JP2001064593A - Adhesive composition and adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ultraviolet curing type adhesive composition enabling viscosity to be easily adjusted and having excellent suitability for a coating. SOLUTION: An adhesive composition comprises the following component (A), (B), (C) and (D). The component (A) is a reactive polymer in which a double bond is introduced through a reaction of a functional group derived from the following component (b) and a functional group of the following component (d) with a compolymer obtained from the following component (a) and the component (b), or the component (a) and (b), and the following component (c); the component (a) is a (meth)acrylate monomer, the component (b) is a monomer copolymerizable with the component (a) and having a fuctional group, the component (c) is a monomer copolymerizable with the component (a) and (b), and the component (d) is a compound having a functional group and a double bond, the functional group forming a bond by reacting with a functional group of the component (b); the component (B) is a (meth)acrylate monomer; the component (C) is a single functional monomer copolymerizable with the component (B); and the component (D) is a photopolymerization initiator or a mixture of the photopolymerization initiator with a sensitizer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a pressure-sensitive adhesive composition and a pressure-sensitive adhesive obtained by curing the composition.

[0002]

2. Description of the Related Art A (meth) acrylate monomer of an alkyl alcohol having 4 to 14 carbon atoms has been used as a raw material for an acrylic pressure-sensitive adhesive, and the following are known. (1) A (meth) acrylate monomer of an alkyl alcohol having 4 to 14 carbon atoms and a monofunctional monomer copolymerized therewith are polymerized by a solution polymerization method or an emulsion polymerization method, and an appropriate amount of a crosslinking agent or the like is added. (2) a (meth) acrylate monomer of an alkyl alcohol having 4 to 14 carbon atoms, a monofunctional monomer copolymerized therewith, a polyfunctional acrylate oligomer serving as a crosslinking agent, and photopolymerization initiation UV-curable adhesive composition comprising an agent (US Pat. No. 4,181,752 and JP-A-7-331198).

[0003] However, the pressure-sensitive adhesive obtained from the pressure-sensitive adhesive composition of the above (1) has insufficient cohesive force at high temperatures and cannot be used for applications requiring heat resistance. Also,
The pressure-sensitive adhesive composition must volatilize a solvent or water upon curing after application, and requires a large amount of thermal energy. Furthermore, VOC (Volatile Organ)
ic Compound, volatile organic substances) and HAP
(Hazardous Air Pollutant) There is also a problem from the viewpoint of measures.

The acrylic ultraviolet-curable pressure-sensitive adhesive composition which becomes a pressure-sensitive adhesive by irradiating the ultraviolet light of the above (2) has a low viscosity of 2 to 20 centipoise and has a problem in coating suitability. Therefore, a polymer or a filler compatible with the (meth) acrylic acid ester monomer component is added to the acrylic UV-curable pressure-sensitive adhesive composition to increase the viscosity, and the composition is prepolymerized to increase the viscosity of the composition. A method for increasing the viscosity has been proposed (JP-A-7-278500). However, when a polymer is blended, the cohesive force of the pressure-sensitive adhesive at a high temperature is insufficient, and the heat-resistant holding power is reduced. When a filler is added, the thickening effect is small,
When added in a large amount, the tackiness of the pressure-sensitive adhesive is insufficient, the reliability of the adhesive strength is poor, and the transmission of ultraviolet rays is hindered, which may cause insufficient curing. Furthermore, when pre-polymerizing the composition, it has been difficult to control the degree of polymerization so as to have an appropriate viscosity.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art, and it is an ultraviolet-curable pressure-sensitive adhesive composition which is easily adjusted in viscosity and has excellent coating suitability. It is an object of the present invention to provide a product and a pressure-sensitive adhesive obtained by curing the composition and having excellent adhesive strength, heat-resistant holding power, and adhesive reliability at high temperatures.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a (meth) acrylate monomer and a monomer having a functional group copolymerizable with the monomer. A reactive polymer having a double bond introduced into the side chain of the copolymer obtained from the above through the functional group, a (meth) acrylate monomer,
By including in a UV-curable pressure-sensitive adhesive composition containing a monofunctional monomer copolymerizable with the monomer and a photopolymerization initiator, the viscosity of the pressure-sensitive adhesive composition is easily adjusted to improve coating suitability. The present inventors have found that a suitable adhesive can be obtained, and that, when the pressure-sensitive adhesive composition is cured, a pressure-sensitive adhesive excellent in adhesive strength, heat-resistant holding power, and adhesion reliability at high temperatures can be obtained, and the present invention has been completed.

That is, the present invention is as follows. [1] A pressure-sensitive adhesive composition containing the following (A), (B), (C) and (D). (A) A copolymer obtained from the following (a) and (b) or a copolymer obtained from the following (a), (b) and (c) is added with a functional group derived from (b) and the following ( d) a reactive polymer having a double bond introduced through reaction with a functional group: (a) (meth) acrylate monomer (b) a monomer copolymerizable with (a) and having a functional group ( c) a monomer copolymerizable with (a) and (b); (d) a compound having a functional group capable of forming a bond by reacting with a functional group of (b) and a double bond, (B) a (meth) acrylate ester A monomer, (C) a monofunctional monomer copolymerizable with (B), (D) a photopolymerization initiator, or a mixture of a photopolymerization initiator and a sensitizer. [2] (A) is the following structural units (I) and (II):

[0008]

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[Wherein, R ¹ represents hydrogen or a methyl group, R ² represents an alkyl group, R ³ represents hydrogen, a methyl group,
-R ^4a -R ^5a -R ^6a -C (-R ^7a ) = CH ₂ or -R
^4a -R ^8a represents, R ^4, R ^4a and R ^4b or is absent independently of each other, or a carbonyl group, an alkylene ^{group, -R a -O-R b -} , - COO-R c - or -C
^{OO-R d -OCO-R e} - represents, R ⁵ and R ^5a independently of one another are -OCONH -, - NHCOO -, - C
OO-R ^f - or an -R ^f -OCO-, or R ⁶ and R ^6a are not present independently of each other, or a carbonyl group, an alkylene ^{group, -R b -O-R a -} , - R c -
OCO- or an ^{-R e -COO-R d -OCO-,} R 7 and R ^7a represents hydrogen, methyl or -R ^4b -R ^8b independently of each other, and R ^8a and R ^8b are independently Represents a hydroxyl group, a carboxyl group, an epoxy group or an isocyanato group (where R ^a ,
R ^b , R ^d and R ^e independently represent an alkylene group, and R ^c is an alkylene which may be substituted with at least one substituent selected from the group consisting of an aryloxy group, a cycloalkyl group and an alkenyl group. Represents a group,
And R ^f represent an alkylene group substituted with a hydroxyl group)), wherein the structural unit (I) is 50 to 99.99 mol% and the structural unit (II) is 0.01% The pressure-sensitive adhesive composition according to [1], which is a reactive polymer containing about 50 mol%. [3] (A) is the following structural units (I), (II) and (III):

[0010]

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[Wherein, R¹Represents a hydrogen or methyl group
Then R^TwoRepresents an alkyl group;^ThreeIs hydrogen, methyl,
-R^4a-R^5a-R^6a-C (-R^7a) = CH_TwoOr -R
^4a-R^8aAnd R^Four, R^4aAnd R^4bAre independent of each other
Not present, or carbonyl group, alkylene
Group, -R^a-OR^b-, -COO-R^c-Or -C
OO-R^d-OCO-R^e-Represents R^FiveAnd R^5aIs
Independently of one another, -OCONH-, -NHCOO-, -C
OO-R^f-Or -R^f-OCO-, R⁶And
And R^6aDo not exist independently of each other or
Nil group, alkylene group, -R^b-OR^a-, -R^c−
OCO- or -R^e-COO-R^d-OCO-
Then R⁷And R^7aAre independently of each other hydrogen, methyl or
Or -R^4b-R^8bAnd R⁸, R^8aAnd R
^8bAre independently of each other a hydroxyl group, a carboxyl group,
Represents an epoxy group or an isocyanato group (where,
R^a, R^b, R ^dAnd R^eAre independent of each other
A group represented by^cIs an aryloxy group, cycloalkyl
At least one selected from the group consisting of
Also represents an alkylene group which may be substituted with one substituent
Represents, and R^fIs an alkyl substituted with a hydroxyl group
A reactive polymer comprising:
49.99 to 99.98 mol% of the structural unit (I),
The structural unit (II) in an amount of 0.01 to 50 mol% and the structural unit
A reactive polymer containing 0.01 to 25 mol% of position (III)
The pressure-sensitive adhesive composition according to [1], which is a limer. [4] (A) is the following structural units (I), (II), and
(IV):

[0012]

