JP5510131B2 - Active energy ray-curable composition and method for producing sheet using the same - Google Patents

Description

  The present invention relates to an active energy ray-curable composition particularly useful as an adhesive, a sheet having a cured film of the composition, and a method for producing the sheet.

As a method for producing a polymer, particularly a method for producing a polymer by radical polymerization of a monomer such as an acrylic polymer, aqueous polymerization such as solution polymerization, emulsion polymerization or suspension polymerization using an organic solvent is possible. In addition, bulk polymerization without using a solvent is known.
However, when a polymer obtained by solution polymerization is used, a large amount of energy is required to dry the organic solvent at a high temperature after being applied or impregnated on the substrate, and air pollution by the organic solvent is prevented. For this reason, a large-scale recovery device is required. Further, since organic solvents are easily flammable, a sufficient safety device is required to maintain safety.

  In the case of aqueous polymerization, it is necessary to polymerize a monomer in the presence of an emulsifier or a suspending agent, but the obtained polymer has a drawback that durability and water resistance are lowered by these additives. It was. Even in a system that does not use an emulsifier or the like, since the latent heat of water as a dispersion medium is considerably high, when removing the polymer from the obtained aqueous polymer, for example, when making it into a sheet, it is useful for removing water. Had the problem of requiring enormous energy. Furthermore, in these systems, since water-soluble monomers cannot be used, monomer types are limited, and it is difficult to meet various needs.

  In the case of bulk polymerization, water and solvent are not substantially used, so there is no problem of water removal, solvent removal, or solvent recovery, but it is difficult to control the polymerization rate, and in particular, an acrylic ester having a high polymerization rate is used. It was difficult to carry out the polymerization reaction by controlling the polymerization rate with a reaction apparatus used in aqueous polymerization or solvent polymerization. When using a polymer obtained by bulk polymerization, when applied or impregnated on a substrate, it is necessary to heat and melt and apply it as it is because it has a high viscosity. Since a base material having no heat resistance cannot be used, the base material is limited, and there is a drawback that it is difficult to meet various needs.

Under such circumstances, various methods for producing a pressure-sensitive adhesive or pressure-sensitive adhesive sheet without using water or a solvent have been proposed.
For example, a photopolymerizable liquid composition (Patent Document 1) containing a monomer containing (meth) acrylate as a main component and a photopolymerization initiator having two or more photocleavage points in one molecule, or (meth) acrylate Of a solvent-free acrylic pressure-sensitive adhesive composition containing a monomer having a main component, a (meth) acrylate-based polymer, a photopolymerization initiator and a crosslinking agent, and a solvent-free pressure-sensitive adhesive sheet using the composition A manufacturing method (Patent Documents 2 and 3) has been proposed.

JP-A-2-160802 (Claims) JP 2002-241709 A (Claims) JP 2000-34453 A (Claims)

However, although the composition of Patent Document 1 is improved in terms of reaction efficiency, it is not sufficient in terms of stability during photopolymerization, and the product lot of an adhesive tape manufactured using the composition is different. As a result, there is a possibility that a predetermined performance variation may occur.
On the other hand, in Patent Documents 2 and 3, a monomer containing (meth) acrylate as a main component is partially polymerized by heat or ultraviolet irradiation to produce a syrup, and this is combined with other components to prepare a composition. Manufactured. The obtained composition is applied to a substrate and then heated or irradiated with ultraviolet rays to produce an adhesive sheet. However, in this method, it is difficult to control partial polymerization, and in order to obtain a predetermined reaction rate, it takes time to sample and quantify the residual monomer amount by gas chromatography, or to obtain the nonvolatile content from the heated residue. It was a thing.
Further, the compositions of Patent Documents 2 and 3 are cross-linked by heating together with a commonly used cross-linking agent such as an isocyanate compound or an epoxy compound. However, when using a crosslinking agent such as these, a work called aging is necessary to complete the crosslinking reaction, and the disadvantage of agingless (no aging required) by photopolymerization is impaired. was there.
In Patent Document 3, polyfunctional (meth) acrylate is used as a cross-linking agent. However, the compatibility and polymerization rate of polyfunctional (meth) acrylate and other components are large and different, so that the cross-linking density is increased. There are cases where the heat resistance is insufficient due to the difference between the front and back surfaces and the surface layer of the sheet.

