JP2008119894A - Composite body having perfluoroelastomer molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composite body having a perfluoroelastomer molding in which the perfluoroelastomer molding is firmly adhered to an adherend such as a metal body. <P>SOLUTION: The perfluoroelastomer molding (A) is adhered to the adherend (C) through an adhesive layer (B). The adhesive layer (B) is a laminate composed of a first adhesive layer (B1) arranged on the side of the adherend (C) and a second adhesive layer (B2) arranged on the side of the perfluoroelastomer molding (A). An adhesive containing an aromatic vinyl benzyl ether and a maleimide compound or an adhesive containing an aromatic vinyl benzylamine compound and a maleimide compound is used in the first adhesive layer (B1). A fluororubber adhesive incorporated with an organic silane compound is used in the second adhesive layer (B2). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a composite in which a perfluoroelastomer molded product is firmly bonded to an adherend and a seal comprising the composite.

  Fluorine-based elastomers are used as rubber elastic members in various devices and mechanisms because of their excellent chemical resistance. In particular, perfluoroelastomer exhibits outstanding chemical resistance, so its molded product (rubber elastic member) can be used in extremely harsh environments where various plasmas and radicals fly, such as semiconductor manufacturing equipment that performs etching. Often served. Specifically, for example, a seal material for a gate valve seal (that is, a gate seal) that forms an opening / closing portion between chamber gates such as between a load lock chamber and a transfer chamber, between a transfer chamber and a process chamber in a semiconductor manufacturing apparatus, Or it is used as a sealing material used for the connection part of piping of a semiconductor manufacturing apparatus.

  However, since perfluoroelastomer has outstanding chemical resistance, it is not easy to bond to other members (parts), and the above-mentioned gate seal is usually made of a sealing material made of a perfluoroelastomer molded product. Fixing to the sealing metal fitting (main body metal fitting) is performed by forming a fitting groove on the sealing metal fitting and fitting a fitting protrusion formed on the sealing material into the fitting groove.

  By the way, in a gate valve of a semiconductor manufacturing apparatus, in order to increase production efficiency, the gate valve is often operated in L motion. In other words, when closing (sealing) the opening formed in the valve body that serves as a semiconductor inlet / outlet, the gate seal serving as the opening / closing lid is contacted with the valve body from its initial position. After moving to a position facing the opening, the gate seal is pressed against the opening to seal (seal) the opening. When opening the opening, the gate seal is moved away from the opening and moved downward (or up) while being in contact with the valve body. Position). However, in such an L-motion operation, the gate seal moves while contacting the valve body, which causes a problem that the seal material of the gate seal is detached from the fixing groove of the body fitting (sealing fitting). Yes.

Therefore, the present inventors have examined bonding a sealing material made of perfluoroelastomer to the main body metal fitting (sealing metal fitting), but as described above, bonding the perfluoroelastomer to other members (components). It was not easy, and satisfactory adhesive strength (adhesive strength) could not be obtained by a known adhesion method. That is, for example, in Patent Document 1, it is said that the perfluoroelastomer is firmly bonded to a metal through a vulcanized adhesive layer mainly composed of a silane coupling agent and a fluororubber layer. When the gate seal produced using such an adhesion method was subjected to L-motion, the sealing material peeled off from the seal fitting relatively early. In addition, “Chemlock No. 607” (trade name) manufactured by Road Far East Co., Ltd. is known as an adhesive for perfluoroelastomer, but also in a gate seal produced using the adhesive, After the L-motion, the sealing material was peeled off from the sealing metal fittings relatively early.
JP 2000-272045 A

In view of the above circumstances, the problem to be solved by the present invention is that a composite having a perfluoroelastomer molded product in which the perfluoroelastomer molded product is extremely firmly bonded to an adherend made of metal or the like, particularly a perfluoroelastomer Perfluoroelastomer molding in which the perfluoroelastomer molded product hardly peels off from the adherend even when the molded product is moved in contact with another object (that is, when it is slid with another object). It is providing the composite which has a thing.
Further, it is a seal in which a sealing material made of a perfluoroelastomer molded product is bonded to a sealing metal fitting (main metal fitting). For example, even if it is used in a moving state while maintaining a sealing property such as a gate seal of a semiconductor device, the seal It is to provide a seal in which peeling (separation) between a material and a seal metal fitting (main metal fitting) is extremely difficult to occur.

