TW201815885A - Photocurable fluoropolyether rubber composition and cured product thereof - Google Patents

Abstract

Provided are a photocurable fluoropolyether-based rubber composition with reduced foaming of rubber during sealed curing and a cured product of the photocurable fluoropolyether-based rubber composition in the photocurable fluoropolyether-based rubber composition using a photoactive hydrosilylation reaction catalyst. The photocurable fluoropolyether-based rubber composition of the present invention comprises: 100 parts by mass of a linear polyfluoro compound (A) which not only has two or more alkenyl groups in one molecule, but also has a linear perfluoropolyether structure in a main chain thereof; a fluorine-containing organohydrogenpolysiloxane (B) having 40 mass% or more of a fluorine content as well as two or more hydrogen atoms (Si-H group) directly coupled to a silicon atom in one molecule in an amount in which the Si-H group in the component (B) becomes 0.5 to 3 moles with respect to 1 mole of an alkenyl group in the component (A); and the photoactive hydrosilylation reaction catalyst (C) in an amount corresponding to 0.1 to 500 ppm in terms of metal atoms with respect to the mass of the component (A).

Description

   Photocurable fluoropolyether rubber composition and its cured product   

The present invention relates to a light-curable fluoropolyether-based rubber composition and a cured product thereof, in which the foaming of a rubber in an airtight curing system is improved and cured by irradiation with light, particularly ultraviolet rays.

Heat-curable fluoropolyether-based rubber compositions have been well-balanced in properties such as heat resistance, low temperature resistance, chemical resistance, solvent resistance, and oil resistance, and have excellent characteristics. Therefore, they have been used mainly in the automotive industry. Wide fields (Patent Documents 1, 2, and 3: Japanese Patent Laid-Open No. 2001-192,546, Japanese Patent No. 3,646,775, and Japanese Patent No. 4,016,239). However, since the above heat-curable composition requires heating in order to obtain a cured product, it has a large space for installing a heating furnace, and is difficult to apply to large parts or non-heatable parts that cannot be placed in a heating furnace. Problems such as lower productivity and lower productivity.

On the other hand, a fluoropolyether-based rubber composition of room temperature curing type has been found. As such a composition, a condensation curing type and a fluorene crosslinked type have been invented at present. These compositions are used to obtain hardened materials without heat treatment, and the obtained hardened materials are excellent in heat resistance, low temperature resistance, chemical resistance, solvent resistance, and oil resistance, so they are expected to be applied in various fields (Patent Document 4) , 5, 6, 7 and 8: Japanese Patent No. 3,232,221, Japanese Patent No. 3,183,624, Japanese Patent No. 3,350,347, Japanese Patent No. 3,617,568, Japanese Patent No. 5,146,690). However, the conventional room-temperature-curable rubber composition has a problem in terms of both storage stability and quick-curing properties, such as thickening over time during storage and requiring 24 hours or more for curing.

On the other hand, among silicone elastomer materials, it is known to use a photoactive silylation reaction catalyst that is activated by irradiation with UV light of 230 to 400 nm, and has sufficient storage properties in the absence of light. A photocurable composition having good curability when irradiated with light (Patent Documents 9 and 10: Japanese Patent No. 5,384,524, Japanese Patent No. 5,342,830). However, in the case of the above-mentioned photocurable silicone elastomer, there are problems such as insufficient chemical resistance, solvent resistance, and oil resistance depending on the application.

By changing the conventionally known thermally curable fluoropolyether-based rubber composition's hydrosilylation reaction catalyst to the aforementioned photoactive type hydrosilylation reaction catalyst, it is possible to obtain photohardenability having both storage stability and quick-hardening property. A fluoropolyether-based rubber composition. However, when the composition is hardened in a closed system at room temperature after light irradiation, it causes problems such as foaming of rubber, poor appearance, and unstable physical properties.

    [Previous Technical Literature]         [Patent Literature]    

[Patent Document 1] Japanese Patent Laid-Open No. 2001-192,546

[Patent Document 2] Japanese Patent No. 3,646,775

[Patent Document 3] Japanese Patent No. 4,016,239

[Patent Document 4] Japanese Patent No. 3,232,221

[Patent Document 5] Japanese Patent No. 3,183,624

[Patent Document 6] Japanese Patent No. 3,350,347

[Patent Document 7] Japanese Patent No. 3,617,568

[Patent Document 8] Japanese Patent No. 5,146,690

[Patent Document 9] Japanese Patent No. 5,384,524

[Patent Document 10] Japanese Patent No. 5,342,830

The present invention has been made in view of the above-mentioned facts, and provides a photocurable fluoropolyether-based rubber composition using a photoactive type hydrosilylation reaction catalyst to reduce photo-curable fluoropolyethers that are used for rubber foaming during closed curing. It is intended to be a rubber composition and a cured product thereof.

As a result of diligent research in order to solve the above-mentioned problems, the present inventors have found that a linear polyfluoro compound containing a specified amount of (A) 1 molecule having two or more alkenyl groups and having a perfluoropolyether structure in the main chain, (B ) Fluorine-containing organohydrogenpolysiloxane and (A) having good solubility in component (A) by having more than two hydrogen atoms directly bonded to silicon atoms in a molecule and having a specific amount of fluorine content or more C) A photoactive curable fluoropolyether-based rubber composition that is a photoactive type hydrosilylation catalyst, which can suppress foaming of the rubber during the aforementioned closed curing, and completed the present invention.

In addition, in the present invention, the "linear linear polyfluoro compound", "linear linear perfluoropolyether structure", or "linear linear perfluoropolyether group" means a divalent perfluoropolyether structure constituting the main chain. Fluorooxyalkylene repeating units are bonded to each other to form a linear chain. Individual divalent fluorooxyalkylene units may be linear fluorooxyalkylene units, or may be-[CF ₂ CF (CF ₃ ) O]-and other fluorooxyalkylene units having a branched structure.

Therefore, the present invention provides the following photocurable fluoropolyether rubber composition and its cured product.

[1] A photocurable fluoropolyether-based rubber composition, characterized in that it contains (A) a linear polyfluoride having two or more alkenyl groups in one molecule and a linear perfluoropolyether structure in the main chain. Fluorine compound: 100 parts by mass of fluorine-containing organic hydrogen polysiloxane containing 1 or more hydrogen atoms (Si-H groups) directly bonded to a silicon atom in a molecule of (B) and having a fluorine content of 40% by mass or more: The amount of the Si-H group in the component (A) is 0.5 to 3 moles relative to 1 mole of the alkenyl group in the component (A), and (C) the photoactive type hydrosilylation catalyst: A) The mass of the component is 0.1 to 500 ppm in terms of metal atoms.

[2] The photocurable fluoropolyether-based rubber composition according to [1], wherein the fluorine-containing organohydrogen polysiloxane of the component (B) is 1 mole relative to the alkenyl group in the component (A), When the amount of Si-H groups in the component (B) becomes 0.5 to 3 moles, the component (A) can be uniformly and transparently dispersed in the component (A).

