TW201209064A - Acrylic elastomer and composition using the same - Google Patents

Abstract

The present invention provides an acrylic elastomer and an acrylic elastomer composition using the same, which can provide excellent electrical insulation under high temperature and moisture and has excellent long-term reliability. The acrylic elastomer has the structures of formula (I), (II) and (III) shown below as the structural unit; in formula (I), X represents the C5-22 alicyclic hydrocarbon substituent, and R1 represents the hydrogen or methyl group; in formula (II), Y represents the C1-10 hydrocarbon substituent, and R2 represents the methyl group; Z represents the OH or a substituent containing a functional group selected from the group consisting of carboxyl, hydroxyl, anhydride, amino, amide, and epoxy group, and R3 represents the hydrogen or methyl.

Description

201209064 6. TECHNOLOGICAL FIELD OF THE INVENTION [Technical Field] The present invention relates to an acid-based elastomer which can be preferably used in an acid-based elastomer and an acrylic elastomer using the same. [Prior Art] In recent years, miniaturization of electronic equipment has been accompanied. In addition, the semiconductors mounted on the electronic devices are also required to be mounted. Further, it is required that the substrate on which the semiconductor package is mounted be further refined toward the wiring on the substrate side. Conventionally, electronic materials such as an adhesive for a semiconductor element and a mounting substrate for a device are required to have a bonding property and long-term reliability. In order to meet these requirements, an epoxy resin and a curing agent are blended in a combination of propylene and an acrylic elastomer containing acrylonitrile (see, for example, Patent Document 1). However, with the recent rapid semiconductor sealing and miniaturization of wiring, it is required to be more electronic. However, the use of a composition of an acrylonitrile butadiene-based elastomeric olefinic elastomer has clearly revealed the disadvantage of poor electrical insulation. One of the reasons for this is to propose a technique of adding an ion trapping agent to solve the above-mentioned document 2), but there is no effect in the field of fine wiring. Further, a propylene composition for a propylene electronic material containing no acrylonitrile is also proposed. Lightweight and high-speed packaging is moving toward higher density and higher density. In addition, it is equipped with various electronic materials such as electronic zero-resistance, heat resistance, and electric insulation, and has a strict reliance on a high-nickel butadiene-based elastomer to form a component in a rubber or a substrate. There are problems with ionic impurities under high temperature and high humidity (see, for example, the olefinic elastomer which is sufficiently satisfactory by the special method (see, for example, Patent Document 3), but there is still no moisture absorption rate. The problem to be solved is that it is not possible to obtain sufficient long-term reliability. The inventors of the present invention have found that a substituent having an alicyclic hydrocarbon having 5 to 22 carbon atoms is an essential component, and propylene-free is used. The acrylic elastomer of nitrile can obtain excellent electrical insulation properties under high temperature and high humidity (Patent Document 4). However, if it is required to further improve electrical insulation, the acrylic elastomer of the invention does not necessarily satisfy the required characteristics. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. 2002-60716 (Patent Document 3) Japanese Patent No. 3 483 1 6 1 [Problem to be Solved by the Invention] The object of the present invention is to provide an excellent electrical insulation property under high temperature and high humidity and excellent long-term reliability. The acrylic elastomer for electronic materials and the acrylic elastomer composition using the same. [Means for Solving the Problems] The present inventors have repeated the positive review to solve the above problems, and found that by using a specific single Body as acrylic-free elastomer without acrylonitrile

S -6- 201209064 The essential component of the body is an acrylic elastomer which has excellent electrical insulation properties under high temperature and high humidity. That is, the present invention relates to an acrylic elastomer comprising at least the structures of the following general formulae (I), (Π) and (III) as structural units, [Chemical Formula 1]

(X represents a substituent containing an alicyclic hydrocarbon having 5 to 22 carbon atoms, and R1 represents hydrogen or a methyl group).

• · (Π)

(Y represents a substituent containing a hydrocarbon group having 1 to 10 carbon atoms, and R2 represents a methyl group), [Chemical 3 I

• (ΠΙ) (Z represents OH, or a substituent containing at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, an acid anhydride group, an amine group, a decylamino group, and an epoxy group, and R3 represents hydrogen or a methyl group. ). 201209064 The acrylic elastomer of the present invention is preferably obtained by polymerizing a monomer mixture containing the following monomers: a methacrylate or acrylate having an alicyclic hydrocarbon group having 5 to 22 carbon atoms in the ester moiety, and an ester a methacrylate partially having a hydrocarbon group having 1 to 10 carbon atoms, and at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, an acid anhydride group, an amine group, a mercaptoamine group, and an epoxy group, and at least one carbon- A functional group monomer containing a carbon double bond. In the present invention, it is preferred to use the above-mentioned methacrylate or propyl group having an alicyclic hydrocarbon group having a carbon number of 5 to 22 in the ester moiety in an amount of 5 to 94. 5 parts by mass based on 100 parts by mass based on the total mass parts of the monomer. The acid ester, 5 to 65 parts by mass of the above-mentioned methacrylate having a hydrocarbon group having 1 to 1 carbon atom in the ester portion, 0.5 to 30 parts by mass of the above-mentioned functional group-containing monomer, and 〇 to 90 parts by mass A monomer mixture of monomers copolymerized with the materials is used as a monomer mixture. Further, the above alicyclic hydrocarbon group having 5 to 22 carbon atoms in the present invention preferably contains at least one selected from the group consisting of a cyclohexyl group, an ornidyl group, a tricyclodecyl group, an isobornyl group and an adamantyl group. Further, the acrylic elastomer of the present invention preferably has a saturated moisture absorption rate of 0.6% or less. Further, the present invention relates to an acrylic elastomer composition for an electronic material comprising the obtained acrylic elastomer and a solvent. [Effects of the Invention] The acrylic acid-based elastomer of the present invention has a low moisture absorption rate under high temperature and high humidity.

