JPH06346026A - Composition for activating energy ray curing type hot-melt pressure sensitive adhesive and adhesive product using this composition and production of adhesive product - Google Patents

Abstract

(57) [Summary] [Structure] A high molecular weight polymer having an ethylenically unsaturated group and a number average molecular weight of 1 to 100,000, and a number average molecular weight having or not having an ethylenically unsaturated group of 500 to 80
A hot melt pressure sensitive adhesive composition that cures with active energy rays containing a low molecular weight polymer of 00 and a reactive diluent. [Effect] Before curing, the hot melt coating property at low temperature (about 80 ° C) is excellent, and the curing reaction requires only a small amount of irradiation of active energy rays such as ultraviolet rays or electron beams, and after curing Due to its excellent heat-resistant cohesive strength, it is used in the fields of pressure-sensitive adhesive (adhesive) tapes, sheets, labels and the like.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a high molecular weight polymer having an ethylenically unsaturated group and a low molecular weight polymer having or not having an ethylenically unsaturated group, a reactivity having an ethylenically unsaturated group. The present invention relates to an active energy ray-curable hot melt pressure-sensitive adhesive composition containing a diluent. More specifically, before curing, the hot melt coatability at low temperature (about 80 ° C) is excellent, and the curing reaction requires only a small amount of irradiation of active energy rays such as ultraviolet rays or electron beams. The present invention relates to an acrylic active energy ray-curable hot melt pressure-sensitive adhesive composition having excellent heat-resistant cohesive strength after curing.

[0002]

2. Description of the Related Art Acrylic pressure-sensitive adhesives are used for various purposes such as pressure-sensitive labels, pressure-sensitive sheets, and pressure-sensitive tapes because of their excellent weather resistance, deterioration resistance and adhesiveness. However, at present, the solvent type or emulsion type is predominant. On the other hand, as a hot-melt pressure-sensitive adhesive, a composition using a styrene-isoprene-styrene block copolymer as a base polymer is currently used, but its weather resistance and deterioration resistance are poor. Therefore, solvent-based or emulsion-type acrylic pressure-sensitive adhesives are usually used for adhesive products that are required to have heat resistance or weather resistance. However, in particular, when the coating amount is 40 μm or more, the drying step for volatilizing the solvent or water takes a long time, and the productivity at the time of manufacturing the adhesive product is not improved at present. With the increasing demand for solvent-free pressure sensitive adhesives, several attempts have been made to hot melt acrylic pressure sensitive adhesives. For example, the acrylic hot-melt pressure-sensitive adhesives described in JP-A-59-75975, JP-A-58-125774, JP-A-56-161484 and JP-A-1-315409 are generally hot-melt coated. Or the cohesive strength of the pressure sensitive adhesive is insufficient.

In order to improve the above-mentioned drawbacks, JP-A-3-2
A moisture-curable hot melt adhesive composition described in Japanese Patent No. 59984 has been proposed, but the composition is (meth) acrylic acid alkyl ester, macromer (polymeric monomer), and (meth) acrylic having a silyl group. Because it consists of acid ester and isocyanate compounds,
There is a problem in hot melt coatability before moisture curing, and particularly, a toxic gas generated from an isocyanate compound when melted at a high temperature is greatly restricted in terms of work. The moisture-curable adhesive composition described in JP-A-3-139584 is composed of (meth) acrylic acid alkyl ester, a polymerizable polymer and unsaturated isocyanate,
There is a drawback that the change in melt viscosity is large. Further, in order to reduce the melt viscosity, a styrene-based tackifying resin is added, but since the compatibility between the tackifying resin and the (meth) acrylic acid alkyl ester moiety is poor, the tackiness is bad. Further, in order to improve the drawback that the change in melt viscosity is large, a moisture-curable hot melt adhesive composition comprising an alkyl (meth) acrylate ester, a polymerizable polymer, an unsaturated isocyanate, an organic tin compound and an organic phosphorus compound However, when an organic phosphorus compound is added to reduce the change in melt viscosity, the moisture curing rate becomes slower. Furthermore, the graft copolymers described in JP-A-3-139584 and JP-A-4-31482 alone are suitable at relatively low temperatures (about 120 ° C.) in order to achieve excellent hot melt coatability. Melt viscosity (10
Even if it is 0000 cps or less), initial adhesiveness and initial cohesive force before moisture curing are insufficient. In general, the moisture-curable hot melt adhesive composition, by the end of curing,
It has to be cured for at least 3 to 7 days, and there is a problem in productivity. On the other hand, JP-A-2-276879, JP-A-3-2763
Although the active energy ray-curable hot melt pressure-sensitive adhesives described in JP-A-119082 and JP-A-3-220275 are proposed, the melting temperature is as high as 150 ° C. and the increase in melt viscosity over time is a problem.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have already found that a high molecular weight polymer (A) having an ethylenically unsaturated group and a low molecular weight polymer (B) having or not having an ethylenically unsaturated group. A patent has been filed for an active energy ray-curable hot melt pressure-sensitive adhesive composition characterized in that it contains a compound, but in this case, a relatively large amount of active energy ray irradiation is required. . As described above, there is no acrylic hot-melt pressure-sensitive adhesive composition that sufficiently satisfies the market demand, and in particular, the change in melt viscosity before curing is small, and excellent hot-melt coatability is exhibited. The reaction requires a small amount of irradiation of active energy rays such as ultraviolet rays or electron rays, and after curing, a hot-melt pressure-sensitive adhesive composition having excellent adhesive strength and heat-resistant cohesive strength is desired. Is the current situation. Therefore, the object of the present invention is to overcome the conventional drawbacks of acrylic hot-melt pressure-sensitive adhesives. In particular, before curing, the hot-melt coatability at a low temperature (about 80 ° C.) is excellent, and the curing reaction is high. To provide an acrylic active energy ray-curable hot-melt pressure-sensitive adhesive composition which has a small irradiation dose of active energy rays typified by ultraviolet rays or electron beams and has excellent heat-resistant cohesive strength after curing. It is in.

