WO2024248159A1 - Fluorine-containing polymer, release agent composition, and mold release method - Google Patents

Abstract

Provided is a fluorine-containing polymer having a fluorine-containing monomer (A) and a repeating unit derived from a radical polymerization reactive monomer (B) having no functional group, wherein the fluorine-containing monomer (A) is a compound represented by the formula, CH₂=C(–X¹¹)–C(=O)–Y¹¹–Y¹²–R^A (wherein each symbol is as defined in the specification).

Description

Fluorine-containing polymer, release agent composition and release method

This disclosure relates to a fluorine-containing polymer, a release agent composition, and a release method.

When molding synthetic resins, rubber, etc., it is necessary to apply a release agent (external release agent) to the inner surface of the molding die (metal mold) beforehand to improve releasability.

　Traditionally, fluorine-based release agents have been used as release agents, in addition to wax-based and silicone-based release agents (Patent Documents 1 to 4).

Patent No. 5060847 Special Publication No. 3-8245 Japanese Patent Application Laid-Open No. 60-262870 JP 2014-129517 A

The purpose of this disclosure is to provide a new release agent composition that has excellent release properties.

[1] A fluorine-containing polymer having a repeating unit derived from (A) a fluorine-containing monomer and (B) a radical-polymerizable monomer having no functional group,
The fluorine-containing monomer (A) is represented by the formula:
CH ₂ =C(-X ¹¹ )-C(=O)-Y ¹¹ -Y ¹² -R ^A
[Wherein,
R ^A is CF ₃ -, CF ₃ O-, CF ₃ NH-, CF ₃ CH ₂ NH-, (CF ₃ ) ₂ N-, (CF ₃ CH ₂ ) ₂ N-, CF ₃ S-, CF ₃ C(=O)-, CF ₃ CH ₂ C(=O)-, CF ₃ C(=O)O-, CF ₃ CH ₂ OC(=O)-, CF ₃ CONH-, CF ₃ CH ₂ CONH-, CF ₃ NHCO-, CF ₃ CH ₂ NHCO-, CF ₃ CON(CF ₃ )-, CF ₃ CH ₂ CON(CF ₃ )-, CF ₃ CON(CH ₂ CF ₃ )-, CF _3CH2CON ( _{CH2CF3 )} -, _{( CF3} ) _{2NCO- or} ( _CF3CH2 ) _2NCO- ;
^X11 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 group.
A fluorine-containing polymer, which is a compound represented by the formula:
[2] In the fluorine-containing monomer (A), Y ¹² is a group represented by formula (I):
-(Ar) _a1 -(CFH) _b1 -(CH ₂ ) _c1 -(O) _d1 - (I)
[Wherein:
Ar is a divalent aromatic group optionally substituted by a fluorine atom or R ^A ;
R ^A is CF ₃ -, CF ₃ O-, CF ₃ NH-, CF ₃ CH ₂ NH-, (CF ₃ ) ₂ N-, (CF ₃ CH ₂ ) ₂ N-, CF ₃ S-, CF ₃ C(=O)-, CF ₃ CH ₂ C(=O)-, CF ₃ C(=O)O-, CF ₃ CH ₂ OC(=O)-, CF ₃ CONH-, CF ₃ CH ₂ CONH-, CF ₃ NHCO-, CF ₃ CH ₂ NHCO-, CF ₃ CON(CF ₃ )-, CF ₃ CH ₂ CON(CF ₃ )-, CF ₃ CON(CH ₂ CF ₃ )-, CF _3CH2CON ( _{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 repeating units denoted by symbols a1, b1, c1, and d1 and enclosed in parentheses may be present in any order.]
The fluorine-containing polymer according to the above-mentioned [1], wherein the R is a group represented by the following formula:
[3] The fluorine-containing polymer according to the above [1] or [2], wherein in the fluorine-containing monomer (A), R ^A is CF ₃ O—, CF ₃ NH—, or (CF ₃ ) ₂ N—.
[4] The fluorine-containing polymer according to any one of the above [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 radical polymerization reactive monomer (B) is represented by the formula (II):
[Wherein,
_R3 is a linear or branched monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, or a monovalent cyclic aliphatic hydrocarbon group;
_R4 is a hydrogen atom or a methyl group.
The fluorine-containing polymer according to any one of the above [1] to [4], wherein the alkyl (meth)acrylate is represented by the following formula:
[6] A release agent composition comprising: (1) the fluorine-containing polymer according to any one of the above [1] to [5]; and (2) a liquid medium which is at least one kind selected from water and an organic solvent.
[7] The release agent composition according to the above [6], which is a solution or aerosol containing an organic solvent, or an aqueous emulsion containing water.
[8] The release agent composition according to the above [6] or [7], wherein the content of the fluorine-containing polymer (1) is 0.1 to 50% by weight based on the weight of the release agent composition.
[9] (i) A method for forming a release agent coating, comprising a step of applying the release agent composition according to any one of the above [6] to [8] to an inner surface of a molding die to form a coating of the release agent composition.
[10] (i) a step of applying the release agent composition according to any one of the above items [6] to [8] to the inner surface of a molding die to form a coating of the release agent composition;
(ii) filling a molding composition into a mold having a coating of the mold release agent composition to obtain a molded body; and (iii) removing the molded body from the mold.

The present disclosure provides a new release agent composition with excellent release properties.

