JP6876499B2 - Adhesive composition for semiconductor devices and adhesive tape for semiconductor devices - Google Patents

Description

The present invention is for a semiconductor device in which the wafer does not peel off during the treatment even when used in the semiconductor chip processing step of performing the heat treatment, and the wafer can be easily peeled off from the adhesive tape after the treatment is completed. The present invention relates to an adhesive composition and an adhesive tape for a semiconductor device.

In the semiconductor chip manufacturing process, adhesive tape is used to facilitate handling of wafers and semiconductor chips during processing 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 obtain a thin film wafer, grinding is performed after attaching an adhesive tape to the thick film wafer.

The adhesive composition used for such an adhesive tape has high adhesiveness enough to firmly fix the wafer or semiconductor chip during the processing process, and can be peeled off without damaging the wafer or semiconductor chip after the process is completed. Required (hereinafter, also referred to as "high adhesion easy peeling").
As an adhesive composition that achieves high adhesiveness and easy peeling, Patent Document 1 describes a method for processing a wafer using a double-sided adhesive tape having an adhesive layer containing a gas generator that generates a gas by stimulation with an azo compound or the like. Has been done. In the wafer processing method described in Patent Document 1, first, the wafer is fixed to the support plate via double-sided adhesive tape. When a stimulus is applied after performing a grinding process or the like in this 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 of the gas is peeled off by the pressure. If the double-sided adhesive tape of Patent Document 1 is used, the wafer can be peeled off without being damaged and without adhesive residue.

On the other hand, as the performance of semiconductor chips has improved, a process of applying a chemical solution treatment, a heat treatment, or a treatment accompanied by heat generation to the surface of the wafer has come to be performed. For example, as a next-generation technology, three-dimensional stacking technology using TSV (Through Silicon Via), which is made by stacking a plurality of semiconductor chips to dramatically improve the performance and size of the device, is attracting attention. .. In addition to being able to increase the density of semiconductor mounting, TSV can reduce noise and resistance by shortening the connection distance, has dramatically faster access speed, and is excellent in releasing heat generated during use. .. In the production of such TSVs, it is necessary to perform a high temperature treatment process of 200 ° C. or higher, such as bumping a thin film wafer obtained by grinding, forming bumps on the back surface, and performing reflow during three-dimensional lamination. It becomes. However, if such a high-temperature treatment process is performed with the 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, resulting in an unintended gas. There was a problem that peeling occurred due to the occurrence of.

Japanese Unexamined Patent Publication No. 2003-231872

In view of the above situation, the present invention does not cause the wafer to peel off during the processing even when used in the semiconductor chip processing step of performing the heat treatment, and the wafer can be easily removed from the adhesive tape after the processing is completed. An object of the present invention is to provide an adhesive composition for a semiconductor device that can be peeled off and an adhesive tape for a semiconductor device.

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

In formula (1), R ¹ , R ² and R ³ are independently hydrogen, halogen, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, cyano group, nitro group, nitroso group, sulfino group and 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. Represents an aryl group of, an arylalkyl group having 7 to 15 carbon atoms, a saturated aliphatic ring, an unsaturated aliphatic ring, an aromatic ring or an organic group, and may be the same or different. In the case of a cyclic structure, a hetero atom may be contained. Two or more of R ¹ and R ² may be bonded to form a cyclic structure, and the cyclic structure is any ring structure such as a saturated aliphatic ring, an unsaturated aliphatic ring, and an aromatic ring. It may be present or may contain a heteroatom.

In the formula (2), R ⁴ is hydrogen, halogen, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a cyano group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group , Phosphono group, phosphonat 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. Represents an arylalkyl group, a saturated aliphatic ring, an unsaturated aliphatic ring, an aromatic ring or an organic group. When R ⁴ has a cyclic structure, it may contain a hetero atom. Further, B is a basic compound.
The present invention will be described in detail below.

As a result of diligent studies, the present inventor has found that the photoacid generator and the photobase generator have high heat resistance that does not decompose even by heat during heat treatment. However, it was found that the photoacid generator produces metal ions as a by-product during photodecomposition, which becomes a residue and contaminates the wafer. 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 studies based on these findings, the present inventor used a photobase generator having a specific structure during the treatment even when it was used in the semiconductor chip processing step of performing the heat treatment. It has been found that the wafer does not peel off and the wafer can be easily peeled off from the adhesive tape after the processing is completed, and the present invention has been completed.

The pressure-sensitive adhesive composition for semiconductor devices of the present invention contains a pressure-sensitive adhesive.
The above-mentioned adhesive is not particularly limited and may be a curable type or a non-curable type. However, by curing the adhesive before the heat treatment or the treatment accompanied by heat generation, the adhesion promotion due to heat is suppressed, and the wafer after the treatment is completed. A curable pressure-sensitive adhesive is preferable because it can be easily peeled off without adhesive residue.

Examples of the curable pressure-sensitive adhesive include a photo-curable pressure-sensitive adhesive that is cross-linked and cured by light irradiation, and a thermosetting pressure-sensitive adhesive that is cross-linked and cured by heating.
Examples of the photocurable pressure-sensitive adhesive include a photo-curable pressure-sensitive adhesive containing a polymerizable polymer as a main component and a photopolymerization initiator as a polymerization initiator.
Examples of the thermosetting pressure-sensitive adhesive include a thermosetting pressure-sensitive adhesive containing a polymerizable polymer as a main component and a heat-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 reacted with the functional group in the molecule. It can be obtained by reacting a functional group to be subjected to a compound having a radically polymerizable unsaturated bond (hereinafter, referred to as a functional group-containing unsaturated compound).

The functional group-containing (meth) acrylic polymer is a polymer having adhesiveness at room temperature. The functional group-containing (meth) acrylic polymer mainly contains an acrylic acid alkyl ester and / or a methacrylate alkyl ester in which the number of carbon atoms of the alkyl group is usually in the range of 2 to 18, and the functional group-containing monomer and the functional group-containing monomer are used. Further, if necessary, it can be obtained by copolymerizing with another copolymerizable monomer for modification by a conventional method. 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 a carboxyl group-containing monomer such as acrylate and methacrylic acid, a hydroxyl group-containing monomer such as hydroxyethyl acrylate and hydroxyethyl methacrylate, and an epoxy such as glycidyl acrylate and glycidyl methacrylate. Examples thereof include a group-containing monomer, an isocyanate group-containing monomer such as isocyanate ethyl acrylate and isocyanate ethyl methacrylate, and an amino group-containing monomer such as aminoethyl acrylate and aminoethyl methacrylate.