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[Wherein, R¹Or R⁹Are independent of each other
Represents hydrogen or a methyl group;^TwoRepresents an alkyl group,
R^ThreeIs hydrogen, a methyl group, -R^4a-R^5a-R^6a-C (-R
^7a) = CH_TwoOr -R^4a-R^8aAnd R^Four, R^4aYou
And R^4bDo not exist independently of each other or
Bonyl group, alkylene group, -R^a-OR^b-, -CO
OR^c-Or -COO-R^d-OCO-R^e-
Then R^FiveAnd R^5aAre independently -OCONH-,
-NHCOO-, -COO-R^f-Or -R^f-OC
O-, R⁶And R^6aDo not exist independently of each other
Squid or carbonyl group, alkylene group, -R^b−
OR^a-, -R^c-OCO- or -R ^e-COO-
R^d-OCO-, R⁷And R^7aAre independent of each other
Hydrogen, methyl group or -R^4b-R^8bAnd R^8aAnd
And R^8bAre independently a hydroxyl group, a carboxyl
Group, an epoxy group or an isocyanato group; and
R^TenIs acetoxy, phenyl, cyano, carboxyl
Represents a sil group or a carbamoyl group (where R^a, R
^b, R^dAnd R^eRepresents an alkylene group independently of each other
Then R^cIs an aryloxy group, a cycloalkyl group and
At least one selected from the group consisting of alkenyl groups
Represents an alkylene group which may be substituted with a substituent,
And R^fRepresents an alkylene group substituted with a hydroxyl group.
A) a reactive polymer comprising the structural unit
49 to 99.99 mol% of (I), the structural unit (II)
0.01 to 50 mol% and the structural unit (IV) is 1
~ 29.99 mol% reactive polymer
[1] The pressure-sensitive adhesive composition according to [1]. [5] (A) is the following structural unit (I), (II), (II)
I) and (IV):

[0014]

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[Wherein R¹Or R⁹Are independent of each other
Represents hydrogen or a methyl group;^TwoRepresents an alkyl group,
R^ThreeIs hydrogen, a methyl group, -R^4a-R^5a-R^6a-C (-R
^7a) = CH_TwoOr -R^4a-R^8aAnd R^Four, R^4aYou
And R^4bDo not exist independently of each other or
Bonyl group, alkylene group, -R^a-OR^b-, -CO
OR^c-Or -COO-R^d-OCO-R^e-
Then R^FiveAnd R^5aAre independently -OCONH-,
-NHCOO-, -COO-R^f-Or -R^f-OC
O-, R⁶And R^6aDo not exist independently of each other
Squid or carbonyl group, alkylene group, -R^b−
OR^a-, -R^c-OCO- or -R ^e-COO-
R^d-OCO-, R⁷And R^7aAre independent of each other
Hydrogen, methyl group or -R^4b-R^8bAnd R⁸, R
^8aAnd R^8bAre independently of each other a hydroxyl group,
Represents a xyl group, an epoxy group or an isocyanato group.
Rabi ni R^TenRepresents an acetoxy group, a phenyl group, a cyano group,
Represents a ruboxyl group or a carbamoyl group (where R
^a, R^b, R^dAnd R^eAre independently alkylene
R represents a group^cIs an aryloxy or cycloalkyl group
And at least selected from the group consisting of alkenyl groups
An alkylene group which may be substituted with one substituent
And R^fIs an alkylene substituted with a hydroxyl group
A reactive polymer comprising:
48.99 to 98.98 mol% of the structural unit (I),
The unit (II) is present in an amount of 0.01 to 50 mol% and the structural unit (I)
II) in an amount of 0.01 to 25 mol% and the structural unit (I)
V) a reactive polymer containing from 1 to 29.99 mol%
[1] The pressure-sensitive adhesive composition according to [1]. [6] The weight average molecular weight of (A) is 1 × 10^Four~ 1 × 10
⁶[1] The pressure-sensitive adhesive composition according to [1]. [7] (B) is an alkyl alcohol having 1 to 14 carbon atoms
(1).
Pressure-sensitive adhesive composition described above. [8] The amount of the double bond introduced into the side chain of (A) is 0.00
The pressure-sensitive adhesive according to [1], which has a value of from 0.5 to 0.500 meq / g.
Composition.

[9] (A) is 1 to 80 parts by weight, (B) is 1 to 80 parts by weight, (C) is 1 to 30 parts by weight, and (D) is 0.01 to 90 parts by weight.
The pressure-sensitive adhesive composition according to [1], containing 10 parts by weight. [10] The pressure-sensitive adhesive composition according to [1], further comprising (E) a polyfunctional (meth) acrylate monomer or a polyfunctional oligomer. [11] (A) 1 to 80 parts by weight, (B) 1 to 80 parts by weight, (C) 1 to 30 parts by weight, (D) 0.01 to 1 part by weight
The pressure-sensitive adhesive composition according to [10], comprising 0 parts by weight and 0.001 to 10 parts by weight of (E). [12] An adhesive obtained by curing the adhesive composition according to any one of [1] to [11].

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION In the present specification, "(meth) acryl" in the compounds represents acryl or methacryl, and "(meth) acrylate" represents acrylate or methacrylate. Similarly, “(meth) acryloyl” represents acryloyl or methacryloyl, “(meth) acrylonitrile” represents acrylonitrile or methacrylonitrile, and “(meth) allyl” represents allyl or methallyl.

In the present invention, the "alkyl group" includes
Preferably, a linear or branched alkyl group having 1 to 14 carbon atoms is exemplified. For example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-
Butyl, tert-butyl, pentyl, isopentyl,
Neopentyl, tert-pentyl, hexyl, isohexyl, neohexyl, n-octyl, isooctyl,
2-ethylhexyl, decyl, dodecyl and the like can be mentioned. More preferably, a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably, a linear or branched alkyl group having 1 to 8 carbon atoms is used.

The "alkylene group" is preferably a linear or branched alkylene group having 1 to 18 carbon atoms, for example, methylene, ethylene, trimethylene,
Tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, dimethylmethylene, diethylmethylene, propylene, methylethylene, ethylethylene, propylethylene, isopropylethylene, methylpentaethylene,
Ethyl hexamethylene, dimethylethylene, methyltriethylene, dimethyltrimethylene, octadecylmethylene and the like can be mentioned. More preferably, a linear or branched alkylene group having 1 to 10 carbon atoms, more preferably, a linear or branched alkylene group having 1 to 6 carbon atoms is used.

The aryl group in the "aryloxy group" is preferably an aryl group having 6 to 12 carbon atoms, and more preferably a phenyl group.

The "cycloalkyl group" is preferably a cycloalkyl group having 3 to 12 carbon atoms, and more preferably a cyclohexyl group.

The "alkenyl group" is preferably an alkenyl group having 2 to 12 carbon atoms, and more preferably a pentenyl group.

In the present invention, the "alkylene group which may be substituted" means an unsubstituted alkylene group or an alkylene group substituted with at least one substituent.

The pressure-sensitive adhesive composition of the present invention comprises the following (A):
(B), (C) and (D). (A) A copolymer obtained from the following (a) and (b) or a copolymer obtained from the following (a), (b) and (c) is added with a functional group derived from (b) and the following ( d) a reactive polymer having a double bond introduced through reaction with a functional group: (a) (meth) acrylate monomer (b) a monomer copolymerizable with (a) and having a functional group ( c) a monomer copolymerizable with (a) and (b); (d) a compound having a functional group capable of forming a bond by reacting with a functional group of (b) and a double bond, (B) a (meth) acrylate ester A monomer, (C) a monofunctional monomer copolymerizable with (B), (D) a photopolymerization initiator, or a mixture of a photopolymerization initiator and a sensitizer.

In the reactive polymer (A), the (meth) acrylate monomer (a) is preferably a (meth) acrylate of a linear or branched alkyl alcohol having 1 to 14 carbon atoms. Examples of the monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, and n.
-Octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, etc., more preferably, ethyl (meth) acrylate, n-butyl (Meth) acrylate, isooctyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.

The amount of the monomer (a) used is 50 to 99% by weight, preferably 70 to 99% by weight, based on the total amount of the monomers used for forming the copolymer.

In the reactive polymer (A), two or more of the above monomers (a) may be used in combination.

In the reactive polymer (A), the monomer (b) which is copolymerizable with the above (a) and has a functional group is preferably a double polymer which can be copolymerized with a (meth) acrylate monomer. A monomer having a bond and having at least one functional group other than the double bond is exemplified. Examples of the functional group include a hydroxyl group, a carboxyl group, an epoxy group, an isocyanato group and the like, and preferably a hydroxyl group and a carboxyl group.

Specific examples of the monomer (b) having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and phenylglycidyl ether (meth). Examples include acrylate and the like, and preferably include 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.

Specific examples of the monomer (b) having a carboxyl group include (meth) acrylic acid, itaconic acid, β
-(Meth) acryloyloxyethyl hydrogen succinate and the like, and preferably (meth) acrylic acid.

Specific examples of the monomer (b) having an epoxy group include glycidyl (meth) acrylate and (meth) allyl glycidyl ether, and preferably glycidyl (meth) acrylate.

Specific examples of the monomer (b) having an isocyanate group include vinyl isocyanate, (meth) acrylic isocyanate, 2- (meth) acryloyloxyethyl isocyanate and the like, and preferably methacrylic isocyanate, 2-methacryloyl Oxyethyl isocyanate is mentioned.

