JP2005082700A - Primer composition for thermosetting type fluorine-based elastomer and bonding method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for bonding a thermosetting type fluorine-based elastomer to various kinds of substrates each composed of an inorganic material such as a metal or a glass and an organic material such as a plastic. <P>SOLUTION: The primer composition is used for bonding the thermosetting type fluorine-based elastomer to the inorganic or organic material and consists essentially of (a) a straight-chain fluoropolyether compound having at least two alkenyl groups in one molecule and having a perfluoropolyether structure in the main chain, (b) a fluorine-containing organohydrogensiloxane, (c) a hydrosilylation reaction catalyst and (d) a compound having at least one of epoxy group and/or alkoxysilyl group in one molecule and has ≥0.3 and <1.0 ratio (SiH/alkenyl) of an SiH group and an alkenyl group in the composition. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for bonding various substrates made of an inorganic material such as metal or glass, or an organic material such as plastic, and a thermosetting fluorine-based elastomer.

  A thermosetting elastomer composition mainly composed of a polymer having at least two alkenyl groups in one molecule and a perfluoropolyether structure in the main chain has heat resistance, chemical resistance, and solvent resistance. It gives an elastomer cured product having excellent properties such as water resistance, but at the same time it has excellent release properties, and on the other hand, it is a material that is difficult to adhere.

  In order to adhere to various base materials without causing deterioration of these physical properties, it is necessary to use a primer or the like instead of internally adding an adhesion assistant.

  As a primer, a silane primer mainly composed of a silane coupling agent, a primer mainly composed of synthetic rubber, a primer mainly composed of an acrylic resin, a primer mainly composed of a urethane resin, and an epoxy resin as a main component. Primers and the like are on the market, but these primers are inferior in affinity with the thermosetting elastomer composition and wettability at the interface, so that sufficient adhesion cannot be obtained.

  Patents relating to curable compositions have been proposed in which the primer component is added to a thermosetting fluoroelastomer to give a thermosetting fluoroelastomer having good adhesion to various substrates. (Refer patent documents 1-3) These compositions adhere | attach well with various base materials, such as a metal and a plastic, by the (D) and (E) component in a composition.

  JP-A-9-95615 (Patent Document 1) relates to an addition reaction curable curable composition, and particularly relates to a curable composition that gives a fluorine-containing elastomer having good adhesion to various substrates. A) a linear fluorinated amide compound having vinyl groups at both ends and having a perfluoropolyether structure in the main chain, (B) one or more monovalent perfluorooxyalkyl groups in one molecule , A fluorine-containing organohydrogensiloxane having a monovalent perfluoroalkyl group, a divalent perfluorooxyalkylene group or a divalent perfluoroalkylene group and having two or more hydrosilyl groups, (C) a catalytic amount A platinum group compound, (D) a hydrogen atom directly bonded to a silicon atom in one molecule, an epoxy group bonded to the silicon atom via a carbon atom or a carbon atom and an oxygen atom, and / or Curable composition comprising an organosiloxane having one or more each and trialkoxysilyl groups are disclosed. The curable composition of the present invention provides a cured product excellent in solvent resistance, chemical resistance, heat resistance, low temperature characteristics, low moisture permeability, etc., and is used for metals, plastics and the like by heating at a relatively low temperature for a short time. It is said that a cured product having good adhesion to a substrate can be provided.

  Japanese Patent Laid-Open No. 2001-72868 (Patent Document 2) relates to a curable composition that forms a fluorine-containing elastomer after curing and adheres firmly to various substrates at the time of curing. The curable composition characterized by having (E) a carboxylic acid anhydride as an essential component in the components () to (D). As in the previous publication, the curable composition of the present invention can provide a cured product having good adhesion to various substrates, and in particular, provides a fluorine-containing elastomer having excellent adhesion to PPS and nylon. Therefore, it is said that it is effective for adhesion to articles such as cases based on PPS and nylon.

  Japanese Patent Application Laid-Open No. 2002-105319 (Patent Document 3) relates to a curable composition that forms a fluorine-containing elastomer after curing and adheres firmly to various substrates at the time of curing. A) to (D) component, (E) hydrogen atom bonded to silicon atom in one molecule, cyclic carboxylic anhydride residue bonded to silicon atom via carbon atom, bonded to silicon atom via carbon atom A curable composition characterized by comprising as an essential component an organosiloxane having at least one monovalent perfluorooxyalkyl group or at least one monovalent perfluoroalkyl group is disclosed. The curable composition of the present invention can provide a cured product having good adhesion to various substrates, as in the above publication, and particularly excellent adhesion to polyphenylene sulfide resin, polyamide resin, and polyimide resin. Since the fluorine-containing elastomer is provided, it is considered useful for bonding various automobile parts and electric / electronic parts based on these plastics.

