JPH09194798A - Tacky resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition causing lowering of the adhesiveness by irradiation of high energy beam, containing a specific polymer and a (meth) acryloyl-containing compound, free from lowering of adhesiveness and discoloration under irradiation of visible light and ultraviolet rays and capable of readily releasing by irradiation of high energy beam. SOLUTION: This tacky resin composition does not cause lowering of adhesiveness by irradiation of light having >=300nm wavelength and develops lowering of adhesiveness by irradiation of high energy beam such as X rays, α rays, βrays or γ rays and the resin composition contains (A) 100 pts.wt. (co)polymer (e.g. having 5×10<3> to 5×10<6> weight average molecular weight) containing (meth) acrylic acid (ester) and (meth)acrylic amide as a monomer component and (B) 1-300 pts.wt. compound having (meth)acyloyl in the molecule (e.g. dipenta erythritol hexacrylate) and does not contain a photopolymerization initiator.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an adhesive resin composition. More specifically, electron beam, X-ray, α-ray, β
Before irradiation with high energy rays such as gamma rays and γ rays, the adhesive strength to adherends of various metals, various plastics, glass, etc. is high, but after irradiation with the above high energy rays, the adhesive strength to these adherends is remarkable. The present invention relates to a pressure-sensitive adhesive resin composition that can be easily peeled off.

[0002]

2. Description of the Related Art Conventionally, an adhesive composition used for an adhesive tape or the like has a substantially constant adhesive force while being used by being adhered to an adherend, and is used for applications requiring a strong adhesive force. There is a problem in that a tacky composition having a large adhesive strength cannot be easily peeled off when it is desired to be peeled, and conversely, a tacky composition designed to be easily peeled cannot provide a necessary adhesive strength.

In order to solve the above problems, conventionally, a heat-crosslinking component or a light-crosslinking component is mixed in the pressure-sensitive adhesive composition, and when peeling is desired, the former is heated. Therefore, in the latter, a method has been adopted in which a three-dimensional crosslinked structure is produced in the pressure-sensitive adhesive composition by irradiating light, thereby reducing the adhesive force and easily peeling.

However, in the method of reducing the adhesive force by blending a heat-crosslinking component into the pressure-sensitive adhesive composition and heating it, the adherend is preferably deformed, discolored, and deteriorated in function. There is a possibility that it may cause deterioration. Further, in the case of using a pressure-sensitive adhesive composition in which a crosslinking reaction proceeds even at a relatively low temperature in order to prevent deterioration of the adherend, the crosslinking reaction progresses with time even at room temperature, so that the adhesive strength gradually decreases. There is a problem.

On the other hand, a method of blending a component which crosslinks by light irradiation into the pressure-sensitive adhesive composition and irradiating with light when necessary to reduce the adhesive force has already been used in the semiconductor industry.
It has been put to practical use as an adhesive tape called a dicing tape used when cutting a C wafer into individual IC chips (Japanese Patent Publication No. 6-16524 and Japanese Patent Laid-Open No. 4-30).
0981 and Japanese Patent Laid-Open No. 6-264033). However, the method of lowering the adhesive force by light irradiation has a problem that the adhesive force gradually decreases because it is irradiated with visible light or ultraviolet rays in a normal environment and the adhesive force is peeled off even when it is not desired to peel it off.

[0006]

An object of the present invention is to provide a novel adhesive resin composition. Another object of the present invention is to maintain a suitable adhesive force required for a long time even in an environment where it is exposed to visible light and ultraviolet rays, without discoloration, and when peeling is desired, an electron beam, X line,
An object of the present invention is to provide an adhesive resin composition that can be easily peeled off by irradiating high energy rays such as α rays, β rays, and γ rays. Still other objects and advantages of the present invention will become apparent from the following description.