[3] The photocurable fluoropolyether-based rubber composition according to [1] or [2], wherein the component (A) is a linear polyfluoro compound represented by the following formula (1), and CH ₂ = CH- (X) _a -Rf ^1- (X ') _a -CH = CH ₂ (1)

[In formula (1), X is -CH _2- , -CH ₂ O-, -CH ₂ OCH _2- , or -Y-NR ¹ -CO- [herein, Y is -CH _2- , -Si (CH ₃ ) ₂ CH ₂ CH ₂ CH _2- , -Si (CH ₃ ) (CH = CH ₂ ) CH ₂ CH ₂ CH _2- , -Si (CH = CH ₂ ) ₂ CH ₂ CH ₂ CH ₂ -or the following Structural formula (Z) (In formula (Z), R ³ and R ⁴ are each independently -CH ₃ or -CH = CH _2. )

The o-, m- or p-silylphenylene group shown, and R ¹ is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group. ], X 'is -CH _2- , -OCH _2- , -CH ₂ OCH ₂ -or -CO-NR ² -Y'- [here, Y' is -CH _2- , -CH ₂ CH ₂ CH ₂ Si (CH ₃ ) _2- , -CH ₂ CH ₂ CH ₂ Si (CH ₃ ) (CH = CH ₂ )-, -CH ₂ CH ₂ CH ₂ Si (CH = CH ₂ ) ₂ -or the following structural formula ( Z') (In the formula (Z '), R ^3' and R ^{4 '} are independent of each other and are -CH ₃ or -CH = CH _2. ) O-, m-, or p-silylphenylene represented by R, and R ² is hydrogen Atomic or unsubstituted or substituted monovalent hydrocarbon group. 〕. a is independently 0 or 1. Rf ¹ is the following formula (i) or (ii) (In formula (i), p and q are each an integer of 0 or 1 to 150, and the average of the sum of p and q is 2 to 200. r is an integer of 0 to 6, and t is 2 or 3.)

(In formula (ii), u is an integer of 1 to 200, v is an integer of 1 to 50, and t is 2 or 3.) A divalent linear perfluoropolyether group represented by the formula. A

[4] The photocurable fluoropolyether-based rubber composition according to any one of [1] to [3], in which the fluorine-containing organic hydrogen polysiloxane containing component (B) has one or more in one molecule One of a monovalent perfluoroalkyl group, a monovalent perfluorooxyalkyl group, a divalent perfluoroalkylene group, or a divalent perfluorooxyalkylene group.

[5] The photocurable fluoropolyether-based rubber composition according to any one of [1] to [4], wherein the photoactive silylation reaction catalyst of the component (C) is (η ⁵ -cyclopentane Alkenyl) tri (σ-alkyl) platinum (IV) complex compound and / or β-diketoplatinum (II) complex compound.

[6] The photocurable fluoropolyether-based rubber composition according to any one of [1] to [5], which further has a BET specific surface area of 0.5 to 30 parts by mass relative to 100 parts by mass of the component (A) as 50m2 / g or more of hydrophobic silica powder as the component (D).

[7] The photocurable fluoropolyether-based rubber composition according to any one of [1] to [6], which further contains a reaction control agent for a hydrosilylation reaction as the (E) component.

[8] A fluoropolyether rubber composed of a cured product of the photocurable fluoropolyether rubber composition according to any one of [1] to [7].

According to the present invention, it is possible to provide a photocurable fluoropolyether-based rubber composition and a cured product thereof that reduce rubber foaming during hermetic curing. By reducing the foaming of the rubber, the physical properties of the rubber obtained during hermetic curing can be stabilized.

     [Best Mode for Implementing Invention]     

The present invention is described in detail below, but the present invention is not limited to these.

     [(A) Linear Polyfluoro Compound]     

The component (A) in the photocurable fluoropolyether rubber composition of the present invention is used as a main agent (matrix polymer) of the composition of the present invention, and has two or more alkenyl groups in one molecule and A linear polyfluoro compound having a linear perfluoropolyether structure in the main chain. Here, the number of alkenyl groups is preferably from 2 to 30, especially from 2 to 6.

The component (A) is particularly preferably a linear polyfluoro compound represented by the following formula (1).

CH ₂ = CH- (X) _a -Rf ^1- (X ') _a -CH = CH ₂ (1) [In formula (1), X is -CH _2- , -CH ₂ O-, -CH ₂ OCH ₂ -or -Y-NR ¹ -CO- [here, Y is -CH _2- , -Si (CH ₃ ) ₂ CH ₂ CH ₂ CH _2- , -Si (CH ₃ ) (CH = CH ₂ ) CH ₂ CH ₂ CH _2- , -Si (CH = CH ₂ ) ₂ CH ₂ CH ₂ CH ₂ -or the following structural formula (Z) (In formula (Z), R ³ and R ⁴ are each independently -CH ₃ or -CH = CH _2. ) O-, m- or p-silylphenylene represented by R-, and R ¹ is a hydrogen atom or Substituted or substituted monovalent hydrocarbon group. ], X 'is -CH _2- , -OCH _2- , -CH ₂ OCH ₂ -or -CO-NR ² -Y'- [here, Y' is -CH _2- , -CH ₂ CH ₂ CH ₂ Si (CH ₃ ) _2- , -CH ₂ CH ₂ CH ₂ Si (CH ₃ ) (CH = CH ₂ )-, -CH ₂ CH ₂ CH ₂ Si (CH = CH ₂ ) ₂ -or the following structural formula ( Z') (In the formula (Z '), R ^3' and R ^{4 '} are independent of each other and are -CH ₃ or -CH = CH _2. ) O-, m-, or p-silylphenylene represented by R, and R ² is hydrogen Atomic or unsubstituted or substituted monovalent hydrocarbon group. 〕. a is independently 0 or 1. Rf ¹ is the following formula (i) or (ii) (In formula (i), p and q are each an integer of 0 to 150, preferably an integer of 1 to 150, and the average of the sum of p and q is 2 to 200. r is an integer of 0 to 6, and t is 2 or 3.)

(In the formula (ii), u is an integer of 1 to 200, v is an integer of 1 to 50, and t is 2 or 3.) The divalent linear perfluoropolyether group represented by the formula is preferably one having A divalent linear perfluoropolyether group of-[CF ₂ CF (CF ₃ ) O]-with a branched structure of fluorooxyalkylene units. A

Here, R ¹ and R ² are preferably a hydrogen atom, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and particularly 1 to 10, and specifically, the monovalent hydrocarbon group may be, for example, a methyl group. , Ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, etc .; aryl groups such as phenyl, tolyl; aralkyl groups such as benzyl, phenylethyl, and the like A substituted monovalent hydrocarbon group, etc., in which a part of or all of the hydrogen atoms are replaced by halogen atoms such as fluorine.

Rf ¹ in the above formula (1) is a divalent linear perfluoropolyether group, and is preferably a group represented by the following formula (i) or (ii). More preferred is a divalent linear perfluoropolyether group containing-[CF ₂ CF (CF ₃ ) O]-containing a fluorooxyalkylene unit having a branched structure.

(In formula (i), p and q are each an integer of 0 to 150, preferably an integer of 1 to 150, more preferably an integer of 10 to 100, and the average of the sum of p and q is 2 to 200. It is preferably 20 to 160. Also, r is an integer of 0 to 6, preferably an integer of 0 to 4, and t is 2 or 3.)

(In formula (ii), u is an integer of 1 to 200, preferably an integer of 20 to 160, v is an integer of 1 to 50, preferably an integer of 5 to 40, and t is 2 or 3.)

As a preferable example of the Rf ¹ group, the following three may be mentioned. Among them, the divalent base of the first structure is particularly preferred.

(In the formula, p1 and q1 are each an integer of 1 to 150, and p1 + q1 (average) = 2 to 200. L is an integer of 2 to 6.)

(In the formula, p2 and q2 are each an integer of 1 to 150, and p2 + q2 (average) = 2 to 200. L is an integer of 2 to 6.)

(In the formula, u1 is an integer from 1 to 200, and v1 is an integer from 1 to 50.)

As a preferable example of a component (A), the compound represented by following formula (2) is mentioned, for example.

[In formula (2), X ¹ is -CH _2- , -CH ₂ O-, -CH ₂ OCH _2- , or -Y-NR ¹¹ -CO- (Y is the same as above, R ¹¹ is a hydrogen atom, a methyl group, Phenyl or allyl.) X ¹ 'is -CH _2- , -OCH _2- , -CH ₂ OCH ₂ -or -CO-NR ¹² -Y'- (R ^{12 is the} same as R ¹¹ Y ′ is the same as the foregoing.), A is independently 0 or 1, L is an integer of 2 to 6, p3 and q3 are each an integer of 1 to 150, and p3 + q3 (average) = 2 to 200. A

Specific examples of the linear polyfluoro compound represented by the formula (1) include those represented by the following formula.

