JP6344256B2 - Method for bonding photocurable fluoropolyether elastomer composition - Google Patents

Description

  The present invention relates to a method for adhering a specific photocurable fluoropolyether elastomer composition to a substrate.

  Conventionally, a curable fluorine-containing elastomer composition using an addition reaction between an alkenyl group and a hydrosilyl group is known. Further, as a third component, an organopolysiloxane having a hydrosilyl group, an epoxy group, and / or a trialkoxysilyl group is used. Compositions imparted with self-adhesive properties by addition have been proposed (Patent Documents 1 and 2). This can be cured by heating for a relatively short time, and the resulting cured product is excellent in solvent resistance, chemical resistance, heat resistance, low temperature characteristics, low moisture permeability, and electrical characteristics. Used in adhesive applications in various industrial fields where properties are required. In particular, it is frequently used as an adhesive sealant for electrical components in the automobile industry.

  In recent years, from the viewpoint of energy saving and productivity improvement, development of an elastomer material that can be cured and bonded at a lower temperature and in a shorter time has been demanded. If you try to obtain fast curability with the above heat-curing type adhesive composition, storage stability and pot life will be sacrificed, conversely fast curing to ensure good storage stability and pot life. There was a dilemma that sex was sacrificed. In addition, since the curing process and the bonding process are carried out by a single heat treatment, when trying to obtain the adhesiveness between the cured product and the substrate at a lower temperature, the curing process takes time, resulting in a short time. It was difficult to obtain a cured product and adhesion.

  On the other hand, as an elastomer composition excellent in water and oil repellency, chemical resistance, etc., (A) a linear fluoropolyether compound having at least two alkenyl groups and having a perfluoropolyether structure, (B) A photo-curable fluoropolyether rubber composition containing at least two mercapto groups, an organopolysiloxane having a monovalent fluoroalkyl group or a monovalent fluoropolyether group, and (C) a photoinitiator has been developed. It is expected to be used as a coating material and potting material for various electric and electronic parts such as for automobiles, chemical plants, inkjet printers, and semiconductor production lines (Patent Document 3).

  However, the photo-curable fluoropolyether rubber composition is a gel or rubber-like cured product and is very soft and has no adhesiveness to various substrates. Although it is a suitable material, it is a material that is difficult to be applied to uses such as a sealing material and an adhesive seal material that require adhesion to a base material and uses that require strength as an elastomer material.

  Therefore, it has been desired to develop a fluoroelastomer material that can be applied to the latter type of use, has both good storage stability and fast curability at room temperature, and exhibits self-adhesiveness by low-temperature and short-time heat treatment. .

Japanese Patent No. 3329717 Japanese Patent No. 35679773 JP 2007-106875 A

  Therefore, the present invention provides a photo-curable fluoropolyether elastomer composition having the characteristics that the composition has both good storage stability and fast curability and can be bonded in a short time at a relatively low temperature. An object of the present invention is to provide an adhesion method.

  As a result of diligent research to achieve the above object, the present inventors have made a photocurable fluoropolyether elastomer composition at a lower temperature and through a two-step process of a photocuring process and a heat bonding process. The inventors have found that it is possible to adhere to various substrates in a short time, and completed the present invention. That is, this invention provides the adhesion method of the following photocurable fluoropolyether-type elastomer composition.

[1]
The photocurable fluoropolyether elastomer composition containing the following components (A), (B), (C), (D) and (E) is cured by light irradiation, and the resulting cured product is 80 ° C to A method of adhering a photocurable fluoropolyether elastomer composition to a substrate, characterized by heating to 200 ° C.,
In the light irradiation, the light used has a maximum peak wavelength in the region of 300 to 400 nm in the emission spectrum, and the irradiance of each wavelength in the wavelength region shorter than 300 nm of the light is the irradiance 5 of the maximum peak wavelength. % Or less,
How 365nm integrated light quantity of the irradiated light is ^{1,000mJ / cm 2 ~50,000mJ / cm 2} .
(A) the following formula represented by (1), chain fluoropolyether compound having a branched _{CH 2 = CH- (X) g} -Rf 1 - (X ') g -CH = CH 2 (1)
[Wherein, X is _{-CH 2 -, - CH 2 O} -, - CH 2 OCH 2 - or ^-Y-NR 1 -CO-
(Where 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. )
An o-, m- or p-silylphenylene group represented by
R ¹ is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group)
X ′ represents —CH ₂ —, —OCH ₂ —, —CH ₂ OCH ₂ —, or —CO—NR ² —Y′—.
(Wherein, 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 formula (Z ′), R ^{3 ′} and R ^{4 ′} are each independently —CH ₃ or —CH═CH _2. )
O-, m- or p-silylphenylene group, and R ² is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group.
g is independently 0 or 1.
Rf ¹ represents the following formula (i) or (ii)

(In the formula, 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 the formula, u is an integer of 1 to 200, v is an integer of 1 to 50, and t is 2 or 3.)
It is a bivalent perfluoropolyether group represented by these. ]
(B) a fluorine-containing organohydrogensiloxane having two or more hydrogen atoms directly bonded to silicon atoms in one molecule (C) a photoactive hydrosilylation catalyst (D) a hydrophobic silica powder, and
(E) Organosiloxane having one or more hydrogen atoms directly bonded to silicon atoms and one or more epoxy groups and / or trialkoxysilyl groups bonded to silicon atoms via carbon atoms or carbon atoms and oxygen atoms in one molecule

[2]
The fluorine-containing organohydrogensiloxane of the component (B) is one or more monovalent perfluoroalkyl group, monovalent perfluorooxyalkyl group, divalent perfluoroalkylene group, or divalent perfluoro molecule in one molecule. The method to adhere | attach the photocurable fluoropolyether-type elastomer composition as described in [1] which has a perfluorooxyalkylene group to a base material.

[3]
The photocurable fluoropolyether according to [1] or [2], wherein the photoactive hydrosilylation reaction catalyst of the component (C) is (η ⁵ -cyclopentadienyl) tri (σ-alkyl) platinum (IV) A method of adhering a base elastomer composition to a substrate.
[4]
The method for adhering the photocurable fluoropolyether elastomer composition according to [1] or [2], wherein the photoactive hydrosilylation catalyst of the component (C) is a β-diketonatoplatinum (II) complex .

[5]
The monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group in which the organosiloxane of component (E) is further bonded to a silicon atom via a carbon atom or a divalent linking group containing a carbon atom and an oxygen atom A method of adhering the photocurable fluoropolyether-based elastomer composition according to any one of [1] to [4], which has one or more of the above, to a substrate.
[6]
Furthermore, the method of making the base material adhere | attach the photocurable fluoropolyether-type elastomer composition of any one of [1]-[5] containing the reaction control agent of hydrosilylation reaction as (F) component.
[7]
Furthermore, the method to adhere | attach the photocurable fluoropolyether-type elastomer composition of any one of [1]-[6] containing a carboxylic acid anhydride as (G) component to a base material.