The amount of the monomer (b) used is 1 to 50% by weight, preferably 1 to 30% by weight, based on the total amount of the monomers used to form the copolymer.

In the reactive polymer (A), two or more of the above monomers (b) may be used in combination.

In the reactive polymer (A), the monomer (c) copolymerizable with the above (a) and (b) preferably has a glass transition point of 3 as a polymer.
Monomers having a temperature of 0 to 106 ° C, for example, vinyl acetate, styrene, (meth) acrylonitrile, (meth) acrylic acid, (meth) acrylamide, and the like, more preferably (meth) acrylic acid, vinyl acetate, (meth) Acrylonitrile is mentioned.

The monomer (c) is used as a substitute for a part (20% by weight or less) of the predetermined (a).

In the reactive polymer (A), two or more of the above monomers (c) may be used in combination.

The copolymer obtained from each of the monomers (a) and (b) or (a), (b) and (c) can be produced by ordinary solution polymerization. It can also be produced by bulk polymerization or suspension polymerization. The polymerization initiator is not particularly limited,
Examples of the azobis-based radical generator include, for example, 2,
2'-azobisisobutyronitrile (AIBN), 2,
2′-azobis (2-methylbutyronitrile) and the like. The amount of the polymerization initiator to be used is 0.05 to 10.0 parts by weight (preferably 0.1 to 100 parts by weight) based on 100 parts by weight of the whole monomers used to form the copolymer.
-5 parts by weight). Examples of the solvent used for performing the solution polymerization include ketone, ester, and aromatic organic solvents, among which toluene, ethyl acetate,
In general, good solvents of acrylic polymers such as benzene, methyl cellosolve, ethyl cellosolve, acetone, and methyl ethyl ketone are mentioned, and among them, solvents having a boiling point of 60 to 120 ° C are preferable. In the case of solution polymerization, use the above solvent,
The reaction temperature is 40 to 120C (preferably 60 to 11C).
0 ° C.) and a reaction time of 3 to 10 hours (preferably 5 to
8 hours). After completion of the reaction, the solvent is removed to obtain a copolymer. Further, a double bond introduction reaction described below can be carried out without removing the solvent.

The molecular weight of the copolymer obtained is used.
Adjust by adjusting the solvent and reaction temperature.
Can be. To obtain the desired molecular weight copolymer
The solvent used, the reaction temperature, etc.
Can be determined as appropriate depending on the
(A) 9-ethylhexyl acrylate as a mer
0 parts by weight, (b) 2-hydroxyethyl acrylate
10 parts by weight, 10 parts by weight of (c) methyl methacrylate
Parts, and 110 parts by weight of toluene as a solvent,
When the reaction temperature is 90 to 100 ° C., the molecular weight is 5 × 1
0^Four~ 1 × 10^FiveA degree of copolymer is obtained. Also,
(A) 2-ethylhexyl acrylate as a nomer
90 parts by weight, (b) 2-hydroxyethyl acrylate
10 parts by weight, and (c) 10 parts by weight of methyl methacrylate
Parts and 110 parts by weight of ethyl acetate as solvent
When the reaction temperature is 60 to 70 ° C., the molecular weight is 8 ×
10 ⁶~ 1 × 10⁷A degree of copolymer is obtained.

In addition, a specific solvent may be mixed with the above solvent.
And controlling the molecular weight of the resulting copolymer
Can be. Such solvents include, for example, mercap
Tan-based (for example, n-octyl mercaptan, n-dode)
Sir mercaptan, t-dodecyl mercaptan, merca
Peptethanol, etc.), carbon tetrachloride (for example,
Butyl chloride, propylene chloride and the like).
Ratio of mixing these solvents with the solvent used in the above reaction
Depends on the monomer, solvent, reaction conditions, etc.
Can be determined as appropriate, for example,
(A) 90 weight of 2-ethylhexyl acrylate
Parts, (b) 10-fold 2-hydroxyethyl acrylate
Parts by weight, (c) 10 parts by weight of methyl methacrylate,
And 110 parts by weight of ethyl acetate as a solvent and n-
Using 0.5 parts by weight of decyl mercaptan, the reaction temperature
Is 60 to 70 ° C., the molecular weight is 5 × 10^Four~ 1 ×
10 ^FiveA degree of copolymer is obtained.

The glass transition temperature of the above copolymer is preferably from -70 to 10 ° C, particularly preferably from -60 to 0 ° C, from the viewpoints of adhesive properties, heat resistance and solvent removal. In order to keep the glass transition temperature of the copolymer in such a range, (a) in the above (A) should be replaced with (1) a (meth) acryl of a linear or branched alkyl alcohol having 6 to 14 carbon atoms. A mixture of an acid ester monomer and (2) a (meth) acrylic acid ester monomer of a linear or branched alkyl alcohol having 1 to 5 carbon atoms may be used, and the ratio of the amounts of both may be appropriately adjusted. An appropriate ratio differs depending on (1) and (2) to be used.
-When using ethylhexyl acrylate and using methyl methacrylate as (2), the ratio of the amount of (2) used to (1) ((1) / (2); weight ratio) is:
85/15 to 35/65 (preferably 75/25 to 4
0/60).

After obtaining the above copolymer, a functional group derived from (b) present in the side chain of the copolymer has a double bond and a functional group other than the double bond. Reacting with the functional group of the compound (d) having at least one functional group that forms a bond by reacting with the functional group of (b),
A double bond derived from (d) can be introduced into the side chain of the copolymer. The “double bond” in (d) means a group having a double bond that can be copolymerized with a (meth) acrylate monomer, for example, a vinyl group,
Examples include an isopropenyl group, a (meth) allyl group, and a (meth) acryloyl group, and preferably a (meth) acryloyl group.

The functional group which reacts with the functional group of (b) in the compound (d) to form a bond can be variously selected according to the type of the functional group of (b). For example, (b)
When the functional group of (d) is a hydroxyl group, the functional group of (d) includes an isocyanato group, an epoxy group, an aldehyde group, a carboxyl group, a methylol group, a hydroxyl group,
Examples include an ethyleneimino group, and preferably an isocyanato group. Specific examples of (d) having an isocyanato group include those specified as specific examples of the monomer (b). Conversely, when the functional group of (b) is an isocyanato group, the functional group of (d) is preferably a hydroxyl group. As a specific example of (d) having a hydroxyl group, a specific example of the above monomer (b) Those specified.

When the functional group (b) is a carboxyl group, examples of the functional group (d) include an epoxy group and a hydroxyl group, preferably an epoxy group. Specific examples of (d) having an epoxy group include those specified as specific examples of the monomer (b). Conversely, when the functional group of (b) is an epoxy group, the functional group of (d) is preferably a carboxyl group,
Specific examples of (d) having a carboxyl group include those specified as specific examples of the monomer (b).

The amount of double bonds introduced into the copolymer through the reaction between the functional group derived from (b) and the functional group described in (d) is preferably 0.0005 to 0.500 meq / g.
And particularly preferably 0.005 to 0.1 meq /
g. The amount of double bond introduced here is a value calculated from the amount of compound (d) having a double bond,
It is expressed as a double bond equivalent (in terms of vinyl group) per 1 g of the obtained reactive polymer (A). If the amount of the double bond introduced is less than 0.0005 meq / g, the adhesive obtained by curing the adhesive composition tends to have insufficient cohesive strength and poor heat resistance holding power. 0.500me
If it exceeds q / g, the tack tends to be insufficient and the adhesion reliability at high temperatures tends to be low.

In the reactive polymer (A), two or more of the above compounds (d) may be used in combination.

The reaction for introducing a double bond into the copolymer is as follows:
A double bond may be introduced into all of the structural units derived from (b) present in the copolymer, or some of them may not be introduced. When a structural unit derived from (b) into which a double bond is not introduced is present in the reactive polymer (A), its abundance is preferably 0.01% of the total structural units of the reactive polymer (A). ２５25 mol%, more preferably 0.05-20 mol%. When the structural unit derived from (b) into which a double bond is not introduced exceeds 25 mol%, a crosslinking reaction occurs with other functional groups in the pressure-sensitive adhesive composition at a high temperature. The pressure-sensitive adhesive obtained by curing becomes insufficient in tack and tends to have low adhesion reliability at high temperatures.