[Components of release agent composition]
The release agent composition is
The composition comprises (1) a fluoropolymer, and (2) a liquid medium which is water and/or an organic solvent.
In the release agent composition, the fluorine-containing polymer functions as a release agent. The release agent composition is preferably in the form of a solution or an aqueous emulsion.

(1) Fluorine-Containing Polymer The fluorine-containing polymer is the active ingredient in the release agent composition, that is, the release agent.

The fluorine-containing polymer is
The fluorine-containing polymer has (A) a repeating unit derived from a fluorine-containing monomer, and (B) a repeating unit derived from a radical-polymerizable monomer having no functional group. In addition to the repeating units (A) and (B), the fluorine-containing polymer may have another repeating unit (C) (a repeating unit derived from another monomer (C)).

(A) Fluorine-containing monomer The fluorine-containing monomer (A) is a monomer represented by the formula:
CH ₂ =C(-X ¹¹ )-C(=O)-Y ¹¹ -Y ¹² -R ^A
[Wherein,
R ^A is CF ₃ -, CF ₃ O-, CF ₃ NH-, CF ₃ CH ₂ NH-, (CF ₃ ) ₂ N-, (CF ₃ CH ₂ ) ₂ N-, CF ₃ S-, CF ₃ C(=O)-, CF ₃ CH ₂ C(=O)-, CF ₃ C(=O)O-, CF ₃ CH ₂ OC(=O)-, CF ₃ CONH-, CF ₃ CH ₂ CONH-, CF ₃ NHCO-, CF ₃ CH ₂ NHCO-, CF ₃ CON(CF ₃ )-, CF ₃ CH ₂ CON(CF ₃ )-, CF ₃ CON(CH ₂ CF ₃ )-, CF _3CH2CON ( _{CH2CF3 )} -, ( _CF3 ) _{2NCO- or} ( _CF3CH2 ) _{2NCO- ;}
^X11 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 group.
It is a compound represented by the formula:

R ^A is CF ₃ -, CF ₃ O-, CF ₃ NH-, CF ₃ CH ₂ NH-, (CF ₃ ) ₂ N-, (CF ₃ CH ₂ ) ₂ N-, CF ₃ S-, CF ₃ C(=O)-, CF ₃ CH ₂ C(=O)-, CF ₃ C(=O)O-, CF ₃ CH ₂ OC(=O)-, CF ₃ CONH-, CF ₃ CH ₂ CONH-, CF ₃ NHCO-, CF ₃ CH ₂ NHCO-, CF ₃ CON(CF ₃ ) -, CF ₃ CH ₂ CON (CF ₃ )-, CF ₃ CON(CH ₂ CF ₃ )-, CF _{R A} is _{preferably CF} ³ _{O— ,} CF _{3 NH— , ( CF 3} ) _2N- , _CF3S- , _CF3C (=O)-, _CF3C (=O)O-, _CF3OC (=O)-, _CF3CONH- , _CF3NHCO- , CF _{CF 3} CON(CF ₃ )-, or (CF ₃ ) ₂ NCO-, and more preferably CF ₃ O-, CF ₃ NH-, or (CF ₃ ) ₂ N-.

In one embodiment, R ^A can be CF ₃ O—.

In another embodiment, R ^A can be CF ₃ NH-- or (CF ₃ ) ₂ N--, preferably CF ₃ NH--.

X ¹¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom). X ¹¹ is preferably a hydrogen atom, a methyl group, or a chlorine atom.

Y ¹¹ is a direct bond, —O— or —NH—. Y ¹¹ is preferably —O—. That is, the fluorine-containing monomer (A) is preferably an acrylate ester.

Y ¹² is a direct bond or a divalent group. Y ¹² is preferably
-(Ar) _a1 -(CFH) _b1 -(CH ₂ ) _c1 -(O) _d1 -
[Wherein:
Ar is a divalent aromatic group optionally substituted by a fluorine atom or R ^A ;
R ^A is CF ₃ -, CF ₃ O-, CF ₃ NH-, CF ₃ CH ₂ NH-, (CF ₃ ) ₂ N-, (CF ₃ CH ₂ ) ₂ N-, CF ₃ S-, CF ₃ C(=O)-, CF ₃ CH ₂ C(=O)-, CF ₃ C(=O)O-, CF ₃ CH ₂ OC(=O)-, CF ₃ CONH-, CF ₃ CH ₂ CONH-, CF ₃ NHCO-, CF ₃ CH ₂ NHCO-, CF ₃ CON(CF ₃ )-, CF ₃ CH ₂ CON(CF ₃ )-, CF ₃ CON(CH ₂ CF ₃ )-, CF _3CH2CON ( _{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 repeating units denoted by symbols a1, b1, c1, and d1 and enclosed in parentheses may be present in any order.]
In the formula, however, it is preferable that no consecutive oxygen atoms exist. In other words, it is preferable that no -O-O- bond exists. Note that the right side of ^Y12 bonds to ^R1A .

The above aromatic groups include aromatic rings containing only carbon as ring atoms (so-called arylenes), as well as aromatic rings containing nitrogen, oxygen or sulfur (so-called heteroarylenes), and groups having multiple aromatic rings.

The aromatic group preferably has a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, a tetracene ring, a pentacene ring, a benzopyrene ring, a chrysene ring, a pyrene ring, a triphenylene ring, a corannulene ring, an ovalene ring, 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, a pyrazine ring, a biphenyl ring, a terphenyl ring, a triphenylmethane ring, or a benzophenone ring.