[8]
[7] The photocurable fluoropolyether elastomer composition according to [7], wherein an optical filter is used for light irradiation, and the irradiance of each wavelength in a wavelength region shorter than 300 nm is 5% or less of the irradiance of the maximum peak wavelength. A method of adhering a substrate to a substrate.

  The bonding method of the present invention mainly comprises a step of curing a photocurable fluoropolyether elastomer composition on a substrate by light irradiation of 300 to 400 nm (photocuring step), and a photocurable fluoropolyether elastomer. In the process of adhering the cured product to various base materials by heat treatment at 80 ° C. to 200 ° C. (heat bonding process), the photocurable fluoropolyether elastomer composition can be applied to various base materials at a relatively low temperature and in a short time. Can be glued to.

  Hereinafter, the present invention will be described in detail.

Photocurable fluoropolyether elastomer composition The photocurable fluoropolyether elastomer composition used in the present invention contains the following components (A), (B), (C), (D) and (E). Is.

[Component (A)]
The component (A) in the photocurable fluoropolyether elastomer composition is represented by the above formula (1).
Here, as R ¹ and R ² , a hydrogen atom and a hydrocarbon group having 1 to 12 carbon atoms, particularly 1 to 10 carbon atoms are preferable. Specific examples of the hydrocarbon group include a methyl group, an ethyl group, and a propyl group. Group, butyl group, hexyl group, cyclohexyl group, octyl group and other alkyl groups; phenyl group, tolyl group and other aryl groups; benzyl group, phenylethyl group and other aralkyl groups, and a part of hydrogen atoms of these groups Or the substituted monovalent hydrocarbon group etc. which substituted all with halogen atoms, such as a fluorine, are mentioned as a preferable thing.

Here, Rf ¹ in the above formula (1) is a divalent perfluoropolyether group, and is represented by the following formula (i) or (ii).

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

(In the 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. .)

Preferable examples of the Rf ¹ group include the following three groups. Of these, a divalent group having the structure of the first formula is particularly preferable.

(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 of 1 to 200, and v1 is an integer of 1 to 50.)

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

Wherein (2), ^{X 1} is _{-CH 2 -, - CH 2 O} -, - CH 2 OCH 2 - or ^-Y-NR 11 -CO- (Y have the same meanings as defined ^{above, R 11} is hydrogen X ¹ ′ is —CH ₂ —, —OCH ₂ —, —CH ₂ OCH ₂ — or —CO—NR ¹² —Y′— (R ¹² is an atom, methyl group, phenyl group or allyl group). The same as R ¹¹ above, and Y ′ represents the same as above), g 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. ]

  Specific examples of the chain fluoropolyether 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, which indicates a number satisfying p ′ + q ′ = 6 to 200.)

(In the formula, p ″ and q ″ are each an integer of 1 to 150, indicating a number satisfying p ″ + q ″ = 2 to 200.)

  The amount of alkenyl group contained in the chain fluoropolyether compound represented by the above formula (1) is preferably 0.005 to 0.050 mol / 100 g, more preferably 0.007 to 0.040 mol / 100 g. . If the amount of alkenyl groups contained in the chain fluoropolyether compound is too small, the physical strength of the cured product may be reduced or the cured product may not be obtained. If the amount of alkenyl groups contained in the chain fluoropolyether compound is too large, the resulting cured product may be brittle and easily cracked.

  In addition, the viscosity (23 degreeC) of the chain | strand-shaped fluoro polyether compound of the said Formula (1) is 100-100,000 mPa * s, More preferably, it is 500-50,000 mPa * s, More preferably, it is 1,000-20, When the photocurable fluoropolyether elastomer composition is used for sealing, potting, coating, impregnation, etc., the cured product has appropriate physical properties within the range of 000 mPa · s. So desirable. The chain fluoropolyether compound of formula (1) is selected to have the most appropriate viscosity according to the application. It is also possible to mix a low-viscosity polymer and a high-viscosity polymer and use them after adjusting to a desired viscosity.

  Further, in order to use the chain fluoropolyether compound of the above formula (1) by adjusting to a desired weight average molecular weight according to the purpose, the chain fluoropolyether compound as described above is previously incorporated in the molecule with a hydrosilyl group ( It is also possible to use as a component (A) a product obtained by subjecting an organosilicon compound containing two Si—H groups) to a hydrosilylation reaction in the usual manner and conditions and extending the chain length.

  These chain fluoropolyether compounds can be used alone or in combination of two or more.

  The blending amount of the component (A) in the composition of the chain fluoropolyether compound having two or more alkenyl groups in one molecule is preferably 50 to 99% by mass, particularly 70 to 95% by mass. Furthermore, it is preferable to set it as 80-95 mass%.

[(B) component]
The component (B) has 2 or more, preferably 1 to 10 fluorine-containing organic groups in one molecule, and 2 hydrogen atoms (that is, a hydrosilyl group represented by Si—H) directly bonded to a silicon atom. It is a fluorine-containing organohydrogensiloxane having at least 1, preferably 3-50. The component (B) functions as a crosslinking agent and / or chain extender for the component (A), and is compatible with the component (A), dispersibility, and uniformity after curing. To one or more monovalent perfluoroalkyl group, monovalent perfluorooxyalkyl group, divalent perfluoroalkylene group, or divalent perfluorooxyalkylene group per molecule as the fluorine-containing organic group. Those having a fluorine-containing group such as are preferred.

  Examples of the monovalent or divalent fluorine-containing organic group include those represented by the following formula.

C _g F _{2g + 1} −
−C _g F _2g −

(In the formula, g is an integer of 1 to 20, preferably an integer of 2 to 10.)

(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, each of i and j is 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 to 50, preferably an integer of 1 to 40.)

  The perfluoroalkyl group, perfluorooxyalkyl group, perfluoroalkylene group or perfluorooxyalkylene group and the silicon atom are preferably connected by a divalent linking group, and as the divalent linking group, May be an alkylene group, an arylene group and a combination thereof, or an ether bond oxygen atom, an amide bond, a carbonyl bond, an ester bond, a diorganosilylene group, etc. interposed in these groups. The divalent linking group having 2 to 12 carbon atoms and the like are not limited thereto.

(In the formula, Ph is a phenyl group, and Ph 'is a phenylene group.)

  In addition, as the monovalent substituent bonded to the silicon atom other than the monovalent or divalent fluorine-containing organic group and the hydrogen atom bonded to the silicon atom in the fluorine-containing organohydrogensiloxane of the component (B), for example, Alkyl group such as methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, octyl group and decyl group; alkenyl group such as vinyl group and allyl group; aryl group such as phenyl group, tolyl group and naphthyl group An aralkyl group such as a benzyl group or a phenylethyl group and a hydrogen atom of these groups partially or entirely substituted with a chlorine atom, a cyano group, or the like, for example, a carbon such as a chloromethyl group, a chloropropyl group, or a cyanoethyl group Examples thereof include an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20, preferably 1 to 12.

  The fluorine-containing organohydrogensiloxane as the component (B) may be any of cyclic, chain, three-dimensional network, and combinations thereof. The number of silicon atoms in the fluorine-containing organohydrogenpolysiloxane is not particularly limited, but is usually 2 to 60, preferably about 3 to 30.

