Fluoropolymer, release agent composition and release method

Abstract

Provided is a fluorine-containing polymer having repeating units derived from (a) a fluorine-containing monomer, (b) a non-fluorine monomer having a hydrocarbon group, and (c) a non-fluorine monomer having a phosphoric acid group, the fluorine-containing monomer (a) being a compound represented by formula CH2 = C (-X11)-C (= O)-Y11-Y12-RA [wherein each symbol is the same as defined in the description], and the fluorine-containing monomer (b) being a compound represented by formula CH2 = C (-X11)-C (= O)-Y11-Y12-RA [wherein each symbol is the same as the description]; the content of a repeating unit derived from the phosphoric acid group-containing non-fluorine monomer (c) is 0.1-4.0 wt% or less with respect to the fluorine-containing polymer.

Description

Technical Field

[0001] This invention relates to fluoropolymers, mold release agent compositions, and mold release methods. Background Technology

[0002] When molding synthetic resins or rubber, a release agent (external release agent) needs to be pre-applied to the inner surface of the molding die (metal mold) to improve the release properties.

[0003] In the past, in addition to wax-based and silicone-based mold release agents, fluorine-based mold release agents have also been used as mold release agents (Patent Documents 1-4).

[0004] Existing technical documents Patent documents Patent Document 1: Japanese Patent No. 5060847 Patent Document 2: Japanese Patent Publication No. 3-8245 Patent Document 3: Japanese Patent Application Publication No. 60-262870 Patent Document 4: Japanese Patent Application Publication No. 2014-129517 Summary of the Invention

[0005] The problem that the invention aims to solve The purpose of this invention is to provide a novel release agent composition with excellent release properties.

[0006] Technical solutions for solving the problem [1] A fluoropolymer having repeating units derived from the following monomers: (a) Fluorine-containing monomers, (b) Non-fluorinated monomers with hydrocarbon groups, and (c) Non-fluorinated monomers with phosphate groups, The fluorine-containing monomer (a) is a compound represented by the following formula: CH2=C(-X) 11 ) - C (= O) - Y 11 -Y 12 -R A [In the formula,] R AFor CF3-, CF3O-, CF3NH-, CF3CH2NH-, (CF3)2N-, (CF3CH2)2N-, CF3S-, CF3C (=O)-, CF3CH2C (=O)-, CF3C (=O)O-, CF3CH2OC (=O)-, CF3CONH-, CF3C H2CONH-, CF3NHCO-, CF3CH2NHCO-, CF3CON (CF3)-, CF3CH2CON (CF3)-, CF3CON (CH2CF3)-, CF3CH2CON (CH2CF3)-, (CF3)2NCO- or (CF3CH2)2NCO-, X 11 It consists of hydrogen atoms, alkyl groups with 1 to 10 carbon atoms, or halogen atoms. Y 11 For direct bonding, -O- or -NH-, Y 12 [These are direct bonds or divalent groups.] The hydrocarbon-containing non-fluorinated monomer (b) is a compound represented by the following formula: CH2=C(-X) 21 )-C(=O)-O-Y 21 [In the formula,] X 21 It can be a hydrogen atom or a methyl group. Y 21 It consists of hydrocarbon groups with 1 to 40 carbon atoms. The phosphate-containing non-fluorinated monomer (c) is a compound represented by the following formula: [CH2=C(-X)] 31 )-C(=O)-O-(Y 31 ) p - (O) q -] n P(=O)(O-Y) 32 ) 3－n [In the formula,] X 31 It can be a hydrogen atom or a methyl group. Y 31 It is an alkylene or oxoalkylene group having 1 to 5 carbon atoms. Y 32 It consists of hydrogen atoms, alkali metal atoms, or ammonium groups. p is a number from 1 to 10. q is 0 or 1. n is 1, 2, or 3. The content of repeating units derived from phosphate-containing nonfluorinated monomers (c) is less than 0.1 to 4.0% by weight relative to the fluoropolymer.

[0007] [2] The fluoropolymer as described in [1] above, wherein, in the fluoromonomer (a), Y 12 The group is shown in the following formula: — (Ar) a1 - (CFH) b1 - (CH2) c1 - (O) d1 - [In the formula,] Ar can be converted by fluorine atoms or R A Substituted divalent aromatic groups, R A For CF3-, CF3O-, CF3NH-, CF3CH2NH-, (CF3)2N-, (CF3CH2)2N-, CF3S-, CF3C (=O)-, CF3CH2C (=O)-, CF3C (=O)O-, CF3CH2OC (=O)-, CF3CONH-, CF3C H2CONH-, CF3NHCO-, CF3CH2NHCO-, CF3CON (CF3)-, CF3CH2CON (CF3)-, CF3CON (CH2CF3)-, CF3CH2CON (CH2CF3)-, (CF3)2NCO- or (CF3CH2)2NCO-, a1 is an integer from 0 to 10. b1 is an integer from 0 to 200. c1 is an integer from 0 to 200. d1 is an integer from 0 to 10. The order in which the repeating units marked with symbols a1, b1, c1, and d1, enclosed in parentheses, exist is arbitrary.

[0008] [3] The fluoropolymer as described in [1] or [2] above, wherein, in the fluoromonomer (a), R A It can be CF3O-, CF3NH- or (CF3)2N-.

[0009] [4] The fluoropolymer as described in any one of [1] to [3] above, wherein, in the fluoromonomer (a), X 11 It can be a hydrogen atom, a methyl atom, or a chlorine atom.

[0010] [5] The fluoropolymer as described in any one of [1] to [4] above, wherein, in the hydrocarbon-containing nonfluorinated monomer (b), X 21 Y is a hydrogen atom. 21 It is a monovalent aliphatic hydrocarbon group that is straight-chain or branched with 14 to 28 carbon atoms.

[0011] [6] The fluoropolymer as described in any one of [1] to [5] above, wherein, in the hydrocarbon-containing nonfluorinated monomer (b), Y 21 The number of carbon atoms ranges from 16 to 26.

[0012] [7] The fluoropolymer as described in any one of [1] to [6] above, wherein, in the hydrocarbon-containing nonfluorinated monomer (c), X 31 Y is methyl 31 It is an alkylene group, Y 32 It is a hydrogen atom.

[0013] [8] The fluoropolymer as described in any one of [1] to [7] above, wherein the phosphate-containing nonfluorinated monomer (c) is a single phosphate monoester or a mixture of phosphate monoester and phosphate diester, wherein the weight ratio of phosphate monoester to phosphate diester in the mixture of phosphate monoester and phosphate diester is 95:5 to 50:50.

[0014] [9] The fluoropolymer as described in any one of [1] to [8] above, wherein the content of repeating units derived from monomer (a) is 20% by weight or more relative to the fluoropolymer, and the content of repeating units derived from monomer (b) is 5 to 75% by weight relative to the total of repeating units derived from monomer (a) and repeating units derived from monomer (b).

[0015]

[10] The fluoropolymer as described in any one of [1] to [9] above, wherein the fluoropolymer comprises repeating units derived from monomers (d) other than monomers (a), (b) and (c), and the content of repeating units derived from other monomers (d) is 0.1 to 50 parts by weight relative to 100 parts by weight of repeating units derived from fluoropolymer (a).

