TWI792007B - Composition for forming fluorine-containing sealing material - Google Patents

Abstract

An objective of this invention is to provide a sealing material with high chemical resistance.

This invention provides a composition for forming a fluorine-containing sealing material, which includes (I) a fluoropolymer containing a structural unit derived from a fluoroalkyl group-containing (meth)acrylic acid ester monomer represented by formula (1), and is one or both of the fluoropolymers shown in (A) and (B) below, and (II) carbon black.

[In the formula, each symbol has the same meaning as described in the specification.]

(A) A fluoropolymer containing a structural unit derived from a monomer component containing the fluoroalkyl group-containing (meth)acrylic acid ester monomer and a Si atom-containing polymerizable monomer,

(B) A fluoropolymer containing a structural unit derived from a monomer component containing the fluoroalkyl group-containing (meth)acrylic acid ester monomer and a structural unit derived from a Si atom-containing mercaptan.

Description

Composition for forming fluorine-containing sealing material

This disclosure relates to a composition for forming a fluorine-containing sealing material.

In gaps (gaps, for example, minute gaps) between electronic components in electronic devices such as displays and printed boards, a sealing material is provided to fill the gaps. In this sealing material, waterproofness and the like for protecting components included in electronic equipment are pursued.

A coating composition containing a fluorine-containing compound has been disclosed as the above-mentioned sealing material (Patent Document 1).

[Prior Art Literature]

[Patent Document]

Patent Document 1: Japanese Patent Laid-Open No. 2018-172677

The above-mentioned sealing materials require chemical resistance (for example, resistance to fatty acids, etc.). Therefore, the purpose of this disclosure is to provide a sealing material with high chemical resistance.

This disclosure includes the following aspects.

[1] A composition for forming a fluorine-containing sealing material, comprising: (I) a fluorine-containing polymer comprising a (meth)acrylate monomer derived from a fluorine-containing alkyl group represented by the following formula (1) and is one or both of the fluoropolymers shown in (A) and (B) below; and (II) carbon black,

[where:

Rf is a fluoroalkyl group;

X is hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, CFX ¹ X ² group (wherein, X ¹ and X ² are hydrogen atom, fluorine atom or chlorine atom identically or differently), cyano group, Linear or branched fluoroalkyl groups with 1 to 21 carbons, substituted or unsubstituted benzyl groups, substituted or unsubstituted phenyl groups, or linear or branched alkyl groups with 1 to 20 carbons ;

Y is a single bond, or a divalent organic group];

(A) A fluorine-containing polymer comprising constituents derived from monomer components of the aforementioned fluoroalkyl-containing (meth)acrylate monomer and Si atom-containing polymerizable monomer;

(B) A fluorine-containing polymer comprising a constituent component derived from a monomer component of the aforementioned fluoroalkyl-containing (meth)acrylate monomer and a constituent component derived from a Si atom-containing thiol,

(Here, at least one Si atom contained in the aforementioned Si atom-containing polymerizable monomer and the aforementioned Si atom-containing thiol each independently has a hydroxyl group or a hydrolyzable group).

[2] The composition for forming a fluorine-containing sealing material according to the above [1], wherein, in formula (1), Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms.

[3] The composition for forming a fluorine-containing sealing material as described in the above [1] or [2], wherein, in formula (1), Y is a single bond, and may have an oxygen atom or a sulfur atom having a carbon number of from 1 to Aliphatic group with 10 carbon atoms, aromatic group with 6 to 10 carbon atoms which may have oxygen atom, cyclic aliphatic group with 6 to 10 carbon atoms which may have oxygen atom, aromatic group with 6 to 10 carbon atoms which may have oxygen atom Aliphatic group, -CH ₂ CH ₂ N(R ¹ )SO ₂ - group (in the formula, R ¹ is an alkyl group with 1 to 4 carbons), -CH ₂ CH(OY ¹ )CH ₂ - group (in the formula , Y ¹ is a hydrogen atom or an acetyl group), or a -(CH ₂ ) _n SO ₂ - group (where n is an integer from 1 to 10).

[4] The composition for forming a fluorine-containing sealing material according to any one of the above [1] to [3], wherein, in the formula (1), Rf is a linear or branched chain having 4 to 6 carbon atoms. Branched fluoroalkyl, X is an atom or group other than hydrogen.

[5] The composition for forming a fluorine-containing sealing material according to any one of [1] to [4] above, wherein the carbon black is furnace black, acetylene black, or Ketjen black.

[6] The composition for forming a fluorine-containing sealing material according to any one of the above [1] to [5], wherein the content of the aforementioned carbon black relative to the solid content in the composition for forming a fluorine-containing sealing material is 0.1 to 10% by mass.

[7] The composition for forming a fluorine-containing sealing material according to any one of the above-mentioned [1] to [6], wherein in the fluorine-containing polymer represented by the above-mentioned (A), the polymerizable The monomer is a compound shown in formula (2):

[where:

R ² , R ³ and R ⁴ are identically or differently hydroxyl groups, hydrolyzable groups or monovalent organic groups, but at least one of R ² , R ³ and R ⁴ is hydroxyl groups or hydrolyzable groups;

R ⁵ is a group containing a polymerizable unsaturated bond].

[8] The composition for forming a fluorine-containing sealing material according to any one of the above-mentioned [1] to [7], wherein the fluorine-containing polymer represented by the above-mentioned (A) is represented by the following formula (5): Those who show the structure part:

[where:

X is hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, CFX ¹ X ² group (wherein, X ¹ and X ² are hydrogen atom, fluorine atom or chlorine atom identically or differently), cyano group, Linear or branched fluoroalkyl groups with 1 to 21 carbons, substituted or unsubstituted benzyl groups, substituted or unsubstituted phenyl groups, or linear or branched alkyl groups with 1 to 20 carbons ;

Y is a single bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom or a sulfur atom, an aromatic group having 6 to 10 carbon atoms which may have an oxygen atom, or a ring having 6 to 10 carbon atoms which may have an oxygen atom aliphatic group, araliphatic group with 6 to 10 carbon atoms which may have an oxygen atom, -CH ₂ CH ₂ N(R ¹ )SO ₂ - group (in the formula, R ¹ is an alkyl group with 1 to 4 carbon atoms ), -CH ₂ CH(OY ¹ )CH ₂ -group (wherein, Y ¹ is a hydrogen atom or acetyl group), or -(CH ₂ ) _n SO ₂ -group (wherein, n is 1 to 10 integer);

Rf is a linear or branched fluoroalkyl group with 1 to 20 carbons;

R ² , R ³ and R ⁴ are the same or different alkyl groups with 1 to 4 carbons or alkoxy groups with 1 to 4 carbons, but at least one of R ² , R ³ and R ⁴ is alkoxy base;

R ⁵ ' is a trivalent group derived from a group containing a polymerizable unsaturated bond;

l and m are each an integer of 1 or more, and the total of l and m is a value such that the weight average molecular weight of the fluoropolymer becomes 3,000 to 500,000, and each repeating unit marked with l and m and enclosed in brackets The order of existence is arbitrary in the formula].

[9] The composition for forming a fluorine-containing sealing material according to any one of the above-mentioned [1] to [8], wherein in the fluorine-containing polymer represented by the above-mentioned (B), the monomer component further contains Polymerizable monomer of Si atom.

[10] The composition for forming a fluorine-containing sealing material according to any one of the above [1] to [9], wherein, in the fluorine-containing polymer represented by the above-mentioned (B), the Si atom-containing thiol Be the compound shown in formula (3):

[where:

R ⁷ , R ⁸ and R ⁹ are identically or differently hydroxyl groups, hydrolyzable groups or monovalent organic groups, but at least one of R ⁷ , R ⁸ and R ⁹ is hydroxyl groups or hydrolyzable groups;

R ¹⁰ is a linear alkylene group having 1 to 12 carbon atoms].

[11] The composition for forming a fluorine-containing sealing material according to any one of the above [1] to [10], wherein the fluorine-containing polymer represented by the above-mentioned (B) is represented by the following formula (6): Compounds:

[where:

X is hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, CFX ¹ X ² group (wherein, X ¹ and X ² are hydrogen atom, fluorine atom or chlorine atom identically or differently), cyano group, Linear or branched fluoroalkyl group with 1 to 21 carbons, substituted or unsubstituted benzyl group, substituted or unsubstituted phenyl group, or linear or branched alkyl group with 1 to 20 carbons ;

Y is a single bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom or a sulfur atom, an aromatic group having 6 to 10 carbon atoms which may have an oxygen atom, or a ring having 6 to 10 carbon atoms which may have an oxygen atom aliphatic group, araliphatic group with 6 to 10 carbon atoms which may have an oxygen atom, -CH ₂ CH ₂ N(R ¹ )SO ₂ - group (in the formula, R ¹ is an alkyl group with 1 to 4 carbon atoms ), -CH ₂ CH(OY ¹ )CH ₂ -group (wherein, Y ¹ is a hydrogen atom or acetyl group), or -(CH ₂ ) _n SO ₂ -group (wherein, n is 1 to 10 integer);

Rf is a linear or branched fluoroalkyl group with 1 to 20 carbons;

R ⁷ , R ⁸ and R ⁹ are identically or differently alkyl groups with 1 to 4 carbon atoms or alkoxy groups with 1 to 4 carbon atoms, and at least one of R ⁷ , R ⁸ and R ⁹ is an alkoxy group;

R ¹⁰ is a straight-chain alkylene group with 1 to 12 carbons;

k is a numerical value such that the weight average molecular weight of the fluoropolymer becomes 3,000 to 500,000].

[12] The composition for forming a fluorine-containing sealing material according to any one of the above [1] to [11], further comprising (III) a fluorine-based solvent.

[13] The composition for forming a fluorine-containing sealing material according to the above [12], wherein the fluorine-based solvent is selected from the group consisting of hydrofluoroethers, hydrofluorocarbons, and perfluorocarbons at least one of them.