In one embodiment, the aromatic group preferably has a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, a tetracene ring, a pentacene ring, a benzopyrene ring, a chrysene ring, a pyrene ring, a triphenylene ring, a corannulene ring, or an ovalene ring, more preferably a benzene ring or a naphthalene ring, and even more preferably a benzene ring.

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, more preferably an indole ring.

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

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

In another embodiment, Ar is a divalent aromatic group substituted with a fluorine atom or R 3 ^A.

In another embodiment, Ar is a divalent aromatic group substituted by R 3 ^A.

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

The number of substituents on the aromatic group is not particularly limited, but may be, for example, 1 to 10, 1 to 5, 1 to 3, 1, 2, or 3. In one embodiment, the number of substituents on the aromatic group is 1 or more. In another embodiment, the aromatic group is fully substituted.

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

In one embodiment, a1 is 0.

In another embodiment, a1 is 1.

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

c1 is an integer between 0 and 200, preferably between 0 and 30.

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

In one embodiment, Y ¹² is
-(CH ₂ ) _c1 -(O) _d1 -(Ar) _a1 -
[Wherein:
Ar is a divalent aromatic group which may be substituted by a fluorine atom or R ^A , preferably an unsubstituted divalent aromatic group;
R ^A is CF ₃ -, CF ₃ O-, CF ₃ NH-, CF ₃ CH ₂ NH-, (CF ₃ ) ₂ N-, (CF ₃ CH ₂ ) ₂ N-, CF ₃ S-, CF ₃ C(=O)-, CF ₃ CH ₂ C(=O)-, CF ₃ C(=O)O-, CF ₃ CH ₂ OC(=O)-, CF ₃ CONH-, CF ₃ CH ₂ CONH-, CF ₃ NHCO-, CF ₃ CH ₂ NHCO-, CF ₃ CON(CF ₃ )-, CF ₃ CH ₂ CON(CF ₃ )-, CF ₃ CON(CH ₂ CF ₃ )-, CF _3CH2CON ( _{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 an integer from 1 to 9, an integer from 1 to 3, or an integer from 2 to 3;
d1 is 0 or 1;
The repeating units denoted by symbols a1, c1, and d1 and enclosed in parentheses may be present in any order.]
The right side of ^Y12 bonds to ^RA .

In one embodiment, Y ¹² is
-(CH ₂ ) _c1 -
[In the formula, c1 is an integer from 1 to 36, preferably an integer from 1 to 30, and may be, for example, an integer from 1 to 9, or an integer from 1 to 3.]
It is a group represented by the following formula:

In one embodiment, Y ¹² is -Ar-
[Wherein:
Ar is a divalent aromatic group which may be substituted by a fluorine atom or R ^A , preferably an unsubstituted divalent aromatic group;
R ^A is CF ₃ -, CF ₃ O-, CF ₃ NH-, CF ₃ CH ₂ NH-, (CF ₃ ) ₂ N-, (CF ₃ CH ₂ ) ₂ N-, CF ₃ S-, CF ₃ C(=O)-, CF ₃ CH ₂ C(=O)-, CF ₃ C(=O)O-, CF ₃ CH ₂ OC(=O)-, CF ₃ CONH-, CF ₃ CH ₂ CONH-, CF ₃ NHCO-, CF ₃ CH ₂ NHCO-, CF ₃ CON(CF ₃ )-, CF ₃ CH ₂ CON(CF ₃ )-, CF ₃ CON(CH ₂ CF ₃ )-, CF _3CH2CON ( _{CH2CF3 )} -, _{( CF3} ) _{2NCO- or} ( _CF3CH2 ) _2NCO- .]
The right side of ^Y12 bonds to ^RA .

Specific examples of the fluorine-containing monomer include, but are not limited to, the following:
CH ₂ =C(-H)-C(=O)-O-CH ₂ -R ^A
CH ₂ =C(-H)-C(=O)-O-(CH ₂ ) ₂ -R ^A
CH ₂ =C(-H)-C(=O)-O-C ₆ H ₄ -R ^A
CH ₂ =C(-H)-C(=O)-NH-(CH ₂ ) ₂ -R ^A
CH ₂ =C(-CH ₃ )-C(=O)-O-CH ₂ -R ^A
CH ₂ =C(-CH ₃ )-C(=O)-O-(CH ₂ ) ₂ -R ^A
CH ₂ =C(-CH ₃ )-C(=O)-O-(CH ₂ ) ₃ -R ^A
CH ₂ =C(-CH ₃ )-C(=O)-NH-(CH ₂ ) ₂ -R ^A
CH ₂ =C(-F)-C(=O)-O-(CH ₂ ) ₂ -R ^A
CH ₂ =C(-F)-C(=O)-NH-(CH ₂ ) ₂ -R ^A
CH ₂ =C(-F)-C(=O)-NH-(CH ₂ ) ₃ -R ^A
CH ₂ =C(-Cl)-C(=O)-O-(CH ₂ ) ₂ -R ^A
CH ₂ =C(-Cl)-C(=O)-NH-(CH ₂ ) ₂ -R ^A
[In the above formula, R ^A has the same meaning as above.]

(B) Radical polymerization reactive monomer having no functional group

Monomer (B) is a monomer that does not have a functional group. Since monomer (B) does not contain a functional group, it is possible to avoid a reaction between the release agent and the molding material during use.

Monomer (B) is a monomer that can be copolymerized with monomer (A).