(In the formula, p 'and q' are each an integer of 1 to 150, and p '+ q' (average) = 6 to 200.)

(In the formula, p 'and q' are each an integer of 1 to 150, and p '+ q' (average) = 6 to 200.)

(In the formula, p 'and q' are each an integer of 1 to 150, and p '+ q' (average) = 6 to 200.)

(In the formula, p "and q" are each an integer of 1 to 150, and p "+ q" (average) = 2 to 200.)

The amount of alkenyl groups contained in the linear polyfluoro compound represented by formula (1) is preferably 0.005 to 0.050 moles / 100g, and more preferably 0.007 to 0.040 moles / 100g. If the amount of alkenyl groups contained in the linear polyfluoro compound is too small, the physical strength of the cured product may be reduced, and the cured product may not be obtained. When the amount of alkenyl groups is too large, the obtained hardened product may become brittle and easily fracture, and the light transmittance of the polymer may be reduced, and a sufficiently hardened product may not be obtained.

In addition, the viscosity (23 ° C) of the linear polyfluoro compound of formula (1) is preferably 100 to 100,000 mPa. s, more preferably 500 ~ 50,000mPa. s. Even better is 1,000 ~ 20,000mPa. within s. When the photocurable fluoropolyether-based rubber composition having a viscosity within this range is used for sealing, embedding, coating, impregnation, etc., the photocured product has suitable physical properties and is preferred. The linear polyfluoro compound of the formula (1) is selected with the most suitable viscosity depending on the application. At this time, a polymer with a low viscosity and a polymer with a high viscosity may be mixed and adjusted to a desired viscosity and used.

In the present invention, the viscosity (23 ° C) can be measured by a rotary viscometer (for example, BL type, BH type, BS type, cone plate type, rheometer, etc.), but it is particularly limited in accordance with JIS K7117-1. The conditions are preferably determined. The repeating number (or degree of polymerization) of each perfluorooxyalkylene repeating unit in the linear perfluoropolyether structure constituting the main chain of the linear polyfluoro compound is usually a fluorine-based solvent as the developing solvent. It is calculated by polystyrene-equivalent number average polymerization degree (or number average molecular weight) and the like analyzed by colloidal permeation chromatography (GPC).

Furthermore, in the present invention, in order to adjust the linear polyfluoro compound of formula (1) to a desired number average molecular weight or weight average molecular weight according to the purpose, the linear perfluoropolyether compound may be contained in the molecule in advance. Two hydrosilyl (Si-H group) organosilicon compounds are subjected to a hydrosilylation reaction under normal methods and conditions, and a product having a chain length extension is used as the component (A).

These linear polyfluoro compounds can be used singly or in combination of two or more kinds.

     [(B) Fluorine-Containing Organic Hydrogen Polysiloxane]     

(B) The component is a fluorine-containing organic group (for example, a monovalent or divalent fluorine-containing hydrocarbon group which may also contain an oxygen atom), usually having one or more, and preferably 1 to 10 molecules in one molecule, and has two or more Fluorine-containing organic hydrogen polysilicon, preferably 3 to 50 hydrogen atoms directly bonded to a silicon atom (that is, a hydrosilyl group shown by Si-H), and having a fluorine content of 40% by mass or more in the molecule It is preferred that the oxane has a function as a crosslinking agent and / or a chain length extender as the component (A), and is preferably a component that is soluble in the component (A). Herein, "soluble" in the component (A) means that at room temperature (23 ° C ± 10 ° C), the component (A) and the component (B) are mixed with each other relative to the alkenyl group contained in the component (A). In the ear, when the Si-H group in the component (B) is mixed in an amount of 0.5 to 3 moles, the component (B) can be transparently and uniformly dispersed (mixed) in the component (A).

The component (B) has compatibility with (A) component, dispersibility, uniformity after hardening, etc., and has one or more monovalent perfluoroalkyl groups and monovalent perfluorooxyalkyl groups in one molecule. Fluorine-containing groups such as divalent perfluoroalkylene or divalent perfluorooxyalkylene are preferred. The monovalent or divalent fluorinated organic group may be represented by the following formula such as perfluoroalkyl, perfluorooxyalkyl, perfluoroalkylene, and perfluorooxyalkylene.

C _g F _{2g + 1-}

-C _g F _2g- (where g is an integer from 1 to 20, preferably an integer from 4 to 6.)

(In the formula, f is an integer of 1 to 200, preferably an integer of 1 to 100, and h is an integer of 1 to 3.)

(In the formula, i and j are each an integer of 1 or more, preferably an integer of 1 to 100, and the average of i + j is 2 to 200, preferably 2 to 100.)

-(CF ₂ O) _d- (CF ₂ CF ₂ O) _e -CF _2- (In the formula, d and e are each an integer of 1-50, preferably an integer of 1-40.)

The above-mentioned perfluoroalkyl group, perfluorooxyalkyl group, perfluoroalkylene group, or perfluorooxyalkylene group and the silicon atom in the component (B) are preferably connected by a divalent bonding group. As for the bonding group, it may be an alkylene group, an alkylene group, or a combination thereof, or these groups may intervene in an ether bond oxygen atom, an amidine bond, a carbonyl bond, an ester bond, or a diorganosilylene group. ) And the like include, for example, a divalent bond group having 2 to 12 carbon atoms as described below.

-CH ₂ CH _2- , -CH ₂ CH ₂ CH _2- , -CH ₂ CH ₂ CH ₂ O-, -CH ₂ CH ₂ CH ₂ OCH _2- , -CH ₂ CH ₂ CH ₂ -NH-CO-, -CH ₂ CH ₂ CH ₂ -N (Ph) -CO-, -CH ₂ CH ₂ CH ₂ -N (CH ₃ ) -CO-, -CH ₂ CH ₂ CH ₂ -N (CH ₂ CH ₃ ) -CO -, -CH ₂ CH ₂ -Si (CH ₃ ) ₂ -Ph'-N (CH ₃ ) -CO-, -CH ₂ CH ₂ CH ₂ -Si (CH ₃ ) ₂ -Ph'-N (CH ₃ ) -CO-, -CH ₂ CH ₂ CH ₂ -O-CO- (In the formula, Ph is phenyl and Ph 'is phenylene.)

The (B) component of the fluorine-containing organohydrogen polysiloxane is bonded to the monovalent substituent of the silicon atom other than the monovalent or divalent fluorine-containing organic group and the hydrogen atom of the silicon atom. , For example, methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, decyl and other alkyl groups; vinyl, allyl and other alkenyl groups; phenyl, tolyl, naphthyl Aryl groups such as benzyl, arylalkyl such as phenylethyl, and some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as chlorine atom, cyano, etc. such as chloromethyl, chloropropyl Non-substituted or substituted (especially halogen atom or cyano) monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms such as cyanoethyl.

(B) The fluorine content in the fluorine-containing organohydrogen polysiloxane must be 40% by mass or more, preferably 40 to 80% by mass, more preferably 40 to 70% by mass, and even more preferably 40.5 to 68% by mass. %. If it is lower than this fluorine content, there is a possibility that the compatibility with the component (A) is insufficient, and foaming of the rubber may occur during hermetic curing.

Moreover, the fluorine-containing organohydrogenpolysiloxane of the component (B) may be any of a ring, a chain, a three-dimensional network, and a combination thereof. Although the number of silicon atoms of the fluorine-containing organic hydrogen polysiloxane is not particularly limited, it is usually 2 to 60, preferably about 3 to 30.