As a result of diligent research to solve the above problems, the present inventors have found that an adhesive containing an aromatic vinyl benzyl ether compound and a maleimide compound, or an adhesive containing an aromatic vinyl benzylamine compound and a maleimide compound, and an organic The present invention was completed by finding that an adhesive layer obtained by laminating a fluororubber adhesive containing a silane compound can extremely strongly bond a perfluoroelastomer molded product to other members (particularly metal members). It came to do.
That is, the present invention
(1) A composite comprising a perfluoroelastomer molded product (A) bonded to an adherend (C) via an adhesive layer (B),
The adhesive layer (B) includes a first adhesive layer (B1) arranged on the adherend (C) side and a second adhesive layer (on the perfluoroelastomer molded product (A) side). A laminate with B2),
The first adhesive layer (B1) is made of an adhesive containing an aromatic vinyl benzyl ether compound and a maleimide compound, or an adhesive containing an aromatic vinyl benzylamine compound and a maleimide compound, and the second adhesive layer (B2). A composite having a perfluoroelastomer molded product, characterized in that it comprises a fluororubber adhesive containing an organosilane compound,
(2) The composite according to (1) above, wherein the adhesive containing an aromatic vinyl benzyl ether compound and a maleimide compound, or the adhesive containing an aromatic vinyl benzylamine compound and a maleimide compound further contains an allyl compound,
(3) The composite according to (1) or (2), which is for a semiconductor manufacturing apparatus,
(4) A seal made of the composite according to (1) or (2) above, wherein the perfluoroelastomer molded product (A) is a sealing material, and the adherend (C) is a sealing metal fitting, and (5) The seal according to (4) above, which is used for sealing a semiconductor manufacturing apparatus,
About.

  According to the present invention, it is possible to obtain a composite having a perfluoroelastomer molded product in which the perfluoroelastomer molded product is extremely firmly bonded to an adherend made of metal or the like. Therefore, for example, when a sealing material is formed from a perfluoroelastomer molded product and this is adhered to a sealing metal fitting (main body metal fitting) to form a seal (composite), the seal slides the sealing material with another object. Even when used, a highly durable seal is obtained in which peeling (separation) of the sealing material from the sealing metal fitting (main metal fitting) hardly occurs. Therefore, for example, when applied to a seal used in a moving state while maintaining a sealing property such as a gate seal of a semiconductor manufacturing apparatus, even if the seal is operated in L motion, the sealing material is peeled off from the seal fitting. It can be prevented for a long time.

Hereinafter, the present invention will be described in more detail with reference to the drawings.
FIG. 1 is a diagram schematically showing a cross section of a composite (hereinafter simply referred to as “composite”) having a perfluoroelastomer molded product of the present invention.
As shown in FIG. 1, in the composite 100 having the perfluoroelastomer molded product of the present invention, the perfluoroelastomer molded product (A) is bonded to the adherend (C) via the adhesive layer (B). The first adhesive layer (B1) disposed on the adherend (C) side and the second disposed on the perfluoroelastomer molded product (A) side. An adhesive comprising an adhesive layer (B2) and a first adhesive layer (B1) containing an aromatic vinylbenzyl ether compound and a maleimide compound, or an adhesive containing an aromatic vinylbenzylamine compound and a maleimide compound The second adhesive layer (B2) is formed of a fluororubber adhesive containing an organosilane compound.

  The composite having the perfluoroelastomer molded product of the present invention can be applied to a known composite member in which the perfluoroelastomer molded product is integrated with another member (component) in various technical fields and applications. Examples of the composite member include a seal and a cushion.

In the composite of the present invention, examples of the material of the adherend (C) to which the perfluoroelastomer molded product (A) is bonded include organic, inorganic, and composite materials thereof. Specifically, metals, ceramics, Resin, rubber, etc. Here, examples of the metal include iron, stainless steel, aluminum, aluminum alloy, copper, and brass. Examples of the ceramic include oxide (Al ₂ O ₃ , MgO, ZrO ₂ , UO ₂ SiO ₂ , ZnO, BaTi ₃ , ferrite, PZT, MgAl ₂ O ₄ , SrZnO ₃ ), carbide (SiC, B ₄ C, WC, UC), nitride (Si ₃ N ₄ , AlN, BN), boride (ZrB ₂ , TiB ₂ , LaB ₆ ), silicide (MoSi ₂ ), fluoride (CaF ₂ , BaF ₂ , MgF ₂ ), sulfide (ZnS, MxMoS ₆ (M = Pb, Cu, Gd), TiS ₂ ), etc. It is done. Examples of the resin include polyetheretherketone (PEEK), polysulfone (PSF), polyetherimide (PEI), liquid crystal polymer (LCP), polyphenylene sulfide (PPS), polyimide (PIm), and polyamideimide (PAI). ), Polyarylate (PAr), polycarbonate (PC), polybutylene terephthalate (PBT), maleimide resin and the like. The shape of the adherend (C) is appropriately determined according to the intended use of the composite (composite member).

  Since the adhesive layer (B) having a specific composition and a specific laminated structure used in the present invention exhibits particularly good adhesion to metal, the adherend (C) is a metal in the composite of the present invention. In some cases, an extremely high adhesive force (adhesive strength) can be obtained between the perfluoroelastomer molded product (A) and the adherend (C). Specifically, in addition to seals and other components in semiconductor manufacturing equipment used in clean environments, seals used in medical equipment (seal that requires chemical resistance), seals used in coating machines, etc. Seals that require paint resistance and cleaning fluid resistance), among others, seals that require particularly high adhesive strength between the sealing material (perfluoroelastomer molded product) and the metal fittings for sealing. It is suitable for a seal used in a state of moving while maintaining its properties, specifically suitable for a seal of a semiconductor device (a seal used for a connection place such as a gate seal and piping), and particularly suitable for a gate seal. It is.