Examples of the other copolymerizable monomer for modification include various monomers used in 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 one as the above-mentioned functional group-containing monomer is used depending on the functional group of the functional group-containing (meth) acrylic polymer. 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 that are activated by irradiating light having a wavelength of 250 to 800 nm, and examples of such a photopolymerization initiator include acetophenone derivative compounds such as methoxyacetophenone. , 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, and bis (η5-cyclopentadienyl) titanosen derivative compounds. Examples thereof include photoradical polymerization initiators such as benzophenone, Michler ketone, chlorothioxanthone, todecylthioxanthone, dimethylthioxanthone, diethylthioxanthone, α-hydroxycyclohexylphenylketone, and 2-hydroxymethylphenylpropane. These photopolymerization initiators may be used alone or in combination of two or more.

Examples of the above-mentioned thermal polymerization initiator include those that generate active radicals that are decomposed by heat to initiate polymerization curing. For example, dicumyl peroxide, di-t-butyl peroxide, and t-butyl peroxybenzoale. , T-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentan 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. Examples of such a thermal polymerization initiator having a high thermal decomposition temperature include cumene hydroperoxide, paramentan hydroperoxide, and di-t-butyl peroxide.
Of these thermal polymerization initiators, those commercially available are not particularly limited, but for example, perbutyl D, perbutyl H, perbutyl P, perpenta H (all of which are manufactured by NOF CORPORATION) and the like are suitable. These thermal polymerization initiators may be used alone or in combination of two or more.

The curable pressure-sensitive adhesive preferably contains a radically polymerizable polyfunctional oligomer or monomer. By containing a radically polymerizable polyfunctional oligomer or monomer, photocurability and thermosetting are improved.
The polyfunctional oligomer or monomer preferably has a molecular weight of 10,000 or less, and more preferably has a molecular weight of 5000 so that the curable pressure-sensitive adhesive layer can be efficiently reticulated by heating or irradiation with light. The number of radically polymerizable unsaturated bonds in the molecule is 2 to 20 below.

The polyfunctional oligomer or monomer is, for example, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate or the same methacrylate as above. Kind 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 above. Kind 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).
Since the adhesive tape of the present invention contains a photobase generator represented by the following general formulas (1) and (2), it stimulates the adhesive tape from the wafer when it is peeled off from the photobase generator. By generating carbon dioxide, the adhesive tape can be easily peeled off without leaving adhesive residue. Further, the photobase generator represented by the following general formulas (1) and (2) has high heat resistance that is not decomposed by heat during high temperature treatment or treatment accompanied by heat generation, and is therefore unintended during heat treatment. It is possible to prevent the release of gas. Here, the photobase generator means a compound that is decomposed by irradiation with ultraviolet rays to generate an organic base such as amine and carbon dioxide. Further, the photobase generator may be either an ionic type or a non-ionic type.
Although the photoacid generator also has high heat resistance, it is not suitable for use as an adhesive tape for protecting the device material because metal ions are generated when gas is generated and become a residue to contaminate the wafer.

In formula (1), R ¹ , R ² and R ³ are independently hydrogen, halogen, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, cyano group, nitro group, nitroso group, sulfino group and 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. Represents an aryl group of, an arylalkyl group having 7 to 15 carbon atoms, a saturated aliphatic ring, an unsaturated aliphatic ring, an aromatic ring or an organic group, and may be the same or different. In the case of a cyclic structure, a hetero atom may be contained. Two or more of R ¹ and R ² may be bonded to form a cyclic structure, and the cyclic structure is any ring structure such as a saturated aliphatic ring, an unsaturated aliphatic ring, and an aromatic ring. It may be present or may contain a heteroatom.

In the formula (2), R ⁴ is hydrogen, halogen, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a cyano group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group , Phosphono group, phosphonat 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. Represents an arylalkyl group, a saturated aliphatic ring, an unsaturated aliphatic ring, an aromatic ring or an organic group. When R ⁴ has a cyclic structure, it may contain a hetero atom. Further, B is a basic compound.

The basic compound is not particularly limited. Examples of the basic compound include amines, compounds containing a pyridyl group, hydrazine compounds, amide compounds, quaternary ammonium hydroxide salts, mercapto compounds, sulfide compounds and phosphine compounds.