  The present inventor is a solvent-free composition obtained without using water or a solvent, the cured film has good adhesiveness and heat resistance, and variation in adhesiveness between product lots. In order to find an active energy ray-curable composition excellent in adhesion stability such as a small amount and a pressure-sensitive adhesive sheet obtained from the composition, intensive studies were conducted.

As a result of repeated various studies, the inventor has found that a composition containing an ethylenically unsaturated compound having a maleimide group, a low molecular weight ethylenically unsaturated compound, a polymer, and a photopolymerization initiator can solve the above-mentioned problems. The headline and the present invention were completed.
The present invention is described in detail below.

  According to the composition and the pressure-sensitive adhesive sheet of the present invention, it is a solvent-free composition, and its cured film has good adhesiveness and heat resistance, and there is variation in adhesiveness between product lots. It has excellent adhesion stability such as a small amount.

The present invention relates to a compound (A) having a maleimide group and an ethylenically unsaturated group other than a maleimide group (hereinafter referred to as the component (A)), a compound other than the component (A) and having an molecular weight of 300 or less. (B) containing alkyl (meth) acrylate (hereinafter referred to as component (B)) and polymer (C) including a polymer having a maleimide group (hereinafter referred to as component (C)) Containing 0.1 to 15% by weight of component (A), 45 to 97.9% by weight of component (B) based on the total amount of components (A) to (C) (C) It is related with the active energy ray hardening-type composition containing 2 to 40 weight% of components.
Hereinafter, each component will be described.

1. Component (A) The component (A) is a compound having an ethylenically unsaturated group other than a maleimide group and a maleimide group.
The maleimide group in component (A) is preferably a group represented by the following general formula (1).

[However, in General Formula (1), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an alkyl group, or an aryl group, or R ¹ and R ² are combined to form a 5-membered ring. Alternatively, it represents a hydrocarbon group forming a 6-membered ring. ]

As the alkyl group, an alkyl group having 4 or less carbon atoms is preferable.
As the alkenyl group, an alkenyl group having 4 or less carbon atoms is preferable.
A phenyl group etc. can be mentioned as an aryl group.
Examples of the hydrocarbon group that forms a 5-membered ring or 6-membered ring together include a group —CH ₂ CH ₂ CH ₂ —, a group —CH ₂ CH ₂ CH ₂ CH ₂ —, and a group —CH═CH—CH _2. CH ₂ — and the like can be mentioned.

  Preferred specific examples of the maleimide group in the general formula (1) are shown in the following formulas (3) to (8). In the formula (7), X represents a chlorine atom or a bromine atom. Ph in Formula (8) represents a phenyl group.

As R ¹ and R ² , one is a hydrogen atom and the other is an alkyl group having 4 or less carbon atoms, both R ¹ and R ² are alkyl groups having 4 or less carbon atoms, and each forms one to form a carbocycle Saturated hydrocarbon groups are preferred.

  Examples of the ethylenically unsaturated group other than the maleimide group include a vinyl group, a vinyl ether group, a (meth) acryloyl group, and a (meth) acrylamide group, and a (meth) acryloyl group is preferable in terms of easy production.

Examples of the component (A) include compounds in which an ethylenically unsaturated group and a maleimide group are bonded to a skeleton such as an ether skeleton, an ester skeleton, or a urethane skeleton.
As the component (A), a compound represented by the following general formula (2) is preferable because it is easy to produce and excellent in curability.

[However, in Formula (2), R < ¹ > and R < ² > are synonymous with the above. R ³ represents an alkylene group, R ⁴ represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 6. ]

The alkylene group for R ³ may be linear or branched. More preferably, it is a C1-C6 alkylene group.