S -8- 201209064 The volume resistance 値 hardly changes, and the long-term reliability is excellent. Therefore, by using the elastomer in the use of electronic materials, it is possible to provide an electronic material having high electrical insulating properties and long-term reliability. [Embodiment] The acrylic acid-based elastomer of the present invention is characterized by having at least a structure of the following general formulae (I), (II) and (ΙΠ) as a structural unit.

(X represents a substituent containing an alicyclic hydrocarbon having 5 to 22 carbon atoms, and R1 represents hydrogen or a methyl group).

(Y represents a substituent containing a hydrocarbon group having 1 to 10 carbon atoms, and R2 represents a methyl group).

(ill) 201209064 (Z represents OH, or a substituent containing at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, an acid anhydride group, an amine group, a decylamino group, and an epoxy group, and R3 represents hydrogen or methyl). In the present invention, the substituent of the above-mentioned alicyclic hydrocarbon group having 5 to 22 carbon atoms represented by X in the above formula (I) is not particularly limited as long as it is a substituent having an alicyclic hydrocarbon group having 5 to 22 carbon atoms. The limitation is exemplified by an alkoxy group having an alicyclic hydrocarbon group having 5 to 22 carbon atoms, an amine group having an alicyclic hydrocarbon group having 5 to 22 carbon atoms, and the like, and a carbon number of 5 in the above formula (I). The alicyclic hydrocarbon group of ~22 is described later. In the present invention, the substituent of the hydrocarbon group having 1 to 10 carbon atoms represented by Y in the above formula (II) is not particularly limited as long as it is a substituent having a hydrocarbon group having 1 to 10 carbon atoms, and is exemplified as having carbon. An alkoxy group of a hydrocarbon group of 1 to 10, an amine group having a hydrocarbon group of 1 to 10 carbon atoms, and the like. Further, the hydrocarbon group having 1 to 10 carbon atoms in the above formula (II) will be described later. In the present invention, the OH represented by Z in the above formula (III) or a substituent containing at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, an acid anhydride group, an amine group, a phosphonium group and an epoxy group Described later. The acrylic elastomer is preferably obtained by polymerizing a monomer mixture containing a monomer having a methacrylate or acrylate having an alicyclic hydrocarbon group having 5 to 22 carbon atoms in the ester portion and carbon in the ester portion. a methacrylate having a hydrocarbon group of 1 to 10, and containing a group selected from the group consisting of a carboxyl group, a hydroxyl group, an acid anhydride group, an amine group, a decyl group and a ring

S -10- 201209064 At least one functional group of the group consisting of oxy groups and at least one functional group containing carbon-carbon double bond. As for one of the monomer components used in the polymerization for obtaining an acrylic elastomer, it is preferably used in a methacrylate or acrylate having an alicyclic hydrocarbon group having a carbon number of 5 to 22 in the ester moiety (hereinafter also referred to as " The alicyclic monomer ") When the carbon number of the ruthenium is 5 or more, the chemical stability of the monomer is sufficiently high, and the effect of reducing the moisture absorption rate of the obtained elastomer is sufficient. When the carbon number is 22 or less, it becomes the Tg of the obtained elastomer. The alicyclic monomers preferably have a carbon number of from 6 to 15, more preferably from 6 to 10. The alicyclic monomer is preferably a monomer having at least one alicyclic hydrocarbon group selected from the group consisting of a cyclohexyl group, a source borneol group, a tricyclodecanyl group, an isobornyl group and an adamantyl group. When the above alicyclic monomer is used as a monomer component of the acrylic elastomer, the moisture absorption rate can be effectively lowered, and it is preferable in terms of electrolytic corrosion resistance. The above alicyclic monomers are specifically exemplified by cyclopentyl acrylate, cyclohexyl acrylate, methylcyclohexyl acrylate, trimethylcyclohexyl acrylate, borneol acrylate, borneol methyl acrylate, benzo acrylate. Base borneol ester, cyanoacetone acrylate, isobornyl acrylate, acrylic borneol vinegar, menthyl vinegar, Fenchyl ester, adamantyl acrylate, dimethyl acrylate Adamantyl ester, tricyclo[5.2.1.02'6]non-8-yl acrylate, tricyclo[5.2·1·02'0]indol-4-yl methyl ester, cyclodecyl acrylate, methacrylic acid ring Amyl ester, cyclohexyl methacrylate, methylcyclohexyl methacrylate, trimethylcyclohexyl methacrylate, borneol methacrylate, borneol methyl methacrylate, methyl-11 - 201209064 Acrylic acid cyanoformone, phenyl borneol methacrylate, isobornyl methacrylate, borneol methacrylate, menthyl methacrylate, fenyl methacrylate, adamantyl methacrylate, Methyl methacrylate fund Alkyl ester, tricyclo[5·2·1·02'6]癸-8-yl methacrylate, tricyclo[5.2.1.0''6]non-4-yl methyl methacrylate, methacrylic acid ring Ester ester and the like. These may be used alone or in combination of two or more. Further, the alicyclic monomer may be used by mixing the above methacrylate and acrylate. Among these, in terms of low hygroscopicity, cyclohexyl acrylate, isobornyl acrylate, borneol acrylate, borneol methyl acrylate, acrylonitrile tricyclo [5.2.1.02'6] 癸-8 -yl ester, tricyclo[5.1.02'6]non-4-ylmethyl acrylate, adamantyl acrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, methylcyclohexyl methacrylate, Trimethylcyclohexyl methacrylate, borneol methacrylate, borneol methyl methacrylate, isobornyl methacrylate, borneol methacrylate, menthyl methacrylate, cumin methacrylate Ester, adamantyl methacrylate, dimethyl adamantyl methacrylate, tricyclo[5.2.1.02,6]non-8-yl methacrylate, trimethyl methacrylate [5.2.1.02'6] Methyl-4-methylmethyl ester, cyclodecyl methacrylate, phenyl borneol methacrylate, and the like are preferred. Further, from the viewpoint of low hygroscopicity and adhesion, it is preferably cyclohexyl acrylate, isobornyl acrylate, borneol acrylate, ortho-acrylic acid methyl ester, acrylic tricyclo [5.2.1.02'6] fluorene. -8-yl ester, tricyclo[5.2.1.0''6]non-4-ylmethyl acrylate, adamantyl acrylate, and the like. An acrylamide having an alicyclic hydrocarbon group having 5 to 22 carbon atoms may also be used.