[0007]

According to the present invention, the above objects and advantages of the present invention are at least one selected from the group consisting of (A) (meth) acrylic acid, (meth) acrylic acid ester and (meth) acrylamide. (Co) polymer containing seed as a monomer (hereinafter referred to as "polymer (A)") 1
00 parts by weight, and at least one (meth) in the molecule
It contains 1 to 300 parts by weight of a compound having an acryloyl group, does not substantially contain a photopolymerization initiator, and (B) the adhesiveness is not substantially reduced by irradiation with light having a wavelength of 300 nm or more, however, This is achieved by an adhesive resin composition characterized by exhibiting a property of lowering adhesiveness by irradiation with high energy rays.

The essential monomer (hereinafter referred to as "monomer (A)") constituting the polymer (A) contained in the adhesive resin composition of the present invention is (meth) acrylic as described above. Acid, (meth) acrylic acid ester or (meth) acrylamide. (Meth) acrylic acid is acrylic acid or methacrylic acid. Examples of (meth) acrylic acid ester, that is, acrylic acid ester or methacrylic acid ester include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and methyl (meth). Acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) ) Acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl Le (meth) acrylate, nonyl (meth) acrylate,
Decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) Acrylate, benzyl (meth)
Acrylate, cyclohexyl (meth) acrylate,
Phenoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tricyclodecanyl (meth) acrylate, isobornyl (Meth) acrylate, bornyl (meth) acrylate and the formula (1) in the molecular structure

-SiR ¹ R ² R ³ (1)

(In the formula, R ¹ , R ² and R ³ , which may be the same or different, each represents an alkyl group having 1 to 6 carbon atoms or an alkoxyl group having 1 to 6 carbon atoms.
^At least one of ¹ , R ² and R ³ is an alkoxyl group having 1 to 6 carbon atoms. (Meth) acrylic acid ester having at least one silicon-containing group on average.

Examples of the compound having a silicon-containing group include
For example, (meth) acryloxymethyltrimethoxysilane, (meth) acryloxymethyltriethoxysilane,
(Meth) acryloxymethyltripropoxysilane,
(Meth) acryloxymethyltributoxysilane, (meth) acryloxymethyltrihexyloxysilane, 3
-(Meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropylmethyldibutoxysilane, etc. Can be mentioned. Examples of (meth) acrylamide include diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide,
N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, t-octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, 7-amino-3,7 -Dimethyloctyl (meth) acrylamide, N, N'-dimethylaminopropyl (meth) acrylamide, (meth) acryloylmorpholine and the like can be mentioned. The monomer (A) may be used alone or in combination of two or more. The monomer (A) is usually copolymerized in the polymer (A) by 40% by weight or more, preferably 50% by weight or more.

Monomers other than the monomer (A) containing a polymerizable double bond copolymerizable with the monomer (A) in the molecule (hereinafter,
A "monomer (B)") can be contained as a component constituting the copolymer (A). Examples of the monomer (B) include N-vinylpyrrolidone, N-vinylcaprolactam, vinyl acetate, vinyl propionate, maleic anhydride, itaconic acid, fumaric acid, (meth) acrylic acid,
Examples thereof include (meth) acrylonitrile and styrene. These monomers (B) may be used alone or in combination of two or more.

Examples of the method for producing the polymer (A) include a radical polymerization method, an anionic polymerization method and a cationic polymerization method of the monomer (A) or the monomer (A) and the monomer (B). To be

The polystyrene equivalent weight average molecular weight (hereinafter referred to as Mw) of the polymer (A) used in the present invention by gel permeation chromatography is 5 × 10 ^{3 to} 5
× 10 ⁶ is preferable. If the Mw is lower than 5 × 10 ³ , sufficient adhesive strength cannot be obtained, or the pressure-sensitive adhesive composition may be transferred from the support to the adherend after irradiation with high energy rays.
If it exceeds 10 ⁶ , the compatibility with a compound having at least three (meth) acryloyl groups in the molecule may decrease.