JP-A-9-95615 JP-A-2001-72868 JP 2002-105319 A

  The thermosetting fluoroelastomer composition having adhesiveness disclosed in the above-mentioned publication is an alkoxysilyl group or epoxy group represented by the components (D) and (E) in the known thermosetting fluoroelastomer composition. By adding various compounds (adhesion aids) having a carboxyl group and an acid anhydride structure, it became possible to adhere to metal, glass, ceramics, and plastics. However, when these adhesion aids are added, problems such as a decrease in the mechanical strength of the rubber and a decrease in compression set characteristics may occur. The present inventors have aimed to solve problems such as a decrease in mechanical strength of rubber and a decrease in compression set characteristics due to the internal addition of such adhesive components.

  In the above disclosed technique, the ratio of SiH groups to alkenyl groups (SiH / alkenyl) contained in the entire composition is usually 1.0 or more. Even if the thermosetting fluoroelastomer is cured after being applied and cured on the surface of the substrate, no adhesiveness is developed between the primer layer and the thermosetting fluoroelastomer. On the other hand, the composition in which the ratio of SiH groups to alkenyl groups (SiH / alkenyl) contained in the entire composition was adjusted to 0.3 or more and less than 1.0 was applied to the surface of various substrates and cured. When the thermosetting elastomer composition is cured thereon, adhesiveness is exhibited.

  The present invention has been made in view of the above circumstances, and in particular, a thermosetting elastomer mainly comprising a polymer having at least two alkenyl groups in one molecule and a perfluoropolyether structure in the main chain. It has been found that a method for bonding the composition and various substrates in a well-balanced manner has been provided, and the present invention has been completed.

  As a result of intensive studies to achieve the above object, the present inventors have (a) a linear chain having at least two alkenyl groups in one molecule and a perfluoropolyether structure in the main chain. A fluoropolyether compound (b) a fluorinated organohydrogensiloxane (c) a hydrosilylation catalyst (d) a compound having at least one epoxy group and / or trialkoxysilyl group in one molecule, (a) Various inorganic or organic material groups using as a primer a primer composition in which the component (d) is essential and the ratio of SiH group to alkenyl group (SiH / alkenyl) in the composition is 0.3 or more and less than 1.0 By applying and curing on the material, and then applying and curing a thermosetting fluoroelastomer on it, it can be adhered to various substrates in a well-balanced manner. Theft has been found to be able to.

  For this reason, when (SiH / alkenyl) is 1.0 or more, all the alkenyl groups in the composition are consumed, whereas the method of the present invention, that is, (SiH / alkenyl) is 0.3. When the ratio is less than 1.0, an alkenyl group remains in the composition and on the surface of the composition. Therefore, when a thermosetting fluorine-based elastomer is cured on the composition, a cross-linking reaction occurs with each other, which is strong. This is probably because the adhesiveness is developed.

  The method of the present invention comprises various substrates made of inorganic materials such as metal, glass, ceramics, cement, and mortar, and organic materials such as carbon and plastic, and at least two alkenyl groups in one molecule, and A thermosetting elastomer composition mainly composed of a polymer having a perfluoropolyether structure in the main chain can be suitably adhered.

  Hereinafter, the present invention will be described in more detail. The linear fluoropolyether compound (a) used in the present invention has at least two alkenyl groups in one molecule and is divalent in the main chain. Having a perfluoroalkyl ether structure.

Here, examples of the perfluoroalkyl ether structure include those represented by the following general formula.
_{CH 2 = CH- (X) a} -Rf 1 - (X ') a -CH = CH 2
[Wherein, X is _{-CH 2 -, - CH 2 O} -, - CH 2 OCH 2 - or ^-Y-NR 1 -CO- (Y is -CH ₂ - or the following structural formula (Z)

で示されるｏ，ｍ又はｐ−ジメチルシリルフェニレン基）で表される基、Ｒ^１は水素原子、置換若しくは非置換の一価炭化水素基、Ｘ’は−ＣＨ_２−、−ＯＣＨ_２−、−ＣＨ_２ＯＣＨ_２−又は−ＣＯ−ＮＲ^１−Ｙ’−（Ｙ’は−ＣＨ_２−又は下記構造式（Ｚ’）

O, m or a p-dimethylsilylphenylene group represented by formula (I), R ¹ is a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group, X ′ is —CH ₂ —, —OCH ₂ —, —CH ₂ OCH ₂ — or —CO—NR ¹ —Y′— (Y ′ is —CH ₂ — or the following structural formula (Z ′)

で示されるｏ，ｍ又はｐ−ジメチルシリルフェニレン基）で表される基であり、Ｒ^１は上記と同じ基である。Ｒｆ^１は二価のパーフルオロポリエーテル基であり、ａは独立に０又は１である。］