[14] An article comprising a sealing material formed using the composition for forming a fluorine-containing sealing material according to any one of [1] to [13] above.

[15] The article as described in [14] above, which is an electronic component.

[16] The article as described in [15] above, which is an electronic device including electronic components.

The coating composition containing a fluorine-containing compound of the present disclosure can form a sealing material with high chemical resistance by containing carbon black.

When used in this specification, a "monovalent organic group" means a monovalent group containing carbon. The said monovalent organic group is not specifically limited, A hydrocarbon group is mentioned.

When used in this specification, a "divalent organic group" means a divalent group containing carbon. The above-mentioned divalent organic group is not particularly limited, and further includes a divalent group in which one hydrogen atom is detached from a hydrocarbon group.

When used in this specification, the above-mentioned "hydrocarbon group" means a group containing carbon and hydrogen. The hydrocarbon group is not particularly limited, and examples thereof include hydrocarbon groups having 1 to 20 carbon atoms that may be substituted with one or more substituents, such as aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and the like. The aforementioned "aliphatic hydrocarbon group" may be any of linear, branched or cyclic, and may be either saturated or unsaturated. Furthermore, the hydrocarbon group may contain one or more ring structures. In addition, the above-mentioned hydrocarbon group may have one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at its terminal or in the molecular chain.

The substituent of the above-mentioned "hydrocarbon group" is not particularly limited, for example: halogen atom; _{C 1-6} alkyl, C 2-6 alkenyl, C _2-6 alkynyl which may be substituted by one or more halogen atoms , C _3-10 cycloalkyl, C _3-10 unsaturated cycloalkyl, 5 to 10 membered heterocyclic group, 5 to 10 membered unsaturated heterocyclic group, C _6-10 aryl, 5 to 10 membered The heteroaryl and so on.

In the present specification, the alkyl group and the phenyl group may be unsubstituted or substituted unless otherwise specified. The substituent of the above-mentioned group is not particularly limited, and examples thereof include one or more groups selected from a halogen atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, and a C _2-6 alkynyl group.

In this specification, the term "hydrolyzable group" means a group that can undergo a hydrolysis reaction, that is, a group that can be detached from the main skeleton of a compound by a hydrolysis reaction. Examples of hydrolyzable groups include: -OR, -OCOR, -ON=CR ₂ , -NR ₂ , -NHR, halogen (in these formulas, R represents a substituted or unsubstituted alkyl group with 1 to 4 carbon atoms ), etc., preferably -OR (ie, alkoxy). Examples of R include: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl and other unsubstituted alkyl groups; chloromethyl and other substituted alkyl groups. Among them, an alkyl group is preferable, especially an unsubstituted alkyl group, and a methyl group or an ethyl group is more preferable. In this specification, the "hydroxyl group" described together with the "hydrolyzable group" is not particularly limited, and may be produced by hydrolysis of the hydrolyzable group.

[Composition for forming fluorine-containing sealing material]

The composition for forming a fluorine-containing sealing material of the present disclosure is a composition for forming a fluorine-containing sealing material suitable for filling, for example, voids (gaps) of electronic parts or electronic devices containing electronic parts. In the following, it may be described that the gap-filling property is good as described above, which is suitable for filling the voids.

The composition for forming a fluorine-containing sealing material of the present disclosure contains a fluorine-containing polymer and carbon black.

[Fluoropolymer]

The fluorine-containing polymer contained in the composition for forming a fluorine-containing sealing material of the present disclosure is a fluorine-containing polymer containing a constituent unit derived from a (meth)acrylate monomer of a fluorine-containing alkyl group represented by the following formula (1) Polymer, and it is a fluorine-containing polymer represented by the following (A) and/or (B):

[where:

Rf is a fluoroalkyl group;

X is hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, CFX ¹ X ² base (wherein, X ¹ and X ² are hydrogen atom, fluorine atom or chlorine atom identically or differently), cyano group, Linear or branched fluoroalkyl groups with 1 to 21 carbons, substituted or unsubstituted benzyl groups, substituted or unsubstituted phenyl groups, or linear or branched alkyl groups with 1 to 20 carbons ;

Y is a single bond, or a divalent organic group].

(A) A fluorine-containing polymer comprising constituents derived from monomer components of the aforementioned fluoroalkyl-containing (meth)acrylate monomer and Si atom-containing polymerizable monomer;

(B) A fluorine-containing polymer comprising a constituent component derived from a monomer component of the aforementioned fluoroalkyl-containing (meth)acrylate monomer and a constituent component derived from a Si atom-containing thiol,

(Here, at least one Si atom contained in the aforementioned Si atom-containing polymerizable monomer and the aforementioned Si atom-containing thiol each independently has a hydroxyl group or a hydrolyzable group).

Hereinafter, each component for obtaining the above-mentioned fluoropolymer will be described.

[(Meth)acrylate Monomer Containing Fluorinated Alkyl Group]

The above fluoroalkyl-containing (meth)acrylate monomer system is one in which a fluoroalkyl group is directly or via a divalent organic ester bonded to an acrylic acid which may have a substituent at the α position. In this specification, the fluoroalkyl-containing acrylate monomer and the fluoroalkyl-containing methacrylate monomer are collectively referred to as "fluoroalkyl-containing (meth)acrylate monomer". The above-mentioned fluorine-containing alkyl (meth)acrylate monomer system contributes to the chemical resistance (for example, to salt water, acid or alkali) of the fluorine-containing sealing material formed by using the composition for forming a fluorine-containing sealing material of the present disclosure. Enhanced resistance to aqueous solutions, acetone, oleic acid or hexane, especially to salt water).

The (meth)acrylate monomer system containing a fluoroalkyl group is represented by the following formula (1).

In the above-mentioned formula (1), X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (wherein, X ¹ and X ² are identically or differently hydrogen atoms, fluorine atoms or chlorine atom), cyano, straight-chain or branched fluoroalkyl with 1 to 21 carbons, substituted or unsubstituted benzyl, substituted or unsubstituted phenyl, or straight-chain or branched fluoroalkyl with 1 to 20 carbons Chain or branched alkyl. X is preferably a hydrogen atom, a fluorine atom, a chlorine atom, or a methyl group.

In other aspects, X is preferably a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (wherein, X ¹ and X ² have the same meaning as above), a cyano group, and a carbon number of 1 Straight-chain or branched fluoroalkyl to 21, substituted or unsubstituted benzyl, substituted or unsubstituted phenyl, or straight-chain or branched alkyl with 1 to 20 carbons, and more Preferably, it is a fluorine atom, a chlorine atom or a methyl group.

In the above formula (1), Y is a single bond or a divalent organic group. The divalent organic group has the same meaning as above. Y is preferably a single bond, an aliphatic group with 1 to 10 carbon atoms which may have an oxygen atom or a sulfur atom, an aromatic group with 6 to 10 carbon atoms which may have an oxygen atom, or an aromatic group with 6 to 10 carbon atoms which may have an oxygen atom Cyclic aliphatic group, araliphatic group with 6 to 10 carbon atoms which may have an oxygen atom, -CH ₂ CH ₂ N(R ¹ )SO ₂ - group (wherein, R ¹ is a group with 1 to 4 carbon atoms Alkyl group), -CH ₂ CH(OY ¹ )CH ₂ -group (in the formula, Y ¹ series, hydrogen atom or acetyl group), or -(CH ₂ ) _n SO ₂ -group (in the formula, n series , an integer of 1 to 10), more preferably a single bond, an aliphatic group with a carbon number of 1 to 10 or a -CH ₂ CH(OH)CH ₂ - group, and more preferably an aliphatic group with a carbon number of 1 to 4 or -CH ₂ CH(OY ¹ )CH ₂ -yl.

Examples of the aforementioned aliphatic group include alkylene groups having 1 to 10 carbon atoms.

The aforementioned aliphatic group is preferably, for example, an alkylene group having 1 to 4 carbon atoms.

Examples of the above-mentioned aromatic groups include phenylene groups.

Examples of the above-mentioned cyclic aliphatic group include cycloalkylene (Cycloalkylene) rings.

The aforementioned araliphatic group includes, for example, -Y ²¹ -Ar-Y ²² -. Y ²¹ and Y ²² may each independently be a single bond or an alkylene group having 1 to 12 carbons, and Ar may include a substituted or unsubstituted aryl group (more systematically a phenylene group).

In the above formula (1), Rf is a fluoroalkyl group, preferably a linear or branched fluoroalkyl group having 1 to 20 carbon atoms. Here, the fluoroalkyl group referred to is an alkyl group in which at least one hydrogen atom is replaced by a fluorine atom. In one aspect, Rf is a perfluoroalkyl group in which all hydrogen atoms are replaced with fluorine atoms.

In the fluoroalkyl-containing (meth)acrylate monomer represented by the above formula (1), Rf is preferably carbon from the viewpoint of good solubility in fluorine-based solvents described later, especially hydrofluoroethers. A linear or branched fluoroalkyl group with a number of 4 to 6. In order to further improve the water resistance of the formed gap filler (sealing material), the fluoroalkyl-containing (meth)acrylate monomer represented by the above formula (1) is more preferably a substituent at the α position represented by X It is a group other than a hydrogen atom or an α-position substituted acrylate. The substituent X at the α-position is preferably a methyl group, a chlorine atom, or a fluorine atom from the viewpoint of forming a gap filler with good water resistance using inexpensive raw materials. The substituent X at the α-position is particularly preferably a methyl group from the viewpoint of favorable film-forming properties.

