WO2021002186A1 - Composition for forming fluorine-containing sealing material - Google Patents

Abstract

The present invention provides a composition for forming a fluorine-containing sealing material, said composition containing: (I) a fluorine-containing polymer which contains a constituent unit derived from a fluoroalkyl group-containing (meth)acrylic acid ester monomer represented by formula (1), and which is composed of one or both of the fluorine-containing polymers (A) and (B) described below; and (II) carbon black. (A) a fluorine-containing polymer which contains a constituent derived from a monomer component containing the above-described fluoroalkyl group-containing (meth)acrylic acid ester monomer and an Si atom-containing polymerizable monomer (B) a fluorine-containing polymer which contains a constituent derived from a monomer component containing the above-described fluoroalkyl group-containing (meth)acrylic acid ester monomer and a constituent derived from an Si atom-containing mercaptan (In the formulae, the symbols are as defined in the description.)

Description

Composition for forming fluorine-containing sealant

The present disclosure relates to a composition for forming a fluorine-containing sealant.

A sealing material is provided in the gaps (gap, for example, minute gaps) between electronic members in electronic devices such as displays and printed circuit boards to fill the gaps. This sealing material is required to have waterproofness or the like for protecting members contained in electronic devices.

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

JP-A-2018-172677

The sealant as described above is required to have chemical resistance (for example, resistance to fatty acids and the like). Therefore, an object of the present disclosure is to provide a sealing material having high chemical resistance.

The present disclosure includes the following aspects.
[1] Equation (I) (1):

[During the ceremony:
Rf is a fluoroalkyl group;
X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and CFX ¹ X ² groups (in the formula, X ¹ and X ² are the same or different, hydrogen atom, fluorine atom or chlorine atom. ), Cyan group, linear or branched fluoroalkyl group having 1 to 21 carbon atoms, substituted or unsubstituted benzyl group, substituted or unsubstituted phenyl group, linear or linear or branched group having 1 to 20 carbon atoms. It is a branched alkyl group;
Y is a single bond or divalent organic group. ]
A fluoropolymer containing a structural unit derived from a fluoroalkyl group-containing (meth) acrylic acid ester monomer represented by (A) and one or both of the fluoropolymers shown in (A) and (B) below:
(A) A fluoropolymer containing a constituent component derived from a monomer component containing the fluoroalkyl group-containing (meth) acrylic acid ester monomer and a Si atom-containing polymerizable monomer.
(B) A fluorine-containing polymer containing a component derived from a monomer component containing the fluoroalkyl group-containing (meth) acrylic acid ester monomer and a component derived from a Si atom-containing mercaptan (here, the Si atom). The containing polymerizable monomer and at least one Si atom contained in the Si atom-containing mercaptan each independently have a hydroxyl group or a hydrolyzable group), and
(II) A composition for forming a fluorine-containing sealing material containing carbon black.
[2] The composition for forming a fluorine-containing sealant according to the above [1], wherein Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms in the formula (1).
[3] In the formula (1), Y has a single bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom or a sulfur atom, and 6 to 6 carbon atoms which may have an oxygen atom. 10 aromatic groups, cyclic aliphatic groups having 6 to 10 carbon atoms which may have oxygen atoms, aromatic aliphatic groups having 6 to 10 carbon atoms which may have oxygen atoms, -CH ₂ CH ₂ N (R ¹ ) SO ₂ -group (in the formula, R ¹ is an alkyl group having 1 to 4 carbon atoms), -CH ₂ CH (OY ¹ ) CH ₂ -group (in the formula, Y ¹ is , A hydrogen atom or an acetyl group), or-(CH ₂ ) _n SO ₂ -group (in the formula, n is 1 to 10), the fluorine-containing sealing according to the above [1] or [2]. Composition for material formation.
[4] In the formula (1), Rf is a linear or branched fluoroalkyl group having 4 to 6 carbon atoms, and X is an atom or group other than hydrogen, as described above [1] to [3]. The composition for forming a fluorine-containing sealant according to any one of.
[5] The composition for forming a fluorine-containing sealant according to any one of the above [1] to [4], wherein the carbon black is furnace black, acetylene black, or kechen black.
[6] The content of the carbon black is 0.1 to 10% by mass with respect to the solid content in the composition for forming a fluorine-containing sealing material, according to any one of the above [1] to [5]. Composition for forming a fluorine-containing sealant.
[7] In the fluoropolymer shown in (A) above, the Si atom-containing polymerizable monomer is represented by the formula (2):

[During the ceremony:
R ^{2, R 3} and ^{R 4} are the same or different, a hydroxyl group, a hydrolyzable group or an alkyl group having 1 to 4 carbon atoms, provided ^that at least one hydroxyl group of R 2, ^{R 3} and ^{R 4} Or a hydrolyzable group;
R ⁵ is a group containing a polymerizable unsaturated bond. ]
The composition for forming a fluorine-containing sealing material according to any one of the above [1] to [6], which is a compound represented by.
[8] The fluoropolymer represented by the above (A) has the following formula (5):

[During the ceremony:
X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and CFX ¹ X ² groups (in the formula, X ¹ and X ² are the same or different, hydrogen atom, fluorine atom or chlorine atom. ), Cyan group, linear or branched fluoroalkyl group having 1 to 21 carbon atoms, substituted or unsubstituted benzyl group, substituted or unsubstituted phenyl group, linear or linear or branched group having 1 to 20 carbon atoms. It is a branched alkyl group;
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, and an oxygen atom. Cyclic aliphatic groups having 6 to 10 carbon atoms which may have, aromatic aliphatic groups having 6 to 10 carbon atoms which may have oxygen atoms, -CH ₂ CH ₂ N (R ¹ ) SO _2- Group (in the formula, R ¹ is an alkyl group having 1 to 4 carbon atoms), -CH ₂ CH (OY ¹ ) CH ₂ -group (in the formula, Y ¹ is a hydrogen atom or an acetyl group. ), Or-(CH ₂ ) _n SO ₂ -group (in the formula, n is 1-10);
Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms;
R ^{2, R 3} and ^{R 4} are the same or different, an alkyl group or an alkoxy group having 1 to 4 carbon atoms having 1 to 4 carbon atoms, provided ^that at least one of R 2, ^{R 3} and ^{R 4} Alkoxy group;
R 5 ^'is an trivalent group derived from a group containing a polymerizable unsaturated bond;
l and m are integers of 1 or more, respectively, and the total of l and m is a numerical value in which the weight average molecular weight of the fluoropolymer has a weight average molecular weight of 3,000 to 500,000, and l and m are added. The order of existence of each repeating unit enclosed in parentheses is arbitrary in the formula. ]
The composition for forming a fluorine-containing sealing material according to any one of the above [1] to [7], which has a structural portion represented by.
[9] The fluoropolymer according to any one of [1] to [8] above, wherein the monomer component further contains a Si atom-containing polymerizable monomer in the fluoropolymer shown in (B). Composition.
[10] In the fluoropolymer shown in (B) above, the Si atom-containing mercaptan is represented by the formula (3):

[During the ceremony:
R ⁷ , R ⁸ and R ⁹ are the same or different hydroxyl groups, hydrolyzable groups or alkyl groups having 1 to 4 carbon atoms, except that at least one of R ⁷ , R ⁸ and R ⁹ is a hydroxyl group. Or a hydrolyzable group;
R ¹⁰ is a linear alkylene group having 1 to 12 carbon atoms. ]
The composition for forming a fluorine-containing sealing material according to any one of the above [1] to [9], which is a compound represented by.
[11] The fluoropolymer represented by the above (B) has the following formula (6):

[During the ceremony:
X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and CFX ¹ X ² groups (in the formula, X ¹ and X ² are the same or different, hydrogen atom, fluorine atom or chlorine atom. ), Cyan group, linear or branched fluoroalkyl group having 1 to 21 carbon atoms, substituted or unsubstituted benzyl group, substituted or unsubstituted phenyl group, linear or linear or branched group having 1 to 20 carbon atoms. It is a branched alkyl group;
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, and an oxygen atom. Cyclic aliphatic groups having 6 to 10 carbon atoms which may have, aromatic aliphatic groups having 6 to 10 carbon atoms which may have oxygen atoms, -CH ₂ CH ₂ N (R ¹ ) SO _2- Group (in the formula, R ¹ is an alkyl group having 1 to 4 carbon atoms), -CH ₂ CH (OY ¹ ) CH ₂ -group (in the formula, Y ¹ is a hydrogen atom or an acetyl group), Or-(CH ₂ ) _n SO ₂ -group (in the formula, n is 1-10);
Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms;
R ⁷ , R ⁸ and R ⁹ are identical or different alkyl groups having 1 to 4 carbon atoms or alkoxy groups having 1 to 4 carbon atoms, and at least one of R ⁷ , R ⁸ and R ⁹ is an alkoxy group. Is;
R ¹⁰ is a linear alkylene group having 1 to 12 carbon atoms;
k is a numerical value in which the weight average molecular weight of the fluoropolymer has a weight average molecular weight of 3,000 to 500,000. ]
The composition for forming a fluorine-containing sealing material according to any one of the above [1] to [10], which is a compound represented by.
[12] (III) The composition for forming a fluorine-containing sealing material according to any one of the above [1] to [11], which further contains a fluorine-based solvent.
[13] The composition for forming a fluorine-containing sealant according to the above [12], wherein the fluorine-based solvent is at least one selected from the group consisting of hydrofluoroethers, hydrofluorocarbons and perfluorocarbons.
[14] An article containing a sealing material formed by using the composition for forming a fluorine-containing sealing material according to any one of the above [1] to [13].
[15] The article according to the above [14], wherein the article is an electronic member.
[16] The article according to the above [15], which is an electronic device including an electronic member.