The amine is not particularly limited, and any of a primary amine, a secondary amine and a tertiary amine can be used.
Examples of the primary amine include methylamine, ethylamine, n-propylamine, n-butylamine, amylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine and n-un. 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-aminoheptane , 1-Methylheptylamine, 2-ethylhexylamine, 1,5-dimethylhexylamine, tert-octylamine, ethirediamine, 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-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-cyclopentanemethylamine, cyclohexylamine, 2-methylhexylamine, 4-methylcyclohexylamine, 4,4'-methylenebis (cyclohexylamine), 2,3-dimethyl Cyclohexylamine, 4,4'-methylenebis (2-methylcyclohexylamine), 1,2-diaminocyclohexane, cyclohexanemethylamine, 1,8-diamino-p-menthane, 5-amino-1,3,3-trimethylcyclohexane Methylamine, cycloheptylamine, cyclooctylamine, cyclododecylamine, 2-aminonorbornene, bornylamine, miltanylamine, 1-adamantanamine, 1-adamantanmethylamine, allylamine, oleylamine, zelanylamine, 2,2,2-tri Fluoromethylamine, 2-Metoki Siethylamine, 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 dimethylacetal, 4-aminobutylaldehyde diethylacetal, 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-1,2-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-ethylaniline, 3-ethylaniline, 4-ethylaniline, 2-propylaniline, 3 -Propylaniline, 4-propylaniline, 2-isopropylaniline, 3-isopropylaniline, 4-isopropylaniline, 2-butylaniline, 3-butylaniline, 4-Butylaniline, 2-sec-butylaniline, 3-sec-butylaniline, 4-sec-butylaniline, 2-tert-butylaniline, 3-tert-butylaniline, 4-tert-butylaniline, 4-pentyl Aniline, 4-hexyl aniline, 4-heptyl aniline, 4-octyl aniline, 4-decyl aniline, 4-dodecyl aniline, 4-tetradecyl aniline, 4-hexadecyl aniline, 4-cyclohexyl aniline, 2, 2 '-Ethylene aniline, ortho-aniline, meta-aniline, para-aniline, orthophenetidine, metaphenetidine, paraphenetidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-Aminothiophenol, 2-aminobenzyl alcohol, 2-aminophenylethyl alcohol, 3-aminophenylethyl alcohol, 4-aminophenylethyl alcohol, 3- (1-hydroxyethyl) aniline, 2- (methyl mercapto) aniline , 3- (Methyl mercapto) aniline, 4- (Methyl mercapto) aniline, 2-aminophenyl disulfide, 2-isopropenyl aniline, 4,4'-ethylene dianiline, 3,3'-methylene dianiline, 4, 4 '-Methylene dianiline, 4,4'-methylenebis (3-chloro-2,6-diethylaniline), 4,4'-diaminostilben, 4-butoxyaniline, 4-pentyloxyaniline, 4-hexyloxyaniline, 4,4'-oxydianiline, 4,4'-thiodianiline, 4'', 4''''-(hexafluoroisopropyrine) -bis- (4-phenylaniline), oxydianiline, 4-aminophenyl Sulfur, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2,6-dimethylaniline, 3,4-dimethylaniline, 3,5-dimethylaniline, 6-ethylorthotoluidine, 2,6-diethylaniline, 2-isopropyl-6-methylaniline, 2,6-diisopropylaniline, 1-amino-5,6,7,8-tetrahydronaphthalene, 5-aminoindan, 2-fluoroaniline, 3- Fluoroaniline, 4-fluoroaniline, 2-chloroaniline, 3-chloroaniline, 4-chloroaniline, 2-bromoaniline, 3-bromoaniline, 4-bu Lomoaniline, 2-iodaniline, 3-iodaniline, 4-iodaniline, 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-orthoaniline, 3-amino-2-methylbenzyl alcohol, 2-amino-3-methylbenzyl alcohol, 2-aminomethacresol, 2,3-diaminophenol, orthotoluidine, 4,4'-ethylenedi. Metatoluidine, 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 -Fluoroaniline, 4-bromo-2-fluoroaniline, 2-bromo-4-iodoaniline, 2-chloro-4-aminotoluidine, 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- (trifluoromethyl) aniline, 2-bromo-5- (trifluoromethyl) aniline, 2-chloro-5- (trifluoromethyl) aniline, 5,5'-(hexafluoroisopropyridene) di Orthotoluidine, 4-methoxy-2-methylaniline, 2-methoxy-5-methylaniline, 5-methoxy-2-methylaniline, 5-tert-butyl orthoanisidine, 2-methoxy-5- (trifluoromethyl) Aniline, 6-chloromethanisidine, 4-aminoveratrol, 3,4- (methylenedioxy) aniline, 1,4-benzodioxane-6-amine, 4'-aminobenzo-15-crown-5,2, 4-Dimethoxyaniline, 4-aminocresol, 2,5-dimethoxyaniline, 5-amino-2-methoxyphenol, 3-aminoortocresol, 2-aminoortocresol, 2-amino-tert-butylphenol, 2-amino- tert-amylphenol, 6-aminomethacresol, 4-aminomethacresol, 2-amino-5-methylbenzyl alcohol, 3-amino-4-methylbenzyl alcohol, 2-amino-4-chlorophenol, 4-amino- 3-Chlorophenol, 2-amino-5-chlorobenzyl alcohol, 5-chloroorthoanisidine, 3-fluoroparaanisidine, 3-chloroparaanisidine, 2-amino-4- (trifluoromethyl) benzenethiol , 3,5-Dimethylaniline, 3,5-ditert-butylaniline, 3,5-bis (trifluoromethyl) aniline, 3,5-difluororoaniline, 3,5-dichloroaniline, 3,5-dimethoxy Aniline, 3-methoxy-5- (trifluoromethyl) aniline, 2,4,6-trimethylaniline, 4,4'-methylenebis (2,6-dimethylaniline), 4,4'-methylenebis (2,6-methylenebis) 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-fluoroaniline, 2,6-dichloro-4- (tri) Fluoromethyl) 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, 2,4,5-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'-diaminooctafluorobiphenyl, 4-methoxy-3-biphenylamine, 4-bromo-2,3 , 5,6-tetrafluoroaniline, 1,2-phenylenediamine, 2,3-diaminoto Ruene, 3,4-diaminotoluene, 3,3'-diaminobenzidine, 4-chloro-1,2-phenylenediamine, 4-methoxy-1,2-phenylenediamine, 4,5-dimethyl-1,2-phenylene Diamine, 1,2,4,5-benzenetetramine, 4,5-dichloro-1,2-phenylenediamine, 1,3-phenylenediamine, 2,6-diaminotoluene, 2,4-diaminotoluene, 2,4 , 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-phenylenediamine, 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-diphenylethylamine, 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-phenylpropylamine , 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-meth Toxiphenethylamine, 2-ethoxybenzylamine, 2- [2- (aminomethyl) phenylthio] benzyl alcohol, 2-aminobenzylamine, 3-methylbenzylamine, 3- (trifluoromethyl) benzylamine, metaxylene diamine, 3 -Fluorobenzylamine, 3-fluorophenethylamine, 3-chlorobenzylamine, 3-chlorophenethylamine, 3-bromobenzylamine, 3-iodobenzylamine, 3-methoxyphenethylamine, 4-methylbenzylamine, paraxylene diamine, 4- (Trifluoromethyl) benzylamine, α,4-dimethylbenzylamine, 2- (paratoluyl) ethylamine, 4-fluorobenzylamine, 4-fluorophenethylamine, 4-chlorobenzylamine, 4-bromobenzylamine, 4-bromophenethylamine , 4-Fluoro-α-methylbenzylamine, 4-fluorophenethylamine, 4-chlorophenethylamine, 4-methoxybenzylamine, 4-methoxyphenethylamine, 4- (trifluoromethoxy) benzylamine, 4-aminobenzylamine, 2- (4-Aminophenyl) ethylamine, TYRAMINE, 3,5-bis (trifluoromethyl) benzylamine, 3-fluoro-5- (trifluoromethyl) benzylamine, 2,6-difluorobenzylamine, 2,4-difluoro Benzylamine, 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, 3,4,5-trimethoxybenzylamine , 2,4,6-Trimethoxybenzylamine, 1-aminoindanol, 1-naphthalenemethylamine, 1- (1-naphthyl) ethylamine, 9-aminofluorene, 1-pyrenemethylamine, α, ω-diaminopolymine Examples thereof include glycol, α, ω-diaminopolypropylene glycol, α, ω-diaminopolydimethylsiloxane, polyallylamine and the like.