  When the composite of the present invention is applied to a seal, examples of the constituent material of the sealing metal fitting (main metal fitting) that is the adherend (C) include iron, aluminum, aluminum alloy, stainless steel (SUS), and steel ( Carbon steel, special steel) and the like. Among them, aluminum and aluminum alloys are preferable in terms of light weight and recyclability, but when these are used, the surface is hardened (alumite treatment). It is preferable to do this. SUS and the like are preferable from the viewpoint of rust prevention. The shape of the sealing metal fitting (main body metal fitting) is appropriately determined depending on the application of the seal, the shape of the application site of the seal, and the like. In the case of a gate seal of a semiconductor device, it is determined in accordance with the shape of an opening serving as a semiconductor inlet / outlet provided in the gate valve, and is usually a plate having a square or rectangular main surface. Here, the square and rectangle include a shape in which the corners of the four corners are replaced with curved lines. In addition, the main surface is a polygon other than a quadrangle (a polygon having a triangular or pentagonal corner (including a shape in which all corners are replaced with curved lines)), a circle, an oval, an ellipse, etc. And a plate-like body.

  In the composite of the present invention, the perfluoroelastomer molded product (A) was prepared by blending a tetrafluoroethylene-perfluoro (methyl vinyl ether) copolymer with a filler, a vulcanizing agent, a vulcanization accelerator, an acid acceptor and the like. The composition is molded and vulcanized. Usually, a molding composition obtained by adding a vulcanizing agent, a filler and the like to a tetrafluoroethylene-perfluoro (methyl vinyl ether) copolymer and mixing with a known mixer such as roll mixing, kneader mixing, and banbury mixing. Is molded into a desired shape by extrusion molding, pressure molding or the like, and vulcanized simultaneously with molding or after molding.

  The shape of the perfluoroelastomer molded product (A) is appropriately determined according to the intended use of the composite (composite member) and is not particularly limited. However, when the composite is applied to a seal (that is, perfluoroelastomer molding). In the case where the object (A) is used as a sealing material for a seal), a shape that is usually in surface contact with a sealing metal fitting is preferable.

[First adhesive layer (B1)]
In the present invention, the “adhesive containing an aromatic vinyl benzyl ether compound and a maleimide compound” used for the first adhesive layer (B1) of the adhesive layer (B) has at least one vinyl benzyl ether group. It means an adhesive composed mainly of a composition in which 1 to 200 parts by weight of a maleimide compound having one or more maleimide groups in the molecule per 100 parts by weight of the aromatic vinyl benzyl ether compound.

  The “aromatic vinyl benzyl ether compound having at least one vinyl benzyl ether group” is represented by the following formulas (I), (II), (III) and (IV).

(Where n is an integer from 2 to 10)

(In the formula, Y in the general formula (II) represents an aromatic residue (residue obtained by removing a hydroxy group from a polyhydric phenol compound). In the general formula (III) and the general formula (IV), X _{1 to} X ₆ are vinylbenzyl ether groups, R _{1 to} R ₃ are hydrogen or alkyl groups, and a, b, c, d, e, and f are 8 ≧ (a + b) ≧ 2, 7 ≧ (c + d) ≧ 1, 7 ≧ (e + f) ≧ 1 is an integer satisfying the relation: p represents an integer of 0 to 5, A represents a hydrocarbon residue having 1 to 7 carbon atoms, and B represents (Represents a benzene or naphthalene residue having a vinylbenzyl ether group.)

  The aromatic vinyl benzyl ether compounds represented by the formulas (I), (II), (III) and (IV) can be obtained by reacting halomethylstyrene with a polyhydric phenol in the presence of alkali. For example, it can be produced by the method described in JP-A No. 64-65110.

  The polyaromatic phenols or derivatives thereof used as the raw materials of the formulas (I) and (II) include hydroquinone, resorcin, catechol, 2,3-dioxytoluene, 3,4-dioxytoluene, 4-t -Butyl catechol, cresolcin, orcin, β-orcin, m-xylorcine, 4-n-hexyl resorcin, 2-methylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, 2,5-diethoxy Hydroquinone, 2,3,6-trimethylhydroquinone, pyrogallol-2-methyl ether, pyrogallol monoacetate, 1,3,5-trioxybenzene, 4,4-biphenol, 2,4-biphenol, bisphenol F, bisphenol A, Bisphenol S, Bisphenol Z, Bisphenol A Bisphenol SH, tetramethylbisphenol A, 4,4′-dihydroxybenzophenone, 4,4′-dihydroxydiphenyl ether, condensate of bisphenol A having a terminal phenol group and epichlorohydrin, bisphenol A having a phenol group at the terminal, Examples include condensates with 4,4'-dichlorodiphenylsulfone, novolak phenols which are condensates of phenol, alkylphenol or bisphenol A and formalin, and polyhydric phenols such as phenol alkyls.