[0005]

The inventor of the present invention has made earnest studies for the purpose of solving the above-mentioned problems, and arrived at the present invention. That is, the present invention is as described in [a] to [d] below. [A] Number average molecular weight of 100 having an ethylenically unsaturated group
100 parts by weight of a mixture of one kind or two or more kinds selected from a high molecular weight polymer (A) of 100 to 100,000, a low molecular weight polymer having a number average molecular weight of 1,000 to 8,000 with or without an ethylenically unsaturated group An active energy ray-curable hot melt pressure-sensitive adhesive composition comprising (B) 200 parts by weight or less and a reactive diluent (C) in an amount of 5 to 50 parts by weight. High molecular weight polymer (A); a monomer (d) having a vinyl group and an active group in the molecule and a vinyl group at the molecular side chain or at the molecular end, and a number average molecular weight of 2000 or more and 2
A reactive polymer (e) having a glass transition temperature of 0 ° C. or higher is copolymerized with a (meth) acrylic acid alkyl ester (f) having an alkyl group having 1 to 12 carbon atoms, and an ethylenically unsaturated group is further added. And an ethylenic vinyl ester having a (meth) acrylic acid alkyl ester moiety having a glass transition temperature of −75 ° C. to −20 ° C., which is produced by reacting the monomer (g) having a group capable of reacting with the active group. A high molecular weight polymer having a saturated group. Low molecular weight polymer (B); the following (B ₁ ) and / or (B ₂ ). A glass having at least one monomer selected from vinyl acetate and (meth) acrylic acid alkyl ester (f) copolymerized with an ethylenically unsaturated group at the molecular side chain or at the molecular end. Transition temperature is -60 ℃
A low molecular weight polymer (B ₁ ) having a temperature of -80 ° C. The glass transition temperature having no ethylenically unsaturated group, which is produced by copolymerizing at least one monomer selected from vinyl acetate and (meth) acrylic acid alkyl ester (f), is −
A low molecular weight polymer (B ₂ ) having a temperature of 60 ° C to 80 ° C. Reactive diluent (C); a compound having one or more ethylenically unsaturated groups in one molecule and having a molecular weight of less than 1,000. [B] The melt viscosity at 70 to 100 ° C. is 1000 to
200,000 cps, The active energy ray-curable hot melt pressure-sensitive adhesive composition according to [A]. [C] An adhesive product using the active energy ray-curable hot melt pressure-sensitive adhesive composition according to [A]. [D] A method for producing an adhesive product as described in [c].

High molecular weight polymer (A) used in the present invention
Has a number average molecular weight of usually 10,000 to 100,000,
It is preferably 10,000 to 90,000, more preferably 10,000 to 80,000. If the number average molecular weight is less than 10,000, the cohesive force of the pressure-sensitive adhesive is insufficient, and the heat resistance after curing is insufficient. Also, 10
If it exceeds 50,000, the melt viscosity of the pressure-sensitive adhesive becomes too high, resulting in poor coatability. In addition, high molecular weight polymer (A)
In, the glass transition temperature of the (meth) acrylic acid alkyl ester moiety is usually −75 ° C. to −20 ° C., preferably −
70 ° C to -20 ° C, more preferably -70 ° C to -30 ° C
Is. If it is less than -75 ° C, the cohesive force of the pressure-sensitive adhesive will be insufficient, and if it exceeds -20 ° C, the adhesive force after curing will be insufficient. In the present invention, the glass transition temperature of the (meth) acrylic acid alkyl ester moiety can be measured by a differential scanning calorimeter (DSC).

The number average molecular weight of the low molecular weight polymer (B) used in the present invention is usually 100 to 8000, preferably 1000 to 7000, more preferably 1000 to 6
It is 000. If the number average molecular weight exceeds 8,000, the melt viscosity of the pressure-sensitive adhesive is too high, resulting in poor coatability. The glass transition temperature of the low molecular weight polymer (B) is usually -60 ° C to 80 ° C, preferably -60 ° C to 70 ° C, more preferably -50 ° C to 70 ° C. This is -60 ° C
If it is less than 80 ° C, the cohesive force of the pressure-sensitive adhesive will be insufficient, and if it exceeds 80 ° C, the adhesive force will be insufficient. The high molecular weight polymer (A) 1
The low molecular weight polymer (B) is added in an amount of 0 to 200 parts by weight, and the reactive diluent (C) is added in an amount of 5 to 50 parts by weight, based on 00 parts by weight. Preferably, the low molecular weight polymer (B) is 0 to 180 parts by weight, the reactive diluent (C) is 5 to 40 parts by weight, and more preferably the low molecular weight polymer is 100 parts by weight of the high molecular weight polymer (A). Combine (B) from 0 to 150
5 parts by weight of the reactive diluent (C).
When the amount of the low molecular weight polymer (B) exceeds 200 parts by weight and the amount of the reactive diluent (C) exceeds 50 parts by weight, the pressure-sensitive adhesive has a poor balance between adhesive strength and cohesive strength. Reactive diluent (C)
Is less than 5 parts by weight, a relatively large amount of active energy ray irradiation is required during the curing reaction.

Next, a method for producing the high molecular weight polymer (A) of the present invention will be described. The high-molecular weight polymer (A) is obtained by adding a monomer (d) having a vinyl group and an active group in the molecule, a reactive polymer (e) and a (meth) acrylic acid alkyl ester (f) in a solvent. And is copolymerized by solution polymerization in the presence of a polymerization initiator, and further reacted with a monomer (g) having an ethylenically unsaturated group and the above-mentioned group capable of reacting with an active group. The proportion of each component used in the high molecular weight polymer (A) is 0.05 to 10 as the monomer (d).
%, The reactive polymer (e) is 2 to 30% by weight, the (meth) acrylic acid alkyl ester (f) is 97.9 to 50% by weight, and the monomer (f) is
It is preferably 0.05 to 10% by weight.