  Examples of the component (B) having such a monovalent or divalent fluorine-containing organic group and a silicon atom-bonded hydrogen atom include the following compounds. These compounds may be used alone or in combination of two or more. In the following formulae, Me represents a methyl group, and Ph represents a phenyl group.

  The amount of Si—H groups contained in the fluorine-containing organohydrogensiloxane as the component (B) is preferably 0.00050 to 0.01000 mol / g, more preferably 0.00100 to 0.00800 mol / g. If the amount of Si—H groups contained in the fluorinated organohydrogensiloxane is too small, the crosslink density may be insufficient and the physical properties of the resulting cured product may be reduced. Moreover, when there is too much Si-H group amount contained in fluorine-containing organohydrogensiloxane, it may foam at the time of hardening, and the physical characteristic of the hardened | cured material obtained may change a lot over time.

  These fluorine-containing organohydrogensiloxanes can be used alone or in combination of two or more.

  The blending amount of the component (B) is the hydrosilyl group in the component (B), that is, the Si-H group, with respect to 1 mol of alkenyl groups such as vinyl group, allyl group, cycloalkenyl group and the like contained in the component (A). Is preferably 0.5 to 3.0 mol, and particularly preferably 0.8 to 2.0 mol. If there are too few hydrosilyl groups (≡Si—H), the crosslink density becomes insufficient, and as a result, a cured product may not be obtained. Further, if there are too many hydrosilyl groups (≡Si—H), foaming may occur during curing.

[Component (C)]
Component (C) is a photoactive hydrosilylation reaction catalyst. The photoactive hydrosilylation reaction catalyst is activated by irradiation with light, particularly 300 to 400 nm, and promotes the addition reaction between the alkenyl group in component (A) and the hydrosilyl group in component (B). It is. Examples of the photoactive hydrosilylation reaction catalyst include mainly platinum group metal catalysts and nickel metal catalysts. Platinum group metal catalysts include platinum, palladium, rhodium metal complex compounds, nickel metal catalysts. Examples thereof include nickel-based, iron-based, and cobalt-based metal complex compounds. Of these, platinum-based metal complex compounds are preferable because they are relatively easily available and exhibit good catalytic activity.

Examples of photoactive platinum-based metal complex compounds include (η ⁵ -cyclopentadienyl) tri (σ-alkyl) platinum complex compounds and β-diketonatoplatinum complex compounds. Pentadienyl) trimethylplatinum (IV), (cyclopentadienyl) trimethylplatinum (IV), (1,2,3,4,5-pentamethylcyclopentadienyl) trimethylplatinum (IV), (cyclopentadiene) (Enyl) dimethylethylplatinum (IV), (cyclopentadienyl) dimethylacetylplatinum (IV), (trimethylsilylcyclopentadienyl) trimethylplatinum (IV), (methoxycarbonylcyclopentadienyl) trimethylplatinum (IV), ( Dimethylphenylsilylcyclopentadienyl) trimethylcyclopentadienylplatinum (I ), Trimethyl (acetylacetonato) platinum (IV), trimethyl (3,5-heptanedionate) platinum (IV), trimethyl (methylacetoacetate) platinum (IV), bis (2,4-pentanedionato) platinum (II), bis (2,4-hexandionato) platinum (II), bis (2,4-heptanedionate) platinum (II), bis (3,5-heptanedionate) platinum (II), bis (1-phenyl) Examples include -1,3-butanedioato) platinum (II), bis (1,3-diphenyl-1,3-propanedionato) platinum (II), and bis (hexafluoroacetylacetonato) platinum (II).

  When these catalysts are used, they can be used in a solid state when they are solid catalysts, but in order to obtain a more uniform cured product, those dissolved in an appropriate solvent can be used as component (A). It is preferable to use it by being dissolved in a fluoropolyether compound.

  The compounding amount of the component (C) is preferably from 0.1 to 500 ppm, particularly preferably from 1 to 100 ppm, in terms of metal atom with respect to 100 parts by mass of the component (A). If the amount is too small, sufficient photocurability cannot be obtained, while if too large, the heat resistance of the cured product may be adversely affected.

[Component (D)]
Component (D) is a hydrophobic silica powder, which imparts an appropriate physical strength to the cured product obtained from the photocurable fluoropolyether elastomer composition, and simultaneously contains the organosiloxane of component (F) described later. It has the effect | action disperse | distributing uniformly in a composition. As the hydrophobic silica powder of component (D), a known BET specific surface area as silicone rubber filler ^{50 m} 2 / g or more, particularly 50 to 400 m ² / g preferably those treated hydrophobic fine powder silica It is.

When the BET specific surface area is less than 50 m ² / g, the resulting cured product has insufficient physical strength, and the component (F) may not be uniformly dispersed. If it exceeds 400 m ² / g, the kneading operation becomes difficult, and the dispersion of component (D) may become non-uniform. Examples of the fine powder silica include fumed silica, precipitated silica, colloidal silica, and the like. Among these, fumed silica is most preferable. In addition, the BET specific surface area in this application was measured based on DIN 66131.

  Examples of the hydrophobizing agent for fine powder silica include organochlorosilane, organodisilazane, cyclic organopolysilazane, linear organopolysiloxane, etc. Among them, organochlorosilane, organodisilazane, cyclic organo Polysilazane is preferred.

  0.5-30 mass parts is preferable with respect to 100 mass parts of (A) component, and, as for the compounding quantity of this (D) component, 1-25 mass parts is more preferable. When the blending amount is less than 0.5 parts by mass, the physical properties of the obtained cured product may be deteriorated and the adhesiveness may become unstable. On the other hand, when it exceeds 30 mass parts, the fluidity | liquidity of a composition worsens and the sclerosis | hardenability by light may fall remarkably.

[(E) component]
The organosiloxane as the component (E) can sufficiently develop the self-adhesive property in the photocurable fluoropolyether elastomer composition by blending it. The organosiloxane is an organo having one or more hydrogen atoms directly bonded to silicon atoms and one or more epoxy groups and / or trialkoxysilyl groups bonded to silicon atoms via carbon atoms or carbon atoms and oxygen atoms in one molecule. Siloxane, and preferably one monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group bonded to a silicon atom via a carbon atom or a divalent linking group containing a carbon atom and an oxygen atom. It is an organosiloxane having the above.

  The siloxane skeleton of the organosiloxane may be any of cyclic, chain, branched, etc., or a mixed form thereof. As the organosiloxane as the component (E), those represented by the following average composition formula can be used.

(Wherein R ⁸ is independently an unsubstituted or halogen-substituted monovalent hydrocarbon group, and A is an epoxy group and / or trialkoxysilyl group bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom. B represents a monovalent perfluoroalkyl group or a perfluorooxyalkyl group bonded to a silicon atom via a carbon atom or a divalent linking group containing a carbon atom and an oxygen atom, and w is 0 ≦ w. ≦ 100, x is 1 ≦ x ≦ 100, y is 1 ≦ y ≦ 100, and z is 0 ≦ z ≦ 100.