Examples of the component (B) having a monovalent or divalent fluorine-containing organic group and a silicon atom bonded to a hydrogen atom include the following compounds. Next to the compound formula, the fluorine content is described. These compounds may be used alone or in combination of two or more. In the following formula, Me is a methyl group and Ph is a phenyl group. In addition, the following fluorine content (%) is "mass%".

The amount of Si-H groups contained in the fluorine-containing organohydrogen polysiloxane of the component (B) is preferably 0.00050 to 0.01000 mol / g, and more preferably 0.00100 to 0.00800 mol / g. If the amount of Si-H groups contained in the fluorine-containing organohydrogen polysiloxane is too small, the crosslinking density may become insufficient and the physical properties of the obtained hardened product may be reduced. Conversely, if the amount of Si-H groups is too large, it may be hardened. When things become brittle and easily break.

The blending amount of the component (B) is 1 mole relative to the alkenyl group such as vinyl, allyl, and cycloalkenyl contained in the component (A), and the hydrosilyl group in the (B) component, that is, Si The -H group is 0.5 to 3 moles, preferably 0.8 to 2 moles. As a result of too few hydrosilyl groups (≡Si-H) and insufficient crosslinking density, there is a possibility that a photocured material cannot be obtained, and if too many hydrosilyl groups, the photocurable fluoropolyether rubber composition is hardened. The possibility of foaming.

     [(C) Photoactive type hydrosilylation catalyst]     

The component (C) is a photoactive type hydrosilylation catalyst. The photoactive silylation catalyst is activated by irradiation of light, especially ultraviolet rays of 300 to 400 nm, in order to promote the reaction between the addition reaction of the alkenyl group in the component (A) and the hydrosilyl group in the component (B). Media. The photoactive type hydrosilylation catalysts are mainly platinum group metal catalysts or nickel metal catalysts. In terms of platinum group metal catalysts, there are platinum, palladium and rhodium metal complex compounds. Nickel-based metal catalysts include nickel-, iron-, and cobalt-based metal complex compounds. Among them, platinum-based metal complex compounds are relatively easy to obtain and exhibit good catalyst activity.

As for the photoactive platinum-based metal complex compound, for example, (η ⁵ -cyclopentadienyl) tris (σ-alkyl) platinum complex compound or β-diketone platinum complex compound, etc. Specifically, for example, (methylcyclopentadienyl) trimethyl platinum (IV), (cyclopentadienyl) trimethyl platinum (IV), (1,2,3,4,5-penta (Methylcyclopentadienyl) trimethyl platinum (IV), (cyclopentadienyl) dimethylethyl platinum (IV), (cyclopentadienyl) dimethylacetamido platinum (IV) , (Trimethylsilylcyclopentadienyl) trimethyl platinum (IV), (methoxycarbonyl cyclopentadienyl) trimethyl platinum (IV), (dimethylphenylsilyl cyclopentyl) Dienyl) trimethylcyclopentadienyl platinum (IV), trimethyl (acetamone) platinum (IV), trimethyl (3,5-heptanedione acid) platinum (IV), three Methyl (ethyl acetoacetate) platinum (IV), bis (2,4-pentanedione acid) platinum (II), bis (2,4-hexanedione acid) platinum (II), bis ( 2,4-heptanedione acid) platinum (II), bis (3,5-heptanedione acid) platinum (II), bis (1-phenyl-1,3-butanedione acid) platinum (II), bis (1,3-diphenyl-1,3-propanedione acid) platinum (II), bis (hexafluoroacetamidoacetone) platinum (II), and the like.

In the use of these catalysts, they can also be used in a solid state when they are solid catalysts. However, in order to obtain a more uniform hardened product, those who dissolve the catalyst in a suitable solvent are dissolved in the linear polymer of the component (A). It is preferred to use a fluorine compound.

The type of the solvent to be used is not particularly limited as long as it dissolves the catalyst. A solvent in which a part of hydrogen atoms of a hydrocarbon group is replaced by a fluorine atom, or a solvent in which a part of hydrogen atoms of a hydrocarbon group is replaced by a fluorine atom is used. A mixed solvent of a solvent in which all of the atoms are replaced by fluorine atoms is more advantageous in that the catalyst can be more uniformly dispersed in the composition.

Examples of the solvent in which a part of the hydrogen atom of the hydrocarbon group is replaced by a fluorine atom include 1,3-bis (trifluoromethyl) benzene, 1,2-bis (trifluoromethyl) benzene, and 1,4-bis (trifluoromethyl) benzene. Fluoromethyl) benzene, 1-methyl-3- (pentafluoroethyl) benzene, 1,1,1-trifluoro-3- [3- (trifluoromethyl) phenyl] propane-2-one, 4-fluoro-3- (trifluoromethyl) benzoic acid methyl ester, heptafluorobutyric acid n-butyl ester, 3,5-bis (trifluoromethyl) benzoic acid ethyl ester, 2-methyl-5- (tri Fluoromethyl) benzaldehyde, 2,3-dimethoxybenzotrifluoride, and the like.

Examples of solvents in which all hydrogen atoms of the hydrocarbon group are replaced by fluorine atoms include octafluorotoluene, (1,1,2,3,3,3-hexafluoropropoxy) perfluorobenzene and pentafluoroethyl. 2,2,2-trifluoroethyl ether, Fluorinert (manufactured by 3M), PF5060 (manufactured by 3M), perfluoropolyether oligomer, and the like.

When a catalyst is used as the solution, a preferable mixing ratio of the polymer of the component (A) and the catalyst solution is in a range of 100: 0.01 to 100: 1 (mass ratio). When the addition amount of the catalyst solution is more than this range, the physical properties of the photocured material may be reduced. On the other hand, when the amount of the catalyst solution is less than this range, the catalyst may be dispersed to the photocurable fluoropolyether rubber composition Bad possibility. Therefore, the concentration of the catalyst solution may be appropriately adjusted within the range of the mixing ratio.

The amount of the component (C) relative to the mass of the component (A) is 0.1 to 500 ppm, preferably 1 to 500 ppm, based on the mass conversion of the metal atom (especially the mass conversion of the platinum group metal atom or the mass conversion of the nickel-based metal atom). ~ 100ppm. If the amount is too small, the photocurable fluoropolyether-based rubber composition may not be able to obtain sufficient photocurability, while if the amount is too large, the heat resistance of the photocured material may be adversely affected.

     [(D) Hydrophobic silica powder]     

In the photocurable fluoropolyether-based rubber composition of the present invention, any component that can be added as necessary can be added to the hydrophobic silica dioxide powder of the component (D) as a filler without impairing the effect range of the present invention. . Thereby, it is possible to impart appropriate physical strength to the photocured material obtained by the photocurable fluoropolyether-based rubber composition of the present invention. As for the hydrophobic silica powder, it is preferable to hydrophobize a fine powder silica having a BET specific surface area of 50 m ² / g or more, particularly 50 to 400 m ² / g.

When the BET specific surface area is less than 50 m ² / g, the desired physical strength of the obtained photocured material may not be obtained. When the BET specific surface area exceeds 400 m ² / g, the kneading process becomes difficult and there is a possibility that the hardenability due to light is significantly reduced. In terms of fine powdered silica, such as aerosolized silica (dry silica), sedimentary silica (wet silica), colloidal silica, etc., among them, aerosolized silica optimal.

In addition, as for the hydrophobizing treatment agent for the finely powdered silicon dioxide, for example, organochlorosilane, organic disilazane, cyclic organic polysilazane, linear organic polysiloxane, etc. Chlorosilane, organic disilazane, and cyclic organic polysilazane are preferred.

The blending amount of the component (D) is in the range of 0 to 30 parts by mass, preferably 0.5 to 30 parts by mass, and more preferably 1 to 25 parts by mass with respect to 100 parts by mass of the component (A). If the blending amount is less than 0.5 parts by mass, the physical properties of the obtained photocured material may not be adjusted. On the other hand, if it exceeds 30 parts by mass, the fluidity of the photocurable fluoropolyether rubber composition may be deteriorated. , The situation of photo-hardening is also significantly reduced.