[0016]

[11] The fluoropolymer as described in any one of [1] to

[10] above, wherein the fluoropolymer is composed of repeating units derived from monomers (a), (b) and (c).

[0017]

[12] A release agent composition comprising: (1) any one of the fluoropolymers described in [1] to

[10] above, and (2) A liquid medium selected from at least one of water and organic solvents.

[0018]

[13] The release agent composition as described in

[12] above, wherein the release agent composition is a solution or aerosol containing an organic solvent, or an aqueous emulsion containing water.

[0019]

[14] The release agent composition as described in

[12] or

[13] above, wherein the content of the fluoropolymer (1) is 0.1 to 50% by weight relative to the release agent composition.

[0020]

[15] The release agent composition as described in any one of

[12] to

[14] above, wherein the content of free phosphoric acid present in the release agent composition is 1 part by weight or less relative to 100 parts by weight of the fluoropolymer.

[0021]

[16] The release agent composition as described in any one of

[12] to

[15] above, wherein the amount of free phosphoric acid present in the release agent composition is less than 1 part by weight relative to 100 parts by weight of the fluoropolymer.

[0022]

[17] A method for forming a release agent coating, comprising: (i) The step of applying the release agent composition described in any one of

[12] to

[16] above onto the inner surface of a molding die to form a film of the release agent composition.

[0023]

[18] A method for manufacturing a molded article, comprising: (i) The step of applying the release agent composition described in any one of

[12] to

[16] above onto the inner surface of a molding die to form a film of the release agent composition; (ii) The process of filling a molding composition into a molded mold having a release agent composition as a coating to obtain a molded article; and (iii) The process of removing the molded body from the molding die.

[0024] Invention Effects According to the present invention, novel release agent compositions with excellent release properties can be provided. Detailed Implementation

[0025] [Components of the release agent composition] The release agent composition contains: (1) Fluoropolymers, and (2) Liquid medium, which is water and / or organic solvent.

[0026] In the mold release agent composition, the fluoropolymer acts as a mold release agent. The mold release agent composition is preferably a solution or an aqueous emulsion.

[0027] (1) Fluoropolymers Fluoropolymers are the active ingredients in the mold release agent composition, i.e., the mold release agent.

[0028] Fluoropolymers have the following characteristics: (a) Repeating units derived from fluorine-containing monomers, (b) Repeating units derived from nonfluorinated monomers with hydrocarbon groups, and (c) Repeating units derived from nonfluorinated monomers with phosphate groups.

[0029] In addition to repeating units (a), (b) and (c), fluoropolymers may also have other repeating units (d) (repeating units derived from other monomers (d)).

[0030] (a) Fluorine-containing monomers The fluorine-containing monomer (a) is a compound represented by the following formula: CH2=C(-X) 11 ) - C (= O) - Y 11 -Y 12 -R A [In the formula,] R A For CF3-, CF3O-, CF3NH-, CF3CH2NH-, (CF3)2N-, (CF3CH2)2N-, CF3S-, CF3C (=O)-, CF3CH2C (=O)-, CF3C (=O)O-, CF3CH2OC (=O)-, CF3CONH-, CF3C H2CONH-, CF3NHCO-, CF3CH2NHCO-, CF3CON (CF3)-, CF3CH2CON (CF3)-, CF3CON (CH2CF3)-, CF3CH2CON (CH2CF3)-, (CF3)2NCO- or (CF3CH2)2NCO-, X 11 It consists of hydrogen atoms, alkyl groups with 1 to 10 carbon atoms, or halogen atoms. Y 11 For direct bonding, -O- or -NH-, Y 12 It is a direct bond or a divalent group.

[0031] R A For CF3-, CF3O-, CF3NH-, CF3CH2NH-, (CF3)2N-, (CF3CH2)2N-, CF3S-, CF3C (=O)-, CF3CH2C (=O)-, CF3C (=O)O-, CF3CH2OC (=O)-, CF3CONH-, CF3C H2CONH-, CF3NHCO-, CF3CH2NHCO-, CF3CON(CF3)-, CF3CH2CON(CF3)-, CF3CON(CH2CF3)-, CF3CH2CON(CH2CF3)-, (CF3)2NCO- or (CF3CH2)2NCO-. R APreferably, the CF3O-, CF3NH-, (CF3)2N-, CF3S-, CF3C(=O)-, CF3C(=O)O-, CF3OC(=O)-, CF3CONH-, CF3NHCO-, CF3CON(CF3)- or (CF3)2NCO- are used, and can be further preferred to be CF3O-, CF3NH- or (CF3)2N-.

[0032] In one approach, R A It can be CF3O-.

[0033] In another way, R A It can be CF3NH- or (CF3)2N-, preferably CF3NH-.

[0034] X 11 It consists of hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, or halogen atoms (e.g., fluorine, chlorine, bromine, or iodine atoms). X 11 Preferably, it contains hydrogen atoms, methyl groups, or chlorine atoms.

[0035] Y 11 It can be a direct bond, -O-, or -NH-. 11 Preferably, it is -O-. That is, the fluorinated monomer (a) is preferably an acrylate.

[0036] Y 12 It is a direct bond or a divalent group. Y 12 Preferably, the group is represented by the following formula: — (Ar) a1 - (CFH) b1 - (CH2) c1 - (O) d1 - [In the formula:] Ar can be converted by fluorine atoms or R A Substituted divalent aromatic groups, R A For CF3-, CF3O-, CF3NH-, CF3CH2NH-, (CF3)2N-, (CF3CH2)2N-, CF3S-, CF3C (=O)-, CF3CH2C (=O)-, CF3C (=O)O-, CF3CH2OC (=O)-, CF3CONH-, CF3C H2CONH-, CF3NHCO-, CF3CH2NHCO-, CF3CON (CF3)-, CF3CH2CON (CF3)-, CF3CON (CH2CF3)-, CF3CH2CON (CH2CF3)-, (CF3)2NCO- or (CF3CH2)2NCO-, a1 is an integer from 0 to 10. b1 is an integer from 0 to 200. c1 is an integer from 0 to 200. d1 is an integer from 0 to 10. The order of the repeating units marked with symbols a1, b1, c1, and d1 and enclosed in parentheses is arbitrary. In this formula, oxygen atoms are preferably not continuous. That is, -O-O- bonds are preferably not present. Furthermore, Y... 12 The right side and R A Combine.

[0037] The aforementioned aromatic groups also include aromatic rings containing only carbon as ring atoms (so-called aryl groups), aromatic rings containing nitrogen, oxygen, or sulfur (so-called heteroaryl groups), and groups having multiple aromatic rings.

[0038] The aforementioned aromatic group preferably has a benzene ring, naphthalene ring, phenanthrene ring, anthracene ring, tetraphenyl ring, pentaphenyl ring, benzo[a]pyrene ring, piracene ring, pyrene ring, benzo[a]phenanthrene ring, cyclopentene ring, oleene ring, indole ring, furan ring, thiophene ring, pyrrole ring, pyrazole ring, imidazole ring, pyridine ring, pyridazine ring, pyrimidine ring, biphenyl ring, terphenyl ring, triphenylmethane ring, or benzophenone ring.