In the above formula, as the unsubstituted or halogen-substituted monovalent hydrocarbon group for R ⁸ , those having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms are preferable. Specifically, a methyl group, an ethyl group, a propyl group, Alkyl groups such as butyl group, hexyl group, cyclohexyl group and octyl group; aryl groups such as phenyl group and tolyl group; aralkyl groups such as benzyl group and phenylethyl group; and part or all of hydrogen atoms of these groups A substituted monovalent hydrocarbon group in which is substituted with a halogen atom such as fluorine, and the like. Among them, a methyl group is particularly preferable.

  w is preferably 0 ≦ w ≦ 20, x is preferably 1 ≦ x ≦ 20, y is preferably 1 ≦ y ≦ 20, z is preferably 1 ≦ z ≦ 20, and w + x + y + z is preferably 3 ≦ w + x + y + z ≦ 50.

  A represents an epoxy group and / or a trialkoxysilyl group bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom, and specific examples thereof include the following groups.

(In the formula, R ⁹ is a divalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 5 carbon atoms in which an oxygen atom may be interposed. Specifically, a methylene group, an ethylene group, a propylene group, a butylene group, An alkylene group such as a hexylene group and an octylene group, a cycloalkylene group such as a cyclohexylene group, an oxyalkylene group such as an oxyethylene group, an oxypropylene group, and an oxybutylene group.

-R ¹⁰ -Si ^(OR _{11) 3}

(In the formula, R ¹⁰ is a divalent hydrocarbon group having 1 to ¹⁰ carbon atoms, particularly 1 to 4 carbon atoms. Specifically, methylene group, ethylene group, propylene group, butylene group, hexylene group, cyclohexylene group, An alkylene group such as an octylene group, and the like. R ¹¹ is independently a monovalent hydrocarbon group having 1 to 8 carbon atoms, particularly 1 to 4 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, An alkyl group such as an isopropyl group, an n-butyl group, an isobutyl group, or a tert-butyl group is shown.)

(In the formula, R ¹² is independently a monovalent hydrocarbon group having 1 to 8 carbon atoms, particularly 1 to 4 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group. Group, an isobutyl group, an alkyl group such as tert-butyl group, and the like, R ¹³ is a hydrogen atom or a methyl group, and k is an integer of 2 to 10, preferably an integer of 2 to 6.)

  Specific examples of A include those shown below.

  B represents a monovalent perfluoroalkyl group or a perfluorooxyalkyl group bonded to a silicon atom via a carbon atom or a divalent linking group containing a carbon atom and an oxygen atom. Examples of the monovalent perfluoroalkyl group or perfluorooxyalkyl group include those represented by the following formula.

C _g F _{2g + 1} −

(In the formula, g is an integer of 1 to 20, preferably an integer of 2 to 10.)

(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.)

  The divalent linking group containing a carbon atom or a carbon atom and an oxygen atom includes an alkylene group, an arylene group and a combination thereof, or an ether bond oxygen atom, an amide bond, a carbonyl bond, etc. interposed in these groups. Examples thereof include, but are not limited to, the following divalent linking groups having 2 to 12 carbon atoms.

-CH ₂ CH ₂ -,
-CH ₂ CH ₂ CH ₂ -,
_{-CH 2 CH 2 CH 2 OCH 2} -,
_{-CH 2 CH 2 CH 2 -NH-} CO-,
_{-CH 2 CH 2 CH 2 -N (} CH 3) -CO-,
_{-CH 2 CH 2 CH 2 -N (} Ph) -CO-

(In the formula, Ph is a phenyl group.)

  Specific examples of B include those shown below.

(In the formula, Ph is a phenyl group.)

  These organosiloxanes are composed of organohydrogenpolysiloxane having 3 or more hydrogen atoms (Si-H groups) bonded to silicon atoms in one molecule, aliphatic unsaturated groups such as vinyl groups and allyl groups, epoxy groups, and / or Alternatively, a compound containing a trialkoxysilyl group and, if necessary, a compound containing an aliphatic unsaturated group and a perfluoroalkyl group or perfluorooxyalkyl group can be obtained by partial addition reaction according to a conventional method. . Note that the number of the aliphatic unsaturated groups needs to be smaller than the number of Si-H groups.

  In the production of this organosiloxane in a photocurable fluoropolyether elastomer composition, the target substance may be isolated after completion of the reaction, but it is also possible to use a mixture from which unreacted substances and addition reaction catalysts have been removed. it can.

  Specific examples of the organosiloxane used as the component (E) include those represented by the following structural formula. In addition, these compounds may be used independently and may use 2 or more types together. Note that Me is a methyl group and Ph is a phenyl group.

(In the formula, x1 is 1 to 8, y1 is 1 to 3, w1 is 1 to 4, and y2 is 1 to 3.)

(In the formula, x3 is 1 to 8, w2 is 1 to 4, z2 is 1 to 3, and y4 is 1 to 3.)

  (E) As for the compounding quantity of a component, 0.1-10 mass parts is preferable with respect to 100 mass parts of (A) component, and 0.2-5 mass parts is especially preferable. (E) When the compounding quantity of a component is less than 0.1 mass part with respect to 100 mass parts of (A) component, sufficient adhesiveness may not be obtained. When the blending amount of the component (E) exceeds 10 parts by mass with respect to 100 parts by mass of the component (A), the fluidity of the composition deteriorates, the physical strength of the resulting cured product decreases, and the curability is inhibited. There is to do.

The following components may be further added to the photocurable fluoropolyether elastomer composition used in the present invention.
[(F) component]
Component (F) is a reaction control agent for the hydrosilylation reaction. Examples of the reaction control agent herein include, for example, 1-ethynyl-1-hydroxycyclohexane, 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, and 3-methyl. Acetylene alcohols such as -1-penten-3-ol and phenylbutynol; acetylene compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne; A fluorine-containing acetylene alcohol compound represented by the structural formula;

Examples thereof include polymethylvinylsiloxane cyclic compounds and organophosphorus compounds. Since these reaction control agents have different control abilities depending on their chemical structures, the addition amount should be adjusted to an optimum amount. In general, if the addition amount of the control agent is too small, long-term storage stability at room temperature cannot be obtained, and if it is too large, the curability becomes dull and sufficient curability may not be obtained.

[(G) component]
The carboxylic acid anhydride which is the component (G) improves the adhesion imparting ability of the component (E) by blending it, and promotes the expression of the adhesiveness of the photocurable fluoropolyether elastomer composition. Is. Such components include all those used as curing agents for epoxy resins and may be solid or liquid at room temperature and may contain trialkoxysilyl groups.

  Specifically, what is shown by the following structural formula is illustrated. In addition, these compounds may be used independently and may use 2 or more types together.

  The blending amount of the component (G) is preferably 0.1 to 2.0 parts by weight, particularly preferably 0.1 to 1.0 part by weight with respect to 100 parts by weight of the component (A). When the blending amount of the component (G) is less than 0.1 parts by mass with respect to 100 parts by mass of the component (A), a sufficient adhesion promoting effect cannot be obtained. When the blending amount of the component (G) exceeds 2.0 parts by mass with respect to 100 parts by mass of the component (A), the storage stability of the composition is deteriorated, the physical strength of the resulting cured product is lowered, and changes with time. This is not preferable because it often occurs.