     [(E) Reaction control agent]     

In the photocurable fluoropolyether-based rubber composition of the present invention, further optional components can be added as necessary, so as not to impair the effect of the present invention, a conventionally known reaction control agent for the hydrosilylation reaction can be blended as ( E) ingredients. Thereby, the photocurable fluoropolyether-based rubber composition can obtain better storage stability. For reaction control agents, for example, 1-ethynyl-1-hydroxycyclohexane, 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3 -Methyl-1-pentene-3-ol, alkynol such as phenylbutynol or 3-methyl-3-pentene-1-yne, 3,5-dimethyl-3-hexene- 1-alkynes and the like. Further, as the reaction control agent, a fluorine-containing alkynol compound represented by the following structural formula, a polymethylvinylsiloxane ring compound, an organic phosphorus compound, or the like may be used.

These reaction control agents have different control abilities due to their chemical structures, so the added amounts should be adjusted to their optimal amounts. Generally, if the addition amount of the reaction control agent is too small, the long-term storage properties of the photocurable fluoropolyether rubber composition cannot be obtained at room temperature. There is a possibility that the hardenability of the material is passivated and sufficient hardenability cannot be obtained.

     〔Other ingredients〕     

In order to improve the practicality of the photocurable fluoropolyether rubber composition of the present invention, in addition to the components (A) to (E), a plasticizer, a viscosity modifier, a flexibility imparting agent, etc. may be added as necessary. Various admixtures such as inorganic fillers, adhesion promoters, adhesion promoters, and silane coupling agents. The blending amount of these additives is arbitrary as long as the effect of the present invention is not impaired, and the characteristics of the photocurable fluoropolyether-based rubber composition and the physical properties of the photocured material are not impaired.

As the plasticizer, viscosity adjuster, and flexibility imparting agent of optional components that can be added as necessary, a polyfluoromonoalkenyl compound represented by the following formula (3) and / or the following formula (4) or ( 5) The linear polyfluoro compound represented by

Rf ^2- (X ') _b CH = CH ₂ (3) [In the formula (3), X' is the same as above, Rf ² is the following formula (iii), and b is 0 or 1.

(In formula (iii), f1 is an integer of 1 or more, preferably an integer of 2 to 100, t is 2 or 3, and f1 is p + q (average) with respect to the Rf ¹ group of the above (A) component And the sum of r and any of the sum of u and v is preferably small.)]

DO- (CF ₂ CF ₂ CF ₂ O) _c1 -D (4) (In formula (4), D is the formula: C _s F _{2s + 1-} (s is 1 ~ 3), c1 is 1 An integer of ~ 200, preferably an integer of 2 ~ 100, and c1 is any ^one of the p + q (average) and the sum of r and the sum of u and v of the Rf ¹ group than the aforementioned (A) component. And small is better.)

DO- (CF ₂ O) _d1 (CF ₂ CF ₂ O) _e1 -D (5) (In formula (5), D is the formula: C _s F _{2s + 1-} (s is 1 ~ 3) , D1 and e1 are each an integer of 1 to 200, preferably an integer of 1 to 100, and the sum of d1 and e1 is equal to the sum of p + q (average) and r of the Rf ¹ group than the aforementioned (A) component , And any sum of u and v is preferably small.)

Specific examples of the polyfluoromonoalkenyl compound represented by the above formula (3) include, for example, the following (also, the following f1 'meets the requirements of the above f1).

Specific examples of the linear polyfluoro compound represented by the formulae (4) and (5) include the following (also, the following c1 ′, and the sum of d1 ′ and e1 ′ are in accordance with c1 and d1 described above. And the sum of e1.).

CF ₃ O- (CF ₂ CF ₂ CF ₂ O) _{c1 '} -CF ₂ CF ₃ (where c1' is an integer from 1 to 200.)

CF ₃ O-[(CF ₂ O) _{d1 '} (CF ₂ CF ₂ O) _e1' ] -CF ₃ (where d1 'is an integer from 1 to 200, e1' is an integer from 1 to 200, and d1 ' + e1 '= 2 ~ 201.)

When the compounds of the formulae (3) to (5) are added, the blending amount is preferably 1 to 100 parts by mass of the component (A) in the composition, especially the linear polyfluoro compound of the formula (1). 300 parts by mass, more preferably 50 to 250 parts by mass. In addition, the viscosity (23 ° C) in terms of rotational viscosity is 5 to 100,000 mPa for the same reason as a linear polyfluoro compound. The range of s is better.

In the photocurable fluoropolyether rubber composition of the present invention, an inorganic filler may be blended as an optional component in addition to the hydrophobic silica powder of the component (D), and the inorganic filler may be, for example, quartz powder. , Fused or quasi-reinforcing fillers for fused quartz powder, diatomaceous earth, calcium carbonate, etc., inorganic pigments such as iron oxide, carbon black, cobalt aluminate, titanium oxide, iron oxide, carbon black, cerium oxide, hydrogen Heat-resistance enhancer of cerium oxide, zinc carbonate, magnesium carbonate, manganese carbonate, etc., heat conductivity imparting agent of alumina, boron nitride, silicon carbide, metal powder, etc., conductivity of carbon black, silver powder, conductive zinc oxide, etc. Imparting agent, etc.

Further, in the present invention, if necessary, an adhesion promoter such as a carboxylic anhydride, a titanate, and the like, an adhesion imparting agent, and / or a silane coupling agent may be added.

     [Photocurable fluoropolyether-based rubber composition]     

The photocurable fluoropolyether rubber composition of the present invention can be obtained by combining the components (A) to (C), preferably the components (A) to (D), and more preferably (A) to (E). The ingredients and other arbitrary ingredients are produced by uniformly mixing using a mixing device such as a planetary mixer, a Ross mixer, a Hobart mixer, and a kneading device such as a three-roller as necessary.

The method for producing the photocurable fluoropolyether rubber composition of the present invention is not particularly limited, and it can be produced by kneading the above-mentioned components. In addition, two kinds of compositions can be prepared and mixed during use.

The following is an example of a method for producing a photocurable fluoropolyether rubber composition when the components (A) to (E) are blended. When a composition is produced from the components (A) to (C), the components (A) to (C) may be simply blended and mixed in order.

In the manufacturing method of the photocurable fluoropolyether-based rubber composition containing the components (A) to (E), for example, the component (D) is first heated or unheated with respect to a part or all of the component (A). Blend with the (A) component and heat. Under reduced pressure or heating. The method of kneading the component (A) and the component (D) under pressure, and then finally diluting the remaining component (A) to a specified blending ratio. By this method, the photocuring characteristics of the photocurable fluoropolyether-based rubber composition can be improved.

Here, part or all of the component (A) is blended with the component (D). The kneading is performed so that the surface of the hydrophobic silica powder of the component (D) is sufficiently covered with the linear polyfluoro compound of the component (A). As a result, the component (B) becomes less likely to be adsorbed on the silica surface of the component (D), and the components (B) and (D) become difficult to aggregate with each other, whereby the photocurable fluoropolyether rubber composition The viscosity is reduced and the light hardening is improved. (A) Some or all of the ingredients are blended with (D) ingredients. Kneading can be performed by a kneading device such as a planetary mixer, a frame mixer, a kneader, and the like.

About blending. The temperature and time of kneading may be appropriately determined, but the heat treatment temperature is 120 to 180 ° C. In order to uniformly disperse the components, kneading is preferably performed for 1 hour or more.