  Examples of the naphthalene derivatives used as the raw materials of the general formulas (III) and (IV) include 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, , 6-Dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,2,3-trihydroxynaphthalene 1,2,4-trihydroxynaphthalene, 1,4,5-trihydroxynaphthalene, 1,2,3,4-tetrahydroxynaphthalene, 1,2,3,4,5,8-hexahydroxynaphthalene, naphthol , Novolak, naphthol, and phenol by condensation of formaldehyde Novolak, such as by condensation with formalin, and the like.

  On the other hand, “maleimide compound having one or more maleimide groups in the molecule” means a known maleimide compound, for example, monofunctional maleimide such as phenylmaleimide, cyclohexylmaleimide, laurylmaleimide, N, N′-phenylenebismaleimide, N , N'-xylene bismaleimide, N, N'-tolylene bismaleimide, N, N'-diphenylmethane bismaleimide, N, N'-diphenyl ether bismaleimide, N, N'-diphenylmethane bismethylmaleimide, N, N ' Examples include diphenyl ether bismethylmaleimide, bismaleimides partially modified with aromatic diamine, bismaleimides partially modified with an aromatic amine added with an epoxy resin, and polymaleimide having an aniline resin skeleton. The maleimide compound can be used alone, but may be used by mixing with an allyl compound having one or more allyl groups in the molecule. Examples of the allyl compound having one or more allyl groups in the molecule include allylphenol, allyloxybenzene, triallyl cyanurate, triallyl isocyanurate, diallyl ether of bisphenol A, diallyl ether of biphenol, o, o'- Examples include diallyl-substituted bisphenol A, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl maleate, eugenol, safrole, allyl glycidyl ether, and allyl resins.

  The blending amount of the maleimide compound (when an allyl compound having one or more allyl groups in the molecule is not used) is preferably 1 to 200 parts by weight, and 50 to 150 parts by weight per 100 parts by weight of the aromatic vinyl benzyl ether compound. More preferred. When the amount is less than 1 part by weight or exceeds 200 parts by weight, any of them is not preferable because of poor adhesion.

  When the maleimide compound is used in combination with an allyl compound, the maleimide compound is preferably a maleimide compound mixed at a weight ratio of polyfunctional maleimide / monofunctional maleimide = 20/80 to 95/5. The mixing ratio of the compound and the allyl compound is 1 to 200 parts by weight, preferably 50 to 150 parts by weight of the allyl compound per 100 parts by weight of the maleimide compound. When the weight ratio of polyfunctional maleimide / monofunctional maleimide exceeds the above range, the adhesiveness decreases, and when the allyl compound exceeds 200 parts by weight per 100 parts by weight of the maleimide compound, the adhesiveness decreases. The amount of the maleimide compound and allyl compound used is preferably 1 to 200 parts by weight, more preferably 50 to 150 parts by weight, per 100 parts by weight of the aromatic vinyl benzyl ether compound. When the amount is less than 1 part by weight or exceeds 200 parts by weight, the adhesiveness becomes poor in any case, which is not preferable.

A composition in which a maleimide compound is blended with an aromatic vinyl benzyl ether compound having one or more vinyl benzyl ether groups, or a maleimide compound and an allyl compound are blended in an aromatic vinyl benzyl ether compound having at least one vinyl benzyl ether group. The resulting composition may further contain an organosilane compound. By blending the organosilane compound, the adhesiveness is further improved.
As the organosilane compound, the general formula (V):

(In the formula, R represents a vinyl group, an amino group, a mercapto group, a methacryloyloxy group, a 3,4-epoxycyclohexyl group, a glycidyloxy group, an N-β-aminoethyl-γ-amino group, etc., and X represents a halogen. R ′ represents an alkoxy group, an alkoxyalkoxy group, an alkyl group, an alkoxyalkyl group, m represents 0 to 3, and n represents 0 to 2), and specific examples include: Vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, γ-glycidoxypropyltri Methoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxy Sisilane, N-β- (aminomethyl) -γ-aminopropyltrimethoxysilane, N-bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ-chloropropyltri Methoxysilane, γ-mercaptopropyltrimethoxysilane, N- (dimethoxymethylsilylpropyl) ethylenediamine, γ-glycidoxypropylmethyldiethoxysilane, vinyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, etc. Can be mentioned.

