodiimide, glycol, ester, hydrazide, aldehyde, ketone, and combinations thereof.

3. The polymer latex composition according to claim 1 or 2, wherein the silane compound (II) has the structure of the following formula: 【Chemistry 1】 During the ceremony, X is a thermoreversible bond (II-b) selected from the group consisting of disulfides, tetrasulfides, carbonates, ureas, thioureas, esters, β-hydroxyesters, thioesters, β-hydroxyamines, β-hydroxythioethers, amides, urethanes, enamines, imines, hemiacetals, acetals, hemiketals, ketals, boronate esters, siloxanes, oximes, acylhydrazones, aldols, thiuram disulfide, and trithiocarbonates; R is independently selected from hydrogen, halogen, hydroxyl, alkoxy, hydrocarbyl, silane, or a combination thereof; R １ These are independently linear or branched C １ -C ２０ Alkandiyl, cyclic C ３ -C ２０ It is an alkyl or alkenyl or arylendyl; and / or Silane compounds (II) include bis[3-(trialkoxysilylpropyl)]disulfide, bis[3-(trialkoxysilyl)propyl]tetrasulfide, bis[3-(trialkoxysilyl)propyl]carbonate, N,N'-bis[3-(trialkoxysilyl)propyl]urea, N,N'-bis[3-(trialkoxysilyl)propyl]thiourea, 2-hydroxy-3-[3-(trialkoxysilyl)propoxy]propyl-3-(trihydroxysilyl)propanoate, 2-hydroxy-7-(trialkoxysilyl)heptyl-3-(trihydroxysilyl)propanoate, and 9,9-dialkoxy-1,1,1-trihydroxy-10-oxa-5-thia-1,9-disiladodecane Selected from the group consisting of -4-one, N-[3-(trialkoxysilyl)propyl]-3-(trihydroxysilyl)propenamide, (trialkoxysilyl)methyl N-[3-(trialkoxysilyl)propyl]carbamate, (7E)-4,4,12,12-tetraalkoxy-3,13-dioxa-8-aza-4,12-dicilapentadeca-7-ene, 4,4,11,11-tetraalkoxy-3,6,12-trioxa-4,11-dicilatetradecane-7-ol, 4,4,10,10-tetraalkoxy-7-[3-(trialkoxysilyl)propyl]-3,6,8,11-tetraoxa-4,10-dicilatridecane, oligomer siloxanes, and combinations thereof; and / or Silane compound (II) is formed in situ from a first silane compound (IV) which includes one terminal silane functional group (IV-a) and at least one additional functional group (IV-b) which can form a thermoreversible bond (IV-c) with an additional functional group (IV-b) of a second silane compound (IV).

4. Polymer latex composition according to claim 3: Here, at least one additional functional group (IV-b) of the first silane compound (IV) and / or at least one additional functional group (IV-b) of the second silane compound (IV) is protected, and / or Silane compound (IV) has the structure shown in the following formula: 【Chemistry 2】 During the ceremony, R ２ These are independently selected from hydrogen, halides, hydroxyl, alkoxyl, hydrocarbyl, or combinations thereof. R ３ is a straight-chain or branched C １ -C ２０ alkanediyl, cyclic C ３ -C ２０ alkyl or alkenyl, or arylenediyl; Y is a functional group (IV-b) selected from the group consisting of epoxy, thiol, hydroxy, hydroxylamine, primary or secondary amino, isocyanate, oxazolino, azilidino, imino, carbodiimide, glycol, ester, acetoxy, carboxylic acid, dioxolanone, hydrazide, aldehyde, ketone and combinations thereof; and / or Silane compounds (IV) include (3-glycidyloxypropyl)trialkoxysilane, (3-glycidyloxypropyl)trialkoxysilane, β-(3,4-epoxycyclohexylethyltrialkoxysilane), dialkoxy(3-glycidyloxypropyl)alkylsilane, 3-glycidoxypropyldialkylalkoxysilane, 5,6-epoxyhexyltrialkoxysilane, aminopropyltrialkoxysilane, hydroxymethyltrialkoxysilane, 3-mercaptopropyltrialkoxysilane, and 3-chloropropyltrialkoxysilane. The following are selected from the group consisting of silanes, vinyltrialkoxysilanes, 3-(trialkoxysilyl)furans, norvonenyltrialkoxysilanes, carboxyethylsilanetriols, 3-isocyanatopropyltrialkoxysilanes, tris[3-(trialkoxysilyl)propyl]isocyanurate, trialkoxysilylbutyraldehyde, ureidopropyltrialkoxysilanes, cyanomethyl[3-(trialkoxysilyl)propyl]trithiocarbonate, S-(octanoyl)mercaptopropyltrialkoxysilanes, and combinations thereof.