Monomer (B) has a radical polymerization reactive site. The radical polymerization reactive site is not particularly limited, but examples thereof include an acrylate group, a methacrylate group, a vinyl group, a vinylidene group, and an allyl group. The radical polymerization reactive site is preferably an acrylate group or a methacrylate group.

The structure of the portion of monomer (B) other than the radical polymerization reactive portion can be selected from a wide range of structures as long as the effect of the present invention is not impaired. In addition to the radical polymerization reactive portion, monomer (B) may further have one or more substituents, such as an alkyl group, which are inactive in reaction with the molding material. Monomer (B) may further have bonds, such as an ester bond, which are inactive in reaction with the molding material, inserted between the substituents or between the substituent and the radical polymerization reactive portion.

As the monomer (B), for example, a monomer represented by the following formula (II):
[Wherein,
_R3 is a linear or branched monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, or a monovalent cyclic aliphatic hydrocarbon group;
_R4 is a hydrogen atom or a methyl group.
Examples of the (meth)acrylic acid esters include those represented by the following formula:

In formula (II), _R3 is a linear or branched monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, or a monovalent cyclic aliphatic hydrocarbon group. _R3 is preferably a linear or branched monovalent aliphatic hydrocarbon group having 1 to 30 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, or a monovalent cyclic aliphatic hydrocarbon group having 6 to 12 carbon atoms.

In the above, the linear or branched monovalent aliphatic hydrocarbon group having 1 to 30 carbon atoms is not particularly limited, but examples include alkyl groups having 1 to 30 carbon atoms, preferably alkyl groups having 1 to 22 carbon atoms, and more preferably alkyl groups having 10 to 22 carbon atoms.

Specific examples of alkyl groups having 1 to 22 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, neopentyl, t-pentyl, n-hexyl, 2-ethylbutyl, n-heptyl, n-octyl, 2-ethylhexyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, cetyl, stearyl, and behenyl.

Specific examples of monovalent aromatic hydrocarbon groups having 6 to 12 carbon atoms include phenyl, 2-ethylphenyl, indenyl, toluyl, and benzyl groups.

Specific examples of monovalent cyclic aliphatic hydrocarbon groups having 6 to 12 carbon atoms include cyclohexyl, norbornyl, norbornylmethyl, isobornyl, bornyl, menthyl, octahydroindenyl, adamantyl, and dimethyladamantyl groups.

Specific examples of (meth)acrylic acid esters represented by formula (II) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, neopentyl (meth)acrylate, t-pentyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, and p) Decyl acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate, norbornyl (meth)acrylate, norbornylmethyl (meth)acrylate, isobornyl (meth)acrylate, bornyl (meth)acrylate, menthyl (meth)acrylate, octahydroindenyl (meth)acrylate, adamantyl (meth)acrylate, dimethyladamantyl (meth)acrylate, phenyl (meth)acrylate, 2-ethylphenyl (meth)acrylate, indenyl (meth)acrylate, toluyl (meth)acrylate, and benzyl (meth)acrylate. Stearyl acrylate and behenyl acrylate are particularly preferred.

The release agent of the present invention may be a release agent consisting of a fluoropolymer obtainable by copolymerizing one of the above-mentioned monomers (B) with monomer (A), or may be a release agent consisting of a fluoropolymer structure obtainable by copolymerizing two or more of the monomers (B) with monomer (A).

(C) Other monomers The fluorine-containing polymer may have a repeating unit derived from another monomer. The fluorine-containing polymer preferably does not have a repeating unit derived from another monomer. That is, the fluorine-containing polymer is preferably composed of repeating units derived from monomers (A) and (B). Examples of the other monomer (C) include silicon-containing monomers, such as modified silicone oils, such as amino-modified silicone oils and acrylic-modified silicone oils; and di(meth)acrylate monomers. Other examples of the other monomers include ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, and vinyl alkyl ether.

Each of the monomers (A) to (C) may be a single type or a mixture of two or more types.

The number average molecular weight (Mn) of the fluorine-containing polymer may generally be 1,000 to 1,000,000, for example, 2,000 to 500,000, and particularly 3,000 to 200,000. The number average molecular weight (Mn) of the fluorine-containing polymer is generally measured by GPC (gel permeation chromatography).

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

The amount of the liquid medium may be 30 to 99.1% by weight, particularly 50 to 99% by weight, based on the weight of the release agent composition.

(3) Other Forming and Parting Agents The composition may contain other components.

When the release agent composition is an aqueous emulsion, it is preferable that it contains an emulsifier. The emulsifier may be at least one selected from a nonionic emulsifier, a cationic emulsifier, an anionic emulsifier, and an amphoteric emulsifier.

The release agent composition may contain additives as other components.

Examples of additives include silicon-containing compounds, waxes, and acrylic emulsions. Other examples of additives include other fluorine-containing polymers, drying speed regulators, crosslinking agents, film-forming aids, compatibilizers, surfactants, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, defoamers, texture adjusters, slip adjusters, antistatic agents, hydrophilizing agents, antibacterial agents, preservatives, insect repellents, fragrances, and flame retardants.

The amount of the other components may be 0.1 to 20% by weight, for example 0.5 to 10% by weight, based on the weight of the release agent composition.

[Production of release agent composition (production of fluoropolymer)]
The release agent of the present invention is
The polymerizable composition can be produced by a method including a step of copolymerizing (A) a fluorine-containing monomer and (B) a radically polymerizable monomer having no functional group.