  The amount of the organic silane compound used is 200 parts by weight or less, preferably 100 parts by weight or less, preferably 100 parts by weight of a composition in which a maleimide compound is blended with an aromatic vinyl benzyl ether compound or an allyl compound. 1 to 20 parts by weight. When the amount of the organic silane compound exceeds 200 parts by weight, the adhesiveness is lowered, which is not preferable. Further, a phenol resin may be further blended in a composition in which a maleimide compound is blended with an aromatic vinyl benzyl ether compound, or in a composition in which an allyl compound is blended with these. By adding a phenol resin, further improvement in adhesiveness can be expected. The phenol resin may be any of a resole, novolac, and cresol phenol resin. The amount of the phenol resin used is 200 per 100 parts by weight of a composition comprising an aromatic vinyl benzyl ether compound and a maleimide compound or 100 parts by weight of a composition comprising a mixture of an aromatic vinyl benzyl ether compound, a maleimide compound and an allyl compound. It is 1 to 20 parts by weight or less, preferably 1 to 20 parts by weight. When the blending amount of the phenol resin exceeds 200 parts by weight, the adhesive layer becomes brittle, which is not preferable.

  The adhesive is dissolved in a solvent such as N, N-dimethylformamide or methyl ethyl ketone and used as a 20 to 80% solution. Other solvents that can be used include acetone, 4-methoxy-4-methylpentanol, ethyl acetate, methyl acetate, butyl acetate, N-methyl-2-pyrrolidone, tetrahydrofuran and the like.

  In the present invention, the “adhesive containing an aromatic vinylbenzylamine compound and a maleimide compound” used for the first adhesive layer (B1) of the adhesive layer (B) includes aromatic amines and halomethyl. A composition comprising 1 to 200 parts by weight of a maleimide compound having one or more maleimide groups in the molecule per 100 parts by weight of an N-vinylbenzyl-substituted aromatic amine compound obtained by reacting styrene with an alkali. It means the adhesive composed mainly.

Here, “the N-vinylbenzyl-substituted aromatic amine compound obtained by reacting an aromatic amine with halomethylstyrene in the presence of an alkali”
Formula (VI)

(In the formula, X represents a residue obtained by removing y hydrogen atoms in the amino group of the amine, and y represents a value of 1 to 6 in the formula).

  This N-vinylbenzyl-substituted aromatic amine compound can be produced, for example, by the method described in JP-A-3-290414.

  As aromatic amines used as a raw material of the general formula (VI), o-toluidine, m-toluidine, p-toluidine, o-ethylaniline, m-ethylaniline, p-ethylaniline, on-propylaniline, pn-propylaniline, o-isopropylaniline, p-isopropylaniline, o-3-xylidine, o-4-xylidine, m-2-xylidine, m-4-xylidine, m-5-xylidine, p-2 -Aromatic monoamines such as xylidine, pseudocumidine (2,4,5-trimethylaniline), mesitidine (2,4,6-trimethylaniline), p-aminoacetanilide;

  o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, N-methyl-p-phenylenediamine, N-phenyl-p-phenylenediamine, N, N'-dimethyl-p-phenylenediamine, 4-amino-p -Diphenylamine, N, N'-diphenyl-p-phenylenediamine, 2,3-diaminotoluene, 2,4-diaminotoluene, 3,4-diaminotoluene, 2,6-diaminotoluene, 3,5-diaminotoluene, 2,5-diaminotoluene, 2,4-diaminodiphenylamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl ketone, 4, Aromatic dia such as 4'-diaminodiphenylsulfone Down like; and

  Aromatic polyvalent amines such as 1,2,3-triaminobenzene, 1,2,4-triaminobenzene, 1,3,5-triaminobenzene; α-methylphenylhydrazine, β-methylphenylhydrazine And aromatic hydrazines such as α-ethylphenylhydrazine and β-ethylphenylhydrazine.

  Also, o-aminophenol, m-aminophenol, p-aminophenol, N-methyl-p-aminophenol, N-phenyl-p-aminophenol, 3-amino-2-oxytoluene, 4-amino-2- Oxytoluene, 5-amino-2-oxytoluene, 6-amino-2-oxytoluene, 2-amino-3-oxytoluene, 4-amino-3-oxytoluene, 5-amino-3-oxytoluene, 6- Amino-3-oxytoluene, 2-amino-4-oxytoluene, 3-amino-4-oxytoluene, 5-amino-3-oxytoluene, 6-amino-3-oxy-o-xylene, 3-amino- 4-oxy-o-xylene, 5-amino-4-oxy-o-xylene, 5-amino-2-oxy-m-xylene, 5-amino-4-oxy -M-xylene, 2-amino-5-oxy-m-xylene, 4-amino-5-oxy-m-xylene, 3-amino-2-oxy-p-xylene, 5-amino-2-oxy-p -Xylene, 6-amino-2-oxy-p-xylene, 3-aminocatechol, 4-aminocatechol, 3-aminoguaiacol, 6-aminoguaiacol, 4-aminoguaiacol, 5-aminoguaiacol, 2-aminoresorcin, 4-aminoresorcin, 5-aminoresorcin, 2-aminohydroquinone, 2,4-diaminophenol, 2,6-diaminophenol, 2,5-diaminophenol, 4,5-diaminophenol, 3,4-diaminophenol, 3,5-diaminophenol, 4,6-diaminoresorcin, 2,4,6-triaminopheno Aminophenols, such as can be used.

