The invention relates to the use of vinyl acetate-copolymers as a shrinkage-reducing additive (low profile additive) in cold-curing systems for producing composite materials, characterized in that vinyl acetate-copolyerisate of 40 to 95 wt % vinyl acetate and 5 to 60 wt % of one or more co-monomers from the group containing vinyl esters of unbranched or branched carboxylic acids having 3 to 20 C-atoms and methacrylic acid esters and acrylic acid esters of unbranched or branched alcohols having 2 to 15 C-atoms are used, wherein the specifications in wt % relate to the total weight of the co-monomers and add up to 100 wt %.

The invention relates to the use of vinyl acetate-copolymers as a shrinkage-reducing additive (low profile additive) in cold-curing systems for producing composite materials, characterized in that vinyl acetate-copolyerisate of 40 to 95 wt % vinyl acetate and 5 to 60 wt % of one or more co-monomers from the group containing vinyl esters of unbranched or branched carboxylic acids having 3 to 20 C-atoms and methacrylic acid esters and acrylic acid esters of unbranched or branched alcohols having 2 to 15 C-atoms are used, wherein the specifications in wt % relate to the total weight of the co-monomers and add up to 100 wt %.

Provided herein are processes for the generation of composite polymer materials utilizing a single resin. The processes utilize diffusion between a region undergoing a polymerization reaction preferentially polymerizing one monomer component and an unreactive region. Diffusion and subsequent/concurrent polymerization results in a higher concentration of the more reactive monomer component in the reacting region and a higher concentration of the less reactive monomer components in the unreactive region. The unreactive region may be later polymerized. In embodiments, photopolymerization is used and the regions are generated by a mask or other mechanism to pattern the light.

Provided herein are processes for the generation of composite polymer materials utilizing a single resin. The processes utilize diffusion between a region undergoing a polymerization reaction preferentially polymerizing one monomer component and an unreactive region. Diffusion and subsequent/concurrent polymerization results in a higher concentration of the more reactive monomer component in the reacting region and a higher concentration of the less reactive monomer components in the unreactive region. The unreactive region may be later polymerized. In embodiments, photopolymerization is used and the regions are generated by a mask or other mechanism to pattern the light.

A multistage emulsion polymerization process comprises polymerizing a first monomer composition comprising from 50 to 95 weight percent of vinyl acetate, from 5 to 40 weight percent of at least one vinyl ester of a C.sub.5 to C.sub.18 unsaturated carboxylic acid, and optionally up to 40 weight percent of ethylene, all based on the total weight of monomers in the first monomer composition, to produce a first stage polymer. A second monomer composition comprising 40 to 89.95 weight percent of at least one ester of methacrylic acid or a vinyl aromatic monomer, 10 to 59.95 weight percent of at least one ester of acrylic acid, and from 0.05 to 10 weight percent of at least one comonomer with acid functionality, based on the total weight of monomers in the second monomer composition, is then polymerized in the presence of the first stage polymer to produce a second stage polymer.

A multistage emulsion polymerization process comprises polymerizing a first monomer composition comprising from 50 to 95 weight percent of vinyl acetate, from 5 to 40 weight percent of at least one vinyl ester of a C.sub.5 to C.sub.18 unsaturated carboxylic acid, and optionally up to 40 weight percent of ethylene, all based on the total weight of monomers in the first monomer composition, to produce a first stage polymer. A second monomer composition comprising 40 to 89.95 weight percent of at least one ester of methacrylic acid or a vinyl aromatic monomer, 10 to 59.95 weight percent of at least one ester of acrylic acid, and from 0.05 to 10 weight percent of at least one comonomer with acid functionality, based on the total weight of monomers in the second monomer composition, is then polymerized in the presence of the first stage polymer to produce a second stage polymer.

A multistage emulsion polymerization process comprises polymerizing a first monomer composition comprising from 50 to 95 weight percent of vinyl acetate, from 5 to 40 weight percent of at least one vinyl ester of a C.sub.5 to C.sub.18 unsaturated carboxylic acid, and optionally up to 40 weight percent of ethylene, all based on the total weight of monomers in the first monomer composition, to produce a first stage polymer. A second monomer composition comprising 40 to 89.95 weight percent of at least one ester of methacrylic acid or a vinyl aromatic monomer, 10 to 59.95 weight percent of at least one ester of acrylic acid, and from 0.05 to 10 weight percent of at least one comonomer with acid functionality, based on the total weight of monomers in the second monomer composition, is then polymerized in the presence of the first stage polymer to produce a second stage polymer.

A modified polymer including (a) a main chain containing a fluorine-containing polymer and (b) a side chain represented by the following formula (b1′) and/or a side chain represented by the following formula (b2′). The formula (b1′) is —CH.sub.2—CR.sup.b1(—X)—C(═O)—Y—Z—Rf, wherein X is a hydrogen atom, a methyl group, or a halogen atom; Y is —O— or —NH—; Z is a direct bond or a divalent organic group; Rf is a C1-C20 fluoroalkyl group; and R.sup.b1 is a hydrogen atom or a monovalent organic group. The formula (b2′) is —CH.sub.2—CR.sup.b2(—R.sup.1)—C(═O)—O—Si(—CH.sub.3).sub.2—[O—Si(—CH.sub.3).sub.2].sub.n—O—Si(—CH.sub.3).sub.2—R.sup.2, wherein R.sup.1 is a hydrogen atom or a methyl group; R.sup.2 is a hydrogen atom or a methyl group; R.sup.b2 is a hydrogen atom or a monovalent organic group; and n is 3 to 200.

A modified polymer including (a) a main chain containing a fluorine-containing polymer and (b) a side chain represented by the following formula (b1′) and/or a side chain represented by the following formula (b2′). The formula (b1′) is —CH.sub.2—CR.sup.b1(—X)—C(═O)—Y—Z—Rf, wherein X is a hydrogen atom, a methyl group, or a halogen atom; Y is —O— or —NH—; Z is a direct bond or a divalent organic group; Rf is a C1-C20 fluoroalkyl group; and R.sup.b1 is a hydrogen atom or a monovalent organic group. The formula (b2′) is —CH.sub.2—CR.sup.b2(—R.sup.1)—C(═O)—O—Si(—CH.sub.3).sub.2—[O—Si(—CH.sub.3).sub.2].sub.n—O—Si(—CH.sub.3).sub.2—R.sup.2, wherein R.sup.1 is a hydrogen atom or a methyl group; R.sup.2 is a hydrogen atom or a methyl group; R.sup.b2 is a hydrogen atom or a monovalent organic group; and n is 3 to 200.

To provide a fluorinated copolymer dispersion, whereby it is possible to obtain an article being excellent in water-and-oil repellency and less susceptible to a decrease in the water-and-oil repellency by alkali, etc. and which presents little impact to the environment by an organic solvent; a method for its production; and an article which is excellent in water-and-oil repellency and is less susceptible to a decrease in the water-and-oil repellency by alkali, etc. The fluorinated copolymer dispersion comprises an aqueous medium and a fluorinated copolymer dispersed in the aqueous medium, wherein the fluorinated copolymer has units based on the following monomer (a) and units based on the following monomer (b), the proportion of the units based on the monomer (a) being from 20 to 60 mol % to all units constituting the fluorinated copolymer, and the fluorinated copolymer has a number average molecular weight of from 10,000 to 100,000: Monomer (a): a compound represented by CH.sub.2═CH—R.sup.f (R.sup.f is a C.sub.1-8 perfluoroalkyl group); and Monomer (b): a monomer copolymerizable with the monomer (a).