O, m or p-dimethylsilylphenylene group represented by formula (I), and R ¹ is the same group as described above. Rf ¹ is a divalent perfluoropolyether group, and a is independently 0 or 1. ]

Here, as R ¹ , in the case other than a hydrogen atom, those having 1 to 12 carbon atoms, particularly 1 to 10 carbon atoms are preferable, and specifically, methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group. Groups, alkyl groups such as octyl groups; aryl groups such as phenyl groups and tolyl groups; aralkyl groups such as benzyl groups and phenylethyl groups; and some or all of the hydrogen atoms of these groups are halogen atoms such as fluorine. Examples include substituted monovalent hydrocarbon groups.

Here, Rf ¹ in the above general formula is a divalent perfluoropolyether structure, and compounds represented by the following general formulas (i) and (ii) are preferable.

（式中、ｐ及びｑは１〜１５０の整数であって、かつｐとｑの和の平均は、２〜２００である。また、ｒは０〜６の整数、ｔは２又は３である。）

(In the formula, p and q are integers of 1 to 150, and the average of the sum of p and q is 2 to 200. Also, r is an integer of 0 to 6, and t is 2 or 3. .)

（式中、ｕは１〜２００の整数、ｖは１〜５０の整数、ｔは上記と同じである。）

(In the formula, u is an integer of 1 to 200, v is an integer of 1 to 50, and t is the same as above.)

  (A) As a preferable example of a component, the compound represented by following General formula (1) is mentioned.

［式中、Ｘ及びＸ’は上記と同じである。ａは独立に０又は１、Ｌは２〜６の整数、ｂ及びｃはそれぞれ０〜２００の整数である。］

[Wherein, X and X ′ are the same as above. a is independently 0 or 1, L is an integer of 2 to 6, and b and c are integers of 0 to 200, respectively. ]

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

（式中、ｍ及びｎはそれぞれ０〜２００，ｍ＋ｎ＝６〜２００を満足する整数を示す。）

(In the formula, m and n are integers satisfying 0 to 200 and m + n = 6 to 200, respectively.)

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

  Next, the fluorine-containing organohydrogensiloxane as the component (b) acts as a crosslinking agent and a chain extender as the component (a). In consideration of compatibility with the component (a), dispersibility, and uniformity after curing, one or more monovalent perfluoroalkylene group, monovalent perfluorooxyalkyl group, divalent perfluoro group in one molecule The organic silicon compound is particularly limited as long as it has a fluoroalkylene group or a divalent perfluorooxyalkylene group and has at least two, preferably three or more hydrogen atoms bonded to a silicon atom in one molecule. It is not something.

Examples of the perfluoroalkyl group, perfluorooxyalkyl group, perfluoroalkylene group, and perfluorooxyalkylene group include groups represented by the following general formula.
C _g F _{2g + 1} −
(In the formula, g is an integer of 1 to 20, preferably 2 to 10.)
−C _g F _2g −
(In the formula, g is an integer of 1 to 20, preferably 2 to 10.)

（式中、ｆは２〜２００、好ましくは２〜１００、ｈは１〜３の整数である。）

(In the formula, f is 2 to 200, preferably 2 to 100, and h is an integer of 1 to 3.)

（式中、ｉ及びｊは１以上の整数、ｉ＋ｊの平均は２〜２００、好ましくは２〜１００である。）
−（ＣＦ_２Ｏ）_ｋ−（ＣＦ_２ＣＦ_２Ｏ）_ｓ−ＣＦ_２−
（但し、ｋ及びｓはそれぞれ１〜５０の整数である。）

(In the formula, i and j are integers of 1 or more, and the average of i + j is 2 to 200, preferably 2 to 100.)
_{- (CF 2 O) k -} (CF 2 CF 2 O) s -CF 2 -
(However, k and s are each an integer of 1 to 50.)

These perfluoro (oxy) alkyl groups and perfluoro (oxy) alkylene groups may be directly bonded to the silicon atom, but may be bonded to the silicon atom through a divalent linking group. . Here, the divalent linking group may be an alkylene group, an arylene group, a combination thereof, or an ether bond oxygen atom, an amide bond, a carbonyl bond, etc. interposed therebetween. The thing of 2-12 carbon atoms is preferable, and the following group etc. are mentioned.
—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 (Ph) —CO— (where Ph is a phenyl group)
_{-CH 2 CH 2 CH 2 -N (} CH 3) -CO-
—CH ₂ CH ₂ CH ₂ —O—CO—
And those having 2 to 12 carbon atoms such as

  The monovalent or divalent fluorine-containing substituent in the organosilicon compound of component (b), that is, a monovalent containing a perfluoroalkyl group, a perfluorooxyalkyl group, a perfluorooxyalkylene group or a perfluoroalkylene group. Examples of the monovalent substituent bonded to the silicon atom other than the organic group include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, an octyl group, and a decyl group; a phenyl group, Aryl groups such as tolyl group and naphthyl group; aralkyl groups such as benzyl group and phenylethyl group: or a part of hydrogen atoms of these groups are substituted by chlorine atom, cyano group, etc., for example, chloromethyl group, chloropropyl group And an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms such as a cyanoethyl group.