The compound having at least one (meth) acryloyl group in the molecule used in the present invention is 2
-Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, Butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth)
Acrylate, hexyl (meth) acrylate, heptyl
(Meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (Meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) Acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) acrylate, Toxyethoxyethyl (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate,
Tricyclodecanyl (meth) acrylate, isobornyl (meth) acrylate, bornyl (meth) acrylate, diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, N, N-dimethyl (Meth) acrylamide, t-octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, N,
N-diethyl (meth) acrylamide, N, N'-dimethylaminopropyl (meth) acrylamide, (meth) acryloylmorpholine, and a mono (meth) acrylic compound represented by the following formulas (2) to (4),

[0016]

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(Wherein R ⁴ is a hydrogen atom or a methyl group, R ⁵ is an alkylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, R ⁶ is a hydrogen atom or 1 to 12 carbon atoms,
Preferably it is a 1-9 alkyl group, m is 0-12,
It is preferably an integer of 1 to 8. )

[0018]

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(In the formula, R ^{4 is} as defined above, R ⁷ is an alkylene group having 2 to 8 carbon atoms, preferably 2 to 5 carbon atoms, and p is 0 to 8, preferably 1 to 4 It is an integer.)

[0020]

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[Wherein R ⁴ , R ⁷ and p are as defined above, R ⁸ and R ⁹ are hydrogen atoms and have 1 to 6 carbon atoms.
Alkyl group or a group represented by -R ¹⁰ -A (where R
¹⁰ is an alkylene group having 1 to 6 carbon atoms, and A is (meth)
It represents an acryloyloxy group). ]

Ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate,
1,4-butanediol di (meth) acrylate, 1.6
-Hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tricyclodecane dimethanol di (Meth) acrylate, diacrylate such as epoxy (meth) acrylate obtained by adding (meth) acrylate to diglycidyl ether of bisphenol A, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane Trioxyethyl (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Trimethylolpropane tetra (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexamethylolmelamine tri (meth) acrylate, hexamethylolmelamine tetra (meth) acrylate, hexamethylolmelamine penta (meth) acrylate, hexamethylol melamine hexa (meth) acrylate, a compound represented by the formula ^{(5), R 11 R 12} R 13 C-CH 2 OCH 2 -CR 14 R 15 R 16 ··· (5) [ (In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ may be the same or different, and are represented by the following formula (6), formula (7), formula (8) and formula (9) Represents any one of the organic groups represented by, provided that R ¹¹ , R ¹² , R ¹³ , R ¹⁴ ,
At least three of R ¹⁵ and R ¹⁶ must be organic groups represented by any one of formula (6), formula (7) and formula (8). )

[0023]

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[0024]

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[0025]

[Chemical 6]

--CH ₂ OH (9) (wherein, R ¹⁷ is an alkylene group having 2 to 6 carbon atoms, R ¹⁸ is a hydrogen atom or a methyl group, and q and n are 1 to 5 respectively.
Indicates an integer. )] A compound represented by formula (10) or formula (11), CH (OR ¹⁹ ) (CH ₂ OR ²⁰ ) (CH ₂ OR ²¹ ) ... (10)

[0027]

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(In the formula, R ¹⁹ , R ²⁰ , and R ²¹ may be the same or different and each represents an organic group represented by the following formula (12).)

[0029]

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(In the formula, R ²⁰ is an alkylene group having 2 to 6 carbon atoms, R ¹⁶ is a hydrogen atom or a methyl group, and r is 1 to 5).
Indicates an integer. )

Examples thereof include polyfunctional acrylates and the like.

As commercially available products, Aronix M111,
M113, M114, M117 (all manufactured by Toagosei Kagaku Co., Ltd.), KAYARAD TC110S, R62
9, R644 (Nippon Kayaku Co., Ltd.), Viscoat 3
700 (Osaka Organic Chemical Co., Ltd.), Upimer UV, SA
1002, SA2007 (all manufactured by Mitsubishi Petrochemical Co., Ltd.), Viscoat 700 (manufactured by Osaka Organic Chemical Co., Ltd.), KAYAR
ADR-604, DPCA-20, -30, -60,
-120, HX-620, D-310, D-330 (all manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210, M-
215, M-315, M-325 (all manufactured by Toa Gosei Kagaku Co., Ltd.) and the like.