Examples of the secondary amine include dimethylamine, N-ethylmethylamine, diethylamine, N-methylpropylamine, N-methylisopropylamine, N-ethylisopropylamine, dipropylamine, diisopropylamine, and N-methylbutylamine. 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'-dimethylethylenediamine, 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-methylcyclohexylamine, N-ethylcyclohexylamine, N-isopropylcyclohexylamine, N-tert-butylcyclohexylamine, dicyclohexyl Amine, N, N'-bis (3,3-dimethylbutyl) -1,2-cyclohexanediamine, 1-cyclohexylethylamine, 1,3-cyclohexanebis (methylamine), N-methylallylamine, N-methyl-2 -Methylallylamine, diallylamine, N, N'-diethyl-2-butylene-1,4-diamine, N-allylcyclopentylamine, N-allylcycloamine, 2- (1-cyclohexene) ethylamine, 6- (dimethylamino) Fluben, bis (2-methoxyethyl) amine, methylaminoacetaldehyde dimethylacetal, diethylaminoacetaldehyde diethylacetal, 2-methylaminoethyl-1,3-dioxolane, diethanolamine, diisopropanolamine, N, N'-bis (2-hydroxy) Ethyl) ethylenediamine, 1,3-bis [tris (hydroxymethyl) methylamino] propane, N-methylglucamine, 2-methylaziridine, azetidine, pyrrolidine, 2,5-dimethyl Pyrrolidine, 3-pyrrolidinol, 2-pyrrolidin methanol, 3-pyrrolin, 2,5-dimethyl-3-pyrrolin, piperidine, 1,2,3,6-tetotahydropyridine, 2-methylpiperidine, 2-ethylpiperidine, 3 -Methylpiperidine, 4-methylpiperidine, 4,4'-bipiperidine, 4,4'-ethylenebipiperidine, 4,4'-trimethylonebipiperidine, 3,3-dimethylpiperidine, 2,6-dimethylpiperidine, 3 , 5-Dimethylpiperidine, 2,2,6,6-tetramethylpiperidine, 1,4-dioxa-8-azaspiridine [4.5] decane, 2-piperidine methanol, 2-piperidine ethanol, 3-hydroxypiperidine, 3 -Piperidine Methanol, 4-hydroxypiperidine, 2,2,6,6-trimethyl-4-piperidinol, 7,7,9,9-tetramethyl-1,4-dioxa-8-azaspiro [4.5] decane- 2-Methanol, hexamethyleneimine, heptamethyleneimine, piperidine, 2-methylpiperazine, 2,6-dimethylpiperazine, 2,5-dimethylpiperazine, homopiperidine, acetaldehyde ammonia trimer, 1,4,7-triaza Cyclononane, 1,5,9-triazacyclododecane, CYCLEN, 1,4,8,11-tetraazacyclotetradecane, 1,4,8,12-tetraazacyclopentadecane, HEXACYCREN, 1,3,3- Trimethyl-6-azabicyclo [3.2.1] octane, dodecahydroquinolin, spartein, 4,4-dimethyloxadridinidine, 4-ethyl-2-methyl-2- (3-methylbutyl) oxadridinine, morpholin, 2 , 6-Dimethylmorpholin, 1-aza-12-crown-4, 1-aza-15-crown-5, 1-aza-18-crown-6, 1,4,10-trioxa-7,13-diaza Cyclopentadecane, 1,4,10,13-tetraxa-7,16-diazacyclooctadecane, piperidine, thiomorpholin, N-methylaniline, N-ethylaniline, N-butylaniline, diphenylamine, N-phenylbenzylamine, 1,2-Dianilinoetan, N-allylaniline, 2-anilinoethanol, N-ethylorthotoluidine, N-ethylmethatruidine, N-ethylparatoluidine, 4-chloro-N-methylaniline, 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'-(hexafluoroisopropyridene) dianiline, 4,4'-(hexafluoroisopropyridene) 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-aminoflurene, 2-aminoflurene, 2,7-diaminoflurene, 3,7 −Diamino-2-methoxyfurene, 2-amino-7-bromofurene, 2-amino-9-hydroxyfurene, 2-amino-3-bulmo-9-hydroxyfurene, 1-aminoanthracene, 2-aminoanthracene , 9-Aminophenanthrene, 9,10-Diaminophenanthrene, 3-aminofluoransene, 1-aminopyrene, 6-aminocrysen, N, α-dimethylbenzylamine, N-benzyl-α-methylbenzyl Amine, N-benzylmethylamine, N-ethylbenzylmethylamine, N-isopropylbenzylmethylamine, N-butylbenzylmethylamine, N-tert-butylbenzylmethylamine, dibenzylamine, N, N'-dibenzylethylenediamine , 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, indolin, 2-methylindrin, 1,2,3,4-tetrahydrocarbazole, 2,3-dimethylindrin, Indolin-2-carboxylic acid, 1,2,3,4-tetrahydroquinoline, 1,2,3,4-tetrahydroisoquinoline, 6,7-dimethoxy-1,2,3,4-tetrahydroisoquinolin, iminodibenzyl , 5,6,11,12-tetrahydrodibenz [B, F] azocine, phenothiazine, phenothiazine and the like.