Next, the low molecular weight heavy bodies (B ₁ ) and (B ₁
The manufacturing method of ₂ ) is explained. Low molecular weight polymer (B ₁ )
The production method differs depending on the position of the vinyl group in the molecule. When a vinyl group is introduced into the side chain of a molecule, at least one monomer selected from the group consisting of vinyl acetate and (meth) acrylic acid alkyl ester (f), and a vinyl group and an active group are introduced in the molecule. The monomer (d) which is usually copolymerized by solution polymerization in the presence of a polymerization initiator in a solvent, and further a monomer (g) having an ethylenically unsaturated group and a group capable of reacting with the above active group. It is manufactured by reacting with. The ratio of each component is
At least one monomer selected from the group consisting of vinyl acetate and alkyl (meth) acrylate (f) is 99.8 to 30% by weight, and the monomer (d) is at least 0. 1 to 50% by weight, and as a monomer (g), 0.
It is preferably from 1 to 50% by weight. When a vinyl group such as a methacryloyl group or an acryloyl group is introduced at the terminal of the molecule, it is synthesized by a living anion termination method or a chain transfer polymerization method. What is the living anion stop method?
Living anion polymerization of at least one monomer selected from the group consisting of vinyl acetate and alkyl (meth) acrylate (f), and reacting the growing living anion with a terminating agent having a double bond. To synthesize,
US Pat. No. 3,786,116 and US Pat. No. 3,84.
Milkov, as described in the specification of No. 2,059.
ich et al. The second way to stop is
An alkylene oxide such as ethylene oxide is introduced into the living anion to form an alkoxide ion, which is further protonated to obtain a hydroxy-terminated polymer. Then, a low molecular weight polymer having a vinyl group is synthesized by reacting a hydroxy group with an isocyanate alkyl acrylate or methacrylate having, for example, 1 to 4 carbon atoms in the alkyl group. In the chain transfer polymerization method, radical polymerization is performed with a polymerization initiator such as 4,4′-azobis-4-cyano-valeric acid in the presence of a chain transfer agent such as thioglycolic acid, and a carboxyl group or the like is added to the polymer terminal. The low-molecular weight polymer having a vinyl group at the molecular end is synthesized by introducing the functional group (1) and reacting the functional group with, for example, glycidyl methacrylate. In the presence of a chain transfer agent such as 2-mercaptoethanol, 2,2 '
Radical polymerization is carried out with a polymerization initiator such as azobis-2-hydroxy-propionitrile to introduce a functional group such as a hydroxyl group at the polymer terminal, and the functional group and, for example, m-
By reacting with isopropenyl-α, α'-dimethylbenzyl isocyanate or the like, a low molecular weight polymer having a vinyl group at the molecular end is similarly synthesized. The low molecular weight polymer (B ₂ ) is usually obtained by adding at least one monomer selected from the group consisting of vinyl acetate and (meth) acrylic acid alkyl ester (f) in a solvent in the presence of a polymerization initiator. It is produced by copolymerization by solution polymerization. The high molecular weight polymer (A) solution and the low molecular weight polymer (B) solution prepared as described above are mixed in a predetermined amount, the solvent is removed, and then the reactive diluent (C) is added.
An adhesive can be manufactured by mixing a predetermined amount of.

Next, the raw materials and the reactive diluent (C) used in the production of the high molecular weight polymer (A) and the low molecular weight polymer (B) will be described. Examples of the monomer (d) having a vinyl group and an active group in the molecule include m-
Isopropenyl-α, α'-dimethylbenzyl isocyanate, p-isopropenyl-α, α'-dimethylbenzyl isocyanate, methacryloyl isocyanate,
2-methacryloyloxymethyl isocyanate, 2-
Methacryloyloxyethyl isocyanate, 2-methacryloyloxypropyl isocyanate, acryloyl isocyanate, acryloyloxymethyl isocyanate, acryloyloxyethyl isocyanate and a monomer having an isocyanate group as an active group represented by acryloyloxypropyl isocyanate, acrylic acid, methacrylic acid, Α, β-unsaturated carboxylic acids such as crotonic acid, maleic acid and fumaric acid and their anhydrides, hydroxyethyl (meth) acrylate, (meth)
A monomer having a hydroxyl group such as hydroxypropyl acrylate, a monomer having a glycidyl group such as glycidyl (meth) acrylate, (meth) acrylamide, N-
At least one selected from the group consisting of unsaturated carboxylic acid amides having an amide group such as methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide and diacetone (meth) acrylamide.

Reactive polymer (e) used in the present invention
Has a glass transition temperature of 20 ° C. or higher and a number average molecular weight of 2000 or higher. If the glass transition temperature is less than 20 ° C. or the number average molecular weight is less than 2000, the cohesive force of the pressure-sensitive adhesive after curing may be insufficient. More preferably, 5
It has a number average molecular weight of 0000 or less. If the number average molecular weight is too large, the melt viscosity of the pressure-sensitive adhesive is too high, which may result in poor coatability. The production method of the reactive polymer (e) differs depending on the position of the vinyl group in the molecule. When a vinyl group is present in the side chain of a molecule, styrene,
At least one monomer selected from aromatic monomers represented by t-butylstyrene, α-methylstyrene, vinyltoluene, etc., (meth) acrylic acid ester (f), acrylonitrile, vinyl acetate, etc. The monomer and the monomer (d) having a vinyl group and an active group in the molecule are usually mixed in a solvent in the presence of a polymerization initiator so as to have a glass transition temperature of 20 ° C. or higher and a number average molecular weight of 2000 or higher. Is copolymerized by solution polymerization, and is further reacted with a monomer (g) having an ethylenically unsaturated group and the above-mentioned group capable of reacting with an active group. When a vinyl group is present at the molecular terminal, an aromatic monomer represented by styrene, t-butylstyrene, α-methylstyrene, vinyltoluene, etc., (meth) acrylic acid ester (f), acrylonitrile, acetic acid. At least one kind of monomer selected from vinyl or the like is synthesized by the living anion termination method or the chain transfer polymerization method, as in the case of the low molecular weight polymer. As the (meth) acrylic acid alkyl ester (f) used in the present invention,
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate,
Isobutyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Decyl (meth) acrylate, lauryl (meth) acrylate, pentyl (meth) acrylate, and the like. With respect to suitability for use ratio, the range described in the above invention [a] is preferable and there is no particular limitation. More preferably, the glass transition temperature of the (meth) acrylic acid alkyl ester moiety of the high molecular weight polymer (A) is in the range of −75 to −20 ° C., or the glass transition temperature of the low molecular weight polymer (B). Is -60 to 80 ° C
The above (meth) acrylic acid alkyl ester (f) may be appropriately selected and used so that the above range is satisfied.

The monomer (g) having an ethylenically unsaturated group and a group capable of reacting with the active group of the monomer (d) in the molecule is m-isopropenyl-α, α'-dimethylbenzyl isocyanate. , P-isopropenyl-α, α'-
Dimethylbenzyl isocyanate, methacryloyl isocyanate, 2-methacryloyloxymethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 2-methacryloyloxypropyl isocyanate, acryloyl isocyanate, acryloyloxymethyl isocyanate, acryloyloxyethyl isocyanate and acryloyloxypropyl isocyanate, and tolylene diisocyanate , Polyisocyanates such as hexamethylene diisocyanate and diphenylmethane diisocyanate, and hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate,
Monomers having isocyanate groups represented by 1: 1 addition reaction products with acrylic acid, methacrylic acid, etc., α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid and fumaric acid And its anhydrides,
A monomer having a hydroxyl group such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate, a monomer having a glycidyl group such as glycidyl (meth) acrylate, (meth) acrylamide, N-methylol ( At least one selected from the group consisting of unsaturated carboxylic acid amides having an amide group such as (meth) acrylamide, N-butoxymethyl (meth) acrylamide and diacetone (meth) acrylamide. The monomer (g) may be used in a known combination depending on the active group of the monomer (d) used. For example, when the active group of the monomer (d) is an isocyanate group, a single amount is used. A monomer having a hydroxyl group such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate as the body (g), and a monomer when the active group of the monomer (d) is a carboxyl group. As (g), a monomer having a glycidyl group such as glycidyl (meth) acrylate is subjected to a corresponding reaction.