The copolymerization may be emulsion polymerization or solution polymerization.

Emulsion polymerization is not particularly limited, but can be carried out, for example, as follows: In the presence of a polymerization initiator and an emulsifier, various monomers are emulsified in water, and after nitrogen replacement, the mixture is copolymerized at 50 to 80°C for 1 to 10 hours while stirring.

In emulsion polymerization, the polymerization initiator is not particularly limited, but examples include water-soluble polymerization initiators such as benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, azobisisobutyronitrile, sodium peroxide, potassium persulfate, and ammonium persulfate, as well as oil-soluble polymerization initiators such as azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, and azobismethylpropionate.

In emulsion polymerization, the polymerization initiator is usually used in the range of 0.01 to 10 parts by weight per 100 parts by weight of monomer.

In emulsion polymerization, in order to obtain an aqueous copolymer dispersion with excellent shelf stability, it is preferable to atomize the monomer in water using an emulsifying device capable of imparting strong crushing energy, such as a high-pressure homogenizer or ultrasonic homogenizer, and then polymerize using an oil-soluble polymerization initiator.

In emulsion polymerization, various emulsifiers, such as anionic, cationic or nonionic emulsifiers, can be used. The emulsifier is usually used in the range of 0.5 to 20 parts by weight per 100 parts by weight of monomer. Nonionic or anionic emulsifiers are preferred as emulsifiers.

The nonionic emulsifier is not particularly limited, but examples thereof include polyoxyethylene alkyl ethers, sorbitan alkylates, and sorbitan alkyl esters.
The polyoxyethylene alkyl ether is not particularly limited, but examples thereof include polyethylene lauryl ether.

Anionic emulsifiers include alkyl sulfates, alkyl sulfonates, and alkyl phosphates. Examples of alkyl sulfates include, but are not limited to, sodium alkyl sulfate.

Cationic emulsions include quaternary ammonium salts and alkylamine salts.

Quaternary ammonium salts are not particularly limited, but examples include lauryltrimethylammonium chloride.

If the monomers are not completely compatible in emulsion polymerization, it is preferable to add a compatibilizer that makes the monomers sufficiently compatible, such as a water-soluble organic solvent or a low molecular weight monomer. The addition of a compatibilizer can improve emulsifiability and copolymerizability.

Water-soluble organic solvents as compatibilizers are not particularly limited, but examples include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, diethylene glycol diethyl ether, tripropylene glycol, and ethanol. The water-soluble organic solvent is usually used in the range of 1 to 50 parts by weight per 100 parts by weight of water. The water-soluble organic solvent is preferably used in the range of 10 to 40 parts by weight per 100 parts by weight of water.

In emulsion polymerization, a chain transfer agent may be used to adjust the molecular weight of the resulting polymer. Examples of chain transfer agents include, but are not limited to, lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, 2-ethylhexyl thioglycolate, and 2,3-dimethylcapto-1-propanol. One or more types of chain transfer agents may be used as necessary. Chain transfer agents are usually used in the range of 0.001 to 7.0 parts by weight per 100 parts by weight of monomer.

The solution polymerization can be carried out, for example, as follows, but is not limited to the above. In the presence of a polymerization initiator, the monomer is dissolved in an organic solvent, and after nitrogen replacement, the mixture is heated and stirred at a temperature in the range of 30 to 120°C for 1 to 10 hours. Examples of polymerization initiators include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is usually used in the range of 0.01 to 20 parts by weight per 100 parts by weight of the monomer. The polymerization initiator is preferably used in the range of 0.01 to 10 parts by weight per 100 parts by weight of the monomer.

In solution polymerization, the organic solvent is not particularly limited as long as it is inert to the monomers and dissolves them. Examples of organic solvents include acetone, chloroform, isopropyl alcohol, 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 usually used in the range of 50 to 2000 parts by weight per 100 parts by weight of the total monomers. The organic solvent is preferably used in the range of 50 to 1000 parts by weight per 100 parts by weight of the total monomers.

[Form and Use of Release Agent Composition]
The form of the release agent composition can be appropriately selected depending on the purpose of use, and may be, for example, a solution, an emulsion, or an aerosol. It is preferable that the release agent composition is a solution or an aerosol containing an organic solvent, or an aqueous emulsion containing water.

The release agent composition preferably contains 0.5% to 50% by weight of the fluorine-containing polymer, more preferably 1.0% to 30% by weight, and particularly preferably 1.5% to 20% by weight, based on the weight of the release agent composition.

The release agent composition may further contain a surfactant (emulsifier) for the purpose of improving wettability to the mold. As the surfactant, a fluorine-based or non-fluorine-based surfactant, etc. can be used. As the fluorine-based or non-fluorine-based surfactant, an anionic surfactant, a nonionic surfactant, and a cationic surfactant can be used.

Fluorosurfactants include fluorine-containing polyoxyethylenes, sulfonates, carboxylates, and quaternary ammonium salts.

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

Examples of non-fluorinated nonionic surfactants include polyoxyethylene alkyl ethers, sorbitan alkylates, and sorbitan alkyl esters. Examples of polyoxyethylene alkyl ethers include polyoxyethylene lauryl ether.

Non-fluorinated cationic surfactants include quaternary ammonium salts and alkylamine salts.

Examples of quaternary ammonium salts include lauryltrimethylammonium chloride.

If a surfactant is contained, the amount of the surfactant may be 0.01% by weight to 20% by weight, preferably 0.01% by weight to 15% by weight, and more preferably 0.05% by weight to 10% by weight, based on the release agent composition.