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

As used herein, "divalent organic group" means a carbon-containing divalent group. The divalent organic group is not particularly limited, and examples thereof include a divalent group in which one hydrogen atom is eliminated from the hydrocarbon group.

As used in the present specification, the above-mentioned "hydrocarbon group" means a group containing carbon and hydrogen. The hydrocarbon group is not particularly limited, but may be substituted with one or more substituents, such as a hydrocarbon group having 1 to 20 carbon atoms, for example, an aliphatic hydrocarbon group. Examples include aromatic hydrocarbon groups. The "aliphatic hydrocarbon group" may be linear, branched or cyclic, and may be saturated or unsaturated. In addition, the hydrocarbon group may contain one or more ring structures. In addition, such a hydrocarbon group may have one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy and the like in its terminal or molecular chain.

The substituent of the above "hydrocarbon group" is not particularly limited, but is, for example, a halogen atom; a C _1-6 alkyl group, C which may be substituted with one or more halogen atoms. _2-6 alkenyl group, C _2-6 alkynyl group, C _3-10 cycloalkyl group, C _3-10 unsaturated cycloalkyl group, 5-10 member heterocyclyl group, 5-10 member unsaturated heterocyclyl group, C _Examples thereof include a _6-10 aryl group and a 5 to 10 member heteroaryl group.

As used herein, alkyl and phenyl groups may be unsubstituted or substituted unless otherwise specified. The substituent of such a group is not particularly limited, and for example, 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 can be used. Can be mentioned.

As used herein, the term "hydrolyzable group" means a group capable of undergoing a hydrolysis reaction, that is, a group capable of being eliminated from the main skeleton of a compound by a hydrolysis reaction. Examples of hydrolyzable groups are -OR, -OCOR, -ON = CR ₂ , -NR ₂ , -NHR, halogen (in these formulas, R is substituted or unsubstituted carbon number 1 to 4). (Indicating an alkyl group of) and the like, preferably −OR (that is, an alkoxy group). Examples of R include an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and an isobutyl group; and a substituted alkyl group such as a chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. In the present specification, the “hydroxyl group” described together with the “hydrolyzable group” is not particularly limited, but may be generated by hydrolyzing a hydrolyzable group.

[Composition for Forming Fluorine-Containing Sealant]
The composition for forming a fluorine-containing sealing material of the present disclosure is, for example, a composition for forming a fluorine-containing sealing material suitable for filling voids (gap) of an electronic member or an electronic device including an electronic member. In the following, it may be described that the gap fill property is good when it is suitable for filling the voids as described above.

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

[Fluororesin]
The fluorine-containing polymer contained in the composition for forming a fluorine-containing sealant of the present disclosure has the following formula (1):

[During the ceremony:
Rf is a fluoroalkyl group;
X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and CFX ¹ X ² groups (in the formula, X ¹ and X ² are the same or different, hydrogen atom, fluorine atom or chlorine atom. ), Cyan group, linear or branched fluoroalkyl group having 1 to 21 carbon atoms, substituted or unsubstituted benzyl group, substituted or unsubstituted phenyl group, linear or linear or branched group having 1 to 20 carbon atoms. It is a branched alkyl group;
Y is a single bond or divalent organic group. ]
It is a fluoropolymer containing a structural unit derived from a fluoroalkyl group-containing (meth) acrylic acid ester monomer represented by, and is a fluoropolymer shown in (A) and / or (B) below.

(A) Fluoroalkyl-containing polymer (B) Fluoroalkyl group-containing (meth) acrylic containing a component derived from a monomer component containing the fluoroalkyl group-containing (meth) acrylic acid ester monomer and the Si atom-containing polymerizable monomer. A fluorine-containing polymer containing a component derived from a monomer component containing an acid ester monomer and a component derived from a Si atom-containing mercaptan (here, contained in the Si atom-containing polymerizable monomer and the Si atom-containing mercaptan). At least one Si atom to be formed has an independent hydroxyl group or a hydrolyzable group).

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

[Fluoroalkyl group-containing (meth) acrylic acid ester monomer]
The fluoroalkyl group-containing (meth) acrylic acid ester monomer is an ester bond of a fluoroalkyl group directly or via a divalent organic group to an acrylic acid which may have a substituent at the α-position. Is. In the present specification, the fluoroalkyl group-containing acrylic acid ester monomer and the fluoroalkyl group-containing methacrylic acid ester monomer are also collectively referred to as "fluoroalkyl group-containing (meth) acrylic acid ester monomer". The fluoroalkyl group-containing (meth) acrylic acid ester monomer is a chemical resistance (for example, salt water, acid or basic aqueous solution) of a fluorine-containing sealing material formed by using the composition for forming a fluorine-containing sealing material of the present disclosure. Contributes to improving resistance to acetone, oleic acid or hexane, especially salt water).

The fluoroalkyl group-containing (meth) acrylic acid ester monomer has the following formula (1):

It is represented by.

In the above formula (1), X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and CFX ¹ X ² groups (in the formula, X ¹ and X ² are the same or different, hydrogen atom, fluorine. Atomic or chlorine atom), cyano group, linear or branched fluoroalkyl group with 1-21 carbon atoms, substituted or unsubstituted benzyl group, substituted or unsubstituted phenyl group, or carbon number 1 ~ 20 linear or branched alkyl groups. X is preferably a hydrogen atom, a fluorine atom, a chlorine atom, or a methyl group.

In another embodiment, X is preferably 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 have the same meaning as described above), a cyano group. , A linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a linear or branched alkyl having 1 to 20 carbon atoms. It is a group, preferably 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 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, and the like. Cyclic aliphatic group having 6 to 10 carbon atoms which may have an oxygen atom, aromatic aliphatic group having 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 having 1 to 4 carbon atoms), -CH ₂ CH (OY ¹ ) CH ₂ -group (in the formula, Y ¹ is a hydrogen atom or an acetyl group). (), Or-(CH ₂ ) _n SO ₂ -group (in the formula, n is 1 to 10), more preferably a single bond, an aliphatic group having 1 to 10 carbon atoms. Alternatively, it is an −CH ₂ CH (OH) CH ₂ − group, more preferably an aliphatic group having 1 to 4 carbon atoms, or an −CH ₂ CH (OY ¹ ) CH ₂ − group.

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

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

Examples of the aromatic group include a phenylene group.

Examples of the cyclic aliphatic group include a cycloalkylene ring.

Examples of the aromatic aliphatic group, for ^example, -Y 21 ^{-Ar-Y 22} - can be exemplified. Y ²¹ and Y ²² are independently single-bonded or alkylene groups having 1 to 12 carbon atoms, and Ar can be a substituted or unsubstituted arylene group (more specifically, 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 is an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. In one embodiment, Rf is a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms.

The fluoroalkyl group-containing (meth) acrylic acid ester monomer represented by the above formula (1) has a carbon number of 4 to 6 in that it has good solubility in a fluorosolvent described later, particularly a hydrofluoroether. It is preferably a linear or branched fluoroalkyl group. In order to further improve the waterproof resistance of the formed gapfill material (sealing material), the fluoroalkyl group-containing (meth) acrylic acid ester monomer represented by the above formula (1) is further represented by α represented by X. It is preferable that the substituent at the position is an α-substituted acrylic acid ester which is a group or atom other than a hydrogen atom. From the viewpoint that a gapfill material having good waterproof property can be formed by using a low-priced raw material, the substituent X at the α-position is preferably a methyl group, a chlorine atom or a fluorine atom. From the viewpoint of improving the film-forming property, it is particularly preferable that the substituent X at the α-position is a methyl group.