  The organosilicon compound as component (b) may be cyclic or chain-like, and may be a three-dimensional network. Further, the number of silicon atoms in the molecule of the organosilicon compound is not particularly limited, but usually 2 to 60, particularly about 3 to 30 is preferable.

Examples of such organosilicon compounds include the following compounds, and these compounds may be used alone or in combination of two or more. In the following formulae, Me represents a methyl group Ph represents a phenyl group.

  The amount of component (b) is usually the sum of hydrosilyl groups, ie, SiH groups, in component (b) with respect to 1 mole of alkenyl groups such as vinyl, allyl, and cycloalkenyl groups contained in component (a). The amount is preferably 0.1 to 0.9 mol, more preferably 0.2 to 0.8 mol. When the blending amount in the component (b) is too small, the degree of crosslinking may be insufficient and the cured product may not be obtained. When the blending amount is too large, it will not adhere to the upper thermosetting fluoroelastomer. In addition, when there exists a compound containing an alkenyl group or a hydrosilyl group in other components, such as the below-mentioned (d) component, the whole hydrosilyl group with respect to the whole alkenyl group is 0. 0 also considering the amount of those functional groups. It should be 3 times mol or more and less than 1.0 times mol. Moreover, this (b) component may be used individually by 1 type, and may use 2 or more types together.

As the hydrosilylation reaction catalyst of component (c), transition metals, for example, platinum group metals such as Pt, Rh, and Pd, and compounds of these transition metals are preferably used. In the present invention, since these compounds are generally precious metal compounds and are expensive, platinum compounds that are relatively easily available are preferably used. Specific examples of the platinum compound include chloroplatinic acid or a complex of chloroplatinic acid and olefin such as ethylene, a complex of alcohol or pinylsiloxane, platinum / silica, alumina or carbon. It is not limited to.

As platinum group metal compounds other than platinum compounds, rhodium, ruthenium, iridium, palladium compounds and the like are known. For example, RhCl (PPh ₃ ) ₃ , RhCl (CO) (PPh ₃ ) ₂ , RhC1 (C ₂ H ₄ ) ₂ , Ru ₃ (CO) ₁₂ , IrCl (CO) (PPh ₃ ) ₂ , Pd (PPh ₃ ) ₄ (Ph represents a phenyl group). The amount of these catalysts used is not particularly limited, and a desired curing rate can be obtained with the amount of catalyst. However, in order to obtain an economical viewpoint or a good cured product, the total amount of the curable composition is used. On the other hand, it is good to set it as the range of about 0.1-1,000 ppm (platinum group metal conversion), More preferably about 0.1-500 ppm (same as above).

  Component (d) is for causing the composition of the present invention to exhibit adhesion or adhesion to various substrates. Any compound having one or more epoxy groups or trialkoxysilyl groups in one molecule may be used. More preferably, a compound having at least one epoxy group and trialkoxysilyl group in one molecule is preferable. As long as the component (d) does not inhibit the curing (hydrosilylation) reaction of the present invention, the chemical structure and the like are not limited.

  These organosiloxanes are compounds containing a trialkoxy (trialkyl) silyl group and an aliphatic unsaturated group in an organohydrogenpolysiloxane having three or more hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule. And / or a compound having an aliphatic unsaturated group and an epoxy group, such as allyl glycidyl ether, and a compound containing an aliphatic unsaturated group and a perfluoroalkyl group or a perfluorooxyalkyl group according to a conventional method. It can be obtained by addition reaction.

  The sum of the number of aliphatic unsaturated groups needs to be the same as or less than the number of SiH groups. In the production of the organosiloxane in the present invention, the target substance may be isolated after completion of the reaction, but a mixture in which only the unreacted substance and the addition reaction catalyst are removed can also be used.

  Examples of alkoxy include lower alkoxy groups such as methoxy group, ethoxy group, n-propoxy group and i-propoxy group, lower alkyl groups such as methyl group, ethyl group, n-propyl group and i-propyl group. It is done. Of these, a methoxy group is preferred.

  (D) The usage-amount of a component is 0.1-20 mass parts with respect to 100 mass parts of (a) component, Preferably it is the range of 0.3-10 mass parts. When the amount is less than 0.1 parts by mass, sufficient adhesive strength cannot be obtained, and when it exceeds 20 parts by mass, the physical properties of the obtained cured product are deteriorated, and the curability may be inhibited.