The release agent composition may further contain at least one release enhancing additive selected from the group consisting of silicone compounds, wax-based compounds, fluorine-based compounds, etc., for the purpose of improving the release properties and/or finish.

Examples of silicone compounds include dimethyl silicone oil, methylphenyl silicone oil, modified silicone oil (e.g., amino-modified silicone oil), fluorosilicone oil, and silicone resin. Examples of wax-based compounds include polyethylene wax, paraffin wax, and carnauba wax. Examples of fluorine-based compounds include polytetrafluoroethylene, fluoropolyether, and fluorochloropolyether.

The amount of the release enhancer additive may be 0.01% to 20% by weight, preferably 0.02% to 15% by weight, based on the weight of the release agent composition.

When the release agent composition is an aqueous emulsion, it preferably contains at least one emulsifier selected from the group consisting of nonionic emulsifiers, anionic emulsifiers, and cationic emulsifiers.

The nonionic emulsifier may be any that can emulsify the fluoropolymer of the present disclosure and disperse it in an aqueous emulsion, and examples of such an emulsifier include polyoxyethylene alkyl ethers, sorbitan alkylates, and sorbitan alkyl esters. Examples of polyoxyethylene alkyl ethers include polyoxyethylene lauryl ether.

Anionic emulsifiers include alkyl sulfates, alkyl sulfonates, and alkyl phosphates. Alkyl sulfates include sodium alkyl sulfate.

Cationic emulsifiers include quaternary ammonium salts and alkylamine salts. Quaternary ammonium salts include lauryltrimethylammonium chloride.

The amount of emulsifier is usually 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, per 100 parts by weight of the fluoropolymer.

When the release agent composition is a solution, it may further contain an organic solvent, etc.

When the release agent composition is an aerosol, it can be filled into an aerosol can using a propellant. Examples of propellants include LPG, dimethyl ether, and carbon dioxide. The amount of propellant is usually 10 to 95% by weight, preferably 20 to 90% by weight, and more preferably 30 to 90% by weight, based on the total amount of the release agent composition and the propellant. If the amount of propellant is 10% by weight or more, the spraying can be performed better and a more uniform coating tends to be obtained. Also, if the amount of propellant is 95% by weight or less, the coating does not tend to become too thin and the release properties do not tend to decrease too much.

The release agent composition can be used as an internal or external release agent. It is preferably used as an external release agent.

　The release agent composition is usually used as follows: The release agent composition is applied to the inner surface of a mold. After the solvent and dispersant are dried and removed, a release agent coating (a fluoropolymer coating) is formed on the mold. The mold is filled with a molding composition to form a molding material, and the molding material is then removed from the mold.

Examples of molds for which the release agent composition can be used include metal molds such as aluminum, SUS, and iron, epoxy resin and wooden molds, and nickel electroformed or chrome plated molds.

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

The following examples are provided to further explain the present disclosure, but the present disclosure is not limited to these examples.

Synthesis Example 1
Referring to the description in WO2020/168011Al, silver triflate, potassium fluoride, 1-(chloromethyl)-4-fluoro-4-diazoniabicyclo[2.2.2]octane, a salt of tetrafluoroborate, and benzyloxyethanol were reacted in ethyl acetate for 16 hours at 30° C. to obtain [2-(trifluoromethoxy)ethoxy]methyl]benzene (compound 1).

Synthesis Example 2
[2-(Trifluoromethoxy)ethoxy]methyl]benzene (compound 1) was reduced with hydrogen in the presence of a palladium catalyst (50 psi, 35° C., 24 hours) to give 2-(trifluoromethoxy)ethanol (compound 2).

Synthesis Example 3
The alcohol obtained in Synthesis Example 2 was reacted with methyl methacrylate in the presence of a basic catalyst (calcium hydroxide) to obtain a fluorine-containing methacrylate (compound 3).

Production Example 1
After thoroughly dissolving 41 g of the compound obtained in Synthesis Example 3: CF ₃ O-CH ₂ CH ₂ -OCO-C(CH ₃ )=CH ₂ and 10 g of stearyl acrylate, 4 g of polyoxyethylene (n=20) lauryl ether (nonionic emulsifier), 0.2 g of lauryl mercaptan, 7 g of dipropylene glycol monomethyl ether and 95 g of ion-exchanged water were added and emulsified with a high-pressure homogenizer. The resulting emulsion was placed in a 300 ml four-neck flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer and a stirrer, and kept at 60°C for about 1 hour under a nitrogen stream. 0.3 g of ammonium persulfate dissolved in 5 g of water was added as an initiator to initiate polymerization. The mixture was heated and stirred at 60°C for 3 hours to prepare an aqueous copolymer emulsion, and the resulting aqueous emulsion was adjusted with ion-exchanged water so that the solid content concentration was 0.3% by mass.

Production Example 2
After thoroughly dissolving 35 g of the compound obtained in Synthesis Example 3: CF ₃ O—CH ₂ CH ₂ —OCO—C(CH ₃ )═CH ₂ and 25 g of stearyl acrylate, an aqueous copolymer emulsion was prepared in the same manner as in Production Example 1, and the solids concentration was adjusted to 0.3 mass% with ion-exchanged water.