In one embodiment, the fluoroalkyl group-containing (meth) acrylic acid ester monomer represented by the above formula (1) is a fluorine-based solvent described later, for example, at least one hydrogen atom is composed of a fluorine atom and at least one. It is preferable that Rf is a linear or branched fluoroalkyl group having 4 to 6 carbon atoms in that the hydrogen atom has good solubility in an olefin substituted with a chlorine atom. In order to further improve the waterproof resistance of the formed gapfill material, the fluoroalkyl group-containing (meth) acrylic acid ester monomer represented by the above formula (1) is further represented by a substituent at the α-position represented by X. Is preferably an α-substituted acrylic acid ester which is a group or atom other than a hydrogen atom. From the viewpoint that a gapfill material having good waterproof property can be formed by using a low-priced raw material, the substituent X at the α-position is preferably a methyl group, a chlorine atom or a fluorine atom. From the viewpoint of improving the film-forming property, it is particularly preferable that the substituent X at the α-position is a methyl group.

In one embodiment, Rf is a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms, and more preferably a linear or branched perfluoroalkyl group having 4 to 6 carbon atoms. ..

Examples of the fluoroalkyl group-containing (meth) acrylic acid ester monomer represented by the general formula (1) described above include the following compounds.

The above-mentioned fluoroalkyl group-containing (meth) acrylic acid ester monomer may be used alone or in combination of two or more.

[Si atom-containing polymerizable monomer]
The Si atom-containing polymerizable monomer contains a Si atom bonded to at least one hydroxyl group or a hydrolyzable group. The Si atom-containing polymerizable monomer preferably contains at least one hydroxyl group or a Si element bonded to a hydrolyzable group and at least one polymerizable functional group in the molecule. The Si atom-containing polymerizable monomer contributes to the improvement of the adhesiveness to the wall surface of the void or the member previously filled in the void, and the improvement of the wear resistance of the fluorine-containing sealing material.

In the Si atom-containing polymerizable monomer, the polymerizable functional group is preferably a group containing a polymerizable unsaturated bond, and more preferably a group containing a polymerizable ethylenically unsaturated bond. There is preferably one polymerizable functional group in the molecule of the Si atom-containing polymerizable monomer.

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

The Si atom-containing polymerizable monomer preferably has the following formula (2):

It is a compound represented by.

In the above formula (2), R ² , R ³ and R ⁴ are the same or different hydroxyl groups, hydrolyzable groups or alkyl groups having 1 to 4 carbon atoms, and are of R ² , R ³ and R ⁴ . At least one is a hydroxyl group or a hydrolyzable group. Hydrolyzable groups have the same meaning as above. More preferably, R ² , R ³ and R ⁴ are the same or different alkyl groups with 1 to 4 carbon atoms or alkoxy groups with 1 to 4 carbon atoms (-OR), and are R ² , R ³ and R. ^At least one of 4 is an alkoxy group having 1 to 4 carbon atoms. R has the same meaning as above. It is more preferable that R ² , R ³ and R ⁴ are independently alkoxy groups, and it is further preferable that they are independently methoxy groups or ethoxy groups. For example, R ² , R ³ and R ⁴ can all be methoxy groups.

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

Specifically, the compound represented by the above formula (2) can be represented by the following formula (2').

In the above formula (2'), R ² , R ³ and R ⁴ have the same meaning as above. R ¹⁴ represents a hydrogen atom, a fluorine atom, a chlorine atom, or an alkyl group having 1 to 4 carbon atoms, and is 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 having 1 to 10 carbon atoms or an aromatic aliphatic group having 6 to 15 carbon atoms. The aromatic aliphatic group has the same meaning as described above.

Specific examples of the Si atom-containing polymerizable monomer include a monomer represented by the following formula.

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

In one ^embodiment, R 2, ^{R 3} and ^{R 4} is methoxy group or ethoxy group, preferably a methoxy group, ^{R 6} is methyl group, h is an integer of 1 to 12.

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

[Other monomers]
The monomer component may include a high softening point monomer or other monomer, if necessary.

The high softening point monomer is a monomer having a glass transition point or melting point of 100 ° C. or higher, preferably 120 ° C. or higher, of a homopolymer composed of a high softening point monomer. In this case, the polymer having a glass transition point needs to have a glass transition point of 100 ° C. or higher, preferably 120 ° C. or higher, and the polymer having no glass transition point needs to have a melting point of 100 ° C. or higher, preferably 120 ° C. or higher. Needs to be 120 ° C. or higher.

The glass transition point and melting point are the extra glass transition end temperature ( _Teg ) and the melting peak temperature (T _pm ) specified in JIS K7121-1987 “Method for measuring transition temperature of plastics”, respectively.

The high softening point monomer 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 the fluorine-containing sealing material. Further, by containing the high softening point monomer, the hardness of the fluorine-containing sealing material can be improved, and the durability such as abrasion resistance can be improved.

In particular, by using the high softening point monomer as a monomer component, the sealing material has very good dynamic water repellency, which is an index showing the removal performance of water droplets adhering to the surface. The dynamic water repellency can be evaluated by the falling angle of water.

The high softening point monomer has the following general formula (4).
CH ₂ = C (R ¹¹ ) COOR ¹² (4)
(In the formula, R ¹¹ is H or CH ₃ , and R ¹² is a group having a saturated alkyl group having 4 to 20 carbon atoms and a ratio of carbon atoms to hydrogen atoms of 0.55 or more.)
(Meta) acrylic acid ester represented by; Methyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate and the like can be mentioned.

The high softening point monomer is preferably a (meth) acrylic acid ester represented by the general formula (4).

In the 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, 4 to 20 carbon atoms and a ratio of carbon atoms to hydrogen atoms is Specific examples of (saturated alkyl groups of 0.58 or more) include isobornyl, bornyl, fencil (all of which are C ₁₀ H ₁₇ , carbon atom / hydrogen atom = 0.58), adamantyl (C ₁₀ H ₁₅ , carbon atom). / hydrogen = 0.66), norbornyl _{(C 7 H 12,} includes a group having a crosslinked hydrocarbon ring, such as carbon atoms / hydrogen atoms = 0.58). These crosslinked hydrocarbon rings may be single-bonded to a carboxyl group, or may be bonded to a carboxyl group via a linear or branched alkylene group having 1 to 5 carbon atoms. .. These crosslinked hydrocarbon rings may be further substituted with a hydroxyl group or an alkyl group (number of carbon atoms, for example, 1 to 5).

The ratio of carbon atoms to hydrogen atoms represents the ratio of carbon atoms to hydrogen atoms.

Examples of the (meth) acrylic acid ester represented by the general formula (4) include (meth) acrylate having an isobornyl group, (meth) acrylate having a norbornyl group, (meth) acrylate having an adamantyl group, and the like. it can. Among these, examples of the (meth) acrylate having a norbornyl group include 3-methyl-norbornylmethyl (meth) acrylate, norbornylmethyl (meth) acrylate, norbornyl (meth) acrylate, 1,3,3-. Trimethyl-norbornyl (meth) acrylate, myrtanylmethyl (meth) acrylate, isopinocampanyl (meth) acrylate, 2-{[5- (1', 1', 1'-trifluoro-2'-trifluoromethyl-2) '-Hydroxy) propyl] norbornyl} (meth) acrylate and the like can be exemplified, and examples of the (meth) acrylate having an adamantyl group include 2-methyl-2-adamantyl (meth) acrylate and 2-ethyl-2-adamantyl (meth). Examples thereof include acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, and 1-adamantyl-α-trifluoromethyl (meth) acrylate.

The other monomer may be a monomer copolymerizable with a fluoroalkyl group-containing (meth) acrylic acid ester monomer, and can be widely selected as long as it does not adversely affect the performance of the obtained fluoropolymer. For example, aromatic alkenyl compounds, vinyl cyanide compounds, conjugated diene compounds, halogen-containing unsaturated compounds, silicon-containing unsaturated compounds, unsaturated dicarboxylic acid compounds, vinyl ester compounds, allyl ester compounds, unsaturated group-containing ether compounds, maleimides. Examples include, but are not limited to, compounds, (meth) acrylic acid esters, acrolein, methacrolein, cyclizable polymerizable monomers, N-vinyl compounds and the like.

[Si atom-containing mercaptan]
The Si atom-containing mercaptan contains at least one hydroxyl group or a Si element bonded to a hydrolyzable group.

The Si atom-containing mercaptan acts as a chain transfer agent, and the degree of polymerization of the fluoropolymer can be adjusted by adding it. Further, a part of the Si atom-containing mercaptan, specifically, a hydroxyl group bonded to a Si atom or a hydrolyzable group contained in the Si atom-containing mercaptan is contained in the fluoropolymer. As a result, the adhesion between the formed fluorine-containing sealant and the wall surface of the elastomer (for example, silicone) and / or the void is improved. Therefore, the Si atom-containing mercaptan can contribute to the formation of a fluorine-containing sealing material having excellent wear resistance.