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

（上記一般式中、Ｒ^４はハロゲン置換又は非置換の１価炭化水素基であり、Ａ、Ｂは下記に示す。ｗは０≦ｗ≦１００、ｘは１≦ｘ≦１００、ｙは１≦ｙ≦１００、ｚは０≦ｚ≦１００を示す。）

(In the above general formula, R ⁴ is a halogen-substituted or unsubstituted monovalent hydrocarbon group, A and B are shown below. W is 0 ≦ w ≦ 100, x is 1 ≦ x ≦ 100, and y is 1. <= Y <= 100 and z shows 0 <= z <= 100.)

The halogen-substituted or unsubstituted monovalent hydrocarbon group represented by R ⁴ is preferably a group having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, or a hexyl group. Alkyl groups such as cyclohexyl group and octyl group; aryl groups such as phenyl group and tolyl group; aralkyl groups such as benzyl group and phenylethyl group; and some or all of hydrogen atoms of these groups are halogen such as fluorine. Examples thereof include a substituted monovalent hydrocarbon group substituted with an atom, and among these, 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 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.

［式中、Ｒ^５は酸素原子が介在してもよい炭素数１〜１０、特に１〜５の２価炭化水素基（アルキレン基、シクロアルキレン基等）を示す。］

[Wherein, R ⁵ represents a divalent hydrocarbon group (an alkylene group, a cycloalkylene group, etc.) having 1 to 10 carbon atoms, particularly 1 to 5 carbon atoms in which an oxygen atom may intervene. ]

-R ⁶ -Si (OR ⁷ ) ₃
[Wherein R ⁶ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 4 carbon atoms (alkylene group, etc.), and R ⁷ is a monovalent hydrocarbon group having 1 to 8 carbon atoms, particularly 1 to 4 carbon atoms. (Alkyl group and the like). ]

[Wherein R ⁸ represents a monovalent hydrocarbon group (alkyl group or the like) having 1 to ⁸ carbon atoms, particularly 1 to 4 carbon atoms, R ⁹ represents a hydrogen atom or a methyl group, and k represents an integer of 2 to 10. ]

B represents a monovalent perfluoroalkyl group or a perfluorooxyalkyl group bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom. Examples of the monovalent perfluoroalkyl group or perfluorooxyalkyl group include those represented by the following general formula.
C _s F _{2s + 1} −
(Wherein s is the same as above)
_{F- [CF (CF 3) CF} 2 O] n '-C t F 2t -
(Where n 'and t are the same as above)

  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 It is possible to obtain a compound containing a trialkoxysilyl group and / or a compound containing an aliphatic unsaturated group and a perfluoroalkyl group or a perfluorooxyalkyl group by partial addition reaction according to a conventional method. it can.

  In addition, when the sum of the number of the aliphatic unsaturated groups is smaller than the number of SiH groups, these organosiloxanes contain SiH groups together with epoxy groups and / or trialkoxysilyl groups in one molecule. . Accordingly, it is necessary that the ratio of the sum of the SiH groups of the component (d) and the SiH groups of the component (b) to the alkenyl groups of the component (a) be 0.3 or more and less than 1.0.

  In the production of the organosiloxane in the present invention, the target substance may be isolated after completion of the reaction, but a mixture in which only the unreacted substance and the addition reaction catalyst are removed can also be used.

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

(E) Other components (solvent, filler, etc.)
In the primer composition, a solvent can be used to adjust the viscosity to be suitable for the primer application operation. The solvent is not particularly limited as long as it dissolves or disperses the components (a) to (d) of the present invention. Specific examples of such solvents include hydrocarbon solvents such as toluene, xylene, heptane, hexane, petroleum solvents, halogen solvents such as trichloroethylene, ester solvents such as ethyl acetate and butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl. Ketone solvents such as ketones, alcohol solvents such as methanol, ethanol and isopropanol, silicone solvents such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane, trifluoromethylbenzene, 1,3- Examples thereof include fluorinated solvents such as bistrifluoromethylbenzene and HCFC-225. These solvents may be used alone or in combination of two or more.

  Moreover, you may use various fillers for this primer composition as needed. Specific examples of these fillers include wood powder, pulp, cotton chips, asbestos, glass fiber, carbon fiber, mica, walnut shell powder, rice husk powder, graphite, diatomaceous earth, white clay, fumed silica, precipitated silica, Examples include anhydrous silicic acid, carbon black, calcium carbonate, magnesium carbonate, clay, talc, titanium oxide, cerium oxide, magnesium carbonate, quartz powder, fine aluminum powder, iron oxide, flint powder, and zinc dust. These fillers may be used alone or in combination of two or more.