Urethane acrylate can also be used. Examples thereof include a urethanization reaction product of a hydroxyl group-containing (meth) acrylate compound and a polyisocyanate compound, a reaction product of a hydroxyl group-containing (meth) acrylate compound, a polyisocyanate compound and alcohols, and a hydroxyl group-containing (meth) acrylate compound. Examples thereof include reaction products of polyisocyanate compounds and polymer diol compounds, reaction products of hydroxyl group-containing (meth) acrylate compounds, polyisocyanate compounds, alcohols and polymer diol compounds.

Here, examples of the hydroxyl group-containing (meth) acrylate compound include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 2-hydroxy-. 3-phenyloxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, 1,6-hexanediol mono ( (Meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethanedi (meth) acrylate, pentaerythritol tri (meth) acrylate
Acrylate, dipentaerythritol penta (meth)
Examples thereof include acrylates and (meth) acrylates represented by the following general formula (13) or (14).

[0035]

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[0036]

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(In the formula, R ⁴ represents a hydrogen atom or a methyl group, and s represents a number of 1 to 15.) Further, glycidyl group-containing compounds such as alkyl glycidyl ether, aryl glycidyl ether, and glycidyl (meth) acrylate. The compound obtained by the addition reaction of (meth) acrylic acid with (meth) acrylic acid can be used as the hydroxyl group-containing (meth) acrylate compound.

Examples of the above polyisocyanate compound include, for example, 2,4-tolylene diisocyanate and 2,6-
Tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,
5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,
3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate,
4,4'-biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, bis (2-isocyanatoethyl) fumarate,
6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethyl xylylene diisocyanate and the like can be mentioned.

Examples of the above alcohols include methanol, ethanol, n-propyl alcohol, iso-
Propyl alcohol, n-butyl alcohol, iso-
Butyl alcohol, sec-butyl alcohol, ter
t-butyl alcohol, n-amyl alcohol, iso
-Amyl alcohol, sec-amyl alcohol, te
rt-amyl alcohol, n-hexanol, cyclohexanol, 4-methyl-2-pentanol, n-heptanol, 3-methyl-1-hexanol, 5-methyl-1-hexanol, 2-ethylhexyl alcohol,
3,5,5-Trimethyl-1-hexanol, n-octyl alcohol, 2-octyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2- Ethylhexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, tetraethylene Glycol monob Ether, pentaethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, monohydric alcohols such as benzyl alcohol,

(Poly) ethylene glycol represented by the general formula (16), such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, HO- (C ₂ H ₄ O) _t -H. · (16) (Here, t is an integer of 1 to 20.) (Poly) propylene glycol represented by the general formula (17) such as propylene glycol, dipropylene glycol, tripropylene glycol, and hexapropylene glycol. s, HO- (wherein, t is an integer of _{1~20.) (C 3 H 6} O) t -H ··· (17) butylene glycol, dibutylene glycol, formulas such as tri-butylene glycol ( 18) represented by the (poly) butylene _{glycol, HO- (C 4 H 8 O} ) t -H ··· (18) (Here, t is an integer of 1 to 20.)

1,5-Pentanediol, 1,6-hexanediol, glycerin, trimethylolpropane and its ethylene oxide / propylene oxide adduct, sorbitol, pentaerythritol, dipentaerythritol, 1,4-cyclohexanediol, 1,4. Four
-Cyclohexanedimethanol, 1,2-bis (hydroxyethyl) cyclohexane, 2,2-diethyl-1,3
-Propanediol, alkylene oxide addition polyol, TMP30, PNT4Gly manufactured by Nippon Emulsifier Co., Ltd.
col, EDA P4, EDA P8, quadrol manufactured by Asahi Denka Co., Ltd., tone polyol 0200, 0221, 0301, 0310, 220 manufactured by Union Carbide.
And polyhydric alcohols such as polycaprolactone such as 1,2221. Further, the polyhydric alcohol may be a saturated polyester of the above polyhydric alcohol. As such an example, a reaction product of trimethylolpropane and ε-caprolactone, the above-mentioned ethylene glycols,
Propylene glycols, butylene glycols, 1,
5-pentanediol, 1,6-hexanediol, 1,4
-Cyclohexanediol, 1,4-cyclohexanedimethanol, ratio of 1 mol of saturated dicarboxylic acid to 2 mol of diol such as 1,2-bis (hydroxyethyl) cyclohexane and 2,2-diethyl-1,3-propanediol The reaction product of Incidentally, examples of the saturated dicarboxylic acid, oxalic acid, malonic acid, methylmalonic acid, succinic acid, ethylmalonic acid, methylsuccinic acid, glutaric acid,
Adipic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, pimelic acid, suberic acid, azelaic acid, Sebacic acid etc. are mentioned.