Preferred polymerization initiators used in producing the high molecular weight polymer (A) and the low molecular weight polymer (B) of the present invention include dicumyl peroxide, benzoyl peroxide and t-butyl peroxy. 2-ethylhexanoate, 1,1-bis (t-butylperoxy) cyclohexane, α, α′-azobisisobutyronitrile, acetyl peroxide, t-butylperoxypivalate, t-butylhydro Peroxide, cumene hydroperoxide, t-hexyl peroxypivalate, 2,
2'-azobis- (2,4-dimethylvaleronitrile), lauroyl peroxide, t-butyl peroxyneohexanoate, peroxide-di-t-butyl, azodicyclohexylcarbonitrile, dimethyl α, α-azodiisobutyrate. , Succinic acid peroxide, dicumene peroxide, dichlorobenzoyl peroxide and the like can be used. As a preferable solvent used in producing the high molecular weight polymer (A) and the low molecular weight polymer (B) of the present invention, ethyl acetate,
Butyl acetate, benzene, toluene, xylene, cyclohexane, methyl ethyl ketone, etc. can be used.

When the high molecular weight polymer (A) and the low molecular weight polymer (B) of the present invention are synthesized, copolymerization with the above-mentioned constituents is carried out within a range not impairing the features of the present invention, preferably 30% by weight or less. Other possible monomers may be used as the copolymerization component. Examples of such a monomer include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid and fumaric acid. Acid and its anhydrides,
A monomer having a hydroxyl group such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate, a monomer having a glycidyl group such as glycidyl (meth) acrylate, (meth) acrylamide, N-methylol ( Unsaturated carboxylic acid amides having an amide group such as (meth) acrylamide, N-butoxymethyl (meth) acrylamide and diacetone (meth) acrylamide,
Monomers having amino groups such as vinyl pyridine, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, etc., and further acid phosphooxyethyl (meth) acrylate, acid phosphooxypropyl (meth) acrylate And the like having a phosphate group. Further, monomers such as vinyl acetate (excluding the case of the low molecular weight polymer (B)) and (meth) acrylonitrile can also be copolymerized. Further, polyfunctional acrylates typified by triethylene glycol diacrylate, pentaerythritol triacrylate, ethylene glycol dimethacrylate, polyfunctional methacrylates typified by trimethylolpropane trimethacrylate, and divinylbenzene can also be copolymerized.

In the reactive diluent (C), poly (meth) acrylates such as polyols such as ethylene glycol diacrylate, diethylene glycol dimethacrylate and tetraethylene glycol diacrylate are used as polyfunctional monomers, Ethylene glycol diglycidyl ether diacrylate, diethylene glycol diglycidyl ether dimethacrylate, triethylene glycol diglycidyl ether dimethacrylate, propylene glycol diglycidyl ether diacrylate,
Poly (meth) acrylates of epoxy compounds such as bisphenol A diglycidyl ether diacrylate, (meth) allyl (meth) acrylates such as allyl acrylate and allyl methacrylate, diallyl malate, diallyl fumarate, diallyl itaconate, diallyl Tertiary amino alcohols such as (meth) allyl ester of polycarboxylic acid such as phthalate, triallyl cyanurate, triallyl isocyanurate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, etc. (Meth) acrylic acid esters of dimethylaminopropyl acrylamide,
Tertiary aminoalkyl-substituted (meth) acrylamides such as dimethylaminopropylmethacrylamide, 1,9-
Examples thereof include diene-based monomers such as decadiene and 1,13-tetradecadiene. Monofunctional monomers include oxyalkylene monomers such as ethylene glycol methyl ether acrylate, ethylene glycol n-butyl methyl ether acrylate, ethylene glycol phenol ether acrylate, ethylene glycol nonyl phenol ether acrylate, and diethylene glycol 2-ethylhexyl ether acrylate. Is mentioned. The polyfunctional monomers of these reactive diluents (C) are
The monofunctional monomers are used alone or in combination depending on the application for the purpose of enhancing the crosslinking effect and enhancing the adhesive performance. Among these polyfunctional monomers, it is preferable to use poly (meth) acrylates such as polyol in consideration of odor and volatility.

The active energy ray-curable hot melt pressure-sensitive adhesive composition of the present invention is cured by irradiation with active energy rays such as ultraviolet rays or electron beams, but a photopolymerization initiator is added to further accelerate the curing. May be. In particular, when the curing means is ultraviolet light, a photopolymerization initiator is preferably used, for example, benzoin, benzoin ethyl ether, benzoin methyl ether and benzoin isopropyl ether, benzoin compounds, acetophenone, benzylacetyl, anthraquinone, methylanthraquinone, Examples thereof include carbonyl compounds such as benzophenone, benzoquinone and chloroacetone, sulfur compounds such as diphenyl sulfide and dithiol carbamate, naphthalene compounds such as α-chloromethylnaphthalene, and metal salts such as anthracene and iron chloride. The preferable mixing ratio of the photopolymerization initiator is 0.01 to 20 parts by weight, more preferably 0.1 to 100 parts by weight of the composition of the present invention.
The range of 10 to 10 parts by weight is preferable. When the curing means is electron beam or γ ray, it is not necessary to use a photopolymerization initiator.

The active energy ray-curable hot melt pressure-sensitive adhesive composition of the present invention prevents gelation during storage and increases storage stability, and the composition is thermally deteriorated during heat coating. It is preferable to use a small amount of an anti-aging agent in order to prevent thermal polymerization and increase thermal stability. Preferred antiaging agents include, for example, hydroquinone, hydroquinone monomethyl ether, catechol, octadecyl-3- (3,5-di-t-butyl-
4-hydroxyphenyl) propionate, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and other phenols, benzoquinone, naphthoquinone, diphenylbenzoquinone and other quinones, tris Phosphites such as (nonylphenyl) phosphite and bis (nonylphenyl) pentaerythritol diphosphite, phenyl-1
-Aromatic amines such as naphthylamine and phenothiazine. The preferred blending ratio of these antioxidants is in the range of 0.001 to 1 part by weight per 100 parts by weight of the composition. In the active energy ray-curable hot melt pressure-sensitive adhesive composition of the present invention, a thermoplastic resin, a tackifying resin, a plasticizer, a filler and the like can be added and blended within a range that does not impair the characteristics thereof.

