JP2018178009A - Adhesive composition for semiconductor device and adhesive tape for semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive composition for a semiconductor device and an adhesive tape capable of easily peeling a wafer from the adhesive tape. SOLUTION: A pressure-sensitive adhesive composition for a semiconductor device containing a pressure-sensitive adhesive and a photobase generator represented by the formulas (1) and (2). (R1 to R3 are independent of H, halogen, hydroxyl group, etc.) (R4 is hydrogen, halogen, hydroxyl group, etc.; B is a basic compound) [Selection diagram] None

Description

The present invention is directed to a semiconductor device capable of easily peeling off a wafer from an adhesive tape after completion of processing without causing peeling of the wafer during processing even when used in a semiconductor chip processing step of performing heat treatment. The present invention relates to a pressure-sensitive adhesive composition and a pressure-sensitive adhesive tape for semiconductor devices.

In the manufacturing process of a semiconductor chip, an adhesive tape is used in order to facilitate handling at the time of processing of a wafer or a semiconductor chip and to prevent damage. For example, when a thick film wafer cut out from a high purity silicon single crystal or the like is ground to a predetermined thickness to form a thin film wafer, grinding is performed after an adhesive tape is attached to the thick film wafer.

The adhesive composition used for such a pressure-sensitive adhesive tape is capable of being peeled off without damaging the wafer or the semiconductor chip after the process, as well as having high adhesiveness which allows the wafer or the semiconductor chip to be firmly fixed during the processing process. It is required (hereinafter, also referred to as "high adhesion easy peeling").
Patent Document 1 describes a wafer processing method using a double-sided adhesive tape having an adhesive layer containing a gas generating agent that generates a gas upon stimulation with an azo compound or the like as an adhesive composition that achieves high adhesion and easy peeling. It is done. In the method of processing a wafer described in Patent Document 1, first, the wafer is fixed to a support plate via a double-sided adhesive tape. If stimulation is applied after performing a grinding process or the like in that state, the gas generated from the gas generating agent is released to the interface between the surface of the tape and the wafer, and at least a part thereof is peeled off by the pressure. If the double-sided adhesive tape of Patent Document 1 is used, peeling can be performed without damaging the wafer and without adhesive residue.

On the other hand, with the advancement of the performance of semiconductor chips, a process of performing a chemical treatment, a heating treatment or a treatment involving heat generation on the surface of a wafer has come to be performed. For example, as a next-generation technology, a three-dimensional lamination technology using TSV (through-silicon via / through Si via) that achieves high performance and miniaturization of devices by laminating a plurality of semiconductor chips is attracting attention . In addition to the high density of semiconductor mounting, TSV can reduce noise and resistance by shortening the connection distance, access speed is extremely fast, and it is excellent in heat release during use. . In the production of such TSVs, it is necessary to carry out a high-temperature treatment process at 200 ° C. or more, such as bumping a thin film wafer obtained by grinding, bumping on the back surface, reflowing during three-dimensional lamination, etc. It becomes. However, if such a high temperature treatment process is performed with a double-sided adhesive tape having an adhesive layer containing a conventional gas generating agent attached, the gas generating agent is decomposed by the heat of the high temperature treatment, and unintended gas There is a problem that peeling occurs due to the occurrence of

Unexamined-Japanese-Patent No. 2003-231872

In view of the above situation, the present invention prevents peeling of the wafer during processing even when it is used in the semiconductor chip processing step of heat treatment, and the wafer can be easily removed from the adhesive tape after processing. An object of the present invention is to provide a pressure-sensitive adhesive composition for semiconductor devices and a pressure-sensitive adhesive tape for semiconductor devices, which can be peeled off.

The present invention is a pressure-sensitive adhesive composition for a semiconductor device, which contains a pressure-sensitive adhesive and photobase generators represented by the following general formulas (1) and (2).

In the formula (1), R ¹ , R ² and R ³ are each independently hydrogen, halogen, hydroxyl, mercapto, sulfide, silyl, silanol, cyano, nitro, nitroso, sulfino, sulfo Group, sulfonato group, phosphino group, phosphinyl group, phosphono group, phosphonato group, amino group, alkoxy group, amide group, alkyl group having 1 to 12 carbon atoms, cycloalkyl group having 5 to 10 carbon atoms, 6 to 14 carbon atoms And an arylalkyl group having 7 to 15 carbon atoms, a saturated aliphatic ring, an unsaturated aliphatic ring, an aromatic ring or an organic group, which may be the same or different. In the case of a cyclic structure, it may contain a heteroatom. Two or more of R ¹ and R ² may be combined to form a cyclic structure, and the cyclic structure is any ring structure such as a saturated aliphatic ring, unsaturated aliphatic ring, aromatic ring, etc. It may be or may contain a hetero atom.

In the formula (2), R ⁴ is hydrogen, halogen, hydroxyl group, mercapto group, sulfide group, silyl group, silyl group, silanol group, cyano group, nitro group, nitroso group, sulfino group, sulfo group, sulfonato group, phosphino group, phosphinyl group , Phosphono group, phosphonato group, amino group, alkoxy group, amide group, alkyl group having 1 to 12 carbon atoms, cycloalkyl group having 5 to 10 carbon atoms, aryl group having 6 to 14 carbon atoms, 7 to 15 carbon atoms It represents an arylalkyl group, a saturated aliphatic ring, an unsaturated aliphatic ring, an aromatic ring or an organic group. When R ⁴ is a cyclic structure, it may contain a hetero atom. B is a basic compound.
The present invention will be described in detail below.

As a result of intensive studies, the present inventor has found that the photoacid generator and the photobase generator have high heat resistance which is not decomposed even by heat at the time of heat treatment. However, it has been found that the photoacid generator forms metal ions as a by-product during photolysis and this contaminates the wafer as a residue. On the other hand, it was also found that the photobase generator does not generate metal ions and does not contaminate the wafer. As a result of further investigations based on these findings, the present inventors have further studied, and by using a photo base generator having a specific structure, even during the semiconductor chip processing step of applying heat treatment, The present inventors have found that the wafer can be easily peeled off from the adhesive tape after the processing is completed without peeling of the wafer, and the present invention has been completed.

The pressure-sensitive adhesive composition for a semiconductor device of the present invention contains a pressure-sensitive adhesive.
The pressure-sensitive adhesive is not particularly limited, and may be a curing type or a non-curing type, but curing by adhesion before heat treatment or treatment accompanied by heat generation suppresses adhesion growth due to heat, and a wafer after treatment is completed. It is preferable that it is a curable pressure-sensitive adhesive because it can be easily peeled off without adhesive residue.

Examples of the curable pressure-sensitive adhesive include a photo-curable pressure-sensitive adhesive which is crosslinked and cured by light irradiation, and a thermosetting pressure-sensitive adhesive which is crosslinked and cured by heating.
As said photocurable adhesive, the photocurable adhesive which has a polymeric polymer as a main component and contains a photoinitiator as a polymerization initiator is mentioned, for example.
Examples of the thermosetting adhesive include a thermosetting adhesive containing a polymerizable polymer as a main component and a thermal polymerization initiator as a polymerization initiator.

For the polymerizable polymer, for example, a (meth) acrylic polymer having a functional group in the molecule (hereinafter referred to as a functional group-containing (meth) acrylic polymer) is synthesized in advance, and the above-mentioned functional group is reacted with the molecule. It can be obtained by reacting a compound having a functional group with a radical polymerizable unsaturated bond (hereinafter referred to as a functional group-containing unsaturated compound).

The said functional group containing (meth) acrylic-type polymer is a polymer which has adhesiveness at normal temperature. The functional group-containing (meth) acrylic polymer has, as a main monomer, an acrylic acid alkyl ester and / or a methacrylic acid alkyl ester in which the carbon number of the alkyl group is usually in the range of 2 to 18, and this and a functional group containing monomer Furthermore, they can be obtained by copolymerizing these with other modifying monomers that can be copolymerized in a conventional manner, as required. The weight average molecular weight of the functional group-containing (meth) acrylic polymer is usually about 200,000 to 2,000,000.

Examples of the functional group-containing monomer include carboxyl group-containing monomers such as acrylic acid and methacrylic acid, hydroxyl group-containing monomers such as hydroxyethyl acrylate and hydroxyethyl methacrylate, and epoxy such as glycidyl acrylate and glycidyl methacrylate Examples thereof include group-containing monomers, isocyanate group-containing monomers such as isocyanate ethyl acrylate and ethyl methacrylate methacrylate, and amino group-containing monomers such as amino ethyl acrylate and amino ethyl methacrylate.

Examples of the other copolymerizable modifying monomer include various monomers used for general (meth) acrylic polymers such as vinyl acetate, acrylonitrile and styrene.

As the functional group-containing unsaturated compound to be reacted with the functional group-containing (meth) acrylic polymer, the same functional group-containing monomer as described above according to the functional group of the functional group-containing (meth) acrylic polymer is used it can. For example, when the functional group of the functional group-containing (meth) acrylic polymer is a carboxyl group, an epoxy group-containing monomer or an isocyanate group-containing monomer is used. When the functional group is a hydroxyl group, an isocyanate group-containing monomer is used. When the functional group is an epoxy group, a carboxyl group-containing monomer or an amide group-containing monomer such as acrylamide is used. When the functional group is an amino group, an epoxy group-containing monomer is used.

Examples of the photopolymerization initiator include those activated by irradiation with light having a wavelength of 250 to 800 nm. Examples of such a photopolymerization initiator include acetophenone derivative compounds such as methoxyacetophenone and the like, and Benzoin ether compounds such as benzoin propyl ether and benzoin isobutyl ether, ketal derivative compounds such as benzyl dimethyl ketal and acetophenone diethyl ketal, phosphine oxide derivative compounds, bis (η5-cyclopentadienyl) titanocene derivative compounds, Benzophenone, Michler's ketone, chlorothioxanthone, todecyl thioxanthone, dimethyl thioxanthone, diethyl thioxanthone, α-hydroxycyclohexyl phenyl ketone, 2-hydroxymethyl phenyl phenyl ether Photo radical polymerization initiators such as Lopan are mentioned. These photopolymerization initiators may be used alone or in combination of two or more.