S -12- 201209064 A methacrylamide having an alicyclic hydrocarbon group having 5 to 22 carbon atoms, and the like, which is used in combination with or substituted for the above-mentioned cyclic monomer, to obtain acrylic acid constituting the structure of the above formula (1) It is the monomer component of the elastomer. The above acrylamide having an alicyclic hydrocarbon group having 5 to 22 carbon atoms is specifically exemplified by N-cyclopentyl acrylamide, N-cyclohexyl acrylamide, N-methylcyclohexyl acrylamide, N- Trimethylcyclohexylpropene decylamine, N-orinelyl acrylamide, N-originyl methacrylamide, N-phenyl borneol acrylamide, N-cyano borneol acrylamide , N-isobornyl acrylamide, N-borneoprene acrylamide, N-menthyl acrylamide, N-fennel acrylamide, N-adamantyl acrylamide, N-dimethyl fund Alkyl acrylamide, triterpene [5.2.1.02'6] 癸-8-yl acrylamide, triclosan [5.2.1.02,6] 癸-4-yl methacrylamide, N-ring 癸Acrylamide and the like. Further, the above-mentioned methacrylamide having an alicyclic hydrocarbon group having 5 to 22 carbon atoms is specifically exemplified by N-cyclopentylmethyl acrylamide, N-cyclohexyl methacrylamide, N-methyl. Cyclohexyl methacrylamide, N-trimethylcyclohexyl methacrylamide, N-orinelyl methacrylamide, N-orinelyl methyl methacrylate, N-phenyl phenyl Borneol-based methacrylamide, N-cyano-formyl methacrylamide, N-isobornyl methacrylamide, N-borneyl methacrylamide, N-menthyl methacrylate Amine, N- fenyl methacrylamide, N-adamantyl methacrylamide, N-dimethyl hydroxy-cycloalkyl methacrylamide, N-tricyclo[5.2.1.02,6]癸-8-ylmethacrylamide, N-tricyclo[5.2.1.0''6]non-4-ylmethylmethacrylamide, N-cyclodecylmethylpropenamide, and the like. Further, it is preferably used as one of the monomer components used in the polymerization for obtaining an acrylic elastomer by using a methylpropane-13-201209064 enoate having a hydrocarbon group having a carbon number of 1 to 10 in the ester moiety. These constitute the structure of the above formula (II). When the carbon number is 10 or less, the electrical insulating properties are sufficiently 'and' satisfied with the measurement of the melting point and material of the monomer and the feeding workability. The ester portion of the methacrylate preferably has a carbon number of 2 to 8, preferably 4 to 8. The structure of the hydrocarbon group may be linear, branched or cyclic, but has a structure of a tertiary carbon in a portion other than the annular structure, and at a lower temperature, the quality is liable to be reduced due to thermal decomposition. It is not good from the viewpoint of heat resistance. Accordingly, a methacrylate having a carbon number of 10 and a linear hydrocarbon group and a branched hydrocarbon group having no tertiary carbon is preferred. When the above methacrylate is used as the monomer component of the acrylic elastomer, it is preferable because the electrolytic corrosion resistance is further improved. The methacrylate having a hydrocarbon group having a carbon number of 1 to 10 in the ester moiety is specifically exemplified by methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, methacrylic acid. N-butyl ester, isobutyl methacrylate, dibutyl methacrylate, amyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, methyl Ethyl acrylate and the like. Further, the hydrocarbon group having 1 to 10 carbon atoms of the methacrylate having a hydrocarbon group having 1 to 10 carbon atoms in the ester moiety is preferably an aliphatic group. Among these, from the viewpoint of the Tg of the obtained elastomer, n-butyl methacrylate, amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate and the like are preferable. a methacrylic acid having a hydrocarbon group having 1 to 10 carbon atoms and the above ester moiety