  Furthermore, you may add various additives to a primer composition as needed. Examples of such additives include anti-aging agents, radical inhibitors, metal deactivators, ozone degradation inhibitors, storage stability improvers, adhesion promoters, various pigments, dyes, and the like. .

Thermosetting fluorinated elastomer The thermosetting fluorinated elastomer described in the present invention is mainly composed of a polymer having at least two alkenyl groups in one molecule and a perfluoropolyether structure in the main chain. In addition to this, an elastomer composition that is heat-cured by a hydrosilylation reaction using a compound having at least two, preferably three or more SiH groups in one molecule, and a platinum group catalyst may be mentioned. Examples of this type of elastomer composition include those described in Japanese Patent No. 2990646, Japanese Patent Application Laid-Open No. 11-116684, Japanese Patent Application Laid-Open No. 2002-12769, and the like. Moreover, as what hardens | cures by peroxide bridge | crosslinking by adding an organic peroxide to the said polymer, what is described in Unexamined-Japanese-Patent No. 2000-7835, Japanese Patent Application No. 2002-001257 etc. can be mentioned, for example. .

Inorganic or organic materials As inorganic materials to be bonded to the thermosetting fluorine-based elastomer of the present invention, various metals such as iron, stainless steel, aluminum, nickel, zinc, gold, silver, copper, carbon, glass, ceramics, Various base materials such as cement, slate, marble and granite, mortar, etc., and the surface of which is plated with metal, organic materials include acrylic resin, phenol resin, epoxy resin, polycarbonate resin, polybutylene terephthalate resin, etc. And various substrates obtained by plating these surfaces with metal. According to this method, these inorganic organic materials etc. and the said thermosetting elastomer composition can be adhere | attached firmly.

Application method, usage method The adhesion method of the present invention uses a coating method in which the composition A is usually employed, for example, a brush coating method, a spray coating method, a wire bar method, a blade method, a roll coating method, a dipping method and the like. To coat the substrate.
Next, it is usually air-dried at room temperature for 1 to 30 minutes, preferably 2 to 15 minutes, and then heated at 50 to 180 ° C. (preferably 80 to 150 ° C.) for 1 to 60 minutes (preferably 5 to 30 minutes). To form.
Thereafter, a thermosetting fluoroelastomer is heat-cured on the film under predetermined conditions, whereby a molded product bonded to the substrate and integrated is obtained.

  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 the following formulae, Me represents a methyl group.

[Production Example 1] (Specific example of thermosetting fluorine-based elastomer composition (B))
Following formula (3)

で表されるポリマー（粘度５，５００ｃｓ、平均分子量１５，３００、ビニル基量０．０１２モル／１００ｇ）１００質量部にヘキサメチルジシラザンと１，３−ジビニル−１，１，３，３−テトラメチルジシラザンとの混合処理剤で処理された比表面積２００ｍ^２／ｇの煙霧質シリカ２０質量部を加え、プラネタリーミキサーで混合および１２０℃熱処理の後、三本ロールミル上にて混合し、更に下記式（４）

The polymer represented by the formula (viscosity 5,500 cs, average molecular weight 15,300, vinyl group content 0.012 mol / 100 g) was added to 100 parts by mass of hexamethyldisilazane and 1,3-divinyl-1,1,3,3- Add 20 parts by mass of fumed silica with a specific surface area of 200 m ² / g treated with a mixed treatment agent with tetramethyldisilazane, mix with a planetary mixer and heat-treat at 120 ° C., then mix on a three roll mill, Furthermore, the following formula (4)

で表される含フッ素有機ケイ素化合物３．３６質量部、塩化白金酸をＣＨ_２＝ＣＨＳｉＭｅ_２ＯＳｉＭｅ_２ＣＨ＝ＣＨ_２で変性した触媒のトルエン溶液（白金濃度０．５重量％）０．２質量部及びエチニルシクロヘキサノールの５０％トルエン溶液０．４質量部を加え、混合し、組成物（Ｂ）を作製した。この組成物（Ｂ）を１５０℃で１０分間加熱したところ、硬化し、ゴムになることを確認した。

3.36 parts by mass of a fluorine-containing organosilicon compound represented by the formula: toluene solution of a catalyst obtained by modifying chloroplatinic acid with CH ₂ ═CHSiMe ₂ OSiMe ₂ CH═CH ₂ (platinum concentration 0.5% by weight) 0.2 mass And 0.4 parts by mass of a 50% toluene solution of ethynylcyclohexanol were added and mixed to prepare a composition (B). When this composition (B) was heated at 150 ° C. for 10 minutes, it was confirmed that it hardened and became rubber.