[Other ingredients]
In the photo-curable fluoropolyether-based elastomer composition, in addition to the above-described components, a plasticizer, a viscosity modifier, a flexibility-imparting agent, an inorganic filler, an adhesion promoter, a silane cup, in order to enhance its practicality Various compounding agents such as a ring agent can be added as necessary. The blending amount of these additives is arbitrary as long as the object of the present invention is not impaired and the properties of the composition and the physical properties of the cured product are not impaired.

  As a plasticizer, a viscosity modifier, and a flexibility imparting agent, a polyfluoromonoalkenyl compound represented by the following formula (3) and / or a linear polyfluoro compound represented by the following formula (4) or (5) Can be used in combination.

Rf ^3- (X ′) _a CH═CH ₂ (3)

[Wherein, X ′ and a are the same as above, and Rf ³ is the following formula (iii).

(Wherein f1 is an integer of 1 or more, preferably an integer of 2 to 100, t is the same as above, and the sum of p + q (average) and r for Rf ¹ group of component (A) above, and smaller than any sum of u and v)]]

_{D-O- (CF 2 CF 2} CF 2 O) c1 -D (4)

(In the formula, D is a group represented by the formula: C _s F _{2s + 1-} (s is 1 to 3), c1 is an integer of 1 to 200, preferably an integer of 2 to 100, and ( A) smaller than the sum of p + q (average) and r and the sum of u and v for Rf ¹ group of the component)

_{D-O- (CF 2 O)} d1 (CF 2 CF 2 O) e1 -D (5)

(Wherein D is the same as above, 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 Rf ^{1 of the} component (A)) Less than or equal to the sum of p + q (average) and r for the group, and the sum of u and v.)

  Specific examples of the polyfluoromonoalkenyl compound represented by the above formula (3) include, for example, the following compounds (note that f1 ′ below satisfies the above requirements).

  Specific examples of the linear polyfluoro compound represented by the above formula (4) or (5) include the following (for example, the following c1 ′ and the sum of d1 ′ and e1 ′ are: Meet the above requirements).

_{CF 3 O- (CF 2 CF 2} CF 2 O) c1 '-CF 2 CF 3
_{CF 3 - [(OCF 2 CF} 2) e1 '(OCF 2) d1'] -O-CF 3

(Wherein c1 'is an integer of 1 to 200, d1' is an integer of 1 to 200, e1 'is an integer of 1 to 200, and d1' + e1 '= 2 to 200).

  The compounding amount of the compounds of the above formulas (3) to (5) is based on 100 parts by mass of the component (A) in the photocurable fluoropolyether elastomer composition, particularly the polyfluorodialkenyl compound of the above formula (1). 1 to 300 parts by mass is preferable, and 50 to 250 parts by mass is particularly preferable. Further, the viscosity (23 ° C.) by the rotational viscometer is desirably in the range of 5 to 100,000 mPa · s for the same reason as that of the polyfluorodialkenyl compound.

  As inorganic fillers, for example, reinforcing or semi-reinforcing fillers such as quartz powder, fused quartz powder, diatomaceous earth, calcium carbonate, inorganic pigments such as titanium oxide, iron oxide, carbon black, cobalt aluminate, titanium oxide, oxidation Heat improver such as iron, carbon black, cerium oxide, cerium hydroxide, zinc carbonate, magnesium carbonate, manganese carbonate, thermal conductivity imparting agent such as alumina, boron nitride, silicon carbide, metal powder, carbon black, silver powder, A conductivity-imparting agent such as conductive zinc white can be added.

  Moreover, adhesion promoters, such as a titanate ester, and silane coupling agents, such as an epoxy-group containing silane, can be added.

  The photocurable fluoropolyether-based elastomer composition comprises the above-described components (A) to (E) and other optional components, a mixing device such as a planetary mixer, a loss mixer, a Hobart mixer, and a kneader, three It can manufacture by mixing uniformly using kneading apparatuses, such as this roll.

Adhesion Method of Photocurable Fluoropolyether Elastomer Composition The adhesion method of the photocurable fluoropolyether elastomer composition of the present invention is described below as “photocuring method of photocurable fluoropolyether elastomer composition” and “ A heat-bonding method of a photocurable fluoropolyether elastomer composition ”.

Photocuring method of photocurable fluoropolyether elastomer composition The photocurable fluoropolyether elastomer composition is cured by light irradiation. During curing, the irradiated light is in the region where the maximum peak wavelength in the emission spectrum is 300 to 400 nm, and the irradiance of each wavelength in the wavelength region shorter than 300 nm is preferably 5% or less of the irradiance of the maximum peak wavelength, preferably Is 1% or less, more preferably 0.1% or less, that is, the closer to 0, the better. Irradiation with light having a wavelength shorter than 300 nm and having an irradiance greater than 5% of the irradiance of the maximum peak wavelength may cause degradation of polymer end groups or decomposition of part of the catalyst. There is a possibility that a sufficient cured product cannot be obtained.

The actinic ray species used for curing the photocurable fluoropolyether elastomer composition is not particularly limited, but is preferably ultraviolet rays. The ultraviolet irradiation amount (illuminance) is preferably 1,000 mJ / cm ^{2 to} 50,000 mJ / cm ² , more preferably 2,000 mJ / cm ^{2 to} 20,000 mJ / cm ² , and still more preferably 5,000 as the integrated light amount. In order to obtain good curability, it is desirable to set it to 10,000 mJ / cm ² . When the ultraviolet irradiation amount (illuminance) is less than the above range, there is a possibility that sufficient energy cannot be obtained to activate the photoactive hydrosilylation reaction catalyst in the composition and a sufficient cured product cannot be obtained. On the other hand, if the UV irradiation amount (illuminance) is more than the above range, the composition is irradiated with more energy than necessary, the polymer end groups may be decomposed, or a part of the catalyst may be deactivated. There is a possibility that a sufficient cured product cannot be obtained.

  The ultraviolet irradiation may be light having a plurality of emission spectra or light having a single emission spectrum. The single emission spectrum may have a broad spectrum in the region of 300 nm to 400 nm. Light having a single emission spectrum is light having a peak (ie, maximum peak wavelength) in the range of 300 nm to 400 nm, preferably 350 nm to 380 nm. Examples of the light source for irradiating light include ultraviolet light emitting diodes (ultraviolet LEDs) and ultraviolet light emitting semiconductor element light sources such as ultraviolet light emitting semiconductor lasers.

  Light sources that emit light having multiple emission spectra include metal halide lamps, xenon lamps, carbon arc lamps, chemical lamps, sodium lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, etc., nitrogen, etc. Examples thereof include a gas laser, a liquid laser of an organic dye solution, and a solid laser in which rare earth ions are contained in an inorganic single crystal.