Examples of the thermal polymerization initiator include those which generate an active radical which is decomposed by heat to initiate polymerization and curing, and examples thereof include dicumyl peroxide, di-t-butyl peroxide, and t-butyl peroxy benzal. And t-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide, di-t-butyl peroxide and the like.
However, in order for the curable pressure-sensitive adhesive to exhibit high heat resistance, it is preferable to use a thermal polymerization initiator having a thermal decomposition temperature of 200 ° C. or higher as the thermal polymerization initiator. As such a thermal polymerization initiator having a high thermal decomposition temperature, cumene hydroperoxide, paramentan hydroperoxide, di-t-butyl peroxide and the like can be mentioned.
Among these thermal polymerization initiators, commercially available ones are not particularly limited, and, for example, perbutyl D, perbutyl H, perbutyl P, perpenta H (all manufactured by NOF Corporation) and the like are preferable. These thermal polymerization initiators may be used alone or in combination of two or more.

It is preferable that the said curable adhesive contains a radically polymerizable polyfunctional oligomer or monomer. By containing a radically polymerizable polyfunctional oligomer or monomer, photocurability and thermosetting are improved.
The above-mentioned polyfunctional oligomer or monomer preferably has a molecular weight of 10,000 or less, more preferably 5,000 so that three-dimensional reticulation of the curable pressure-sensitive adhesive layer by heating or light irradiation can be efficiently performed. Below, the number of radically polymerizable unsaturated bonds in the molecule is 2 to 20.

The polyfunctional oligomer or monomer is, for example, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol monohydroxy pentaacrylate, dipentaerythritol hexaacrylate or the same methacrylate And the like. In addition, 1,4-butylene glycol diacrylate, 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, commercially available oligoester acrylate, urethane acrylate, silicone acrylate, epoxy acrylate, polypropylene glycol diacrylate, or the same methacrylate as described above And the like. These polyfunctional oligomers or monomers may be used alone or in combination of two or more.

The pressure-sensitive adhesive composition for a semiconductor device of the present invention contains a photobase generator represented by the following general formulas (1) and (2).
The pressure-sensitive adhesive tape according to the present invention contains a photobase generator represented by the following general formulas (1) and (2) to give a stimulus when peeling off the pressure-sensitive adhesive tape from the wafer and to give a photobase generator By generating carbon dioxide, the adhesive tape can be easily peeled off without adhesive residue. Moreover, since the photobase generator represented by following General formula (1), (2) has high heat resistance which does not decompose | disassemble by the heat | fever at the time of the process in which high temperature processing and heat_generation | fever occur, It is possible to prevent the release of gas. Here, the photobase generator means a compound which is decomposed by irradiation with ultraviolet light to generate an organic base such as an amine and carbon dioxide. The photobase generator may be either of the ion type or the nonion type.
Although the photoacid generator also has high heat resistance, it is not suitable for use in a pressure-sensitive adhesive tape for protecting device materials because metal ions are generated during gas generation to form a residue and contaminate the wafer.

In the formula (1), R ¹ , R ² and R ³ are each independently hydrogen, halogen, hydroxyl, mercapto, sulfide, silyl, silanol, cyano, nitro, nitroso, sulfino, sulfo Group, sulfonato group, phosphino group, phosphinyl group, phosphono group, phosphonato group, amino group, alkoxy group, amide group, alkyl group having 1 to 12 carbon atoms, cycloalkyl group having 5 to 10 carbon atoms, 6 to 14 carbon atoms And an arylalkyl group having 7 to 15 carbon atoms, a saturated aliphatic ring, an unsaturated aliphatic ring, an aromatic ring or an organic group, which may be the same or different. In the case of a cyclic structure, it may contain a heteroatom. Two or more of R ¹ and R ² may be combined to form a cyclic structure, and the cyclic structure is any ring structure such as a saturated aliphatic ring, unsaturated aliphatic ring, aromatic ring, etc. It may be or may contain a hetero atom.

In the formula (2), R ⁴ is hydrogen, halogen, hydroxyl group, mercapto group, sulfide group, silyl group, silyl group, silanol group, cyano group, nitro group, nitroso group, sulfino group, sulfo group, sulfonato group, phosphino group, phosphinyl group , Phosphono group, phosphonato group, amino group, alkoxy group, amide group, alkyl group having 1 to 12 carbon atoms, cycloalkyl group having 5 to 10 carbon atoms, aryl group having 6 to 14 carbon atoms, 7 to 15 carbon atoms It represents an arylalkyl group, a saturated aliphatic ring, an unsaturated aliphatic ring, an aromatic ring or an organic group. When R ⁴ is a cyclic structure, it may contain a hetero atom. B is a basic compound.

The above basic compound is not particularly limited. Examples of the basic compound include an amine, a compound containing a pyridyl group, a hydrazine compound, an amide compound, a quaternary ammonium hydroxide salt, a mercapto compound, a sulfide compound or a phosphine compound.

