JPH09241584A - Resin composition for actinic radiation-curable, pressure-sensitive adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin compsn. for an actinic radiation-curable, pressure- sensitive adhesive substantially free from a solvent, having good storage stability and good balance between adhesive properties, such as cohesive force, adhesive strength, and tackiness, and to provide a pressure-sensitive adhesive tape, having a layer formed of the above resin compsn., cured by actinic irradiation. SOLUTION: This resin compsn. for an actinic radiation-curable, pressure- sensitive adhesive comprises: 15 to 100wt.% radical polymerizable oligomer having an acid group equivalent of 1,000 to 100,000 and a radical polymerizable group equivalent of 1,000 to 100,000; and 0 to 85wt.% monofunctional radical polymerizable monomer. The pressure-sensitive adhesive tape having a layer formed of the above resin compsn. has been cured by actinic irradiation.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention is applied to paper, plastic, metal, etc., and by irradiation with active energy rays,
A resin composition for a non-polluting active energy ray-curable pressure-sensitive adhesive that exhibits high adhesive strength, cohesive strength, and tack, and essentially does not require the use of a solvent, and this active energy ray-curable pressure-sensitive resin composition. The present invention relates to a pressure-sensitive adhesive tape obtained by providing a resin composition for an adhesive on one side or both sides of a support and curing the resin composition by irradiation with active energy rays.

[0002]

2. Description of the Related Art Conventionally, pressure-sensitive adhesives are made of organic solvents.
Since it is a polymer rubber-based or acrylic-based copolymer diluted, (1) it deforms the base material that is weak to heat during heating and drying, (2) environmental pollution by the organic solvent that evaporates,
(3) Harm to workers, (4) Slow drying process,
(5) There were various problems such as the risk of fire.

In order to solve these problems, an active energy ray-curable pressure-sensitive adhesive which does not require the use of an organic solvent and utilizes curing by irradiation with an active energy ray has been studied. However, most of conventional radiation-curable pressure-sensitive adhesives are those obtained by dissolving an acrylic copolymer in a low-boiling acrylic monomer, and therefore (1) have a bad odor peculiar to the low-boiling acrylic monomer, (2) There is a problem that the low boiling point acrylic monomer easily becomes vapor at room temperature and is not completely solvent-free.

A pressure-sensitive adhesive using a polymer having a (meth) acryloyl group and a tackifying resin having a (meth) acryloyl group has been proposed (JP-A-4-18).
No. 3770), adhesiveness, cohesive force, and tack are still insufficient. It has also been proposed to add a chain transfer agent such as a thiol to the composition (Japanese Patent Publication No. 60-2).
No. 5070, Japanese Patent Publication No. 60-28318),
(1) The odor of the thiol compound and (2) the dark reaction between the thiol and the acryloyl group causes the storage stability to decrease.

[0005]

The problem to be solved by the present invention is an active energy ray which is substantially solvent-free, has good storage stability, and is excellent in a good balance of cohesive strength, adhesive strength, tackiness and other tacky physical properties. It is an object of the present invention to provide a pressure-sensitive adhesive tape which has a curable pressure-sensitive adhesive resin composition and a layer made of the resin composition, and which is cured by active energy rays.

[0006]

[Means for Solving the Problems] As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that the acid group equivalent is 1,000 to 100,000 and the radical polymerizable group equivalent is 1 The resin composition containing the radically polymerizable oligomer (A) of 1,000 to 100,000 has no solvent, has good storage stability, is cured by irradiation with active energy rays, and is excellent in balance. , Cohesive strength, adhesive strength,
They have found that they exhibit tacky physical properties such as tack, and have completed the present invention.

That is, the present invention has an acid group equivalent of 1,000 to
100,000 and the radical polymerizable group equivalent is 1,0
An active energy ray-curable pressure-sensitive adhesive characterized by containing 15 to 100% by weight of a radically polymerizable oligomer (A) of 100 to 100,000 and 0 to 85% by weight of a monofunctional radically polymerizable monomer (B). It is a resin composition for agents.

More specifically, in the present invention, the radical-polymerizable oligomer (A) is an acid group-containing alcohol (a-1).
And a polyisocyanate compound (a-2), a polymer polyol (a-3), and a hydroxyl group-containing radically polymerizable compound (a-4) are reacted to obtain a resin composition. Alternatively, the radically polymerizable oligomer (A) is an acid group-containing alcohol (a-1), a polyisocyanate compound (a-2), a polymer polyol (a-3), and a monovalent active hydrogen-containing compound (a -5)
And a hydroxyl group-containing radically polymerizable compound (a-4) are obtained by the reaction with the active energy ray-curable pressure-sensitive adhesive resin composition.

In the resin composition of the present invention, the radical-polymerizable oligomer (A) is particularly a carboxylic acid group-containing urethane (meth) acrylate oligomer, or a monofunctional radical polymerization. In which the functional monomer (B) is, in particular, an acid group-containing monofunctional radically polymerizable monomer (b-1) and / or a cyclic structure-containing monofunctional radically polymerizable monomer (b-2). It is a resin composition for energy ray-curable pressure-sensitive adhesives.

Further, the present invention is characterized by having a layer comprising the active energy ray-curable resin composition for pressure-sensitive adhesives of the present invention on one or both sides of a support, which is cured by active energy rays. It includes a pressure-sensitive adhesive tape formed of

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The radical polymerizable oligomer (A) used in the present invention has an acid group equivalent of 1,000 to 100,000 and a radical polymerizable group equivalent of 1,000 to 100,
000.

Specific examples of the radical-polymerizable group of the radical-polymerizable oligomer (A) include (meth) acryloyl group, (meth) acrylamide group, vinyl group, vinyl ether group, vinyl ester group and maleimide group. .
(Meth) because of high reactivity when irradiated with active energy rays
Acryloyl group and (meth) acrylamide group are particularly preferable.

The acid group of the radically polymerizable oligomer (A) includes a carboxylic acid group, a sulfonic acid group and a phosphoric acid group. When the acid group equivalent of the radical-polymerizable oligomer (A) is less than 1,000, water resistance and the like are reduced to 100,
If it is more than 000, the cohesive force and the adhesive force will decrease. More preferably, it is 3,000 to 50,000. If the radical-polymerizable group equivalent is less than 1,000, the tack is inferior, and if it is more than 100,000, curability and cohesive force due to active energy rays are inferior. More preferably, it is 3,000 to 50,000.

The radical-polymerizable oligomer (A) may be an oligomerized product obtained by radical polymerization of an acrylic copolymer or the like as long as it has a radical-polymerizable group and an acid group in the molecule, or by condensation polymerization of polyester or the like. Alternatively, it may be an oligomer.

The radical-polymerizable oligomer (A) having a radical-polymerizable group and an acid group and oligomerized by radical polymerization includes, for example, (1) a radical-polymerizable monomer containing an acid group such as (meth) acrylic acid. A radical copolymer containing an acid group is produced by a method of polymerizing a radically polymerizable monomer or a method of radical polymerization in the presence of a thiol compound having an acid group, and glycidyl is added to a part of the acid group in the copolymer. A method of reacting a radically polymerizable monomer having a group that reacts with an acid group such as (meth) acrylate,

(2) A radical copolymer containing a hydroxyl group is prepared by a method of polymerizing a radical polymerizable monomer containing a hydroxyl group-containing radical polymerizable monomer such as hydroxyethyl (meth) acrylate, and the hydroxyl group in the copolymer is prepared. To 1 part of (meth) acrylic acid chloride or (meth) acryloyl ethyl isocyanate with a radical polymerizable monomer having a group capable of reacting with a hydroxyl group such as an isocyanate group, and a part or all of the remaining hydroxyl group. It can be obtained by a method of reacting with an acid anhydride such as maleic anhydride or succinic anhydride.