As the thermoplastic resin, ethylene-vinyl acetate copolymer resin, ethylene-ethyl acrylate copolymer resin, ethylene-methyl methacrylate copolymer resin,
Styrene-isoprene-styrene block copolymer resin,
Styrene-butadiene-styrene block copolymer resin,
Styrene-ethylene-butylene-styrene block copolymer resin, styrene-ethylene-propylene-styrene block copolymer resin, styrene- (meth) acrylic acid alkyl ester graft copolymer resin, styrene- (meth)
Examples thereof include acrylic acid alkyl ester-vinyl acetate graft copolymer resins and polyesters. As the tackifying resin, hydrogenated rosin which is rosin and its derivative,
Polymerized rosin, (hydrogenated) polymerized rosin, rosin glycerin ester, (hydrogenated) rosin glycerin ester, rosin pentaerythritol ester, (hydrogenated) rosin pentaerythritol ester, disproportionated rosin glycerin ester and disproportionated rosin pentaerythritol ester ,, terpene phenol resin, (hydrogenated) terpene phenol resin, ketone resin, petroleum resin (aliphatic type, aromatic type, their copolymerization type and alicyclic type, etc.) and their hydrogenated products, terpene resin, (Hydrogenated) terpene resin, coumarone-indene resin, xylene resin and the like are particularly preferable, and rosin and its derivative, terpene phenol resin, (hydrogenated) terpene phenol resin, petroleum resin and hydrogenated products thereof, ketone resin. Is used. Examples of the plasticizer include liquid polyisobutene, liquid polybutene, liquid (hydrogenated) polyisoprene, liquid (hydrogenated) polybutadiene, paraffin-based oil, naphthene-based oil, epoxy plasticizer, phosphoric acid esters, phthalic acid esters, Representative examples are fatty acid dibasic acid esters and glycol esters.

The filler is selected from zinc oxide powder, magnesium oxide powder, metal powder, silica powder (including colloidal silica powder), calcium carbonate powder, titanium oxide powder, talc powder, alumina powder, carbon black powder, and the like. Also, one or more dry fillers are preferable. In particular, it has been found that the use of zinc oxide powder, calcium carbonate powder, titanium oxide powder, talc powder, carbon black powder, etc. is preferable because the weather resistance is greatly improved and the thermal stability of the system is high. However, if the filler is used in an amount of more than 30% by weight, the system exhibits a high thixotropic property in terms of viscosity and the workability is deteriorated. In addition, it is not preferable because there is an adverse effect such that the wear of the hot melt applicator is significantly accelerated. The active energy ray-curable hot melt pressure-sensitive adhesive composition of the present invention is heat-melted according to a generally known method, coated on various substrates with an appropriate thickness, and then the formed composition The pressure-sensitive adhesive layer can be formed on the substrate by curing by irradiating with active energy rays to such an extent that the pressure-sensitive adhesive property of the layer is not lost. The melting temperature is, for example, 7
A range of 0 to 100 ° C. is preferable, and a temperature of 150 ° C. or higher is not preferable because a rapid increase in viscosity of the composition during heat melting or gelation occurs. Further, the melt viscosity at 70 to 100 ° C. is preferably 1,000 to 200,000 cps.

Active energy rays include ultraviolet rays, electron beams,
Ionizing radiation such as α-rays, β-rays, γ-rays, or X-rays, which has problems with equipment, is easy to handle, and uses a pressure-sensitive adhesive composition with better storage stability and thermal stability. It is preferable to use an electron beam from the viewpoint of causing damage.
The irradiation dose of the active energy rays is, for example, when the active energy rays are ultraviolet rays, the irradiation dose is 10 to 10 depending on the composition coating thickness by adjusting the intensity of the lamp, the distance to the surface to be irradiated and the irradiation time. 1000 mJ / cm
Adjusted in the range of ² . If the coating thickness is 40μm is, 150~300mJ / cm ^2, in the case of 80μm is, 300~500mJ / cm ² of about desirable. Further, for example, in the case of an electron beam, the irradiation dose is adjusted in the range of 0.5 to 10 Mrad by adjusting the composition coating thickness by adjusting the voltage, current and irradiation time. When the coating thickness is 40 μm, 1 to 3 Mrad, and when it is 80 μm, about 3 to 5 Mrad is desirable. By applying an active energy ray-curable hot melt pressure-sensitive adhesive composition as a pressure-sensitive adhesive composition when producing a processed pressure-sensitive adhesive product which is coated with a coating amount of 40 μm or more,
The productivity in the production of adhesive products is greatly improved. 40 μm
There is no problem even if an active energy ray-curable hot melt pressure-sensitive adhesive composition is used as the pressure-sensitive adhesive composition when producing a processed pressure-sensitive adhesive product coated with a coating amount of less than However, the productivity improvement is not significant.

Examples of adhesive products include the following. However, depending on the adhesive products listed below,
This patent is not limiting. Paper, non-woven fabric,
One example is a pressure-sensitive adhesive tape produced by applying a pressure-sensitive adhesive to one side of a substrate such as cloth, plastic film (olefin film, polyester film, vinyl chloride film, etc.), metal foil, etc. that has been subjected to release treatment on one side. To be Also, paper,
One-side coating of pressure-sensitive adhesive on base materials such as cloth, non-woven fabric, plastic film, plastic foam, metal foil, molded body (plastic molded body, metal molded body, inorganic molded body, composite molded body such as gypsum board) Then, the adhesive sheet, the adhesive label, or the adhesiveness, which is produced by bonding it to a release paper or release film, or by applying it to one side of the release paper or release film and transferring it to the above substrate. There is a molded body to which is added. Further, the pressure-sensitive adhesive composition is coated on both sides of a support such as rayon paper or non-woven fabric and laminated on a double-sided release paper or double-sided release film, or double-sided release paper or double-sided release film. There is a double-sided pressure-sensitive adhesive tape which is produced by applying double-sided coating to and then transferring it to the support. Further, a double-sided adhesive product which is a kind of a non-carrier type double-sided adhesive tape produced by coating the double-sided release paper or the double-sided release film with the pressure-sensitive adhesive composition on both sides without using the support. There is also. A double-sided adhesive tape is particularly preferable as the adhesive product.