Production Example 3
After thoroughly dissolving 44 g of the compound obtained in Synthesis Example 3 (CF ₃ O—CH ₂ CH ₂ —OCO—C(CH ₃ )═CH ₂ ) and 5 g of isobornyl methacrylate, an aqueous copolymer emulsion was prepared in the same manner as in Production Example 1, and the solids concentration was adjusted to 0.3 mass% with ion-exchanged water.

Production Example 4
After thoroughly dissolving 23 g of the compound obtained in Synthesis Example 3: CF ₃ O—CH ₂ CH ₂ —OCO—C(CH ₃ )═CH ₂ and 50 g of stearyl methacrylate, an aqueous copolymer emulsion was prepared in the same manner as in Production Example 1, and the solids concentration was adjusted to 0.3 mass% with ion-exchanged water.

Production Example 5
After thoroughly dissolving 14 g of the compound obtained in Synthesis Example 3: CF ₃ O—CH ₂ CH ₂ —OCO—C(CH ₃ )═CH ₂ and 70 g of lauryl acrylate, an aqueous copolymer emulsion was prepared in the same manner as in Production Example 1, and the solids concentration was adjusted to 0.3 mass% with ion-exchanged water.

Production Example 6
After 50 g of glycidyl methacrylate was sufficiently dissolved, an aqueous copolymer emulsion was prepared in the same manner as in Production Example 1, and the solid content was adjusted to 0.3% by mass with ion-exchanged water.

Production Example 7
After 61 g of glycidyl methacrylate and 19 g of stearyl acrylate were sufficiently dissolved, an aqueous copolymer emulsion was prepared in the same manner as in Production Example 1, and the solid content was adjusted to 0.3% by mass with ion-exchanged water.

Production Example 8
After 10 g of hydroxybutyl acrylate and 50 g of stearyl acrylate were sufficiently dissolved, an aqueous copolymer emulsion was prepared in the same manner as in Production Example 1, and the solid content was adjusted to 0.3% by mass with ion-exchanged water.

Production Example 9
A compound (control compound 2) prepared with reference to Example 1 of Japanese Patent No. 5664745 was adjusted with ion-exchanged water to a solid content concentration of 0.3% by mass.

Production Example 10
50 g of dimethyl silicone emulsion, SM67036EX (Comparative Compound 2, manufactured by Dow Toray Co., Ltd.) was adjusted with ion-exchanged water to a solids concentration of 0.3% by mass.

Examples Each test was carried out using 10 compounds. That is, the following tests were carried out using the compounds in Production Examples 1 to 5 as Examples 1 to 5 and the compounds in Production Examples 6 to 10 as Comparative Examples 1 to 5.
The results are shown in Table 1.

"Mold release test"
The experiment was carried out under the following conditions:
(1) 100 parts by weight of peroxide vulcanization type silicone rubber KE-941U (manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.6 parts by weight of C-8A (manufactured by Shin-Etsu Chemical Co., Ltd.) as a vulcanizing agent were kneaded with a rubber kneading roll to obtain an unvulcanized rubber material.
(2) The compounds prepared in Examples 1 to 5 and Comparative Examples 1 to 5 were each applied using a spray gun under the same conditions to a 36-cavity mold (medium mold) kept at 180°C, and 36 pieces of 1g of the rubber material pieces (1) cut into small pieces were placed in the medium mold. Then, two molds of the same size as the medium mold were placed on the top (upper mold) and bottom (lower mold) of the medium mold, and press molding was performed at 180°C for 10 minutes.
(3) After molding, the upper and lower dies were removed and only the middle die was taken out. After that, the molded rubber pieces were pushed out with a push-pull gauge, and the pushing force required at that time was measured, and the average value of the force required when 36 pieces were pushed out was taken as the mold release force (N).
(4) The fluoropolymer composition was again applied and molded in the same manner as in (2) above, and the evaluation was repeated in the same manner as in (3) up to four consecutive times.

"Ratio of the area of release agent covering the molded product"
The unvulcanized rubber material obtained during the release test was cut to 100 x 100 x 10 mm, placed on a SUS plate, and press molded at 180°C for 10 minutes to produce a silicone rubber sheet. Next, the rubber sheet thus produced was placed in a vertical position, and the release agents prepared in Production Examples 1 to 10 were sprayed using a spray gun, adjusting the spray discharge amount and time so that the wet weight was 5 g/m2. The coverage area of the compounded liquid when applied was measured and classified as follows:
◎: The coverage area of the release agent is 80% or more (the release agent has excellent wettability with respect to the molded product)
○: The coverage area of the release agent is 60 to 80% or more (the release agent has good wettability with respect to the molded product)
△: The coverage area of the release agent is 20 to 60% or more (the release agent has poor wettability with respect to the molded product)
×: Coverage area rate of the release agent is less than 20% (wettability of the release agent to the molded product is very poor)

"Mold fouling evaluation"
The above mold release test was carried out four times in succession, and then the mold dirt adhering to the mold was sampled. The amount of the mold dirt was compared with the weight of Comparative Example 9.
◎: 1/20 of Comparative Example 10
○: 1/10 of Comparative Example 10
△: 1/4 of Comparative Example 10
×: equivalent to Comparative Example 9

In the table, each abbreviation indicates the following compound.
"STA": stearyl acrylate, "IBM": isobornyl methacrylate, "STMA": stearyl methacrylate, "LA": lauryl acrylate, "GMA": glycidyl methacrylate, "HBA": hydroxybutyl acrylate

The release agent composition of the present disclosure can be used as an internal or external release agent. The release agent composition of the present disclosure can be used in various moldings.
The release agent composition of the present disclosure is generally in the form of a coating material. The release agent composition of the present disclosure can be used as a rust inhibitor, a moisture inhibitor, a waterproof agent, a water repellent, and an antifouling agent.