  When the light has a peak in a wavelength region shorter than 300 nm in the emission spectrum, or a wavelength having an irradiance greater than 5% of the irradiance of the maximum peak wavelength in the emission spectrum exists in a wavelength region shorter than 300 nm ( For example, when the emission spectrum is broad over a wide wavelength region), it is preferable to remove light having a wavelength in a wavelength region shorter than 300 nm by an optical filter. Thereby, the irradiance of each wavelength in a wavelength region shorter than 300 nm is set to 5% or less, preferably 1% or less, more preferably 0.1% or less, and further preferably 0% of the irradiance of the maximum peak wavelength. When a plurality of peaks are present in the wavelength region of 300 nm to 400 nm in the emission spectrum, the peak wavelength showing the maximum absorbance is set as the maximum peak wavelength. The optical filter is not particularly limited as long as it cuts a wavelength shorter than 300 nm, and a known one may be used. For example, a 365 nm band pass filter or the like can be used. The illuminance and spectral distribution of ultraviolet rays can be measured with a spectral irradiance meter such as USR-45D (USHIO).

  Although it does not specifically limit as a light irradiation apparatus, For example, irradiation apparatuses, such as a spot type irradiation apparatus, a surface type irradiation apparatus, a line type irradiation apparatus, a conveyor type irradiation apparatus, can be used.

  When curing the photocurable fluoropolyether elastomer composition, the light irradiation time is, for example, 1 to 300 seconds, preferably 10 to 200 seconds, more preferably 30 to 150 seconds, and 1 to 60 minutes of light irradiation. Later, particularly after 5 to 30 minutes, the composition loses fluidity and a rubber elastic body can be obtained.

  In the present invention, the photocurable fluoropolyether elastomer composition may be applied to the base material by applying the composition to the base material, followed by light irradiation according to the method described above, or by separately applying light irradiation. The method of apply | coating the performed composition to a base material before hardening may be sufficient.

Method of Heat Adhesion of Photocurable Fluoropolyether Elastomer Composition The method of heat adhesion of the photocurable fluoropolyether elastomer composition is such that after the light irradiation is performed, the heat treatment is performed and the adhesion to the substrate is improved. How to get.

  More specifically, the photocurable fluoropolyether elastomer cured product that is in close contact with the substrate through the photocuring step is 80 ° C to 200 ° C, preferably 80 ° C to 150 ° C, 10 minutes to 1 hour, Preferably, it is a method capable of firmly bonding the substrate and the photocurable fluoropolyether elastomer cured product by heating for 15 minutes to 1 hour.

  According to the present invention, it is possible to complete curing at room temperature in a short time by the photocuring process. Can be obtained.

  The bonding method of the present invention is useful as a method for bonding a photocurable elastomer composition to automobile-related parts, various electric / electronic parts and the like. For example, various pressure sensors used in automobile control systems, gas concentration detectors, temperature sensors and other detectors / sensor adhesive sealants, protective coating agents, potting agents, and various gases, hot water, chemicals, etc. Protective sealants for sensors, adhesives for ink jet printers, adhesives / sealants for printer heads, roll and belt coatings for laser printers and copying machines, adhesive sealants for various circuit boards, This is useful as a method for adhering a photocurable fluoropolyether elastomer composition to a coating agent, potting agent or the like.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, in the following example, a part shows a mass part. Moreover, a viscosity shows the measured value in 23 degreeC (based on JISK7117-1).

Preparation of photocurable fluoropolyether elastomer composition [Preparation Example 1]
55.1 parts of a polymer represented by the following formula (6) (viscosity 10,000 mPa · s, number average molecular weight 16,700, vinyl group content 0.012 mol / 100 g) was charged in a planetary mixer, and the internal temperature was 50 While maintaining at ~ 100 ° C, 17.5 parts of fumed silica (BET specific surface area 110 m ^{2 /} g) surface-treated with dimethyldichlorosilane was added in portions. Thereafter, heating was stopped and kneading was performed under reduced pressure (gauge pressure; -0.093 MPa) for 1 hour. Subsequently, the apparatus was heated while kneading, and after the internal temperature reached 130 ° C., heat treatment was performed under reduced pressure (gauge pressure: −0.093 MPa) for 3 hours while maintaining the temperature at 130 to 160 ° C. Next, after cooling the content to 40 ° C. or lower, 42 parts of a polymer represented by the following formula (6) was added and kneaded for 30 minutes under reduced pressure (gauge pressure; −0.093 MPa). The contents were taken out and passed through three rolls twice to obtain Base Compound I.

  Also, 25 parts of a solid carboxylic acid anhydride represented by the following formula (7) and 75 parts of a polymer represented by the following formula (6) were charged into a planetary mixer, mixed at room temperature for 30 minutes, and further reduced in pressure for 30 minutes. (Gauge pressure; -0.093 MPa). This mixture was taken out and passed through three rolls twice to obtain a carboxylic anhydride paste.

  75.0 parts of the polymer represented by the following formula (6) and 0.8 part of the carboxylic acid anhydride paste were charged in a planetary mixer to 29.5 parts of the base compound I and mixed until uniform. To this, 0.06 part of 1,3-bis (trifluoromethyl) benzene solution (platinum concentration: 3.0% by mass) of (methylcyclopentadienyl) trimethylplatinum (IV), 1-ethynyl-1-hydroxycyclohexane 0.03 part of a toluene solution (5.0% by mass) was added and mixed until uniform. Next, 1.8 parts of fluorine-containing organohydrogensiloxane represented by the following formula (8) (Si-H group amount 0.00393 mol / g), 1.2 parts of fluorine-containing organohydrogensiloxane represented by the following formula (9) (Si-H group amount 0.00683 mol / g), 2.0 parts of an adhesion-imparting agent represented by the following formula (10), and 0.1 part of an epoxy group-containing silane compound represented by the following formula (11) were sequentially added. And mixed to be uniform. Then, the composition was prepared by performing defoaming operation.

[Preparation Example 2]
100 parts of a polymer represented by the above formula (6) (viscosity 10,000 mPa · s, number average molecular weight 16,700, vinyl group content 0.012 mol / 100 g) is charged in a planetary mixer, and the internal temperature is 50-100. While maintaining the temperature at 10 ° C., 10 parts of fumed silica (BET specific surface area 110 m ² / g) surface-treated with dimethyldichlorosilane was added in portions. Thereafter, heating was stopped and kneading was performed under reduced pressure (gauge pressure; -0.093 MPa) for 1 hour. Subsequently, the apparatus was heated while kneading, and after the internal temperature reached 130 ° C., heat treatment was performed under reduced pressure (gauge pressure: −0.093 MPa) for 3 hours while maintaining the temperature at 130 to 160 ° C. Next, after the contents were cooled to 40 ° C. or lower, the contents were taken out and passed through three rolls twice to obtain a base compound II.