[0022]

EXAMPLES The present invention will be specifically described below based on examples. The% and parts described in the examples represent% by weight and parts by weight, respectively. The methods for preparing the raw materials and the like and for evaluating the compositions and the like in each example and comparative example are as follows. (Change in melt viscosity) 80 ° C. at the beginning and after 24 hours, 10
The melt viscosity at 0 ° C. or 150 ° C. was measured with a B type rotational viscometer. (Number average molecular weight) It was measured by gel permeation chromatography (GPC) manufactured by JASCO Corporation using a tetrahydrofuran solvent. It is a number average molecular weight in terms of polystyrene. (Glass transition temperature) It was measured by a differential scanning calorimeter (DSC) manufactured by Seiko Instruments Inc. The temperature rising rate was 10 ° C./min. (Productivity) The thickness of the pressure sensitive adhesive is 25 μm, 40 μm,
And 80 μm, the active energy ray-curable hot melt pressure-sensitive adhesive, solvent-based acrylic pressure-sensitive adhesive and emulsion-type acrylic pressure-sensitive adhesive of the present invention are applied to a polyethylene terephthalate film having a thickness of 25 μm. And dry for 6 seconds with a dryer set at 120 ° C (line speed 100m / min, assuming a drying process of 10m length), immediately take out and dry the surface of the pressure sensitive adhesive. (The state in which the solvent or water was volatilized) was judged as follows by comparison with the one dried at 120 ° C. for 2 minutes. The results are shown in Table 1. Drying rate (%) = pressure-sensitive adhesive dried for 2 minutes / pressure-sensitive adhesive dried for 6 seconds × 100 ○ ... Drying rate of 95% or more Δ ... Drying rate of 70% or more and less than 95% × ... Drying rate of 70 % (Preparation of pressure-sensitive adhesive sheet) After melting the active energy ray-curable hot melt pressure-sensitive adhesive composition at 80 ° C., 120 ° C. or 150 ° C., a pressure-sensitive adhesive composition is formed on a polyethylene terephthalate film having a thickness of 25 μm. 25μ thickness
m, 40 μm, 80 μm by hot melt coating, and the surface of the layer of the composition obtained is irradiated with an electron beam of 1 to 5 Mrad or 150 to 50 Mrad depending on the coating thickness.
Each pressure-sensitive adhesive sheet was obtained by irradiating with ultraviolet rays of 0 mJ / cm ² and curing. Using this pressure sensitive adhesive sheet,
The performance of the pressure sensitive adhesive was evaluated by the following method. (180 degree peel strength) Pressure sensitive adhesive sheet, JIS Z
According to 0237, a 180 ° peel strength was measured using a stainless steel plate as an adherend. Peeling speed is 300m
It was m / min. (Shear holding power) Adhesive area of pressure-sensitive adhesive sheet is 25mm ×
Stick it on a stainless steel plate to be 25 mm,
In accordance with JIS Z 0237, 1K in a constant temperature room at 40 ° C
The load (weight) of g was applied, and the time until the weight fell was measured. (Ball tack) The initial tackiness was measured with a ball tack. J. According to Dow method, measurement angle 30 degrees, measurement temperature 2
It was measured at 0 ° C.

(Production Example of Reactive Polymer) Production Example 1 300 parts of methyl methacrylate and m-isopropenyl-α, α'-dimethylbenzyl isocyanate as the monomer (c) in 207 parts of toluene as a solvent. (ACC
1.5 parts) and 6 parts of benzoyl peroxide as a polymerization initiator were added, and the mixture was polymerized at a reaction temperature of 90 ° C. for 5 hours. Further, 2-hydroxyethyl acrylate as a monomer (g) was added to 0.1 part. 9 parts were added and the reaction was carried out at a reaction temperature of 90 ° C. for 4 hours to obtain a reactive polymer (d-1) solution. The number average molecular weight of this reactive polymer (d-1) is about 11,000,
The glass transition temperature was about 100 ° C. Production Example 2 1000 parts of cyclohexane distilled and purified in a flask,
52 parts of styrene, 50 parts of methyl methacrylate and s
10 ml of a cyclohexane solution containing 2.0 mol / l of ec-butyllithium was added, and polymerization was carried out at a temperature of 50 ° C. under a nitrogen atmosphere. After the polymerization, ethylene oxide gas was introduced to cause a substantial reaction with poly (t-butylstyryl) lithium. Then, 3.0 parts of acryloyl chloride was added to prepare a reactive polymer (d-2) solution. The number average molecular weight of this reactive polymer (d-2) was about 6000, and the glass transition temperature was about 100 ° C.

(Production Example of High Molecular Weight Polymer) Production Example 3 As a solvent, in 50 parts of toluene, 90 parts of n-butyl acrylate, and as a monomer (c), m-isopropenyl-
1.0 part of α, α′-dimethylbenzylisocyanate (manufactured by ACC) and 15.6 g of the reactive polymer (d-1) solution prepared in Preparation Example 1 were added to prepare t as a polymerization initiator.
Add 0.2 parts of hexyl peroxypivalate, polymerize at a reaction temperature of 100 ° C. for 5 hours, and further add 0.4 parts of 2-hydroxyethyl acrylate as a monomer (g) at a temperature of 1
The reaction was carried out at 00 ° C for 3 hours to give a high molecular weight polymer (A-1).
A solution was obtained. This high molecular weight polymer (A-1) had a number average molecular weight of about 24,000 and a glass transition temperature of about -44 ° C. Production Example 4 In 50 parts of toluene as a solvent, 90 parts of n-butyl acrylate and m-isopropenyl- as a monomer (c).
1.0 part of α, α′-dimethylbenzylisocyanate (manufactured by ACC) and 97.2 g of the reactive polymer (d-2) solution prepared in Preparation Example 2 were added to prepare t as a polymerization initiator.
Add 0.2 parts of hexyl peroxypivalate, polymerize for 5 hours at a reaction temperature of 10 ° C., and further add 0.5 parts of glycidyl methacrylate as a monomer (g) at a temperature of 100 ° C. for 3 hours.
The reaction was carried out for a time to obtain a high molecular weight polymer (A-2) solution. This high molecular weight polymer (A-2) had a number average molecular weight of about 23,000 and a glass transition temperature of about -49 ° C. Production Example 5 As a solvent, in 50 parts of toluene, 100 parts of n-butyl acrylate and m-isopropenyl- as a monomer (c).
1.0 part of α, α′-dimethylbenzylisocyanate (manufactured by ACC) and 0.2 part of t-hexylperoxypivalate as a polymerization initiator were added, and the mixture was polymerized at a reaction temperature of 10 ° C. for 5 hours, and then a single amount was added. As a body (g), 0.6 part of 2-hydroxyethyl acrylate was reacted at a temperature of 100 ° C. for 3 hours to obtain a high molecular weight polymer (A-3) solution. The number average molecular weight of this high molecular weight polymer (A-3) is about 24,000,
The glass transition temperature was about -53 ° C.