Radical-polymerizable oligomer (A) having a radical-polymerizable group and an acid group and oligomerized by condensation polymerization
(1) Part of the hydroxyl groups of polymer polyols having hydroxyl groups such as polyether polyols, polyester polyols and polycarbonate polyols prepared by polycondensation, and hydroxyl groups such as (meth) acrylic acid chloride and (meth) acryloylethyl isocyanate A method of reacting a radically polymerizable monomer having a group that reacts with, and reacting an acid anhydride such as maleic anhydride or succinic anhydride with part or all of the remaining hydroxyl groups,

(2) Polymer polycarboxylic acid having an acid group such as polyester polycarboxylic acid prepared by polycondensation. A part of the acid group of polycarboxylic acid is a glycidyl group such as glycidyl (meth) acrylate or hydroxyethyl (meth) acrylate. A method of reacting a radically polymerizable monomer having a group that reacts with an acid group such as a hydroxyl group,

(3) After reacting a polymer polyol or a polymer polycarboxylic acid with epichlorohydrin to prepare a glycidyl ether or a glycidyl ester, (meth) acrylic acid is reacted therewith, and a part or all of the generated hydroxyl group is anhydrous. It can be obtained by a method of reacting an acid anhydride such as maleic acid or succinic anhydride.

It is solvent-free, has good storage stability, cures upon irradiation with active energy rays, and has a well-balanced and excellent cohesive force.
In order to exert adhesive properties such as adhesive strength and tackiness, the radical polymerizable oligomer (A) includes an acid group-containing alcohol (a-1) and a polyisocyanate compound (a-).
Those obtained by reacting 2) with the polymer polyol (a-3) and the hydroxyl group-containing radically polymerizable compound (a-4) are preferred.

Specific examples of the acid group-containing alcohol (a-1) of the present invention include (1) hydroxypivalic acid, glycolic acid, malic acid, β-hydroxy-n-butyric acid, polyhydric alcohols and acid anhydrides. Carboxyl group-containing alcohol compounds such as acid group-containing amino alcohols obtained by Michael addition of carboxylic acid group-containing polyester polyols obtained by the reaction of substances, primary and secondary amino alcohols and carboxylic acid group-containing acrylic compounds such as acrylic acid,

(2) Sulfonic acid group-containing alcohol compounds such as 2,5-dihydroxy-1,4-benzenedisulfonic acid, 1-naphthol-3,6disulfonic acid and 1-naphthol-4-sulfonic acid, (3) Obtained by Michael addition of a phosphoric acid group-containing polyester polyol obtained by the reaction of phosphoric anhydride and a polyhydric alcohol with a primary and secondary amino alcohol and a phosphoric acid group-containing acrylic compound such as 2-acryloyloxyethyl acid phosphate Examples include phosphoric acid group-containing alcohol compounds such as phosphoric acid group-containing amino alcohols.

Any alcohol having an acid group is effective, but in particular, the carboxylic acid polyol represented by the general formula 1 gives a radical polymerizable oligomer (A) having high adhesive strength and cohesive strength. , Particularly preferred.

(Formula 1) (OH) _X --R--COOH (where X is an integer of 2-3, R is a saturated, unsaturated or aromatic hydrocarbon having 2 to 29 carbon atoms). Or represents a saturated, unsaturated or aromatic hydrocarbon having 2 to 29 carbon atoms including a nitrogen atom.)

Specific examples of the carboxylic acid polyol represented by the general formula 1 include, for example, bis (hydroxymethyl).
Acetic acid, bis (hydroxyethyl) acetic acid, bis (4-hydroxyphenyl) acetic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxyethyl)
Propionic acid, 2,2-bis (hydroxypropyl) propionic acid, α-α-dimethylolbutyric acid, α-α-
Examples include dipropyrrole butyric acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid, tartaric acid, N, N-dihydroxyethylglycine, and 3,5-dihydroxybenzoic acid.

As the polyisocyanate compound (a-2), 2,4-tolylene diisocyanate, 2,4-tolylene diisocyanate dimer, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m
Aromatic diisocyanate compounds such as xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3′-dimethylbiphenyl-4,4′-diisocyanate,

Aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate, isophorone diisocyanate,
Alicyclic diisocyanate compounds such as 4,4′-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, 1,3- (isocyanatomethyl) cyclohexane,

Hexamethylene diisocyanate trimer,
Examples thereof include polyisocyanate compounds such as isophorone diisocyanate trimer and diisocyanate compounds which are reaction products of diol and diisocyanate such as 1 mol of 1,3-butylene glycol and 2 mol of tolylene diisocyanate.

As the polymer polyol (a-4) of the present invention, any polymer polyol having a molecular weight of 500 to 50,000 can be used. For example, propylene glycol, polyethylene glycol, polytetramethylene glycol, a copolymer of ethylene oxide and propylene oxide, a copolymer of propylene glycol and tetrahydrofuran, a copolymer of ethylene oxide and tetrahydrofuran, polyalkylene polyols such as polybutylene glycol, Hydrocarbon-based polyols such as polyisoprene polyol, hydrogenated polyisoprene polyol, polybutadiene polyol, hydrogenated polybutadiene polyol,

Polycaprolactone polyol, polymethylvalerolactone polyol, aliphatic dicarboxylic acids such as adipic acid and dimer acid, and polyols such as neopentyl glycol and methylpentanediol, which are reactants, and aliphatic polyester polyols, terephthalic acid and other fragrances. There are polyester polyols such as aromatic polyester polyols, which are reaction products of group dicarboxylic acids with polyols such as neopentyl glycol, polycarbonate polyols, acrylic polyols, and the like.

Acid group-containing alcohol (a-1), polyisocyanate compound (a-2), polymer polyol (a-3), and hydroxyl group-containing radically polymerizable compound (a-
In order to reduce the viscosity of the radically polymerizable oligomer (A) obtained by reacting with 4) and improve the workability, the polymer polyol (a-3) has a weight average molecular weight of 1,00.
It is preferable to use 0 to 5,000 polyalkylene polyols.

Hydroxyl group-containing radically polymerizable compound (a-
4) includes 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-chloro-2-
A reaction product of a monoglycidyl compound such as hydroxypropyl (meth) acrylate or butyl glycidyl ether and (meth) acrylic acid,

Glycerol mono (meth) acrylate,
Caprolactone-modified 2-hydroxyethyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2- (meth) acryloyloxyethyl-2-
Hydroxyethylphthalic acid, 2- (meth) acryloyloxyethyl-2-hydroxypropylphthalic acid, glycerin di (meth) acrylate,

A reaction product of a polyglycidyl compound such as 1,6-hexanediol diglycidyl ether and (meth) acrylic acid, a hydroxyl group-containing (meth) acrylate compound such as pentaerythritol tri (meth) acrylate, N-
There are hydroxyl group-containing (meth) acrylamide compounds such as methylol (meth) acrylamide, and vinyl ether compounds such as hydroxybutyl vinyl ether, hydroxyethyl vinyl ether, and cyclohexanedimethanol monovinyl ether. Any of these may be used, or two or more thereof may be used in combination.