The reaction for introducing a double bond into the copolymer is as follows:
It can be performed according to a known method. For example, when the functional group derived from (b) in the copolymer is a hydroxyl group and the functional group of (d) that reacts with the hydroxyl group is an isocyanato group, the introduction reaction can be represented as follows. Reaction formula 1

[0048]

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(Wherein R ³ , R ⁴ , R ⁶ and R ⁷ are as defined above) In this reaction, the hydroxyl group of the structural unit (III-a) derived from (b) of the copolymer is Compound (d) (V
-A) reacts with the isocyanato group to form a bond,
Since II-a becomes II-a, a double bond derived from compound (d) is introduced into the side chain of the copolymer as a result.
The above reaction uses, for example, a chemical equivalent of Va equal to the hydroxyl group of III-a, and a reaction temperature of 20 to
100 ° C., preferably 40 to 80 ° C., particularly preferably at the boiling point of the solvent used (under reflux), the reaction time is 2 hours.
The reaction can be performed for 10 to 10 hours, preferably 3 to 6 hours. Examples of the solvent to be used include a solvent used in the polymerization reaction of the acrylic copolymer. After the polymerization reaction, the solvent can be used for the double bond introduction reaction without removing the solvent. The reaction can be carried out in the presence of a catalyst and a polymerization inhibitor, if necessary. Here, the catalyst is preferably a tin-based or amine-based substance, and specific examples include dibutyltin laurate and triethylamine. The catalyst is used in an amount of 0.01 to 20.0 with respect to the compound having a double bond to be used.
What is necessary is just to add in the range of weight%. Further, as the polymerization inhibitor, hydroquinone, hydromonomethyl ether,
2,6-di-t-butyl hydrotoluene and the like are used, and the amount of use is 0.01 to 5.0% by weight based on the compound (d) having a double bond to be used. The progress of the reaction may be determined by determining the presence or absence of the isocyanato group in the reaction system by infrared absorption spectrum (IR), and stopping the reaction when the absorption disappears.

When the functional group derived from (b) in the copolymer is a carboxyl group and the functional group of (d) which reacts with the carboxyl group is an epoxy group, the reaction can be represented as follows. Reaction formula 2

[0051]

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(Wherein R ³ , R ⁴ , R ⁶ and R ⁷ have the same meanings as described above). In this reaction, as in Reaction Scheme 1, the structural unit derived from the copolymer (b) (III- The carboxyl group of b) reacts with the epoxy group of compound (d) (Vb) to form a bond, and III-b becomes II-b. A bond is introduced into the side chain of the copolymer. The above reaction can be carried out, for example, using the same chemical equivalent of Vb as the carboxyl group of III-b under the same reaction conditions as in Reaction Scheme 1. However, the catalyst is preferably an amine-based or ammonium chloride-based substance. Specifically, as the amine-based substance, triethylamine, tributylamine, dimethylaminoethanol, diethylaminoethanol, methylamine, ethylamine, n-propylamine, Isopropylamine,
Examples thereof include 3-methoxypropylamine, butylamine, allylamine, hexylamine, 2-ethylhexylamine, and benzylamine. Examples of the ammonium chloride-based substance include triethylbenzylammonium chloride. When these are used as a catalyst, the compound (d) having a double bond to be used is used in an amount of 0.0
What is necessary is just to add in the range of 1-20.0 weight%. Further, the polymerization inhibitor can be the same as in the reaction formula 1. The progress of the reaction may be measured by measuring the acid value of the reaction system and stopping the reaction when the acid value becomes zero.

Preferred reactive polymers (A) in the present invention include the following structural units (I) and (II):

[0054]

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[Wherein, R ¹ represents hydrogen or a methyl group, R ² represents an alkyl group, R ³ represents hydrogen, a methyl group,
-R ^4a -R ^5a -R ^6a -C (-R ^7a ) = CH ₂ or -R
^4a -R ^8a represents, R ^4, R ^4a and R ^4b or is absent independently of each other, or a carbonyl group, an alkylene ^{group, -R a -O-R b -} , - COO-R c - or -C
^{OO-R d -OCO-R e} - represents, R ⁵ and R ^5a independently of one another are -OCONH -, - NHCOO -, - C
OO-R ^f - or an -R ^f -OCO-, or R ⁶ and R ^6a are not present independently of each other, or a carbonyl group, an alkylene ^{group, -R b -O-R a -} , - R c -
OCO- or an ^{-R e -COO-R d -OCO-,} R 7 and R ^7a represents hydrogen, methyl or -R ^4b -R ^8b independently of each other, and R ^8a and R ^8b are independently Represents a hydroxyl group, a carboxyl group, an epoxy group or an isocyanato group (where R ^a ,
R ^b , R ^d and R ^e independently represent an alkylene group, and R ^c is an alkylene which may be substituted with at least one substituent selected from the group consisting of an aryloxy group, a cycloalkyl group and an alkenyl group. Represents a group,
And R ^f represent an alkylene group substituted with a hydroxyl group)), wherein the structural unit (I) is 50 to 99.99 mol% and the structural unit (II) is 0.01% ５０50 mol%.

In particular, the structural unit (I) may be 60-99.
Those containing 95 mol% and 0.05 to 40 mol% of the structural unit (II) are particularly preferred.

Further, as another preferred reactive polymer (A) in the present invention, the following structural units (I) and (I)
I) and (III):

[0058]

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[Wherein, R¹Represents a hydrogen or methyl group
Then R^TwoRepresents an alkyl group;^ThreeIs hydrogen, methyl,
-R^4a-R^5a-R^6a-C (-R^7a) = CH_TwoOr -R
^4a-R^8aAnd R^Four, R^4aAnd R^4bAre independent of each other
Not present, or carbonyl group, alkylene
Group, -R^a-OR^b-, -COO-R^c-Or -C
OO-R^d-OCO-R^e-Represents R^FiveAnd R^5aIs
Independently of one another, -OCONH-, -NHCOO-, -C
OO-R^f-Or -R^f-OCO-, R⁶And
And R^6aDo not exist independently of each other or
Nil group, alkylene group, -R^b-OR^a-, -R^c−
OCO- or -R^e-COO-R^d-OCO-
Then R⁷And R^7aAre independently of each other hydrogen, methyl or
Or -R^4b-R^8bAnd R⁸, R^8aAnd R
^8bAre independently of each other a hydroxyl group, a carboxyl group,
Represents an epoxy group or an isocyanato group (where,
R^a, R^b, R ^dAnd R^eAre independent of each other
A group represented by^cIs an aryloxy group, cycloalkyl
At least one selected from the group consisting of
Also represents an alkylene group which may be substituted with one substituent
Represents, and R^fIs an alkyl substituted with a hydroxyl group
A reactive polymer comprising:
49.99 to 99.98 mol% of the structural unit (I),
The structural unit (II) in an amount of 0.01 to 50 mol% and the structural unit
Those containing 0.01 to 25 mol% of the position (III)
I can do it.

In particular, the structural unit (I) is
99.90 mol%, structural unit (II) is 0.05 to 40
Those containing from 0.05 to 20 mol% of the structural unit (III) are particularly preferred.

Still another preferred reactive polymer (A) in the present invention includes the following structural units (I) and (I)
I) and (IV):

[0062]

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[Wherein R¹Or R⁹Are independent of each other
Represents hydrogen or a methyl group;^TwoRepresents an alkyl group,
R^ThreeIs hydrogen, a methyl group, -R^4a-R^5a-R^6a-C (-R
^7a) = CH_TwoOr -R^4a-R^8aAnd R^Four, R^4aYou
And R^4bDo not exist independently of each other or
Bonyl group, alkylene group, -R^a-OR^b-, -CO
OR^c-Or -COO-R^d-OCO-R^e-
Then R^FiveAnd R^5aAre independently -OCONH-,
-NHCOO-, -COO-R^f-Or -R^f-OC
O-, R⁶And R^6aDo not exist independently of each other
Squid or carbonyl group, alkylene group, -R^b−
OR^a-, -R^c-OCO- or -R ^e-COO-
R^d-OCO-, R⁷And R^7aAre independent of each other
Hydrogen, methyl group or -R^4b-R^8bAnd R^8aAnd
And R^8bAre independently a hydroxyl group, a carboxyl
Group, an epoxy group or an isocyanato group; and
R^TenIs acetoxy, phenyl, cyano, carboxyl
Represents a sil group or a carbamoyl group (where R^a, R
^b, R^dAnd R^eRepresents an alkylene group independently of each other
Then R^cIs an aryloxy group, a cycloalkyl group and
At least one selected from the group consisting of alkenyl groups
Represents an alkylene group which may be substituted with a substituent,
And R^fRepresents an alkylene group substituted with a hydroxyl group.
A) a reactive polymer comprising the structural unit
49 to 99.99 mol% of (I), the structural unit (II)
0.01 to 50 mol% and the structural unit (IV) is 1
To 29.99 mol%.

In particular, when the structural unit (I) is 50.05-
95 mol%, structural unit (II) is 0.05 to 45 mol%
And 4.95 to 24.95 mol% of the structural unit (IV)
Those containing are particularly preferred.