Blend. The pressure at the time of kneading varies depending on the device used, so it is better to carry out under pressure or reduced pressure depending on the device. For example, when kneading is performed with a planetary mixer or a frame mixer, the pressure condition is preferably under a reduced pressure of gauge pressure-0.05 MPa or less. When kneading is performed with a kneader, the pressure conditions are preferably under a pressure of 0.4 to 0.6 MPa in gauge pressure. The reason for operating under these conditions is because the component (A) easily wets the surface of the component (D) (easy to apply).

The remainder of the component (A), the component (B), the component (C), and the component (E) are blended with a liquid substrate composed of a part or all of the component (A) and component (D) obtained as described above. ) Component to obtain a photocurable fluoropolyether-based rubber composition.

In addition, when the photocurable fluoropolyether rubber composition of the present invention is used, it can be used in an appropriate fluorine-based solvent such as 1,3-bis (trifluoromethyl) benzene, Fluorinert (3M Co., Ltd.) depending on its use and purpose. (Manufactured), perfluorobutyl methyl ether, perfluorobutyl ethyl ether, perfluoropolyether oligomer, or a mixture thereof, etc., and the composition is dissolved at a desired concentration and used. In particular, it is preferable to use a solvent in a film coating application.

     [Photocuring method of photocurable fluoropolyether-based rubber composition]     

The produced photocurable fluoropolyether-based rubber composition can be cured by light irradiation. During hardening, the maximum peak wavelength of the irradiated light in the emission spectrum is in the range of 300 to 400 nm, and the radiance of each wavelength in the wavelength range shorter than 300 nm is less than 5% of the radiance of the aforementioned maximum peak wavelength, It is preferably 1% or less, more preferably 0.1% or less, that is, the closer to 0, the better. If the light is irradiated in a wavelength range shorter than 300 nm and the irradiance has a wavelength greater than 5% of the aforementioned maximum irradiance, the polymer terminal group may be decomposed and the hardenability may be insufficient.

The active light species used to harden the photocurable fluoropolyether rubber composition of the present invention is not particularly limited, but ultraviolet rays, particularly near ultraviolet rays having a maximum peak wavelength of 300 to 400 nm are preferred. To obtain good UV curable light irradiation amount (illuminance), as the accumulated light quantity of 100 ~ 100,000mJ / cm ^2, preferably 1,000 ~ 10,000mJ / cm ^2, more preferably 5,000 ~ 10,000mJ / cm ^2. When the amount of ultraviolet radiation (illumination) falls below the above range, sufficient energy required to activate the photoactive silylation reaction catalyst in the photocurable fluoropolyether rubber composition cannot be obtained, and sufficient light cannot be obtained Possibility of hardening. In addition, when the amount of ultraviolet radiation (illumination) exceeds the above range, the photocurable fluoropolyether rubber composition is irradiated with more than necessary energy to cause the decomposition of polymer terminal groups, and some catalysts lose their activity. The possibility of light hardening.

The ultraviolet radiation may be light having a plurality of light emission spectrums, or light having a single light emission spectrum. In addition, a single light emission spectrum may be a person having a broad spectrum in a range from 300 nm to 400 nm. The light having a single emission spectrum is light having a peak (that is, a maximum peak wavelength) in a range of 300 nm to 400 nm, preferably 350 nm to 380 nm. As a light source for radiating such light, an ultraviolet light emitting semiconductor element light source such as an ultraviolet light emitting diode (ultraviolet LED) or an ultraviolet light emitting semiconductor laser can be mentioned.

As the light source for radiating light having a plurality of light emission spectrums, for example, a metal halide lamp, a xenon lamp, a carbon arc lamp, a chemical lamp, a sodium lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, etc., a gas laser such as nitrogen Liquid laser of organic pigment solution, solid laser containing rare earth ion in inorganic single crystal, etc.

When the light has a peak in a wavelength range shorter than 300 nm in the emission spectrum, or when a wavelength having a radiance greater than 5% of the radiance of the maximum peak wavelength in the emission spectrum exists in a wavelength range shorter than 300 nm (for example, When the emission spectrum spans a wide wavelength range, the light filter removes light with a wavelength shorter than 300 nm. As a result, the radiation illuminance of each wavelength in a wavelength range shorter than 300 nm can be 5% or less, preferably 1% or less, more preferably 0.1% or less, and more preferably 0% of the radiation illuminance of the maximum peak wavelength. . When there is a complex peak in a wavelength range from 300 nm to 400 nm in the emission spectrum, the peak wavelength showing the maximum absorbance is used as the maximum peak wavelength. The optical filter is not particularly limited as long as it shields a wavelength shorter than 300 nm, and a person skilled in the art can use it. For example, a 365 nm band-pass filter can be used. The illuminance and spectrum distribution of ultraviolet rays can be measured with a spectroradiometer, for example, USR-45D (Bulltail Motor).

The light irradiation device is not particularly limited, and an irradiation device such as a spot type irradiation device, a surface type irradiation device, a line type irradiation device, or a conveyor type irradiation device can be used.

When the photocurable fluoropolyether rubber composition of the present invention is cured, the light irradiation time is, for example, 1 to 300 seconds, preferably 10 to 200 seconds, more preferably 30 to 150 seconds, and light irradiation for 1 to 60 minutes. Then, especially after 5 to 30 minutes, the photocurable fluoropolyether-based rubber composition loses fluidity, and a rubber elastic body (rubber hardened product) can be obtained.

     [Photocurable fluoropolyether-based rubber hardened product]     

The photocurable fluoropolyether-based rubber composition of the present invention containing the above components (A) to (C), preferably (A) to (D), and more preferably (A) to (E) as a main component. By the above-mentioned photo-curing method, a rubber-hardened product having excellent chemical resistance and solvent resistance and low moisture permeability can be formed. Further, even when the rubber is hardened while being sealed, foaming of the rubber can be suppressed. For example, even when the substrate is held and hardened, a rubber hardened product having a smooth surface and providing stable rubber properties can be obtained. Moreover, it can also be used as a rubber-type adhesive which hold | maintains on the base material previously coated with the silane-type primer, hardens | cures, and provides adhesiveness to a base material. In this case, since foaming of the rubber can be suppressed, stable adhesion characteristics can be obtained.

The hardened material can be formed by injecting the photocurable fluoropolyether rubber composition of the present invention into a suitable container or coating it on a suitable substrate and then light-irradiate and harden it. Two transparent substrates can be used. A conventionally known method such as holding a photocurable fluoropolyether rubber composition, and irradiating with light through a transparent substrate to harden it is easily performed.

The photocurable fluoropolyether-based rubber cured product of the present invention can be suitably used, for example, for automobiles, chemical plants, semiconductor manufacturing lines, and analysis. Components for various applications such as physical and chemical equipment, medical equipment, fuel cells, inkjet printers, aircraft, and organic EL panels.

In more detail, the hardened product and the rubber product containing the hardened product of the present invention can be used in, for example, rubber parts for automobiles, specifically, diaphragms, valves, or sealing materials; rubber parts for chemical plants, specifically Sealing materials for pump diaphragms, valves, brake hoses, packings, oil seals, conductive buffer materials, sealing materials for tank piping repairs, etc .; rubber parts for semiconductor manufacturing lines, specifically, Diaphragms, valves, packings, conductive cushioning materials, etc. for materials that come into contact with medicines, valves that require low friction and abrasion resistance, etc .; analysis. Rubber parts for physical and chemical machinery, specifically, diaphragms, valves, seals (fillers, etc.) for pumps; rubber parts for medical equipment, specifically, pumps, valves, joints, etc .; rubber parts for fuel cells, Specifically, it is the sealing material for fuel cells; rubber parts for inkjet printers; rubber parts for aircrafts; rubber parts for organic EL panels; other rubber parts, specifically, tent film materials, sealants, molding parts, extrusion Parts, coating materials, photocopier roll materials, moisture-proof coating materials for electrical appliances, built-in materials for sensors, sealing materials for working machines, laminated rubber cloths, etc.

