The present invention is directed to partially fluorinated copolymers and the production thereof. More specifically, the copolymers, which are preferably produced by a solution polymerization process, preferably have at least three units, the first unit selected from 2,3,3,3-tetrafluoropropene and 1,3,3,3-tetrafluoropropene, the second unit having a polymerized monomer selected from the vinyl esters and vinyl ethers, and the third unit having a polymerized monomer derived from a hydroxyl group-containing vinyl ether. The resulting copolymer is environmentally friendly, has favorable molecular weight characteristics, and may be shipped economically in high concentration.

The fluorine-containing copolymer of the present invention includes: a structural unit (A) represented by the following formula (1); and at least one selected from the group consisting of a structural unit (B) represented by the following formula (2), a structural unit (C) represented by the following formula (3), and a structural unit (D) represented by the following formula (4):

##STR00001##

in the formula (1), R.sub.ff.sup.1 to R.sub.ff.sup.4 each independently represent a fluorine atom, a perfluoroalkyl group having 1 to 7 carbon atoms, or a perfluoroalkyl ether group having 1 to 7 carbon atoms, and R.sub.ff.sup.1 and R.sub.ff.sup.2 are optionally linked to form a ring;

##STR00002##

in the formula (2), R.sup.1 to R.sup.3 each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 7 carbon atoms, R.sup.4 represents a perfluoroalkyl group having 1 to 7 carbon atoms, the perfluoroalkyl group optionally has a ring structure, one or some of the fluorine atoms are optionally substituted by a halogen atom other than a fluorine atom, and one or some of fluorine atoms in the perfluoroalkyl group are optionally substituted by a halogen atom other than a fluorine atom;

##STR00003##

in the formula (3), R.sup.5 to R.sup.8 each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 7 carbon atoms, the perfluoroalkyl group optionally has a ring structure, one or some of the fluorine atoms are optionally substituted by a halogen atom other than a fluorine atom, and one or some of fluorine atoms in the perfluoroalkyl group are optionally substituted by a halogen atom other than a fluorine atom; and

##STR00004##

in the formula (4), Z represents an oxygen atom, a single bond, or —OC(R.sup.19R.sup.20)O—, R.sup.9 to R.sup.20 each independently represent a fluorine atom, a perfluoroalkyl group having 1 to 5 carbon atoms, or a perfluoroalkoxy group having 1 to 5 carbon atoms, one or some of the fluorine atoms are optionally substituted by a halogen atom other than a fluorine atom, one or some of fluorine atoms in the perfluoroalkyl group are optionally substituted by a halogen atom other than a fluorine atom, one or some of fluorine atoms in the perfluoroalkoxy group are optionally substituted by a halogen atom other than a fluorine atom, s and t are each independently 0 to 5, and s+t represents an integer of 1 to 6 (when Z is —OC(R.sup.19R.sup.20)O—, s+t is optionally 0).

The multifunctional compound is represented by formula X—C(R)RF—Y, in which X and Y are each independently —C(O)—O-M, —C(O)-HAL, —C(O)—NR.sup.1.sub.2, —C≡N, —C(O)NR.sup.1—SO.sub.2—R.sub.f.sup.1-W, or a fluorinated alkenyl group that is optionally interrupted by one or more —O— groups. HAL is —F, —Cl, or —Br. R.sub.f.sup.1 is a fluorinated alkylene group that is optionally interrupted by one or more —O— groups. W is —F, —SO.sub.2Z, —CF═CF.sub.2, —O—CF═CF.sub.2, or —O—CF.sub.2—CF═CF.sub.2. Z is —F, —Cl, —NR.sup.1.sub.2, or —OM. Each R.sup.1 is a hydrogen atom or alkyl having up to four carbon atoms. M is an alkyl group, a trimethylsilyl group, a hydrogen atom, a metallic cation, or a quaternary ammonium cation. R is a bromine, chloride, fluorine or hydrogen atom; and RF is a fluorinated alkenyl group that is unsubstituted or substituted by at least one chlorine atom, aryl group, or a combination thereof or RF is a fluorinated alkyl group or arylalkylenyl group that is substituted by bromine or iodine and uninterrupted or interrupted by at least one —O— group. A process for making the compound is also disclosed. A fluoropolymer made from the compound and a method of making the fluoropolymer are also disclosed.

The multifunctional compound is represented by formula X—C(R)RF—Y, in which X and Y are each independently —C(O)—O-M, —C(O)-HAL, —C(O)—NR.sup.1.sub.2, —C≡N, —C(O)NR.sup.1—SO.sub.2—R.sub.f.sup.1-W, or a fluorinated alkenyl group that is optionally interrupted by one or more —O— groups. HAL is —F, —Cl, or —Br. R.sub.f.sup.1 is a fluorinated alkylene group that is optionally interrupted by one or more —O— groups. W is —F, —SO.sub.2Z, —CF═CF.sub.2, —O—CF═CF.sub.2, or —O—CF.sub.2—CF═CF.sub.2. Z is —F, —Cl, —NR.sup.1.sub.2, or —OM. Each R.sup.1 is a hydrogen atom or alkyl having up to four carbon atoms. M is an alkyl group, a trimethylsilyl group, a hydrogen atom, a metallic cation, or a quaternary ammonium cation. R is a bromine, chloride, fluorine or hydrogen atom; and RF is a fluorinated alkenyl group that is unsubstituted or substituted by at least one chlorine atom, aryl group, or a combination thereof or RF is a fluorinated alkyl group or arylalkylenyl group that is substituted by bromine or iodine and uninterrupted or interrupted by at least one —O— group. A process for making the compound is also disclosed. A fluoropolymer made from the compound and a method of making the fluoropolymer are also disclosed.