S 14 - 201209064 The ester group has a carbon number of 1 to 1 Å or the like as a monomer component for obtaining the body of the above formula (II). The methyl propyl group having a hydrocarbon group having 1 to 1 carbon atom is N-methyl methacrylamide, N,N-dimethyl methacrylamide, N,N-diethylmethylpropyl Acrylamide, hydrazine, hydrazine-di-n-propyl methacryl acrylamide, hydrazine, hydrazine-diisopropylmethyl propylene decyl amide, hydrazine, hydrazine-di-n-butyl methacrylamide amide, hydrazine , Ν-diisobutyl methacrylamide, decylamine, hydrazine, hydrazine-di-second butyl methacrylamide, hydrazine, hydrazine-dipentyl methacrylamide, hydrazine-hydrazine, hydrazine-di-n-hexane Methyl propylene decylamine, Ν-正; Ν, Ν-di-n-octyl methacrylamide, Ν-2-ethyl, hydrazine, Ν-di-2-ethylhexyl methacrylamide, hydrazine , Ν-dimercaptomethyl methacrylate and the like. Further, the hydrocarbon group having a methyl group having a hydrocarbon group of 1 to 10 carbon atoms is preferably an aliphatic group. Further, it is preferred to use a single energy used in the polymerization of a urethane-containing elastomer having a group selected from the group consisting of an amine group, an amine group, an epoxy group and an epoxy group and at least one polymerizable carbon-carbon double bond. The monomer of the above formula (III) is a structure of the above formula (III). The above-mentioned functional group-containing monomer can be a hydrocarbyl amide containing a hydrocarbyl amide. The exemplified is methacrylamide, fluorene-ethylene. Indoleamine, Ν-n-propylformamide, Ν-isopropylmethylamine, Ν-n-butylmethyl propyl, Ν-isobutyl methacryl oxime - second butyl methacryl, Ν-pentyl methacrylate Hexyl methacrylamide, lysyl methacrylamide, hexyl methacrylamide, hydrazine-mercaptomethyl propylene acrylamide, carbon number 1 to 10, at least one functional group of a carboxyl group, a hydroxyl group, or an acid anhydride group The base, the energy-based monomer is used as one of the components. Containing the following monomers in the official residence: Example -15- 201209064 Such as 2-propenyloxyethyl succinic acid, 2-propenyl methoxyethyl phthalate, 2-propenyl methoxyethyl hexahydrobenzene Dicarboxylic acid, 2-methacryloxyethyl succinic acid, 2-methylpropenyloxyethyl phthalic acid, 2-methylpropenyloxyethyl hexahydrophthalic acid, 2-methyl a monomer having a carboxyl group such as acryloxypropyl hexahydrophthalic acid (Z in the above formula (III), "substituent having a carboxyl group"); an unsaturated carboxylic acid monomer such as acrylic acid or methacrylic acid (described above) In formula (III), Z = OH); hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, cyclohexane a monomer having a hydroxyl group such as dimethanol monoacrylate, cyclohexane dimethanol monomethacrylate, N-methylol acrylamide, N-methylol methacrylamide or the like (in the above formula (III), "Substituent containing a hydroxyl group"); trimellitic anhydride propylene methoxyethyl ester, trimellitic anhydride methacryloxyloxy group An acid anhydride-containing monomer such as ethyl ester, cyclohexane tricarboxylic anhydride propylene methoxyethyl ester or cyclohexane tricarboxylic acid anhydride methacryloxyethyl ester (in the above formula (III), Z = "containing an acid anhydride group Substituent "); diethylaminoethyl acrylate, diethylaminoethyl methacrylate, 2,2,6,6-tetramethylpiperidine methacrylate, methacrylic acid-1,2 , an amine group-containing monomer such as 2,6,6-pentamethylpiperidine ester (in the above formula (Z), Z = "substituent having an amine group"); acrylamide, methacrylamide, etc. a monomer containing a guanamine group (in the above formula (III), Z = "substituent having an amine group");

S -16- 201209064 N-acryloyl glyceryl phthalamide or the like containing a guanamine group (in the above formula ,), z = "substituent containing a guanamine group"); glycidyl acrylate, methacrylic acid shrinkage Glyceryl ester, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 2-(2,3-epoxypropoxy)ethyl acrylate , 2-(2,3-epoxypropoxy)ethyl methacrylate, 3-(2,3-epoxypropoxy)propyl acrylate, 3-(2,3 methacrylate -Epoxypropoxy)propyl ester, 4-(2,3-epoxypropoxy)butyl acrylate, 4-(2,3-epoxypropoxy)butyl methacrylate , 5-(2,3-epoxypropoxy)pentyl acrylate, 5-(2,3-epoxypropoxy)pentyl methacrylate, 6-(2,3-cyclopropene acrylate Oxypropoxy)hexyl ester, 6-(2,3-epoxypropoxy)hexyl methacrylate,-3,4-epoxybutyl acrylate,-3,4-cyclomethacrylate Oxybutyl butyl ester, 4,5-epoxypentyl acrylate, 4,5-epoxypentyl methacrylate, acrylic acid-6, 7-epoxyheptyl ester, -6,7-epoxyheptyl methacrylate, α-ethyl acrylate-6,7-epoxyheptyl ester, 3-methyl-3,4-cyclo acrylate Oxybutyl butyl ester, 3-methyl-3,4-epoxybutyl methacrylate, 4-methyl-4,5-epoxypentyl acrylate, 4-methyl methacrylate 4,5-epoxypentyl ester, 5-methyl-5,6-epoxyhexyl acrylate, 5-methyl-5,6-epoxyhexyl methacrylate, acrylic-β- Methyl glycidyl ester, β-methyl glycidyl methacrylate, α-ethyl acrylate-β-methyl glycidyl ester, 3-methyl-3,4-epoxybutyl acrylate, A 3-methyl-3,4-epoxybutyl acrylate, 4-methyl-4,5-epoxypentyl acrylate, 4-methyl-4,5-epoxy methacrylate Ethyl amyl ester, 5-methyl-5,6-epoxyhexyl acrylate, -17-201209064 5-methyl-5,6-epoxyhexyl methacrylate, etc. In III), Z = "substituent containing an epoxy group" may be used singly or in combination of two or more. Among these, in terms of storage stability, an epoxy group is contained, more preferably glycidyl methacrylate. In the present invention, in addition to the alicyclic monomer, the methacrylate of the hydrocarbon group of the ester portion 1 to 10, and the above-mentioned functional group, an acrylic elastomer which can be copolymerized with other monomers may be used. The monomer component used for the polymerization of the body. The monomer which can be copolymerized is not particularly limited as long as it does not impair the polymer, heat resistance and stability, and specifically, etc.: methyl acrylate, ethyl acrylate, acrylic acid Propyl propyl acrylate, n-butyl acrylate, isobutyl acrylate, amyl acrylate, n-hexyl acrylate, 2-ethylhexyl octyl acrylate, dodecyl acrylate, octadecyl acrylate, ethyl acrylate Acrylates such as phenyl acrylate, benzyl acrylate, naphthyl acrylate, and tetrahydrofurfuryl acrylate; butoxyethyl methacrylate, benzyl phenyl methacrylate, phenoxy methacrylate Ethyl esters such as esters, tetrahydrofurfuryl methacrylate, etc.: 4-vinylpyridine, 2-vinylpyridine, α-methylphenyl styrene, α-gas benzene, α-chlorobenzene Ethylene, α-indigenous benzene A monomer of an aryl group such as ethylene, chlorostyrene, bromostyrene, methylstyrene, methyl, (o-, m-, p-)hydroxystyrene or styrene ( ). The monomers which are preferably a carbon number group are preferably used as a monomer for obtaining low hygroscopicity as the following, isobutyl acrylate, ester, butoxyethyl acrylate, A, Propenyl vinyl ester, methyl ethylene, α-ethylene ethylene, fluorophenoxybenzene