As a ratio of (A) component, it is necessary to set it as 0.1-15 weight% on the basis of the total amount of (A)-(C) component, Preferably it is 0.5-10 weight%.
By setting the ratio of the component (A) to 0.1% by weight or more, the curability by active energy rays is excellent, and the cured product has excellent heat resistance. Can be excellent.

2. Component (B) The component (B) is a compound other than the component (A) and having an ethylenically unsaturated group having a molecular weight of 300 or less.

As the component (B), various compounds can be used as long as they have an ethylenically unsaturated group having a molecular weight of 300 or less. Specifically, low molecular weight (meth) acrylates, vinyl compounds, vinyl esters, and allyl compounds. Etc.
As these compounds, compounds having one ethylenically unsaturated group are preferred.

Examples of (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) ) Acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, i-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate , Alkyls such as i-nonyl (meth) acrylate, i-myristyl (meth) acrylate, n-decyl (meth) acrylate, i-decyl (meth) acrylate, n-lauryl (meth) acrylate and tridecyl (meth) acrylate ( (Meth) acrylate;
Cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate and tricyclodecane (meth) ) Alicyclic alkyl (meth) acrylates such as acrylates;
Methoxyethyl glycol (meth) acrylate such as methoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, etc. Alkoxy group-containing (meth) acrylates of
Benzyl (meth) acrylate, phenol alkylene oxide modified (meth) acrylate, alkylphenol alkylene oxide modified (meth) acrylate, p-cumylphenol alkylene oxide modified (meth) acrylate and o-phenylphenol alkylene oxide modified (meth) acrylate, etc. (Meth) acrylate having an aromatic ring (the alkylene oxide includes ethylene oxide and propylene oxide);
(Meth) acrylates having a heterocyclic ring such as pentamethylpiperidinyl (meth) acrylate, tetramethylpiperidinyl (meth) acrylate and tetrahydrofurfuryl (meth) acrylate;
Alkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and t-butylaminoethyl (meth) acrylate; and 2- (acetoacetoxy) ethyl (meth) acrylate; and glycidyl ( And (meth) acrylate.

  Examples of the vinyl compound include N-vinylpyrrolidone, N-vinylformamide, acryloylmorpholine, vinyltoluene, N-vinylcaprolactone, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, vinyl acetate, and styrene. .

Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl chloride, vinyl pivalate, vinyl laurate, and vinyl versatate.
Examples of allyl compounds include allyl acetoacetate, allyltrimethylammonium chloride, and dimethylallyl vinyl ketone.

In the composition of the present invention, when a crosslinking agent described later is used in combination, it is preferable that the component (B) contains a compound having a functional group reactive with the crosslinking agent.
Examples of the compound having a functional group reactive with the crosslinking agent include an ethylenically unsaturated compound having a hydroxyl group and an ethylenically unsaturated compound having a carboxyl group.

  Examples of the ethylenically unsaturated compound having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate 3-chloro 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. Hydroxyalkyl (meth) acrylates; polyalkylene glycol mono (meth) acrylates such as glycerol mono (meth) acrylate and diethylene glycol mono (meth) acrylate; hydroxy group-containing aromatics such as 2-hydroxy3-phenoxypropyl (meth) acrylate (Meth) acrylate; N-methylol (meth) acrylamide; and allyl alcohol.

  Examples of the ethylenically unsaturated compound having a carboxyl group include (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, acrylamide N-glycolic acid, cinnamic acid, and (meth) acrylic acid. Michael adduct (eg, acrylic acid dimer, methacrylic acid dimer, acrylic acid trimer, methacrylic acid trimer, acrylic acid tetramer, methacrylic acid tetramer, etc.), 2- (meth) acryloyloxyethyl dicarboxylic acid monoester (eg, 2-acryloyl) Oxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, 2-acryloyloxyethyl phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexa Dorofutaru acid monoester, 2-methacryloyloxyethyl hexahydrophthalic acid mono ester) and the like.