Method of forming pattern in photoresist layer includes forming photoresist layer over substrate, selectively exposing photoresist layer to actinic radiation forming latent pattern. Latent pattern is developed by applying developer to form pattern. Photoresist layer includes photoresist composition including polymer:

##STR00001##

A.sub.1, A.sub.2, L are direct bond, C4-C30 aromatic, C4-C30 alkyl, C4-C30 cycloalkyl, C4-C30 hydroxylalkyl, C4-C30 alkoxy, C4-C30 alkoxyl alkyl, C4-C30 acetyl, C4-C30 acetylalkyl, C4-C30 alkyl carboxyl, C4-C30 cycloalkyl carboxyl, C4-C30 hydrocarbon ring, C4-C30 heterocyclic, —COO—, A1 and A2 are not both direct bonds, and are unsubstituted or substituted with a halogen, carbonyl, or hydroxyl; A.sub.3 is C6-C14 aromatic, wherein A.sub.3 is unsubstituted or substituted with halogen, carbonyl, or hydroxyl; R.sub.1 is acid labile group; Ra, Rb are H or C1-C3 alkyl; R.sub.f is direct bond or C1-C5 fluorocarbon; PAG is photoacid generator; 0≤x/(x+y+z)≤1, 0≤y/(x+y+z)≤1, and 0≤z/(x+y+z)≤1.

Method of forming pattern in photoresist layer includes forming photoresist layer over substrate, selectively exposing photoresist layer to actinic radiation forming latent pattern. Latent pattern is developed by applying developer to form pattern. Photoresist layer includes photoresist composition including polymer:

##STR00001##

A.sub.1, A.sub.2, L are direct bond, C4-C30 aromatic, C4-C30 alkyl, C4-C30 cycloalkyl, C4-C30 hydroxylalkyl, C4-C30 alkoxy, C4-C30 alkoxyl alkyl, C4-C30 acetyl, C4-C30 acetylalkyl, C4-C30 alkyl carboxyl, C4-C30 cycloalkyl carboxyl, C4-C30 hydrocarbon ring, C4-C30 heterocyclic, —COO—, A1 and A2 are not both direct bonds, and are unsubstituted or substituted with a halogen, carbonyl, or hydroxyl; A.sub.3 is C6-C14 aromatic, wherein A.sub.3 is unsubstituted or substituted with halogen, carbonyl, or hydroxyl; R.sub.1 is acid labile group; Ra, Rb are H or C1-C3 alkyl; R.sub.f is direct bond or C1-C5 fluorocarbon; PAG is photoacid generator; 0≤x/(x+y+z)≤1, 0≤y/(x+y+z)≤1, and 0≤z/(x+y+z)≤1.

An aqueous dispersion comprising a tetrafluoroethylene core-shell polymer and at least one surfactant corresponding to the general formula R.sub.10-[CH.sub.2CH.sub.20].sub.n[R.sub.20].sub.m-R.sub.3 wherein R.sub.1 represents a linear or branched aliphatic hydrocarbon group having at least 8 carbon atoms, preferably 8 to 18 carbon atoms, R2 represents an alkylene having 3 carbon atoms, R3 represents hydrogen, a C1-C3 alkyl group, or a C1-C3 hydroxyalkyl group, n has a value of 0 to 40, m has a value of 0 to 40 and the sum of n+m is at least 2, wherein the dispersion is free of fluorinated emulsifiers or contains them in an amount of less than 50 ppm based on the weight of the dispersion and wherein the core-shell polymer contains an outer shell of tetrafluoroethylene homopolymer. Further provided are methods of making the dispersions, coating compositions comprising the dispersions and article coated by the coating composition.

An aqueous dispersion comprising a tetrafluoroethylene core-shell polymer and at least one surfactant corresponding to the general formula R.sub.10-[CH.sub.2CH.sub.20].sub.n[R.sub.20].sub.m-R.sub.3 wherein R.sub.1 represents a linear or branched aliphatic hydrocarbon group having at least 8 carbon atoms, preferably 8 to 18 carbon atoms, R2 represents an alkylene having 3 carbon atoms, R3 represents hydrogen, a C1-C3 alkyl group, or a C1-C3 hydroxyalkyl group, n has a value of 0 to 40, m has a value of 0 to 40 and the sum of n+m is at least 2, wherein the dispersion is free of fluorinated emulsifiers or contains them in an amount of less than 50 ppm based on the weight of the dispersion and wherein the core-shell polymer contains an outer shell of tetrafluoroethylene homopolymer. Further provided are methods of making the dispersions, coating compositions comprising the dispersions and article coated by the coating composition.

Disclosed are copolymers formed by copolymerization of: (1) one or more hydrofluoroolefin monomer(s) such as hydrofluoropropenes, (2) one or more of an alkyl vinyl ether monomer(s) that are not substituted with a reactive group, and (3) one or more reactive group substituted, lower alkyl vinyl ether monomer(s) wherein the copolymer has a MWn of from about 1000 to about 6000 grams/mole and other advantageous properties.

A liquid repellent composition which can provide an article with good alcohol repellency is provided. A liquid repellent composition comprising a fluorinated polymer and an aqueous medium, wherein the fluorinated polymer comprises units based on a monomer a, units based on a monomer b and units based on a monomer c. Monomer a: a compound represented by CH.sub.2═CH—R.sup.f (wherein R.sup.f is a C.sub.1-8 perfluoroalkyl group). Monomer b: a fluorine-free nonionic surfactant having a polymerizable carbon-carbon double bond. Monomer c: another monomer copolymerizable with the monomer a and the monomer b.