[Example 1]
Following formula (5)

で表されるポリマー（粘度２，２００ｃｓ、平均分子量６，２００、ビニル基量０．０３１モル／１００ｇ）１００質量部にヘキサメチルジシラザンと１，３−ジビニル−１，１，３，３−テトラメチルジシラザンとの混合処理剤で処理された比表面積３００ｍ^２／ｇの煙霧質シリカ１０質量部を加え、プラネタリーミキサーで混合および１２０℃熱処理の後、三本ロールミル上にて混合し、更に下記式（６）

The polymer represented by the formula (viscosity 2,200 cs, average molecular weight 6,200, vinyl group amount 0.031 mol / 100 g) is added to 100 parts by mass of hexamethyldisilazane and 1,3-divinyl-1,1,3,3- Add 10 parts by mass of fumed silica with a specific surface area of 300 m ² / g treated with a mixed treating agent with tetramethyldisilazane, mix with a planetary mixer and heat treatment at 120 ° C., then mix on a three roll mill, Further, the following formula (6)

で表される含フッ素有機ケイ素化合物１．８９質量部、下記式（７）

1.89 parts by mass of a fluorine-containing organosilicon compound represented by the following formula (7)

で表される有機ケイ素化合物１．００質量部、下記式（８）

1.00 parts by mass of an organosilicon compound represented by the following formula (8)

で表される含フッ素有機ケイ素化合物３．００質量部、塩化白金酸をＣＨ_２＝ＣＨＳｉＭｅ_２ＯＳｉＭｅ_２ＣＨ＝ＣＨ_２で変性した触媒のトルエン溶液（白金濃度０．５重量％）０．２質量部及びエチニルシクロヘキサノールの５０％トルエン溶液０．４質量部を加え、プラネタリーミキサーで混合した。次いでこの混合物に１，３−ビストリフルオロメチルベンゼン４４０質量部を加えて均一に溶解分散させてプライマー組成物（Ｉ）を調整した。なお、この組成物（Ｉ）におけるＳｉＨ基とアルケニル基の理論比率（ＳｉＨ／アルケニル）は０．７０である。

3.00 parts by mass of a fluorine-containing organosilicon compound represented by the formula: toluene solution of a catalyst obtained by modifying chloroplatinic acid with CH ₂ ═CHSiMe ₂ OSiMe ₂ CH═CH ₂ (platinum concentration 0.5% by weight) 0.2 mass And 0.4 parts by mass of a 50% toluene solution of ethynylcyclohexanol were added and mixed with a planetary mixer. Next, 440 parts by mass of 1,3-bistrifluoromethylbenzene was added to this mixture and uniformly dissolved and dispersed to prepare primer composition (I). In addition, the theoretical ratio (SiH / alkenyl) of the SiH group and the alkenyl group in the composition (I) is 0.70.

[Example 2]
Instead of the fluorine-containing organosilicon compound represented by the formula (6) in [Example 1], the following formula (9)

で表される含フッ素有機ケイ素化合物４．１２質量部を配合する以外は、［実施例１］と同様の操作によってプライマー組成物（II）を調製した。なお、この組成物（II）におけるＳｉＨ基とアルケニル基の理論比率（ＳｉＨ／アルケニル）は０．９５である。

A primer composition (II) was prepared in the same manner as in [Example 1] except that 4.12 parts by mass of the fluorine-containing organosilicon compound represented by formula (1) was added. The theoretical ratio of SiH groups to alkenyl groups (SiH / alkenyl) in this composition (II) is 0.95.

[Comparative Example 1]
The primer composition (III) was prepared in the same manner as in [Example 2] except that the amount of the fluorine-containing organosilicon compound represented by formula (9) in [Example 2] was increased to 5.89 parts by mass. Was prepared. In addition, the theoretical ratio (SiH / alkenyl) of the SiH group to the alkenyl group in the composition (III) is 1.20.

The primer compositions I to III of Examples 1 and 2 and Comparative Example 1 were applied to a test piece (100 mm × 25 mm × 1 mm) of iron, aluminum, glass, phenol resin, and epoxy resin with a brush, and 5 at room temperature. The mixture was air-dried and heat-treated at 120 ° C. for 15 minutes.
On these primer surfaces, a mold having a bead shape of 100 mm × 2 mm × 2 mm was applied, and the heat-curable fluorine-based elastomer composition of Production Example 1 was injected and cured by heating at 150 ° C. for 30 minutes. The adhesive strength of these integrally molded products was measured with a 90-degree peel adhesion strength tester according to JIS K 6854-1. The results are shown in Table 1.