S -18- 201209064 compound; vinyl cyanide compound such as acrylonitrile or methacrylonitrile; unsaturated dicarboxylic anhydride such as maleic anhydride; N-methyl maleimide, N_ethyl malayan Amine, N-propylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-isobutylmaleimide, N-t-butyl N-substrate, such as maleic imine, N-lauryl maleimide, N-cyclohexylmaleimide, N-benzyl maleimide, N-phenylmaleimide, etc. The maleic acid of the maleic acid; the vinyl acetate, preferably ethyl acrylate, ethyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate. These may be used alone or in combination of two or more. Further, in the present invention, the vinyl cyanide compound (nitrile monomer) such as acrylonitrile or methacrylonitrile is not easily used because it cannot maintain electrical insulation under high temperature and high humidity, and is inferior in electric uranium resistance. In the present invention, the mixing ratio of each monomer is 100 parts by mass based on the total mass parts of the monomers, preferably the mixing ratio is 5 to 94.5 parts by mass of the alicyclic monomer, and the carbon number is 1 to 1 in the ester moiety. 5 to 65 parts by mass of the methacrylate of 1 hydrazine, 5 to 30 parts by mass of the monomer having a functional group, and 0 to 90 parts by mass of the monomer copolymerizable with the above. The blending amount of the alicyclic monomer in the present invention is preferably from 5 to 94.5 parts by mass', but more preferably from 10 to 80 parts by mass in terms of hygroscopicity. When the amount of the alicyclic monomer is 5 parts by mass or more, the hygroscopicity can be satisfied, and when it is 94.5 parts by mass or less, the mechanical strength can be sufficient. In the present invention, the amount of the methacrylic acid-19-201209064 ester having a hydrocarbon group having a carbon number of 1 to 10 is preferably from 5 to 65 parts by mass, but it is preferably from the viewpoint of corrosion resistance and flexibility. I5 to 55 parts by mass. When the amount of the methacrylate having a hydrocarbon group having a carbon number is 5 parts by mass or more, the effect of improving the uranium resistance is sufficient, and when it is 65 parts by mass or less, the Tg can be satisfied. The compounding amount of the functional group-containing monomer in the present invention is preferably from 5 to 30 parts by mass, more preferably from 1 to 20 parts by mass. When the blending amount is 5% by mass or more, the adhesiveness and the strength become sufficient. When the blending amount is 30 parts by mass or less, the crosslinking reaction does not occur at the time of copolymerization, and the storage stability is good. In the present invention, a polymerization method for producing an elastomer may be carried out by a conventional method such as bulk polymerization, suspension polymerization, solution polymerization, precipitation polymerization, emulsion polymerization or the like. Among them, the suspension polymerization method is preferred in terms of cost. The suspension polymerization is carried out in an aqueous medium, and a suspension is added. As the suspending agent, there are water-soluble polymers such as polyvinyl alcohol, methyl cellulose, and polypropylene decylamine; and poorly soluble inorganic substances such as calcium phosphate and magnesium pyrophosphate, among which nonionic water-soluble polymers such as polyvinyl alcohol are used. Preferably. When an ionic water-soluble polymer or a poorly soluble inorganic substance is used, there is a tendency that a large amount of ionic impurities remain in the obtained elastomer. The water-soluble polymer is preferably used in an amount of from 1 to 1 part by mass per 100 parts by mass of the total of the monomers. A radical polymerization initiator can be used in the polymerization in the present invention. As the radical polymerization initiator, the following may be used: benzammonium peroxide, laurel peroxide, ditributylbutylperoxy hexahydroterephthalate, tert-butylperoxy-2-ethyl Organic peroxides such as hexanoyl ester, l,l-t-butylperoxy-3,3,5-trimethylcyclohexane, and tert-butylperoxyisopropyl carbonate; azo Diisobutyronitrile, azobis-4-methoxy-2,4-dimethylvaleronitrile,