Radical polymerizable oligomer (A) of the present invention
Is an acid group-containing alcohol (a-1), a polyisocyanate compound (a-2), and a polymer polyol (a-
It is obtained by reacting 3) with a hydroxyl group-containing radically polymerizable compound (a-4).

(1): Acid group-containing alcohol (a-1),
The polyisocyanate compound (a-2) and the polymer polyol (a-3) are added, for example, to an acid group-containing alcohol (a-
1) is a divalent alcohol, the polyisocyanate compound (a-2) is a divalent polyisocyanate, and the polymer polyol (a-3) is a divalent polyol (in the case of other conditions, alcohol and The number of moles to be reacted may be adjusted by taking the valences of isocyanate and polyol into consideration),

Acid group-containing alcohol (a-1) + polymer polyol (a-3); polyisocyanate compound (a-2), α; α + 0.8 to α; α + 1.2 (α
Is reacted at a molar ratio of 1, 2 or 3) to prepare a urethane oligomer (a-6) having a terminal isocyanate group, and then a hydroxyl group-containing radically polymerizable compound (a-
4) may be reacted,

(2): Acid group-containing alcohol (a-1),
The polyisocyanate compound (a-2) and the polymer polyol (a-3) are added, for example, to an acid group-containing alcohol (a-
1) is a divalent alcohol, the polyisocyanate compound (a-2) is a divalent polyisocyanate, and the polymer polyol (a-3) is a divalent polyol (in the case of other conditions, alcohol and The number of moles to be reacted may be adjusted by taking the valences of isocyanate and polyol into consideration),

Acid group-containing alcohol (a-1) + polymer polyol (a-3); polyisocyanate compound (a-2), β + 0.8: β to β + 1.2; β (β
Are reacted at a molar ratio of 1, 2 or 3) to prepare a terminal hydroxyl group urethane oligomer (a-7), and separately, a polyisocyanate compound (a-2) and a hydroxyl group-containing radically polymerizable compound (a-4). ) May be produced by a method of reacting with an isocyanate compound (a-8) having a radically polymerizable group, which is produced by reacting a) in a molar ratio of 2: 0.8 to 2; 1.2.

A urethane oligomer (a-6) having a terminal isocyanate group or a urethane oligomer having a terminal hydroxyl group (a-7) and a hydroxyl group-containing radically polymerizable compound (a-
4) or the isocyanate compound (a-8) having a radically polymerizable group may be reacted at a molar ratio of 1: 0.25 to 1: 1.2. Preferably, 1: 0.4 to 1: 0.
8 If it is less than 1: 0.25, the cohesive force decreases. If it is larger than 1: 1.2, the storage stability tends to decrease.

The radical-polymerizable oligomer (A) is converted into an acid group-containing alcohol (a-1), a polyisocyanate compound (a-2), a polymer polyol (a-3), an active hydrogen-containing compound (a-5) and a hydroxyl group. It is preferable that the radical-polymerizable compound (a-4) contained is reacted to improve the adhesion and tack.

As the active hydrogen-containing compound (a-5),
Alcohols such as 2-ethylhexanol, n-butylamine, amines such as 3-aminopropyltriethoxysilane, and thiols such as n-butylmercaptan are available, but alcohols are particularly preferable because they improve tack.

Examples of alcohols include methanol, ethanol, 1-butanol, 2-butanol, 1
-Pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 2-ethylhexanol, isooctyl alcohol, n-decyl alcohol, cyclohexanol, 2-ethoxyethanol, 2-methoxyethanol, 2-dimethyl Amino ethanol, 2-morpholino ethanol, tetrahydrofurfuryl alcohol,
Tetrahydropyran-2-methanol,

Triethylene glycol monomethyl ether, tripropylene glycol monomethyl ether, hydroxyacetone, allyl alcohol, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, p-hydroxybenzophenone, 4-
(2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone and the like. 4 to 30 carbon atoms
The above alcohols improve tack and are more preferable.

The active hydrogen-containing compound (a-5) is a urethane oligomer (a-6) having a terminal isocyanate group.
And a hydroxyl group-containing radically polymerizable compound (a-4) are reacted, a urethane oligomer (a-6) having a terminal isocyanate group; a hydroxyl group-containing radically polymerizable compound (a-4) + active hydrogen-containing compound (a -5) = 1: 1
The reaction may be performed at a molar ratio of ˜1: 1.2.

Urethane oligomer having a terminal hydroxyl group (a-7)
And an isocyanate compound having a radically polymerizable group (a
-8) is reacted, the polyisocyanate compound (a-2) and the active hydrogen-containing compound (a-5) are separately reacted at a molar ratio of 2: 0.8 to 2; 1.2. Isocyanate compound (a- that reacted with the prepared active hydrogen group
9) is prepared, and the terminal hydroxyl group urethane oligomer (a-
7): The isocyanate compound (a-8) having a radical polymerizable group + the isocyanate compound (a-9) reacted with the active hydrogen group may be reacted at a molar ratio of 1: 1 to 1.2: 1.

Acid group-containing alcohol (a-1) and / or polymer polyol (a-3) and / or active hydrogen-containing compound (a-5) and / or hydroxyl group-containing radically polymerizable compound (a-4). ), And the polyisocyanate compound (a-2) at a reaction temperature of 20 to 90 ° C., preferably 30 to 80 ° C., and a urethane-forming catalyst such as dibutyltin laurate, a polymerization inhibitor such as phenothiazine, and the like. The reaction is carried out in the presence of an inert organic solvent and / or a monofunctional radically polymerizable monomer (B) which is copolymerizable with the radically polymerizable oligomer (A) used in the present invention.

Radical-polymerizable oligomer (A) of the present invention
Has a weight average molecular weight of 1,000 to 100,000, preferably 3,000 to 50,000. If the weight average molecular weight is less than 1,000, the tack is inferior and
If it is greater than 0,000, the cohesive force will be poor.
Furthermore, the viscosity becomes high and the coatability at room temperature becomes poor.

In order to adjust the weight average molecular weight of the radically polymerizable oligomer (A), the acid group-containing alcohol (a
-1), the polyisocyanate compound (a-2) and the polymer polyol (a-3) are reacted to prepare a urethane hydroxyl group-terminated terminal oligomer (a-7), and the polyisocyanate compound (a-2) and a hydroxyl group are separately contained. An isocyanate compound (a-8) and / or a polyisocyanate compound (a-2) having a radical polymerizable group prepared by reacting a radical polymerizable compound (a-4) with an active hydrogen-containing compound (a-5). The method of reacting the isocyanate compound (a-9) reacted with the active hydrogen group prepared by the reaction is preferable.

Acid group-containing alcohol (a-1): polyisocyanate compound (a-2): polymer polyol (a
-3): Isocyanate compound having radically polymerizable group (a-8): Isocyanate compound (a-9) reacted with active hydrogen group = 0.5 to 10 parts by weight: 5 to 20 parts by weight: 60 to 90 parts by weight When designed so that the total amount is 100 parts by weight at a ratio of 1: 1 to 20 parts by weight: 1 to 20 parts by weight, a radically polymerizable oligomer (A) having a weight average molecular weight of 1,000 to 100,000 is obtained. be able to.