In one aspect, the fluoroalkyl-containing (meth)acrylate monomer represented by the above formula (1) is for the fluorine-based solvent described later, for example, at least one hydrogen atom passes through a fluorine atom, and at least Rf is preferably a linear or branched fluoroalkyl group having 4 to 6 carbon atoms in terms of good solubility of an olefin in which one hydrogen atom is substituted by a chlorine atom. In order to further improve the water resistance of the formed gap filler (sealing material), the fluoroalkyl-containing (meth)acrylate monomer represented by the above formula (1) is more preferably a substituent at the α position represented by X It is a group other than a hydrogen atom or an α-position substituted acrylate. The substituent X at the α-position is preferably a methyl group, a chlorine atom, or a fluorine atom from the viewpoint of forming a gap filler with good water resistance using low-cost raw materials. The substituent X at the α-position is particularly preferably a methyl group from the viewpoint of favorable film-forming properties.

In one aspect, Rf is more preferably a perfluoroalkyl group in which all hydrogen atoms are replaced by fluorine atoms, or a linear or branched perfluoroalkyl group with 4 to 6 carbon atoms.

Examples of the fluoroalkyl-containing (meth)acrylate monomer system represented by the above general formula (1) include the following compounds.

Rf-SO ₂ (CH ₂ ) ₃ -OCO-CH=CH ₂

CH ₂ =C(-F)-C(=O)-O-(CH ₂ ) ₂ -S-Rf

CH ₂ =C(-F)-C(=O)-O-(CH ₂ ) ₂ -S-(CH ₂ ) ₂ -Rf

CH ₂ =C(-F)-C(=O)-O-(CH ₂ ) ₂ -SO ₂ -Rf

CH ₂ =C(-F)-C(=O)-O-(CH ₂ ) ₂ -SO ₂ -(CH ₂ ) ₂ -Rf

CH ₂ =C(-Cl)-C(=O)-O-(CH ₂ ) ₂ -S-Rf

CH ₂ =C(-Cl)-C(=O)-O-(CH ₂ ) ₂ -S-(CH ₂ ) ₂ -Rf

CH ₂ =C(-Cl)-C(=O)-O-(CH ₂ ) ₂ -SO ₂ -Rf

CH ₂ =C(-Cl)-C(=O)-O-(CH ₂ ) ₂ -SO ₂ -(CH ₂ ) ₂ -Rf

CH ₂ =C(-Cl)-C(=O)-O-(CH ₂ ) ₃ -S-Rf

CH ₂ =C(-Cl)-C(=O)-O-(CH ₂ ) ₃ -SO ₂ -Rf

CH ₂ =C(-CH ₃ )-C(=O)-O-(CH ₂ ) ₂ -Rf

CH ₂ =C(H)-C(=O)-O-(CH ₂ ) ₂ -Rf

The above fluorinated alkyl group-containing (meth)acrylate monomers may be used alone or in combination of two or more.

[Polymerizable monomer containing Si atom]

The aforementioned Si atom-containing polymerizable monomer contains Si atoms bonded to at least one hydroxyl group or hydrolyzable group. The aforementioned Si atom-containing polymerizable monomer preferably contains, in the molecule, a Si atom bonded to at least one hydroxyl group or a hydrolyzable group and at least one polymerizable functional group. The above-mentioned polymerizable monomer containing Si atoms contributes to the improvement of the adhesiveness of the walls of the voids or the components pre-filled in the voids, and improves the wear resistance of the fluorine-containing sealing material.

In the above-mentioned Si atom-containing polymerizable monomer, the above-mentioned polymerizable functional group is preferably a group containing a polymerizable unsaturated bond, more preferably a group containing a polymerizable ethylenically unsaturated bond. It is preferable that one polymerizable functional group exists in the molecule of the above-mentioned Si atom-containing polymerizable monomer.

In the aforementioned Si atom-containing polymerizable monomer, the aforementioned Si atom is preferably bonded to 1 to 3 hydroxyl groups or hydrolyzable groups, more preferably 3 hydroxyl groups or hydrolyzable groups. The hydrolyzable groups have the same meaning as above.

The aforementioned Si atom-containing polymerizable monomer is preferably a compound represented by the following formula (2).

In the above formula (2), R ² , R ³ and R ⁴ are identically or differently hydroxyl groups, hydrolyzable groups or monovalent organic groups, and at least one of R ² , R ³ and R ⁴ is hydroxyl groups or can be base of hydrolysis. The hydrolyzable groups have the same meaning as above. Preferably, the aforementioned monovalent organic group is an alkyl group having 1 to 4 carbon atoms. More preferably, R ² , R ³ and R ⁴ are identically or differently alkyl with 1 to 4 carbons or alkoxy with 1 to 4 carbons (-OR), and at least one of R ² , R ³ and R ⁴ One is an alkoxy group having 1 to 4 carbon atoms. The R series has the same meaning as above. R ² , R ³ and R ⁴ are more preferably each independently an alkoxy group, and more preferably each independently are a methoxy group or an ethoxy group. For example, R ² , R ³ and R ⁴ can all be methoxy.

In the above formula (2), R ⁵ is a group containing a polymerizable unsaturated bond, preferably a group containing a polymerizable ethylenically unsaturated bond.

The compound represented by the above formula (2) may be specifically represented by the following formula (2').

In the above formula (2'), R ² , R ³ and R ⁴ have the same meanings as above. R ¹⁴ represents a hydrogen atom, a fluorine atom, a chlorine atom, or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom, a chlorine atom, or a methyl group. Y ² represents a single bond or a divalent organic group, preferably a single bond, an alkylene group with 1 to 10 carbons, or an araliphatic group with 6 to 15 carbons. The araliphatic group has the same meaning as above.

As the Si atom-containing polymerizable monomer, specifically, monomers represented by the following formulas can be exemplified.

In the above formulas, R ² , R ³ and R ⁴ have the same meanings as above, R ⁶ is a hydrogen atom, a methyl group or a chlorine atom, and h is an integer from 1 to 12 (for example, 1 to 10).

In one aspect, R ² , R ³ and R ⁴ are methoxy or ethoxy, preferably methoxy, R ⁶ is methyl, and h is an integer from 1 to 12.

The aforementioned Si atom-containing polymerizable monomers may be used alone or in combination of two or more.

[Other monomers]

The above-mentioned monomer components may contain high softening point monomers or other monomers as needed.

The above-mentioned high softening point monomer is a monomer whose glass transition point or melting point of a homopolymer composed of high softening point monomer is 100°C or higher, preferably 120°C or higher. At this time, there is a glass transition The glass transition point of polymers with shift point must be above 100°C, preferably above 120°C, and the melting point of polymers without glass transition point must be above 100°C, preferably above 120°C.

In addition, the glass transition point and melting point are extrapolated glass transition end temperature (Teg) and melting peak temperature (Tpm) according to JIS K7121-1987 "Measurement method of transition temperature of plastics", respectively.

The above-mentioned single system with a high softening point can contribute to the improvement of the waterproof and/or moisture-proof performance of the fluorine-containing sealing material formed from the composition for forming an oil-containing fluorine-containing sealing material. Furthermore, by containing a monomer with a high softening point, the hardness of the above-mentioned fluorine-containing sealing material system can be improved, and durability such as abrasion resistance becomes better.

In particular, by using the above-mentioned high softening point monomer as a monomer component, the above-mentioned sealing material has very good dynamic water repellency, and this dynamic water repellency becomes an index showing the removal performance of water droplets attached to the surface. In addition, the dynamic water repellency can be evaluated by the water sliding angle.

Examples of the above-mentioned high softening point monomer system include (meth)acrylates represented by the following general formula (4): methyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, and the like.

CH ₂ =C(R ¹¹ )COOR ¹² (4)

(wherein, R ¹¹ is H or CH ₃ , R ¹² is a saturated alkyl group having 4 to 20 carbon atoms and a ratio of carbon atoms to hydrogen atoms of 0.55 or more)

The above-mentioned high softening point monomer is preferably (meth)acrylate represented by the above-mentioned general formula (4).

In general formula (4), a saturated alkyl group having 4 to 20 carbon atoms and a ratio of carbon atoms to hydrogen atoms of 0.55 or more (more specifically, a saturated alkyl group having 4 to 20 carbon atoms and a ratio of carbon atoms to hydrogen atoms of 0.58 or more saturated alkyl) specific examples include: isocamphoryl, camphenyl, fenzyl (all of the above are C ₁₀ H ₁₇ , carbon atom/hydrogen atom = 0.58), adamantyl (C ₁₀ H ₁₅ , carbon atom/hydrogen atom=0.66), norcamphoryl (C7H12, carbon atom/hydrogen atom=0.58), etc. have a cross-linked hydrocarbon ring. These cross-linked hydrocarbon ring systems may be bonded to the carboxyl group with a single bond, or bonded to the carboxyl group via a linear or branched chain alkylene group having 1 to 5 carbons. These cross-linked hydrocarbon ring systems may be further substituted with hydroxyl or alkyl groups (number of carbons, eg, 1 to 5).

In addition, the above ratio of carbon atoms to hydrogen atoms means the ratio of the number of carbon atoms to the number of hydrogen atoms.

The (meth)acrylates represented by the above-mentioned general formula (4) include (meth)acrylates having an isobornyl group, (meth)acrylates having a norbornyl group, and (meth)acrylates having an adamantyl group. base) acrylate, etc. Among these, examples of (meth)acrylates having a norbornyl group include: 3-methyl-norbornyl methyl (meth)acrylate, norbornyl methyl (meth)acrylate, (meth)acrylate ) norbornyl acrylate, 1,3,3-trimethyl-norbornyl (meth)acrylate, myrtanyl methyl (meth)acrylate, iso (meth)acrylate Isopinocampheyl ester, 2-{[5-(1',1',1'-trifluoro-2'-trifluoromethyl-2'-hydroxy)propyl]norcampheyl (meth)acrylate (meth)acrylic acid esters having an adamantyl group include: 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate Alkyl esters, 3-hydroxy-1-adamantyl (meth)acrylate, 1-adamantyl-α-trifluoromethyl (meth)acrylate, and the like.