The Si atom-containing mercaptan can be used without particular limitation 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. Preferred Si atom-containing mercaptans include compounds represented by the following formula (3).

In the above formula (3), R ⁷ , R ⁸ and R ⁹ are the same or different hydroxyl groups, hydrolyzable groups or alkyl groups having 1 to 4 carbon atoms, and are of R ⁷ , R ⁸ and R ⁹ . At least one is a hydroxyl group or a hydrolyzable group. Hydrolyzable groups have the same meaning as above. R ⁷ , R ⁸ and R ⁹ are identical or different alkyl groups with 1 to 4 carbon atoms or alkoxy groups with 1 to 4 carbon atoms (-OR), and are at least one of R ⁷ , R ⁸ and R ⁹ . More preferably, it is an alkoxy group having 1 to 4 carbon atoms. It is more preferable that R ⁷ , R ⁸ and R ⁹ are independently alkoxy groups, and it is particularly preferable that they are independently methoxy groups or ethoxy groups. For example, R ⁷ , R ⁸ and R ⁹ can all be methoxy groups.

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

In one embodiment, R ⁷ , R ⁸ and R ⁹ are independently methoxy or ethoxy groups, preferably methoxy groups, and R ¹⁰ is an alkylene group having 1 to 5 carbon atoms.

In the Si atom-containing mercaptan represented by the general formula (3), it is preferable that R ¹⁰ is a linear alkylene group having 1 to 4 carbon atoms from the viewpoint of solubility in a fluorine-based solvent described later.

The above-mentioned Si atom-containing mercaptans may be used alone or in combination of two or more.

Hereinafter, the fluoropolymer contained in the composition for forming a fluoropolymer of the present disclosure will be described. The fluoropolymer is a fluoropolymer shown in (A) below (hereinafter, also referred to as “fluoropolymer 1”) and a fluoropolymer shown in (B) below (hereinafter, also referred to as “fluoropolymer 2”). is there.
(A) A fluoropolymer containing a component derived from a monomer component containing the fluoroalkyl group-containing (meth) acrylic acid ester monomer and a Si atom-containing polymerizable monomer.
(B) A fluorine-containing polymer containing a component derived from a monomer component containing the fluoroalkyl group-containing (meth) acrylic acid ester monomer and a component derived from a Si atom-containing mercaptan (here, the Si atom). The containing polymerizable monomer and at least one Si atom contained in the Si atom-containing mercaptan each independently have a hydroxyl group or a hydrolyzable group).

[Fluororesin 1]
The fluoropolymer 1 is obtained by polymerizing a monomer component containing a fluoroalkyl group-containing (meth) acrylic acid ester monomer and a Si atom-containing polymerizable monomer as essential components. That is, the fluoropolymer 1 is a fluoropolymer obtained by polymerizing a monomer component containing a fluoroalkyl group-containing (meth) acrylic acid ester monomer and a Si atom-containing polymerizable monomer. The fluoropolymer 1 is a copolymer having a structural unit derived from a fluoroalkyl group-containing (meth) acrylic acid ester monomer and a structural unit derived from a Si atom-containing polymerizable monomer.

The weight average molecular weight of the fluoropolymer 1 is preferably 3,000 to 500,000, more preferably 5,000 to 300,000, and even more preferably 20,000 to 100,000. The weight average molecular weight of the fluoropolymer 1 can be determined by GPC (gel permeation chromatography). For example, the weight average molecular weight can be determined by GPC using a mixed solvent of HCFC225 / hexafluoroisopropanol (= 90/10 weight) as an elution solvent (standard polymethylmethacrylate equivalent).

The fluoroalkyl group-containing (meth) acrylic acid ester monomer and the Si atom-containing polymerizable monomer have the same meanings as described above.

The fluoropolymer 1 contains a structural unit derived from the fluoroalkyl group-containing (meth) acrylic acid ester monomer and a structural unit derived from the Si atom-containing polymerizable monomer in a mass ratio of 99.9: 0.1 to It is preferably contained in the range of 50:50, more preferably in the range of 96: 4 to 70:30, and even more preferably in the range of 96: 4 to 90:10.

In a preferred embodiment, in the fluoropolymer 1, the fluoroalkyl group-containing (meth) acrylic acid ester monomer is represented by the following formula (1), and the Si atom-containing polymerizable monomer is represented by the following formula (2). To. Wherein, Rf, X, Y, and ^R 2 ~ ^{R 5} are as defined above.

In this embodiment, the obtained fluoropolymer 1 is a copolymer having a structural portion represented by the following formula (5). The end of the fluoropolymer 1 can be a stop agent-derived group, an initiator-derived group, or a monomer-derived group.

The composition for forming a fluorine-containing sealing material containing the fluorine-containing polymer 1 can contribute to the formation of a thick fluorine-containing sealing material. The composition for forming a fluorine-containing sealing material containing the fluorine-containing polymer 1 can contribute to the formation of a sealing material having excellent wear resistance, good waterproof and / or moisture-proof performance, excellent water repellency, and good drainage. Further, the composition for forming a fluororesin containing the fluoropolymer 1 has chemical resistance, for example, against salt water (for example, 5% salt water), an acid or a basic aqueous solution, acetone, oleic acid or hexane, particularly salt water. It can contribute to the formation of a sealing material with good resistance.

In the above formula (5), X, Y, Rf , and ^R 2 ~ ^{R 4} are as defined above. R 5 ^'is a trivalent group derived from a radical R ⁵ in the formula (2), i.e., a trivalent group derived from a group containing a polymerizable unsaturated bond.

In the above formula (5), the structural unit in parentheses with l is a structural unit derived from the fluoroalkyl group-containing (meth) acrylic acid ester monomer, and is enclosed in parentheses with m. The structural unit is a structural unit derived from a Si atom-containing polymerizable monomer. The order of existence of each repeating unit in parentheses with l and m is arbitrary in the equation.

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

In one embodiment, 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. It is preferably in the range of 95: 5 to 80:20, more preferably in the range of 95: 5 to 85:15.

In one embodiment, 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 embodiment, the monomer component contains a high softening point monomer in addition to a fluoroalkyl group-containing acrylic acid ester and a Si atom-containing polymerizable monomer. In this embodiment, the fluoropolymer 1 is a copolymer further containing a structural unit based on the high softening point monomer. The high softening point monomer has the same meaning as described above.

The composition for forming a fluorine-containing sealing material containing a fluorine-containing polymer obtained in this embodiment has good waterproof and moisture-proof properties, and can contribute to the formation of a sealing material having good hardness.

In a preferred embodiment
The fluoroalkyl group-containing (meth) acrylic acid ester monomer is represented by the following formula (1);

The Si atom-containing polymerizable monomer is represented by the following formula (2);

The high softening point monomer is represented by the formula (4) (meth) acrylic acid ester CH ₂ = C (R ¹¹ ) COOR ¹² (4).
Is. ^{Wherein, Rf, X, Y, R} 2 ~ R 5, R 11 and ^{R 12} are as defined above.

In this embodiment, the obtained fluoropolymer 1 is a copolymer having a structural portion represented by the following formula (5'). The composition for forming a fluorine-containing sealant containing this copolymer has excellent wear resistance, good waterproof and / or moisture-proof performance, and further, has excellent water repellency and good drainage. Can contribute to. The end of the fluoropolymer 1 can be a stop agent-derived group, an initiator-derived group, or a monomer-derived group.

In the above formula ^{(5 '), X, Y} , Rf, R 2 ~ R 4, R 11 and ^{R 12} are as defined above. R 5 ^'is a trivalent group derived from a radical R ⁵ in the formula (2), i.e., a trivalent group derived from a group containing a polymerizable unsaturated bond.

In the above formula (5), the structural unit enclosed in parentheses with l'is a structural unit derived from the fluoroalkyl group-containing (meth) acrylic acid ester monomer, and is enclosed in parentheses with m'. The resulting structural unit is a structural unit derived from a Si atom-containing polymerizable monomer, and the structural unit enclosed in parentheses with n'is a structural unit derived from a high softening point monomer. The order of existence of each repeating unit in parentheses with l', m'and n'is arbitrary in the equation.

In the above equation (5'), l', m'and n'are independently integers of 1 or more. The total of l', m'and n'is preferably a numerical value having a weight average molecular weight of 3,000 to 500,000.

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

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

The above-mentioned monomer component can further contain other monomers, if necessary. Other monomers have the same meaning as described above.

The above other monomers are preferably contained in an amount of 0.1 to 20% by mass with respect to 100% by mass of the entire fluoropolymer 1.