Still another preferred reactive polymer (A) in the present invention includes the following structural unit (I):
(II), (III) and (IV):

[0066]

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[Wherein, R¹Or R⁹Are independent of each other
Represents hydrogen or a methyl group;^TwoRepresents an alkyl group,
R^ThreeIs hydrogen, a methyl group, -R^4a-R^5a-R^6a-C (-R
^7a) = CH_TwoOr -R^4a-R^8aAnd R^Four, R^4aYou
And R^4bDo not exist independently of each other or
Bonyl group, alkylene group, -R^a-OR^b-, -CO
OR^c-Or -COO-R^d-OCO-R^e-
Then R^FiveAnd R^5aAre independently -OCONH-,
-NHCOO-, -COO-R^f-Or -R^f-OC
O-, R⁶And R^6aDo not exist independently of each other
Squid or carbonyl group, alkylene group, -R^b−
OR^a-, -R^c-OCO- or -R ^e-COO-
R^d-OCO-, R⁷And R^7aAre independent of each other
Hydrogen, methyl group or -R^4b-R^8bAnd R⁸, R
^8aAnd R^8bAre independently of each other a hydroxyl group,
Represents a xyl group, an epoxy group or an isocyanato group.
Rabi ni R^TenRepresents an acetoxy group, a phenyl group, a cyano group,
Represents a ruboxyl group or a carbamoyl group (where R
^a, R^b, R^dAnd R^eAre independently alkylene
R represents a group^cIs an aryloxy or cycloalkyl group
And at least selected from the group consisting of alkenyl groups
An alkylene group which may be substituted with one substituent
And R^fIs an alkylene substituted with a hydroxyl group
A reactive polymer comprising:
48.99 to 98.98 mol% of the structural unit (I),
The unit (II) is present in an amount of 0.01 to 50 mol% and the structural unit (I)
II) in an amount of 0.01 to 25 mol% and the structural unit (I)
V) of 1 to 29.99 mol%.
You.

In particular, the structural unit (I) may be
94.95 mol%, 0.05 to 40 of the structural unit (II)
Particularly preferred is one containing 0.05 to 20 mol% of the structural unit (III) and 4.95 to 24.95 mol% of the structural unit (IV).

In the above structural unit (I), R ¹ is hydrogen or a methyl group, preferably hydrogen, and R ² is a methyl group, an ethyl group, an n-butyl group, an isobutyl group, a pentyl group, a hexyl group, Particularly preferred are n-octyl, isooctyl, 2-ethylhexyl, decyl or dodecyl, preferably ethyl, n-butyl, isooctyl or 2-ethylhexyl.

The structural unit (II) includes R^ThreeBut water
, Methyl, carboxyl, carboxymethyl, etc.
Or -R^Four'-R ^Five'-R⁶'-C (-R^{7 '}) = CH_Two(here
And R^Four'Is absent or a methylene group;
^Five'Is -COO-CH_TwoCH (-OH)-and R⁶'Is
-CH_Two-OCO- or -CH_Two-O-CH_Two-
And R^{7 '}Is hydrogen or a methyl group, preferably hydrogen
), Preferably a hydrogen or methyl group, more preferably
Is hydrogen, and R^FourDoes not exist or
Nyl group, methylene group, -CH_Two-O-CH _Two-, -CO
O- (CH_Two)_n-(Where n is a positive integer from 1 to 4
Number), -COO-CH_TwoCH (-CH_Two-OC
₆H_Five)-Or -COO- (CH_Two)_Two-OCO-
(CH_Two)_Two-, Preferably not present, or-
COO-CH_Two-, -COO- (CH_Two)_Two-Or-
COO- (CH_Two)_Four-, More preferably absent
Or -COO- (CH_Two)_Two-Or -COO
− (CH_Two) _Four-And R^FiveIs -OCONH-, -N
HCOO-, -COO-CH_TwoCH (-OH)-or
-CH (-OH) CH_Two-OCO-, preferably -OC
ONH- or -COO-CH_TwoCH (-OH)-
R⁶Is not present, or a carbonyl group or methyl
Len group, -CH_Two-O-CH _Two-,-(CH_Two)_n-O
CO- (where n is a positive integer from 1 to 4), -CH (-
CH_Two-OC₆H_Five) CH_Two-OCO- or-(C
H_Two)_Two-COO- (CH_Two)_Two-OCO-, preferably
Is absent or a carbonyl group, -CH_Two-O
-CH_Two-, -CH_Two-OCO- or-(CH_Two)
_Two-OCO-, more preferably a carbonyl group, -CH_Two
-OCO- or-(CH_Two)_Two-OCO-
And R⁷Is hydrogen, methyl, carboxyl, or
A boxymethyl group, preferably a hydrogen or methyl group, and more
Those which are preferably hydrogen are particularly preferred.

As the structural unit (III), R ³ and R ⁴ are each the above-mentioned particularly preferable structural unit (I
Particularly preferred are the same as R ³ and R ⁴ shown in I), and wherein R ⁸ is a hydroxyl group, a carboxyl group, an epoxy group or an isocyanato group, preferably a hydroxyl group or a carboxyl group, more preferably a hydroxyl group. .

In the structural unit (IV), R ⁹ is the same as R ¹ shown in the particularly preferred structural unit (I), and R ¹⁰ is acetoxy, phenyl, cyano, carboxyl or carbamoyl. Those which are groups, preferably carboxyl groups, acetoxy groups or cyano groups, are particularly preferred.

The range of the molecular weight of the reactive polymer (A) is as follows.
Preferably, the weight average molecular weight is 1 × 10 ⁴ to 1 × 10 ⁶ ,
More preferably, it is in the range of 5 × 10 ⁴ to 8 × 10 ⁵ .
Here, the weight average molecular weight is a value measured by a measuring method described later. When the weight average molecular weight is less than 1 × 10 ⁴ , the pressure-sensitive adhesive composition obtained by mixing with other components has a low viscosity, which may cause a problem in coating suitability.
The pressure-sensitive adhesive obtained by curing the pressure-sensitive adhesive composition,
Insufficient cohesion tends to result in poor heat retention. On the other hand, if the weight average molecular weight exceeds 1 × 10 ⁶ , the resulting pressure-sensitive adhesive tends to have insufficient tackiness, and the adhesion reliability at high temperatures tends to be low.

The amount of the reactive polymer (A) used in the pressure-sensitive adhesive composition of the present invention is preferably 1 to 80 parts by weight, more preferably 10 to 70 parts by weight. If the amount is less than 1 part by weight, the viscosity of the pressure-sensitive adhesive composition tends to be too low, and if it is more than 80 parts by weight, the viscosity of the pressure-sensitive adhesive composition tends to be too high, so that the coating aptitude is problematic. May occur.

In the pressure-sensitive adhesive composition of the present invention, two or more reactive polymers (A) may be used in combination.

The reactive polymer (A) is compatible with the other components in the pressure-sensitive adhesive composition of the present invention, and easily adjusts the viscosity of the composition by adjusting the molecular weight and the amount used. Thus, the composition is useful as a viscosity modifier for the composition. In addition, the reactive polymer (A)
Has a double bond in the side chain, and thus is useful as a crosslinking agent when the pressure-sensitive adhesive composition of the present invention cures. Therefore,
By appropriately adjusting the molecular weight of (A) and the amount of double bonds to be introduced, when the pressure-sensitive adhesive composition of the present invention is cured to form a pressure-sensitive adhesive, the pressure-sensitive adhesive composition does not become insufficient in tackiness and has sufficient heat resistance. A cohesive force that produces a holding force can be provided. Therefore, by containing the reactive polymer (A), the pressure-sensitive adhesive composition of the present invention can be easily adjusted in viscosity and has excellent coating suitability, and the pressure-sensitive adhesive obtained by curing the composition includes:
The adhesive strength, the heat-resistant holding power, and the adhesive reliability at high temperatures are excellent.

In the pressure-sensitive adhesive composition of the present invention, (meth)
As the acrylate monomer (B), a (meth) acrylate monomer of an alkyl alcohol having preferably 1 to 14 carbon atoms (preferably 4 to 14 carbon atoms), for example, methyl (meth) acrylate, ethyl ( (Meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) Acrylate, dodecyl (meth) acrylate and the like can be mentioned, and more preferably, n-butyl (meth) acrylate, isooctyl (meth) acrylate and 2-ethylhexyl (meth) acrylate can be mentioned.

The amount of (B) used in the pressure-sensitive adhesive composition of the present invention is preferably 1 to 80 parts by weight, more preferably 1 to 80 parts by weight.
0 to 70 parts by weight.

In the pressure-sensitive adhesive composition of the present invention, two or more monomers (B) may be used in combination.

The monofunctional monomer (C) copolymerizable with the monomer (B) is preferably an ultraviolet-polymerizable monomer, for example, (meth) acrylic acid, cyclic alkyl, or a linear or linear alkyl group having 1 to 3 carbon atoms. Examples include (meth) acrylic acid ester monomers of branched alkyl alcohols and other (meth) acrylic acid derivatives. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobonyl (meth) acrylate, Ethoxy (meth) acrylate, butoxy (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, vinyl acetate and the like can be mentioned.

The amount of (C) used in the pressure-sensitive adhesive composition of the present invention is preferably 1 to 30 parts by weight, more preferably 5 to 30 parts by weight.
２５25 parts by weight.

In the pressure-sensitive adhesive composition of the present invention, two or more monofunctional monomers (C) may be used in combination.

The above (B) and (C) show that the pressure-sensitive adhesive obtained by curing the pressure-sensitive adhesive composition of the present invention has a glass transition temperature of -1.
When the temperature exceeds 5 ° C., the adhesive strength (tack) at room temperature decreases. Therefore, it is preferable to use the adhesive in an appropriate ratio so that the glass transition temperature does not exceed −15 ° C.
The appropriate ratio varies depending on (B) and (C) used. For example, when 2-ethylhexyl acrylate is used as (B) and methyl methacrylate is used as (C), the ratio of (B) to (B) The ratio of the amounts used ((B) / (C); weight ratio) is 95/5 to 30/70,
Preferably it is 80/20 to 40/60.