As long as the above-mentioned other monomers are monomers that can be copolymerized with (meth)acrylate monomers containing fluoroalkyl groups, they can be widely used under the limitation that they will not adversely affect the properties of the obtained fluoropolymers. Choose from a range. Examples include: aromatic alkene compounds, vinyl cyanide compounds, conjugated diene compounds, halogen-containing unsaturated compounds, silicon-containing unsaturated compounds, unsaturated dicarboxylate compounds, vinyl ester compounds, allyl ester compounds, Ether compounds containing unsaturated groups, maleimide compounds, (meth)acrylates, acrolein, methacrolein, monomers capable of cyclopolymerization, N-vinyl compounds, etc., but not limited to etc.

[Mercaptan containing Si atom]

The aforementioned Si atom-containing thiol is saturated with Si atoms bonded to at least one hydroxyl group or hydrolyzable group.

The above-mentioned thiol containing Si atom acts as a chain transfer agent, and the degree of polymerization of the fluorine-based polymer can be adjusted by adding it. Furthermore, a part of the Si atom-containing thiol, specifically, a hydroxyl group or a hydrolyzable group bonded to the Si atom contained in the Si atom-containing thiol is contained in the fluoropolymer. Thereby, the adhesion between the formed fluorine-containing sealing material and the elastomer (for example, polysiloxane) and/or the wall surface of the void is improved. Therefore, the Si atom-containing mercaptan system contributes to the formation of a fluorine-containing sealing material excellent in abrasion resistance.

The aforementioned Si atom-containing thiol is not particularly limited as long as it is a compound having a Si atom bonded to at least one hydroxyl group or a hydrolyzable group, and a mercapto group. Preferable examples of the Si atom-containing thiol include compounds represented by the following formula (3).

In the above formula (3), R ⁷ , R ⁸ and R ⁹ are identically or differently hydroxyl groups, hydrolyzable groups or monovalent organic groups, and at least one of R ⁷ , R ⁸ and R ⁹ is hydroxyl group or hydrolyzable foundation. The hydrolyzable groups have the same meaning as above. Preferably, the aforementioned monovalent organic group is an alkyl group having 1 to 4 carbon atoms. R ⁷ , R ⁸ and R ⁹ are preferably identically or differently alkyl with 1 to 4 carbons or alkoxy with 1 to 4 carbons (-OR), at least 1 of R ⁷ , R ⁸ and R ⁹ Each is an alkoxy group having 1 to 4 carbon atoms. R ⁷ , R ⁸ and R ⁹ are more preferably each independently an alkoxy group, particularly preferably each independently an methoxy group or an ethoxy group. For example, R ⁷ , R ⁸ and R ⁹ may all be methoxy.

In the above formula (3), R ¹⁰ is an alkylene group having 1 to 12 carbon atoms. The above-mentioned alkylene group is linear or branched, preferably a linear alkylene group.

In one aspect, R ⁷ , R ⁸ and R ⁹ are each independently methoxy or ethoxy, preferably methoxy, and R ¹⁰ is an alkylene group having 1 to 5 carbons.

Among the Si atom-containing thiols represented by the above general formula (3), R ¹⁰ is preferably a straight-chain alkane having 1 to 4 carbons from the viewpoint of solubility in fluorine-based solvents described later. base.

The aforementioned Si atom-containing mercaptans may be used individually or in combination of two or more.

Hereinafter, the fluorine-containing polymer contained in the composition for forming a fluorine-containing sealing material of the present disclosure will be described. The above-mentioned fluoropolymer is a fluoropolymer represented by the following (A) (hereinafter also referred to as "fluoropolymer 1") and a fluoropolymer represented by the following (B) (hereinafter also referred to as as "fluoropolymer 2").

(A) A fluorine-containing polymer comprising constituents derived from monomer components of the aforementioned fluoroalkyl-containing (meth)acrylate monomer and Si atom-containing polymerizable monomer;

(B) A fluorine-containing polymer comprising a constituent component derived from a monomer component of the aforementioned fluoroalkyl-containing (meth)acrylate monomer and a constituent component derived from a Si atom-containing thiol,

(Here, at least one Si atom contained in the aforementioned Si atom-containing polymerizable monomer and the aforementioned Si atom-containing thiol each independently has a hydroxyl group or a hydrolyzable group).

[Fluoropolymer 1]

The above-mentioned fluoropolymer 1 can be obtained by polymerizing a monomer component containing a fluorine-containing alkyl group-containing (meth)acrylate monomer and a Si atom-containing polymerizable monomer as essential components. That is, the fluoropolymer 1 is a fluoropolymer obtained by polymerizing monomer components of a fluoroalkyl-containing (meth)acrylate monomer and a Si atom-containing polymerizable monomer. Fluoropolymer 1 is a copolymer having a structural unit derived from a fluoroalkyl-containing (meth)acrylate monomer and a structural unit derived from a Si atom-containing polymerizable monomer.

The weight average molecular weight of the above-mentioned fluoropolymer 1 is preferably from 3,000 to 500,000, more preferably from 5,000 to 300,000, and still more preferably from 20,000 to 100,000. Fluorinated poly The weight average molecular weight of compound 1 can be obtained by GPC (gel permeation chromatography). For example, the above-mentioned weight average molecular weight can be obtained by GPC using a mixed solvent of HCFC225/hexafluoroisopropanol (=90/10 by weight) as an eluting solvent (standard polymethyl methacrylate conversion).

Fluoroalkyl-containing (meth)acrylate monomers and Si atom-containing polymerizable monomers have the same meanings as above.

The above-mentioned fluorine-containing polymer 1 is preferably composed of the above-mentioned constituent units derived from the fluoroalkyl-containing (meth)acrylate monomer and the above-mentioned constituent units derived from the polymerizable monomer containing Si atoms, preferably by mass. It is contained in the range of 99.9:0.1 to 50:50, more preferably in the range of 96:4 to 70:30, still more preferably in the range of 96:4 to 90:10.

In a preferred aspect, in the fluorine-containing polymer 1, the above-mentioned fluoroalkyl-containing (meth)acrylate monomer system is represented by the following formula (1), and the above-mentioned Si atom-containing polymerizable monomer system is represented by the following formula (2) said. In the formula, Rf, X, Y, and ^R2 to ^R5 have the same meanings as above.

In this aspect, the obtained fluoropolymer 1 is a copolymer having a structural part represented by the following formula (5). The terminal of the fluoropolymer 1 may be a group derived from a stopper, a group derived from an initiator, or a group derived from a monomer.

The composition for forming a fluorine-containing sealing material containing the above-mentioned fluoropolymer 1 contributes to the formation of a thicker fluorine-containing sealing material. A composition for forming a fluorine-containing sealing material containing a fluorine-containing polymer 1, which contributes to forming Good sealant. Further, the composition for forming a fluorine-containing sealing material containing the fluorine-containing polymer 1 can help to form a composition with good chemical resistance, for example, to salt water (for example, 5% salt water), acid or alkaline aqueous solution, acetone, oleic acid or hexane, and in particular, a sealant with good resistance to salt water.

In the above formula (5), X, Y, Rf and R ² to R ⁴ have the same meanings as above. R ⁵ ′ is a trivalent group derived from the group R ⁵ in formula (2), that is, a trivalent group derived from a group containing a polymerizable unsaturated bond.

In the above formula (5), the structural units marked with l and enclosed in brackets are structural units derived from (meth)acrylate monomers containing fluoroalkyl groups, and the structural units marked with m and enclosed in parentheses are derived from A constituent unit of a polymerizable monomer containing Si atoms. In addition, the presence order of each repeating unit enclosed in parentheses with l and m indicated is arbitrary in the formula.

In the above formula (5), l and m are each independently an integer of 1 or more. The total of l and m is preferably a numerical value such that the weight average molecular weight becomes 3,000 to 500,000.

In one aspect, in the above formula (5), l:m is preferably in the range of 99.9:0.5 to 50:50, more preferably in the range of 95:5 to 70:30, and more preferably in the range of 95:5 To 80:20 range, especially in the range of 95:5 to 85:15.

In one aspect, in the above formula (5), l:m may be in the range of 93:7 to 80:20, or in the range of 90:10 to 80:20.

In one aspect, the above-mentioned monomer components may contain high softening point monomers in addition to fluoroalkyl-containing acrylates and Si atom-containing polymerizable monomers. In this aspect, the fluoropolymer 1 It is a copolymer containing more constituent units based on high softening point monomers. The single system with high softening point has the same meaning as above.

The composition for forming a fluorine-containing seal material containing the fluorine-containing polymer obtained in this aspect contributes to the formation of a seal material having good water and moisture resistance and good hardness.

In a better form,

The (meth)acrylate monomer system of the above-mentioned fluorine-containing alkyl group is represented by the following formula (1);

The above-mentioned polymerizable monomer system containing Si atoms is shown in the following formula (2);

The (meth)acrylate represented by the above-mentioned high softening point monomer formula (4);

CH ₂ =C(R ¹¹ )COOR ¹² (4).

In the formula, Rf, X, Y, R ² to R ⁵ , R ¹¹ and R ¹² have the same meanings as above.

In this aspect, the obtained fluoropolymer 1 is a copolymer having a structural moiety represented by the following formula (5'). The composition for forming a fluorine-containing sealing material containing this copolymer contributes to the formation of a fluorine-containing sealing material with excellent abrasion resistance, good waterproof and/or moisture-proof performance, and further, excellent water repellency and good drainage. The terminal of the fluoropolymer 1 may be a group derived from a stopper, a group derived from an initiator, or a group derived from a monomer.

In the above formula (5'), X, Y, Rf, R ² to R ⁴ , R ¹¹ and R ¹ 2 have the same meanings as above. R ⁵ ′ is a trivalent group derived from the group R ⁵ in formula (2), that is, a trivalent group derived from a group containing a polymerizable unsaturated bond.