From the results of Table 1, according to the method of adhering using the primer compositions I and II in which the theoretical ratio of SiH group to alkenyl group (SiH / alkenyl) is 0.3 or more and less than 1.0, the thermosetting type The fluorine-based elastomer and various adherends could be adhered well.
On the other hand, in Comparative Example 1 (use of Composition III) in which the theoretical ratio of SiH groups to alkenyl groups (SiH / alkenyl) is 1.0 or more, a thermosetting fluoroelastomer and various adherends are used. Could not be adhered.

[Example 3]
Test samples according to JIS K6251 and JIS K6262 were prepared using the composition of [Production Example 1]. In addition, the hardening conditions at the time of test sample preparation were 150 degreeC-1 hour. Using the prepared test sample, a tensile strength test (JIS K6251) and a compression set (JIS K6262) after 120% at 72 ° C. under 25% compression were measured. The results are shown in Table 2.

[Comparative Example 2]
In the composition of [Production Example 1], the addition amount of the fluorine-containing organosilicon compound represented by the formula (4) was changed to 2.80 parts by mass, and the fluorine-containing organosilicon compound represented by the formula (7) A composition (C) to which 0.61 part by mass was added was prepared. A test sample similar to [Example 3] was prepared using this composition, and a tensile strength test (JIS K6251) and a compression set (JIS K6262) after 120% at 72 ° C. under 25% compression were measured (JIS K6262). did. The results are shown in Table 2.

Comparison of compression set characteristics

Comparative Example 2 is obtained by adding a compound containing a trialkoxysilyl group and an epoxy group represented by the formula (7) to the thermosetting fluorine-based elastomer composition (B). It can be seen that the mechanical properties and compression set properties of the rubber are impaired.

Claims (9)

A primer composition used for adhesion between a thermosetting fluorine-based elastomer and an inorganic or organic material, and the following (a) to (d) components are essential, and SiH groups and alkenyl groups in the composition are included. A primer composition having a ratio (SiH / alkenyl) of 0.3 or more and less than 1.0.
(A) a linear fluoropolyether compound having at least two alkenyl groups in one molecule and a perfluoropolyether structure in the main chain (b) a fluorinated organohydrogensiloxane (c) hydrosilylation reaction Catalyst (d) Compound having at least one epoxy group and / or trialkoxysilyl group in one molecule The composition according to claim 1, wherein the component (a) is represented by the following general formula.
_{CH 2 = CH- (X) a} -Rf 1 - (X ') a -CH = CH 2
[Wherein, X is _{-CH 2 -, - CH 2 O} -, - CH 2 OCH 2 - or ^-Y-NR 1 -CO- (Y is -CH ₂ - or the following structural formula (Z)

O, m or a p-dimethylsilylphenylene group represented by formula (I), R ¹ is a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group, X ′ is —CH ₂ —, —OCH ₂ —, —CH ₂ OCH ₂ — or —CO—NR ¹ —Y′— (Y ′ is —CH ₂ — or the following structural formula (Z ′)

O, m or p-dimethylsilylphenylene group represented by formula (I), and R ¹ is the same group as described above. Rf ¹ is a divalent perfluoropolyether group, and a is independently 0 or 1. ] The fluorine-containing organohydrogensiloxane of component (b) is one or more monovalent perfluorooxyalkyl groups, monovalent perfluoroalkyl groups, divalent perfluorooxyalkylene groups or divalent perfluoro in one molecule. The composition according to any one of claims 1 to 3, which has an alkylene group and has two or more hydrogen atoms bonded to a silicon atom. The compound of component (d) has at least one perfluoroalkyl group or perfluorooxyalkyl group bonded to a silicon atom via a carbon atom in organopolysiloxane. The composition as described. The thermosetting fluorine-based elastomer is mainly composed of a polymer having at least two alkenyl groups in one molecule and a perfluoropolyether structure in the main chain, and at least two SiH groups in one molecule. The composition according to claim 1, which is an elastomer obtained by heat-curing a composition containing a compound having a platinum group catalyst and a hydrosilylation reaction. The thermosetting fluorine-based elastomer is mainly composed of a polymer having at least two alkenyl groups in one molecule and a perfluoropolyether structure in the main chain, and at least two SiH groups in one molecule. The composition according to claim 1, which is an elastomer that is cured by peroxide crosslinking by adding an organic peroxide to a compound having the following. The inorganic material is a material selected from various metals, carbon, glass, ceramics, cement, slate, stone such as marble and granite, various base materials such as mortar, and those whose surfaces are coated with metal. The composition according to 1 to 4. The composition according to any one of claims 1 to 4, wherein the organic material is a material selected from an acrylic resin, a phenol resin, an epoxy resin, a polycarbonate resin, a polybutylene terephthalate resin, and a material whose surface is coated with a metal. A method for adhering a material to a thermosetting fluoroelastomer comprising applying and curing a primer composition on the surface of an inorganic or organic material, and further curing a thermosetting fluoroelastomer thereon.