The pressure-sensitive adhesive composition of the present invention contains a photopolymerization initiator or a mixture (D) of a photopolymerization initiator and a sensitizer in order to be curable by ultraviolet rays or the like. In general, it is well known that a curing reaction is accelerated when a photoinitiator and a sensitizer are used in combination.

As the photopolymerization initiator in the above (D), acetophenones (for example, 2,2-dimethoxy-
1,2-diphenylethan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one and the like, benzophenones (for example, benzophenone, benzoylbenzoic acid, hydroxybenzophenone, 3,
Carbonyl compounds such as 3′-dimethyl-4-methoxybenzophenone, acrylated benzophenone, etc.), Michler ketones (eg, Michler ketone), and benzoins (eg, benzoin, benzoin methyl ether, benzoin isopropyl ether), tetramethylthiurammono Sulfur compounds such as sulfide and thioxanthones (for example, thioxanthone, 2-chlorothioxanthone and the like), and azo compounds (for example, azobisisobutylnitrile and the like) and the like, preferably 2,2-dimethoxy-1, 2-diphenylethan-1-one, benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one.

The sensitizer in (D) includes n
-Butylamine, di-n-butylamine, tri-n-butylphosphine, allylthiouric acid, triethylamine,
Examples thereof include diethylaminoethyl methacrylate and the like, preferably, diethylaminoethyl methacrylate and triethylamine.

In the mixture of the photopolymerization initiator and the sensitizer in (D), the ratio of the photopolymerization initiator and the sensitizer used (photopolymerization initiator / sensitizer; weight ratio) is 20. / 80-
80/20, preferably 30/70 to 70/30.

The amount of (D) used in the pressure-sensitive adhesive composition of the present invention is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight. If the amount is less than 0.01 part by weight, the effect of addition may not be expected,
If the amount exceeds 10 parts by weight, the curing rate is too high, so that the resulting pressure-sensitive adhesive (copolymer) has a low molecular weight,
This is because the heat retention tends to be insufficient.

In the pressure-sensitive adhesive composition of the present invention, two or more of the above (D) may be used in combination.

Since the pressure-sensitive adhesive obtained by curing the pressure-sensitive adhesive composition of the present invention tends to have insufficient cohesive strength, the pressure-sensitive adhesive composition of the present invention is used as a cross-linking agent in a polyfunctional (meth) acrylic acid ester monomer or It is preferable to contain a polyfunctional oligomer (E).

Examples of the polyfunctional (meth) acrylate monomer in the above (E) include 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, , 9-nonanediol diacrylate, polyethylene glycol (# 200) diacrylate, polyethylene glycol (# 400) diacrylate, polyethylene glycol (# 600) diacrylate, diethylene diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate , Tripropylene glycol diacrylate, propylene glycol (# 400) diacrylate, 2,2'-bis [4
-(Acryloxydiethoxy) phenyl] propane, hydroxypivalic acid ester neopentyl glycol diacrylate, trimethylolpropane diacrylate, bis (acryloxyethoxy) bisphenol A,
Bis (acryloxyethoxy) tetrabromobisphenol A, 1,3-bis (hydroxyethyl) 5,5-dimethylhydantoin 3-methylpentanediol diacrylate, trimethylolpropane triacrylate,
Pentaerythritol triacrylate, tri (dihydroxyethyl) isocyanate pentaerythritol monohydroxypentaacrylate, tetramethylolmethanetetraacrylate, dipentaerythritol hexaacrylate or methacrylates equivalent thereto, and the like, preferably 1,6-hexanediol Examples include diacrylate, trimethylolpropane triacrylate, and their corresponding methacrylates.

The polyfunctional oligomer in (E) includes, for example, bifunctional urethane acrylate, tetrafunctional urethane acrylate, hexafunctional urethane acrylate,
Epoxy acrylates or methacrylates corresponding thereto are exemplified, and preferably, bifunctional urethane acrylate and tetrafunctional urethane acrylate are exemplified.

The amount of (E) used in the pressure-sensitive adhesive composition of the present invention is preferably 0.001 to 10 parts by weight, more preferably 0.005 to 5 parts by weight. 0.
If the amount is less than 001 parts by weight, the cohesive strength becomes insufficient, and there is a possibility that a problem may occur in the heat-resistant holding power.

In the pressure-sensitive adhesive composition of the present invention, two or more of the above (E) may be used in combination.

The pressure-sensitive adhesive composition of the present invention can contain components other than those described above, for example, a leveling agent and an antifoaming agent, if necessary.

Since the pressure-sensitive adhesive composition of the present invention contains a photopolymerization initiator and the like, the pressure-sensitive adhesive composition is cured by a photopolymerization reaction using ultraviolet rays or the like to form a pressure-sensitive adhesive. This reaction is performed, for example, at a wavelength of 352.
It can be performed using a straight tubular fluorescent lamp for insect traps that selectively emits light of nm. In this case, it is preferable to use several fluorescent lamps and to adjust the intensity to about 1.0 mW / cm ² . In order to shorten the reaction time, the irradiation intensity may be increased stepwise. At this time, it is preferable to proceed with irradiation of ultraviolet rays (wavelength 352 nm) generated from a low-pressure, medium-pressure, high-pressure or ultra-high-pressure mercury lamp. There must be. In addition, when irradiating with ultraviolet rays, it is hindered by oxygen radicals generated from air in an air atmosphere. Therefore, it is preferable to replace the air with an inert gas or coat the reaction system with a film or the like to block the air.

The pressure-sensitive adhesive composition of the present invention is cured by a photopolymerization reaction as described above, and does not contain an organic solvent which evaporates and evaporates when the composition is cured. Therefore, in the pressure-sensitive adhesive composition of the present invention, there is no environmental problem due to VOC or the like.

Since the pressure-sensitive adhesive composition of the present invention contains the reactive polymer (A), the viscosity can be easily adjusted and the coating property is excellent, and the pressure-sensitive adhesive obtained by curing the composition can be obtained. Has excellent adhesive strength, heat-resistant holding power and adhesive reliability at high temperatures. Therefore, the pressure-sensitive adhesive composition of the present invention can be suitably used, for example, for bonding building materials, automobile assembly parts, electronic device parts, and the like.

[0099]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below with reference to embodiments.

In Examples and Comparative Examples, various pressure-sensitive adhesive compositions were produced, and then double-sided pressure-sensitive adhesive tapes were prepared therefrom. The obtained pressure-sensitive adhesive composition and double-sided pressure-sensitive adhesive tape were measured for various items and evaluated. Specifically, the viscosity was measured for the pressure-sensitive adhesive composition, and the weight average molecular weight was measured for the reactive polymer (A), which is a component thereof. Furthermore, for double-sided adhesive tape,
The adhesive strength, tack and heat retention were measured. The measurement method for each item is shown below.

[Weight average molecular weight of reactive polymer (A)] The weight average molecular weight of the reactive polymer (A) was determined by size exclusion chromatography [size exclusio].
n chromatography (SEC) or g
el permeation chromatogra
phy (GPC)]. The column uses polystyrene gel and the mobile phase is THF (tetrahydrofuran).
And the converted value from a polystyrene standard substance was used.

[Viscosity of pressure-sensitive adhesive composition] The viscosity of the pressure-sensitive adhesive composition was measured by using an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) to obtain about 1 sample.
The measurement was performed while maintaining the ml at a predetermined temperature.

[Adhesive strength of double-sided pressure-sensitive adhesive tape] The adhesive strength of the double-sided pressure-sensitive adhesive tape was measured according to JIS Z0237. As the adherend, a stainless plate having a thickness of 2 mm, a width of 30 mm, and a length of 120 mm and a polyimide film of 0.025 mm in thickness (manufactured by DuPont: Kapton 100H) polished with a water-resistant abrasive paper of No. 280 was used. The double-sided pressure-sensitive adhesive tape was cut into a width of 25 mm and a length of 100 mm, and the polyester film subjected to the single-sided peeling treatment was peeled off and temporarily attached to a stainless plate. Next, the other polyester film was peeled off, and the polyimide film was placed thereon.
Crimping was performed at 10 cm ² for 10 seconds. Next, the adhesive test piece was heated to 160 ° C.
500 hours in the air circulation oven adjusted to
It was taken out after 1,000 hours, peeled off at a speed of 300 mm / min in the direction of 180 degrees under the condition of 23 ° C. × 65% RH, and the adhesive strength was measured.

[Tack of double-sided pressure-sensitive adhesive tape] The tack of the double-sided pressure-sensitive adhesive tape was measured according to the measuring method (ball rolling method) of JIS Z0237. Peel and paste a single-sided peeled polyester film of double-sided pressure-sensitive adhesive tape cut into a length of 250 mm and a width of 15 mm on a slope with a slope angle of 30 degrees. The film was peeled off and the tack was measured.