The amount of the compound having at least one (meth) acryloyl group in the molecule is such that the amount of the polymer (A) is 100.
It is preferably 1 to 300 parts by weight with respect to parts by weight,
More preferably, it is 5 to 100 parts by weight. When the amount of the compound having at least one (meth) acryloyl group in the molecule is less than 1 part by weight, the crosslink density due to irradiation with high energy rays is unlikely to be high and the decrease in adhesiveness is small. Further, when the amount of the compound having at least one (meth) acryloyl group in the molecule exceeds 300 parts by weight, transfer of the pressure-sensitive adhesive tends to occur when peeling after irradiation with high energy rays. .

In the composition of the present invention, in addition to the polymer (A), natural rubber, isoprene rubber, styrene-butadiene rubber, styrene / butadiene block copolymer, styrene / isoprene block copolymer, butyl rubber, polyisobutylene, It is also possible to add rubber-based resins such as silicone rubber, polyvinyl isobutyl ether, chloroprene rubber, nitrile rubber, graft rubber and recycled rubber, if necessary.

When the composition of the present invention contains the polymer (A) having a silicon-containing group, the silicon groups in the polymer (A) are condensed with each other before the composition is applied to the support. To this end, amines or organotin compounds can be added to the composition. Examples of such amines include ethylamine, diethylamine, triethylamine,
1,4-diazabicyclo [2,2,2] octane, 1,4-
Diazabicyclo-2-methyl [2,2,2] octane, γ
Examples include-(2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-anilinopropyltrimethoxysilane, and γ-dibutylaminopropyltrimethoxysilane. Examples of the organic tin compound include di-n-butyltin dilaurate, bis (2-ethylhexanoic acid) di-n-butyltin, tris (2-ethylhexanoic acid) n-butyltin, and diethanoic acid di-n-butyltin. Examples thereof include n-butyltin, di-n-methyltin di-n-decanoate, dioctylic acid, and dilauryltin. The amount of amines or organotin compounds is 10 in total of the polymer (A) and the compound having at least one (meth) acryloyl group in the molecule.
It is 0.01 to 1 part by weight with respect to 0 part by weight. The composition of the present invention contains substantially no photopolymerization initiator. When the photopolymerization initiator is contained, the adhesiveness is lowered under a normal environment where it is irradiated with light having a wavelength of 300 nm or more such as infrared rays, visible rays and ultraviolet rays.

In the composition of the present invention, if necessary, rosin, hydrogenated rosin, ester gum, polyterpene resin, polyolefin resin, polystyrene resin, aromatic petroleum resin, alicyclic hydrogenated petroleum oil. It is also possible to add a tackifier such as a resin.

Further, the composition of the present invention contains an antiaging agent, an ultraviolet absorber, a solvent, a coloring agent, a light stabilizer, a coupling agent, a thermal polymerization inhibitor, a leveling agent, a surfactant, a storage stabilizer, A plasticizer, a filler and the like can be added if necessary.

Examples of the above antiaging agents include Irgan
ox 245, 259, 565, 1010, 1035,
1076, 1081, 1098, 1222, 1330
(Above, manufactured by Ciba Geigy) and the like.