S -20- 201209064 Azo compound such as azobiscyclohexanone-i-carbonitrile or azobisbenzoquinone; water-soluble catalyst such as potassium persulfate or ammonium persulfate; and peroxide or persulfate and reduction Any one of the users of the usual radical polymerization may be used as the redox catalyst obtained by the combination of the agents. The polymerization initiator is preferably used in an amount of 100 parts by mass based on the total mass of the monomer. The "monomer mixture" in the present invention is preferably a methacrylate containing an alicyclic monomer, a hydrocarbon group having an ester moiety having 1 to 10 carbon atoms, a monomer having a functional group, and optionally copolymerized with the same. The single one. Further, a thiol compound, a thiol diol, a carbon tetrachloride, or a (X-methyl styrene dimer) may be added as a chain transfer agent as needed. When the thermal polymerization is used, the polymerization temperature may be from 0 to 200 ° C. Preferably, it is preferably from 40 to 120 ° C. The molecular weight of the elastomer produced as described above is not particularly limited, but the weight average molecular weight (in terms of polystyrene measured by gel permeation chromatography) is preferably 1 The range of 0,000 to 2,000,000 is preferably in the range of 100,000 to 1,500,000. When the weight average molecular weight is 10,000 or more, the adhesiveness or strength is sufficient, and when it is 2,000,000 or less, the solubility in a solvent is good and the workability is good. The acrylic elastomer of the present invention preferably has a saturated moisture absorption rate of 0.6% or less, and when the saturated moisture absorption rate is 0.6% or less, the electrical insulation property under high temperature and high humidity can be suppressed from being lowered. The saturated moisture absorption rate is 0.6. Below %, the state of the acyl methacrylate can be appropriately selected. The dryness is determined to be measured and the ratio is adjusted to adjust the moisture absorbing and tempering package, and the composition is divided into the body and the body. The individual is selected - 21 - 201209064 After the quality, Degree 85 ° C, humidity 85% moisture up to a certain level, and the following formula is calculated. [Number 1] moisture absorption rate (%) = mass after moisture absorption - quality before moisture absorption before moisture absorption X 100 The acrylic elastomer of the present invention preferably has a Tg of 15 ° C or less, more preferably 10 ° C or less, more preferably 5 ° C or less. If Tg is high, flexibility and adhesion are lowered. The Tg of the obtained elastomer can be designed by appropriately adjusting the type and/or the amount of the monomer component. The acrylic elastomer of the present invention can also be dissolved in a solvent to form a solution-like acrylic elastomer composition. It is used as an electronic material for semiconductor devices, wiring boards, etc. Toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate can be used as the solvent. An organic solvent such as tetrahydrofuran or N-methylpyrrolidone. The amount of the solvent can be changed without impairing the workability. The amount of the acrylic elastomer is proportional to the total amount of the acrylic elastomer. (solid concentration) The amount is preferably from 5 to 45% by mass, more preferably from 1 to 40% by mass. The acrylic elastomer of the present invention may be mixed with an epoxy resin and further with an epoxy resin hardener to form a polymer alloy. As the electronic material, the epoxy resin and the epoxy resin hardener can be used without any particular limitation, and the materials can be used, such as a chelating agent, a hardening accelerator, a decane coupling agent, various materials, and the like. In order to improve the reactivity, adhesion, and strength, the form of the β-electron material may be in the form of a film, and may be in the form of a paste or a solution.

S -22-201209064 The mixing ratio of the acrylic elastomer to the epoxy resin of the present invention is not particularly limited. For example, the former/the latter (mass ratio) may be used in a ratio of 10/90 to 90/10. The epoxy resin may be used as long as it is cured, and an epoxy resin having a general difunctional group or more (two or more epoxy groups in one molecule) may be used. The difunctional epoxy resin is exemplified by a bisphenol A type or a bisphenol F type epoxy resin. Further, a polyfunctional epoxy resin having a trifunctional or higher (“containing three or more epoxy groups in a molecule”) may be used, and a trifunctional or higher polyfunctional epoxy resin is exemplified as a phenol novolak epoxy. Resin, cresol novolak type epoxy resin, etc. As the epoxy resin hardener, those generally used as hardeners for epoxy resins can be used, and amines, polyamines, acid anhydrides, polythioethers, boron trifluoride, and compounds having two or more phenolic hydroxyl groups in one molecule can be used. Bisphenol A, bisphenol F, bisphenol S or phenol resin. From the viewpoint of excellent electric corrosion resistance at the time of moisture absorption, a phenol novolak resin, a bisphenol novolak resin, a cresol novolak resin, or the like is preferably used. The epoxy resin hardener is generally preferably used in an amount of from 1 to 1.4 equivalents based on 1 equivalent of the epoxy group of the epoxy resin to the epoxy group of the epoxy resin hardener, more preferably 0.8 to 1.2 equivalents. use. The epoxy resin hardener can satisfy heat resistance if it is in an appropriate amount. Further, a hardening accelerator may be used together with the epoxy resin hardener, and the hardening accelerator may be exemplified by various imidazoles and the like. The blending amount in the case of using a hardening accelerator is preferably from 0.1 to 20 parts by mass, more preferably from 0.5 to 15 parts by mass, per 100 parts by mass of the total of the epoxy resin and the epoxy resin hardener. When the amount is 0.1 parts by mass to -23-201209064, the curing rate becomes sufficient, and if it is 20 parts by mass or less, the usable period can be satisfied. The method for forming a film is not particularly limited. For example, it can be produced by applying a coating material of the above-mentioned semiconductor device adhesive to a base film and drying it using various coating apparatuses. The acrylic elastomer of the present invention is preferably used for an adhesive for a semiconductor such as a film-like adhesive, a substrate material for a flexible wiring board, an adhesive for the above, and an electronic material such as a film for connection for circuit connection. [Examples] Hereinafter, the present invention will be specifically described by examples, but it is not intended to limit the scope of the invention. (Example 1) Mixed tricyclo[5.2.1.02'6]non-8-yl ester (manufactured by Hitachi Chemical Co., Ltd., FA-513A) 300 g, butyl acrylate (BA) 350 g, ethyl methacrylate (EMA) 3 00 g and 50 g of glycidyl methacrylate (GM A ), and further, 5 g of peroxidized lauryl hydrazine and 0.45 g of n-octyl mercaptan as a chain transfer agent were dissolved in the obtained monomer mixture to obtain a mixed liquid. In a 5 L autoclave equipped with a stirrer and a condenser, 0.04 g of polyvinyl alcohol was added as a suspending agent and 2000 g of ion-exchanged water, and the mixed liquid was added while stirring, and the mixture was stirred at 250 rpm under a nitrogen atmosphere at 60 rpm. The polymerization was carried out for 5 hours at °C, followed by polymerization at 90 °C for 2 hours to obtain resin particles (the polymerization rate was 99% by mass method). The resin particles are washed with water and dehydrated