(B) As a component, the compound (henceforth a polyfunctional unsaturated compound) which has a 2 or more ethylenically unsaturated group can also be used.
Examples of the polyfunctional unsaturated compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, di Propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide modified bisphenol A type di (meth) acrylate, propylene oxide modified bisphenol A Type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, pentaerythri Di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, hydroxypivalic acid modified neopentyl glycol di (meth) acrylate Bifunctional (meth) acrylic monomers such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly (meth) a Trifunctional or more (meth) acrylic monomers such relations are exemplified.
In addition to the above, it is also possible to use acrylate compounds such as urethane (meth) acrylate compounds and epoxy (meth) acrylate compounds.

Component (B), of these, include alkyl and (meth) acrylate as an essential component, an alkyl of carbon atoms in the alkyl group 2-20 (meth) acrylate is good preferred, more preferably the number of carbon atoms in the alkyl group 4 to 18 alkyl (meth) acrylates, more preferably (meth) acrylates having 4 to 10 carbon atoms in the alkyl group.
Particularly preferred specific examples are n-butyl (meth) acrylate, n-octyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.

As a ratio of (B) component, it is necessary to set it as 45-97.9 weight% on the basis of the total amount of (A)-(C) component, Preferably it is 60-92.5 weight%.
By setting the proportion of the component (B) to 45% by weight or more, it is possible to make the properties of the target composition excellent, for example, if it is a pressure sensitive adhesive, and the proportion of the component (B) is 97.9. By setting it as weight% or less, the composition can be made excellent in coatability.

3. Component (C) The composition of the present invention contains a large amount of the component (B), which is a low molecular weight compound, and has low viscosity, so that the coating property to the substrate becomes insufficient. End up. For this reason, in this invention, the polymer of (C) component is mix | blended in order to improve the viscosity of a composition and to improve the coating property to a base material.

The molecular weight of the component (C) is preferably a weight average molecular weight (hereinafter referred to as Mw) of 10,000 or more, more preferably 30,000 or more. The upper limit of the Mw of the component (C) is preferably 3 million or less, particularly 2.5 million or less, and more preferably 2 million or less.
By setting Mw of component (C) to 10,000 or more, the cohesive force of the cured product can be made sufficient, while by setting Mw to 3 million or less, component (C) Are compatible with each other.
In addition, Mw in the present invention means a weight average molecular weight in terms of standard polystyrene molecular weight, and is used in high performance liquid chromatography (manufactured by Japan Waters, “Waters 2695 (main body)” and “Waters 2414 (detector)”) in a column. : Shodex GPC KF-806L (exclusion limit molecular weight: 2 × 10 7, separation range: 100 to 2 × 10 7, theoretical plate number: 10,000 plates / piece, filler material: styrene-divinylbenzene copolymer, filler particle size : 10 μm) is measured by using three series.

  Further, the dispersity (Mw / Mn) of the component (C) is preferably 20 or less, particularly preferably 15 or less. When the degree of dispersion (Mw / Mn) of the polymer (A) is too large, there is a tendency for fluctuation due to cohesive force and heat-resistant active energy ray irradiation conditions to increase. The lower limit of the degree of dispersion (Mw / Mn) is usually 2.

Various glass transition temperatures (hereinafter referred to as Tg) of the component (C) can be used according to the purpose, and when the composition is used as an adhesive sheet, it is preferably -80 to 20 ° C. More preferably, it is −60 to 0 ° C., and further preferably −55 to −10 ° C. When the Tg of the component C) is −80 ° C. or higher, the cohesive force can be made excellent. On the other hand, if the Tg is too high, the pressure-sensitive adhesive tends to become brittle.
In the present invention, Tg means a value calculated from the Fox equation.

As a ratio of (C) component, it is necessary to set it as 2-40 weight% on the basis of the total amount of (A)-(C) component, Preferably it is 3-15 weight%.
If it is lower than 2% by weight, the liquid viscosity necessary for obtaining a smooth sheet becomes low, and there is a possibility that repellency may occur and a smooth surface cannot be obtained. On the other hand, if it is higher than 40% by weight, the liquid viscosity becomes high and handling may be deteriorated, or there may be a streak during coating and a smooth coated surface may not be obtained.