  27.9 parts of the base compound I, 41.3 parts of the base compound II, and 38.9 parts of the polymer represented by the above formula (6) were charged in a planetary mixer and mixed until uniform. To this, 0.06 part of 1,3-bis (trifluoromethyl) benzene solution (platinum concentration: 3.0% by mass) of (methylcyclopentadienyl) trimethylplatinum (IV), 1-ethynyl-1-hydroxycyclohexane 0.03 part of a toluene solution (5.0% by mass) was added and mixed until uniform. Next, 1.6 parts of fluorine-containing organohydrogensiloxane represented by the following formula (12) (Si-H group content: 0.00387 mol / g), 1.2 parts of fluorine-containing organohydrogensiloxane represented by the above formula (9) (Si-H group amount 0.00683 mol / g), 2.0 parts of an adhesion imparting agent represented by the following formula (13), 0.5 part of an adhesion imparting agent represented by the following formula (14) were sequentially added, Mixed to be uniform. Then, the composition was prepared by performing defoaming operation.

[Preparation Example 3]
In Preparation Example 1, a photoactive hydrosilylation reaction catalyst; (methylcyclopentadienyl) trimethylplatinum (IV) in 1,3-bis (trifluoromethyl) benzene solution (platinum concentration: 3.0% by mass); The composition was the same except that 06 parts were changed to 0.48 parts of 2- (2-butoxyethoxy) ethyl acetate (platinum concentration 0.5% by mass) of bis (2,4-heptanedionato) platinum (II). A product was prepared.

[Preparation Example 4]
In Preparation Example 1 above, photoactive hydrosilylation reaction catalyst; 1,3-bis (trifluoromethyl) benzene solution of methylcyclopentadienyl) trimethylplatinum (IV) (platinum concentration 6.0 mass%) 0.06 Non-photoactive hydrosilylation reaction catalyst; curable composition in the same manner except that the ethanol solution of platinum-divinyltetramethyldisiloxane complex (platinum concentration: 3.0% by mass) was changed to 0.07 part Was prepared.

[Preparation Example 5]
In Preparation Example 1 above, photoactive hydrosilylation reaction catalyst; 1,3-bis (trifluoromethyl) benzene solution of methylcyclopentadienyl) trimethylplatinum (IV) (platinum concentration 6.0 mass%) 0.06 Non-photoactive hydrosilylation catalyst instead of parts: 0.20 parts of a platinum-divinyltetramethyldisiloxane complex in toluene solution (platinum concentration 0.5% by mass), 1-ethynyl-1-hydroxycyclohexane in toluene solution (5.0% by mass) A curable composition was prepared in the same manner except that 0.03 part was changed to 0.25 part of a toluene solution of 1-ethynyl-1-hydroxycyclohexane (60% by mass).

[Preparation Example 6]
In Preparation Example 2, photoactive hydrosilylation reaction catalyst; 1,3-bis (trifluoromethyl) benzene solution of methylcyclopentadienyl) trimethylplatinum (IV) (platinum concentration 6.0 mass%) 0.06 Non-photoactive hydrosilylation catalyst instead of parts: a toluene solution of platinum-divinyltetramethyldisiloxane complex (platinum concentration 0.5 mass%) 0.39 parts, a toluene solution of 1-ethynyl-1-hydroxycyclohexane (5.0% by mass) A curable composition was prepared in the same manner except that 0.03 part was changed to 0.25 part of a toluene solution of 1-ethynyl-1-hydroxycyclohexane (50% by mass).

Storage stability of photocurable fluoropolyether elastomer composition [Reference Examples 1 to 3]
The storage stability at 23 ° C. during light shielding of the compositions obtained from Preparation Examples 1 to 3 was confirmed. At that time, as an evaluation method of storage stability, based on JIS K7117-1, initial viscosity at 23 ° C. and 23 ° C. × 2 weeks after using a TV-10U type rotational viscometer (manufactured by Toki Sangyo Co., Ltd.) Evaluation was made from the change in viscosity.

[Comparative Example 1]
In the composition obtained from Preparation Example 4, the storage stability was confirmed in the same manner as in Reference Examples 1 to 3.

  From the results in Table 1, it was confirmed that good storage stability was obtained with the composition of this reference example using a photoactive hydrosilylation reaction catalyst.

Evaluation of Photocurability of Photocurable Fluoropolyether Elastomer Composition [Example 1]
About 2 g of the composition obtained from Preparation Example 1 above was potted on an aluminum substrate and irradiated with light using an SP-V type ultraviolet irradiator (USHIO INC.) Equipped with a uniform irradiation optical unit. Went. At that time, light in a wavelength region shorter than 300 nm is removed by a 365 nm band pass filter (manufactured by USHIO INC.), And irradiation is performed for 90 seconds so that the integrated light amount of main 365 nm light becomes 9,000 mJ / cm ^2. Went.

  Immediately after light irradiation, the light was shielded, and the curability after 23 ° C. × 30 minutes was evaluated. (The case where a sufficient rubber elastic body was obtained was evaluated as “◯”, and the case where the surface was incompletely cured such as stringing was evaluated as “×”.)

[Example 2]
In Example 1 above, the composition used was changed to the composition obtained from Preparation Example 2. The results are shown in Table 2.

[Example 3]
In Example 1 above, the composition used was changed to the composition obtained from Preparation Example 3. The results are shown in Table 2.

[Comparative Example 2]
In Example 1, the same operation was performed except that a 365 nm bandpass filter (USHIO Inc.) was not used during the ultraviolet irradiation. The results are shown in Table 2.

  From the results shown in Table 2, in the comparative example in which the 365 nm bandpass filter was not used, a sufficient cured product was not obtained.

[Example 4]
In Example 1 above, the integrated light quantity of main 365 nm light was set to 1,000 mJ / cm ^2, and the curability after 23 ° C. × 120 minutes was evaluated. The results are shown in Table 3.

[Example 5]
In Example 1, the integrated light amount of main 365 nm light was set to 50,000 mJ / cm ^2, and the curability immediately after irradiation was evaluated. The results are shown in Table 3.

[Comparative Example 3]
In Example 1 above, the integrated light quantity of main 365 nm light was set to 500 mJ / cm ^2, and the curability after 23 ° C. × 24 hours was evaluated. The results are shown in Table 3.

[Comparative Example 4]
In Example 1 above, the integrated light quantity of main 365 nm light was set to 100,000 mJ / cm ^2, and the curability immediately after irradiation was evaluated. The results are shown in Table 3.

From the results in Table 3, it was confirmed that the photocurable composition of the present example exhibited good photocurability under UV irradiation conditions of 1,000 mJ / cm ^{2 to} 50,000 mJ / cm ² . On the other hand, in Comparative Example 3, the amount of light was not sufficient at 500 mJ / cm ² , and a cured product was not obtained. In Comparative Example 4, the amount of light was excessive at 100,000 mJ / cm ² , and polymer decomposition was confirmed on the surface of the cured product.

Adhesive evaluation of photocured material [Example 6]
About 2 g of the composition obtained in Preparation Example 1 was potted on an iron, aluminum, epoxy glass, PBT, or PPS substrate, and a photocured product was prepared in the same manner as in Example 1. Thereafter, heat treatment was performed under a total of 3 conditions of 100 ° C. × 60 minutes, 120 ° C. × 20 minutes, 150 ° C. × 10 minutes, and after standing to cool for 23 ° C. × 2 hours, the adhesion to various substrates was confirmed. . (When rubber cohesive failure was confirmed, it was evaluated as ◯, and when interface peeling was confirmed, it was evaluated as x.) The results are shown in Table 4.