The above-mentioned amine is not particularly limited, and any of primary amines, secondary amines and tertiary amines can be used.
Examples of the primary amines include methylamine, ethylamine, n-propylamine, n-butylamine, amylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine and n-unne Decylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-octadecylamine, isopropylamine, isobutylamine, sec-butylamine, tert-butylamine 1-Methylbutylamine, 1-ethylpropylamine, isoamylamine, 1,2-dimethylpropylamine, tert-amylamine, 1,3-dimethylbutylamine, 3, 3-dimethylbutylamine, 2-aminoheptane, 3-amino 1-methylheptylamine, 2-ethylhexylamine, 1,5-dimethylhexylamine, tert-octylamine, ethylediamine, 1,3-diaminopropane, 1,2-diaminopropane, 1,4-diaminobutane, 1 , 2-Diamino-2-methylpropane, 1,5-diaminopentane, 1,3-diaminopentane, 1,5-diamino-2-methylpentane, 1,7-diaminoheptane, 1,8-diaminooctane, 1 9,9-diaminononane, 1,10-diaminodecane, 1,12-diaminododecane, 2-butyl-2-ethyl-1,5-pentanediamine, cyclopropylamine, (aminomethyl) cyclopropane, cyclobutylamine, cyclopentylamine , 5-amino-2,2,4-trimethyl-1-cyclopene Methylamine, cyclohexylamine, 2-methylhexylamine, 4-methylcyclohexylamine, 4,4'-methylenebis (cyclohexylamine), 2,3-dimethylcyclohexylamine, 4,4'-methylenebis (2-methylcyclohexylamine), 1,2-diaminocyclohexane, cyclohexane methylamine, 1,8-diamino-p-menthane, 5-amino-1,3,3-trimethylcyclohexane methylamine, cycloheptylamine, cyclooctylamine, cyclododecylamine, 2- Amino norbornene, bornylamine, miltanilamine, 1-adamantanamine, 1-adamantan methylamine, allylamine, oleylamine, geranylamine, 2,2,2-trifluoromethylamine, 2-methoxy Thiylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 3-butoxypropylamine, 2-amino-1-methoxypropane, 3-isopropoxypropylamine, 2,2'-oxybis (ethyleneamine), 2,2 '-(Ethylenedioxy) bis (ethylamine), 4,9-dioxa-1,12-dodecanediamine, 4,7,10-trioxa-1,13-tridecanediamine, 3-amino-1-propanol vinyl ether, Tetrahydrofurfurylamine, 2,5-dihydro-2,5-dimethoxyfurfurylamine, aminoacetaldehyde dimethyl acetal, 4-aminobutyraldehyde diethyl acetal, ethanolamine, 3-amino-1-propanol, 2-amino-1-propanol, 1-amino-2- Propanol, 4-amino-1-butanol, 2-amino-1-butanol, 2-amino-2-methyl-1-propanol, 5-amino-1-pentanol, 2-amino-1-pentanol, 2- Amino-3-methyl-1-butanol, 6-amino-1-hexanol, 2-amino-1-hexanol, 1-amino-1-cyclopentanemethanol, 2-aminocyclohexanol, 4-aminocyclohexanol, 1- Aminomethyl-1-cyclohexanol, 3-aminomethyl-3,5,5-trimethylcyclohexane, 2- (2-aminoethoxy) ethanol, 2- (methylamino) ethanol, 2- (ethylamino) ethanol, 2- (Propylamino) ethanol, 2- (tert-butylamino) ethanol, 3-amino-1, Propanediol, SERINOL, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, tris (hydroxymethyl) aminomethane, BIS-HOMOTORIS, 1, 3-diamino-2-hydroxypropane, 1-amino-deoxysorbitol, 2-aminomethyl-15-crown-5, 2-aminomethyl-18-crown-6, aniline, orthotoluidine, metatoluidine, paratoluidine, 2 -Ethyl aniline, 3-ethyl aniline, 4-ethyl aniline, 2-propyl aniline, 3-propyl aniline, 4-propyl aniline, 2-isopropyl aniline, 3-isopropyl aniline, 4-isopropyl aniline, 2-butyl aniline, 3 -Butyl aniline, 4- Thiylaniline, 2-sec-butylaniline, 3-sec-butylaniline, 4-sec-butylaniline, 2-tert-butylaniline, 3-tert-butylaniline, 4-tert-butylaniline, 4-pentylaniline, 4 -Hexylaniline, 4-heptylaniline, 4-octylaniline, 4-decylaniline, 4-dodecylaniline, 4-tetradecylaniline, 4-hexadecylaniline, 4-cyclohexylaniline, 2,2'-ethylene Dianiline, ortho-anisidine, meta-anisidine, para-anisidine, ortho-phenetidine, meta-phenetidine, para-phenetidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothio Phenol, 2-aminobenzyl alcohol, 2-aminophenylethyl alcohol, 3-aminophenylethyl alcohol, 4-aminophenylethyl alcohol, 3- (1-hydroxyethyl) aniline, 2- (methylmercapto) aniline, 3- (3- Methylmercapto) aniline, 4- (methylmercapto) aniline, 2-aminophenyl disulfide, 2-isopropenylaniline, 4,4'-ethylenedianiline, 3,3'-methylenedianiline, 4,4'-methylenedianiline Aniline, 4,4'-methylenebis (3-chloro-2,6-diethylaniline), 4,4'-diaminostilbene, 4-butoxyaniline, 4-pentyloxyaniline, 4-hexyloxyaniline, 4,4 ' -Oxydianiline, 4,4'-thiodianiline, 4 '', 4 ''''-(Hexafluoroisopropylidene) -bis- (4-phenylaniline), oxydianiline, 4-aminophenyl sulfide, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2 , 6-dimethylaniline, 3,4-dimethylaniline, 3,5-dimethylaniline, 6-ethyl ortho toluidine, 2,6-diethylaniline, 2-isopropyl-6-methylaniline, 2,6-diisopropylaniline, 1 -Amino-5,6,7,8-tetrahydronaphthalene, 5-aminoindane, 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2-chloroaniline, 3-chloroaniline, 4-chloroaniline, 2 -Bromoaniline, 3-bromoaniline, 4-bromoaniline, 2-iodo Aniline, 3-iodoaniline, 4-iodoaniline, 2- (trifluoromethyl) aniline, 3- (trifluoromethyl) aniline, 4- (trifluoromethyl) aniline, 3- (trifluoromethoxy) aniline, 4- (Trifluoromethoxy) aniline, 3- (1,1,2,2-tetrafluoroethyl) aniline, 3-fluoro-2-methylaniline, 3-chloro-2-methylaniline, 2-chloro-6-methylaniline 2,6-Difluoroaniline, 2,3-Difluoroaniline, 2,6-Dichloroaniline, 2,3-Dichloroaniline, 2,6-Dibromoaniline, 2-Methoxy-6-methylaniline, 3-Fluoro-Orthoani Cidin, 3-amino-2-methylbenzyl alcohol, 2-amino-3-methylbenzyl alcohol 2-aminometacresol, 2,3-diaminophenol, orthotoluidine, 4,4'-ethylenedimethotoluidine, 2,5-di-tert-butylaniline, 3-fluoro-4-methylaniline, 2-fluoro- 4-methylaniline, 5-fluoro-2-methylaniline, 2-fluoro-5-methylaniline, 4-fluoro-2-methylaniline, 2-fluoro-6-methylaniline, 2,5-bis (trifluoromethyl) ) Aniline, 2-fluoro-6- (trifluoromethyl) aniline, 2-fluoro-3- (trifluoromethyl) aniline, 2,4-difluoroaniline, 3,4-difluoroaniline, 2,5-difluoroaniline, 3-chloro-4-fluoroaniline, 2-chloro-4-fluoroaniline, 2-bromo-4-flu Roaniline, 4-bromo-2-fluoroaniline, 2-bromo-4-iodoaniline, 2-chloro-4-aminotoluene, 2-chloro-4-methylaniline, 2-chloro-5-methylaniline, 5-chloro -2-Methylaniline, 4-chloro-2-methylaniline, 3,4-dichloroaniline, 2,4-dichloroaniline, 2,5-dichloroaniline, 4-bromo-2-methylaniline, 4-bromo-3 -Methylaniline, 3-bromo-4-methylaniline, 2-bromo-4-methylaniline, 4-bromo-2-chloroaniline, 2,4-dibromoaniline, 2,5-dibromoaniline, 4-fluoro-2 -(Trifluoromethyl) aniline, 4-fluoro-3- (trifluoromethyl) aniline, 2-fluoro-5- (trifluoromethyl) ) Aniline, 4-chloro-3- (trifluoromethyl) aniline, 4-chloro-2- (trifluoromethyl) aniline, 4-bromo-2- (trifluoromethyl) aniline, 4-bromo-3- (triol) Fluoromethyl) aniline, 2-bromo-5- (trifluoromethyl) aniline, 2-chloro-5- (trifluoromethyl) aniline, 5,5 ′-(hexafluoroisopropylidene) diortho toluidine, 4-methoxy- 2-methylaniline, 2-methoxy-5-methylaniline, 5-methoxy-2-methylaniline, 5-tert-butyl orthoanisidine, 2-methoxy-5- (trifluoromethyl) aniline, 6-chloromethani Cidin, 4-amino veratrol, 3,4- (methylenedioxy) aniline, 1,4-benzodioxa -6-amine, 4'-aminobenzo-15-crown-5, 2,4-dimethoxyaniline, 4-aminocresol, 2,5-dimethoxyaniline, 5-amino-2-methoxyphenol, 3-amino orthocresol, 2-amino orthocresol, 2-amino-tert-butylphenol, 2-amino-tert-amylphenol, 6-aminometacresol, 4-aminometacresol, 2-amino-5-methylbenzyl alcohol, 3-amino-4 -Methyl benzyl alcohol, 2-amino-4-chlorophenol, 4-amino-3-chlorophenol, 2-amino-5-chlorobenzyl alcohol, 5-chloro orthoanisidine, 3-fluoroloparaanisidine, 3- Chloroparaanisidine, 2-amino-4- (trifluoromethane) ) Benzenethiol, 3,5-dimethylaniline, 3,5-ditert-butylaniline, 3,5-bis (trifluoromethyl) aniline, 3,5-difluoroloaniline, 3,5-dichloroaniline, 3 5-Dimethoxyaniline, 3-methoxy-5- (trifluoromethyl) aniline, 2,4,6-trimethylaniline, 4,4'-methylenebis (2,6-dimethylaniline), 4,4'-methylenebis ( 2,6-diethylaniline),
4,4'-methylenebis (2,6-diisopropylaniline), 2,4,6-tri-tert-butylaniline, 2-chloro-4,6-dimethylaniline, 2,6-dichloro-3-methylaniline, 3-chloro-2,4-difluoroaniline, 2,3,4-trichloroaniline, 2,3,4-trifluoroaniline, 2,3,6-trifluoroaniline, 2,4,6-trifluoroaniline, 2,6-Dibromo-4-methylaniline, 3-chloro-2,6-diethylaniline, 4-bromo-2,6-dimethylaniline, 2-chloro-3,5-difluoroaniline, 4-bromo-2, 6-Difluoroaniline, 2-bromo-4-chloro-6-fluoroaniline, 2,4-dibromo-6-fluoroaniline, 2,6-dibromo-4-fluoroanilyl , 2,6-dichloro-4- (trifluoromethyl) aniline, 4-chloro-2,6-dibromoaniline, 4-amino-2,6-dichlorophenol, 3,4,5-trichloroaniline, 3 ,, 4,5-Trimethoxyaniline, 3,3 ', 5,5'-Tetramethylbenzidine, 2-bromo-4,6-difluoroaniline, 2,4,6-trichloroaniline, 2,6-dichloro-4- (Trifluoromethoxy) aniline, 2-bromo-3,5-bis (trifluoromethyl) aniline, 2,4,6-tribromoaniline, 2-chloro-4-fluoro-5-methylaniline, 2,4,6 5-trifluoroaniline, 2,4,5-trichloroaniline, 4-chloro-2-methoxy-5-methylaniline, 4-amino-2,5-dimethylphenol, 4-amino -2,6-Dibromophenol, 3,5-dichloro-2,6-diethylaniline, 2,3,5,6-tetrachloroaniline, 2,3,5,6-tetrafluoroaniline, 2,3,4 5-tetrafluoroaniline, 2,3,4,6-tetrafluoroaniline, 2-bromo-3,4,6-trifluoroaniline, 2-bromo-4,5,6-trifluoroaniline, 2-amino -2,4-Dichloro-3-methylphenol, 2,3,5,6-tetrafluoro-4-trifluoromethylaniline, 2,3,4,5,6-pentafluoroaniline, 4,4'-diamino Octafluorobiphenyl, 4-methoxy-3-biphenylamine, 4-bromo-2,3,5,6-tetrafluoroaniline, 1,2-phenylenediamine, 2,3-diaminotoluene 3,4-diaminotoluene, 3,3'-diaminobenzidine, 4-chloro-1,2-phenylenediamine, 4-methoxy-1,2-phenylenediamine, 4,5-dimethyl-1,2-phenylenediamine 1,2,4,5-benzenetetramine, 4,5-dichloro-1,2-phenylenediamine, 1,3-phenylenediamine, 2,6-diaminotoluene, 2,4-diaminotoluene, 2,4,4, 6-trimethyl-1,3-phenylenediamine, 4-methoxy-1,3-phenylenediamine, 2,4-diaminophenol, 4- (2-hydroxyethylthio) -1,3-phenylenediamine, 1,4- Phenylenediamine, 2,5-diaminotoluene, 2,5-dimethyl-1,4-phenylenediamine, 2-chloro-1,4-phenylenedia , 2,5-dichloro-1,4-phenylenediamine, 2-methoxy-1,4-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 2-aminobiphenyl, 4 -Aminobiphenyl, 2,4,6-triphenylaniline, 2-amino-4-phenylphenol, 5-phenylorthoanisidine, benzylamine, α-methylbenzylamine, aminodiphenylmethane, tritylamine, 1,2-diphenyl Ethylamine, 2,2-diphenylethyleneamine, 2-amino-1,2-diphenylethanol, phenethylamine, 2-amino-3-phenyl-1-propanol, 2-phenylcyclopropylamine, 3-phenyl-1-propylamine , 3,3-diphenylpropylamine, 1-methyl-3-phenyl Nylpropylamine, 4-phenylbutylamine, 1,2-diphenylethylenediamine, 1,2-bis (4-methoxyphenyl) ethylenediamine, 4- (2,4-di-tert-amylphenoxy) butylamine, 2-amino-1 -Phenylethanol, 2-phenylglycinol, 2-amino-3-phenyl-1-propanol, NOREPHEDRINE, 2-methylbenzylamine, 1-aminoindane, 2-aminoindane, 1,2,3,4-tetrahydro- 1-naphthylamine, 2- (trifluoromethyl) benzylamine, 2-fluorobenzylamine, 2-fluorophenethylamine, 2-chlorobenzylamine, 2-chlorophenethylamine, 2-bromobenzylamine, 2-methoxybenzylamine, 2- Methoxy Phenethylamine, 2-ethoxybenzylamine, 2- [2- (aminomethyl) phenylthio] benzyl alcohol, 2-aminobenzylamine, 3-methylbenzylamine, 3- (trifluoromethyl) benzylamine, meta-xylene diamine, 3- Fluorobenzylamine, 3-fluorophenethylamine, 3-chlorobenzylamine, 3-chlorophenethylamine, 3-bromobenzylamine, 3-iodobenzylamine, 3-methoxyphenethylamine, 4-methylbenzylamine, paraxylenediamine, 4- ( Trifluoromethyl) benzylamine, α, 4-dimethylbenzylamine, 2- (paratoluyl) ethylamine, 4-fluorobenzylamine, 4-fluorophenethylamine, 4-chlorobenzylamine, 4-bromobenzene Dylamine, 4-bromophenethylamine, 4-fluoro-α-methylbenzylamine, 4-fluorophenethylamine, 4-chlorophenethylamine, 4-methoxybenzylamine, 4-methoxyphenethylamine, 4- (trifluoromethoxy) benzylamine, 4- (trifluoromethoxy) benzylamine Aminobenzylamine, 2- (4-aminophenyl) ethylamine, TYRAMINE, 3,5-bis (trifluoromethyl) benzylamine, 3-fluoro-5- (trifluoromethyl) benzylamine, 2,6-difluorobenzylamine 2,4-difluorobenzylamine, 2,5-difluorobenzylamine, 3,4-difluorobenzylamine, 2,4-dichlorobenzylamine, 3,4-dichlorobenzylamine, 2,4-dichlorophenethylamine, 2 , 3-dimethoxybenzylamine, 3,5-dimethoxybenzylamine, 2,4-dimethoxybenzylamine, 3,4-dimethoxybenzylamine, 2,5-dimethoxyphenethylamine, 3,4-dimethoxyphenethylamine, piperonylamine, 3,4 3,5-Trimethoxybenzylamine, 2,4,6-trimethoxybenzylamine, 1-aminoindanol, 1-naphthalenemethylamine, 1- (1-naphthyl) ethylamine, 9-aminofluorene, 1-pyrenemethylamine Α, ω-diaminopolyethylene glycol, α, ω-diaminopolypropylene glycol, α, ω-diaminopolydimethylsiloxane or polyallylamine.