[0039] In one embodiment, the aromatic group preferably has a benzene ring, a naphthyl ring, a phenanthrene ring, an anthracene ring, a tetraphenyl ring, a pentaphenyl ring, a benzo[a]pyrene ring, a cyclo[a]pyrene ring, a benzo[a]phenanthrene ring, a cycloene ring, or an oleene ring, more preferably a benzene ring or a naphthyl ring, and even more preferably a benzene ring.

[0040] In another embodiment, the aromatic group preferably has an indole ring, a furan ring, a thiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, or a pyrazine ring, and more preferably has an indole ring.

[0041] In yet another embodiment, the aromatic group preferably has a biphenyl ring, a terphenyl ring, a triphenylmethane ring, or a benzophenone ring.

[0042] In one embodiment, Ar is an unsubstituted divalent aromatic group.

[0043] In another way, Ar is the atom surrounded by fluorine or R A Substituted divalent aromatic groups.

[0044] In yet another way, Ar is R A Substituted divalent aromatic groups.

[0045] In another embodiment, Ar is a divalent aromatic group substituted with a fluorine atom.

[0046] The number of substituents in the aromatic group is not particularly limited, and can be, for example, 1 to 10, 1 to 5, 1 to 3, 1, 2, or 3. In one embodiment, the number of substituents in the aromatic group is one or more. In another embodiment, the aromatic group is fully substituted.

[0047] a1 is an integer from 0 to 10, preferably 0 or 1.

[0048] In one mode, a1 is 0.

[0049] In another way, a1 is 1.

[0050] b1 is an integer from 0 to 200, preferably an integer from 0 to 6.

[0051] c1 is an integer from 0 to 200, preferably an integer from 0 to 30.

[0052] d1 is an integer from 0 to 10, preferably an integer from 0 to 3.

[0053] In one approach, Y 12 The group is shown in the following formula: — (Ar) a1 - (O) d1 - (CH2) c1 - [In the formula,] Ar can be converted by fluorine atoms or R A The substituted divalent aromatic group, preferably the unsubstituted divalent aromatic group, R A For CF3-, CF3O-, CF3NH-, CF3CH2NH-, (CF3)2N-, (CF3CH2)2N-, CF3S-, CF3C (=O)-, CF3CH2C (=O)-, CF3C (=O)O-, CF3CH2OC (=O)-, CF3CONH-, CF3C H2CONH-, CF3NHCO-, CF3CH2NHCO-, CF3CON (CF3)-, CF3CH2CON (CF3)-, CF3CON (CH2CF3)-, CF3CH2CON (CH2CF3)-, (CF3)2NCO- or (CF3CH2)2NCO-, a1 is 0 or 1. c1 is an integer from 1 to 36, preferably an integer from 1 to 30, for example, it can be an integer from 1 to 9, an integer from 1 to 3, or an integer from 2 to 3. d1 is either 0 or 1. The order in which the repeating units marked with symbols a1, c1, and d1 and enclosed in parentheses exist is arbitrary.

[0054] Among them, Y 12 The right side and R A Combine.

[0055] In one approach, Y 12 The group is shown in the following formula: - (CH2) c1 - [In the formula, c1 is an integer from 1 to 36, preferably an integer from 1 to 30, for example, it can be an integer from 1 to 9 or an integer from 1 to 3.]

[0056] In one approach, Y 12 The group is represented by -Ar-. [In the formula:] Ar can be converted by fluorine atoms or R A The substituted divalent aromatic group, preferably the unsubstituted divalent aromatic group, R A For CF3-, CF3O-, CF3NH-, CF3CH2NH-, (CF3)2N-, (CF3CH2)2N-, CF3S-, CF3C (=O)-, CF3CH2C (=O)-, CF3C (=O)O-, CF3CH2OC (=O)-, CF3CONH-, CF3C H2CONH-, CF3NHCO-, CF3CH2NHCO-, CF3CON(CF3)-, CF3CH2CON(CF3)-, CF3CON(CH2CF3)-, CF3CH2CON(CH2CF3)-, (CF3)2NCO- or (CF3CH2)2NCO-. ].

[0057] Among them, Y 12 The right side and R A Combine.

[0058] Specific examples of fluorinated monomers include the following, but are not limited to these examples.

[0059] CH2=C(-H)-C(=O)-O-CH2-R A CH2=C(-H)-C(=O)-O-(CH2)2-R A CH2=C(-H)-C(=O)-O-C6H4-R A CH2=C(-H)-C(=O)-NH-(CH2)2-R A CH2=C(-CH3)-C(=O)-O-CH2-R A CH2=C(-CH3)-C(=O)-O-(CH2)2-R A CH2=C(-CH3)-C(=O)-O-(CH2)3-R A CH2=C(-CH3)-C(=O)-NH-(CH2)2-R A CH2=C(-F)-C(=O)-O-(CH2)2-R A CH2=C(-F)-C(=O)-NH-(CH2)2-R A CH2=C(-F)-C(=O)-NH-(CH2)3-R A CH2=C(-Cl)-C(=O)-O-(CH2)2-R A CH2=C(-Cl)-C(=O)-NH-(CH2)2-R A [In the above formula, R] A The meaning is the same as above. (b) Non-fluorinated monomers containing hydrocarbon groups The hydrocarbon-containing non-fluorinated monomer (b) is a compound represented by the following formula: CH 2 =C(-X) 21 )-C(=O)-O-Y 21 [In the formula,] X 21 It can be a hydrogen atom or a methyl group. Y 21 It consists of hydrocarbon groups with 1 to 40 carbon atoms.

[0060] X 21 It can be a hydrogen atom or a methyl group. Due to its high release properties, X... 21 The preferred atom is hydrogen. That is, acrylate is preferred.

[0061] Y 21 Preferably, it is a straight-chain or branched monovalent aliphatic hydrocarbon group with 1 to 40 carbon atoms, an aromatic hydrocarbon group with 6 to 12 carbon atoms, or a cyclic aliphatic hydrocarbon group with 6 to 12 carbon atoms.

[0062] Examples of monovalent aliphatic hydrocarbon groups with 1 to 40 carbon atoms, either straight-chain or branched, are alkyl groups. The aliphatic hydrocarbon group preferably has 5 to 35 carbon atoms, for example 10 to 30, particularly 14 to 28, and especially preferably 16 to 26.

[0063] Examples of aromatic hydrocarbon groups with 6 to 12 monovalent carbon atoms include phenyl, 2-ethylphenyl, indene, tolyl, and benzyl.

[0064] Examples of monovalent cyclic aliphatic hydrocarbon groups with 6 to 12 carbon atoms include cyclohexyl, norbornyl, norbornylmethyl, isobornyl, borneol, menthyl, octahydroindenyl, adamantyl, and dimethyladamantyl.

[0065] Specific examples of hydrocarbon-containing nonfluorinated monomers include: cyclohexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, lauryl methacrylate, tridecyl methacrylate, tetradecyl methacrylate, hexadecyl methacrylate, stearyl methacrylate, behenyl methacrylate, norbornyl methacrylate, norbornyl methacrylate, isobornyl methacrylate, borneol methacrylate, menthyl methacrylate, octahydroindene methacrylate, adamantane methacrylate, dimethyl adamantane methacrylate, phenyl methacrylate, 2-ethylphenyl methacrylate, indene methacrylate, toluene methacrylate, and benzyl methacrylate, etc. Lauryl (meth)acrylate, stearyl acrylate, and isobornyl (meth)acrylate are preferred. Stearyl acrylate is particularly preferred.