The radical-polymerizable oligomer (A) in the present invention can be used alone, but when it is applied at room temperature, a monofunctional radical-polymerizable monomer (B) is added to reduce the viscosity. Is also good. The active energy ray-curable pressure-sensitive adhesive resin composition of the present invention contains 15 to 100% by weight of the radically polymerizable oligomer (A) and 0 to 85% by weight of the monofunctional radically polymerizable monomer (B). It is a thing.

When the radical-polymerizable oligomer (A) is less than 15% by weight, active energy ray curability, tackiness and adhesive strength are poor. Particularly preferably, the radical polymerizable oligomer (A) is blended in an amount of 15 to 80% by weight, and the monofunctional radically polymerizable monomer (B) is blended in an amount of 20 to 85% by weight.

The monofunctional radically polymerizable monomer (B) of the present invention is a reactive diluent for adjusting the viscosity so that it can be coated, and is not particularly limited.
Ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, isostearyl (meth) acrylate, methoxyethyl (meth ) Acrylate, ethoxyethyl (meth) acrylate, methylcarbitol (meth) acrylate,

(Meth) acrylate compounds such as ethyl carbitol (meth) acrylate, phenoxy (meth) acrylate, methoxydipropylene glycol (meth) acrylate, dimethylamino (meth) acrylate, morpholinoethyl (meth) acrylate, N, N
There are acrylamide compounds such as dimethyl (meth) acrylamide and N, N-dimethylaminopropyl (meth) acrylamide.

Further, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-
Hydroxybutyl (meth) acrylate, 3-chloro-
2-hydroxypropyl (meth) acrylate, epichlorohydrin-modified butyl (meth) acrylate, glycerol (meth) acrylate, caprolactone-modified 2-
A hydroxyl group-containing (meth) acrylate compound such as hydroxyethyl (meth) acrylate or phenoxyhydroxypropyl (meth) acrylate may be used.

These monofunctional radically polymerizable monomers may be used alone or in combination of two or more. When the acid group-containing monofunctional radically polymerizable monomer (b-1) is used as the monofunctional radically polymerizable monomer (B), not only the viscosity of the resin composition can be lowered but also the cohesive force and the adhesive force can be improved. it can.

Examples of the acid group-containing monofunctional radically polymerizable monomer (b-1) include phosphoric acid group-containing (meth) acrylates such as (meth) acryloyloxyethyl acid phosphate and (meth) acryloyloxybutyl acid phosphate. Compounds, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxypropylphthalic acid,

2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethyltetrahydrophthalic acid, 2- (meth)
Acryloyloxypropyl tetrahydrophthalic acid, 2
-(Meth) acryloyloxyethyl maleic acid,

Ω-carboxy-polycaprolactone mono (meth) acrylate, (meth) acrylic acid dimer,
2- (meth) acrylic acid and acid anhydrides such as itaconic anhydride, trimellitic anhydride, and hymic acid anhydride
Examples thereof include a reaction product with a hydroxyl group-containing (meth) acrylate compound such as hydroxypropyl (meth) acrylate. These acid group-containing monofunctional radically polymerizable monomers (b-
1) may be used alone or in combination of two or more.

Furthermore, when the cyclic structure-containing monofunctional radically polymerizable monomer (b-2) is used as the monofunctional radically polymerizable monomer (B), cohesive force, adhesive force and tack can be improved. As the cyclic structure-containing monofunctional radically polymerizable monomer (b-2), cyclohexyl (meth) acrylate, 4-t-butylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, Dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate,

Phenoxy (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, nonylphenoxy (meth) acrylate and the like ( There are vinyl compounds such as (meth) acrylate compounds, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylcarbazole, and N-vinyl-1-imidazole. These cyclic structure-containing monofunctional radically polymerizable monomers (b-2) may be used alone or in combination of two or more.

The amount of the acid group-containing monofunctional radically polymerizable monomer (b-1) added is 0 in 100% by weight of the resin composition.
-50% by weight, preferably 5-30% by weight. 50
If it exceeds 5% by weight, tack decreases and water resistance deteriorates.

The amount of the monofunctional radically polymerizable monomer having a cyclic structure (b-2) added is 100% by weight of the resin composition.
It is 0 to 50% by weight, preferably 3 to 30% by weight. 5
If it exceeds 0% by weight, the adhesive strength and tack will be reduced. The acid group-containing monofunctional radically polymerizable monomer (b-1) and the cyclic structure-containing monofunctional radically polymerizable monomer (b-2) are
It is preferable to use them in combination, but they may be used alone.

When ultraviolet rays are used as a curing means for the resin composition of the present invention, it is usually necessary to add a photopolymerization initiator (C) to the composition. The photopolymerization initiator (C) is added in an amount of 0.01 to 10% by weight, preferably 1 to 5% by weight in the active energy ray-curable pressure-sensitive adhesive resin composition.

The photopolymerization initiator (C) can be roughly classified into two types, that is, an intramolecular bond cleavage type and an intramolecular hydrogen abstraction type. Examples of the former include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-.
1-one, 4- (2-hydroxyethoxy) phenyl-
(2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenyl ketone, 2-methyl-2
-Morpholino (4-thiomethylphenyl) propane-1
-ON,

2-benzyl-2-dimethylamino-1-
Acetophenones such as (4-morpholinophenyl) -butanone; benzoins such as benzoin, benzoin isopropyl ether and benzoin isobutyl ether;
Examples include acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; benzyl, methylphenylglyoxyester and the like.

On the other hand, examples of the latter include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, and acrylate. Benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3′-dimethyl-
Benzophenones such as 4-methoxybenzophenone; 2
-Isopropylthioxanthone,

2,4-dimethylthioxanthone, 2,4
Thioxanthones such as diethylthioxanthone and 2,4-dichlorothioxanthone; Michler's ketone, 4,
Aminobenzophenone series such as 4'-diethylaminobenzophenone; 10-butyl-2-chloroacridone, 2
-Ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone and the like.

When the resin composition of the present invention is cured by irradiation with ultraviolet rays, it can be cured only by adding the above-mentioned photopolymerization initiator (C), but a photosensitizer ( It is preferable to use D) together. Examples of the sensitizer (D) include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and benzoic acid (2- Dimethylamino) ethyl,

Examples of amines include (n-butoxy) ethyl 4-dimethylaminobenzoate and 2-ethylhexyl 4-dimethylaminobenzoate. The compounding amount of the photosensitizer (D) is 0.01 to 10% by weight, preferably 0.05 to 5% by weight in the active energy ray-curable pressure-sensitive adhesive resin composition.

In addition to the above, the resin composition of the present invention contains a polyfunctional radical-polymerizable monomer, a well-known and commonly used non-reactive oligomer or tackifier, an inorganic filler, an organic filler, a polymerization inhibitor, and a defoaming agent. Agents, leveling agents, plasticizers, antioxidants,
An ultraviolet absorber, a flame retardant, a pigment, a dye, an adhesion improver such as a coupling, and the like may be added.

As the polyfunctional radically polymerizable monomer,
For example, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
1,6-hexanediol di (meth) acrylate,
There are (meth) acrylate compounds such as 1,9-nonanediol di (meth) acrylate. Addition of a polyfunctional radically polymerizable monomer improves cohesive force. The addition of 1 to 5% by weight is preferred. If it exceeds 5% by weight, the tack is inferior.