Examples of the secondary amines include dimethylamine, N-ethylmethylamine, diethylamine, N-methylpropylamine, N-methylisopropylamine, N-ethylisopropylamine, dipropylamine, diisopropylamine, N-methylbutylamine, and the like. N-ethylbutylamine, N-methyl-tert-butylamine, N-tert-butylisopropylamine, dibutylamine, di-sec-butylamine, diisobutylamine, tert-amyl-tert-butylamine, dipentylamine, N-methylhexylamine, Dihexylamine, tert-amyl-tert-octylamine, dioctylamine, bis (2-ethylhexyl) amine, didecylamine, N-methyloctadecylamine, N, N'-dimethyl ether N, N'-diethylethylenediamine, N, N'-diisopropylethylenediamine, N, N'-dimethyl-1,3-propanediamine, N, N'-diethyl-1,3-propanediamine, N, N '-Diisopropyl-1,3-propanediamine, N, N'-dimethyl-1,6-hexanediamine, N-propylcyclopropanemethylamine, N-methylcyclohexysilamine, N-ethylcyclohexylamine, N-isopropyl Cyclohexylsilamine, N-tert-butylcyclohexylamine, dicyclohexylamine, N, N′-bis (3,3-dimethylbutyl) -1,2-cyclohexanediamine, 1-cyclohexylethylamine, 1,3-cyclohexanebis ( Methylamine), N-methylallyl Min, N-methyl-2-methylallylamine, diallylamine, N, N'-diethyl-2-butylene-1,4-diamine, N-allylcyclopentylamine, N-allylcycloamine, 2- (1-cyclohexene) ethylamine 6- (dimethylamino) fulvene, bis (2-methoxyethyl) amine, methylaminoacetaldehyde dimethylacetal, diethylaminoacetaldehyde diethylacetal, 2-methylaminoethyl-1,3-dioxolane, diethanolamine, diisopropanolamine, N, N '-Bis (2-hydroxyethyl) ethylenediamine, 1,3-bis [tris (hydroxymethyl) methylamino] propane, N-methylglucamine, 2-methylaziridine, azetidine, pyrrolidine, 2,5-dimethyl Pyrrolidine, 3-pyrrolidinol, 2-pyrrolidinemethanol, 3-pyrroline, 2,5-dimethyl-3-pyrroline, piperidine, 1,2,3,6-tetetahydropyridine, 2-methylpiperidine, 2-ethylpiperidine, 3 -Methylpiperidine, 4-methylpiperidine, 4,4'-bipiperidine, 4,4'-ethylenebipiperidine, 4,4'-trimethylenebipiperidine, 3,3-dimethylpiperidine, 2,6-dimethylpiperidine, 3 5-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine, 1,4-dioxa-8-azaspiro [4.5] decane, 2-piperidine methanol, 2-piperidine ethanol, 3-hydroxypiperidine, 3 -Piperidine methanol, 4-hydroxypiperidine, 2,2,6,6-trimethyl- -Piperidinol, 7,7,9,9-tetramethyl-1,4-dioxa-8-azaspiro [4.5] decane-2-methanol, hexamethyleneimine, heptamethyleneimine, piperazine, 2-methylpiperazine, 2 , 6-dimethylpiperazine, 2,5-dimethylpiperazine, homopiperazine, acetaldehyde ammonia trimer, 1,4,7-triazacyclononane, 1,5,9-triazacyclododecane, CYCLEN, 1,4, 8,11-Tetraazacyclotetradecane, 1,4,8,12-Tetraazacyclopentadecane, HEXACYCLEN, 1,3,3-Trimethyl-6-azabicyclo [3.2.1] octane, Dodecahydroquinoline, Sparteine , 4,4-Dimethyloxadolizine, 4-ethyl-2-methyl-2- (3) Methylbutyl) oxadolizine, morpholine, 2,6-dimethylmorpholine, 1-aza-12-crown-4, 1-aza-15-crown-5, 1-aza-18-crown-6, 1,4,10-trioxax -7,13-Diazacyclopentadecane, 1,4,10,13-tetraxa-7,16-diazacyclooctadecane, thiazolidine, thiomorpholine, N-methylaniline, N-ethylaniline, N-butylaniline, diphenylamine , N-phenylbenzylamine, 1,2-dianilinoethane, N-allylaniline, 2-anilinoethanol, N-ethyl ortho toluidine, N-ethyl meta toluidine, N-ethyl para toluidine, 4-chloro-N-methyl aniline , N-methylparaanisidine, 4-aminomethylphenol, N- Ethyl-2,3-xylidine, N-ethyl-3,4- (methylenedioxy) aniline, 2,4,6-tri-tert-butyl-N-methylaniline, N, N'-diphenyl-1,4 -Phenylenediamine, N, N'-diphenylbenzidine, 3,3 '-(hexafluoroisopropylidene) dianiline, 4,4'-(hexafluoroisopropylidene) dianiline, 2-benzylaniline, 1-amino-4-bromo Naphthalene, 1-amino-2-naphthol, 4-amino-1-naphthol, 5-amino-1-naphthol, 3-amino-2-naphthol, 2,2'-dithiobis (1-naphthalene), 2,3- Diaminonaphthalene, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 1,1'-binaphthyl-2,2'-diamine, 1- Minoflurane, 2-aminofurlene, 2,7-diaminofurlene, 3,7-diamino-2-methoxyfurlene, 2-amino-7-bromofurrene, 2-amino-9-hydroxyfurrene, 2-amino-3- Bulomo-9-hydroxyflurane, 1-aminoanthracene, 2-aminoanthracene, 9-aminophenanthrene, 9,10-diaminophenanthrene, 3-aminofluorancene, 1-aminopyrene, 6-aminochrysene N, α-dimethylbenzylamine, N-benzyl-α-methylbenzylamine, N-benzylmethylamine, N-ethylbenzylmethylamine, N-isopropylbenzylmethylamine, N-butylbenzylmethylamine, N-tert- Butylbenzyl methylamine, dibenzylamine, N, N'-diben Luethylenediamine, N-methylphenethylamine, N-benzyl-2-phenethylamine, β-methylphenethylamine, N-benzylethanolamine, 2- (benzylamino) cyclohexanemethanol, α- (methylaminomethyl) benzyl alcohol, EPHEDRINE, α- Diphenyl-2-pyrrolidinemethanol, 4-benzylpiperazine, 4-phenyl-1,2,3,6-tetrahydropyridine, indoline, 2-methylindoline, 1,2,3,4-tetrahydrocarbazole, 2,3-dimethyl Indoline, indoline-2-carboxylic acid, 1,2,3,4-tetrahydroquinoline, 1,2,3,4-tetrahydroisoquinoline, 6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline, iminodi Benzyl, , 6,11,12- tetrahydrodicyclopentadiene benz [B, F] azocine, Fenozajin or phenothiazine and the like.