S-24 - 201209064, which was dried, and dissolved in methyl ethyl ketone to dissolve the residual portion in an amount of 35% by mass to prepare a resin paint. Next, 200 parts by mass of a resin paint, bisphenol A type epoxy resin (made by Epoxy Epoxy Co., Ltd., Epicote 8 2 8 ) as an epoxy resin, and 15 parts by mass of a phenol resin (DIC) were used. LF2 8 82 ) 1 5 parts by mass, as a hardening accelerator, cyanoethyl 2 - phenylimidazole (manufactured by Shikoku Chemical Industries Co., Ltd., Curzol 2PZ-CN) 5·5 parts by mass The film was placed on an aluminum plate having a thickness of 500 μm and dried at 170 ° C for 3 hours to prepare a film having a film thickness of 150 μm. (Example 2) A film was prepared in the same manner as in Example 1 except that the monomer mixture having the composition ratio shown in Table 1 was used. (Example 3) A film was prepared in the same manner as in Example 1 except that the monomer mixture having the composition ratio shown in Table 1 was used. (Example 4) A film was prepared in the same manner as in Example 1 except that the monomer mixture having the composition ratio shown in Table 1 was used. (Example 5) A film was prepared in the same manner as in Example 1 except that the monomer mixture having the composition ratio shown in Table 1 was used. -25-201209064 (Example 6) A film was prepared in the same manner as in Example 1 except that the monomer mixture having the composition ratio shown in Table 1 was used. (Example 7) A film was prepared in the same manner as in Example 1 except that the monomer mixture having the composition ratio shown in Table 1 was used. (Comparative Example 1) A film was prepared in the same manner as in Example 1 except that a commercially available acrylonitrile was used and a monomer mixture having a composition ratio shown in Table 2 was used. (Comparative Example 2) The same procedure as in Example 1 except that the alicyclic monomer and the methacrylate having a carbon number of 1 to 1 Å were used, and the monomer mixture having the composition ratio shown in Table 2 was used. A film was prepared. (Comparative Example 3) A film was prepared in the same manner as in Example 1 except that the methacrylate having a carbon number of 1 to 1 Å was not used and the monomer mixture having the composition ratio shown in Table 2 was used. (Comparative Example 4) A methacrylate having a carbon number of 12 in addition to the ester moiety, and a use table