[0066] (c) Phosphate-containing non-fluorinated monomers The phosphoric acid-containing non-fluorinated monomer (c) is an acrylate monomer. The phosphoric acid-containing non-fluorinated monomer (c) is a compound represented by the following formula: [CH2=C(-X)] 31 )-C(=O)-O-(Y 31 ) p - (O) q -] n P(=O)(O-Y) 32 ) 3－n [In the formula,] X 31 It can be a hydrogen atom or a methyl group. Y 31 It is an alkylene or oxoalkylene group having 1 to 5 carbon atoms. Y 32 It consists of hydrogen atoms, alkali metal atoms, or ammonium groups. p is a number from 1 to 10. q is 0 or 1. n is 1, 2, or 3.

[0067] X31 It can be a hydrogen atom or a methyl group. X is preferred due to its high release properties. 31 It is methyl.

[0068] Y 31 It is an alkylene group having 1 to 5 carbon atoms or an oxoalkylene group having 1 to 5 carbon atoms. 31 Preferably, it is an alkylene group.

[0069] Y 32 It can be a hydrogen atom, an alkali metal atom, or an ammonium group. Due to its high release properties, Y is preferred. 32 The atom is hydrogen. Examples of alkali metal atoms are lithium, sodium, and potassium. The ammonium group (or amino group) can be replaced by substituents, such as alkyl groups with 1 to 4 carbon atoms and hydroxyalkyl groups with 1 to 4 carbon atoms.

[0070] p is a number from 1 to 10. Preferably, p is from 1 to 6.

[0071] q is either 0 or 1. In Y 31 In the case of alkylene groups, q is 0 or 1. In Y... 31 In the case of alkylene groups, q is preferably 1. In Y 31 In the case of alkylene oxides, q is 0.

[0072] n is 1, 2, or 3. n is preferably 1 or 2. That is, the phosphate-containing non-fluorinated monomer is preferably a monophosphate or a diester. Preferably, it is a single monophosphate or a mixture of monophosphate and diester. In the mixture of monophosphate and diester, the weight ratio of monophosphate to diester can be 95:5 to 50:50, preferably 90:10 to 60:40, and more preferably 85:15 to 65:35.

[0073] Phosphoric acid-containing non-fluorinated monomers are manufactured by reacting phosphoric acid with a raw material compound such as chlorinated (meth)acrylic acid. After manufacturing the phosphoric acid-containing non-fluorinated monomer, sometimes the phosphoric acid (free phosphoric acid) used as a raw material remains unreacted. This free phosphoric acid can sometimes adversely affect mold release properties, solubility, and storage stability. The amount of free phosphoric acid relative to 100 parts by weight of the fluoropolymer is preferably 1 part by weight or less, for example, 0.5 parts by weight or less, and particularly preferably 0.2 parts by weight or less. The lower limit of the amount of free phosphoric acid relative to 100 parts by weight of the fluoropolymer can be, for example, 0.01 parts by weight.

[0074] Specific examples of phosphate-containing non-fluorinated monomers are shown below.

[0075] CH2=C(CH3)COOCH2CH2OP(=O)(OH)2 CH2=CHCOOCH2CH2OP(=O)(OH)2 CH2=C(CH3)COOCH2CH(CH3)OP(=O)(OH)2 CH2=C(CH3)COO(CH2CH2O) n P(=O)(OH)2(n=1~90) CH2=C(CH3)COO(CH2CH(CH3)O) n P(=O)(OH)2(n=1~90) CH2=C(CH3)COOCH2CH2OP(=O)(OH)(ONH3-CH2CH2-OH) CH2=C(CH3)COOCH2CH2OP(=O)(OH)(ONH(CH3)2-CH2CH2-OOC(CH3)C=CH2) CH2=C(CH3)COOCH2CH2OP(=O)(OH)(ONH(CH2CH3)2-CH2CH2-OOC(CH3)C=CH2) CH2=C(CH3)COOCH2CH2OP(=O)(OH)(OCH2CH2OOC(CH3)C=CH2) (d) Other monomers Fluoropolymers may have repeating units derived from other monomers. Fluoropolymers preferably do not have repeating units derived from other monomers. That is, fluoropolymers are preferably composed of repeating units derived from monomers (a), (b), and (c). Examples of other monomers are silicon-containing monomers, such as modified silicone oils, for example, amino-modified silicone oils and acrylic-modified silicone oils; and di(meth)acrylate monomers, etc. Other examples of other monomers include ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxy polyethylene glycol (meth)acrylate, methoxy polypropylene glycol (meth)acrylate, and vinyl alkyl ethers, etc.

[0076] Each of the monomers (a) to (d) can be a single type or a mixture of two or more types.

[0077] The content of repeating units derived from the phosphate-containing nonfluorinated monomer (c) is typically 0.1 to 8.0% by weight relative to the fluoropolymer. The content of repeating units derived from the phosphate-containing nonfluorinated monomer (c) is preferably 0.1 to 5.0% by weight, more preferably 0.1 to 4.0% by weight, and even more preferably 0.2 to 4.0% by weight. The lower limit of the content of repeating units derived from the phosphate-containing nonfluorinated monomer (c) can be 0.1% by weight, for example 0.2% by weight, particularly 0.5% by weight, and especially 0.8% by weight. The upper limit of the content of repeating units derived from the phosphate-containing nonfluorinated monomer (c) can be 5.0% by weight, for example 4.0% by weight, and especially 3.0% by weight.

[0078] The content of repeating units derived from fluorinated monomer (a) relative to the fluorinated polymer can be 20 to 95% by weight, for example 30 to 90% by weight, especially 35 to 80% by weight, particularly 40 to 75% by weight.

[0079] In fluoropolymers, the content of repeating units derived from hydrocarbon-containing nonfluorinated monomers (b) is 0.1 to 200 parts by weight, for example, 1 to 100 parts by weight, particularly 3 to 50 parts by weight, relative to 100 parts by weight of fluorinated monomers (a), and the content of repeating units derived from other monomers (d) can be 0 to 50 parts by weight (or 0 to 10 parts by weight), 0.1 to 30 parts by weight, particularly 0.5 to 20 parts by weight.

[0080] The content of repeating units derived from monomer (b) relative to the total of repeating units derived from monomer (a) and repeating units derived from monomer (b) is preferably 5 to 75% by weight, 5 to 50% by weight, for example 10 to 40% by weight, and particularly 15 to 35% by weight.

[0081] In another manner, the content of repeating units derived from monomer (b) is preferably 4 to 95% by weight, for example 10 to 75% by weight, particularly 15 to 50% by weight, relative to the fluoropolymer.

[0082] The number-average molecular weight (Mn) of fluoropolymers is typically between 1,000 and 1,000,000, for example, 2,000 to 500,000, and particularly 3,000 to 200,000. The number-average molecular weight (Mn) of fluoropolymers is usually determined by GPC (gel permeation chromatography).