Examples of the tertiary amines include trimethylamine, N, N-dimethylethylamine, N, N-diethylmethylamine, triethylamine, tripropylamine, N, N-dimethylisopropylamine, N, N-diisopropylethylamine, N, N- Dimethylbutylamine, N-methyldibutylamine, tributylamine, triisobutylamine, tripentylamine, N, N-dimethylhexylamine, trihexylamine, N, N-dimethyloctylamine, N-methyldioctylamine, trioctylamine, Triisooctylamine, Triisodecylamine, N, N-Dimethylundecylamine, N, N-Dimethyldodecylamine, Tridodecylamine, N-Methyldioctadecylamine, N, N, N ', N'-Tetramethyl Jia Nomethane, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetraethylethylenediamine, N, N, N ', N'-tetramethyl-1,3-propanediamine, N , N, N ′, N′-tetraethyl-1,3-propanediamine, N, N, N ′, N′-tetraethyl-1,3-butanediamine, N, N, N ′, N′-tetramethyl- 1,4-butanediamine, N, N, N ', N'-tetramethyl-1,5-pentanediamine, N, N, N', N'-tetramethyl-1,6-hexanediamine, N, N N ′, N′-tetrabutyl-1,6-hexanediamine, tris (dimethylamino) methane, N, N, N ′, N ′, N ′ ′-pentamethyldiethylene triamine, N, N-dimethylcyclohexylamine, N , N Diethylcyclohexylamine, N-methyldicyclohexylamine, N-ethyldicyclohexylamine, N, N-dimethylcyclohexanemethylamine, triallylamine, tris (2-methylallyl) amine, N, N, N ', N'-tetramethyl-2 -Butene-1,4-diamine, tetrakis dimethylaminoethylene, perfluoroisobutylamine, tris [2- (2-methoxyethoxy) ethyl] amine, tert-butoxybis (dimethylamino) methane, 2- (diethylamino) ethanol vinyl ether, N, N'-dimethylformamide dimethyl acetal, N, N'-dimethylformamide diethyl acetal, N, N'-dimethylformamide dipropyl acetal, N, N'-dimethylformamide diisopropyl ester Acetal, N, N'-dimethylformamide di-tert-butyl acetal, N, N'-dimethylformamide dineopentyl acetal, N, N'-dimethylformamide dicyclohexyl acetal, N, N-dimethylacetamide dimethyl acetal, dimethylaminoacetaldehyde Diethyl acetal, diethylaminoacetaldehyde diethyl acetal, N, N'-bis (2,2-dimethoxyethyl) methylamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, 2- (diisopropylamino) ethanol, 2 -(Dibutylamino) ethanol, 3-dimethylamino-1-propanol, 3-diethylamino-1-propanol, 1-dimethylamino-2-propanol, 1-diethylamino 2-propanol, 2-dimethylamino-2-methyl-1-propanol, 5-diethylamino-2-pentanol, N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, 1- [N, N-bis ( 2-Hydroxyethyl) amino] -2-propanol, triisopropanolamine, 3- (dimethylamino) -1,2-propanediol, 3- (diethylamino) -1,2-propanediol, 3- (dipropylamino) -1,2-propanediol, 3- (diisopropylamino) -1,2-propanediol, 2-{[2- (dimethylamino) ethyl] methylamino} ethanol, 1,3-bis (dimethylamino) -2 -Propanol, N, N, N ', N'-tetrakis (2-hydroxy Pill) ethylenediamine, 2- [2- (dimethylamino) ethoxy] ethanol, PENTROL, 1-aziridineethanol, 1-methylpyrrolidine, 1-butylpyrrolidine, 1-pyrrolidino-1-cyclopentene, 1-pyrrolidino-1-cyclohexene, 1- (2-hydroxyethyl) pyrrolidine, 3-pyrrolidino-1,2-propanediol, 1-methyl-3-pyrazinol, 1-ethyl-3-pyrazinol, 1-methyl-2-pyrrolidine methanol, 2-methyl- 1-pyrroline, 1-methylpiperidine, 1-ethylpiperidine, dipiperidinomethane, 1-ethylpiperidine, 1,1'-methylenebis (3-methylpiperidine), 4,4'-trimethylenebis (1-methyl) Piperidine), 1,2,2,6,6-pentamethylpiperidine 1-piperidine acetaldehyde diethyl acetal, 1-piperidine ethanol, 3-piperidino-1,2-propanediol, 3-hydroxy-1-methylpiperidine, 1-ethyl-3-hydroxypiperidine, 1-methyl-3-piperidinemethanol 4,4,4'-trimethylene bis (1-piperidineethanol), N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) -1,6-hexadiamine, 1,2, 3,6-tetrahydropyridine, 1,4-dimethylpiperazine, 4- (dimethylamino) -1,2,2,6,6-pentamethylpiperazine, 1,4-bis (2-hydroxyethyl) piperazine, 1,3 3,5-Tetramethylhexahydro-1,3,5-triazine, 1,3,5-tetraethylhexahydro-1, 5-triazine, 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,5,9-trimethyl-1,5,9-triazacyclododecane, 1,4,8,11 -Tetramethyl-1,4,8,11-tetraazacyclotetradecane, 1,4,7,10,13,16-hexamethyl-1,4,7,10,13,16-hexaazacyclooctadecane, TROPANE, QUINULIDINE, 3-QUINULIDINOL, 1,4-diazabicyclo [2.2.2] octane, hexamethylenetetramine, 4-methylmorpholine, 4-ethylmorpholine, 4- (1-cyclopenten-1-yl) morpholine, 1-morpholino -1-cyclohexene, 1-morpholino-1-cycloheptene, 4- (2-hydroxyethyl) morpholine 3-morpholino-1,2-propanediol, 4- [2- (dimethylamino) ethyl] morpholine, 5-ethyl-1-aza-3,7-dioxabicyclo [3.3.0] octane, 1- Aza-3,7-dioxabicyclo [3.3.0] octane-5-methanol, 4,7,13,18-tetraoxa-1,10-diazabicyclo [8.5.5] eicosane, 4,7, 13,16,21-pentaoxa-1,10-diazabicyclo [8.8.5] trichosan, 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo [8.8.8] hexacosan, N, N-dimethylaniline, N-ethyl-N-methylaniline, N, N-diethylaniline, N, N-dibutylaniline, 1-phenylpiperidine, triphenylamine, N-be Ndidyl-N-ethylaniline, 2- (N-ethylanilino) ethanol, N-phenyldiethanolamine, N- (ethoxyethyl) -N-methylaniline, N, N-dimethyl orthotoluidine, N, N-dimethylmethatolidine, N , N-dimethyl paratoluidine, N, N-diethyl ortho toluidine, N, N- diethyl meta toluidine, N, N- diethyl para toluidine, 3-dimethylaminophenol, 3- diethyl amino phenol, 2- (N- ethyl meta toluidine No.) ethanol, 4-tert-butyl-N, N-dimethylaniline, 4-bromo-N, N-dimethylaniline, 2,2 '-(paratoluylimino) dimethanol, 4- (dimethylamino) phenethyl alcohol, N, N, N ', N'- tetramethyl benzidine, N, '-Diglycidyl-4-glycidyloxyaniline, 2,6-diisopropyl-N, N-dimethylaniline, 4-bromo-N, N-dimethyl-3- (trifluoromethyl) aniline, N, N, 3,5- Tetramethylaniline, N, N, 2,4,6-pentamethylaniline, 4,4'-methylenebis (2,6-diisopropyl-N, N-dimethylaniline), 2,6-di-tert-butyl-4 -(Dimethylaminomethyl) phenol, N, N, N ', N'-tetramethyl-1,4-phenylenediamine, 4,4'-methylenebis (N, N-dimethylaniline), 4,4'-methylenebis ( N, N-diglycidyl aniline), 4,4'-vinylidene bis (N, N-dimethyl aniline), leucomalachite green, 4,4'-bis (dimethyl) Mino) benzidorole, 1, 8-bis (dimethylamino) naphthalene, 2- (dimethylamino) furene, N, N- dimethyl- 1-phenethylamine, 3- (N- benzyl- N- methylamino) 1, 2 -Propanediol, N, N-dimethylbenzylamine, N, N, N ', N'-tetrabenzylmethanediamine, N-methyldiphenylethyleneamine, tribenzylamine, N- (2-chloroethyl) dibenzylamine, N -Benzyl-N-methylethanolamine, 3-dibenzylamino-1-propanol, 2-dibenzylamino-3-phenyl-1-propanol, N-ethyl-3,3'-diphenyldipropylamine, 3-methoxy -N, N-dimethylbenzylamine, 4-bromo-N, N-diisopropylbenzylamine, 1 -(Diphenylmethyl) azetidine, 1-benzyl-3-pyrroline, 1-benzyl-3-pyrrolidinol, 1-benzyl-2-pyrrolidinemethanol, 1- (3,4-dihydro-2-naphthyl) pyrrolidine, 1-methyl -4-phenyl-1,2,3,6-tetrahydropyridine, 4-diphenylmethoxy-1-methylpiperazine, 1-benzyl-4-hydroxypiperazine, 1,3,5-tribenzylhexahydro-1,3, 5-triazine, 4-phenylmorpholine, 2,5-dimethyl-4- (morpholinomethyl) phenol, N, N'-dibenzyl-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane, 2 -Methylene-1,3,3-trimethylindoline, JULODINE, 8-hydroxy JULODINE, , 10-dihydro-5,10-dimethylphenazine, 10 methylphenothiazine, TROGER'S BASE or 5,6-benzo-4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo [8.8] .8] Hexacosane etc. may be mentioned.