Examples of the tertiary amine 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 Diaminomethane, 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''-pentamethyldiethylenetriamine, 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, tetrakisdimethylaminoethylene, perfluoroisobutylamine, tris [2- (2-methoxyethoxy) ethyl] amine, tert-butoxybis (dimethylamino) methane, 2- (diethylamino) ) Ethanolvinyl ether, N, N'-dimethylformamide dimethylacetal, N, N'-dimethylformamide diethylacetal, N, N'-dimethylformamidedipropylacetal, N, N'-dimethylformamidediisopropyl 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, diethyl aminoacetoaldehyde 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, tri Isopropanolamine, 3- (dimethylamino) -1,2-propanediol, 3- (diethylamino) -1,2-propanediol, 3- (dipropylamino) -1,2-propanediol, 3- (diisopropylamino) ) -1,2-Propandiol, 2-{[2- (dimethylamino) ethyl] methylamino} ethanol, 1,3-bis (dimethylamino) -2-propanol, N, N, N', N'- Tetrax (2-hydroxypropyl) ethylenediamine, 2- [2- (dimethylamino) ethoxy] ethanol, PENTROLL, 1-aziridine ethanol, 1-methylpyrrolidin, 1-butylpyrrolidin, 1-pyrrolidino-1-cyclopentene, 1-pyrrolidino -1-Cyclohexene, 1- (2-hydroxyethyl) pyrrolidine, 3-pyrrolidino-1,2-propanediol, 1-methyl-3-pyrodinol, 1-ethyl-3-pyrodinol, 1-methyl-2-pyrrolidin methanol , 2-Methyl-1-pyrrolin, 1-methylpiperidin, 1-ethylpiperidin, dipiperidinomethane, 1-ethylpiperidin, 1,1'-methylenebis (3-methylpiperidin), 4,4'-trimethylene Bis (1-methylpiperidin), 1,2,2,6,6-pentamethylpiperidin , 1-Piperidin Acetaldehyde Diethylacetal, 1-Piperidine Ethanol, 3-Piperidino-1,2-Propanediol, 3-Hydroxy-1-methylpiperidine, 1-Ethyl-3-hydroxypiperidine, 1-Methyl-3-piperidinmethanol , 4,4'-Trimethylenebis (1-piperidinethanol), N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) -1,6-hexadiamine, 1,2, 3,6-Tetrahydropyridine, 1,4-dimethylpiperidine, 4- (dimethylamino) -1,2,2,6,6-pentamethylpiperazine, 1,4-bis (2-hydroxyethyl) piperidine, 1, 3,5-Tetramethylhexahydro-1,3,5-triazine, 1,3,5-tetraethylhexahydro-1,3,5-triazine, 1,4,7-trimethyl-1,4,7-triazin Zacyclononane, 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, TOPANE, QUINULIDINE, 3-QUINULIDINOL, 1,4-diazabicyclo [2.2.2] octane, Hexamethylenetetramine, 4-methylmorpholine, 4-ethylmorpholine, 4- (1-cyclopentene-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] Eikosan, 4 , 7,13,16,21-pentaoxa-1,10-diazabicyclo [8.8.5] tricosan, 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 Nzil-N-ethylaniline, 2- (N-ethylanilino) ethanol, N-phenyldiethanolamine, N- (ethoxyethyl) -N-methylaniline, N, N-dimethylortotoluidine, N, N-dimethylmetatoluidine, N , N-dimethylparatoluidine, N, N-diethyl orthotoluidine, N, N-diethylmetatoluidine, N, N-diethylparatoluidine, 3-dimethylaminophenol, 3-diethylaminophenol, 2- (N-ethylmetatoluidine) E) Ethanol, 4-tert-butyl-N, N-dimethylaniline, 4-bromo-N, N-dimethylaniline, 2,2'-(paratoluylimino) dimethanol, 4- (dimethylamino) phenethyl alcohol, N, N, N', N'-tetramethylbenzidine, N, 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-diglycidylaniline), 4,4'-vinylidenebis (N, N-dimethylaniline), leucomarakite green, 4,4' -Bis (dimethylamino) benzidrol, 1,8-bis (dimethylamino) naphthalene, 2- (dimethylamino) flurene, 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) di Benzylamine, 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-pyrrolin, 1-benzyl-3-pyrrolidinol, 1-benzyl-2-pyrrolidin methanol, 1- (3,4-dihydro-2-naphthyl) pyrrolidine, 1-methyl -4-phenyl-1,2,3,6-tetrahydropyridine, 4-diphenylmethoxy-1-methylpiperazin, 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-hydroxyJULODINE, 5,10-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] hexacosan and the like.

Examples of amines that can be used in addition to the primary amine, the secondary amine, and the tertiary amine include N-methylethylenediamine, N-ethylethylenediamine, N-propylethylenediamine, N-isopropylethylenediamine, and 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- Propanediamine, 3-dimethylaminopropylamine, 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), SPERMIDE, bis (Hexamethylene) triamine, N, N', N''-trimethylbis (hexamethylene) triamine, 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, PERMINE, tris (2-aminoethyl) amine, tetraethylenepentamine, pentaethylenehexamine, N-cyclohexyl-1,3-propanediamine, 2- (2-amino Ethylamino) ethanol, 1- (2-aminoethyl) pyrrolidine, 2- (2-aminoethyl) -1-methylpyrrolidin, 1- (2-pyrrolidinylmethyl) pyrrolidine, 4- (1-pyrrolidinyl) pi Peridine, 4-piperidinopiperidin, 1- (2-aminoethyl) piperidin, 1- (3-aminopropyl) -2-pipecholine, 3-aminopiperidin, 1-methyl-4- (methylamino) piperidin, 4 -(Aminoethyl) piperidine, 3- (4-aminobutyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidin, 4-dimethylamino-2,2,6,6-tetramethylpiperidin, 2-Methyl-2-imidazoline, 4,4-dimethyl-2-imidazoline, 1-methylpiperazin, 1-ethylpiperazin, 1- (2-hydroxyethyl) piperazin, 1- [2- (2-hydroxyethoxy) ethyl ] Piperazine, 1- (2-aminoethyl) piperazine, 1,4-bis (3-aminopropyl) piperazine, HEXETIDIEN, 1,4,5,6-tetrahydropyrimidine, 1-methylhomopiperazin, 3-aminoquinuridine , 1,8-diazabicyclo [5.4.0] unde-7-sen, 1,3,4,6,7,8-hexahydro-2H-pyrimid [1,2-A] pyrimidine, 1,3,4 , 6,7,8-Hexahydro-1-methyl-2H-pyrimidin [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-diethyl-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-benzyl Piperazin, 2-phenyl-2-imidazoline, trazoline, 2- (1-naphthylmethyl) -2-imidazoline, fentolamine, 2,3-diphenyl-1,4-diazaspiro [4.5] deca-1,3 − The En, 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'-Isopropyridenebis [(4S) -4-phenyl-2-oxazoline], 2,2'-methylenebis [(4R, 5S) -4,5-diphenyl-2-oxazoline], tetramisol, 1 -Phenyl piperazine, 5-Phenyl-1,4,5,6-tetrahydropyrimidine, 1-benzyl piperazine, 1-cinnamyl piperazine, 1-orthotoluyl piperazine, 1- (2,3-kisilyl) piperazine, 1-( First grade such as 2-methoxy) piperazine, 1- (4-methoxy) piperazine, 1- (2-ethoxy) piperazine, 4-morpholinoaniline, homokine, polyethyleneimine, or polyethyleneimine graft polyalkyl (meth) acrylate copolymer. Examples thereof include amine compounds in which an amino group, a secondary amino group and a tertiary amino group are combined in one molecule.