In the above formula (5), the structural units marked with l' and enclosed in parentheses are structural units derived from (meth)acrylate monomers containing fluoroalkyl groups, and the structural units marked with m' and enclosed in parentheses It is a structural unit derived from a polymerizable monomer containing Si atoms, and the structural unit marked n' and enclosed in brackets is a structural unit derived from a high softening point monomer. In addition, the presence order of each repeating unit enclosed in parentheses with l', m', and n' is arbitrary in the formula.

In the above formula (5'), l', m' and n' are each independently an integer of 1 or more. The total of l', m' and n' is preferably a value such that the weight average molecular weight becomes 3,000 to 500,000.

In one aspect, in the above formula (5'), the ratio of l', m', and n' is preferably l' in the range of 50 to 99.8, m' in the range of 0.1 to 49.5, and n' in the range of 0.1 to 49.9 range. The ratio of l', m', and n' is more preferably l' in the range of 65 to 99.8, m' in the range of 5 to 29.5, and n' in the range of 0.2 to 30.

The ratio of the above l', m' and n' is preferably that l' is in the range of 65 to 75, m' is in the range of 3 to 15, and n' is in the range of 20 to 30.

The above-mentioned monomer components may further contain other monomers as required. Other single systems have the same meaning as above.

It is preferable to contain 0.1 to 20 mass % of the above-mentioned other monomers with respect to 100 mass % of the whole fluorine-containing polymer 1.

The polymerization method of the above-mentioned fluoropolymer 1 is not particularly limited, for example, solution polymerization may be performed in a fluorine-based solvent. According to this method, the fluorine-containing polymer 1 formed has good solubility in fluorine-based solvents, and therefore, no precipitates are formed, and the polymerization reaction proceeds smoothly.

The fluorine-based solvent used in the above-mentioned solution polymerization (hereinafter, sometimes referred to as "the fluorine-based solvent for polymerization") is a solvent that has a fluorine atom in the molecule and has good solubility of the formed fluorine-containing polymer. Any of hydrocarbon compounds, alcohols, ethers, etc. may be used, and any of aliphatic and aromatic may be used. For example, chlorinated fluorinated hydrocarbons (in particular, carbon number 2 to 5), especially, HCFC225 (dichloropentafluoropropane), HCFC141b (dichlorofluoroethane), CFC316 (2,2,3,3 -tetrachlorohexafluorobutane), Vertrel XF (chemical formula C ₅ H ₂ F ₁₀ ) (manufactured by DuPont), hexafluoro-m-xylene, pentafluoropropanol, fluorine-based ethers, and the like.

It is preferable to use the same fluorine-based solvent as the fluorine-based solvent contained in the composition for forming a fluorine-containing sealing material of the present disclosure as the above-mentioned fluorine-based solvent for polymerization. When using hydrofluoroether as the fluorine-based solvent contained in the composition for forming a fluorine-containing sealing material of the present disclosure, it is preferable to also use hydrofluoroether as the fluorine-based solvent for polymerization. By using such a fluorine-based solvent, it is possible to efficiently obtain a fluorine-containing sealing material-forming composition while omitting the step of isolating the fluorine-containing polymer.

The above-mentioned fluorine-based solvents for polymerization may be used alone or in combination of two or more.

When polymerizing a monomer component in a fluorine-based solvent, for example, the monomer component is dissolved in a fluorine-based solvent, and the resulting solution is stirred while adding a polymerization initiator to perform a polymerization reaction.

The above-mentioned polymerization initiator can be used without particular limitation as long as it is a known polymerization initiator for polymerization reaction. As the polymerization initiator, for example, azo-based initiators such as azobisisobutyronitrile, methyl azoisobutyrate, and azodimethylvaleronitrile; benzoyl peroxide, potassium persulfate, Ammonium persulfate, diphenyl ketone derivatives, phosphine oxide derivatives, benzophenone derivatives, phenylene sulfide derivatives, amide derivatives, diazo derivatives, disulfide derivatives, etc. These polymerization initiators may be used individually, respectively, and may be used in combination of 2 or more types.

The amount of the polymerization initiator used is not particularly limited, but generally, it is preferably 0.01 to 10 parts by mass relative to 100 parts by mass of the fluoroalkyl-containing (meth)acrylate monomer used as a monomer component , more preferably try to be 0.1 to 1 part by mass.

Polymerization conditions such as polymerization temperature and polymerization time can be adjusted appropriately according to the type of monomer component, its usage amount, the type of polymerization initiator, its usage amount, etc. Usually, it can be carried out at a temperature of about 50 to 100°C. Polymerization reaction up to 10 hours.

The concentration of the monomer component in the fluorine-based solvent for polymerization is not particularly limited, but usually, it is preferably 10 to 50% by mass, more preferably 20 to 40% by mass.

Among the above monomer components, the amount of the Si atom-containing polymerizable monomer used is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the fluoroalkyl-containing (meth)acrylate monomer.

In one aspect, in the above-mentioned monomer components, the amount of the above-mentioned high softening point monomer is 0.1 to 49.9 parts by mass relative to 100 parts by mass of the fluoroalkyl-containing (meth)acrylate monomer, preferably It is set at 1 to 25 parts by mass.

Based on the total amount of monomer components used to obtain the fluoropolymer 1, the content of other monomers is preferably about 20 mass % or less, more preferably 10 mass % or less.

[Fluoropolymer 2]

The above-mentioned fluoropolymer 2 can be obtained by polymerizing a monomer component of a fluoroalkyl-containing (meth)acrylate monomer in the presence of a Si atom-containing thiol. That is, the fluorine-containing polymer 2 is made of a single (meth)acrylate monomer containing a fluorine-containing alkyl group in the presence of a thiol containing an Si atom. Fluoropolymers formed by polymerizing body components. The (meth)acrylate monomers containing fluoroalkyl groups and the thiols containing Si atoms have the same meanings as above.

The above-mentioned monomer components may contain high softening point monomers and other monomers in addition to the fluoroalkyl-containing (meth)acrylate monomers. High softening point monomers and other monomer systems have the same meanings as above.

The weight average molecular weight of the fluoropolymer 2 is preferably from 3,000 to 500,000, more preferably from 5,000 to 300,000, and still more preferably from 20,000 to 100,000. The weight average molecular weight of the fluoropolymer 2 can be obtained by GPC. For example, the above-mentioned weight average molecular weight can be obtained by GPC using a mixed solvent of HCFC225/hexafluoroisopropanol (=90/10 by weight) as an eluting solvent (standard polymethyl methacrylate conversion).

The fluorine-containing polymer 2 is composed of constituents derived from fluoroalkyl-containing (meth)acrylate monomers and constituents derived from Si-atom-containing mercaptans, preferably in a mass ratio of 100:0.01 to It is contained within the range of 100:25, more preferably contained within the range of 100:0.1 to 100:5.

The fluorine-containing polymer 2 can also combine components derived from fluoroalkyl-containing (meth)acrylate monomers and components derived from thiols containing Si atoms at a mass ratio of 100:0.01 to 100: It is included in the range of 1, and may be included in the range of 100:0.1 to 100:1.

In a preferred aspect, the fluoroalkyl-containing (meth)acrylate monomer represented by the above formula (1) is used as a monomer, and the Si atom-containing thiol represented by the above formula (3) is used . In this aspect, the fluoropolymer 2 is represented by the following general formula (6).

In the fluorine-containing polymer 2 shown in formula (6), the polymer chain of the polymer is linked with the structure derived from the thiol containing Si atom shown in formula (3), wherein the polymer has source A constituent unit derived from a (meth)acrylate monomer containing a fluoroalkyl group. The fluoropolymer 2 represented by the formula (6) may have a Si atom bonded to a hydroxyl group or a hydrolyzable group at at least one end.

In the above general formula (6), X, Y, Rf, and R ⁷ to R ¹⁰ have the same meanings as above. K is a value corresponding to the aforementioned weight average molecular weight, that is, the weight average molecular weight of the polymer of general formula (6) is preferably a value from 3,000 to 500,000, more preferably a value from 3,000 to 500,000, and more preferably Become a value from 20,000 to 100,000.

The composition for forming a fluorine-containing sealing material containing the above-mentioned fluoropolymer 2 contributes to the formation of a thicker fluorine-containing sealing material. The composition for forming a fluorine-containing sealing material containing the fluoropolymer 2 contributes to the formation of a sealing material having excellent abrasion resistance, good waterproof and/or moisture-proof performance, excellent water repellency and good drainage. Further, the composition for forming a fluorine-containing sealing material containing the fluorine-containing polymer 2 can help to form a composition having good chemical resistance, for example, to salt water, acid or alkaline aqueous solution, acetone, oleic acid or hexane, especially, Good sealing against salt water.

In one aspect, when producing the fluoropolymer 2, a fluoroalkyl-containing (meth)acrylate monomer can be used as a monomer component, and a high softening point monomer can be further used. Specific examples of the high softening point monomer are the same as above.

In this aspect, the fluoropolymer 2 contains a structural unit based on a high softening point monomer. More specifically, in addition to the structure represented by the above general formula (6), it further contains a structural unit based on a high softening point monomer.

In the fluoropolymer 2, the component derived from the high softening point monomer is preferably contained in an amount of 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass, with respect to 100 parts by mass of the entire fluoropolymer 2, and More preferably, it contains 1-20 mass parts.

In one aspect, when producing the fluoropolymer 2, a fluoroalkyl-containing (meth)acrylate monomer may be used as a monomer component, and other monomers may be further used. Specific examples of other monomers are the same as above.

In one aspect, when producing the fluorine-containing polymer 2, a polymerizable monomer containing an Si atom may be further used as a monomer component. The polymerizable monomer system containing Si atoms has the same meaning as above.

In this aspect, the fluoropolymer 2 further has a structural unit based on the Si atom-containing polymerizable monomer. By using a polymerizable monomer containing Si atoms, the composition for forming a fluorine-containing sealing material containing the fluorine-containing polymer 2 can help to further improve the adhesion to elastomers (for example, polysiloxane).