(Production Example of Low Molecular Weight Polymer) Production Example 6 n-Acrylic acid was added to 100 parts of ethyl acetate as a solvent.
40 parts of butyl, 50 parts of methyl methacrylate, 10 parts of 2-methacryloyloxyethyl isocyanate (manufactured by Showa Denko KK) as the monomer (c), and 5 parts of benzoyl peroxide as a polymerization initiator were added, and the reaction temperature was 100 ° C. Polymerization was carried out for 5 hours, and acrylic acid was used as a monomer (g).
It was adjusted low molecular weight polymer (B ₁ -1) solution 6 parts reacted for 3 hours at a temperature 100 ° C.. The number average molecular weight of the low molecular weight polymer (B ₁ -1) is about 5000, a Tg of about -5 ° C.. Production Example 7 1000 parts of cyclohexane distilled and purified in a flask,
64 parts of n-butyl acrylate, 5 methyl methacrylate
10 parts of a cyclohexane solution containing 0 parts of sec-butyllithium and 2.0 mol / l was charged, and polymerization was performed at a temperature of 50 ° C. under a nitrogen atmosphere. After the polymerization, ethylene oxide gas was introduced to cause a substantial reaction with poly (t-butylstyryl) lithium. Thereafter, 3.0 parts of acryloyl chloride was added to produce a low molecular weight polymer (B _1-2 ) solution. The number average molecular weight of this low molecular weight polymer (B _1-2 ) is about 60.
00, the glass transition temperature was about 25 ° C. Production Example 8 500 parts of toluene, 500 parts of n-butyl acrylate and 20 parts of thioglycolic acid were placed in a flask and heated at a temperature of 80 ° C. under a nitrogen atmosphere. 30 parts of 4,4'-azobis-4-cyanovaleric acid dissolved in 85 parts of toluene were added drop wise to the flask over 2 hours. Polymerization was completed by additional heating for 1 hour. Further, 20 parts of glycidyl methacrylate and 2 parts of triethylamine were added and reacted at 90 ° C. for 5 hours to give a low molecular weight polymer (B ₁ −
3) A solution was prepared. The low molecular weight polymer (B _1-3 ) has a number average molecular weight of about 6000 and a glass transition temperature of about -50 ° C.
Met. Production Example 9 20 parts of isobutyl acrylate, 75 parts of ethyl methacrylate, 5 parts of vinyl acetate and 10 parts of benzoyl peroxide as a polymerization initiator were added in 100 parts of toluene as a solvent, and the reaction temperature was 100 ° C. for 5 hours. polymerized, to prepare a low molecular weight polymer (B ₂ -1) solution. The number average molecular weight of the low molecular weight polymer (B ₂ -1) is about 2400, a Tg of about 25 ° C..

[0026] Example 1 in Production Example 3 to obtain high molecular weight polymer (A-1) solution and the low molecular weight polymer obtained in Production Example 6 (B ₁ -1) solution weight ratio of (A-1) / (B ₁ −1) = 100/100 were mixed, and a phosphite-based tris (nonylphenyl) phosphite was used as an anti-aging agent.
To 0.1 part by weight, the amount was added to 0.1 part and the solvent was removed to obtain a polymer. The high molecular weight polymer (A-
1) 20 parts of ethylene glycol diacrylate (C-1) was added as a reactive diluent (C) to 100 parts of the mixture, and the mixture was stirred and mixed to obtain the target product. The evaluation results are shown in Table 2. Example 2 The polymer weight ratio of the high molecular weight polymer (A-1) solution obtained in Production Example 3 and the low molecular weight polymer (B _1-2 ) solution obtained in Production Example 7 was (A-1) / ( B _1-2 ) = 100/50, and 0.1 part is added to Irganox 1010 (manufactured by Ciba Geigy), which is a hindered phenol type, as an anti-aging agent with respect to 100 parts by weight of the polymer. Thus, a polymer was obtained by removing the solvent. By adding 30 parts of ethylene glycol diacrylate (C-1) as a reactive diluent (C) to 100 parts of the polymer (A-1) in the polymer composition, and stirring and mixing the mixture. I got the object. The evaluation results are shown in Table 2. High molecular weight polymer obtained in Example 3 Production Example 3 (A-1) solution and the low molecular weight obtained in Production Example 8 polymer (B ₁ -3) solution of the polymer weight ratio of (A-1) / ( B ₁ -3) = 100/150, and phosphite-based tris (nonylphenyl) phosphite was used as an anti-aging agent.
A polymer was obtained by adding 0.1 part to 00 parts and removing the solvent. By adding 40 parts of diethylene glycol dimethacrylate (C-2) as a reactive diluent (C) to 100 parts of the high molecular polymer (A-1) in this polymer composition, stirring and mixing I got the object. The evaluation results are shown in Table 3.

Example 4 Tris (nonylphenyl) phosphite, which is a phosphite-based compound, was added to the solution of the high molecular weight polymer (A-2) obtained in Preparation Example 4 as an antioxidant with respect to 100 parts by weight of the polymer. ．
A polymer was obtained by adding 1 part and removing the solvent. As a reactive diluent (C), 30 parts of diethylene glycol dimethacrylate (C-2) and 10 parts of ethylene glycol methyl ether acrylate (C-3) were added to 100 parts of the polymer (A-2), Stirring
The desired product was obtained by mixing. The evaluation results are shown in Table 3. High molecular weight polymer obtained in Example 5 Production Example 4 (A-2) solution as in Production Example 6 obtained in low molecular weight polymer (B ₁ -1) solution of the polymer weight ratio of (A-2) / ( B ₁ −1) = 100/100, and phosphite-based tris (nonylphenyl) phosphite was used as an antiaging agent.
A polymer was obtained by adding 0.1 part to 00 parts and removing the solvent. Polymer (A-1) 100
20 parts of diethylene glycol dimethacrylate (C-2) is added as a reactive diluent (C) to the parts,
The target product was obtained by stirring and mixing. The evaluation results are shown in Table 4. High molecular weight polymer obtained in Example 6 Production Example 4 (A-2) solution as in Preparation Example low molecular weight polymer obtained in 9 (B ₂ -1) solution of the polymer weight ratio of (A-2) / ( B ₂ −1) = 100/50, and phosphite-based tris (nonylphenyl) phosphite was used as an anti-aging agent.
A polymer was obtained by adding 0.1 part to 0 part and removing the solvent. As a reactive diluent (C), 30 parts of ethylene glycol diacrylate (C-1) and 10 parts of ethylene glycol methyl ether acrylate (C-3) were added to 100 parts of the polymer (A-1), The target product was obtained by stirring and mixing. The evaluation results are shown in Table 4. Example 7 An object product was obtained by adding 3 parts of benzoin ethyl ether as a photopolymerization initiator to 100 parts of the composition prepared in Example 1. This object was evaluated for UV curing. The evaluation results are shown in Table 5. Example 8 An object product was obtained by adding 3 parts of benzoin isopropyl ether as a photopolymerization initiator to 100 parts of the composition prepared in Example 2. This object was evaluated for UV curing. The evaluation results are shown in Table 5.