The polymerization method of the fluoropolymer 1 is not particularly limited, but for example, solution polymerization can be carried out in a fluorosolvent. According to this method, since the formed fluoropolymer 1 has good solubility in a fluorosolvent, the polymerization reaction can proceed smoothly without forming a precipitate.

The fluorine-based solvent used for the above solution polymerization (hereinafter, may be referred to as “fluorine-based solvent for polymerization”) has a fluorine atom in the molecule and has good solubility of the formed fluorine-containing polymer. The solvent may be any of hydrocarbon compounds, alcohols, ethers and the like, and may be any of aliphatic and aromatic solvents. For example, chlorinated fluorinated hydrocarbons (particularly 2-5 carbon atoms), especially HCFC225 (dichloropentafluoropropane), HCFC141b (dichlorofluoroethane), CFC316 (2,2,3,3-tetrachlorohexafluorobutane). , Bertrel XF (chemical formula C ₅ H ₂ F ₁₀ ) (manufactured by DuPont), hexafluoro-m-xylene, pentafluoropropanol, fluorine-based ether and the like can be used.

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

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

When the monomer component is polymerized in a fluorine-based solvent, for example, the monomer component is dissolved in a fluorine-based solvent, and the obtained solution is stirred and a polymerization initiator is added to carry out the polymerization reaction. Can be advanced.

The above-mentioned polymerization initiator can be used without particular limitation as long as it is a known polymerization initiator for a polymerization reaction. Examples of the polymerization initiator include azo initiators such as azobisisobutyronitrile, methyl azoisobutyrate, and azobisdimethylvaleronitrile; benzoyl peroxide, potassium persulfate, ammonium persulfate, benzophenone derivative, phosphine oxide derivative, and benzoketone. Derivatives, phenylthioether derivatives, azide derivatives, diazo derivatives, disulfide derivatives and the like can be used. Each of these polymerization initiators may be used alone, or two or more thereof may be used in combination.

The amount of the polymerization initiator used is not particularly limited, but is usually 0.01 to 10 parts by mass with respect to 100 parts by mass of the fluoroalkyl group-containing (meth) acrylic acid ester monomer used as the monomer component. It is preferably 0.1 to 1 part by mass, and more preferably 0.1 to 1 part by mass.

The polymerization conditions such as the polymerization temperature and the polymerization time may be appropriately adjusted according to the type of the monomer component, the amount used thereof, the type of the polymerization initiator, the amount used, etc., but are usually about 50 to 100 ° C. The polymerization reaction may be carried out at a temperature of 4 to 10 hours.

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

In the above-mentioned monomer component, the amount of the Si atom-containing polymerizable monomer used is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the fluoroalkyl group-containing (meth) acrylic acid ester monomer.

In one embodiment, in the above-mentioned monomer component, the amount of the above-mentioned high softening point monomer used is 0.1 to 49.9 parts by mass with respect to 100 parts by mass of the fluoroalkyl group-containing (meth) acrylic acid ester monomer. It is preferably 1 to 25 parts by mass.

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

[Fluorin-containing polymer 2]
The fluoropolymer 2 can be obtained by polymerizing a monomer component containing a fluoroalkyl group-containing (meth) acrylic acid ester monomer in the presence of a Si atom-containing mercaptan. That is, the fluoropolymer 2 is a fluoropolymer obtained by polymerizing a monomer component containing a fluoroalkyl group-containing (meth) acrylic acid ester monomer in the presence of a Si atom-containing mercaptan. The fluoroalkyl group-containing (meth) acrylic acid ester monomer and the Si atom-containing mercaptan have the same meanings as described above.

The above-mentioned monomer component can contain a high softening point monomer and other monomers in addition to the fluoroalkyl group-containing (meth) acrylic acid ester monomer. The high softening point monomer and other monomers have the same meanings as described above.

The weight average molecular weight of the fluoropolymer 2 is preferably 3,000 to 500,000, more preferably 5,000 to 300,000, and even more preferably 20,000 to 100,000. The weight average molecular weight of the fluoropolymer 2 can be determined by GPC. For example, the weight average molecular weight can be determined by GPC using a mixed solvent of HCFC225 / hexafluoroisopropanol (= 90/10 weight) as an elution solvent (standard polymethylmethacrylate equivalent).

The fluoropolymer 2 contains a component derived from a fluoroalkyl group-containing (meth) acrylic acid ester monomer and a component derived from a Si atom-containing mercaptan in a mass ratio of 100: 0.01 to 100: 25. It is preferable to include in the range of 100: 0.1 to 100: 5.

The fluoropolymer-containing polymer 2 contains a component derived from a fluoroalkyl group-containing (meth) acrylic acid ester monomer and a component derived from a Si atom-containing mercaptan in a mass ratio of 100: 0.01 to 100: 1. It may be contained in the range of 100: 0.1 to 100: 1.

In a preferred embodiment, a fluoroalkyl group-containing (meth) acrylic acid ester monomer represented by the above formula (1) is used as the monomer, and a Si atom-containing mercaptan represented by the above formula (3) is used. In this embodiment, the fluoropolymer 2 has the following general formula (6):

It is represented by. The fluoropolymer 2 represented by the formula (6) is a polymer chain of a polymer having a structural unit derived from a fluoroalkyl group-containing (meth) acrylic acid ester monomer and a Si atom-containing mercaptan represented by the formula (3). It is bound to the structure of origin. 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 general formula (6), X, Y, Rf, and R ⁷ to R ¹⁰ have the same meaning as described above. k is preferably a numerical value corresponding to the above-mentioned weight average molecular weight, that is, a numerical value in which the weight average molecular weight of the polymer of the general formula (6) is 3,000 to 500,000, preferably 3,000 to 500,000. It is more preferable that the value is 20,000 to 100,000.

The composition for forming a fluorine-containing sealing material containing the above-mentioned fluorine-containing polymer 2 can contribute to the formation of a thick fluorine-containing sealing material. The composition for forming a fluorine-containing sealing material containing the fluorine-containing polymer 2 can contribute 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 forms a sealing material having good chemical resistance, for example, resistance to salt water, an acid or a basic aqueous solution, acetone, oleic acid or hexane, particularly salt water. Can contribute to.

In one embodiment, when producing the fluoropolymer 2, a high softening point monomer can be further used as the monomer component together with the fluoroalkyl group-containing (meth) acrylic acid ester monomer. Specific examples of the high softening point monomer are the same as described above.

In this embodiment, 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), a structural unit based on a high softening point monomer is included.

The fluoropolymer 2 preferably contains a component derived from the high softening point monomer by 0.1 to 50 parts by mass with respect to 100 parts by mass of the entire fluoropolymer 2, and more preferably 1 to 30 parts by mass. It is more preferable to contain 1 to 20 parts by mass.

In one embodiment, when the fluoropolymer 2 is produced, other monomers can be further used as the monomer component together with the fluoroalkyl group-containing (meth) acrylic acid ester monomer. Specific examples of other monomers are the same as described above.

In one embodiment, when the fluoropolymer 2 is produced, a Si atom-containing polymerizable monomer can be further used as a monomer component. The Si atom-containing polymerizable monomer has the same meaning as described above.

In this embodiment, the fluoropolymer 2 further has a structural unit based on the Si atom-containing polymerizable monomer. By using the Si atom-containing polymerizable monomer, the composition for forming a fluorine-containing sealing material containing the fluorine-containing polymer 2 can further contribute to the improvement of the adhesion to the elastomer (for example, silicone).

The fluoropolymer 2 contains at least one selected from the group consisting of a fluoroalkyl group-containing (meth) acrylic acid ester monomer, a high softening point monomer, other monomers, and a Si atom-containing polymerizable monomer as a monomer component. Can include.

As described above, when X is a chlorine atom or a fluorine atom, the above general formula (6) is highly useful because it can be obtained by using a low-priced raw material and can form a gapfill material having good waterproofness. It is a polymer.

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

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

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

The fluoropolymer 2 can be polymerized under the same conditions as the fluoropolymer 1.

(II) Carbon Black The composition for forming a fluorine-containing sealing material of the present disclosure contains carbon black. By containing carbon black in the composition of the present disclosure, the chemical resistance of the formed fluorine-containing sealing material is improved.

The type of carbon black is not particularly limited, and is not particularly limited, for example, furnace black, acetylene black, kechen black and the like can be used, and furnace black or acetylene black may be preferable.

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

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

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

The content of the carbon black is, for example, 0.1 to 10% by mass, preferably 1 to 8% by mass, based on the solid content (fluorine-containing polymer and carbon black) in the composition for forming a fluorine-containing sealing material. It can be preferably 3 to 5% by mass. By adding carbon black in such a range, the chemical resistance of the obtained fluorine-containing sealing material is further improved.