[Heat-resistant holding power of double-sided pressure-sensitive adhesive tape] The heat-resistant holding power of the double-sided pressure-sensitive adhesive tape was measured in accordance with JIS Z0237. As the adherend, a stainless steel plate having a thickness of 2 mm and an aluminum foil having a thickness of 0.05 mm polished with No. 280 water-resistant abrasive paper were used. The bonding area is 25 × 25 mm for stainless steel plate and width 2 for aluminum foil.
The length was 5 mm and the length was 50 mm. The bonding method was performed according to the preparation of a test piece for measuring adhesive strength. After bonding, a load of 1 kgf was applied vertically from the aluminum foil side, and after leaving at 180 ° C. for 1 hour, the displacement of the bonded portion was measured.

Example 1 A 2-liter four-necked flask equipped with a condenser, a dropping funnel and a thermometer was charged with toluene (400 g), and then (a) 2-ethylhexyl acrylate (390)
g), (b) 2-hydroxyethyl acrylate (6
g), (c) acrylic acid (4 g) and AIBN (8
The mixture of g) was allowed to react at 100 to 110 ° C. for 8 hours while being dropped through a dropping funnel over about 2 hours. Then, 2-methacryloyloxyethyl isocyanate (d) (manufactured by Showa Denko: Karenz MOI) (8)
g), hydroquinone (0.16 g) and dibutyltin laurate (0.16 g) were added, and an addition reaction was performed at the same temperature for 8 hours. The presence or absence of the isocyanato group was confirmed from the infrared absorption spectrum, and the reaction was stopped when the absorption disappeared. Next, the toluene was removed from the system, and the residual solvent was removed.
% Or less to obtain an acrylic photopolymerizable polymer (reactive polymer (A)). The weight average molecular weight of this reactive polymer (A) was 5 × 10 ⁵ (GPC: converted to polystyrene). This reactive polymer (A) (100 g)
And (B) 2-ethylhexyl acrylate (1
97g), acrylic acid (3 g) as (C), 1,6-hexanediol diacrylate (manufactured by Shin-Nakamura Chemical: NK ester A-HD) (3 g) as (E), and 2,2 as (D) -Dimethoxy-1,2-diphenylethan-1-one (Irgacure 651 manufactured by Nippon Ciba Gaiki) (3 g) and diethylaminoethyl methacrylate (3 g) were added and mixed to obtain an ultraviolet-curable pressure-sensitive adhesive composition. The viscosity of this composition is 5,000 mPa
・ S / 25 ° C. Next, a transfer type double-sided pressure-sensitive adhesive tape was manufactured by the following steps. The pressure-sensitive adhesive composition was applied to one side of a 50 μm-thick transparent polyester film having both sides peeled off with silicone so as to have a thickness of about 50 μm. A 50 μm-thick transparent polyester film having one surface peeled off with silicone was placed thereon, and the thickness was adjusted by passing between rolls so that the pressure-sensitive adhesive layer had a thickness of 50 μm. Next, ultraviolet rays were irradiated until the polymerization rate became 95% or more in an irradiation furnace in which a straight tubular fluorescent lamp for insect trapping with a main wavelength of 352 nm was set as a textbook. Irradiation intensity is 1.0 mW /
cm ² , and the irradiation amount was 450 mJ / cm ² . The obtained double-sided pressure-sensitive adhesive tape was evaluated for adhesive strength, tack and heat-resistant holding power. Table 1 shows the results.

Example 2 The blending amount of the reactive polymer (A) and 2-ethylhexyl acrylate (B) in Example 1 was 3 g / 294 g.
Was prepared, and a double-sided pressure-sensitive adhesive tape was prepared and evaluated in the same manner as in Example 1. Table 1 shows the results.

Example 3 The amount of the reactive polymer (A) and 2-ethylhexyl acrylate (B) in Example 1 was 240 g / 57.
g was prepared, and a double-sided pressure-sensitive adhesive tape was prepared and evaluated in the same manner as in Example 1. Table 1 shows the results.

Example 4 The weight average molecular weight of the reactive polymer (A) in Example 1 was reduced to 1 × 10 ⁴ by using toluene (400 g) and n-dodecyl mercaptan (4 g) as a solvent during polymerization. A modified PSA composition was prepared, and a double-sided PSA tape was prepared and evaluated in the same manner as in Example 1. Table 1 shows the results.

Example 5 An adhesive composition was prepared in which the weight average molecular weight of the reactive polymer (A) in Example 1 was changed to 1 × 10 ⁶ by changing the reaction temperature during the polymerization reaction to 80 ° C. Then, a double-sided pressure-sensitive adhesive tape was prepared and evaluated in the same manner as in Example 1. Table 1 shows the results.

Example 6 In the production of the reactive polymer (A) in Example 1, the amount of (d) 2-methacryloyloxyethyl isocyanate (Karenz MOI, manufactured by Showa Denko) was changed to 0.0.
The amount of vinyl groups (the amount of double bonds) was changed to 0.3 g by changing to 33 g.
The pressure-sensitive adhesive composition was changed to 0005 meq / g, and a double-sided pressure-sensitive adhesive tape was prepared and evaluated in the same manner as in Example 1. Table 1 shows the results.

Example 7 In the production of the reactive polymer (A) in Example 1, the amount of (d) 2-methacryloyloxyethyl isocyanate (Karenz MOI manufactured by Showa Denko) was changed to 33.
5 g, and the amount of vinyl groups (the amount of double bonds) was 0.5
A pressure-sensitive adhesive composition changed to 00 meq / g was prepared, and a double-sided pressure-sensitive adhesive tape was prepared and evaluated in the same manner as in Example 1. Table 1 shows the results.

Example 8 In the production of the reactive polymer (A) in Example 1, methacrylic isocyanate (manufactured by Nippon Paint Co., Ltd .:
MAI) was used to prepare a pressure-sensitive adhesive composition, and a double-sided pressure-sensitive adhesive tape was prepared and evaluated in the same manner as in Example 1. Table 1 shows the results.

Example 9 Instead of 1,6-hexanediol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK ester A-HD) used as (E) in Example 1, trimethylolpropane triacrylate (Shin-Nakamura Chemical Co., Ltd.) Manufactured by: NK Ester A-HD)
Was used in the same amount to prepare a pressure-sensitive adhesive composition, and a double-sided pressure-sensitive adhesive tape was prepared and evaluated in the same manner as in Example 1. Table 1 shows the results.

Example 10 In place of 1,6-hexanediol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK Ester A-HD) used as (E) in Example 1, bifunctional urethane acrylate (manufactured by Toa Gosei Chemical Industry Co., Ltd.) : Aronix M-1310) was used in the same amount to prepare a pressure-sensitive adhesive composition, and a double-sided pressure-sensitive adhesive tape was prepared and evaluated in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 1 Without using the reactive polymer (A) in Example 1,
The amount of 2-ethylhexyl acrylate (B) was adjusted to 29
7 g. As a result, the viscosity of the pressure-sensitive adhesive composition was as low as 10 centipoise, and it was not possible to coat the polyester film at the set film thickness.

Comparative Example 2 In the preparation of the reactive polymer (A) in Example 1, 2-methacryloyloxyethyl isocyanate (Karenz MOI, manufactured by Showa Denko KK) used as (d) was not used. A double-sided pressure-sensitive adhesive tape was prepared and evaluated in the same manner as in Example 1 except that it had no double bond. Table 1 shows the results.

[0118]

[Table 1]

From Table 1, in Examples 1 to 10, both the adhesive strength and the heat-resistant holding power were good, and the change in the adhesive strength after standing at high temperature was small. On the other hand, in Comparative Example 1, the viscosity was as low as 10 centipoise, and the polyester film could not be applied to the set film thickness. In Comparative Example 2, the change in adhesive force after leaving at high temperature was small, but the heat-resistant holding power was poor.