The non-reactive oligomers and resins referred to in the present invention include liquids having low or no radical reactivity,
Or, it means a solid oligomer or resin, (meta)
Alkyl acrylate copolymer, epoxy resin, liquid polybutadiene, liquid polybutadiene derivative, liquid chloroprene, liquid polypentadiene, dicyclopentadiene derivative, saturated polyester oligomer, polyether oligomer, liquid polyamide, polyisocyanate oligomer, xylene resin, ketone resin, Examples include petroleum resins, rosin resins, fluorine-based oligomers, silicon-based oligomers, and polysulfide-based oligomers.

In particular, rosins and rosins such as partially disproportionated or disproportionated rosins, hydrogenated rosins, maleic acid modified rosins, polymerized rosins, formaldehyde modified rosins, esterified rosins reacted with an alcohol such as rosin and pentaerythritol. Derivatives and terpenes and terpene derivatives are effective. Rosin and rosin derivatives and terpenes and terpene derivatives preferably have a softening point of 100 ° C. or higher,
It is effective to add 5 to 40% by weight.

As the inorganic filler, silicon dioxide, silicon oxide, calcium carbonate, calcium silicate, magnesium carbonate, magnesium oxide, talc, kaolin clay, calcined clay, zinc oxide, zinc sulfate, aluminum hydroxide, aluminum oxide, glass, Examples include mica, barium sulfate, alumina white, zeolite, silica balloon, glass balloon and the like.

The resin composition of the present invention does not substantially require a solvent. For example, ketones such as methyl ethyl ketone and methyl isobutyl ketone, acetic acid esters such as ethyl acetate and butyl acetate, and benzene. It is also possible to dilute the resin composition of the present invention with other commonly used organic solvents such as aromatic hydrocarbons such as toluene, xylene and the like before use.

The active energy rays referred to in the present invention refer to ionizing radiation such as ultraviolet rays, electron rays, α rays, β rays, γ rays, visible rays, microwaves, high frequencies, etc., but radical active species are generated. Any energy type will do as long as it can. As the one that generates ultraviolet rays, for example,
Ultra high pressure mercury lamp, high pressure mercury lamp, low pressure mercury lamp,
Metal halide lamp, chemical lamp, black light lamp, mercury-xenon lamp, short arc lamp,
And the like, and may be selected in consideration of the absorption wavelength of the compound that generates the radical active species.

In the present invention, the active energy ray-curable pressure-sensitive adhesive resin composition having the above-mentioned composition is directly coated on an adherend or coated on a release paper, and then 200
~ 1,500mJ / cm ² UV or ² ~ 10M
By irradiating an active energy ray such as an electron beam of rad and curing it, a pressure-sensitive adhesive having pressure-sensitive adhesiveness can be obtained by itself.

Instead of coating on an adherend or a release paper, a synthetic resin film such as a polyester film, a fiber base material, various base materials such as metal such as copper foil are used, and one surface of the base material or A pressure-sensitive adhesive sheet and a pressure-sensitive adhesive film having a sheet-like or tape-like form can be prepared by applying a coating on both sides and irradiating with active energy rays and curing in the same manner as above. The thickness of the pressure sensitive adhesive layer at this time can be set arbitrarily.

[0080]

The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In the examples, all parts are by weight unless otherwise specified. The method for preparing the test piece and the evaluation method are shown below.

(Method for preparing test piece) The active energy ray-curable pressure-sensitive adhesive resin composition of the present invention was applied on a polyester film having a thickness of 25 μm by using an automatic coating machine. The coating amount was set so that the film thickness was 80 ± 10 μm. The resin composition coating layer is covered with a peeling polyester film having a thickness of 75 μm and laminated, and then a thickness of 25
Ultraviolet rays or electron beams were irradiated from the side of the polyester film having a thickness of μm to cure the resin composition layer to prepare a pressure-sensitive adhesive sheet, and the peeling polyester film having a thickness of 75 μm was peeled off to obtain a test piece.

The UV and electron beam doses required for curing were the UV and electron beam doses when the gel fraction of the pressure-sensitive adhesive sheet was saturated. The irradiation conditions of active energy rays are shown below.

(1) Ultraviolet irradiation conditions 80 W / cm high pressure mercury lamp (manufactured by Eye Graphics), lamp height 15 cm, conveyor speed 40
It was irradiated with ultraviolet rays and cured under the condition of m / min.

(2) Electron beam irradiation conditions Using an electron beam irradiation apparatus CB175 (manufactured by ESI, USA),
Acceleration voltage 170KV, oxygen concentration in irradiation atmosphere 300pp
The electron beam irradiation was performed under the condition of m or less.

(Evaluation method) (1) Adhesive force: A test piece having a width of 25 mm and a length of 50 mm was
The pressure-sensitive adhesive layer side is attached to a SUS304 steel plate having a thickness of 1.5 mm, and the pressure-sensitive adhesive layer is reciprocated once with a 2.0 kg roller to press it 1
Left for hours. After that, the temperature is 23 ± 2 ° C and the relative humidity is 65.
Using a tensile tester under ± 5%, the test piece was peeled off at a speed of 300 mm / min in the 90 ° direction, and the average value of the force was obtained.

(2) Holding power: width 25 mm x length 75 mm
In the same manner as in the adhesive strength evaluation, the test piece of No. 2 was pressed onto the SUS304 steel plate so that the area of 25 × 25 mm was in contact,
It was left for 1 hour. Then, under the condition of 100 ° C., 1.0
A load of kg was attached to the test piece, and the time until the test piece dropped from the SUS plate was measured.

(3) Ball tack: width 25 mm x length 1
Open a test piece of 00 mm with an approach distance of 100 mm, and
Attach it to the inclined plate of °. After that, a ball specified in JIS B 1501 was rolled from the ball start position, and the maximum number of balls that were stationary on the test piece was determined.

(4) Gel Fraction A test piece of 100 × 50 mm was immersed in methyl ethyl ketone,
After immersion at room temperature for 24 hours, it was dried at 80 ° C. for 2 hours, and it was determined from the difference in weight of the test piece before and after immersion.

(Synthesis Example 1) 221 g (1 mol) of isophorone diisocyanate, 0.18 g of dibutyltin laurate and 0.18 p-methoxyphenol were placed in a 1 L four-necked flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel.
g, and while maintaining the temperature at 60 ° C, use a dropping funnel to
Hydroxypropyl acrylate 130g (1mol)
Was dripped. After completion of the dropping, the reaction is carried out at 70 ° C. for 3 hours to give an isocyanate compound (a-8) having a radically polymerizable group.
351 g of -I) was obtained.

(Synthesis Example 2) 221 g (1 mol) of isophorone diisocyanate (hereinafter referred to as IPDI) and 0.18 g of dibutyltin laurate were placed in a 1 L four-necked flask equipped with the same equipment as in Synthesis Example 1, and heated to 60 ° C. While maintaining, 130 g of 2-ethylhexanol from the dropping funnel
(1 mol) was added dropwise. After completion of the dropwise addition, the reaction was carried out at 70 ° C. for 3 hours to obtain 351 g of an isocyanate compound (a-9-I) which had reacted with an active hydrogen group.

(Synthesis Example 3) In the same manner as in Synthesis Example 2 except that 59 g (1 mol) of hydroxypivalic acid was used instead of 130 g (1 mol) of 2-ethylhexanol, an active hydrogen group having an acid group was prepared in the same manner. 169 g of reacted isocyanate compound (I) was obtained.