[Example 7]
In Example 6 above, the composition used was changed to the composition obtained from Preparation Example 2, and the heat treatment steps after photocuring were 80 ° C. × 30 minutes, 100 ° C. × 10 minutes, 120 ° C. × 10 minutes. The total was changed to three conditions, and the adhesion to various base materials was confirmed. The results are shown in Table 5.

[Comparative Example 5]
About 2 g of the composition obtained from Preparation Examples 1 to 3 was potted on an iron, aluminum, epoxy glass, PBT, or PPS substrate, and a photocured product was produced in the same manner as in Example 1. Thereafter, the heat treatment was not performed, and adhesion to various base materials was confirmed. (When rubber cohesive failure was confirmed, it was evaluated as ◯, and when interface peeling was confirmed, it was evaluated as x.) The results are shown in Table 6.

  Although the hardened | cured material was obtained by photocuring from the result of Table 6, the adhesiveness to a base material was not confirmed.

[Comparative Example 6]
In Example 4 above, the composition of Preparation Example 1 was changed to the composition of Preparation Example 5, the composition was potted on the same substrate, and light irradiation was not performed, but 100 ° C. × 60 minutes, 120 ° C. Heat treatment was performed under three conditions of × 20 minutes and 150 ° C. × 10 minutes, and after standing to cool at 23 ° C. × 2 hours, adhesion to various substrates was confirmed. (When rubber cohesive failure was confirmed, it was evaluated as ◯, and when interface peeling was confirmed, it was evaluated as x.) The results are shown in Table 7.

  From the results in Table 7, a rubber elastic body was obtained under the conditions of 150 ° C. × 10 minutes only. Under other heat treatment conditions, a sufficient cured product could not be obtained.

[Comparative Example 7]
In Example 7 above, the composition of Preparation Example 2 was changed to the composition of Preparation Example 6, the composition was potted on the same substrate, and light irradiation was not performed, but 80 ° C. × 30 minutes, 100 ° C. Heat treatment was carried out under a total of three conditions of × 10 minutes and 120 ° C × 10 minutes, and after standing to cool for 23 ° C × 2 hours, adhesion to various substrates was confirmed. (When rubber cohesive failure was confirmed, it was evaluated as ◯, and when interface peeling was confirmed, it was evaluated as x.) The results are shown in Table 8.

From the results in Table 8, a sufficient cured product was not obtained under any heat treatment conditions.

Claims (6)

The photocurable fluoropolyether elastomer composition containing the following components (A), (B), (C), (D) and (E) is cured by light irradiation, and the resulting cured product is 80 ° C to wherein the heating to 200 ° C., a photocurable fluoropolyether elastomer composition a method of adhering to a substrate,
In the light irradiation, the light used has a maximum peak wavelength in the region of 300 to 400 nm in the emission spectrum, and the irradiance of each wavelength in the wavelength region shorter than 300 nm of the light is the irradiance 5 of the maximum peak wavelength. % Or less,
How 365nm integrated light quantity of the irradiated light is ^{1,000mJ / cm 2 ~50,000mJ / cm 2} .
(A) the following formula represented by (1), chain fluoropolyether compound having a branched _{CH 2 = CH- (X) g} -Rf 1 - (X ') g -CH = CH 2 (1)
[Wherein, X is _{-CH 2 -, - CH 2 O} -, - CH 2 OCH 2 - or -Y-NR ¹ -CO- (wherein, 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. )
And R ¹ is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group, and X ′ is —CH ₂ —, —OCH _2. —, —CH ₂ OCH ₂ — or —CO—NR ² —Y′— (where Y ′ represents —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 —CH ₃ or —CH═CH ₂ ), an o-, m-, or p-silylphenylene group, and R ² is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group).
g is independently 0 or 1.
Rf ¹ represents the following formula (i) or (ii)
(In the formula, 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 the formula, u is an integer of 1 to 200, v is an integer of 1 to 50, and t is 2 or 3.)
It is a bivalent perfluoropolyether group represented by these. ]
(B) Fluorinated organohydrogensiloxane having two or more hydrogen atoms directly bonded to silicon atoms in one molecule (C) (methylcyclopentadienyl) trimethylplatinum (IV), (cyclopentadienyl) trimethylplatinum (IV ), (1,2,3,4,5-pentamethylcyclopentadienyl) trimethylplatinum (IV), (cyclopentadienyl) dimethylethylplatinum (IV), (cyclopentadienyl) dimethylacetylplatinum (IV) ), (Trimethylsilylcyclopentadienyl) trimethylplatinum (IV), (methoxycarbonylcyclopentadienyl) trimethylplatinum (IV), (dimethylphenylsilylcyclopentadienyl) trimethylcyclopentadienylplatinum (IV), trimethyl ( Acetylacetonato) platinum (IV), trimethyl (3,3) 5-heptanedionate) platinum (IV), trimethyl (methylacetoacetate) platinum (IV), bis (2,4-pentanedionate) platinum (II), bis (2,4-hexanedionate) platinum (II) Bis (2,4-heptanedionato) platinum (II), bis (3,5-heptanedionato) platinum (II), bis (1-phenyl-1,3-butanedionato) platinum (II), bis (1,3 -Photoactive hydrosilylation catalyst (D) hydrophobicity selected from the group consisting of -diphenyl-1,3-propanedionato) platinum (II) and bis (hexafluoroacetylacetonato) platinum (II) Silica powder, and
(E) Organosiloxane having one or more hydrogen atoms directly bonded to silicon atoms and one or more epoxy groups and / or trialkoxysilyl groups bonded to silicon atoms via carbon atoms or carbon atoms and oxygen atoms in one molecule   The fluorine-containing organohydrogensiloxane of the component (B) is one or more monovalent perfluoroalkyl group, monovalent perfluorooxyalkyl group, divalent perfluoroalkylene group, or divalent perfluoro molecule in one molecule. A method for adhering the photocurable fluoropolyether elastomer composition according to claim 1 having a perfluorooxyalkylene group to a substrate. The monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group in which the organosiloxane of component (E) is further bonded to a silicon atom via a carbon atom or a divalent linking group containing a carbon atom and an oxygen atom A method for adhering the photocurable fluoropolyether elastomer composition according to claim 1 or 2 to a substrate. Furthermore, the method to adhere | attach the photocurable fluoropolyether-type elastomer composition of any one of Claims 1-3 containing the reaction control agent of hydrosilylation reaction as a (F) component to a base material. Furthermore, the method to adhere | attach the photocurable fluoropolyether-type elastomer composition of any one of Claims 1-4 containing a carboxylic acid anhydride as (G) component to a base material. 6. The photocurable fluoropolyether elastomer composition according to claim 5 , wherein an optical filter is used for light irradiation, and the irradiance of each wavelength in a wavelength region shorter than 300 nm is 5% or less of the irradiance of the maximum peak wavelength. A method of adhering a substrate to a substrate.