A film was prepared in the same manner as in Example 1 except that the monomer mixture of the composition ratio shown in S-26-201209064 was used. The weight average molecular weight, the glass transition temperature (Tg), the moisture absorption rate, the volume resistance 値, the electrolytic corrosion resistance, and the like of the resins and films of Examples 1 to 7 and Comparative Examples 1 to 4 were measured and shown in Table 1 and Table. 2. Further, each evaluation was carried out by the method shown below. (1) Weight average molecular weight It was measured using a gel permeation chromatograph (elution liquid: THF, column: Gelpack GL-A100M, polystyrene conversion). (2) Glass transition temperature (Tg) Using DSC (manufactured by Rigaku Co., Ltd., Termo Plus DSC 823 0), it is in the range of -60 to 80 °C under a nitrogen atmosphere (temperature up rate: 10 °C / mi η ) Perform the measurement. (3) Moisture absorption rate After the resin was dried, the mass was absorbed at a temperature of 85 ° C and a humidity of 85 % until the mass was constant, and the moisture absorption rate was calculated by the following formula. [Number 2] Moisture absorption rate (%) = mass after moisture absorption - mass before moisture absorption mass before moisture absorption X 100 (4) volume resistance 値 using high resistance meter (manufactured by Hewlett-Packard , 4329A) Determine the volume resistance of the film. (5) Electro-erosion resistance The film thus produced was placed at a temperature of 85 ° C and a humidity of 85 % for 120 hours, and the volume resistance was measured 値 -27 - 201209064 [Table i] Ester-based Examples Examples of Examples EXAMPLES Examples Examples Carbon number 1 2 3 4 5 6 7 Monomer alicyclic monomer 10 FA-513A 300 280 270 230 260 250 300 Mixed 1 MMA 180 methacrylate 2 EMA 300 4 BMA 330 310 Group 8 2EHMA 200 510 190 310 into 12 LMA / -N GMA 50 50 40 40 40 50 Containing functional steroidal acrylate 20 EA Part other monomer BA 350 340 510 220 200 400 470 Acrylonitrile chain brewing amount (mass parts ) 0.45 0.45 0.45 0.45 0.45 0.45 0.45 Thunder weight average molecular weight (Χίο4) 61 65 49 50 50 55 62 Tg cc) 9 -2 -12 -6 6 -10 3 Moisture absorption rate (%) 0.4 0.3 0.4 0.3 0.3 0.3 0.4 Volume resistance Ω (Ω . cm) 3.8χ1016 3.9χ1016 8.3χ1015 3.3χ1016 4.3χ1016 1.5χ1016 1.3χ1016 Electro-erosion resistance (Ω · cm) Ι.όχΙΟ16 8.8χ1015 6_6χ1015 l.lxlO16 l.lxlO16 3.9xl015 1.9^1016 -28- 201209064 [Table 2] Ester-based carbon number Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Monomer mixture composition aliquot alicyclic monomer 10 FA-513A 0 0 280 270 Methacrylate 1 MMA 2 EMA 4 BMA 8 2EHMA 12 LMA 110 Containing functional monomer GMA 50 50 50 50 Acrylic other monomer EA 100 240 280 BA 500 710 390 570 Acrylonitrile 350 chain transfer dose fraction) 0.25 0.20 0.45 0.45 Weight average molecular weight (xio4) 45 103 59 65 Tg ( °C) 12 -40 -12 -21 Moisture absorption rate (%) 1.0 0.5 0.4 0.3 Volume resistance 値 (Ω · cm) 1.5xl015 3.6xl014 1.8xl015 1.3xl015 Electro-erosion resistance (Ω · cm) 4.8xl014 l.lxlO14 2.9 Xl015 1.2xl015 The monomers shown in Table 1 are detailed below. FA-513A: tricyclo[5.2.1. 02'6] 癸-8-yl ester (manufactured by Hitachi Chemical Co., Ltd.), MMA: methyl methacrylate EMA: ethyl methacrylate BMA: methyl Butyl acrylate 2EHMA: 2-ethylhexyl methacrylate LMA: lauryl methacrylate -29- 201209064 GMA: glycidyl methacrylate EA: ethyl acrylate BA: butyl acrylate The alicyclic type of the present invention is used. Examples 1 to 7 in which a monomer, a methacrylate having a carbon number of a hydrocarbon moiety, and a monomer having a functional group are obtained, and an elastomer having a small moisture absorption rate is obtained, and a volume resistance is obtained by using the elastomer.薄膜 and film with improved resistance to electrical corrosion. On the other hand, the flexibility of Comparative Example 1 in which the alicyclic monomer of the present invention was not used, and the alicyclic monomer in which the present invention was not used and the methacrylate in which the ester moiety had a methacrylate having a carbon number of 1 to 10 were used. The resulting film has poor electrical corrosion resistance. In particular, the elastomer of Comparative Example 1 using acrylonitrile has a high moisture absorption rate. Further, the elastomers of Comparative Example 3 and Comparative Example 4 which were not used for the methacrylate having a hydrocarbon group having 1 to 1 Å in the ester portion had a small moisture absorption rate, but the volume resistance was lower than that in the respective examples. [Industrial Applicability] According to the present invention, an acrylic elastomer having excellent electrical insulating properties under high temperature and high humidity and excellent long-term reliability can be provided, and an acrylic elastomer composition using the same can be provided.

S -30-

Claims (1)

201209064 VII. Patent application scope: 1. An acrylic elastomer containing at least the structures of the following general formulae (I), (II) and (ΠΙ) as structural units; (X represents a substituent containing an alicyclic hydrocarbon having 5 to 22 carbon atoms, and R1 represents hydrogen or a methyl group). · 1 (11) (Y represents a substituent containing a hydrocarbon group having 1 to 10 carbon atoms, and R2 represents a methyl group), [Chemical 3] S 1 · · (III) (Z represents OH, or a substituent containing at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, an acid anhydride group, an amine group, a phosphonium group, and an epoxy group, and R3 represents hydrogen or methyl). 2. The acrylic elastomer according to claim 1 which is obtained by polymerizing a monomer mixture of -31 - 201209064 containing a monomer having a carbon number of 5 in the ester moiety. a methacrylate or acrylate of an alicyclic hydrocarbon group of 22, a methacrylate having a hydrocarbon group of 1 to 1 Å in the ester moiety, and a hydroxy group selected from the group consisting of a carboxyl group, a hydroxyl group, an acid anhydride group, an amine group, and a guanamine group. And at least one functional group of the group consisting of epoxy groups and a functional group-containing monomer of at least one carbon-carbon double bond. 3. The acrylic elastomer according to claim 1 or 2, which has a carbon number of 5 to 94.5 parts by mass based on 100 parts by mass based on 100 parts by mass of the total mass of the monomer. a methacrylate or propyl ester of 22 alicyclic hydrocarbon groups, 5 to 65 parts by mass of the above-mentioned methacrylate having a hydrocarbon group having 1 to 10 carbon atoms in the ester moiety, and 0.5 to 30 parts by mass of the above-mentioned A functional group monomer and a monomer mixture of 〇 to 90 parts by mass of a monomer copolymerizable with the materials are obtained by polymerization. 4. The acrylic elastomer according to any one of claims 1 to 3, wherein the alicyclic hydrocarbon group having 5 to 22 carbon atoms is selected from the group consisting of cyclohexyl, borneol, tricyclodecyl, isobornyl At least one of the group consisting of a group and an adamantyl group. 5. The acrylic elastomer according to any one of claims 1 to 4, which has a saturated moisture absorption rate of 0.6% or less. 6. An acrylic elastomer composition comprising the acrylic elastomer and the solvent according to any one of claims 1 to 5, S-32-201209064. The designated representative circle of this case is: None (2) The symbol of the symbol of the representative figure is simple: No 201209064 If there is a chemical formula in the case of this case, please disclose the chemical formula that best shows the characteristics of the invention: no S -4-