Synthesis Example 4 In Synthesis Example 2, n- was used instead of 130 g (1 mol) of 2-ethylhexisanol.
Except that 129 g (1 mol) of dibutylamine was used,
In the same manner, 259 g of an isocyanate compound (a-9-II) reacted with an active hydrogen group was obtained.

Example 1 In a 1 L four-necked flask equipped with the same equipment as in Synthesis Example 1, 44.2 g (0.
2 mol), 0.4 g of 2,6-ditert-butyl-p-cresol (hereinafter referred to as BHT), 0.4 g of dibutyltin laurate, dimethylolpropionic acid 13.
4 g (0.1 mol) was charged and reacted at 80 ° C. for 5 hours.

When the NCO value is measured and the theoretical value is reached, 400 g of polypropylene glycol having a molecular weight of 2,000
(0.2 mol) was added dropwise, and the mixture was reacted at 80 ° C. for 4 hours to contain an acid group-containing urethane oligomer having a terminal hydroxyl group (a-
7) was obtained. 0.1 mol of the acid group-containing terminal hydroxyl group urethane oligomer (a-7) and the isocyanate compound (a-8-I) having the radically polymerizable group obtained in Synthesis Example 1 were obtained.
1 was charged and reacted at 80 ° C. for 4 hours to obtain a radically polymerizable oligomer (A-1).

As a result of measurement by gel permeation chromatography (GPC, manufactured by Tosoh Corporation), the weight average molecular weight was 13,000 in terms of polystyrene. The acid group equivalent of the radically polymerizable oligomer (A-1) is 13,
000, and the radical polymerization group equivalent was 13,000.

This radical-polymerizable oligomer (A-1)
100 parts by weight of 1-hydroxycyclohexyl phenyl ketone (hereinafter referred to as HCPK) as a photoinitiator (C)
Was added and dissolved to obtain a resin composition 1 for pressure-sensitive adhesive.

Example 2 In Example 1, the isocyanate compound (a-8-I) having a radically polymerizable group was used.
In the same manner as above, except that 0.20 mol was charged instead of 0.1 mol.
2) was obtained. Weight average molecular weight is 1 in terms of polystyrene
It was 5,300. Radical polymerizable oligomer (A-
The acid group equivalent of 2) was 15,300, and the radical polymerization group equivalent was 7,650. To 100 parts of this radical-polymerizable oligomer (A-2), as a photoinitiator (C), HC
1 part of PK was added and dissolved to obtain a resin composition 2 for pressure-sensitive adhesive.

(Example 3) The molecular weight of Example 1 was 2,000.
Instead of 0.2 mol of polypropylene glycol of 0, 0.2 m of polypropylene glycol of molecular weight 400
A radically polymerizable oligomer (A-3) was obtained in the same manner except that ol was charged. The weight average molecular weight was 5,200 in terms of polystyrene. The radical-polymerizable oligomer (A-3) had an acid group equivalent of 5,200 and a radical-polymerizable group equivalent of 5,200. To 100 parts of this radical-polymerizable oligomer (A-3), 1 part of HCPK as a photoinitiator (C) was added and dissolved to obtain a resin composition 3 for pressure-sensitive adhesive.

Example 4 1 L of 4 equipped with the above equipment
22.1 g of IPDI (0.1 mo
l), BHT 0.4 g, dibutyltin laurate 0.
4g, polypropylene glycol 4 with a molecular weight of 2,000
00 g (0.2 mol) was charged and reacted at 80 ° C. for 3 hours. After the NCO value was measured and reached the theoretical value, 0.1 mol of the isocyanate compound (I) having an acid group obtained in Synthesis Example 3 and reacted with an active hydrogen group was charged and reacted at 80 ° C. for 4 hours to give an acid at the end. Group and hydroxyl group-containing urethane oligomer (a
-8) was obtained.

0.1% of the isocyanate compound (a-8-I) having a radical polymerizable group obtained in Synthesis Example 1 was added to the urethane oligomer (a-8) containing an acid group and a hydroxyl group at the terminal.
Mol was charged and reacted at 80 ° C. for 5 hours to obtain a radically polymerizable oligomer (A-4). The weight average molecular weight was 11,000 in terms of polystyrene. The acid group equivalent of the radically polymerizable oligomer (A-4) is 11,000,
The radical polymerization group equivalent was 1,100. To 100 parts of this radical-polymerizable oligomer (A-4), 1 part of HCPK as a photoinitiator (C) was added and dissolved to obtain a resin composition 4 for pressure-sensitive adhesive.

Example 5 The isocyanate compound (a-8-I) having a radically polymerizable group in Example 1 was used.
In place of 0.1 mol, the isocyanate compound (a-8-I) having a radically polymerizable group was reacted with 0.1 mol and an active hydrogen group (a-9-
A radically polymerizable oligomer (A-5) was obtained in the same manner except that 0.1 mol of I) was charged. The weight average molecular weight was 16,500 in terms of polystyrene.

The acid group equivalent of the radical polymerizable oligomer (A-5) is 16,500, and the radical polymerizable group equivalent is 1
It was 6,500. Into 60 parts of this radical-polymerizable oligomer (A-5), isooctyl acrylate (hereinafter referred to as IO) was added as a monofunctional radical-polymerizable monomer (B).
A) 30 parts, 2-ethylhexyl carbitol acrylate (hereinafter referred to as EH-EO-A) 10 parts, and as a photoinitiator (C), 1 part of HCPK is added and dissolved to obtain a resin for pressure-sensitive adhesive. A composition 5 was obtained.

(Example 6) In Example 5, the molecular weight was 2
Instead of 400 g of polypropylene glycol of 000, 770 g of polybutylene glycol of molecular weight 3000
A radically polymerizable oligomer (A-6) was obtained in the same manner except that (0.2 mol) was used. The weight average molecular weight was 19,500 in terms of polystyrene. The acid group equivalent of the radically polymerizable oligomer (A-6) is 19,50.
0, the radical polymerization group equivalent was 19,500. 60 parts of this radical-polymerizable oligomer (A-6) was added with IOA 30 as a monofunctional radical-polymerizable monomer (B).
Parts, EH-EO-A 10 parts, as a photoinitiator (C),
1 part of HCPK was added and dissolved to obtain a resin composition 6 for pressure-sensitive adhesive.

(Example 7) In Example 6, as the monofunctional radically polymerizable monomer (B), 30 parts of IOA was used instead of the acid group-containing monofunctional radically polymerizable monomer (b).
A resin composition 7 for pressure-sensitive adhesive was obtained in the same manner except that 30 parts of β-carboxyethyl acrylate (hereinafter referred to as CEA) which was -1) was used.

Example 8 In Example 6, as the monofunctional radically polymerizable monomer (B), 30 parts of IOA,
10 parts of EH-EO-A, 30 parts of CEA that is an acid group-containing monofunctional radically polymerizable monomer (b-1), cyclohexyl acrylate that is a cyclic structure-containing monofunctional radically polymerizable monomer (b-2) (hereinafter, CHA) 10
A resin composition 8 for pressure-sensitive adhesive was obtained in the same manner except that parts were used.

(Example 9) In Example 5, the molecular weight was 2
Polypropylene methylene glycol 3 with a molecular weight of 2000 instead of 400 g of polypropylene glycol 3
In the same manner except that 88 g (0.2 mol) was used,
A radically polymerizable oligomer (A-7) was obtained. The weight average molecular weight was 20,600 in terms of polystyrene. The acid group equivalent of the radically polymerizable oligomer (A-7) is 2
The radical polymerization group equivalent was 0,600 and 20,600.