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

Examples of the quaternary ammonium hydroxide salt include tetramethylammonium hydroxide salt, tetraethylammonium hydroxide salt, tetrapropylammonium hydroxide salt, tetrabutylammonium hydroxide salt, triethylmethylammonium hydroxide salt, and hexadecyl hydroxide. Examples thereof include trimethylammonium salt and benzyltrimethylammonium hydroxide salt.

Examples of the hydrazine compound include phenylhydrazine, 1,1-diphenylhydrazine, 1,2-diphenylhydrazine, 1-methyl-1-phenylhydrazine, orthotoluylhydrazine and the like.

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

Examples of the mercapto compound include 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, and 1,8-octanedithiol. 1,9-Nonandithiol, 2-mercaptoethyl ether, 1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, 1,2-benzenedimethanethiol, 1,3-benzenedimethane Examples thereof include thiol, 1,4-benzenedimethanethiol and 4,4'-thiobenzenethiol.

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

Examples of the phosphine compound include di-tert-butylphosphine, trimethylphosphine, 1,2-bis (dimethylphosphine) ethane, triethylphosphine, tripropylphosphine, triisopropylphosphine, triisobutylphosphine, and tri-tert-butyl. Phosphine, trioctylphosphine, tricyclohexylphosphine, 1,4-bis (dicyclohexylphosphine) butane, phenylphosphine, diphenylphosphine, triphenylphosphine, 1,2-bis (phenylphosphine) ethane, dimethylphenylphosphine, diethylphenyl Phosphine, diallylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, diphenylpropylphosphine, isopropyldiphenylphosphine, diphenylvinylphosphine, allyldiphenylphosphine, dicyclohexylphenylphosphine, tribenzylphosphine, triortotoluylphosphine, trimetatoluylphosphine, tripalatoluyl Phosphine, tris (2,4,6-trimethylphenyl) phosphine, bis (diphenylphosphine) methane, 1,2-bis (diphenylphosphine) ethane, 1,3-bis (diphenylphosphine) propane, 1,4 -Bis (diphenylphosphine) butane, 2,2'-bis (diphenylphosphino) -1,1'-naphthalene and the like can be mentioned.

Examples of the photobase generator represented by the general formula (1) or (2) include imidazol-1-carboxylic acid 1- (anthraquinone-2-yl) ethyl and 1- (Anthracinon-2-yl) ethyl. N-cyclohexylcarbate, 1- (Anthracinon-2-yl) ethyl N, N-dicychlorocarbamate, 1,2-Diisopropyl-3- [Bis (dimethylamino) methylNlyne] gunilide2- N-diethylcarbamate, 9-Anthrylmethyl piperadine-1-carboxylate, 9-Anthrylmethyl N-cyclohexylcarbamate, 9-Anthrylmethyl N, N-dicyclohexylcarbamate, (2-Nitrophenyl) methyl 4- (methacryloyloxy) piperidine-1-carboxylate, (2-Nitrophenyl ) Methyl 4-hydroxypiperidine-1-carboxylate, Cyclohexyllaminium 2- (3-benzylphenyl) ropionate, Dicyllohexyllaminium 2- (3-benzoylpenelyl) -Methylphenyl) -2-oxoethyl, 2-nitrobenzyl cyclohexylcarbamate, 2- (9-oxoxanthen-2-yl) propionic acid 1,5,7-triazabicyclo [4.4.0] deca-5 -En, 2- (9-oxoxanthen-2-yl) propionic acid 1,5-diazabicyclo [4.3.0] nona-5-ene 9-anthrylmethyl N, N-diethylcarbamate , 1- (anthraquinone) -2-yl) Ethylimidazole carboxylate, 2-nitrophenylmethyl 4-methacryloyloxypiperidin-1-carboxylate, 1- (anthraquinone-2-yl) -ethyl N, N-dicyclohexylcarbamate, dicyclohexylammonium 2 -(3-Benzoylphenyl) propionate, cyclohexylammonium 2- (3-benzoylphenyl) propionate, 9-anthrylmethyl N, N-dicyclohexylcarbamate, 1,2-diisopropyl-3- [bis (dimethylamino) methylene] guanidium Examples thereof include 2- (3-benzoylphenyl) propionate and 1,6-hexamethylene-bis (4,5-dimethoxy-2-nitrobenzyl carbamate).

The photobase generator preferably has an upper limit on the long wavelength side of the ultraviolet absorption wavelength range of 300 nm or more.
In conventional gas generators, since the light absorption band exists on the short wavelength side, it is necessary to irradiate high-energy light for a long time in order to generate gas, and as a result, a load is applied to the light source. There was a problem that the wafer could 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 damage to the wafer can be suppressed. In particular, when the upper limit of the ultraviolet absorption wavelength region on the long wavelength side is 300 nm or more, that is, when the absorption band has an absorption band at a wavelength of 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 region 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 the preferable lower limit is 5 parts by weight and the 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 a sufficient amount of gas is used to peel 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.
Since the photosensitizer has the effect of amplifying the stimulation of the photobase generator by light, the gas can be released by irradiating with less light. In addition, the gas can be emitted by light in a wider wavelength region.

The photosensitizer is not particularly limited as long as it has excellent heat resistance.
Examples of the photosensitizer having excellent heat resistance include polycyclic aromatic compounds having at least one alkoxy group. Of these, substituted alkoxy polycyclic aromatic compounds having an alkoxy group partially substituted with a glycidyl group or a hydroxyl group are preferable. These photosensitizers have high sublimation resistance and can be used at high temperatures. Further, by substituting a part of the alkoxy group with a glycidyl group or a hydroxyl group, the solubility in the adhesive component is enhanced and bleed-out can be prevented.