[0083] (2) Liquid medium The liquid medium is selected from at least one of water and organic solvents. The liquid medium can be an organic solvent alone. Alternatively, the liquid medium can be an aqueous medium. The aqueous medium can be water alone, or a mixture of water and an (water-mixed) organic solvent. The amount of the water-mixed organic solvent relative to the liquid medium can be 30% by weight or less, for example, 10% by weight or less (preferably 0.1% or more).

[0084] The amount of liquid medium relative to the release agent composition can be 30 to 99.1% by weight, particularly 50 to 99% by weight.

[0085] (3) Other ingredients The release agent composition may contain other ingredients.

[0086] When the release agent composition is an aqueous emulsion, it preferably contains an emulsifier. The emulsifier may be at least one selected from nonionic emulsifiers, cationic emulsifiers, anionic emulsifiers, and amphoteric emulsifiers.

[0087] The release agent composition may contain additives as other components.

[0088] Examples of additives include silicone compounds, waxes, and acrylic emulsions. Other examples of additives include other fluoropolymers, drying rate regulators, crosslinking agents, film-forming aids, compatibilizers, surfactants, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, defoamers, texture modifiers, slip modifiers, antistatic agents, hydrophilic agents, antibacterial agents, preservatives, insect repellents, fragrances, and flame retardants.

[0089] The amount of other components relative to the mold release agent composition can be 0.1 to 20% by weight, for example 0.5 to 10% by weight.

[0090] [Preparation of release agent composition (Preparation of fluoropolymer)] Fluoropolymers can be manufactured by methods including copolymerizing monomers. Copolymerization can be either emulsion polymerization or solution polymerization.

[0091] Emulsion polymerization can be carried out, for example, as follows: Various monomers are emulsified in water in the presence of a polymerization initiator and an emulsifier, nitrogen is replaced, and the mixture is stirred at 50–80°C for 1–10 hours to copolymerize them.

[0092] In emulsion polymerization, polymerization initiators can include water-soluble polymerization initiators such as benzoyl peroxide, lauroyl peroxide, tert-butyl peroxide, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutyronitrile dihydrochloride, azobisisobutyronitrile, sodium peroxide, potassium persulfate, and ammonium persulfate, as well as oil-soluble polymerization initiators such as azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, tert-butyl peroxypentanoate, diisopropyl peroxydicarbonate, and azobismethylpropionate.

[0093] In emulsion polymerization, polymerization initiators are typically used in the range of 0.01 to 10 parts by weight relative to 100 parts by weight of monomer.

[0094] In emulsion polymerization, in order to obtain a copolymer aqueous dispersion with excellent storage stability, it is preferable to use an emulsification device that can impart strong crushing energy, such as a high-pressure homogenizer or an ultrasonic homogenizer, to micronize the monomer in water and then use an oil-soluble polymerization initiator for polymerization.

[0095] In emulsion polymerization, various emulsifiers, including anionic, cationic, and nonionic emulsifiers, can be used as emulsifiers. Emulsifiers are typically used in the range of 0.5 to 20 parts by weight relative to 100 parts by weight of the monomer.

[0096] Examples of nonionic emulsifiers include polyoxyethylene alkyl ethers, sorbitol alkylates, and sorbitol alkyl esters. Examples of polyoxyethylene alkyl ethers include polyoxyethylene lauryl ether.

[0097] Examples of anionic emulsifiers include alkyl sulfates, alkyl sulfonates, and alkyl phosphates. Examples of alkyl sulfates include sodium alkyl sulfate.

[0098] Examples of cationic emulsions include quaternary ammonium salts and alkylamine salts. Examples of quaternary ammonium salts include lauryltrimethylammonium chloride.

[0099] In emulsion polymerization, when monomers are not completely compatible, it is preferable to add a compatibilizer to make these monomers fully compatible, such as a water-soluble organic solvent or a low molecular weight monomer. The addition of a compatibilizer can improve emulsification and copolymerization properties.

[0100] Examples of water-soluble organic solvents used as compatibilizers include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, diethylene glycol diethyl ether, tripropylene glycol, and ethanol. Water-soluble organic solvents are typically used in the range of 1 to 50 parts by weight relative to 100 parts by weight of water. Preferably, they are used in the range of 10 to 40 parts by weight relative to 100 parts by weight of water.

[0101] In emulsion polymerization, chain transfer agents can be used to adjust the molecular weight of the resulting polymer. Examples of chain transfer agents include lauryl thiol, glycidyl thiol, mercaptoacetic acid, 2-mercaptoethanol, 2-ethylhexyl mercaptoacetic acid, and 2,3-dimethylmercapto-1-propanol. One or more chain transfer agents can be used as needed. Chain transfer agents are typically used in the range of 0.001 to 7.0 parts by weight relative to 100 parts by weight of the monomer.

[0102] Solution polymerization can be carried out, for example, as follows: In the presence of a polymerization initiator, the monomer is dissolved in an organic solvent, nitrogen is substituted, and the solution is heated and stirred at 30–120°C for 1–10 hours. Examples of polymerization initiators include azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, tert-butyl peroxypentanoate, and diisopropyl peroxydicarbonate. The polymerization initiator is typically used in the range of 0.01–20 parts by weight relative to 100 parts by weight of the monomer. Preferably, the polymerization initiator is used in the range of 0.02–10 parts by weight relative to 100 parts by weight of the monomer.

[0103] In solution polymerization, any organic solvent that is inert to the monomers and capable of dissolving them is acceptable; there are no particular limitations. Examples of organic solvents include acetone, chloroform, isopropanol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, and butyl acetate. The organic solvent is typically used in the range of 20 to 2000 parts by weight relative to 100 parts by weight of the monomers. Preferably, the organic solvent is used in the range of 50 to 1000 parts by weight relative to 100 parts by weight of the monomers.

[0104] [Form and Uses of Release Agent Compositions] The form of the mold release agent composition can be appropriately selected according to its intended use, for example, as a solution, emulsion, or aerosol. Preferably, the mold release agent composition is a solution or aerosol containing an organic solvent, or an aqueous emulsion containing water.

[0105] The release agent composition preferably contains 0.5% to 50% by weight, more preferably 1.0% to 30% by weight, and particularly preferably 1.5% to 20% by weight of a fluoropolymer relative to the release agent composition.

[0106] To improve the wettability of the mold release agent composition, it may also contain a surfactant (emulsifier). Fluorinated or non-fluorinated surfactants can be used as surfactants. Anionic, nonionic, and cationic surfactants can be used as fluorinated or non-fluorinated surfactants.

[0107] Fluorinated surfactants include fluorinated polyoxyethylene, sulfonates, carboxylates, quaternary ammonium salts, etc.

[0108] Examples of non-fluorinated anionic surfactants include alkyl sulfates, alkyl sulfonates, and alkyl phosphates. Examples of alkyl sulfates include sodium alkyl sulfate.

[0109] Examples of non-fluorinated nonionic surfactants include polyoxyethylene alkyl ethers, sorbitol alkylates, and sorbitol alkyl esters. Examples of polyoxyethylene alkyl ethers include polyoxyethylene lauryl ether.