    [Example]    

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples. In the following examples, Me is a methyl group and parts are parts by mass. The viscosity is a measured value at 23 ° C (based on JIS K7117-1). The molecular weight is a polystyrene-equivalent number average molecular weight in a GPC analysis using a fluorine-based solvent as a developing solvent. The fluorine content (%) is mass%.

Production of matrix compound for photocurable fluoropolyether rubber composition

    [Manufacture example]    

100 parts of a polymer (viscosity 9,000 mPa · s, vinyl content 0.013 mol / 100 g, number average molecular weight 15,700) of 100 parts of a polymer represented by the following formula (6) will be used as a hydrophobic silica filler (fumed silica) AEROSIL R972: BET specific surface area: 130 m ² / g: Japan AEROSIL (trade name) is added in 10 parts by a planetary mixer and kneaded for 1 hour. Then, the mixture is subjected to a mixed pressure reduction (-0.08 ~ -0.10MPa) heat treatment at 150 ° C for 1 hour, and after cooling, the dispersion treatment is performed with three rolls, and then the matrix composite is manufactured.

    [Confirmation of compatibility between linear polyfluoro compound and fluorine-containing organic hydrogen polysiloxane]         [Reference Example 1]    

To 100 parts of the polymer represented by the above formula (6), 3.12 parts of a fluorine-containing organohydrogen polysiloxane represented by the following formula (7) (Si-H group amount: 0.00500 mole / g, fluorine content; 41.1%), at room temperature (23 ° C), using a mixing device (ARE-310 manufactured by THINKY) at 2,000 rpm for 1 minute, followed by centrifugal degassing at 2,200 rpm for 1 minute, and then left at 23 ° C After 1 hour, the transparency of the mixed liquid was visually confirmed. The results are shown in Table 1.

    [Reference Example 2]    

In addition to the above-mentioned Reference Example 1, 3.12 parts of the fluorine-containing organic hydrogen polysiloxane represented by the formula (7) was changed to 6.29 parts of the fluorine-containing organic hydrogen polysiloxane represented by the following formula (8) (Si- Except for the H group content of 0.00248 mol / g, fluorine content; 45.5%), the transparency of the mixed liquid was visually confirmed by the same operation. The results are shown in Table 1.

    [Reference Example 3]    

In addition to the above-mentioned Reference Example 1, 3.12 parts of the fluorine-containing organic hydrogen polysiloxane represented by the formula (7) was changed to 4.16 parts of the fluorine-containing organic hydrogen polysiloxane represented by the following formula (9) (Si- Except for the H group content of 0.00375 mol / g, fluorine content; 46.3%), the transparency of the mixed liquid was visually confirmed by the same operation. The results are shown in Table 1.

    [Comparative Reference Example 1]    

In addition to the above-mentioned Reference Example 1, 3.12 parts of the fluorine-containing organic hydrogen polysiloxane represented by the above formula (7) was changed to 2.60 parts of the fluorine-containing organic hydrogen polysiloxane represented by the following formula (10) (Si- Except for the H group content of 0.00599 mole / g, fluorine content; 34.2%), the transparency of the mixed liquid was visually confirmed by the same operation. The results are shown in Table 1.

    [Comparative Reference Example 2]    

In addition to the above Reference Example 1, 3.12 parts of the fluorine-containing organic hydrogen polysiloxane represented by the formula (7) was changed to 2.28 parts of the fluorine-containing organic hydrogen polysiloxane represented by the following formula (11) (Si- Except for the H group amount of 0.00683 mol / g, fluorine content; 35.1%), the transparency of the mixed liquid was visually confirmed by the same operation. The results are shown in Table 1.

    [Comparative Reference Example 3]    

In addition to the above Reference Example 1, 3.12 parts of the fluorine-containing organic hydrogen polysiloxane represented by the above formula (7) was changed to 2.55 parts of the fluorine-containing organic hydrogen polysiloxane represented by the following formula (12) (Si- Except for the H group content of 0.00612 mol / g, fluorine content; 37.8%), the transparency of the mixed liquid was visually confirmed by the same operation. The results are shown in Table 1.

From the results in Table 1, it can be seen that the fluorine-containing organic hydrogen polysiloxanes of Reference Examples 1 to 3 of the component (B) of the present invention are uniformly dissolved with the linear polyfluoro compound of the component (A). Dispersed (soluble). On the other hand, it was confirmed that the fluorine-containing organic hydrogen polysiloxanes of Comparative Reference Examples 1 to 3 were insoluble in the linear polyfluoro compound.

    [Preparation of photocurable fluoropolyether rubber composition]         [Modulation Example 1]    

In the matrix composite (110 parts) prepared in the above manufacturing example, 100 parts of the polymer represented by the formula (6) was added in a planetary mixer and mixed until uniform. To this, 0.11 part of (methylcyclopentadienyl) trimethylplatinum (IV) 1,3-bis (trifluoromethyl) benzene solution (platinum concentration 3.0% by mass), and 1-ethynyl- 0.12 parts of a toluene solution (5.0% by mass) of 1-hydroxycyclohexane, 6.24 parts of a fluorine-containing organic hydrogen polysiloxane represented by the above formula (7) (Si-H group amount: 0.00500 mole / g, fluorine content 41.1%) and mixed until homogeneous. Thereafter, a degassing operation was performed to prepare a photocurable fluoropolyether rubber composition.

    [Modulation Example 2]    

In addition to the above-mentioned Preparation Example 1, 6.24 parts of the fluorine-containing organic hydrogen polysiloxane represented by the formula (7) was changed to the fluorine-containing organic hydrogen polysiloxane represented by the formula (8) (Si-H group amount 0.00248 The photocurable fluoropolyether rubber composition was prepared in the same manner as in Preparation Example 1 except for Moore / g, fluorine content 45.5%) 12.58 parts.

    [Modulation Example 3]    

In addition to the above-mentioned Preparation Example 1, 6.24 parts of the fluorine-containing organic hydrogen polysiloxane represented by the formula (7) was changed to the fluorine-containing organic hydrogen polysiloxane represented by the formula (9) (Si-H group amount: 0.00375). Moire / g, fluorine content: 46.3%) Except for 8.32 parts, a photocurable fluoropolyether-based rubber composition was prepared in the same manner as in Preparation Example 1.

    [Modulation Example 4]    

In addition to the above-mentioned Preparation Example 1, 6.24 parts of the fluorine-containing organic hydrogen polysiloxane represented by the formula (7) was changed to the fluorine-containing organic hydrogen polysiloxane represented by the formula (10) (Si-H group amount: 0.00599). Moire / g, fluorine content: 34.2%) Except for 5.20 parts, a photocurable fluoropolyether-based rubber composition was prepared in the same manner as in Preparation Example 1.

    [Modulation Example 5]    

In addition to the above-mentioned Preparation Example 1, 6.24 parts of the fluorine-containing organic hydrogen polysiloxane represented by the formula (7) was changed to the fluorine-containing organic hydrogen polysiloxane represented by the formula (11) (Si-H group amount: 0.00683). The photocurable fluoropolyether-based rubber composition was prepared in the same manner as in Preparation Example 1 except for 4.56 parts per mole / g, fluorine content 35.1%).

    [Modulation Example 6]    

In addition to the above-mentioned Preparation Example 1, 6.24 parts of the fluorine-containing organic hydrogen polysiloxane represented by the formula (7) was changed to the fluorine-containing organic hydrogen polysiloxane represented by the formula (12) (Si-H group amount: 0.00612). The photocurable fluoropolyether-based rubber composition was prepared in the same manner as in Preparation Example 1 except for Moore / g, fluorine content 37.8%), except for 5.10 parts.