5. Further comprising a silane compound (V), wherein the silane compound (V) comprises one terminal silane functional group (V-a) and at least one additional functional group (V-b) that reacts with a functional group (I-a) of the latex polymer (I), A polymer latex composition according to any one of claims 1 to 4.

6. The polymer latex composition according to claim 5, wherein the functional group (V-b) of the silane compound (V) is selected from the group consisting of a carbon-carbon double bond, a halide functional group, epoxy, thiol, hydroxy, hydroxylamine, primary or secondary amino, isocyanate, oxazolino, azilidino, imino, carbodiimide, glycol, ester, acetoxy, carboxylic acid, dioxolanone, hydrazide, aldehyde, ketone and combinations thereof: Here, the silane compound (V) has the structure shown in the following formula: 【Transformation 3】 During the ceremony, R ４ These are independently selected from hydrogen, halides, hydroxyl, alkoxyl, hydrocarbyl, or combinations thereof. R ５ C is a linear or branched C １ -C ２０ Alkandiyl, cyclic C ３ -C ２０ It is an alkyl or alkenyl or arylendyl; Z is a functional group (V-b) that is reactive with the functional group (I-a) of the particles of the latex polymer (I), where the functional group (V-b) is selected from the group consisting of carbon-carbon double bonds, halide functional groups, epoxy, thiol, hydroxy, hydroxylamine, primary or secondary amino, isocyanate, oxazolino, azilidino, imino, carbodiimide, glycol, ester, acetoxy, carboxylic acid, dioxolanone, hydrazide, aldehyde, ketone and combinations thereof; and / or Silane compound (V) includes (3-glycidyloxypropyl)trialkoxysilane, (3-glycidyloxypropyl)trialkoxysilane, β-(3,4-epoxycyclohexylethyltrialkoxysilane), dialkoxy(3-glycidyloxypropyl)alkylsilane, 3-glycidoxypropyldialkylethoxysilane, 5,6-epoxyhexyltrialkoxysilane, aminopropyltrialkoxysilane, hydroxymethyltrialkoxysilane, 3-mercaptopropyltrialkoxysilane, and 3-chloropropyltrialkoxysilane. Selected from the group consisting of lan, vinyltrialkoxysilane, 3-(trialkoxysilyl)furan, norvonenyltrialkoxysilane, carboxyethylsilanetriol, 3-isocyanatopropyltrialkoxysilane, tris[3-(trialkoxysilyl)propyl]isocyanurate, trialkoxysilylbutyraldehyde, ureidopropyltrialkoxysilane, cyanomethyl[3-(trialkoxysilyl)propyl]trithiocarbonate, S-(octanoyl)mercaptopropyltrialkoxysilane, and combinations thereof.

7. The polymer latex composition according to any one of claims 1 to 6, wherein the monomer composition for obtaining particles of latex polymer (I) comprises the following: (i) 15–99% by weight of conjugated dienes; (ii) A monomer selected from ethylenically unsaturated nitrile compounds in an amount of 1 to 80% by weight; (iii) 0 to 10% by weight of an ethylenically unsaturated compound containing functional group (a) that is different from (i) and (ii); (iv) 0 to 80% by weight of vinyl aromatic monomers; and (v) 0 to 65% by weight of an alkyl ester of an ethylenically unsaturated acid; Weight percentage is based on the total weight of monomers in the monomer composition.