[0110] Examples of non-fluorinated cationic surfactants include quaternary ammonium salts and alkylamine salts.

[0111] Examples of quaternary ammonium salts include lauryltrimethylammonium chloride.

[0112] When a surfactant is present, the amount of surfactant relative to the release agent composition is 0.01% to 20% by weight, preferably 0.01% to 15% by weight, and more preferably 0.05% to 10% by weight.

[0113] For the purpose of improving release properties and / or finish, the release agent composition may also contain at least one release-enhancing additive selected from organosilicon compounds, wax compounds, and fluorine compounds.

[0114] Examples of organosilicon compounds include dimethyl silicone oil, methylphenyl silicone oil, modified silicone oil (e.g., amino-modified silicone oil), fluorinated silicone oil, and silicone resins. Examples of wax compounds include polyethylene wax, paraffin wax, and carnauba wax. Examples of fluorinated compounds include polytetrafluoroethylene, fluorinated polyethers, and chlorofluorocarbon polyethers.

[0115] The amount of the release agent additive relative to the release agent composition can be 0.01% to 20% by weight, preferably 0.02% to 15% by weight.

[0116] When the release agent composition is an aqueous emulsion, it is preferable that the emulsifier contains at least one emulsifier selected from nonionic emulsifiers, anionic emulsifiers, and cationic emulsifiers.

[0117] As a nonionic emulsifier, any substance capable of emulsifying and dispersing the fluoropolymer of the present invention in an aqueous emulsion is acceptable; examples include polyoxyethylene alkyl ethers, sorbitol alkylates, and sorbitol alkyl esters. Examples of polyoxyethylene alkyl ethers include polyoxyethylene lauryl ether.

[0118] Examples of anionic emulsifiers include alkyl sulfates, alkyl sulfonates, and alkyl phosphates. Examples of alkyl sulfates include sodium alkyl sulfate.

[0119] Examples of cationic emulsifiers include quaternary ammonium salts and alkylamine salts. Examples of quaternary ammonium salts include lauryltrimethylammonium chloride.

[0120] The amount of emulsifier relative to 100 parts by weight of the fluoropolymer is typically 0.5 to 25 parts by weight, preferably 1.0 to 20 parts by weight, and more preferably 2.0 to 15 parts by weight.

[0121] When the mold release agent composition is a solution, it may also contain organic solvents, etc.

[0122] When the release agent composition is an aerosol, a spraying agent can be used to fill the aerosol can. Examples of spraying agents include LPG, dimethyl ether, and carbon dioxide. The amount of spraying agent is typically 10 to 95% by weight relative to the total amount of the release agent composition and the spraying agent, preferably 20 to 90% by weight, and more preferably 30 to 90% by weight. A spraying agent amount of 10% by weight or more results in better spraying and tends to produce a more uniform coating. Conversely, a spraying agent amount of 95% by weight or less prevents the coating from becoming too thin and avoids excessive reduction in release properties.

[0123] The release agent composition can be used as an internal or external release agent. It is preferred to use it as an external release agent.

[0124] Release agent compositions are typically used as follows: The release agent composition is applied to the inner surface of a molding die, and after the solvent or dispersant has dried and been removed, a release agent coating (a fluoropolymer coating) is formed on the molding die. The molding composition is then filled into the mold, the molding material is formed, and the molding material is removed from the mold.

[0125] Examples of molds that can use mold release agent compositions include molds made of metals such as aluminum, SUS, and iron, molds made of epoxy resin and wood, and molds made of electroformed nickel or chrome plating.

[0126] Examples of molding materials that can be demolded using a release agent composition include, for example, polyurethane rubber, H-NBR, NBR, silicone rubber, EPDM, CR, NR, fluororubber, SBR, BR, IIR and IR rubbers, as well as thermosetting resins such as polyurethane foam, epoxy resin, phenolic resin and FRP (e.g. CFRP and GFRP), thermoplastic resins such as ABS, polycarbonate and PBT.

[0127] Example The present invention is further described in detail below with reference to specific embodiments, but the present invention is not limited to these embodiments.

[0128] Synthesis example 1 Following the method described in WO2020 / 168011Al, silver trifluoromethanesulfonate, potassium fluoride, a salt of 1-(chloromethyl)-4-fluoro-4-diazobicyclo[2.2.2]octane, a tetrafluoroboric acid salt, and benzyloxyethanol were reacted in ethyl acetate at 30°C for 16 hours to give [2-(trifluoromethoxy)ethoxy]methyl)benzene. Furthermore, hydrogen reduction was carried out in the presence of a palladium catalyst (50 psi, 35°C, 24 h) to give 2-(trifluoromethoxy)ethanol (compound 1).

[0129] Synthesis example 2 The alcohol obtained in Synthesis Example 1 was reacted with methyl methacrylate in the presence of calcium hydroxide to obtain fluorinated methyl methacrylate (compound 2).

[0130] Manufacturing Example 1 The compounds obtained in Synthesis Example 2: CF3O-CH2CH2-OCO-C(CH3)=CH2 (9.7 g), phosphate-containing (meth)acrylic acid: CH2=C(CH3)COOCH2CH2OPO(OH)2 (0.3 g), stearate acrylate (8.7 g), and the initiator tert-butyl peroxypentanoate (0.4 g) were dissolved in butyl acetate (80 g). Polymerization was carried out at 65°C for 8 hours to obtain a polymer solution (release agent composition). The monomer composition of the polymer was substantially the same as that of the added monomers. The added monomers are listed in Table 1.

[0131] Manufacturing Example 2 The compounds obtained in Synthesis Example 2: CF3O-CH2CH2-OCO-C(CH3)=CH2 (9.7 g), phosphate-containing (meth)acrylic acid: CH2=C(CH3)COOCH2CH2OPO(OH)2 (0.6 g), stearate acrylate (8.4 g), and the initiator tert-butyl peroxypentanoate (0.4 g) were dissolved in butyl acetate (80 g), and polymerized at 65°C for 8 hours to obtain a polymer solution (release agent composition). The monomer composition of the polymer is substantially the same as that of the added monomers. The added monomers are shown in Table 1.

[0132] Manufacturing Example 3 The compounds obtained in Synthesis Example 2: CF3O-CH2CH2-OCO-C(CH3)=CH2 (12.4 g), phosphate-containing (meth)acrylic acid: CH2=C(CH3)COOCH2CH2OPO(OH)2 (0.6 g), stearate acrylate (2.4 g), and the initiator tert-butyl peroxypentanoate (0.4 g) were dissolved in butyl acetate (80 g), and polymerized at 65°C for 8 hours to obtain a polymer solution (release agent composition). The monomer composition of the polymer is substantially the same as that of the added monomers. The added monomers are shown in Table 1.

[0133] Manufacturing Example 4 The compounds obtained in Synthesis Example 2: CF3O-CH2CH2-OCO-C(CH3)=CH2 (9.7 g), phosphate-containing (meth)acrylic acid: CH2=C(CH3)COOCH2CH2OPO(OH)2 (1.2 g), stearate acrylate (7.8 g), and the initiator tert-butyl peroxypentanoate (0.4 g) were dissolved in butyl acetate (80 g). Polymerization was carried out at 65°C for 8 hours to obtain a polymer solution (release agent composition). The monomer composition of the polymer was substantially the same as that of the added monomers. The added monomers are listed in Table 1.