[0028] Comparative Example 1 Preparation Example 5 obtained in high molecular weight polymer (A-3) solution and the low molecular weight polymer obtained in Production Example 6 (B ₁ -1) solution weight ratio of (A-3) / (B ₁ −1) = 100/100 were mixed, and a phosphite-based tris (nonylphenyl) phosphite was used as an anti-aging agent.
To 0.1 part by weight, the amount was added to 0.1 part and the solvent was removed to obtain a polymer. The high molecular weight polymer (A-
3) 20 parts of ethylene glycol diacrylate (C-1) as a reactive diluent (C) was added to 100 parts of the mixture, and the mixture was stirred and mixed to obtain the target product. The evaluation results are shown in Table 6. High molecular weight polymer obtained in Comparative Example 2 Production Example 5 (A-3) solution and the low molecular weight polymer obtained in Production Example 9 (B ₂ -1) solution of the polymer weight ratio of (A-3) / ( B ₂ −1) = 100/50, and phosphite-based tris (nonylphenyl) phosphite was used as an anti-aging agent.
A polymer was obtained by adding 0.1 part to 0 part and removing the solvent. The high molecular weight polymer (A
-3) 30 parts of ethylene glycol diacrylate (C-1) was added as a reactive diluent (C) to 100 parts of the mixture, and the mixture was stirred and mixed to obtain the target product. The evaluation results are shown in Table 6. High molecular weight polymer obtained in Comparative Example 3 Production Example 3 (A-1) solution as in Production Example 6 obtained in low molecular weight polymer (B ₁ -1) solution of the polymer weight ratio of (A-3) / ( B ₁ -1) = 100/50, and phosphite-based tris (nonylphenyl) phosphite was used as an anti-aging agent.
The desired product was obtained by adding 0.1 part to 0 part and removing the solvent. The evaluation results are shown in Table 7.

Comparative Example 4 The solution of the high molecular weight polymer (A-1) obtained in Production Example 3 was supplemented with 0.1% Irganox 1010 which is a hindered phenol type as an anti-aging agent based on 100 parts by weight of the polymer. Parts were added and the solvent was removed to obtain the desired product. The evaluation results are shown in Table 7. Comparative Example 5 obtained high molecular weight polymer in Preparation Example 3 (A-1) solution and the low molecular weight polymer obtained in Production Example 6 (B ₁ -1) solution weight ratio of (A-1) / (B 1 -1) = 100/300, and a phosphite-based tris (nonylphenyl) phosphite was used as an anti-aging agent.
To 0.1 part by weight, the amount was added to 0.1 part and the solvent was removed to obtain a polymer. The high molecular weight polymer (A-
1) Ethylene glycol methyl ether acrylate (C-3) as a reactive diluent (C) for 100 parts
Was added in 45 parts, and the mixture was stirred and mixed to obtain the desired product. The evaluation results are shown in Table 8. Comparative Example 6 To 100 parts of the composition prepared in Comparative Example 1, 3 parts of benzoin isopropyl ether was added as a photopolymerization initiator to obtain an intended product. This object was evaluated for UV curing. The evaluation results are shown in Table 8.

[0030]

[Table 1]

[0031]

[Table 2]

[0032]

[Table 3]

[0033]

[Table 4]

[0034]

[Table 5]

[0035]

[Table 6]

[0036]

[Table 7]

[0037]

[Table 8]

[0038]

As is clear from the above evaluation results, the reactive hot-melt pressure-sensitive adhesive composition of the present invention solves the drawbacks of conventional acrylic hot-melt pressure-sensitive adhesives, and in particular, Before curing, the hot melt coating property at low temperature (about 80 ° C) is excellent, and the curing reaction requires a small amount of irradiation of active energy rays such as ultraviolet rays or electron beams, and heat resistance after curing. Due to its excellent cohesive strength, it can be effectively used in pressure-sensitive adhesive (adhesive) tapes, sheets, labels and the like.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kosuke Suekaka Mitsui Toatsu Chemical Co., Ltd. 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa

Claims (4)

[Claims] 1. 100 parts by weight of a mixture of one or more selected from high molecular weight polymers (A) having an ethylenically unsaturated group and a number average molecular weight of 10,000 to 100,000,
Low molecular weight polymer (B) 2 having a number average molecular weight of 1,000 to 8,000, with or without an ethylenically unsaturated group
An active energy ray-curable hot melt pressure-sensitive adhesive composition, which comprises 100 parts by weight or less and 5 to 50 parts by weight of a reactive diluent (C). High molecular weight polymer (A); a monomer having a vinyl group and an active group in the molecule, and a vinyl group at the molecular side chain or molecular end, a number average molecular weight of 2000 or more and a glass transition temperature of 20 ° C. or more. Of a reactive polymer having an alkyl group and a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 12 carbon atoms, and further having an ethylenically unsaturated group and a group capable of reacting with the active group. A high molecular weight polymer having an ethylenically unsaturated group having a glass transition temperature of (meth) acrylic acid alkyl ester moiety of −75 ° C. to −20 ° C., which is produced by reacting with a polymer. Low molecular weight polymer (B); the following (B ₁ ) and / or (B ₂ ). At least one monomer selected from vinyl acetate and (meth) acrylic acid alkyl ester is copolymerized, and at this time, a glass transition temperature having an ethylenically unsaturated group at a molecular side chain or at a molecular end, -60 ° C-80
Low molecular weight polymer (B ₁ ) having a temperature of ° C. A glass transition temperature having no ethylenically unsaturated group, which is produced by copolymerizing at least one monomer selected from vinyl acetate and (meth) acrylic acid alkyl ester, is −60 ° C. to 80 ° C.
Low molecular weight polymer (B ₂ ) having a temperature of ° C. Reactive diluent (C); a compound having one or more ethylenically unsaturated groups in one molecule and having a molecular weight of less than 1,000. 2. The melt viscosity at 70 to 100 ° C. is 1.
2,000 to 200,000 cps, The active energy ray-curable hot melt pressure-sensitive adhesive composition according to claim 1. 3. An adhesive product using the active energy ray-curable hot melt pressure-sensitive adhesive composition according to claim 1. 4. The method for manufacturing the adhesive product according to claim 3.