8. The polymer latex composition according to claim 7: where, (i) The conjugated diene is selected from butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, and combinations thereof; (ii) The ethylenically unsaturated nitrile compound is selected from (meth)acrylonitrile, α-cyanoethylacrylonitrile, fumaronitrile, α-chloronitrile, and combinations thereof; (iii) Different ethylenically unsaturated compounds containing functional group (a) from (i) and (ii) are selected from the following: (iii1) Ethylene unsaturated compounds having at least two different ethylenically unsaturated groups; (iii2) Ethylene unsaturated acids and their salts; (iii3) Hydroxy-functionalized ethylenically unsaturated compounds; (iii4) Oxirane-functionalized ethylenically unsaturated compounds; (iii5) Acetoacetyl-functionalized ethylenically unsaturated compounds; (iii6) Ethylene-unsaturated compounds having a primary or secondary amino group; (iii7) Acetoxy-functionalized ethylenically unsaturated compounds; (iii8) Isocyanato-functionalized ethylenically unsaturated compounds; (iii9) Alkoxysilyl functionalized ethylenically unsaturated compounds; (iii10) Alkoxy-functionalized ethylenically unsaturated compounds; (iii11) Dioxolanone-functionalized ethylenically unsaturated compounds; (iii12) Halogenated functional ethylenically unsaturated compounds; (iii13) Thiol-functionalized ethylenically unsaturated compounds; (iii14) Hydroxylamine-functionalized ethylenically unsaturated compounds; (iii15) Oxazolino-functionalized ethylenically unsaturated compounds; (iii16) Azilidino-functionalized ethylenically unsaturated compounds; (iii17) Imino-functional ethylenically unsaturated compounds; (iii18) Carbodiimino-functionalized ethylenically unsaturated compounds; (iii19) Glycol-functionalized ethylenically unsaturated compounds; (iii20) Hydrazide functional group ethylenically unsaturated compounds; (iii21) Aldehyde-functionalized ethylenically unsaturated compounds; (iii22) Ketone-functionalized ethylenically unsaturated compounds; And combinations of these; (iv) The vinyl aromatic monomer is selected from styrene, α-methylstyrene, and combinations thereof; (v) The alkyl ester of the ethylenically unsaturated acid is selected from methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and combinations thereof; And combinations of these; A mixture of ethylenically unsaturated monomers for latex polymer (I) optionally comprises ethylenically unsaturated monomers selected from the following: (vi) vinyl carboxylate; (vii) A monomer having at least two identical ethylenically unsaturated groups; And combinations thereof.

9. Polymer latex composition according to any one of claims 6 to 8: where, - Functional group (I-a) is selected from groups having a carbon-carbon double bond, and functional group (V-b) is selected from groups having a carbon-carbon double bond and thiols; or - Functional group (I-a) is selected from carboxylic acid functional groups, and functional group (V-b) is selected from epoxy, thiol, hydroxy, primary or secondary amino, isocyanate, oxazolino, azilidino, imino, carbodiimide, glycol group, ester group, and acetoxy; or - Functional group (I-a) is selected from hydroxyl, and functional group (V-b) is selected from alkoxysilyl, carboxylic acid functional groups, isocyanates, primary or secondary aminos, aldehydes, boronic acids, and ester groups; or - Functional group (I-a) is selected from epoxy, and functional group (V-b) is selected from carboxylic acid functional groups, hydroxyl groups, and ester groups; or - Functional group (I-a) is selected from acetoacetyl, and functional group (V-b) is selected from groups having a carbon-carbon double bond, isocyanates, aldehydes, hydrazines, hydrazides, and primary or secondary aminos; or - Functional group (I-a) is selected from primary or secondary aminos, and functional group (V-b) is selected from carboxylic acid functional groups, epoxy groups, ester groups, and dioxolanone groups; or - Functional group (I-a) is selected from acetoxy, and functional group (V-b) is selected from hydrazide and primary or secondary amino; or - Functional group (I-a) is selected from isocyanates, and functional group (V-b) is selected from carboxylic acid functional groups, hydroxy, primary or secondary amino and thiols; or - Functional group (I-a) is selected from alkoxysilyl groups, and functional group (V-b) is selected from hydroxy and alkoxysilyl groups; or - Functional group (I-a) is selected from alkoxy groups, and functional group (V-b) is selected from ester groups; or - Functional group (I-a) is selected from ester groups, and functional group (V-b) is selected from hydroxyl groups, carboxylic acid groups, and ester groups; or - Functional group (I-a) is selected from dioxolanone groups, and functional group (V-b) is selected from primary or secondary aminos; or - Functional group (I-a) is selected from halogen functional groups, and functional group (V-b) is selected from carboxylic acids; or - Functional group (I-a) is selected from thiol functional groups, and functional group (V-b) is selected from carbon-carbon double bonds, carboxylic acid functional groups, and isocyanates; or - Functional group (I-a) is selected from hydroxylamines, and functional group (V-b) is selected from aldehydes; or - Functional group (I-a) is selected from oxazolino, and functional group (V-b) is selected from carboxylic acid; or - Functional group (I-a) is selected from azilidino, and functional group (V-b) is selected from carboxylic acid and hydroxyl; or - Functional group (I-a) is selected from iminos, and functional group (V-b) is selected from carboxylic acids; or - Functional group (I-a) is selected from carbodiiminos, and functional group (V-b) is selected from carboxylic acids; or - Functional group (I-a) is selected from glycol groups, and functional group (V-b) is selected from carboxylic acid functional groups; or - Functional group (I-a) is selected from hydrazides, and functional group (V-b) is selected from aldehydes; or - Functional group (I-a) is selected from aldehydes, and functional group (V-b) is selected from hydroxy, acetoacetyl, hydroxylamine, and hydrazides; or - Functional group (I-a) is selected from ketones, and functional group (V-b) is selected from hydroxyl groups.