Examples of the ultraviolet absorber include Tin.
uvin P, 213, 234, 320, 326, 32
7, 328, 329 (above, manufactured by Ciba Geigy), S
EESORB 102, 103, 501, 202, 71
2, (above, manufactured by Cypro Kasei Co., Ltd.) and the like, and as the light stabilizer, for example, Tinuvin 292, 144,
622LD (above, manufactured by Ciba Geigy), Sanol L
S770, LS440 (above, Sankyosha), Sumis
orb TM-061 (manufactured by Sumitomo Chemical Co., Ltd.) and the like. Examples of the coupling agent include γ-aminopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-methacryloxypropyltriethoxysilane, and commercially available products SH6020, 6020.
P, 6062, 6030 (above, manufactured by Toray Dow Corning Silicone Co., Ltd.), KBE 903, 603, 403.
(Above, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene, aromatic naphtha, n-hexane, n-heptane, n-octane and n-.
Decane, dipentene, petroleum spirit, petroleum naphtha, aliphatic hydrocarbons such as turpentine oil, ethyl acetate,
Esters such as n-amyl acetate, 3-methoxybutyl acetate, methyl benzoate, cellosolve acetate, butyl cellosolve acetate, acetone,
Ketones such as methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone, methyl cyclohexanone, methyl alcohol, ethyl alcohol, n
-Propyl alcohol, i-propyl alcohol, n-
Alcohols such as butyl alcohol, i-butyl alcohol, sec-butyl alcohol and t-butyl alcohol can be mentioned.

The composition of the present invention can be produced by appropriately combining the above-mentioned essential components and optional components and mixing them by a conventional method.

The composition of the present invention is applied to one or both of two adherends to be adhered, and then 50 to 150
It is also possible to heat the substrate at 1 ° C. for 1 to 120 minutes and bond the adherends to each other for use. Also, apply to one of the adherends,
After heating at -150 ° C for 1 to 120 minutes, the easily peelable film may be laminated, and before use, the other adherend to be peeled off and adhered may be laminated and used. Moreover, after coating on the easily peelable film and heating at 50 to 150 ° C. for 1 to 120 minutes,
After being adhered to one adherend, the easily peelable film may be peeled off and the other adherend to be adhered may be stuck and used. As an alternative method, apply on an easily peelable film, heat at 50 to 150 ° C. for 1 to 120 minutes, bond a second easily peelable film, and then peel off one of the easily peelable films to adhere. After the other adherend to be bonded is adhered, the other easily peelable film can be peeled off and the other adherend to be adhered can be adhered and used.

The adherend to be adhered with the composition of the present invention is, for example, polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polysulfone, polymethylmethacrylate, polystyrene, polybutadiene, ABS resin, AS resin, AE.
Plastics such as S resin, nylon, cellulose, nitrocellulose and triacetyl cellulose; thermosetting resins such as phenol formaldehyde resin, cresol formaldehyde resin, melamine resin and urea resin;
Glass, pottery, porcelain, ceramics, quartz, silicon,
Inorganic substances such as iron, copper, aluminum and nickel can be mentioned.

When the composition of the present invention is laminated, the peeling adhesive strength sufficient to achieve the purpose is required unless it is irradiated with high energy rays such as electron rays, X rays, α rays, β rays and γ rays. However, when irradiated with a high energy ray, the peeling adhesive force is reduced to 1/10 or less of that before irradiation, and peeling can be easily performed.

[0054]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto. In the following, “parts” means “parts by weight”. The Mw of the polymer (A) is gel permeation chromatography (GP) using standard polystyrene.
It was measured by the C) method. The measurement conditions are as follows. Device: Tosoh high-speed GPC device HLC-802A Detection method: RI Column: Tosoh TSK-GEL, G4000
H _XL , G3000H _XL , G2000H _XL (two) Elution solvent: tetrahydrofuran, flow rate: 1.1 ml / min Column temperature: 40 ° C Sample concentration: 0.006 g / ml (solvent is tetrahydrofuran)

The concentration of the polymer after the polymerization reaction is 23
The concentration of the non-volatile component after removing the volatile components by heating for 15 minutes on a hot plate kept at 0 ° C. was defined as the concentration of the polymer. Peel strength, temperature 23 ℃, relative humidity 50%
Under the environment, the T-peel peeling test was performed at 50 mm / min and the measurement was performed.