[0134] Manufacturing Example 5 The monomers of the compound obtained in Synthesis Example 2: CF3O-CH2CH2-OCO-C(CH3)=CH2 (9.7 g), phosphate-containing (meth)acrylic acid: CH2=C(CH3)COOCH2CH2OPO(OH)2 (0.3 g), isobornyl methacrylate (8.7 g), and the initiator tert-butyl peroxypentanoate (0.4 g) were dissolved in butyl acetate (80 g), and polymerized at 65°C for 8 hours to obtain a polymer solution (release agent composition). The monomer composition of the polymer is substantially the same as that of the added monomers. The added monomers are shown in Table 1.

[0135] Manufacturing Example 6 The monomers of the compound obtained in Synthesis Example 2: CF3O-CH2CH2-OCO-C(CH3)=CH2 (9.7 g), phosphate-containing (meth)acrylic acid: CH2=C(CH3)COOCH2CH2OPO(OH)2 (0.6 g), isobornyl methacrylate (8.4 g), and the initiator tert-butyl peroxypentanoate (0.4 g) were dissolved in 80 g of butyl acetate and polymerized at 65 °C for 8 hours to obtain a polymer solution (release agent composition). The monomer composition of the polymer is substantially the same as that of the added monomers. The added monomers are shown in Table 1.

[0136] Manufacturing Example 7 The compounds obtained in Synthesis Example 2: CF3O-CH2CH2-OCO-C(CH3)=CH2 (9.7 g), phosphate-containing (meth)acrylic acid: CH2=C(CH3)COOCH2CH2OPO(OH)2 (1.2 g), isobornyl methacrylate (7.8 g), and the initiator tert-butyl peroxypentanoate (0.4 g) were dissolved in butyl acetate (80 g). Polymerization was carried out at 65°C for 8 hours to obtain a polymer solution (release agent composition). The monomer composition of the polymer was substantially the same as that of the added monomers. The added monomers are listed in Table 1.

[0137] Manufacturing Example 8 The monomers of phosphate-containing (meth)acrylic acid: CH2=C(CH3)COOCH2CH2OPO(OH)2 (1.0 g), stearate acrylate (9.0 g), and the initiator tert-butyl peroxypentanoate (0.4 g) were dissolved in butyl acetate (80 g), and polymerized at 65°C for 8 hours to obtain a polymer solution (release agent composition). The monomer composition of the polymer is essentially the same as that of the added monomers. The added monomers are shown in Table 1.

[0138] Manufacturing Example 9 The monomers of phosphate-containing (meth)acrylic acid: CH2=C(CH3)COOCH2CH2OPO(OH)2 (1.0 g), isobornyl methacrylate (9.0 g), and the initiator tert-butyl peroxypentanoate (0.4 g) were dissolved in butyl acetate (80 g), and polymerized at 65 °C for 8 hours to obtain a polymer solution (release agent composition). The monomer composition of the polymer is essentially the same as that of the added monomers. The added monomers are shown in Table 1.

[0139] Manufacturing Example 10 Phosphoric acid-containing (meth)acrylic acid: CH2=C(CH3)COOCH2CH2OPO(OH)2 (1.0 g) and initiator tert-butyl peroxypentanoate (0.4 g) were dissolved in butyl acetate (80 g), and polymerized at 65°C for 8 hours to obtain a polymer solution (release agent composition). The monomer composition of the polymer is essentially the same as that of the added monomers. The added monomers are shown in Table 1.

[0140] Example Demolding tests were conducted using all 10 compounds. Specifically, the polymers from Manufacturing Examples 1 to 7 were used as Examples 1 to 7, the polymers from Manufacturing Examples 8 to 10 were used as Comparative Examples 1 to 3, commercially available dimethyl silicone oil (SH200, manufactured by Dow-Toray Industries, Inc.) (Comparative Control Compound 1) was used as Comparative Example 4, and the compound synthesized according to the method described in Synthesis Example 1 of Japanese Patent No. 5184382 (Control Compound 2) was used as Comparative Example 5. The results are shown in Table 2.

[0141] "Demolding test" The release composition was diluted with isohexane to prepare a solution with a solid content of 0.5% by mass. This solution was then sprayed onto an aluminum plate measuring 9.5 cm × 9.5 × 0.15 cm. The plate was then dried at 150°C for 15 minutes to achieve a non-volatile content of 0.2–0.3 mg / cm³. 2Residue remained on the metal surface. Next, a 3.0cm x 3.0cm piece of CFRP prepreg (3K plain-woven carbon cloth, manufactured by Nippon Composite Materials Co., Ltd.) with perforated tape was attached to a coated plate, and an aluminum plate was placed on top to create a test sample for molding. The prepared test sample was clamped in a press and cured at 150°C for 15 minutes under a pressure of 10MPa. After the test sample cooled, the aluminum plate was removed, and the test sample was placed on a push-pull force gauge. The clamps of the push-pull force gauge were installed in the holes of the tape in the test sample, and the tape was pulled up rhythmically to demold the molded CFRP prepreg from the coated plate. The force required to pull up was taken as the demolding force and measured. In addition, the same mold was used to continuously demold the article, and the number of consecutive demoldings (i.e., demolding times) until it could no longer be demolded was measured.

[0142] "Non-transferability evaluation" The demolded surface of the CFRP prepreg after the demolding test was observed using a SEM (JCM-7000JEOL). The composition of the release agent on the surface was determined by SEM-EDX, and its amount was compared. The less the composition of the release agent, the better the non-transferability evaluation. The comparison results are classified as follows.

[0143] ○: There is virtually no residue from the release agent (excellent non-transferability). △: There is some residue from the release agent, but very little (good non-transferability). ×: There is a lot of residue from the release agent (poor transferability). "Evaluation of Coating Film Adhesion" After the demolding test, an acrylic polyurethane coating (manufactured by NY PolynK Shendong Coatings Co., Ltd.) was applied to the demolded surface of the CFRP prepreg using a spray gun and allowed to dry at room temperature for 12 hours. Then, the adhesion between the coating film and the prepreg was evaluated using a cross-cut test based on JIS K5600. Specifically, a 5×5 grid was created on the coating film using a cutter, with each grid measuring 2mm in length and 2mm in width. Transparent tape (registered trademark) was applied to the coating film after the grid was drawn, and after pressing with a finger, the tape was peeled off. The coating film residue rate was calculated from the grid remaining on the prepreg, and the results were categorized as follows.

[0144] ◎: The coating residue rate is over 80% (excellent adhesion). ○: The coating residue rate is over 60-80% (good non-transferability). △: The coating residue rate is 20-60% or more (poor non-transferability). ×: Coating residue rate is less than 20% (very poor non-transferability). [Table 1] [Table 2] Industrial availability The release agent composition of the present invention can be used as an internal or external release agent. The release agent composition of the present invention can be used in various molding processes.

[0145] The release agent compositions of the present invention are typically in the form of coatings. The release agent compositions of the present invention can be used as rust inhibitors, moisture inhibitors, waterproofing agents, water-repellent agents, and antifouling agents.