As the above-mentioned amine which can be used besides the above-mentioned primary amine, the above-mentioned secondary amine, and the above-mentioned tertiary amine, N-methylethylenediamine, N-ethylethylenediamine, N-propylethylenediamine, N-isopropylethylenediamine, N, N-dimethylethylenediamine N, N-diethylethylenediamine, N, N-dibutylethylenediamine, N, N, N'-trimethylethylenediamine, N, N-dimethyl-N'-ethylethylenediamine, N, N-diethyl-N'-methylethylenediamine, N , N, N'-triethylethylenediamine, N-methyl-1,3-propanediamine, N-ethyl-1,3-propanediamine, N-propyl-1,3-propanediamine, N-isopropyl-1,3- Propane diamine, 3-dimethylamino amino acid Pylamine, 3-diethylaminopropylamine, 3-dibutylaminopropylamine, N, N, N'-trimethyl-1,3-propanediamine, N, N, 2,2-tetraethyl-1,3-propanediamine, 2- Amino-5-diethylaminopentane, diethylenetriamine, N1-isopropyldiethylenetriamine, N, N, N ', N'-tetraethyldiethylenetriamine, N- (2-aminoethyl) -1,3-propanediamine, 3,3'-diamino- N-methyldipropylamine, N- (3-aminopropyl) -1,3-propanediamine, 3,3'-iminobis (N, N-dimethylpropylamine), SPERMIDINE, bis (hexamethylene) triamine, N, N ', N' '-trimethylbis (hexamethylene) tri Min, 4- (aminomethyl) -1,8-octanediamine, triethylenetetramine, 1,1,4,7,10,10-hexamethyltriethylenetetramine, N, N'-bis (3-aminopropyl) Ethylenediamine, N, N'-bis (2-aminoethyl) -1,3-propanediamine, N, N'-bis (3-aminopropyl) -1,3-propanediamine, SPERMINE, tris (2-aminoethyl) ) Amine, tetraethylenepentamine, pentaethylenehexamine, N-cyclohexyl-1,3-propanediamine, 2- (2-aminoethylamino) ethanol, 1- (2-aminoethyl) pyrrolidine, 2- (2-amino) Ethyl) -1-methylpyrrolidine, 1- (2-pyrrolidinylmethyl) pyrrolidine, 4- (1-pyrrolidinyl) pi Peridine, 4-piperidinopiperidine, 1- (2-aminoethyl) piperidine, 1- (3-aminopropyl) -2-pipecoline, 3-aminopiperidine, 1-methyl-4- (methylamino) piperidine, 4 -(Aminoethyl) piperidine, 3- (4-aminobutyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-dimethylamino-2,2,6,6-tetramethylpiperidine, 2-Methyl-2-imidazoline, 4,4-dimethyl-2-imidazoline, 1-methylpiperazine, 1-ethylpiperazine, 1- (2-hydroxyethyl) piperazine, 1- [2- (2-hydroxyethoxy) ethyl ] Piperazine, 1- (2-aminoethyl) piperazine, 1,4-bis (3-aminopropyl) piperazine, HEXETIDI N, 1,4,5,6-tetrahydropyrimidine, 1-methylhomopiperazine, 3-aminoquinuridine, 1,8-diazabicyclo [5.4.0] unde-7-cene, 1,3,4,6 7,8-hexahydro-2H-pyrimido [1,2-A] pyrimidine, 1,3,4,6,7,8-hexahydro-1-methyl-2H-pyrimido [1,2-A] pyrimidine, 4 -(2-aminoethyl) morpholine, 4- (3-aminopropyl) morpholine, 5,6-dihydro-2-isopropenyl-4,4,6-trimethyl-4H-1,3-oxazine, N-methyl- 1,2-phenylenediamine, N-phenyl-1,2-phenylenediamine, N, N-dimethyl-1,3-phenylenediamine, N, N-dimethyl-1,4-phenylenediamine, N, N-diethylmethane -1,4-phenylenediamine, N4, N4-diethyl-2-methyl-1,4-phenylenediamine, 2-methoxy-N4-phenyl-1,4-phenylenediamine, N-phenyl-1,4-phenylenediamine N-methyl-4,4'-methylenedianiline, N-phenylethylenediamine, N'-benzyl-N, N-dimethylethylenediamine, N, N ', N' '-tribenzyltris (2-aminoethyl) amine 4- (hexadecylamino) benzylamine, 4-dimethylaminobenzylamine, 4-amino-1-benzylpiperazine, 2-phenyl-2-imidazoline, trazoline, 2- (1-naphthylmethyl) -2-imidazoline, Phentolamine, 2,3-diphenyl-1,4-diazaspiro [4.5] deca-1,3-di Ene, 4-benzyl-2-methyl-2-oxazoline, 4,4-dimethyl-2-phenyl-2-oxazoline, 4-methoxymethyl-2-methyl-5-phenyl-2-oxazoline, 2-methyl-5 -Phenyl-2-oxazoline-4-methanol, 2,2'-bis [(4S) -4-benzyl-2-oxazoline], 2,2'-bis [(4S) -4-phenyl-2-oxazoline] 2,2'-isopropylidenebis [(4S) -4-phenyl-2-oxazoline], 2,2'-methylenebis [(4R, 5S) -4,5-diphenyl-2-oxazoline], tetramisole, 1 -Phenyl piperazine, 5-phenyl-1,4,5,6-tetrahydropyrimidine, 1-benzyl piperazine, 1-cinnamyl piperazine, 1-ortho tolyl pipe Gin, 1- (2,3-xylyl) piperazine, 1- (2-methoxy) piperazine, 1- (4-methoxy) piperazine, 1- (2-ethoxy) piperazine, 4-morpholinoaniline, homocaine, polyethyleneimine, Or an amine compound formed by combining a primary amino group, a secondary amino group and a tertiary amino group in one molecule, such as a polyethyleneimine graft polyalkyl (meth) acrylate copolymer.

Furthermore, nitroamine, a commercially available modified amine, or a modified polyamine can also be used as the above-mentioned amine. Examples of the nitroamine include 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 1- (4-nitrophenyl) piperazine and the like.

Examples of the quaternary ammonium hydroxides include tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide, triethyl methyl ammonium hydroxide, hexadecyl hydroxide. A trimethyl ammonium salt or a benzyl trimethyl ammonium hydroxide salt etc. are mentioned.

Examples of the hydrazine compound include phenylhydrazine, 1,1-diphenylhydrazine, 1,2-diphenylhydrazine, 1-methyl-1-phenylhydrazine and ortho toluylhydrazine.

Examples of the amide compound include malonamide, succinamide, fumaric acid amide, adipic acid amide, NIPECITANIDE, alkyl (meth) acrylate / (meth) acryloylamide copolymer, styrene / alkyl (meth) acrylate / (meth) acryloylamide Examples thereof include copolymers, alkyl (meth) acrylate / (meth) acryloyl morpholine copolymers, and styrene / alkyl (meth) acrylate / (meth) acryloyl morpholine copolymers.

Examples of the mercapto compound include 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 2-mercaptoethyl ether, 1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, 1,2-benzenedimethanethiol, 1,3-benzenedimethane Thiol, 1,4-benzenedimethanethiol, 4,4'-thiobenzenethiol and the like can be mentioned.

Examples of the sulfide compound include ethyl disulfide, methylpropyl disulfide, isopropyl disulfide or phenyl disulfide.

Examples of the phosphine compounds include di-tert-butyl phosphine, trimethyl phosphine, 1,2-bis (dimethyl phosphino) ethane, triethyl phosphine, tripropyl phosphine, triisopropyl phosphine, triisobutyl phosphine, tri-tert-butyl Phosphine, trioctyl phosphine, tricyclohexyl phosphine, 1,4-bis (dicyclohexyl phosphino) butane, phenyl phosphine, diphenyl phosphine, triphenyl phosphine, 1,2-bis (phenyl phosphino) ethane, dimethyl phenyl phosphine, diethyl phenyl Phosphine, diallylphenyl phosphine, methyl diphenyl phosphine, ethyl diphenyl phosphine, diphenyl propyl phosphine, isopropyl diphenyl Nyl phosphine, diphenyl vinyl phosphine, allyl diphenyl phosphine, dicyclohexyl phenyl phosphine, tribenzyl phosphine, triortho toluyl phosphine, trimetatolyl phosphine, triparatolyl phosphine, tris (2,4,6-trimethylphenyl) phosphine, bis (diphenyl phos) Fino) methane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, or 2,2′-bis (diphenylphos) Fino) -1,1'-naphthalene and the like.

Examples of photobase generators represented by the above general formulas (1) and (2) include imidazole-1-carboxylic acid 1- (anthraquinone-2-yl) ethyl, 1- (Anthraquinon-2-yl) ethyl N-cyclohexylcarbamate, 1- (Anthraquinon-2-yl) ethyl N, N-dicyclohexylcarbamate, 1,2-diisopropyl-3- [Bis (dimethylamino) methylene] guanidium 2- (3-benzoylphenyl) propionate, 9-Anthrylmethyl N, N-diethylcarbamate, 9-Anthrylmethyl Piperadine-1-carboxylate, 9- Anthrylmethyl N-cyclohexylcarbamate, 9-Anthrylmethyl N, N-dicyclohexylcarbamate, (2-nitrophenyl) methyl 4- (methacrylyloxy) piperidine-1-carboxylate, (2-nitrophenyl) methyl 4-hydroxypiperidine-1-carboxylate, Cyclohexylammonium 2- (3-nitrohexyl) -Benzoylphenyl) propionate, Dicyclohexyllammonium 2- (3-benzoylphenyl) propionate, Guanidium 2- (3-benzoylphenyl) propio ate, cyclohexylcarbamic acid 1,2-bis (4-methoxyphenyl) -2-oxoethyl, cyclohexylcarbamic acid 2-nitrobenzyl, 2- (9-oxoxanthen-2-yl) propionic acid 1,5,7-tria Xabicyclo [4.4.0] dec-5-ene, 2- (9-oxoxanthen-2-yl) propionic acid 1,5-diazabicyclo [4.3.0] non-5-ene 9-anthryl Methyl N, N-diethylcarbamate, (E) -1- [3- (2-hydroxyphenyl) -2-propenoyl] piperidine, 1- (anthraquinone-2-yl) ethylimidazole carboxylate, 2-nitrophenylmethyl 4 -Methacryloyloxypiperidine-1-carboxylate, 1- (anthraquinone-2-yl) -ethyl N, -Dicyclohexylcarbamate, dicyclohexylammonium 2- (3-benzoylphenyl) propionate, cyclohexylammonium 2- (3-benzoylphenyl) propionate, 9-anthrylmethyl N, N-dicyclohexylcarbamate, 1,2-diisopropyl-3- [bis (Dimethylamino) methylene] guanidinium 2- (3-benzoylphenyl) propionate, 1,6-hexamethylene-bis (4,5-dimethoxy-2-nitrobenzyl carbamate), and the like.