  The N-vinylbenzyl-substituted aromatic amine compound may be a vinylbenzyl ether compound having one or more vinylbenzyl ether groups as represented by the general formula (I). The vinyl benzyl ether compound is produced in various proportions depending on the reaction conditions of aromatic amines and halomethylstyrene.

  The other main component of the adhesive, “maleimide compound having one or more maleimide groups in the molecule” means known maleimide compounds such as phenylmaleimide, cyclohexylmaleimide, laurylmaleimide, etc. Monofunctional maleimide, N, N′-phenylene bismaleimide, N, N′-xylene bismaleimide, N, N′-tolylene bismaleimide, N, N′-diphenylmethane bismaleimide, N, N′-diphenyl ether bismaleimide, N, N'-diphenylmethane bismethylmaleimide, N, N'-diphenylether bismethylmaleimide, bismaleimides partially modified with aromatic diamine, bismaleimides partially modified with aromatic amine with epoxy resin addition, aniline resin Skeletal polymaleimide, etc. And the like. These maleimide compounds may be used alone or in combination with an allyl compound having one or more allyl groups in the molecule.

  Examples of the allyl compound include those similar to the “allyl compound” described in the above “adhesive containing an aromatic vinyl benzyl ether compound and a maleimide compound”.

  When the maleimide compound and the allyl compound are used alone, the maleimide compound and the allyl compound are used in an amount of 1 to 200 parts by weight, preferably 50 to 150 parts by weight, based on 100 parts by weight of the N-vinylbenzyl-substituted aromatic amine compound. Parts by weight. When the maleimide compound is less than 1 part by weight or more than 200 parts by weight with respect to 100 parts by weight of the N-vinylbenzyl-substituted aromatic amine compound, any of them is not preferable because of poor adhesion.

  Moreover, when using a maleimide compound mixed with an allyl compound, the maleimide compound is preferably a maleimide compound mixed at a weight ratio of polyfunctional maleimide / monofunctional maleimide = 20/80 to 95/5. . The mixing ratio of the maleimide compound and the allyl compound is 1 to 200 parts by weight, preferably 50 to 150 parts by weight of the allyl compound with respect to 100 parts by weight of the maleimide compound. Adhesiveness varies depending on the type of adherend, the type of allyl compound, and the amount used, but when the weight ratio of polyfunctional maleimide / monofunctional maleimide exceeds the above range, the adhesiveness generally decreases in the combined system with allyl compound. Tend to. Moreover, when an allyl compound exceeds 200 weight part with respect to 100 weight part of maleimide compounds, adhesiveness falls similarly to the above, and is unpreferable. Furthermore, the usage-amount of the mixture which consists of a maleimide compound and an allyl compound is 1-200 weight part with respect to 100 weight part of N-vinylbenzyl aromatic substituted amine compounds, Preferably it is 50-150 weight part. When the amount is less than 1 part by weight or exceeds 200 parts by weight, the adhesiveness becomes poor in any case, which is not preferable.

  An organic silane compound may be further blended in a composition in which a maleimide compound is blended with an N-vinylbenzyl-substituted aromatic amine compound, or in a composition in which an allyl compound is blended with these. By blending the organosilane compound, the adhesiveness is further improved. Examples of the organic silane compound include organic silanes represented by the general formula (V), and specific examples thereof are the same as those described above.

  The amount of the organic silane compound used is 200 parts by weight or less based on 100 parts by weight of a composition in which a maleimide compound is blended with an N-vinylbenzyl-substituted aromatic amine compound, or a composition in which an allyl compound is further blended. The amount is preferably 1 to 20 parts by weight. When the amount of the organic silane compound exceeds 200 parts by weight, the adhesiveness is lowered, which is not preferable. Further, a phenol resin may be further blended in a composition in which a maleimide compound is blended with an N-vinylbenzyl-substituted aromatic amine compound, or in a composition in which an allyl compound is blended with these. By adding a phenol resin, further improvement in adhesiveness can be expected. The phenol resin may be any of a resole, novolac, and cresol phenol resin. The amount of the phenol resin used is 200 parts by weight or less, preferably 1 part per 100 parts by weight of a composition in which a maleimide compound is blended with an N-vinylbenzyl-substituted aromatic amine compound, or a composition in which an allyl compound is further blended. ~ 20 parts by weight. When the blending amount of the phenol resin exceeds 200 parts by weight, the adhesive layer becomes brittle, which is not preferable.

  The adhesive is also dissolved in a solvent and used as a 20 to 80% solution in the same manner as the adhesive containing the aromatic vinyl benzyl ether compound and the maleimide compound. The above-mentioned thing is mentioned as a specific example of the solvent in that case.