Claims (12)

A fluorine-containing polymer having a repeating unit derived from (A) a fluorine-containing monomer and (B) a radical-polymerizable reactive monomer having no functional group,
The fluorine-containing monomer (A) is represented by the formula:
CH ₂ =C(-X ¹¹ )-C(=O)-Y ¹¹ -Y ¹² -R ^A
[Wherein,
R ^A is CF ₃ -, CF ₃ O-, CF ₃ NH-, CF ₃ CH ₂ NH-, (CF ₃ ) ₂ N-, (CF ₃ CH ₂ ) ₂ N-, CF ₃ S-, CF ₃ C(=O)-, CF ₃ CH ₂ C(=O)-, CF ₃ C(=O)O-, CF ₃ CH ₂ OC(=O)-, CF ₃ CONH-, CF ₃ CH ₂ CONH-, CF ₃ NHCO-, CF ₃ CH ₂ NHCO-, CF ₃ CON(CF ₃ )-, CF ₃ CH ₂ CON(CF ₃ )-, CF ₃ CON(CH ₂ CF ₃ )-, CF _3CH2CON ( _{CH2CF3 )} -, _{( CF3} ) _{2NCO- or} ( _CF3CH2 ) _2NCO- ;
^X11 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 group.
A fluorine-containing polymer which is a compound represented by the formula: In the fluorine-containing monomer (A), Y ¹² is a group represented by the formula (I):
-(Ar) _a1 -(CFH) _b1 -(CH ₂ ) _c1 -(O) _d1 - (I)
[Wherein:
Ar is a divalent aromatic group optionally substituted by a fluorine atom or R ^A ;
R ^A is CF ₃ -, CF ₃ O-, CF ₃ NH-, CF ₃ CH ₂ NH-, (CF ₃ ) ₂ N-, (CF ₃ CH ₂ ) ₂ N-, CF ₃ S-, CF ₃ C(=O)-, CF ₃ CH ₂ C(=O)-, CF ₃ C(=O)O-, CF ₃ CH ₂ OC(=O)-, CF ₃ CONH-, CF ₃ CH ₂ CONH-, CF ₃ NHCO-, CF ₃ CH ₂ NHCO-, CF ₃ CON(CF ₃ )-, CF ₃ CH ₂ CON(CF ₃ )-, CF ₃ CON(CH ₂ CF ₃ )-, CF _3CH2CON ( _{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 repeating units denoted by symbols a1, b1, c1, and d1 and enclosed in parentheses may be present in any order.]
The fluorine-containing polymer according to claim 1 , wherein the fluorine-containing polymer is a group represented by the formula: 3. The fluorine-containing polymer according to claim 1, wherein in the fluorine-containing monomer (A), R ^A is CF ₃ O--, CF ₃ NH-- or (CF ₃ ) ₂ N--. 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. The radical polymerization reactive monomer (B) is represented by the formula (II):

[Wherein,
_R3 is a linear or branched monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, or a monovalent cyclic aliphatic hydrocarbon group;
_R4 is a hydrogen atom or a methyl group.
The fluorine-containing polymer according to any one of claims 1 to 4, which is an alkyl (meth)acrylic acid ester represented by the formula: The fluorine-containing monomer has the formula:
CH ₂ =C(-X ¹¹ )-C(=O)-Y ¹¹ -Y ¹² -R ^A
[Wherein,
R ^A is CF ₃ O—;
^X11 is a hydrogen atom or a methyl group;
Y ¹¹ is -O-;
Y ¹² is a group represented by -(CH ₂ ) _c1 - (wherein c1 is an integer of 1 to 3).
A compound represented by the formula:
The radical polymerization reactive monomer is represented by the formula (II):

[Wherein,
_R3 is a linear alkyl group having 10 to 22 carbon atoms or an isobornyl group;
_R4 is a hydrogen atom or a methyl group.
is an alkyl (meth)acrylic acid ester represented by the formula:
The fluorine-containing polymer according to any one of claims 1 to 5. The fluorine-containing monomer is CF ₃ O—CH ₂ CH ₂ —OCO—C(CH ₃ )═CH ₂ ,
The radical polymerization reactive monomer is stearyl acrylate, stearyl methacrylate, isobornyl methacrylate, or lauryl acrylate;
The fluorine-containing polymer according to any one of claims 1 to 6. (1) A release agent composition comprising the fluoropolymer according to any one of claims 1 to 7, and (2) a liquid medium which is at least one kind selected from water and organic solvents. The release agent composition according to claim 8, wherein the release agent composition is a solution or aerosol containing an organic solvent, or an aqueous emulsion containing water. The release agent composition according to claim 8 or 9, wherein the content of the fluorine-containing polymer (1) is 0.1 to 50% by weight based on the release agent composition. (i) A method for forming a release agent coating, comprising the step of applying the release agent composition according to any one of claims 8 to 10 to an inner surface of a molding die to form a coating of the release agent composition. (i) a step of applying the mold release agent composition according to any one of claims 8 to 10 to the inner surface of a molding die to form a coating of the mold release agent composition;
(ii) filling a molding composition into a mold having a coating of the mold release agent composition to obtain a molded body; and (iii) removing the molded body from the mold.