Fluoropolymer 2 can contain (meth)acrylate monomers containing fluoroalkyl groups as monomer components, and contain monomers selected from high softening point monomers, other monomers, and polymerizable monomers containing Si atoms. At least one of the formed groups.

In addition, as mentioned above, when X is a chlorine atom or a fluorine atom, the above-mentioned general formula (6) can be obtained by using low-cost raw materials, and can form a highly useful polymer with good waterproof gap filler.

In the production of fluoropolymer 2, the type and amount of polymerization initiator used are the same as those of fluoropolymer 1.

In the production of the fluoropolymer 2, the amount of the Si atom-containing mercaptan used is preferably 0.01 with respect to 100 parts by mass of the fluoroalkyl-containing (meth)acrylate monomer used as the monomer component. to 25 parts by mass, more preferably 0.1 to 5 parts by mass.

In the production of fluoropolymer 2, the amount of high softening point monomer used in the monomer component and the amount of polymerizable monomer containing Si atom used are the same as those described in fluoropolymer 1.

The polymerization of fluoropolymer 2 can be carried out under the same conditions as fluoropolymer 1.

(II) Carbon black

The composition for forming a fluorine-containing sealing material of the present disclosure contains carbon black. The composition of the present disclosure improves the chemical resistance of the formed fluorine-containing sealing material by containing carbon black.

The type of the above-mentioned carbon black is not particularly limited, for example, furnace black, acetylene black, ketjen black, etc. can be used without any particular limitation, and it is preferably furnace black or acetylene black.

The particle size of the above-mentioned carbon black is not particularly limited, for example, it may be 5 to 100 nm, preferably 10 to 80 nm, more preferably 20 to 50 nm.

The structure of the above-mentioned carbon black is not particularly limited, for example, it may be 10 to 10,000 nm, preferably 100 to 1,000 nm, more preferably 150 to 500 nm.

The DBP absorption of the carbon black is not particularly limited, for example, it may be 10 to 500 mL/100 g, preferably 50 to 300 mL/100 g, more preferably 100 to 200 mL/100 g.

The content of the above-mentioned carbon black may be, for example, 0.1 to 10% by mass, preferably 1 to 8% by mass, more preferably 3 to 5% by mass. By adding carbon black within the above range, the chemical resistance of the obtained fluorine-containing sealing material can be further improved.

(III) Solvent

The composition for forming a fluorine-containing sealing material of the present disclosure contains a solvent.

In a preferable aspect, the above-mentioned solvent is a fluorine-based solvent. By containing a fluorine-based solvent, the solubility of the above-mentioned fluorine-containing polymer is improved, and moreover, it becomes easy to obtain an optimum viscosity.

As the above-mentioned fluorine-based solvents, those having fluorine atoms in the molecule can be used, and the solvents having good solubility of the formed fluorine-containing polymer can be used, more preferably hydrocarbon compounds, alcohols or ethers having fluorine atoms in the molecular structure. The above-mentioned fluorine-based solvent may be either aliphatic or aromatic.

The above-mentioned fluorine-based solvent is preferably selected from the group consisting of hydrofluoroethers, hydrofluorocarbons, perfluorocarbons, and olefins in which at least one hydrogen atom is replaced by a fluorine atom, and at least one hydrogen atom is replaced by a chlorine atom. at least one of the group.

The fluorine-based solvent is preferably at least one selected from the group consisting of hydrofluoroethers, hydrofluorocarbons, and perfluorocarbons. The above-mentioned fluorine-based solvents include, for example: chlorinated fluorinated hydrocarbons (especially, carbon number 2 to 5), especially HCFC225 (dichloropentafluoropropane), HCFC141b (dichlorofluoroethane), CFC316 (2,2, 3,3-Tetrachlorohexafluorobutane), Vertrel XF (molecular formula C5H2F10) (manufactured by DuPont), hexafluoro-m-xylene, pentafluoropropanol; fluorinated ethers such as hydrofluoroether; perfluorocarbons, especially Fluorinert FC40 (manufactured by 3M company), Fluorinert FC43 (manufactured by 3M company), PFC-5060 (manufactured by SOLVAY company); hydrofluorocarbon, especially Solkan365mfc (manufactured by SOLVAY company).

In the present disclosure, it is particularly preferable to use hydrofluoroether as the fluorine-based solvent. Hydrofluoroether is a solvent with low chemical aggressiveness to various materials. It is an especially suitable solvent for the composition of fluorine-containing sealing materials for electronic parts that are strongly required to eliminate adverse effects caused by solvents. . Furthermore, hydrofluoroether is an ideal solvent with excellent properties such as quick-drying, low environmental pollution, non-flammability, and low toxicity.

In the present disclosure, as the hydrofluoroether, a compound represented by the following formula can be used.

Formula: C _y F _2y+1 -OC _z H _2z+1

[wherein, y is a number from 1 to 6, and z is a number from 1 to 6]

Such hydrofluoroethers can be used, for example: Novec HFE7100 (chemical formula C ₄ F ₉ OCH ₃ ), 7200 (chemical formula C ₄ F ₉ OC ₂ H ₅ ), 7300 (chemical formula C ₂ F ₅ CF(OCH ₃ ) C ₃ F ₇ ) etc.

In another aspect, as the fluorine-based solvent, an olefin in which at least one hydrogen atom is replaced by a fluorine atom and at least one hydrogen atom is replaced by a chlorine atom can be used. Such olefins are preferred from the viewpoint of preventing global warming.

The alkene having at least one hydrogen atom substituted by a fluorine atom and at least one hydrogen atom substituted by a chlorine atom is, for example, a compound having 2 to 5 carbon atoms, more specifically, a compound having 3 to 4 carbon atoms.

As the olefin in which at least one hydrogen atom is substituted by a fluorine atom and at least one hydrogen atom is substituted by a chlorine atom, hydrochlorofluoroolefins or chlorofluoroolefins developed in recent years as low-GWP solvents can be used. In the present specification, the chlorofluoroalkene means an alkene in which at least one of the substituents is substituted with a chlorine atom and the rest is substituted with a fluorine atom. Furthermore, among the hydrochlorofluoroolefin-based substituents, at least one is substituted by a hydrogen atom, at least one is substituted by a chlorine atom, and the rest are substituted by a fluorine atom.

The above-mentioned hydrochlorofluoroolefins include: 1-chloro-3,3,3-trifluoro-1-propene, 1-chloro-2,3,3-trifluoro-1-propene, etc.; the above-mentioned chlorofluoroolefins can be Examples: 1,2-dichloro-1,3,3,3-tetrafluoro-1-propene, 1,1,3-trichloro-2,3,3-trifluoro-1-propene, 1,1- Dichloro-2,3,3,3-tetrafluoro-1-propene, etc.

In a preferred aspect, the content of the fluorine-containing polymer in the composition for forming a fluorine-containing sealing material of the present disclosure is, for example, 7% by mass or more, preferably 10% by mass or more, relative to the entire composition, And, it is preferably at most 33% by mass, more preferably at most 30% by mass, and more preferably at most 25% by mass.

In a preferred aspect, the content of the fluorine-containing polymer in the composition for forming a fluorine-containing sealing material disclosed herein is preferably 7 to 33% by mass, more preferably 10 to 30% by mass, relative to the entire composition. % by mass, and more preferably 10 to 25% by mass.

The composition for forming a fluorine-containing sealing material of the present disclosure can effectively fill the voids of electronic parts, especially small voids (micro voids, for example, 0.1 to 1 mm in width and depth 0.1 to 3mm). The composition system for forming a fluorine-containing sealing material disclosed in the present disclosure is less prone to problems such as void clogging during filling, and can uniformly fill the aforementioned voids. The composition for forming a fluorine-containing sealing material of the present disclosure has the above-mentioned fluorine-containing polymer concentration, and Reduce the volume reduction caused by solvent volatilization, and easily form a fluorine-containing sealing material with a large film thickness. Therefore, by using the composition for forming a fluorine-containing sealing material of the present disclosure, the gap filling property becomes favorable.

The composition for forming the fluorine-containing sealing material disclosed herein contains fluorine-containing polymer 1 and/or fluorine-containing polymer 2, and these polymers all contain fluoroalkyl groups. Therefore, the fluorine-containing sealing material formed by using the above-mentioned composition Shows good water resistance. The composition system for forming a fluorine-containing sealing material of the present disclosure helps to form a sealing material having excellent wear resistance, good waterproof and/or moisture-proof performance, excellent water repellency and good drainage. Fluoropolymer 1 and Fluoropolymer 2 have good chemical resistance, for example, to salt water, acid or alkaline aqueous solution, acetone, oleic acid or hexane, especially to salt water, the fluorine-containing The composition system for forming a sealing material contributes to the formation of a fluorine-containing sealing material having good chemical resistance. Members such as electrodes or resin materials may be formed in advance in the above-mentioned gaps. In this case, by using the composition for forming a fluorine-containing sealing material of the present disclosure, the members such as electrodes or resin materials can be protected from water and the like.

Furthermore, the composition for forming a fluorine-containing sealing material of the present disclosure can obtain a sealing material having high chemical resistance by containing carbon black.

Furthermore, due to the hydroxyl groups or hydrolyzable groups contained in the above-mentioned fluoropolymer 1 and fluoropolymer 2, the adhesiveness of the sealing material formed from the fluorine-containing sealing material-forming composition of the present disclosure to the object to be treated becomes good. The object to be treated can include, for example: the wall surface of the void of electronic parts, or the member that pre-filled the void (such as glass; metal or metal oxide (such as metal wiring); elastomers such as polysiloxane; polyethylene or epoxy Resin materials such as resins), or display peripheral materials (optical adhesives, OCA, polarizing plates, etc.).