The 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.

The polycyclic aromatic compound having at least one alkoxy group is, for example, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 2-t butyl-9,10-dimethoxyanthracene, 2, 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-9,10-dipropoxyanthracene, 9-isopropoxy-10-methylanthracene, 9,10-dibutoxyanthracene, 9,10-dibenzyloxyanthracene, 2-Ethrace-9,10-dibenzyloxyanthracene, 2-tbutyl-9,10-dibenzyloxyanthracene, 2,3-dimethyl-9,10-dibenzyloxyanthracene, 9-benzyloxy-10-methyl Anthracene, 9,10-di-α-methylbenzyloxyanthracene, 2-ethyl-9,10-di-α-methylbenzyloxyanthracene, 2-tbutyl-9,10-di-α-methylbenzyloxyanthracene, 2,3-dimethyl-9,10-di-α-methylbenzyloxyanthracene, 9- (α-methylbenzyloxy) -10-methylanthracene, 9,10-di (2-hydroxyethoxy) anthracene, 2-ethyl Examples thereof include anthracene derivatives such as -9,10-di (2-carboxyethoxy) anthracene.

Examples of the substituted alkoxy polycyclic aromatic compound having an alkoxy group in which a part thereof is substituted with a glycidyl group or a hydroxyl group include 9,10-di (glycidyloxy) anthracene and 2-ethyl-9,10-di (glycidyl). 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-vinyloxyethoxy) -10-methylanthracene, 9,10-di (3-methyl-3-oxetanylmethoxy) Anthracene, 2-ethyl-9,10-di (3-methyl-3-oxetanylmemethoxy) anthracene, 2-tbutyl-9,10-di (3-methyl-3-oxetanylmemethoxy) anthracene, 2,3 −Dimethyl-9,10-di (3-methyl-3-oxetanylmemethoxy) anthracene, 9- (3-methyl-3-oxetanylmemethoxy) -10-methylanthracene, 9,10-di (p-epoxyphenyl) Methyl) anthracene, 2-ethyl-9,10-di (p-epoxyphenylmethoxy) anthracene, 2-tbutyl-9,10-di (p-epoxyphenylmethoxy) anthracene, 2,3-dimethyl-9,10 -Di (p-epoxyphenylmethoxy) anthracene, 9- (p-epoxyphenylmethoxy) -10-methylanthracene, 9,10-di (p-vinylphenylmethoxy) anthracene, 2-ethyl-9,10-di ( p-vinylphenylmethoxy) anthracene, 2-t butyl-9,1-di (p-vinylphenylmethoxy) anthracene, 2,3-dimethyl-9,10-di (p-vinylphenylmethoxy) anthracene, 9- ( p-vinylphenylmethoxy) -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-3-3) Examples thereof include phenoxypropoxy) anthracene and 9,10-di (2,3-dihydroxypropoxy) anthracene.

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 has excellent heat resistance, it prevents the adhesive from being scorched even after being treated with heating at 200 ° C. or higher, and bleeds out to the interface of the adherend at the time of peeling to facilitate peeling. Since the silicone compound has a functional group that can be crosslinked with the pressure-sensitive adhesive, it chemically reacts with the pressure-sensitive adhesive by light irradiation or heating and is incorporated into the pressure-sensitive adhesive, so that the silicone compound adheres to the adherend. And does not contaminate. Further, by blending the silicone compound, the effect of preventing adhesive residue on the wafer is also exhibited.

The pressure-sensitive adhesive composition for semiconductor devices of the present invention has various polyfunctionalities to be blended with general pressure-sensitive adhesives such as isocyanate compounds, melamine compounds, and epoxy compounds, if desired, for the purpose of adjusting the cohesive force as the pressure-sensitive adhesive. The compound may be appropriately contained.
The pressure-sensitive adhesive composition for semiconductor devices of the present invention may contain an inorganic filler such as fumed silica, a known additive such as 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 a predetermined amount of the pressure-sensitive adhesive, the photobase generator and, if necessary, other components are mixed and mixed. ..

The pressure-sensitive adhesive composition for semiconductor devices of the present invention can be used in various forms, for example, it can be used 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 non-support tape (self-supporting tape). An adhesive tape for a semiconductor device having an adhesive layer composed of the adhesive composition for a semiconductor device of the present invention is also one of the present inventions.

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 within this range, it can be attached to the wafer with sufficient adhesive strength, and the semiconductor chip being processed 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 adhesive tape for a semiconductor device of the present invention may be a support type having a base material or a non-support type having no base material. When the adhesive tape for a semiconductor device of the present invention has a base material, the base material is not particularly limited, but a base material having heat resistance is preferable. Examples of such heat-resistant base materials include polyethylene terephthalate, polyethylene naphthalate, polyacetal, polyamide, polycarbonate, polyphenylene ether, polybutylene terephthalate, ultrahigh molecular weight polyethylene, syndiotactic polystyrene, polyarylate, polysulfone, and polyether. Examples thereof include sulfone, polyphenylene sulfide, polyetheretherketone, polyimide, polyetherimide, fluororesin, liquid crystal polymer and the like. Of these, special polyesters containing polyethylene naphthalate, polyamides, polyimides, polyetheretherketones, and polyethersulfones are preferable because of their excellent heat resistance.

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

The thickness of the base material is not particularly limited, but the preferable lower limit is 5 μm and the preferable upper limit is 100 μm. When the thickness of the base material is within this range, an adhesive sheet having an appropriate elasticity and excellent handleability can be obtained. A more preferable lower limit of the thickness of the base material is 10 μm, and a more preferable upper limit is 50 μm.

The method for producing the adhesive tape for semiconductor devices of the present invention is not particularly limited. For example, in the case of a support type having a base material, a curable resin, a polymerization initiator, a cross-linking agent, and other components as necessary are used. It can be produced by a method of dissolving and mixing with a solvent, coating and drying, and then laminating on the base material layer, or a method of directly coating and drying on the base material layer. In the case of a non-support type having no base material, for example, a solution of the above-mentioned pressure-sensitive adhesive is applied onto a film that has undergone a mold release treatment and dried to form a pressure-sensitive adhesive layer, and then a mold release treatment is performed on the pressure-sensitive adhesive layer. It can be manufactured by a method of laminating the applied films or the like.