This radical-polymerizable oligomer (A-7)
In 60 parts, as the monofunctional radically polymerizable monomer (B), an acid group-containing monofunctional radically polymerizable monomer (b-1)
30 parts of CEA, 10 parts of CHA that is a monofunctional radically polymerizable monomer containing a cyclic structure (b-2), and 1 part of HCPK as a photoinitiator (C) are dissolved to obtain a resin for pressure-sensitive adhesive. Composition 9 was obtained.

Example 10 In the same manner as in Example 5, except that 400 g (0.2 mol) of polymethylpentanediol adipate having a molecular weight of 1000 was used instead of 400 g of polypropylene glycol having a molecular weight of 2000, radical polymerization was performed in the same manner. An oligomer (A-8) was obtained.
The weight average molecular weight was 13,800 in terms of polystyrene. The acid group equivalent of the radical polymerizable oligomer (A-8) is 13,800, and the radical polymerizable group equivalent is 13,80.
It was 0.

This radical-polymerizable oligomer (A-8)
In 60 parts, as the monofunctional radically polymerizable monomer (B), an acid group-containing monofunctional radically polymerizable monomer (b-1)
30 parts of CEA, 10 parts of CHA that is a monofunctional radically polymerizable monomer containing a cyclic structure (b-2), and 1 part of HCPK as a photoinitiator (C) are dissolved to obtain a resin for pressure-sensitive adhesive. A composition 10 was obtained.

Example 11 In Example 1, the isocyanate compound (a-8-) having a radically polymerizable group was used.
Instead of 0.1 mol of I), 0.1 mol of the isocyanate compound (a-8-I) having a radically polymerizable group was used.
1 and an isocyanate compound (a-
Radical polymerizable oligomer (A-9) was obtained in the same manner except that 0.1 mol of 9-II) was used. The weight average molecular weight was 18,100 in terms of polystyrene. The acid group equivalent of the radically polymerizable oligomer (A-9) is 18,
100, the radical polymerization group equivalent was 18,100.

This radical-polymerizable oligomer (A-9)
To 60 parts, as a monofunctional radically polymerizable monomer (B), 30 parts of IOA, 10 parts of EH-EO-A, and 1 part of HCPK as a photoinitiator (C) were added and dissolved to prepare a resin for pressure-sensitive adhesive. Composition 11 was obtained.

Example 12 In a 1 L four-necked flask equipped with the same equipment as in Example 1, 44.2 g of IPDI was added.
(0.2 mol), BHT 0.05 g, dibutyltin laurate 0.05 g, dimethylolpropionic acid 1
3.4 g (0.1 mol) was charged and reacted at 80 ° C. for 5 hours to obtain an intermediate (1). In another 4-neck flask equipped with the same equipment as above, 44.2 g (0.2
mol), BHT 0.5 g, and dibutyl tin laurate 0.5 g were charged, and polypropylene glycol 800 g (0.4 mol) having a molecular weight of 2,000 was added dropwise thereto,
The reaction was performed at 80 ° C. for 3 hours.

After measuring the NCO value and reaching the theoretical value, 0.1 mol of the above intermediate (1) was charged and reacted at 80 ° C. for 4 hours to obtain an acid group-containing, terminal hydroxyl group urethane oligomer (a-9). Obtained. 0.1 mol of the isocyanate compound (a-8-I) having a radical-polymerizable group was added to the acid group-containing, hydroxyl-terminated urethane oligomer (a-9), and the mixture was reacted at 80 ° C. for 4 hours to give a radical-polymerizable compound. An oligomer (A-10) was obtained. The weight average molecular weight was 34,000 in terms of polystyrene. The radical polymerizable oligomer (A-10) had an acid group equivalent of 34,000 and a radical polymerizable group equivalent of 34,000.

This radical-polymerizable oligomer (A-1
0) as a monofunctional radically polymerizable monomer (B),
30 parts of CEA that is an acid group-containing monofunctional radically polymerizable monomer (b-1), 10 parts of CHA that is a cyclic structure-containing monofunctional radically polymerizable monomer (b-2), and HCPK as a photoinitiator (C) Was added and dissolved to obtain a resin composition 12 for pressure-sensitive adhesive.

Example 13 In Example 12, as the monofunctional radically polymerizable monomer (B), CEA 3 which is an acid group-containing monofunctional radically polymerizable monomer (b-1) was used.
0 part and a monofunctional radically polymerizable monomer containing a cyclic structure (b
-2), instead of 10 parts CHA, CEA 40
And 30 parts of CHA were used in the same manner as above to obtain a resin composition 13 for pressure-sensitive adhesive.

Example 14 In Example 12, as the monofunctional radically polymerizable monomer (B), CEA 3 which was an acid group-containing monofunctional radically polymerizable monomer (b-1) was used.
0 part and a monofunctional radically polymerizable monomer containing a cyclic structure (b
-2) CHA 10 parts instead of CEA 55
Part and CHA 30 parts were used in the same manner to obtain a resin composition 14 for pressure-sensitive adhesive.

Example 15 The isocyanate compound (a-8-) having a radically polymerizable group in Example 1 was used.
Radical-polymerizable oligomer (A-1) was used in the same manner except that 0.03 mol was used instead of 0.1 mol of I).
1) was obtained. The weight average molecular weight is 9, in terms of polystyrene.
500. Radical polymerizable oligomer (A-1
The acid group equivalent of 1) was 9,500, and the radical polymerization group equivalent was 31,670. To 60 parts of this radical-polymerizable oligomer (A-11), as a monofunctional radical-polymerizable monomer (B), 30 parts of IOA, EH-EO-A
As a photoinitiator (C), 10 parts and 1 part of HCPK were added and dissolved to obtain a resin composition 15 for pressure-sensitive adhesive.

Example 16 In a 1 L four-necked flask equipped with an esterification reactor, 295 g of sodium dimethylsulfoisophthalate and 590 g of 3-methyl-1,5-pentanediol were added to an esterification catalyst (Fascat 14).
00, manufactured by M & T Co., USA) was added thereto and transesterification was carried out by a conventional method to obtain a diol having a sulfonic acid group.

Then, a radically polymerizable oligomer (A-12) was obtained in the same manner except that 1 mol of diol having a sulfonic acid group was used instead of 1 mol of dimethylolpropionic acid in Example 1. The weight average molecular weight was 16,000 in terms of polystyrene. The acid group equivalent of the radically polymerizable oligomer (A-12) is 16,000,
The radical polymerization group equivalent was 16,000. To 100 parts of this radical-polymerizable oligomer (A-12), 1 part of HCPK as a photoinitiator (C) was added and dissolved to obtain a resin composition 16 for pressure-sensitive adhesive.

Example 17 The radical-polymerizable oligomer (A-6) synthesized in Example 6 was used as a resin composition 17 for pressure-sensitive adhesive.

Example 18 To 60 parts of the radically polymerizable oligomer (A-6) synthesized in Example 6, as a monofunctional radically polymerizable monomer (B), 30 parts of IOA and EH were used.
-EO-A (10 parts) was added to the resin composition for pressure-sensitive adhesive 1
8 was obtained.

Example 19 60 parts of the radical-polymerizable oligomer (A-6) synthesized in Example 6 was added to the acid group-containing monofunctional radical-polymerizable monomer (b-) as the monofunctional radical-polymerizable monomer (B). 30 parts of CEA which is 1) and 10 parts of CHA which is a monofunctional radically polymerizable monomer containing a cyclic structure (b-2) are added, and a resin composition for pressure-sensitive adhesive 1
9 was obtained.