[0120]

According to the present invention, the pressure-sensitive adhesive composition comprises a viscosity modifier and a reactive polymer having a double bond in a side chain which acts as a cross-linking agent upon curing. It is possible to provide an ultraviolet-curable pressure-sensitive adhesive composition having excellent workability and a pressure-sensitive adhesive obtained by curing the composition and having excellent adhesive strength, heat-resistant holding power, and adhesion reliability at high temperatures.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J011 QA01 QA02 QA03 QA04 QA05 QA06 QA08 QA09 QA12 QA13 QA14 QA22 QA23 QA24 QA25 QA34 QA35 QA37 QA38 QB02 QB03 SA06 SA22 SA26 SA32 SA34 SA61 SA79 SA01 SA83 SA01 SA83 SA01 AC04 AC06 AE01 AG01 AJ01 AJ02 AJ04 AJ08 BA02 BA06 BA07 BA08 BA10 BA13 BA19 BA23 BA24 BA26 BA28 CB10 CC05 CD09 4J040 FA131 FA141 FA142 FA151 FA152 FA161 FA162 FA231 FA232 GA02 HB19 HC03 HC09 HC14 HD08 HD19 HD22 JB08 LA13 KA13

Claims (12)

[Claims] 1. An adhesive composition comprising the following (A), (B), (C) and (D). (A) A copolymer obtained from the following (a) and (b) or a copolymer obtained from the following (a), (b) and (c) is added with a functional group derived from (b) and the following ( d) a reactive polymer having a double bond introduced through reaction with a functional group: (a) (meth) acrylate monomer (b) a monomer copolymerizable with (a) and having a functional group ( c) a monomer copolymerizable with (a) and (b); (d) a compound having a functional group capable of forming a bond by reacting with a functional group of (b) and a double bond; (B) a (meth) acrylate ester (C) a monofunctional monomer copolymerizable with (B), (D) a photopolymerization initiator or a mixture of a photopolymerization initiator and a sensitizer. 2. The method according to claim 1, wherein (A) is the following structural unit (I) or (I):
I): embedded image [Wherein, R ¹ represents hydrogen or a methyl group, R ² represents an alkyl group, R ³ represents hydrogen, a methyl group, -R ^4a -R ^5a-
R ^6a —C (—R ^7a ) ＝ CH ₂ or —R ^4a —R ^8a , wherein R ⁴ , R ^4a and R ^4b are not present independently of each other, or represent a carbonyl group, an alkylene group, a —R ^a — O
^{-R b -, - COO-R} c - or -COO-R ^d -O
CO-R ^e - represents, R ⁵ and R ^5a independently of one another are -OCONH -, - NHCOO -, - COO-R f - or an -R ^f -OCO-, R ⁶ and R ^6a are independently and do not present, or a carbonyl group, an alkylene ^{group, -R b -O-R a -} , - R c -OCO- or an ^{-R e -COO-R d -OCO-,} R 7 and R
^7a is independently hydrogen, methyl or -R ^4b -R ^8b
And R ^8a and R ^8b independently of one another represent a hydroxyl group, a carboxyl group, an epoxy group or an isocyanato group (where R ^a , R ^b , R ^d and R ^e
Each independently represents an alkylene group; R ^c represents an alkylene group optionally substituted with at least one substituent selected from the group consisting of an aryloxy group, a cycloalkyl group and an alkenyl group; and R ^f represents Which represents an alkylene group substituted with a hydroxyl group)), wherein the structural unit (I) is 50 to 9
9.99 mol% and the structural unit (II) are from 0.01 to
The pressure-sensitive adhesive composition according to claim 1, which is a reactive polymer containing 50 mol%. 3. The method according to claim 1, wherein (A) is the following structural unit (I),
And (III):[Wherein, R¹Represents hydrogen or a methyl group;^TwoIs al
Represents a kill group;^ThreeIs hydrogen, a methyl group, -R^4a-R^5a−
R^6a-C (-R^7a) = CH_TwoOr -R^4a-R^8aThe table
Then R^Four, R^4aAnd R^4bDo not exist independently of each other
Or a carbonyl group, an alkylene group, -R^a-O
-R^b-, -COO-R^c-Or -COO-R^d-O
CO-R^e-Represents R^FiveAnd R^5aAre independent of each other
-OCONH-, -NHCOO-, -COO-R^f−
Or -R^f-OCO-, R⁶And R^6aAre each other
Absent independently, or a carbonyl group,
Len group, -R^b-OR^a-, -R^c-OCO- or
-R^e-COO-R^d-OCO-, R⁷And R
^7aAre independently of each other hydrogen, methyl or -R^4b-R^8b
And R⁸, R^8aAnd R^8bAre independent of each other
Hydroxyl group, carboxyl group, epoxy group or
Represents an isocyanato group (where R^a, R^b, R ^dAnd
And R^eEach independently represents an alkylene group;^cIs
Reeloxy group, cycloalkyl group and alkenyl group
Substituted with at least one substituent selected from the group consisting of
Represents an alkylene group which may be^fHa
Represents an alkylene group substituted with a droxyl group))
A reactive polymer comprising the structural unit (I)
9.99 to 99.98 mol% of the structural unit (II)
0.01 to 50 mol% and the structural unit (III)
A reactive polymer containing 0.01 to 25 mol%
3. The pressure-sensitive adhesive composition according to claim 1. 4. A method according to claim 1, wherein (A) comprises the following structural units (I), (I)
I) and (IV):[Wherein, R¹Or R⁹Are independently hydrogen or
Represents a tyl group;^TwoRepresents an alkyl group;^ThreeIs hydrogen,
Methyl group, -R^4a-R^5a-R^6a-C (-R^7a) = CH_Two
Or -R^4a-R^8aAnd R^Four, R^4aAnd R^4bAre
Are not independently present, or have a carbonyl group,
Alkylene group, -R^a-OR^b-, -COO-R^c−
Or -COO-R^d-OCO-R^e-Represents R^FiveAnd
And R^5aAre independently of each other -OCONH-, -NHCOO
-, -COO-R^f-Or -R^f-OCO-,
R⁶And R^6aDo not exist independently of each other or
Is a carbonyl group, an alkylene group, -R^b-OR^a−,
-R^c-OCO- or -R ^e-COO-R^d-OCO
-Represents R⁷And R^7aAre independently hydrogen and methyl
Or -R^4b-R^8bAnd R^8aAnd R^8bAre each other
Independently hydroxyl group, carboxyl group, epoxy
Or an isocyanato group;^TenIs aceto
Xy, phenyl, cyano, carboxyl or
Represents a carbamoyl group (where R^a, R^b, R^dAnd
And R^eEach independently represents an alkylene group;^cIs
Reeloxy group, cycloalkyl group and alkenyl group
Substituted with at least one substituent selected from the group consisting of
Represents an alkylene group which may be^fHa
Represents an alkylene group substituted with a droxyl group))
A reactive polymer comprising the structural unit (I)
９８98.99 mol%, the structural unit (II) is 0.01 to
50 mol% and the structural unit (IV) is from 1 to 29.99.
2. The viscosity according to claim 1, which is a reactive polymer containing at least one mole%.
Adhesive composition. 5. The method according to claim 1, wherein (A) is the following structural unit (I), (I)
I), (III) and (IV):[Wherein, R¹Or R⁹Are independently hydrogen or
Represents a tyl group;^TwoRepresents an alkyl group;^ThreeIs hydrogen,
Methyl group, -R^4a-R^5a-R^6a-C (-R^7a) = CH_Two
Or -R^4a-R^8aAnd R^Four, R^4aAnd R^4bAre
Are not independently present, or have a carbonyl group,
Alkylene group, -R^a-OR^b-, -COO-R^c−
Or -COO-R^d-OCO-R^e-Represents R^FiveAnd
And R^5aAre independently of each other -OCONH-, -NHCOO
-, -COO-R^f-Or -R^f-OCO-,
R⁶And R^6aDo not exist independently of each other or
Is a carbonyl group, an alkylene group, -R^b-OR^a−,
-R^c-OCO- or -R ^e-COO-R^d-OCO
-Represents R⁷And R^7aAre independently hydrogen and methyl
Or -R^4b-R^8bAnd R⁸, R^8aAnd R^8b
Are independently of each other a hydroxyl group, a carboxyl group,
Represents a oxy group or an isocyanato group;^TenIs
Acetoxy group, phenyl group, cyano group, carboxyl group
Or a carbamoyl group (where R^a, R^b, R
^dAnd R^eEach independently represents an alkylene group;
^cIs an aryloxy group, a cycloalkyl group and an alk
At least one substituent selected from the group consisting of a nyl group
Represents an alkylene group optionally substituted with
^fRepresents an alkylene group substituted with a hydroxyl group.
A) a reactive polymer comprising the structural unit
48.99 to 98.98 mol% of (I), the structural unit
0.01 to 50 mol% of the structural unit (II)
I) in an amount of 0.01 to 25 mol% and the structural unit (IV)
Is a reactive polymer containing 1 to 29.99 mol% of
The pressure-sensitive adhesive composition according to claim 1. 6. The weight average molecular weight of (A) is from 1 × 10 ⁴ to
1 × 10 ⁶ and is claim 1 the adhesive composition. 7. The pressure-sensitive adhesive composition according to claim 1, wherein (B) is a (meth) acrylate monomer of an alkyl alcohol having 1 to 14 carbon atoms. 8. The pressure-sensitive adhesive composition according to claim 1, wherein the amount of the double bond introduced into the side chain of (A) is 0.0005 to 0.500 meq / g. 9. (A) is 1 to 80 parts by weight, (B) is 1 to 80 parts by weight.
The pressure-sensitive adhesive composition according to claim 1, comprising 80 parts by weight, 1 to 30 parts by weight of (C) and 0.01 to 10 parts by weight of (D). 10. The pressure-sensitive adhesive composition according to claim 1, further comprising (E) a polyfunctional (meth) acrylate monomer or a polyfunctional oligomer. 11. (A) 1 to 80 parts by weight, (B) 1 to 80 parts by weight
To 80 parts by weight, (C) 1 to 30 parts by weight, and (D) 0.1 to 0.3 parts by weight.
The pressure-sensitive adhesive composition according to claim 10, comprising 0.01 to 10 parts by weight and 0.001 to 10 parts by weight of (E). 12. A pressure-sensitive adhesive obtained by curing the pressure-sensitive adhesive composition according to claim 1.