    [Evaluation of Foaming of Rubber During Hermetic Hardening]         [Example 1]    

The fluoropolyether-based rubber composition obtained in Preparation Example 1 was put into a mold (H) × (D) × (t) = 105mm × 35mm × 1mm, and decompressed and degassed with a UV-LED (365nm) irradiator The irradiation was performed at 100 mW / cm ² for 45 seconds so as to be 4,500 mJ / cm ² . After the light irradiation, a glass plate was placed on a mold to form a closed system, and the state of the cured product after standing at 23 ° C for 10 minutes was visually observed. In the evaluation, the case where foaming of the rubber was observed was X, and the case where foaming was not observed was ○. The results are shown in Table 2.

    [Example 2]    

A cured product was produced in the same manner as in Example 1 except that the fluoropolyether-based rubber composition used in Example 1 was changed from the one in Preparation Example 1 to the one in Preparation Example 2, and visually observed. The results are shown in Table 2.

    [Example 3]    

A cured product was produced in the same manner as in Example 1 except that the fluoropolyether-based rubber composition used in Example 1 was changed from the one in Preparation Example 1 to the one in Preparation Example 3 and visually observed. The results are shown in Table 2.

    [Comparative Example 1]    

A cured product was produced in the same manner as in Example 1 except that the fluoropolyether-based rubber composition used in Example 1 was changed from Preparation Example 1 to Preparation Example 4, and visual observation was performed. The results are shown in Table 2.

    [Comparative Example 2]    

A cured product was produced in the same manner as in Example 1 except that the fluoropolyether-based rubber composition used in Example 1 was changed from the one in Preparation Example 1 to the one in Preparation Example 5, and visually observed. The results are shown in Table 2.

    [Comparative Example 3]    

A cured product was produced in the same manner as in Example 1 except that the fluoropolyether-based rubber composition used in Example 1 was changed from Preparation Example 1 to Preparation Example 6, and visual observation was performed. The results are shown in Table 2.

From the results in Table 2, in Examples 1 to 3 of the photocurable fluoropolyether-based rubber composition of the present invention, foaming of the rubber during hermetic hardening was suppressed, and hermeticity was confirmed in Comparative Examples 1 to 3. Foaming of rubber occurs during curing.

    [Evaluation of the adhesion between rubber and substrate during hermetic hardening and stability evaluation of rubber properties]         [Examples 4 to 6, Comparative Examples 4 to 6]    

The photocurable fluoropolyether-based rubber composition obtained in the above Preparation Examples 1 to 6 was each coated on two aluminum substrates previously coated with a silane-based primer composition, degassed under reduced pressure, and then The UV-LED (365 nm) irradiator was irradiated at 100 mW / cm ² for 45 seconds so as to become 4,500 mJ / cm ² . After light irradiation, two aluminum substrates were bonded so that the thickness of the fluoropolyether-based rubber composition became 0.08 mm, and left to stand at 40 ° C / 60% RH for 24 hours.

After 24 hours, the test piece was allowed to cool back to room temperature (23 ° C) and adhered to the area in accordance with JIS K6250; 25 mm × 10 mm, tensile speed; 50 mm / min. A tensile shear test was then performed to evaluate the density of the rubber.着 性。 Sex. The results are shown in Table 3.

From the results in Table 3, in Examples 4 to 6 using the photocurable fluoropolyether-based rubber composition of the present invention, it was confirmed that the adhesion between the rubber and the substrate was improved, and the unevenness in adhesion was also reduced. On the other hand, in Comparative Examples 4 to 6, it was confirmed that due to the effect of foaming of the rubber at the time of hermetic hardening, the adhesion to the base material was reduced, and the unevenness was also large.

Claims (8)

    A photocurable fluoropolyether rubber composition, characterized in that it contains (A) a linear polyfluoro compound having two or more alkenyl groups in one molecule and a linear perfluoropolyether structure in the main chain: 100 parts by mass of (B) 1 molecule of (B) 2 or more hydrogen atoms (Si-H groups) directly bonded to a silicon atom and a fluorine content of 40% by mass or more of a fluorine-containing organic hydrogen polysiloxane: A) 1 mol of alkenyl group in the component, Si-H group in the component (B) of 0.5 to 3 mol, and (C) Photoactive type hydrosilylation catalyst: Compared with the component (A) The mass is 0.1 to 500 ppm in terms of metal atoms.         The photocurable fluoropolyether-based rubber composition according to claim 1, wherein the fluorine-containing organic hydrogen polysiloxane of the component (B) is 1 mole relative to the alkenyl group in the component (A), (B When the amount of Si-H group in the component) is 0.5 to 3 moles and the component (A) is mixed, it can be uniformly and transparently dispersed in the component (A).     The photocurable fluoropolyether rubber composition according to claim 1 or 2, wherein the component (A) is a linear polyfluoro compound represented by the following formula (1), and CH ₂ = CH- (X) _a -Rf ^1- (X ') _a -CH = CH ₂ (1) [In the formula (1), X is -CH _2- , -CH ₂ O-, -CH ₂ OCH ₂ -or -Y-NR ¹ -CO- [here, Y is -CH _2- , -Si (CH ₃ ) ₂ CH ₂ CH ₂ CH _2- , -Si (CH ₃ ) (CH = CH ₂ ) CH ₂ CH ₂ CH ₂ -,- Si (CH = CH ₂ ) ₂ CH ₂ CH ₂ CH ₂ -or the following structural formula (Z) (In the formula (Z), R ³ and R ⁴ are each independently -CH ₃ or -CH = CH ₂ ), o-, m- or p-silylphenylene, and R ¹ is a hydrogen atom or unsubstituted Or substituted monovalent hydrocarbon group], X 'is -CH _2- , -OCH _2- , -CH ₂ OCH _2- , or -CO-NR ² -Y'- [herein, Y' is -CH ₂ -,- CH ₂ CH ₂ CH ₂ Si (CH ₃ ) _2- , -CH ₂ CH ₂ CH ₂ Si (CH ₃ ) (CH = CH ₂ )-, -CH ₂ CH ₂ CH ₂ Si (CH = CH ₂ ) _2- Or the following structural formula (Z ') (In the formula (Z '), R ^3' and R ^{4 '} are each independently and are -CH ₃ or -CH = CH ₂ ), o-, m-, or p-silylphenylene, and R ² is a hydrogen atom Or unsubstituted or substituted monovalent hydrocarbon group], a is independently 0 or 1, and Rf ¹ is the following formula (i) or (ii) (In formula (i), p and q are each an integer of 0 or 1 to 150, and the average of the sum of p and q is 2 to 200, r is an integer of 0 to 6, and t is 2 or 3) (In formula (ii), u is an integer of 1 to 200, v is an integer of 1 to 50, and t is 2 or 3) a divalent linear perfluoropolyether group represented by [].     The photocurable fluoropolyether rubber composition according to any one of claims 1 to 3, wherein the fluorine-containing organohydrogen polysiloxane of the component (B) is one or more monovalent perfluorinated molecules per molecule Alkyl, monovalent perfluorooxyalkyl, divalent perfluoroalkylene, or divalent perfluorooxyalkylene.     The photocurable fluoropolyether rubber composition according to any one of claims 1 to 4, wherein the photoactive silylation reaction catalyst of the component (C) is (η ⁵ -cyclopentadienyl) tris ( σ-alkyl) platinum (IV) complex compound and / or β-diketoplatinum platinum (II) complex compound. The photocurable fluoropolyether rubber composition according to any one of claims 1 to 5, which further contains 0.5 to 30 parts by mass relative to 100 parts by mass of the component (A) and has a BET specific surface area of 50 m ² / g. The above-mentioned hydrophobic silica powder is used as the (D) component.     The photocurable fluoropolyether-based rubber composition according to any one of claims 1 to 6, which is a reaction control agent further containing a hydrosilylation reaction as the (E) component.         A fluoropolyether-based rubber composed of a cured product of a photocurable fluoropolyether-based rubber composition according to any one of claims 1 to 7.