The photobase generator preferably has a long wavelength upper limit of 300 nm or more in the ultraviolet absorption wavelength range.
Since the conventional gas generating agent has an absorption band of light on the short wavelength side, it is necessary to irradiate high-energy light for a long time to generate gas, and as a result, the light source is loaded. And there is a problem that the wafer may be damaged. However, since the photobase generator used in the present invention has an absorption band on the higher wavelength side than the conventional gas generator, the load on the light source can be reduced and the damage to the wafer can be suppressed. In particular, when the upper limit on the long wavelength side of the ultraviolet absorption wavelength range has an absorption band at a wavelength of 300 nm or more, that is, 300 nm or more, excellent light source load reduction performance and wafer damage suppression performance can be exhibited. The upper limit on the long wavelength side of the ultraviolet absorption wavelength range is more preferably 320 nm or more. The upper limit of the absorption wavelength range of the photobase generator is not particularly limited, but is substantially about 450 nm.

The content of the photobase generator is not particularly limited, but a preferable lower limit is 5 parts by weight and a preferable upper limit is 50 parts by weight with respect to 100 parts by weight of the pressure-sensitive adhesive. When the content of the photobase generator is in this range, the photobase generator can be sufficiently dissolved in the pressure-sensitive adhesive, and at the same time, a sufficient amount of gas for peeling off the pressure-sensitive adhesive composition for semiconductor devices Can be generated. The more preferable lower limit of the content of the photobase generator is 10 parts by weight, and the more preferable upper limit is 30 parts by weight.

The pressure-sensitive adhesive composition for a semiconductor device of the present invention may further contain a photosensitizer.
The photosensitizer has an effect of amplifying the stimulus of the photobase generator with light, and therefore, the gas can be released by irradiation with less light. In addition, gas can be released by light in a wider wavelength range.

The photosensitizer is not particularly limited as long as it is excellent in heat resistance.
As a photosensitizer excellent in heat resistance, the polycyclic aromatic compound which has an alkoxy group at least one or more is mentioned, for example. Among them, a substituted alkoxy polycyclic aromatic compound having an alkoxy group partially substituted with a glycidyl group or a hydroxyl group is preferable. These photosensitizers are highly resistant to sublimation and can be used under high temperatures. In addition, when a part of the alkoxy group is substituted with a glycidyl group or a hydroxyl group, the solubility in the adhesive component is enhanced, and bleed-out can be prevented.

The above-mentioned polycyclic aromatic compound is preferably an anthracene derivative. The alkoxy group preferably has 1 to 18 carbon atoms, and more preferably 1 to 8 carbon atoms.

Examples of polycyclic aromatic compounds having at least one or more of the above alkoxy groups include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 2-t-butyl-9,10-dimethoxyanthracene, 3-dimethyl-9,10-dimethoxyanthracene, 9-methoxy-10-methylanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-t-butyl-9,10-di Ethoxyanthracene, 2,3-dimethyl-9,10-diethoxyanthracene, 9-ethoxy-10-methylanthracene, 9,10-dipropoxyanthracene, 2-ethyl-9,10-dipropoxyanthracene, 2-t-butyl -9,10-dipropoxyanthracene, 2,3-dimethyl-9, 0-dipropoxyanthracene, 9-isopropoxy-10-methylanthracene, 9,10-dibutoxyanthracene, 9,10-dibenzyloxyanthracene, 2-ethyl-9,10-dibenzyloxyanthracene, 2-t-butyl -9,10-dibenzyloxyanthracene, 2,3-dimethyl-9,10-dibenzyloxyanthracene, 9-benzyloxy-10-methylanthracene, 9,10-di-α-methylbenzyloxyanthracene, 2- Ethyl-9,10-di-α-methylbenzyloxyanthracene, 2-t-butyl-9,10-di-α-methylbenzyloxyanthracene, 2,3-dimethyl-9,10-di-α-methylbenzyloxy Anthracene, 9- (α-methylbenzyloxy) -10-methylanthrase , 9,10-di (2-hydroxyethoxy) anthracene, and the like anthracene derivative such as 2-ethyl-9,10-di (2-carboxyethoxy) anthracene.

As a substituted alkoxy polycyclic aromatic compound which has the alkoxy group by which the said one part was substituted by the glycidyl group or the hydroxyl group, 9,10- di (glycidyloxy) anthracene, 2-ethyl- 9,10- di (glycidyl) is mentioned, for example. Oxy) anthracene, 2-t-butyl-9,10-di (glycidyloxy) anthracene, 2,3-dimethyl-9,10-di (glycidyloxy) anthracene, 9- (glycidyloxy) -10-methylanthracene, 9 10-di (2-vinyloxyethoxy) anthracene, 2-ethyl-9,10-di (2-vinyloxyethoxy) anthracene, 2-t-butyl-9,10-di (2-vinyloxyethoxy) anthracene, 2,3-Dimethyl-9,10-di (2-vinyloxyethoxy) anthracene, 9- (2-vinyl) Oxyethoxy) -10-methylanthracene, 9,10-di (3-methyl-3-oxetanylmethoxy) anthracene, 2-ethyl-9,10-di (3-methyl-3-oxetanylmemethoxy) anthracene, 2- t-Butyl-9,10-di (3-methyl-3-oxetanylmemethoxy) anthracene, 2,3-dimethyl-9,10-di (3-methyl-3-oxetanylmemethoxy) anthracene, 9- (3-methyl-3-oxetanylmemethoxy) anthracene Methyl-3-oxetanylmemethoxy) -10-methylanthracene, 9,10-di (p-epoxyphenylmethoxy) anthracene, 2-ethyl-9,10-di (p-epoxyphenylmethoxy) anthracene, 2-t-butyl -9,10-di (p-epoxyphenylmethoxy) anthracene, 2,3-dimethyl-9,10-di ( -Epoxyphenylmethoxy) anthracene, 9- (p-epoxyphenylmethoxy) -10-methylanthracene, 9,10-di (p-vinylphenylmethoxy) anthracene, 2-ethyl-9,10-di (p-vinylphenyl) Methoxy) anthracene, 2-t-butyl-9,1-di (p-vinylphenylmethoxy) anthracene, 2,3-dimethyl-9,10-di (p-vinylphenylmethoxy) anthracene, 9- (p-vinylphenyl) Methoxy) -10-methylanthracene, 9,10-di (2-hydroxyethoxy) anthracene, 9,10-di (2-hydroxypropoxy) anthracene, 9,10-di (2-hydroxybutoxy) anthracene, 9,10 -Di (2-hydroxy-3-butoxypropoxy) anthracene, 9, 1 0-di (2-hydroxy-3- (2-ethylhexyloxy) propoxy) anthracene, 9,10-di (2-hydroxy-3-allyloxypropoxy) anthracene, 9,10-di (2-hydroxy-3-) And phenoxypropoxy) anthracene, 9,10-di (2,3-dihydroxypropoxy) anthracene and the like.

The pressure-sensitive adhesive composition for a semiconductor device of the present invention may contain a silicone compound having a functional group crosslinkable with the above-mentioned pressure-sensitive adhesive. Since the silicone compound is excellent in heat resistance, it prevents burn-in and the like of the pressure-sensitive adhesive even after the treatment accompanied by heating at 200 ° C. or more, and bleeds out to the interface of the adherend at the time of peeling to facilitate peeling. The silicone compound adheres to the adherend because the silicone compound has a functional group crosslinkable with the pressure-sensitive adhesive, and is chemically reacted with the pressure-sensitive adhesive by light irradiation or heating and taken into the pressure-sensitive adhesive. Do not contaminate. In addition, by blending the silicone compound, the effect of preventing the adhesive residue on the wafer is also exhibited.

The pressure-sensitive adhesive composition for a semiconductor device according to the present invention has various multifunctionality which is optionally mixed with a general pressure-sensitive adhesive such as an isocyanate compound, a melamine compound or an epoxy compound for the purpose of adjusting the cohesion as a pressure-sensitive adhesive. You may contain a compound suitably.
The pressure-sensitive adhesive composition for a semiconductor device of the present invention may contain a known additive such as an inorganic filler such as fumed silica, a plasticizer, a resin, a surfactant, a wax, and a fine particle filler.

The method for producing the pressure-sensitive adhesive composition for a semiconductor device of the present invention is not particularly limited, and examples thereof include a method in which predetermined amounts of the pressure-sensitive adhesive, the photobase generator and other components are mixed and mixed as needed. .

The pressure-sensitive adhesive composition for a semiconductor device of the present invention can be used in various forms, for example, in the form of a pressure-sensitive adhesive tape such as a single-sided pressure-sensitive adhesive tape, a double-sided pressure-sensitive adhesive tape, or a nonsupport tape (self supporting tape). The adhesive tape for semiconductor devices which has an adhesive layer which consists of an adhesive composition for semiconductor devices of this invention is also one of this invention.

The thickness of the pressure-sensitive adhesive layer is not particularly limited, but a preferable lower limit is 5 μm and a preferable upper limit is 300 μm. When the thickness of the pressure-sensitive adhesive layer is in this range, it can be attached to the wafer with sufficient adhesive force, and the semiconductor chip during processing can be protected. The more preferable lower limit of the thickness of the pressure-sensitive adhesive layer is 10 μm, and the more preferable upper limit is 100 μm.

The pressure-sensitive adhesive tape for a semiconductor device of the present invention may be a support type having a substrate or may be a non-support type having no substrate. When the pressure-sensitive adhesive tape for a semiconductor device of the present invention has a substrate, the substrate is not particularly limited, but is preferably a substrate having heat resistance. As such a heat-resistant substrate, for example, polyethylene terephthalate, polyethylene naphthalate, polyacetal, polyamide, polycarbonate, polyphenylene ether, polybutylene terephthalate, ultrahigh molecular weight polyethylene, syndiotactic polystyrene, polyarylate, polysulfone, polyether Examples thereof include sulfone, polyphenylene sulfide, polyetheretherketone, polyimide, polyetherimide, fluorocarbon resin, liquid crystal polymer and the like. Among them, special polyesters including polyethylene naphthalate, polyamides, polyimides, polyetheretherketones, and polyether sulfones are preferable because they are excellent in heat resistance.