(III) Solvent The composition for forming a fluorine-containing sealant of the present disclosure contains a solvent.

In a preferred embodiment, the solvent is a fluorine-based solvent. By containing the fluorosolvent, the solubility of the fluoropolymer is improved, and it becomes easy to obtain the optimum viscosity.

As the fluorine-based solvent, a solvent having a fluorine atom in the molecule and having good solubility of the formed fluorine-containing polymer can be used, and a hydrocarbon compound, alcohol or ether having a fluorine atom in the molecular structure can be used. Is preferably used. The fluorine-based solvent may be either an aliphatic solvent or an aromatic solvent.

The fluorine-based solvent is selected from the group consisting of hydrofluoroethers, hydrofluorocarbons, perfluorocarbons, and olefins in which at least one hydrogen atom is substituted with a fluorine atom and at least one hydrogen atom is substituted with a chlorine atom. It is preferable to use at least 1.

As the fluorine-based solvent, it is preferable to use at least one selected from the group consisting of hydrofluoroether, hydrofluorocarbon and perfluorocarbon. Examples of the fluorinated solvent include chlorinated fluorinated hydrocarbons (particularly 2 to 5 carbon atoms), particularly HCFC225 (dichloropentafluoropropane), HCFC141b (dichlorofluoroethane), and CFC316 (2,2,3,3). -Tetrachlorohexafluorobutane), Bertrel XF (molecular formula C ₅ H ₂ F ₁₀ ) (manufactured by DuPont), hexafluoro-m-xylene, pentafluoropropanol; fluorocarbon ethers such as hydrofluoro ethers; perfluorocarbons, especially fluorocarbons FC40 (manufactured by 3M), Fluorinert FC43 (manufactured by 3M), PFC-5060 (manufactured by Solvay); Hydrofluorocarbons, particularly Solcan 365mfc (manufactured by Solvay).

In the present disclosure, it is particularly preferable to use hydrofluoroether as the fluorine-based solvent. Hydrofluoroether is a solvent having low chemical erosion property to various materials, and is a solvent particularly suitable as a solvent for a composition for forming a fluorine-containing sealant for electronic members, which is strongly required to eliminate adverse effects of the solvent. is there. Further, the hydrofluoroether is an ideal solvent having excellent performances such as quick-drying, low environmental pollution, nonflammability and low toxicity.

In the present disclosure, the hydrofluoroether is referred to as hydrofluoroether.
_{Formula: C y F 2y + 1 -O} -C z H 2z + 1
[In the formula, y is a number from 1 to 6 and z is a number from 1 to 6. ]
It is preferable to use the compound represented by. Examples of such hydrofluoroethers include Novec HFE7100 (chemical formula C ₄ F ₉ OCH ₃ ), 7200 (chemical formula C ₄ F ₉ OC ₂ H ₅ ), and 7300 (chemical formula C ₂ F ₅ CF (OCH)) manufactured by 3M of the United States. ₃ ) C ₃ F ₇ ) and the like can be used.

In another embodiment, 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 as the fluorine-based solvent. The olefin is preferable from the viewpoint of preventing global warming.

The 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 is, for example, a compound having 2 to 5 carbon atoms, and more specifically, a compound having 3 carbon atoms. ~ 4 compounds.

As the 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, a hydrochlorofluoroolefin or a chlorofluoroolefin, which has been recently developed as a low GWP solvent, is used. Can be. As used herein, the chlorofluoroolefin means an olefin in which at least one of the substituents is substituted with a chlorine atom and the rest is substituted with a fluorine atom. Further, in the hydrochlorofluoroolefin, at least one of the substituents is substituted with a hydrogen atom, at least one is substituted with a chlorine atom, and the rest is substituted with a fluorine atom.

Examples of the hydrochlorofluoroolefin include 1-chloro-3,3,3-trifluoro-1-propene and 1-chloro-2,3,3-trifluoro-1-propene; as the above-mentioned chlorofluoroolefin. 1,2-Dichloro-1,3,3,3-tetrafluoro-1-propene, 1,1,3-trichloro-2,3,3-trifluoro-1-propene, 1,1-dichloro-2, Examples thereof include 3,3,3-tetrafluoro-1-propene.

In a preferred embodiment, the content of the fluoropolymer in the fluoropolymer-containing sealant-forming composition of the present disclosure is, for example, 7% by mass or more, preferably 10% by mass or more, and preferably 33% by mass with respect to the entire composition. It is mass% or less, more preferably 30 mass% or less, still more preferably 25 mass% or less.

In a preferred embodiment, the content of the fluoropolymer in the fluoropolymer-containing sealant-forming composition of the present disclosure is preferably 7 to 33% by mass, more preferably 10 to 30% by mass, based on the entire composition. It is preferably 10 to 25% by mass.

The composition for forming a fluorine-containing sealing material of the present disclosure has a fluorine-containing polymer concentration as described above, so that voids of electronic members, particularly small voids (microvoids, for example, width 0.1 to 1 mm, depth 0. It can be effectively filled even for 1 to 3 mm). The composition for forming a fluorine-containing sealing material of the present disclosure is less likely to cause problems such as clogging of voids during filling, and can uniformly fill the voids. Since the composition for forming a fluorine-containing sealing material of the present disclosure has the above-mentioned concentration of a fluorine-containing polymer, the volume reduction due to the volatilization of the solvent is small, and the formation of a fluorine-containing sealing material having a large film thickness can be easily performed. Become. Therefore, by using the composition for forming a fluorine-containing sealing material of the present disclosure, the gap fill property is improved.

The composition for forming a fluorinated sealant of the present disclosure contains a fluorinated polymer 1 and / or a fluorinated polymer 2, and since all of these polymers contain a fluoroalkyl group, a fluorinated polymer formed using the above composition is contained. Fluorine sealant exhibits good waterproof performance. The composition for forming a fluorine-containing sealing material of the present disclosure has excellent wear resistance, good waterproof and / or moisture-proof performance, and can contribute to the formation of a sealing material having excellent water repellency and good drainage. Since the fluoropolymer 1 and the fluoropolymer 2 have good chemical resistance, for example, resistance to salt water, an acid or a basic aqueous solution, acetone, oleic acid or hexane, particularly salt water, the fluoropolymer-containing sealing material of the present disclosure. The forming composition can contribute to the formation of a fluorine-containing sealing material having good chemical resistance. A member such as an electrode or a resin material may be formed in advance in the void. In such a case, the electrode or resin from water or the like can be used by using the fluorine-containing sealing material forming composition of the present disclosure. It is possible to protect members such as materials.

Further, since the composition for forming a fluorine-containing sealing material of the present disclosure contains carbon black, a sealing material having high chemical resistance can be obtained.

Further, due to the hydroxyl groups or hydrolyzable groups contained in the fluoropolymer 1 and the fluoropolymer 2, the adhesiveness of the sealant formed by the fluoropolymer-containing sealant-forming composition of the present disclosure to the object to be treated is good. become. Examples of the object to be treated include the wall surface of the void of the electronic member, or a member (for example, glass; metal or metal oxide (for example, metal wiring); elastomer such as silicone; polyethylene or epoxy, etc., which is pre-filled in the void. Resin material) or display peripheral material (optical adhesive, OCA, polarizing plate, etc.).

In one embodiment, the composition for forming a fluororesin-containing sealant contains a fluoropolymer 1 as a fluoropolymer. The fluoropolymer 1 is good for various treatment objects (for various treatment objects, it has the same meaning as above) due to the hydroxyl group bonded to the Si atom existing in the side chain or the hydrolyzable group. It exhibits excellent adhesiveness and has crosslinkability. Therefore, the fluorine-containing sealing material formed by using the composition for forming a fluorine-containing sealing material of this embodiment has good adhesion to the object to be treated, abrasion resistance, waterproof and / or moisture-proof performance.

In one embodiment, the composition for forming a fluororesin-containing sealant contains a fluoropolymer 2 as a fluoropolymer. In the fluorine-containing polymer 2, at least a part of the Si atom-containing mercaptan present at the time of the polymerization reaction is bonded to the polymer chain, and various treatments are performed by a hydroxyl group or a hydrolyzable group bonded to the Si atom present at the end thereof. It exhibits good adhesiveness to an object (for various treated objects, it has the same meaning as above) and also has crosslinkability. As a result, the fluorine-containing sealing material formed by using the composition for forming the fluorine-containing sealing material of this embodiment has excellent adhesion to the object to be treated and abrasion resistance, and is further waterproof and / or moisture-proof. Performance is also good.

In another embodiment, the fluoropolymer 1 or the fluoropolymer 2 is formed by using a monomer component further containing a high softening point monomer. In this embodiment, the water repellency of the formed fluoropolymer-containing sealing material is improved and the drainage is improved for both the fluoropolymer 1 and the fluoropolymer 2.