Comparative Example 1 44.2 g (0.2%) of IPDI was added to a 1 L four-necked flask equipped with the same equipment as in Example 1.
mol), 0.4 g of BHT and 0.4 g of dibutyltin laurate, and 600 g of polypropylene glycol having a molecular weight of 2,000 while keeping the flask at 60 ° C.
(0.3 mol) was added dropwise, and after completion of the addition, the reaction was carried out at 80 ° C. for 4 hours to give a urethane hydroxyl group-terminated oligomer (a-1).
0) was obtained.

This terminal hydroxyl group urethane oligomer (a-
In 10), 0.15 mol of the isocyanate compound (a-8-I) having a radical-polymerizable group obtained in Synthesis Example 1 was charged and reacted at 80 ° C. for 4 hours to give a radical-polymerizable oligomer (A-1 ′). Got The weight average molecular weight was 11,000 in terms of polystyrene. The radical-polymerizable oligomer (A-1 ′) had an acid group equivalent of 0 and a radical-polymerizable group equivalent of 7,330. To 60 parts of this radical-polymerizable oligomer (A-1 ′), as a monofunctional radical-polymerizable monomer (B), 30 parts of IOA, EH-EO-A
After adding 10 parts, 1 part of HCPK as a photoinitiator (C) was added and dissolved to obtain a resin composition for pressure-sensitive adhesive 1 ′.

(Comparative Example 2) In a 1 L four-necked flask equipped with the same equipment as in Example 1, 22.1 g (0.
1 mol), BHT (0.4 g) and dibutyltin laurate (0.4 g) were charged, while the flask was kept at 60 ° C.
Hydrogenated polybutadiene polyol 60 having a molecular weight of 3,000
0 g (0.2 mol) was added dropwise, and after the completion of the reaction, the reaction was carried out at 80 ° C. for 4 hours to give a urethane oligomer with a hydroxyl group at the terminal (a
-11) was obtained. The isocyanate compound (a-8-I) having the radically polymerizable group obtained in Synthesis Example 1 was added to 0.1 mol of the terminal hydroxyl group urethane oligomer (a-11).
0.1 mol was charged and reacted at 80 ° C. for 4 hours to obtain a radically polymerizable oligomer (A-2 ′).

The weight average molecular weight is 1 in terms of polystyrene.
It was 9,000. Radical polymerizable oligomer (A-
2 ′) has an acid group equivalent of 0 and a radical polymerizable group equivalent of 1
It was 9,000. To 60 parts of this radical-polymerizable oligomer (A-2 ′), as a monofunctional radical-polymerizable monomer (B), 30 parts of IOA and EH-EO-A 10 were used.
And 1 part of HCPK as a photoinitiator (C) were added and dissolved to obtain a resin composition 2 ′ for pressure-sensitive adhesive.

Comparative Example 3 In the same manner as in Example 1, except that neopentyl glycol (0.1 mol) was used in place of dimethylolpropionic acid (0.1 mol), a radically polymerizable oligomer was prepared in the same manner. (A-3 ′) was obtained.
The weight average molecular weight is 12,000 in terms of polystyrene.
Met. The radical-polymerizable oligomer (A-3 ′) had an acid group equivalent of 0 and a radical-polymerizable group equivalent of 12,000. This radical polymerizable oligomer (A-3 ′) 6
In 0 part, as a monofunctional radically polymerizable monomer (B),
30 parts of IOA and 10 parts of EH-EO-A were added, and 1 part of HCPK was added as a photoinitiator (C) and dissolved to obtain a resin composition 3'for a pressure-sensitive adhesive.

(Comparative Example 4) 60 parts of the radically polymerizable oligomer (A-3 ') synthesized in Comparative Example 3 was added to the acid group-containing monofunctional radically polymerizable monomer (b) as the monofunctional radically polymerizable monomer (B). -1) CEA 30 parts and cyclic structure-containing monofunctional radically polymerizable monomer (b-2) CHA 10 parts were added to obtain a resin composition for pressure-sensitive adhesive 4 '.

(Comparative Example 5) The radical polymerizable oligomer (A-3 ') synthesized in Comparative Example 3 was obtained as a resin composition 5'for a pressure sensitive adhesive.

(Comparative Example 6) 60 parts of the radical-polymerizable oligomer (A-3 ') synthesized in Comparative Example 3 was mixed with 30 parts of IOA and EH as the monofunctional radical-polymerizable monomer (B).
10 parts of -EO-A was added to obtain a resin composition 6'for a pressure sensitive adhesive.

Resin compositions 1-16, 1'-4 'for pressure-sensitive adhesives prepared in Examples 1-16 and Comparative Examples 1-4 above.
Then, the test piece was prepared by irradiating it with ultraviolet rays and curing it, and measuring the adhesive force, the holding force, the ball tack, and the gel fraction. The results are shown in Table 1.

The pressure-sensitive adhesive resin compositions 17 to 19 and 5'to 6'prepared in Examples 17 to 19 and Comparative Examples 5 and 6 were irradiated with an electron beam and cured to prepare test pieces, which were then bonded. The force, holding power, ball tack, and gel fraction were measured. Table 2 shows the results.

[0133]

[0134]

[0135]

INDUSTRIAL APPLICABILITY The present invention uses a radically polymerizable oligomer having an acid group, has no solvent, has good storage stability, is cured by irradiation with active energy rays, has a good balance, and has excellent cohesive force. It is possible to provide an active energy ray-curable resin composition for pressure-sensitive adhesives and pressure-sensitive adhesives that exhibit adhesive properties such as adhesive strength and tack.

Claims (6)

[Claims] 1. The acid group equivalent is 1,000 to 100,000.
And the radical polymerizable group equivalent is 1,000 to 100,
Radical polymerizable oligomer (A) 15 to 1
00% by weight and monofunctional radically polymerizable monomer (B) 0
A resin composition for an active energy ray-curable pressure-sensitive adhesive, characterized in that the resin composition contains ˜85% by weight. 2. The radically polymerizable oligomer (A) comprises an acid group-containing alcohol (a-1), a polyisocyanate compound (a-2), a polymer polyol (a-3),
The resin composition according to claim 1, which is obtained by reacting with a hydroxyl group-containing radically polymerizable compound (a-4). 3. The radically polymerizable oligomer (A) comprises an acid group-containing alcohol (a-1), a polyisocyanate compound (a-2), a polymer polyol (a-3),
The resin composition according to claim 1, which is obtained by reacting a monovalent active hydrogen-containing compound (a-5) with a hydroxyl group-containing radically polymerizable compound (a-4). 4. The resin composition according to any one of claims 1 to 3, wherein the radically polymerizable oligomer (A) is a carboxylic acid group-containing urethane (meth) acrylate oligomer. 5. A monofunctional radically polymerizable monomer (B)
Is an acid group-containing monofunctional radically polymerizable monomer (b-1)
And / or a monofunctional radically polymerizable monomer (b-2) containing a cyclic structure, the resin composition according to any one of claims 1 to 4. 6. The support according to claim 1, which is provided on one side or both sides of the support.
A pressure-sensitive adhesive tape cured by active energy rays, comprising a layer formed of the resin composition for active energy ray-curable pressure-sensitive adhesives according to any one of 1.