In one aspect, the composition system for forming a fluorine-containing sealing material contains the fluorine-containing polymer 1 as the fluorine-containing polymer. Fluoropolymer 1 shows good adhesion to various treatment objects (various treatment objects have the same meaning as above) through the hydroxyl group or hydrolyzable group bonded to the Si atom existing in the side chain. , and, those with cross-linking properties. Therefore, using the fluorine-containing The fluorine-containing sealing material formed from the sealing material forming composition has good adhesion, abrasion resistance, and waterproof and/or moisture-proof performance to the above-mentioned object to be treated.

In one aspect, the composition system for forming a fluorine-containing sealing material contains the fluorine-containing polymer 2 as the fluorine-containing polymer. The fluorine-containing polymer 2 is bonded to the polymer chain by at least a part of the Si atom-containing thiol present in the polymerization reaction, and the hydroxyl group or hydrolyzable group bonded to the Si atom present at its terminal, and It exhibits good adhesion to various processing objects (various processing objects have the same meaning as above), and has cross-linking properties. Accordingly, the fluorine-containing seal material formed using the composition for forming a fluorine-containing seal material of this aspect has excellent adhesion and wear resistance to the above-mentioned object to be treated, and further, has waterproof and/or moisture-proof performance. Also become good.

In another aspect, a monomer component containing a monomer having a high softening point is further used to form the fluoropolymer 1 or the fluoropolymer 2 . In this aspect, the water repellency of the formed fluorine-containing sealing material is also improved with respect to any one of the fluorine-containing polymer 1 and the fluorine-containing polymer 2, and drainage becomes favorable.

The viscosity of the composition for forming the fluorine-containing sealing material disclosed herein is preferably in the range of 10 to 1000 mPa. s range, more preferably in the range of 10 to 100mPa. The range of s is more preferably in the range of 10 to 60mPa. The range of s is especially good at 10 to 50mPa. range of s. The above viscosity is a B-type viscometer, and the viscosity at 25°C can be measured according to JIS K7117-1:1999. The composition for forming a fluorine-containing sealing material disclosed in the present disclosure has the above-mentioned viscosity, which makes it difficult to cause clogging of the gaps during filling, and can also fill the gaps between electronic parts, especially small gaps with narrow widths. Fill evenly. The composition for forming a fluorine-containing sealing material of the present disclosure has the above-mentioned viscosity, so that bubbles are not easily generated when filling the void, or, even if bubbles are generated, the generated bubbles will naturally (without special manipulation) land) wiped out. Furthermore, the composition for forming a fluorine-containing sealing material of the present disclosure having the above-mentioned viscosity can form a sealing material having a sufficient film thickness after curing.

In a particularly preferred aspect, the composition for forming a fluorine-containing sealing material is a (meth)acrylic ester monomer containing a fluorine-containing alkyl group represented by formula (1) substituted with a fluorine-containing alkyl group (methyl ) acrylate monomer [in formula (1), Rf is a linear or bifurcated fluoroalkyl group with 4 to 6 carbon atoms; X is a group or atom other than a hydrogen atom, preferably a fluorine atom, a chlorine atom, Or methyl], from fluorine-based solvents to hydrofluoroether. Rf is a fluorine-containing polymer formed by acrylates of fluorine-containing alkyl substituted at the alpha position of a fluoroalkyl group with 4 to 6 carbons. It has good solubility in hydrofluoroether, and the formed fluorine-containing sealing material is waterproof. Good performance and moisture resistance, and good abrasion resistance.

In the above aspect, Y is preferably a single bond, an aliphatic group with 1 to 10 carbons (for example, an alkylene group), or a -CH ₂ CH(OH)CH ₂ - group, and more preferably a carbon number 1 An aliphatic group (eg, alkylene) to 4, or a -CH ₂ CH(OY ¹ )CH ₂ - group. In the formula, ^Y1 is a hydrogen atom or an acetyl group.

In the composition for forming a fluorine-containing sealing material of the present disclosure, by using a fluorine-based solvent, the above-mentioned fluorine-containing polymer can be stably dissolved, and a composition for forming a fluorine-containing sealing material that is not prone to precipitation and good stability can be obtained. things.

The composition for forming a fluorine-containing sealing material disclosed in this disclosure is polymerized in a fluorine-based solvent for polymerization, and the concentration of the polymer is adjusted as required, and can be directly used as a composition for forming a fluorine-containing sealing material, or polymerized After the reaction, the fluorine-containing polymer is separated to form a fluorine-containing sealing material-forming composition containing the separated fluorine-containing polymer and a fluorine-based solvent.

Preferably, after the polymerization reaction is performed using hydrofluoroether as the fluorine-based solvent for polymerization, the composition for forming a fluorine-containing sealing material is produced by using hydrofluoroether and adjusting the polymer concentration as required. By using such a method, the target composition for forming a fluorine-containing sealing material can be efficiently obtained.

The composition for forming a fluorine-containing sealing material of the present disclosure may contain other components in addition to the fluorine-containing polymer and the fluorine-based solvent. Other ingredients include: catalyst (metal-based catalysts such as tin or titanium, or organic catalysts such as acid-base), stabilizing materials (dehydrating agent, molecular sieve, magnesium sulfate or promethazine) acid methyl ester), viscosity modifier, filler (silicon oxide, mica, clay and other inorganic materials), colorant or fluorescent agent, etc.

The composition system for forming the fluorine-containing sealing material disclosed in the present disclosure is not particularly limited. For example, it can be used in electronic components such as displays or printed substrates, and can be applied to materials contained in these components, such as elastomers, plastics, metal, ceramic, etc. Examples of electronic devices containing the above-mentioned electronic components include personal computers, tablet computers, smart phones, digital cameras, and car navigation systems.

According to the composition for forming a fluorine-containing sealing material of the present disclosure, it is possible to form a fluorine-containing sealing material that is excellent in abrasion resistance and has waterproof and moisture-proof properties. When hydrofluoroether is used as a solvent, it can form a fluorine-containing sealing material that does not cause chemical attack, does not cause adverse effects on the environment, and has good waterproof and moisture-proof properties. Furthermore, by using the composition for forming a fluorine-containing sealing material of the present disclosure, a fluorine-containing sealing material having good chemical resistance and a relatively large film thickness can be formed. Furthermore, by using the composition for forming a fluorine-containing sealing material of the present disclosure, no additional adhesive layer is required, and it can be bonded to the wall surface of a member or a cavity, thereby simplifying the steps of forming a fluorine-containing sealing material.

Hereinafter, a treatment method using the composition for forming a fluorine-containing sealing material of the present disclosure will be described.

The above-mentioned processing method is not particularly limited, for example, it can be filled with the composition for forming the fluorine-containing sealing material of the present disclosure in the gap of electronic parts (for example, the laminated part of the housing and the printed circuit board, or the metal terminal formed by resin The gap between the part and the molding resin, etc.), after filling, let it dry.

Thereby, the hydroxyl groups or hydrolyzable groups bonded to the Si atoms of the polymer terminals or side chains of the fluorine-containing polymer introduced into the fluorine-containing sealing material-forming composition of the present disclosure are absorbed by the air in the atmosphere. Moisture is hydrolyzed and converted into silanol groups, and it can be combined with the wall surface of the void of electronic parts, or the components that are pre-filled in this void (such as glass, metal wiring, or elastomers such as polysiloxane, polyethylene, etc.) Resin material such as ethylene or epoxy resin) reacts with the object to be treated, thereby improving the adhesion. The silanol groups that have not reacted with the walls of the voids or the above-mentioned members condense with each other and undergo two-dimensional or three-dimensional crosslinking to form a strong film.

The temperature at the time of treatment is not particularly limited, and it is usually sufficient to treat at room temperature. The treatment time is not particularly limited, and may be, for example, 5 minutes to 1 hour.

In addition, in order to form a fluorine-containing sealing material with high wear resistance, it is preferable to treat the object to be treated with acetone in order to remove oil from the wall surface of the cavity before treating it with the composition for forming a fluorine-containing sealing material of the present disclosure. , hydrofluoroether, etc., and then dried. Furthermore, in addition to the above-mentioned cleaning, by performing pretreatment with UV ozone, oxygen plasma, etc., the abrasion resistance of the fluorine-containing sealing material can be further improved.

Furthermore, before treating with the composition for forming a fluorine-containing sealing material of the present disclosure, as required, a primer treatment (Primer treatment) is applied to the wall surface of the void, etc., so that the composition for forming a fluorine-containing sealing material can be improved. The adhesion of the fluorine-containing sealing material formed by the compound improves the wear resistance. The primer treatment may be performed under the same conditions as the primer treatment when a silane coupling agent is used according to a normal method.

[Example]

Hereinafter, the present disclosure will be described in more detail by means of examples, however, the present disclosure is not limited by these examples.

The abbreviations of the compounds used in Examples and Comparative Examples are as follows.

‧Rf(C6)MA: (perfluorohexyl) ethyl methacrylate (CH ₂ =C(CH ₃ )COOCH ₂ CH ₂ C ₆ F ₁₃ )

‧TMSMA: 3-(trimethoxysilyl)propyl methacrylate

‧MMA: methyl methacrylate

‧IBMA: Isocamphoryl Methacrylate

‧MPS: Mercaptopropyltrimethoxysilane

<Synthesis Example 1>

50 g of Rf(C6)MA, 5 g of TMSMA, and 110 g of perfluorobutyl ethyl ether (HFE7200) were fed into a four-necked flask equipped with a reflux tube. This flask was heated to 80° C. while purging with nitrogen. Thereafter, 0.55 g of azoisobutyronitrile was charged and reacted for 6 hours. After completion of the polymerization, the inside of the system was cooled to room temperature, and the concentration of HFE7200 was adjusted so that the solid content was 5%, to obtain a dilution 1.

<Synthesis Example 2>

Except having used 50 g of Rf(C6)MA, 17.5 g of MMA, and 135 g of HFE7200, it carried out similarly to the said synthesis example 1, and obtained the dilution 2.