The composition for forming a fluorine-containing sealing material of the present disclosure preferably has a viscosity in the range of 10 to 1000 mPa · s, more preferably in the range of 10 to 100 mPa · s, and in the range of 10 to 60 mPa · s. It is more preferably in the range of 10 to 50 mPa · s. The above viscosity is a viscosity at 25 ° C. with a B-type viscometer, and can be measured in accordance with JIS K7117-1: 1999. Since the composition for forming a fluorine-containing sealing material of the present disclosure has the above-mentioned viscosity, it is difficult for voids to be clogged during filling, and even for voids between electronic members, particularly minute voids having a narrow width. , Can be filled uniformly. Since the composition for forming a fluorine-containing sealant of the present disclosure has the above-mentioned viscosity, it is difficult for bubbles to be generated when filling the voids, or even if bubbles are generated, the bubbles are generated. Disappears naturally (without any special manipulation). Further, 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 embodiment, in the composition for forming a fluorine-containing sealant, the fluoroalkyl group-containing (meth) acrylic acid ester monomer is represented by the formula (1) and contains an α-substituted fluoroalkyl group-containing (meth) acrylic acid. It is an ester monomer [in formula (1), Rf is a linear or branched fluoroalkyl group having 4 to 6 carbon atoms; X is a group or atom other than a hydrogen atom, preferably a fluorine atom or chlorine. It is an atom or a methyl group. ], The fluorine-based solvent is hydrofluoroether. The fluorine-containing polymer formed from an α-substituted fluoroalkyl group-containing acrylic acid ester in which Rf is a fluoroalkyl group having 4 to 6 carbon atoms has good solubility in hydrofluoroether and is formed. The sealing material has good waterproof and moisture-proof properties, and also has good wear resistance.

In the above embodiment, Y is preferably a single bond, an aliphatic group having 1 to 10 carbon atoms (for example, an alkylene group), or -CH ₂ CH (OH) CH ₂ -group, and more preferably 1 to 10 carbon atoms. It is an aliphatic group of 4 (for example, an alkylene group), or -CH ₂ CH (OY ¹ ) CH ₂ -group. In the formula, Y ¹ 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 fluorine-containing sealing material having good stability, which is less likely to cause precipitation or the like, is formed. It can be a composition for use.

The composition for forming a fluororesin-containing sealing material of the present disclosure may be used as it is as a composition for forming a fluororesin-containing sealing material by carrying out a polymerization reaction in a fluoropolymer for polymerization and then adjusting the polymer concentration as necessary. Alternatively, after carrying out a polymerization reaction, the fluoropolymer may be separated, and a composition for forming a fluororesin-containing sealant containing the separated fluoropolymer and a fluoropolymer may be used.

Preferably, after the polymerization reaction is carried out using hydrofluoroether as a fluorine-based solvent for polymerization, the polymer concentration is adjusted using hydrofluoroether, if necessary, to obtain a composition for forming a fluorine-containing sealant. .. By using such a method, the desired composition for forming a fluorine-containing sealing material can be efficiently obtained.

The composition for forming a fluorine-containing sealant of the present disclosure may contain other components in addition to the fluorine-containing polymer and the fluorine-based solvent. Other components include catalysts (metal catalysts such as tin or titanium, or organic catalysts such as acid-bases, stabilizers (dehydrating agents, molecular sieves, magnesium sulfate or methyl orthogitate), viscosity modifiers, fillers ( Inorganic materials such as silica, mica, and clay), colorants, fluorescent agents, and the like can be mentioned.

The composition for forming a fluorine-containing sealing material of the present disclosure is not particularly limited, but can be used for, for example, an electronic member such as a display or a printed circuit board, and materials contained in these members such as an elastomer and a plastic. It can be applied to metals, ceramics, etc. Examples of the electronic device including the above electronic member include a personal computer, a tablet personal computer, a smart phone, a digital camera, a car navigation system, and the like.

According to the composition for forming a fluorine-containing sealant of the present disclosure, it is possible to form a fluorine-containing sealant having excellent wear resistance and waterproof and moisture-proof properties. When hydrofluoroether is used as the solvent, a fluorine-containing sealing material having good waterproof and moisture-proof properties can be formed without causing chemical erosion and without adversely affecting the environment or the like. Further, by using the composition for forming a fluorine-containing sealing material of the present disclosure, it is possible to form a fluorine-containing sealing material having good chemical resistance and a large film thickness. Further, by using the composition for forming a fluorine-containing sealing material of the present disclosure, it is possible to adhere to the wall surface of a member or a void without separately providing an adhesive layer, and the process of forming the fluorine-containing sealing material is simplified. Is possible.

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

The above processing method is not particularly limited, and for example, the composition for forming a fluorine-containing sealing material of the present disclosure is molded into a gap between electronic members (for example, a bonded portion between a housing and a printed circuit board, or a resin-molded metal terminal portion and a mold). This can be done by filling the gaps in the resin, etc.), filling, and then drying.

As a result, the hydroxyl group or hydrolyzable group bonded to the Si atom introduced into the polymer terminal or side chain of the fluoropolymer contained in the composition for forming a fluorine-containing sealant of the present disclosure is hydrolyzed by the humidity in the atmosphere. Then, it is converted into a silanol group, for example, the wall surface of the void of the electronic member, or a member prefilled in the void (for example, glass, metal wiring, or an elastomer such as silicone, a resin material such as polyethylene or epoxy), etc. Reacts with the object to be treated and improves adhesion. The silanol groups that have not reacted with the wall surface of the void or the above member are condensed and crosslinked two-dimensionally or three-dimensionally to form a strong film.

There is no particular limitation on the temperature during processing, and normally, processing may be performed at room temperature. The processing time is also not particularly limited, but may be, for example, 5 minutes to 1 hour.

In addition, in order to form a fluorine-containing sealing material having higher wear resistance, prior to the treatment with the composition for forming a fluorine-containing sealing material of the present disclosure, in order to remove oil on the wall surface of the void, the object to be treated is subjected to. It is preferable to wash with acetone, hydrofluoroether or the like and then dry. Further, in addition to the above cleaning, pretreatment with UV ozone, oxygen plasma or the like can further improve the wear resistance of the fluorine-containing sealing material.

Further, prior to the treatment with the fluorine-containing sealing material forming composition of the present disclosure, it is formed from the fluorine-containing sealing material forming composition by subjecting the wall surface of the void or the like to a primer treatment, if necessary. The adhesiveness of the fluorine-containing sealing material can be improved, and the wear resistance can be further improved. The primer treatment may be carried out according to a conventional method under the same conditions as the primer treatment when a silane coupling agent is used.

Hereinafter, the present disclosure will be described in more detail through examples, but the present disclosure is not limited to these examples.

The abbreviations of the compounds used in Examples and Comparative Examples are as follows.
-Rf (C6) MA: Ethyl methacrylate (perfluorohexyl) (CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ C ₆ F ₁₃ )
TMSMA: -3- (trimethoxysilyl) propyl methacrylate ・ MMA: methyl methacrylate ・ IBMA: isobornyl 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 placed in a four-necked flask provided with a reflux tube. The flask was heated to 80 ° C. while purging with nitrogen. Then, 0.55 g of azoisobutyronitrile was added and reacted for 6 hours. After the completion of the polymerization, the inside of the system was cooled to room temperature, and the concentration was adjusted with HFE7200 so that the solid content was 5% to obtain a diluted solution 1.

<Synthesis example 2>
Diluted solution 2 was obtained in the same manner as in Synthesis Example 1 above, except that 50 g of Rf (C6) MA, 17.5 g of MMA, and 135 g of HFE7200 were used.

<Synthesis example 3>
Diluted solution 3 was obtained in the same manner as in Synthesis Example 1 above, except that 50 g of Rf (C6) MA, 10 g of IBMA, 0.15 g of MPS, and 120 g of HFE7200 were used.

<Addition of carbon black>
As carbon black, acetylene black made from acetylene and furnest black made from petroleum oil (both commercially available) were prepared. Acetylene black was added to each of the diluted solutions 1 to 3 obtained above at the ratios shown in the table below, and ultrasonic waves were irradiated at room temperature for 2 hours to obtain a coating solution in which carbon black was dispersed.

<Evaluation>
(Chemical resistance test)
-Appearance test A coating film was prepared on a slide glass so as to have a film thickness of 10 μm, immersed in an oleic acid solution at 65 ° C. for 1 week, and the appearance (visual observation) was observed. The criteria for appearance are as follows.
A: No change in swelling, cracking, or peeling of the coating film B: Slight swelling is observed at the edges of the coating film, but there is no significant change in cracking or peeling.
C: The entire coating film is swollen, and some cracks and peeling marks are observed.