Example 1 160 g of methyl methacrylate was placed in a 2-liter four-necked flask equipped with a stirrer, a thermometer, and a nitrogen introducing tube for bubbling.
(1.60 mol), n-butyl acrylate 240 g
(1.69 mol), 2-hydroxyethyl acrylate 100 g (0.86 mol), 3- (meth) acryloxypropyltrimethoxysilane 5 g (0.025 mol),
0.5 g of 2,2'-azobis (isobutyronitrile) and 500 g of methyl ethyl ketone were added, and the nitrogen in the raw material monomer was replaced with nitrogen by nitrogen bubbling while stirring. Continue heating in an oil bath to keep the internal temperature at 75-85 ° C.
The mixture was kept at the above temperature and stirred for 6 hours to carry out a polymerization reaction. The concentration of the copolymer obtained by the above polymerization reaction was 49.5%. The weight average molecular weight of this copolymer is 15,70.
It was 0. The copolymer solution obtained by this reaction is hereinafter referred to as a copolymer solution A.

After mixing 101 g of the copolymer solution A and 25 g of dipentaerythritol hexaacrylate,
One of the adherends, a PET (polyethylene terephthalate) film with a thickness of 75 μm (trade name Lumirror, manufactured by Toray Industries, Inc.) was applied using an applicator bar 127 μm manufactured by Kumagai Riki Kogyo Co., Ltd. 8 in
The adhesive film was produced by heating at 0 ° C. for 20 minutes to remove volatile components. After the pressure-sensitive adhesive film was returned to room temperature, another adherend, a PET film having a thickness of 25 μm, was attached to the pressure-sensitive adhesive film and left in an environment of a temperature of 23 ° C. and a relative humidity of 50% for 1 hour. After that, when a peeling test was performed by cutting out a part of the laminated films, the peeling strength was 122.
It had a large peel strength of 0 g / 25 mm. on the other hand,
The rest of the laminated films is accelerated from a 25 μm-thick PET film side at an acceleration voltage of 165 kV and an irradiation dose of 1 Mrad.
The peel strength after irradiating with the electron beam at 5 g / 25 mm was very small. Also, the adhesive layer after peeling is all 75 μm
It is on the side of thick PET film and has a thickness of 25 μm.
The transfer phenomenon to the ET film did not occur.

Example 2 A pressure-sensitive adhesive composition was prepared by using 6 g of trimethylolpropane triacrylate instead of 25 g of dipentaerythritol hexaacrylate used in Example 1, and then an adhesive film was prepared in the same manner as in Example 1. Then, a peeling test was performed, and it had a large peeling strength of 930 g / 25 mm. On the other hand, accelerating voltage 165 kV, irradiation dose 1 Mr
The peel strength of the ad after irradiation with the electron beam was as small as 10 g / 25 mm, showing a remarkable decrease in the peel strength. In addition, the transfer phenomenon did not occur.

Example 3 Methyl methacrylate 160 was placed in a 2-liter four-necked flask equipped with a stirrer, a thermometer, and a nitrogen introducing tube for bubbling.
g (1.60 mol), n-butyl acrylate 240 g
(1.69 mol) 100 g (0.86 mol) of 2-hydroxyethyl acrylate, 0.5 g of 2,2'-azobis (isobutyronitrile) and 500 g of methyl ethyl ketone were added, and nitrogen bubbling was carried out while stirring. The oxygen inside was replaced with nitrogen. Then, the mixture was heated in an oil bath, the internal temperature was kept at 75 to 85 ° C., and the mixture was stirred for 6 hours to carry out a polymerization reaction. The concentration of the copolymer obtained by the above polymerization reaction was 49.3%. The weight average molecular weight of this copolymer was 16,500. The copolymer solution obtained by this reaction is hereinafter referred to as a copolymer solution B.