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

Hereinafter, embodiments of the present invention will be described in more detail with reference to 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, and 94 parts by weight of 2-ethylhexyl acrylate as the (meth) acrylic acid alkyl ester and 6 parts by weight of hydroxyethyl methacrylate as the functional group-containing monomer are prepared in the reactor. , 0.01 part by weight of lauryl mercaptan and 80 parts by weight of ethyl acetate were added, and then the reactor was heated to start reflux. Subsequently, 0.01 part by weight of 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane was added as a polymerization initiator into the reactor, and the polymerization was started under reflux. It was. Next, 0.01 parts by weight of 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane was added 1 hour and 2 hours after the start of the polymerization, and further, the polymerization was started. After 4 hours from the above, 0.05 parts by weight of t-hexyl peroxypivalate was added to continue the polymerization reaction. Then, 8 hours after the start of the 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 the resin solid content of the obtained ethyl acetate solution of the functional group-containing (meth) acrylic polymer, 3.5 parts by weight of 2-isocyanatoethyl methacrylate as a functional group-containing unsaturated compound was added and reacted. To obtain an ethyl acetate solution of the polymerizable polymer. Then, with respect to 100 parts by weight of the resin solid content of the ethyl acetate solution of the obtained polymerizable polymer, 20 parts by weight of silicone acrylate (EBECRYL 350, manufactured by Daicel Ornex) and silica filler (Leoloseal MT-10, manufactured by Tokuyama Corporation). 20 parts by weight, 0.5 part by weight of a chemical cross-linking agent (Coronate L-45, manufactured by Sekisui Fuller), and 1 part by weight of a photopolymerization initiator (Esacure One, manufactured by Siebel Hegner Japan) were mixed.

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

The obtained ethyl acetate solution of the pressure-sensitive adhesive composition for semiconductor devices was applied to the corona-treated surface of a transparent polyethylene teleterate film having a thickness of 50 μm in which one side was corona-treated. It was coated with a doctor knife so as to have a thickness of 30 μm. Next, the coating solution was dried by heating at 110 ° C. for 5 minutes, and then a transparent polyethylene teletalate film having a thickness of 50 μm, which had undergone a mold release treatment, was attached to the opposite side and allowed to stand at 40 ° C. for 3 days. To obtain an adhesive tape for semiconductor devices.

(Examples 2 to 6, Comparative Examples 1 to 3)
An adhesive tape for a semiconductor device was produced in the same manner as in Example 1 except that the types and amounts of the photobase generators were as shown in Table 1.

<Evaluation>
The adhesive tapes for semiconductor devices (hereinafter, also simply referred to as adhesive tapes) obtained in Examples and Comparative Examples were evaluated as follows. The results are shown in Table 2.

(Adhesiveness evaluation)
An adhesive tape for a semiconductor device cut into a circle with a diameter of 20 cm was attached to a silicon wafer having a diameter of 20 cm and a thickness of about 750 μm to obtain a laminate. In this state, the end of the adhesive tape was turned over, and the adhesiveness was evaluated as "○" when it could not be peeled off at all, "△" when it could be peeled off lightly, and "×" when it could be peeled off with almost no resistance. ..

(Evaluation of gas generation)
Using an ultra-high pressure mercury lamp, the adhesive tape side of the laminated body was irradiated with ultraviolet rays of 365 nm for 5 minutes by adjusting the illuminance so ^{that the irradiation intensity on the substrate surface of the adhesive tape was 40 mW / cm 2.} Visually observe the laminated body after UV irradiation, and when the silicon wafer is peeled off from the adhesive tape in an area of 90% or more of the adhesive interface, "◎", and in the area of 70% or more, the silicon wafer is removed from the adhesive tape. The gas generation property was evaluated as "◯" when the silicon wafer was peeled off and "x" when the silicon wafer was peeled off from the adhesive tape in an area of less than 70%.

(Evaluation of peelability)
When the adhesive tape is peeled off from the laminated body after gas generation evaluation with a force of 0.1 N per 25 mm width, "◎" indicates that the adhesive tape has peeled off naturally, and "○" indicates that the adhesive tape can be peeled off without any resistance. The peelability was evaluated as "Δ" when the peeling was possible although there was resistance, and as "x" when the peeling was not possible at all.

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

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

Claims (5)

It contains a pressure-sensitive adhesive and a photobase generator represented by the following general formula (1) or (2).
A pressure-sensitive adhesive composition for a semiconductor device, wherein the pressure-sensitive adhesive contains a (meth) acrylic polymer having a radically polymerizable unsaturated bond in the molecule.

In formula (1), R ¹ , R ² and R ³ are independently hydrogen, halogen, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, cyano group, nitro group, nitroso group, sulfino group and 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. Represents an aryl group of, an arylalkyl group having 7 to 15 carbon atoms, a saturated aliphatic ring, an unsaturated aliphatic ring, an aromatic ring or an organic group, and may be the same or different. In the case of a cyclic structure, a hetero atom may be contained. Two or more of R ¹ and R ² may be bonded to form a cyclic structure, and the cyclic structure is any ring structure such as a saturated aliphatic ring, an unsaturated aliphatic ring, and an aromatic ring. It may be present or may contain a heteroatom.

In the formula (2), R ⁴ is hydrogen, halogen, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a cyano group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group , Phosphono group, phosphonat 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. Represents an arylalkyl group, a saturated aliphatic ring, an unsaturated aliphatic ring, an aromatic ring or an organic group. When R ⁴ has a cyclic structure, it may contain a hetero atom. Further, B is a basic compound. The pressure-sensitive adhesive composition for a semiconductor device according to claim 1, wherein the photobase generator has an upper limit on the long wavelength side of the ultraviolet absorption wavelength range of 300 nm or more. The pressure-sensitive adhesive composition for a semiconductor device according to claim 1 or 2, wherein the content of the photobase generator is 5 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the pressure-sensitive adhesive. The pressure-sensitive adhesive composition for a semiconductor device according to any one of claims 1 to 3, wherein the pressure-sensitive adhesive contains a photosensitizer. A pressure-sensitive adhesive tape for a semiconductor device, which comprises a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition for a semiconductor device according to any one of claims 1 to 4.