・ Swelling test (weight change rate)
A coating film was prepared by overcoating on a slide glass so that the film thickness was 50 to 70 μm. After calculating the weight of the coating film, the slide glass was immersed in oleic acid at 60 ° C. for 24 hours. Then, 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.

The present disclosure can be suitably used for forming a fluorine-containing sealing material for filling gaps between electronic members such as a display or a printed circuit board (for example, gaps on the end face of a display) in an electronic device or the like.

Claims (16)

1. Equation (I) (1):
   

   

   [During the ceremony:
   Rf is a fluoroalkyl group;
   X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and CFX ¹ X ² groups (in the formula, X ¹ and X ² are the same or different, hydrogen atom, fluorine atom or chlorine atom. ), Cyan group, linear or branched fluoroalkyl group having 1 to 21 carbon atoms, substituted or unsubstituted benzyl group, substituted or unsubstituted phenyl group, linear or linear or branched group having 1 to 20 carbon atoms. It is a branched alkyl group;
   Y is a single bond or divalent organic group. ]
   A fluoropolymer containing a structural unit derived from a fluoroalkyl group-containing (meth) acrylic acid ester monomer represented by (A) and one or both of the fluoropolymers shown in (A) and (B) below:
   (A) A fluoropolymer containing a component derived from a monomer component containing the fluoroalkyl group-containing (meth) acrylic acid ester monomer and a Si atom-containing polymerizable monomer.
   (B) A fluorine-containing polymer containing a component derived from a monomer component containing the fluoroalkyl group-containing (meth) acrylic acid ester monomer and a component derived from a Si atom-containing mercaptan (here, the Si atom). The containing polymerizable monomer and at least one Si atom contained in the Si atom-containing mercaptan each independently have a hydroxyl group or a hydrolyzable group), and
   (II) A composition for forming a fluorine-containing sealing material containing carbon black.
2. The composition for forming a fluorine-containing sealant according to claim 1, wherein in the formula (1), Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms.
3. In the formula (1), Y is a single bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom or a sulfur atom, and an aromatic having 6 to 10 carbon atoms which may have an oxygen atom. Group group, cyclic aliphatic group having 6 to 10 carbon atoms which may have an oxygen atom, aromatic aliphatic group having 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 having 1 to 4 carbon atoms), -CH ₂ CH (OY ¹ ) CH ₂ -group (in the formula, Y ¹ is a hydrogen atom). The composition for forming a fluorine-containing sealant according to claim 1 or 2, which is an acetyl group) or-(CH ₂ ) _n SO ₂ -group (where n is 1 to 10 in the formula).
4. In any one of claims 1 to 3, in the formula (1), Rf is a linear or branched fluoroalkyl group having 4 to 6 carbon atoms, and X is an atom or group other than hydrogen. The composition for forming a fluorine-containing sealing material according to the above.
5. The composition for forming a fluorine-containing sealant according to any one of claims 1 to 4, wherein the carbon black is furnace black, acetylene black, or kechen black.
6. The fluorine-containing sealing according to any one of claims 1 to 5, wherein the content of the carbon black is 0.1 to 10% by mass with respect to the solid content in the composition for forming a fluorine-containing sealing material. Composition for material formation.
7. In the fluoropolymer shown in (A), the Si atom-containing polymerizable monomer is represented by the formula (2):
   

   

   [During the ceremony:
   R ^{2, R 3} and ^{R 4} are the same or different, a hydroxyl group, a hydrolyzable group or an alkyl group having 1 to 4 carbon atoms, provided ^that at least one hydroxyl group of R 2, ^{R 3} and ^{R 4} Or a hydrolyzable group;
   R ⁵ is a group containing a polymerizable unsaturated bond. ]
   The composition for forming a fluorine-containing sealing material according to any one of claims 1 to 6, which is a compound represented by.
8. The fluoropolymer represented by (A) has the following formula (5):
   

   

   [During the ceremony:
   X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and CFX ¹ X ² groups (in the formula, X ¹ and X ² are the same or different, hydrogen atom, fluorine atom or chlorine atom. ), Cyan group, linear or branched fluoroalkyl group having 1 to 21 carbon atoms, substituted or unsubstituted benzyl group, substituted or unsubstituted phenyl group, linear or linear or branched group having 1 to 20 carbon atoms. It is a branched alkyl group;
   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, and an oxygen atom. Cyclic aliphatic groups having 6 to 10 carbon atoms which may have, aromatic aliphatic groups having 6 to 10 carbon atoms which may have oxygen atoms, -CH ₂ CH ₂ N (R ¹ ) SO _2- Group (in the formula, R ¹ is an alkyl group having 1 to 4 carbon atoms), -CH ₂ CH (OY ¹ ) CH ₂ -group (in the formula, Y ¹ is a hydrogen atom or an acetyl group. ), Or-(CH ₂ ) _n SO ₂ -group (in the formula, n is 1-10);
   Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms;
   R ^{2, R 3} and ^{R 4} are the same or different, an alkyl group or an alkoxy group having 1 to 4 carbon atoms having 1 to 4 carbon atoms, provided ^that at least one of R 2, ^{R 3} and ^{R 4} Alkoxy group;
   R 5 ^'is an trivalent group derived from a group containing a polymerizable unsaturated bond;
   l and m are integers of 1 or more, respectively, and the total of l and m is a numerical value in which the weight average molecular weight of the fluoropolymer has a weight average molecular weight of 3,000 to 500,000, and l and m are added. The order of existence of each repeating unit enclosed in parentheses is arbitrary in the formula. ]
   The composition for forming a fluorine-containing sealing material according to any one of claims 1 to 7, which has a structural portion represented by.
9. The composition for forming a fluorine-containing sealant according to any one of claims 1 to 8, wherein the monomer component of the fluorine-containing polymer shown in (B) further contains a Si atom-containing polymerizable monomer.
10. In the fluoropolymer shown in (B), the Si atom-containing mercaptan is of the formula (3):
    

    

    [During the ceremony:
    R ⁷ , R ⁸ and R ⁹ are the same or different hydroxyl groups, hydrolyzable groups or alkyl groups having 1 to 4 carbon atoms, except that at least one of R ⁷ , R ⁸ and R ⁹ is a hydroxyl group. Or a hydrolyzable group;
    R ¹⁰ is a linear alkylene group having 1 to 12 carbon atoms. ]
    The composition for forming a fluorine-containing sealing material according to any one of claims 1 to 9, which is a compound represented by.
11. The fluoropolymer represented by (B) has the following formula (6):
    

    

    [During the ceremony:
    X is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and CFX ¹ X ² groups (in the formula, X ¹ and X ² are the same or different, hydrogen atom, fluorine atom or chlorine atom. ), Cyan group, linear or branched fluoroalkyl group having 1 to 21 carbon atoms, substituted or unsubstituted benzyl group, substituted or unsubstituted phenyl group, linear or linear or branched group having 1 to 20 carbon atoms. It is a branched alkyl group;
    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, and an oxygen atom. Cyclic aliphatic groups having 6 to 10 carbon atoms which may have, aromatic aliphatic groups having 6 to 10 carbon atoms which may have oxygen atoms, -CH ₂ CH ₂ N (R ¹ ) SO _2- Group (in the formula, R ¹ is an alkyl group having 1 to 4 carbon atoms), -CH ₂ CH (OY ¹ ) CH ₂ -group (in the formula, Y ¹ is a hydrogen atom or an acetyl group), Or-(CH ₂ ) _n SO ₂ -group (in the formula, n is 1-10);
    Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms;
    R ⁷ , R ⁸ and R ⁹ are identical or different alkyl groups having 1 to 4 carbon atoms or alkoxy groups having 1 to 4 carbon atoms, and at least one of R ⁷ , R ⁸ and R ⁹ is an alkoxy group. Is;
    R ¹⁰ is a linear alkylene group having 1 to 12 carbon atoms;
    k is a numerical value in which the weight average molecular weight of the fluoropolymer has a weight average molecular weight of 3,000 to 500,000. ]
    The composition for forming a fluorine-containing sealing material according to any one of claims 1 to 10, which is a compound represented by.
12. (III) The composition for forming a fluorine-containing sealant according to any one of claims 1 to 11, further comprising a fluorine-based solvent.
13. The composition for forming a fluorine-containing sealant according to claim 12, wherein the fluorine-based solvent is at least one selected from the group consisting of hydrofluoroethers, hydrofluorocarbons, and perfluorocarbons.
14. An article containing a sealing material formed by using the composition for forming a fluorine-containing sealing material according to any one of claims 1 to 13.
15. The article according to claim 14, which is an electronic member.
16. The article according to claim 15, which is an electronic device including an electronic member.