10. A method for preparing a polymer latex composition, including the following steps: (A) Polymerizing a composition containing an ethylenically unsaturated monomer for a latex polymer (I) containing at least one monomer that gives a functional group (I-a) after polymerization in an emulsion polymerization process to obtain a latex containing particles of the latex polymer (I) containing the functional group (I-a); and (B1) Adding a silane compound (II) containing at least two terminal silane functional groups (II-a) and a thermoreversible bond (II-b); and (C) Optionally, add a compound (V) comprising one terminal silane functional group (V-a) and at least one additional functional group (V-b) that is reactive with the functional group (I-a) of the latex polymer (I) particles.

11. Use of the polymer latex composition according to any one of claims 1 to 9 for the manufacture of elastomer articles, or for coating or impregnating a substrate.

12. A formulated polymer latex composition suitable for the production of immersion molded articles, comprising the polymer latex composition described in any one of claims 1 to 9, and optionally comprising an auxiliary agent selected from a free radical initiator, a pigment and a combination thereof, and optionally comprising a polyvalent cation and / or a silica-based filler: However, the formulated polymer latex composition does not contain sulfur vulcanizing agents or vulcanization accelerators.

13. Method for manufacturing immersion molded products using the following steps: (a) To provide the formulated latex composition according to claim 12; (b) Immersing 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 coagulation bath and allow it to dry as desired; (d) Immerse the molds processed in steps (b) and (c) in the prepared latex composition of step (a); (e) Solidifying a latex film on the surface of the mold; (f) Removing the latex-coated mold from the prepared latex composition and optionally immersing the latex-coated mold in a water bath; (g) Optionally, dry the latex-coated mold; (h) Heat-treating the latex-coated mold obtained from step (e) or (f) at a temperature of 40°C to 180°C, and / or exposing the latex-coated mold obtained from step (e) or (f) to UV radiation; (i) Removing the latex article from the mold.

14. A method for manufacturing an elastomer article, including the following steps: (a) Obtaining a continuous elastomer film from the polymer latex composition according to any one of claims 1 to 9; (b) Optionally, heat-treating the continuous elastomer film and / or exposing the continuous elastomer film to UV radiation; (c) Overlapping and arranging two separate continuous elastomer films; (d) Cutting or punching out a continuous elastomer film arranged in a stack to a predetermined shape to obtain two layers of elastomer films of the predetermined shape stacked on top of each other; (e) Joining superimposed layers together at at least a pre-selected portion of the surrounding area to form an elastomer article.

15. An article manufactured using the polymer latex composition described in any one of claims 1 to 9 or the formulated latex composition described in claim 12.

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