The shape of the substrate is not particularly limited, and examples thereof include a sheet, a sheet having a mesh structure, and a sheet having holes.

The thickness of the substrate is not particularly limited, but the preferred lower limit is 5 μm and the preferred upper limit is 100 μm. When the thickness of the above-mentioned base material is within this range, it is possible to obtain a pressure-sensitive adhesive sheet excellent in handleability because it has appropriate stiffness. The more preferable lower limit of the thickness of the substrate is 10 μm, and the more preferable upper limit is 50 μm.

The method for producing the pressure-sensitive adhesive tape for a semiconductor device of the present invention is not particularly limited. For example, in the case of a support type having a substrate, a curable resin, a polymerization initiator, a crosslinking agent, and other components as needed. It can be manufactured by a method of dissolving and mixing using a solvent, coating and drying and then laminating on a substrate layer, and a method of directly coating and drying on a substrate layer. In the case of the non-support type having no substrate, for example, a solution of the above-mentioned pressure-sensitive adhesive is applied on a film subjected to a release treatment, dried to form a pressure-sensitive adhesive layer, and a release treatment is applied thereon It can manufacture by the method of laminating | stacking the applied film.

According to the present invention, the semiconductor does not peel off during processing even when it is used in the semiconductor chip processing step of heat treatment, and the semiconductor can be easily peeled off the adhesive tape after the processing is completed. The adhesive composition for devices and the adhesive tape for semiconductor devices can be provided.

EXAMPLES The embodiments of the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

Example 1
A reactor equipped with a thermometer, a stirrer, and a cooling tube is prepared. In this reactor, 94 parts by weight of 2-ethylhexyl acrylate as alkyl (meth) acrylate and 6 parts by weight of hydroxyethyl methacrylate as a functional group-containing monomer After adding 0.01 parts by weight of lauryl mercaptan and 80 parts by weight of ethyl acetate, the reactor was heated to start refluxing. Subsequently, 0.01 parts by weight of 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane as a polymerization initiator is added to the above reactor, and polymerization is initiated under reflux. The Next, 0.01 parts by weight of 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane is added one hour and two hours after the initiation of polymerization, and the polymerization is further initiated. After 4 hours, 0.05 parts by weight of t-hexylperoxypivalate was added to continue the polymerization reaction. Then, 8 hours after initiation of polymerization, an ethyl acetate solution of a functional group-containing (meth) acrylic polymer having a solid content of 55% by weight and a weight average molecular weight of 600,000 was obtained.
To 100 parts by weight of resin solid content of the ethyl acetate solution of the obtained functional group-containing (meth) acrylic polymer, 3.5 parts by weight of 2-isocyanatoethyl methacrylate as a functional group-containing unsaturated compound is added and reacted Thus, an ethyl acetate solution of the polymerizable polymer was obtained. Thereafter, 20 parts by weight of silicone acrylate (EBECRYL 350, manufactured by Daicel Ornex Co., Ltd.) with respect to 100 parts by weight of resin solid content of an ethyl acetate solution of the obtained polymerizable polymer, silica filler (Leorosil MT-10, manufactured by Tokuyama) 20 parts by weight, 0.5 parts by weight of a chemical crosslinking agent (Coronato L-45, manufactured by Sekisui Fuller), and 1 part by weight of a photopolymerization initiator (Esacure One, manufactured by Nippon Shiber-Hegner) were mixed.

Thereafter, a photobase generator (imidazole-1-carboxylic acid 1- (anthraquinone-2-yl) ethyl, absorption wavelength 430 nm) as a gas generator with respect to 100 parts by weight of resin solid content of an ethyl acetate solution of a polymerizable polymer An ethyl acetate solution of a pressure-sensitive adhesive composition for a semiconductor device was obtained by mixing 30 parts by weight and 1 part by weight of 9,10-di (2-hydroxyethoxy) anthracene as a photosensitizer.

The thickness of the pressure-sensitive adhesive layer after drying was obtained on a corona-treated surface of a 50 μm-thick transparent polyethylene telethalate film on one side of which an ethyl acetate solution of the obtained adhesive composition for semiconductor devices was subjected to corona treatment on one side. It coated with a doctor knife so that it might be set to 30 micrometers. Then, after heating at 110 ° C. for 5 minutes to dry the coating solution, a 50 μm-thick transparent polyethylene telethalate film having a release treatment is attached to the opposite side, and standing curing at 40 ° C. for 3 days To obtain an adhesive tape for semiconductor devices.

(Examples 2 to 6, Comparative Examples 1 to 3)
A pressure-sensitive adhesive tape for a semiconductor device was produced in the same manner as in Example 1 except that the type and the blending amount of the photobase generator were as shown in Table 1.

<Evaluation>
The following evaluation was performed about the adhesive tape for semiconductor devices (Hereinafter, it is also only called an adhesive tape.) Obtained by the Example and the comparative example. The results are shown in Table 2.

(Evaluation of tackiness)
The adhesive tape for semiconductor devices cut into a circle with a diameter of 20 cm was attached to a silicon wafer with a diameter of 20 cm and a thickness of about 750 μm to obtain a laminate. In this state, the end of the pressure-sensitive adhesive tape was turned over, and the case where it could not be peeled at all was evaluated as "○", the case where it could be peeled relatively lightly as "△", and the case where it could be peeled almost without resistance as "×" .

(Gas generation evaluation)
Using an extra-high pressure mercury lamp, the adhesive tape side of the laminate was irradiated with ultraviolet light of 365 nm for 5 minutes while adjusting the illuminance so that the irradiation intensity on the substrate surface of the adhesive tape was 40 mW / cm ² . The laminate after UV irradiation was visually observed, and the silicon wafer was peeled off from the adhesive tape in the area of 70% or more when the silicon wafer was peeled off from the adhesive tape in the area of 90% or more of the adhesion interface. When the silicon wafer was peeled from the pressure-sensitive adhesive tape with an area of less than 70%, the case of peeling was evaluated as "X", and the gas generation property was evaluated.

(Evaluation of peelability)
When the pressure-sensitive adhesive tape was peeled off with a force of 0.1 N per 25 mm width from the laminate after gas generation evaluation, it was peeled off naturally as "「 ", and it was peeled off without any resistance" ○ " The peelability was evaluated on the basis of the case where the resistance was peelable but the peelability was evaluated as “Δ”, and the case where the peelable could not be performed at all was evaluated as “x”.

(Heat resistance evaluation)
The adhesive tape for semiconductor devices cut into a circle with a diameter of 20 cm was attached to a silicon wafer with a diameter of 20 cm and a thickness of about 750 μm to obtain a laminate. Then, using a super-high pressure mercury lamp equipped with a filter for cutting a wavelength of 350 nm or less, irradiation of ultraviolet light having a wavelength of 365 nm on the substrate surface of the adhesive tape for a semiconductor device from the adhesive tape side of the laminate for a semiconductor device The intensity was adjusted to 40 mW / cm ² and irradiation was performed for 2 minutes. After ultraviolet irradiation, the laminate was subjected to heat treatment at 180 ° C. for 1 hour, and returned to room temperature. The above-described gas generation evaluation and removability evaluation were performed on the heat-treated laminate. In Comparative Example 3, since the gas was generated during the heat treatment and the adhesive tape for a semiconductor device was peeled off, the evaluation was not performed.

According to the present invention, the semiconductor does not peel off during processing even when it is used in the semiconductor chip processing step of heat treatment, and the semiconductor can be easily peeled off the adhesive tape after the processing is completed. The adhesive composition for devices and the adhesive tape for semiconductor devices can be provided.

Claims (3)

What is claimed is: 1. A pressure-sensitive adhesive composition for a semiconductor device comprising a pressure-sensitive adhesive and a photobase generator represented by the following general formulas (1) and (2).

In the formula (1), R ¹ , R ² and R ³ are each independently hydrogen, halogen, hydroxyl, mercapto, sulfide, silyl, silanol, cyano, nitro, nitroso, sulfino, sulfo Group, sulfonato group, phosphino group, phosphinyl group, phosphono group, phosphonato group, amino group, alkoxy group, amide group, alkyl group having 1 to 12 carbon atoms, cycloalkyl group having 5 to 10 carbon atoms, 6 to 14 carbon atoms And an arylalkyl group having 7 to 15 carbon atoms, a saturated aliphatic ring, an unsaturated aliphatic ring, an aromatic ring or an organic group, which may be the same or different. In the case of a cyclic structure, it may contain a heteroatom. Two or more of R ¹ and R ² may be combined to form a cyclic structure, and the cyclic structure is any ring structure such as a saturated aliphatic ring, unsaturated aliphatic ring, aromatic ring, etc. It may be or may contain a hetero atom.

In the formula (2), R ⁴ is hydrogen, halogen, hydroxyl group, mercapto group, sulfide group, silyl group, silyl group, silanol group, cyano group, nitro group, nitroso group, sulfino group, sulfo group, sulfonato group, phosphino group, phosphinyl group , Phosphono group, phosphonato group, amino group, alkoxy group, amide group, alkyl group having 1 to 12 carbon atoms, cycloalkyl group having 5 to 10 carbon atoms, aryl group having 6 to 14 carbon atoms, 7 to 15 carbon atoms It represents an arylalkyl group, a saturated aliphatic ring, an unsaturated aliphatic ring, an aromatic ring or an organic group. When R ⁴ is a cyclic structure, it may contain a hetero atom. B is a basic compound. 2. The pressure-sensitive adhesive composition for a semiconductor device according to claim 1, wherein the photobase generator has an upper limit of 300 nm or more on the long wavelength side of the ultraviolet absorption wavelength range. A pressure-sensitive adhesive tape for a semiconductor device comprising a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition for a semiconductor device according to claim 1 or 2.