After preparing a pressure-sensitive adhesive composition by mixing 101 g of the copolymer solution B and 25 g of dipentaerythritol hexaacrylate, a pressure-sensitive adhesive film was prepared in the same manner as in Example 1 and a peeling test was carried out.
It had a large peel strength of 25 mm. On the other hand, the peeling strength after the electron beam irradiation with the acceleration voltage of 165 kV and the irradiation amount of 1 Mrad was as small as 5 g / 25 mm.

Example 4 A pressure-sensitive adhesive composition was prepared by using 15 g of ditrimethylolpropane tetraacrylate instead of 25 g of dipentaerythritol hexaacrylate used in Example 3, and then an adhesive film was prepared in the same manner as in Example 1. Then, a peeling test was performed, and it had a large peeling strength of 1050 g / 25 mm. On the other hand, the peel strength after irradiation with an electron beam with an acceleration voltage of 165 kV and a dose of 1 Mrad is 3 g / 25 m.
It was as small as m and showed a remarkable decrease in peel strength. In addition, the transfer phenomenon did not occur.

Example 5 A pressure-sensitive adhesive composition was prepared by using 15 g of tripropylene glycol diacrylate instead of 25 g of dipentaerythritol hexaacrylate used in Example 1, and
When an adhesive film was prepared and a peeling test was conducted in the same manner as in Example 1, it had a large peeling strength of 1160 g / 25 mm. On the other hand, accelerating voltage 165 kV, irradiation dose 1
The peel strength after irradiation of Mrad with an electron beam was as small as 4 g / 25 mm, showing a marked decrease in peel strength. In addition, the transfer phenomenon did not occur.

Example 6 A pressure-sensitive adhesive composition was prepared by using 15 g of phenoxyethyl acrylate instead of 25 g of dipentaerythritol hexaacrylate used in Example 1, and then an adhesive film was prepared in the same manner as in Example 1. When a peeling test was conducted, it had a large peeling strength of 1050 g / 25 mm. On the other hand, the peel strength after irradiation with an electron beam having an accelerating voltage of 165 kV and an irradiation dose of 1 Mrad was as small as 3 g / 25 mm, showing a remarkable decrease in peel strength. In addition, the transfer phenomenon did not occur.

Comparative Example 1 A pressure-sensitive adhesive film was prepared in the same manner as in Example 1 except that the copolymer solution A was used as it was as a pressure-sensitive adhesive composition, and a peeling test was conducted. The peeling strength was as small as 5 g / 25 mm. Had. On the other hand, the peeling strength after the electron beam irradiation with the acceleration voltage of 165 kV and the irradiation amount of 1 Mrad is also 5 g / 25 mm.
Was small.

Comparative Example 2 An adhesive film was prepared by applying it to a PET film in the same manner as in Example 1 except that the copolymer solution B was used as it was as an adhesive composition.
It had a peel strength as small as 5 mm. Further, the peel strength was as small as 5 g / 25 mm even after irradiation with an electron beam having an accelerating voltage of 165 kV and an irradiation dose of 1 Mrad.

[0066]

EFFECT OF THE INVENTION The high energy ray releasable pressure-sensitive adhesive resin composition of the present invention can maintain an appropriate adhesive force required for a long time even in an environment where it is exposed to visible light and ultraviolet rays, and is not discolored. If you want to peel it off, electron beam, X
It can be easily peeled off by irradiating a high energy ray such as a ray, an α ray, a β ray, and a γ ray.

Claims (1)

[Claims] 1. (A) 100 parts by weight of a (co) polymer containing, as a monomer, at least one selected from the group consisting of (meth) acrylic acid, (meth) acrylic acid ester and (meth) acrylamide, and Compounds 1 to 300 having at least one (meth) acryloyl group in the molecule
By weight, it does not substantially contain a photopolymerization initiator, and (B) the adhesiveness is not substantially reduced by irradiation with light having a wavelength of 300 nm or more, and the adhesiveness is reduced by irradiation with high energy rays. An adhesive resin composition characterized by exhibiting the following properties.