Claims

1. A fluoropolymer characterized in that, having repeating units derived from: (a) a fluorine-containing monomer, (b) a non-fluorine monomer having a hydrocarbon group, and (c) a non-fluorine monomer having a phosphoric acid group, the fluorine-containing monomer (a) is a compound represented by the following formula: CH2=C(-X 11 )-C(=O)-Y 11 -Y 12 -R A in the formula, R A CF3-, CF3O-, CF3NH-, CF3CH2NH-, (CF3)2N-, (CF3CH2)2N-, CF3S-, CF3C(=0)-, CF3CH2C(=0)-, CF3C(=0)0-, CF3CH2OC(=0)-, CF3CONH-, CF3CH2CONH-, CF3NHCO-, CF3CH2NHCO-, CF3CON(CF3)-, CF3CH2CON(CF3)-, CF3CON(CH2CF3)-, CF3CH2CON(CH2CF3)-, (CF3)2NCO-, or (CF3CH2)2NCO-, X 11 R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a halogen atom, Y 11 is a direct bond, -O- or -NH-, Y 12 is a direct bond or a divalent radical; the non-fluorine monomer having a hydrocarbon group (b) is a compound represented by the following formula: CH2=C(-X 21 )-C(=O)-O-Y 21 in the formula, X 21 is a hydrogen atom or a methyl group, Y 21 R1is a hydrocarbon group having a carbon number of 1 to 40; the non-fluorine monomer having a phosphoric acid group (c) is a compound represented by the following formula: [CH2=C(-X 31 )-C(=O)-O-(Y 31 ) p -(O) q -] n P(=O)(O-Y 32 ) 3－n in the formula, X 31 is a hydrogen atom or a methyl group, Y 31 is an alkylene or oxyalkylene group having 1 to 5 carbon atoms, Y 32 is a hydrogen atom, an alkali metal atom or an ammonium group, p is a number of 1 to 10, q is 0 or 1, n is 1, 2 or 3, the content of the repeating unit derived from the non-fluorine monomer having a phosphoric acid group (c) is 0.1 to 4.0% by weight or less relative to the fluorine-containing polymer.

2. The fluorine-containing polymer according to claim 1, wherein: In the fluorine-containing monomer (a), Y 12 is a group represented by the following formula: - (Ar) a1 - (CFH) b1 - (CH2) c1 - (O) d1 - in the formula, Ar is a divalent aromatic group which can be substituted by a fluorine atom or R A substituted by a fluorine atom or R R A CF3-, CF3O-, CF3NH-, CF3CH2NH-, (CF3)2N-, (CF3CH2)2N-, CF3S-, CF3C(=0)-, CF3CH2C(=0)-, CF3C(=0)0-, CF3CH2OC(=0)-, CF3CONH-, CF3CH2CONH-, CF3NHCO-, CF3CH2NHCO-, CF3CON(CF3)-, CF3CH2CON(CF3)-, CF3CON(CH2CF3)-, CF3CH2CON(CH2CF3)-, (CF3)2NCO-, or (CF3CH2)2NCO-, a1 is an integer of 0 to 10, b1 is an integer of 0 to 200, c1 is an integer of 0 to 200, d1 is an integer of 0 to 10, the order of presence of each repeating unit indicated by the symbols a1, b1, c1 and d1 enclosed in parentheses is arbitrary.

3. The fluorine-containing polymer according to claim 1 or 2, wherein: In the fluorine-containing monomer (a), R A is CF3O", CF3NH" or (CF3)2N".

4. The fluorine-containing polymer according to any one of claims 1 to 3, wherein: In the fluorine-containing monomer (a), X 11 is a hydrogen atom, a methyl group or a chlorine atom.

5. The fluorine-containing polymer according to any one of claims 1 to 4, wherein: In the non-fluorine-containing monomer (b), X 21 is a hydrogen atom, Y 21 is a linear or branched monovalent aliphatic hydrocarbon group having 14 to 28 carbon atoms.

6. The fluorine-containing polymer according to any one of claims 1 to 5, wherein: In the non-fluorine-containing hydrocarbon group-containing monomer (b), Y 21 is a group having 16 to 26 carbon atoms.

7. The fluorine-containing polymer according to any one of claims 1 to 6, wherein: In the non-fluorine-containing monomer (c) containing a hydrocarbon group, X 31 is a methyl group, Y 31 is an alkylene group, Y 32 is a hydrogen atom.

8. The fluorine-containing polymer according to any one of claims 1 to 7, wherein: the non-fluorine monomer having a phosphoric acid group (c) is a single phosphoric acid monoester, or is a mixture of a phosphoric acid monoester and a phosphoric acid diester, and in the mixture of the phosphoric acid monoester and the phosphoric acid diester, the weight ratio of the phosphoric acid monoester to the phosphoric acid diester is 95:5 to 50:

50.

9. The fluorine-containing polymer according to any one of claims 1 to 8, wherein: the content of the repeating unit derived from the monomer (a) is 20% by weight or more relative to the fluorine-containing polymer, and the content of the repeating unit derived from the monomer (b) is 5 to 75% by weight relative to the total of the repeating unit derived from the monomer (a) and the repeating unit derived from the monomer (b).

10. The fluorine-containing polymer according to any one of claims 1 to 9, wherein: the fluorine-containing polymer contains a repeating unit derived from another monomer (d) other than the monomers (a), (b) and (c), and the content of the repeating unit derived from the other monomer (d) is 0.1 to 50 parts by weight relative to 100 parts by weight of the repeating unit derived from the fluorine-containing monomer (a).

11. The fluorine-containing polymer according to any one of claims 1 to 10, wherein: the fluorine-containing polymer is composed of the repeating units derived from the monomers (a), (b) and (c).

12. A mold release composition characterized in that, containing: (1) the fluorine-containing polymer according to any one of claims 1 to 11, and (2) a liquid medium selected from at least one of water and an organic solvent.

13. The mold release agent composition according to claim 12, wherein: the mold release agent composition is a solution or an aerosol containing an organic solvent, or an aqueous emulsion containing water.

14. The mold release agent composition according to claim 12 or 13, wherein: The content of the fluorine-containing polymer (1) is 0.1 to 50% by weight relative to the mold release agent composition.

15. The mold release composition of any of claims 12 to 14, wherein: The content of the free phosphoric acid present in the mold release agent composition is 1 part by weight or less relative to 100 parts by weight of the fluorine-containing polymer.

16. The release agent composition according to any one of claims 12 to 15, wherein: The content of the free phosphoric acid present in the mold release agent composition is 1 part by weight or less relative to 100 parts by weight of the fluorine-containing polymer.

17. A method for forming a release agent film, characterized by Comprising: (i) a step of applying the mold release agent composition described in any one of claims 12 to 16 to the inner surface of a molding die to form a coating of the mold release agent composition.

18. A method for producing a molded body, characterized by Comprising: (i) a step of applying the mold release agent composition described in any one of claims 12 to 16 to the inner surface of a molding die to form a coating of the mold release agent composition; (ii) a step of filling a molding composition into the molding die having the coating of the mold release agent composition to obtain a molded body; and (iii) a step of taking the molded body out of the molding die.

Images