[Second adhesive layer (B2)]
In the present invention, the “fluororubber-based adhesive compounded with an organosilane compound” constituting the second adhesive layer (B2) of the adhesive layer (B) means at least organic peroxidation of unvulcanized fluororubber. It is a fluororubber composition obtained by blending a vulcanizing agent such as a product and an organic silane compound, and exhibits excellent adhesiveness to perfluoroelastomer by vulcanization.

  Examples of the unvulcanized fluororubber include vinylidene fluoride rubber (FKM) and tetrafluoroethylene-propylene rubber (FEPM), and commercially available products can be used. Examples of vinylidene fluoride rubber (FKM) include DuPont's “Viton”, Daikin Industries' “Daiel G”, “Dyneon”, etc., and tetrafluoroethylene-propylene rubber (FEPM) Asahi Glass Co., Ltd. “Afras” and the like.

  Examples of the organosilane compound include compounds represented by the general formula (V). The amount of the organic silane compound is usually 1 to 100 parts by weight, preferably 5 to 30 parts by weight per 100 parts by weight of the unvulcanized fluororubber. When the compounding amount of the organosilane compound is more than 100 parts by weight, the period in which the adhesive can be used tends to be short, and when it is less than 1 part by weight, it becomes difficult to obtain sufficient adhesiveness.

  The adhesive may be blended with a phenol resin from the viewpoint of further improving adhesiveness, and the phenol resin may be any of a resole, novolac, or cresol phenol resin. The phenol resin is preferably used in an amount of 50 parts by weight or less per 100 parts by weight of the unvulcanized fluoro rubber. When the blending amount of the phenol resin exceeds 50 parts by weight, the heat resistance of the adhesive tends to decrease, which is not preferable. Moreover, since the effect of having mix | blended it will become difficult to express when there are too few compounding quantities of a phenol resin, it is preferable to mix | blend 0.1 weight part or more per 100 weight part of unvulcanized fluororubbers.

  Moreover, you may mix | blend an epoxy resin etc. from viewpoints, such as water resistance other than the said phenol resin. For example, bisphenol type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, cresol type epoxy resin, dimer acid modified epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin, epoxidized oil And epoxy resin.

[Production of complex]
The composite of the present invention is produced, for example, by the following steps.
First, the area | region which should adhere | attach the perfluoroelastomer molding (A) of the surface of a to-be-adhered body (C) is cleaned. When the adherend (C) is a metal, the surface is washed with an organic solvent (for example, trichloroethylene, perchloroethylene, trichloroethane, methyl ethyl ketone, toluene, xylene, etc.), and then an appropriate chemical treatment is applied to the metal. It is preferable to perform physical treatment (for example, sand blasting, sandpaper polishing, etc.).

  Next, an adhesive containing an aromatic vinyl benzyl ether compound and a maleimide compound or a solution of an adhesive containing an aromatic vinyl benzylamine compound and a maleimide compound on the cleaned surface of the adherend (C). And dried at 100 to 200 ° C. to form a coating film (first adhesive layer).

  Next, on the coating film (first adhesive layer), a fluororubber-based adhesive containing an organic silane compound is further applied to form an adhesive layer (second adhesive layer). The vulcanized perfluoroelastomer molded product (A) was firmly bonded to the adherend (C) by superposing the perfluoroelastomer molded product (A) on top of each other and applying heat and pressure. A complex is obtained.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In addition, unless otherwise indicated, the part in description is a weight part.

[Synthesis Example 1]
91 parts (0.8 equivalents) of bisphenol A and 45 parts (0.8 equivalents) of potassium hydroxide are dissolved in 200 parts of dimethyl sulfoxide (hereinafter abbreviated as DMSO) and 30 parts of water, and 124 parts of commercially available chloromethylstyrene are added thereto. Was dissolved in 100 parts of DMSO dropwise at 70 ° C. over 1 hour, and further reacted at 70 ° C. for 2 hours. Next, a large excess of water was added to the system, and after stirring, water-DMSO was separated, and an oily substance was extracted with toluene. The toluene layer was repeatedly washed with water until the pH reached 7. Thereafter, toluene was distilled off under reduced pressure to obtain a reaction product (hereinafter referred to as Compound A) having a melting point of 62 ° C. in a yield of 98%.

[Synthesis Example 2]
An aqueous potassium hydroxide solution (56.1 parts (1.0 equivalent) of potassium hydroxide, 35 parts of water) was added to a solution of 93 parts (1.0 equivalent) of aniline in 150 parts of DMSO, and then N-nitrosophenyl. A solution obtained by diluting 152.5 parts (1.0 equivalent) of commercially available chloromethylstyrene added with 300 ppm of an aluminum salt of hydroxylamine in 50 parts of DMSO was added dropwise at 60 ± 2 ° C. over 40 minutes, and further at 60 ± 2 ° C. The reaction was performed for 4 hours. Next, a large excess of water was added to the system, and after stirring, water-DMSO was separated, and an oily substance was extracted with toluene. The toluene layer was repeatedly washed with water until the pH reached 7. Thereafter, toluene was distilled off under reduced pressure to obtain a reaction product (hereinafter referred to as compound B) in a yield of 97%. The viscosity of this product was 0.28 poise / 25 ° C., and the content of divinylbenzyl ether in the reaction product was 27% from liquid chromatographic analysis.