<Synthesis Example 3>

Except having used 50 g of Rf(C6)MA, 10 g of IBMA, 0.15 g of MPS, and 120 g of HFE7200, it carried out similarly to the said synthesis example 1, and obtained the dilution 3.

<Carbon black addition>

Acetylene black using acetylene as a raw material and Farnest black (both commercially available) using petroleum-based oil as a raw material were prepared as carbon black. Add acetylene black to each of the dilutions 1 to 3 obtained above at the ratio shown in the table below, and irradiate with ultrasonic waves at room temperature for 2 hours to obtain a coating solution in which carbon black is dispersed.

<assessment>

(chemical resistance test)

‧Appearance test

A coating film was formed on a glass slide so as to form a film thickness of 10 μm, immersed in an oleic acid solution at 65°C/1 week with the film thickness, and the appearance was observed (visually). The criteria for judging the appearance are as follows.

A: There is no change corresponding to swelling, cracking, and peeling of the coating film

B: Swelling was observed only at a portion such as the edge of the coating film, and there was no major change corresponding to cracking or peeling.

C: Swelling was observed in the entire coating film, and traces of cracking or peeling were observed in a part.

‧Swelling test (weight change rate)

The coating was repeatedly applied on a glass slide so that the film thickness would be 50 to 70 μm to form a coating film. After calculating the weight of the coated film, the slide glass was immersed in oleic acid at 60° C. for 24 hours. Thereafter, the oleic acid on the surface of the coating film was removed, the weight was measured, and the weight change rate of the coating film was calculated.

[Table 1]

[Industrial availability]

The present disclosure is applicable to the formation of a fluorine-containing sealing material for filling the gap between electronic components such as a display or a printed circuit board (for example, a gap on an end surface of a display) in an electronic device or the like.

Claims (14)

A composition for forming a fluorine-containing sealing material, which contains: (1) a fluorine-containing polymer, which is a structural unit derived from a (meth)acrylate monomer derived from a fluorine-containing alkyl group represented by the following formula (1) And it is one or both of the fluoropolymers shown in the following (A) and (B); and (II) carbon black,

In the formula, Rf is a fluoroalkyl group; X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² base (in the formula, X ¹ and X ² are identically or differently hydrogen atoms, fluorine atom or chlorine atom), cyano, linear or branched fluoroalkyl with 1 to 21 carbons, substituted or unsubstituted benzyl, substituted or unsubstituted phenyl, or 1 to 20 carbons Straight-chain or branched alkyl; Y is a single bond, or a divalent organic group; (A) contains polymerizable monomers derived from (meth)acrylate monomers containing the aforementioned fluorine-containing alkyl groups and Si atoms. (B) a fluorine-containing polymer that is a constituent of the monomer component of the body; (B) a constituent derived from the monomer component of the (meth)acrylate monomer containing the aforementioned fluoroalkyl group, and a constituent derived from the Si atom-containing A fluorine-containing polymer as a constituent of a thiol, wherein at least one Si atom contained in the aforementioned Si atom-containing polymerizable monomer and the aforementioned Si atom-containing thiol each independently has a hydroxyl group or a hydrolyzable group , The content of the carbon black is 0.1 to 10% by mass relative to the fluoropolymer and the carbon black in the composition for forming a fluorine-containing sealing material. The composition for forming a fluorine-containing sealing material according to claim 1, wherein, in formula (1), Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms. The composition for forming a fluorine-containing sealing material according to Claim 1 or 2, wherein, in formula (1), Y is a single bond, an aliphatic group having 1 to 10 carbon atoms that may have an oxygen atom or a sulfur atom, Aromatic group with 6 to 10 carbon atoms which may have an oxygen atom, cycloaliphatic group with 6 to 10 carbon atoms which may have an oxygen atom, araliphatic group with 6 to 10 carbon atoms which may have an oxygen atom, -CH ₂ CH ₂ N(R ¹ )SO ₂ -group (wherein, R ¹ is an alkyl group with 1 to 4 carbons), -CH ₂ CH(OY ¹ )CH ₂ -group (wherein, Y ¹ is a hydrogen atom or acetyl), or -(CH ₂ ) _n SO ₂ - (where n is an integer from 1 to 10). The composition for forming a fluorine-containing sealing material according to Claim 1 or 2, wherein, in formula (1), Rf is a linear or branched fluoroalkyl group having 4 to 6 carbon atoms, and X is hydrogen other atoms or groups. The composition for forming a fluorine-containing sealing material according to claim 1 or 2, wherein the carbon black is furnace black, acetylene black, or Ketjen black. The composition for forming a fluorine-containing sealing material according to claim 1 or 2, wherein, in the fluorine-containing polymer represented by (A), the polymerizable monomer containing Si atoms is represented by the following formula (2) compound of

In the formula, R ² , R ³ and R ⁴ are identically or differently hydroxyl groups, hydrolyzable groups or monovalent organic groups, but at least one of R ² , R ³ and R ⁴ is hydroxyl groups or hydrolyzable groups; R ⁵ is a group containing a polymerizable unsaturated bond. The composition for forming a fluorine-containing sealing material according to claim 1 or 2, wherein the fluorine-containing polymer represented by the aforementioned (A) has a structural moiety represented by the following formula (5),

In the formula, X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a GFX ¹ X ² group (in the formula, X ¹ and X ² are identically or differently hydrogen atoms, fluorine atoms or chlorine atoms), Cyano, linear or branched fluoroalkyl with 1 to 21 carbons, substituted or unsubstituted benzyl, substituted or unsubstituted phenyl, or linear or branched with 1 to 20 carbons An alkyl group; Y is a single bond, an aliphatic group with 1 to 10 carbon atoms that may have an oxygen atom or a sulfur atom, an aromatic group with 6 to 10 carbon atoms that may have an oxygen atom, or an aromatic group with 6 carbon atoms that may have an oxygen atom A cycloaliphatic group with 10 to 10 carbon atoms, an araliphatic group with 6 to 10 carbon atoms which may have an oxygen atom, -CH ₂ CH ₂ N(R ¹ )SO ₂ -group (wherein, R ¹ is a carbon number from 1 to 4 alkyl), -CH ₂ CH(OY ¹ )CH ₂ -group (wherein, Y ¹ is a hydrogen atom or acetyl group), or -(CH ₂ ) _n SO ₂ -group (wherein, n is an integer of 1 to 10); Rf is a linear or branched fluoroalkyl group with 1 to 20 carbons; R ² , R ³ and R ⁴ are the same or different alkyl groups with 1 to 4 carbons or An alkoxy group with 1 to 4 carbons, except that at least one of R ² , R ³ and R ⁴ is an alkoxy group; R ^5' is a trivalent group derived from a group containing a polymerizable unsaturated bond; l and m Each is an integer of 1 or more, and the sum of 1 and m is such that the weight-average molecular weight of the fluoropolymer is 3,000 to 500,000. In addition, the order of existence of each repeating unit marked with 1 and m and enclosed in brackets is arbitrary in the formula. The composition for forming a fluorine-containing sealing material according to claim 1 or 2, wherein, in the fluorine-containing polymer represented by (B), the monomer component further contains a polymerizable monomer containing an Si atom. The composition for forming a fluorine-containing sealing material according to claim 1 or 2, wherein, in the fluorine-containing polymer represented by the aforementioned (B), the thiol containing an Si atom is represented by the following formula (3): compound,

In the formula, R ⁷ , R ⁸ and R ⁹ are identically or differently hydroxyl groups, hydrolyzable groups or monovalent organic groups, but at least one of R ⁷ , R ⁸ and R ⁹ is hydroxyl groups or hydrolyzable groups; R ¹⁰ is a linear alkylene group having 1 to 12 carbons. The composition for forming a fluorine-containing sealing material according to claim 1 or 2, wherein the fluorine-containing polymer represented by the aforementioned (B) is a compound represented by the following formula (6),

In the formula, X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (in the formula, X ¹ and X ² are identically or differently hydrogen atoms, fluorine atoms or chlorine atoms), Cyano, linear or branched fluoroalkyl with 1 to 21 carbons, substituted or unsubstituted benzyl, substituted or unsubstituted phenyl, or linear or branched with 1 to 20 carbons An alkyl group; Y is a single bond, an aliphatic group with 1 to 10 carbon atoms that may have an oxygen atom or a sulfur atom, an aromatic group with 6 to 10 carbon atoms that may have an oxygen atom, or an aromatic group with 6 carbon atoms that may have an oxygen atom A cycloaliphatic group with 10 to 10 carbon atoms, an araliphatic group with 6 to 10 carbon atoms which may have an oxygen atom, -CH ₂ CH ₂ N(R ¹ )SO ₂ -group (wherein, R ¹ is a carbon number from 1 to 4 alkyl), -CH ₂ CH(OY ¹ )CH ₂ -group (wherein, Y ¹ is a hydrogen atom or acetyl group), or -(CH ₂ ) _n SO ₂ -group (wherein, n is an integer of 1 to 10); Rf is a linear or branched fluoroalkyl group with 1 to 20 carbons; R ⁷ , R ⁸ and R ⁹ are the same or different alkyl groups with 1 to 4 carbons or An alkoxy group with 1 to 4 carbons, at least one of R ⁷ , R ⁸ and R ⁹ is an alkoxy group; R ¹⁰ is a linear alkylene group with 1 to 12 carbons; K is a fluorine-containing polymer The weight average molecular weight of the material becomes a value of 3,000 to 500,000. The composition for forming a fluorine-containing sealing material according to claim 1 or 2 further contains (III) a fluorine-based solvent. The composition for forming a fluorine-containing sealing material according to claim 11, wherein the fluorine-based solvent is at least one member selected from the group consisting of hydrofluoroethers, hydrofluorocarbons, and perfluorocarbons. An electronic component comprising a sealing material formed using the composition for forming a fluorine-containing sealing material according to any one of claims 1 to 12. An electronic machine comprising the electronic component as claimed in claim 13.