[Example 1]
(1) Preparation of adhesive composition for first adhesive layer (B1) 100 g of N, N-dimethylformamide (hereinafter abbreviated as DMF), 50 g of compound A, 50 g of BMI, 10 g of γ-aminopropyltri Ethoxysilane and 3 g of phenol / cresol / formaldehyde polycondensate (Sumitomo Bakelite, Sumilite Resin PR-175) were dissolved to prepare an adhesive composition X1.

(2) Preparation of adhesive composition for second adhesive layer (B2) 100 g of three-dimensional peroxide vulcanized fluoro rubber, 50 g of carbon black, 5 g of triallyl isocyanurate, 3 g of 2,5-dimethyl An adhesive composition X2 was prepared by dissolving -2,5-di (t-butylperoxy) hexane and 20 g of γ-aminopropyltriethoxysilane in 500 g of methyl ethyl ketone.

(3) Adhesive evaluation test Adhesive evaluation was performed according to JIS K 6854.
(3-1) Treatment of metal pieces An anodized aluminum plate was used.

(3-2) Preparation of composite The adhesive composition X1 was brushed on one side of an anodized aluminum plate that had been thoroughly cleaned with xylene in advance, and the thickness of the adhesive was adjusted using a 50 μm applicator. After uniform preparation, drying was performed at 150 ° C. for 30 minutes.
Next, the adhesive composition X2 is brush-coated on the adhesive layer B1 thus formed, and the adhesive thickness is uniformly adjusted using a 50 μm applicator, followed by drying at 100 ° C. for 15 minutes. It was.

  Next, an elastomer sheet (thickness 2 mm) formed with perfluoroelastomer “Kalrezto” (manufactured by DuPont Dow Elastomer Co., Ltd.) was layered on the adhesive layer B2, and vulcanized.

  When the obtained adhesive sheet (composite) of the elastomer sheet and the aluminum plate was subjected to a 180 degree peel strength test based on JIS K 6854 (Adhesive peel adhesion strength test method) at 25 ° C., the adhesion strength The thickness was 45.0 N / cm.

[Example 2]
A composite was prepared in the same manner as in Example 1 except that the adhesive composition X1 prepared using Compound B instead of Compound A was used. When evaluated, the adhesive strength was 42.5 N / cm.

[Comparative Example 1]
Adhesive “Chemlock No.607” made by Rhode Far East is brushed on one side of an anodized aluminum plate that has been thoroughly cleaned with xylene in advance, and the thickness of the adhesive is adjusted using a 50 μm applicator. After uniform preparation, drying was performed at 100 ° C. for 15 minutes. The same elastomer sheet as in Example 1 was layered on the obtained adhesive layer and vulcanized. The adhesive strength of the obtained adhesive sheet (composite) between the elastomer sheet and the aluminum plate was evaluated in the same manner as in Example 1. As a result, the adhesive strength was 3.5 N / cm.

It is the figure which showed typically the cross section of the composite_body | complex which has the perfluoroelastomer molding of this invention.

Explanation of symbols

A Perfluoroelastomer molded product B Adhesive layer B1 First adhesive layer B2 Second adhesive layer C Substrate

Claims (5)

A perfluoroelastomer molded product (A) is a composite formed by adhering to an adherend (C) via an adhesive layer (B),
The adhesive layer (B) includes a first adhesive layer (B1) disposed on the adherend (C) side and a second adhesive layer (B) disposed on the perfluoroelastomer molded product (A) side. A laminate with B2),
The first adhesive layer (B1) is composed of an adhesive containing an aromatic vinyl benzyl ether compound and a maleimide compound, or an adhesive containing an aromatic vinyl benzylamine compound and a maleimide compound, and the second adhesive layer (B2). ) Comprises a fluororubber adhesive containing an organosilane compound, and a composite having a perfluoroelastomer molded product.   The composite according to claim 1, wherein the adhesive containing an aromatic vinyl benzyl ether compound and a maleimide compound or the adhesive containing an aromatic vinyl benzylamine compound and a maleimide compound further contains an allyl compound.   The composite according to claim 1 or 2, which is used for a semiconductor manufacturing apparatus.   The seal which consists of a composite_body | complex of Claim 1 or 2 whose perfluoroelastomer molding (A) is a sealing material and to-be-adhered body (C) is a metal fitting for sealing.   The seal according to claim 4, which is used for sealing a semiconductor manufacturing apparatus.

Images