As the component (C), various compounds can be used as long as they are polymers, and examples thereof include polyacrylates, polyethers, polyesters, polyamides, and polycarbonates.
As the component (C), a polymer obtained by radical polymerization using a radical polymerizable monomer is preferable. Among these, a linear polymer is preferable because of its excellent solubility in the composition.
The body is preferred.
As the component (C), a polymer obtained by radical polymerization using a radical polymerizable monomer (hereinafter referred to as (CR) polymer) and a polymer having a maleimide group (hereinafter referred to as (CM) polymer) ] it is rather preferable that, those containing as essential components (CM) polymer.
Hereinafter, the (CR) polymer and the (CM) polymer will be described.

3-1. (CR) Polymer
In the (CR) polymer, as the radically polymerizable monomer, various compounds can be used as long as they are radically polymerizable compounds. Compounds having one (meth) acryloyl group [hereinafter referred to as monofunctional ( (Meth) acrylates], vinyl compounds, vinyl esters, conjugated dienes, and (meth) acrylamides.

Examples of the monofunctional (meth) acrylate, vinyl compound, and vinyl ester include the same compounds as those described above for the component (B).
Examples of the conjugated diene include butadiene, isoprene, chloroprene, and isobutylene.
Examples of (meth) acrylamide include (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-methoxybutyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, 2- (meth) acrylamide-2-methylpropanesulfonic acid, N-isopropyl (meth) acrylamide and the like can be mentioned.

In the composition of the present invention, when a cross-linking agent described later is used in combination, a copolymer obtained by polymerizing a cross-linking agent and a compound having a reactive functional group as the radical polymerizable monomer is preferable.
Examples of the compound having a functional group reactive with the crosslinking agent include an ethylenically unsaturated compound having a hydroxyl group and an ethylenically unsaturated compound having a carboxyl group.
Examples of the ethylenically unsaturated compound having a hydroxyl group and the ethylenically unsaturated compound having a carboxyl group include the same compounds as those described above for the component (B).

As component (C), there is no problem that the polymerization reaction due to active energy rays is hindered, and the cured product is excellent in transparency, and other constituent components are uniformly mixed and turbidity does not occur. Is preferred.
As the component (C), a (meth) acrylate polymer having (meth) acrylate and a main component is preferable in that the compatibility with other components is excellent and the resulting composition does not become cloudy.

  The (C—R) polymer may be produced according to a conventional method, and examples thereof include solution radical polymerization, suspension polymerization, bulk polymerization, and emulsion polymerization.

Examples of the method for producing by radical polymerization by a solution polymerization method include a method in which a raw material monomer to be used is dissolved in an organic solvent and heated and stirred in the presence of a thermal polymerization initiator.
Further, a chain transfer agent can be used to adjust the molecular weight of the polymer, if necessary.
Examples of the thermal polymerization initiator used include peroxides that generate radical species by heat, azo compounds, and redox initiators.
Examples of the organic solvent include hydrocarbon solvents, alcohol solvents, ether solvents, ketone solvents, ester solvents, nitrogen compound solvents, and sulfur compound solvents.

3-2. (CM) Polymer
Examples of the maleimide group in the (CM) polymer include the same groups as those described above for the component (A).

As the (CM) polymer, polymers obtained by various methods can be used, but the following four types of polymers are preferable in view of easy production.
[1] A compound having an ethylenically unsaturated group other than a maleimide group and a maleimide group, and a copolymer of an ethylenically unsaturated monomer copolymerizable therewith (hereinafter referred to as polymer M1)
[2] An addition reaction product of a prepolymer having two or more isocyanate groups and a compound having a maleimide group and an active hydrogen group (hereinafter referred to as polymer M2).
[3] An esterification reaction product of a prepolymer having two or more hydroxyl groups and a carboxylic acid having a maleimide group (hereinafter referred to as polymer M3).
[4] An esterification reaction product of a prepolymer having two or more carboxyl groups and a compound having a maleimide group and an active hydrogen group (hereinafter referred to as polymer M4).
Hereinafter, the polymers M1 to M4 will be described.

3-2-1. Polymer M1
The polymer M1 is a copolymer of a maleimide group and a compound having an ethylenically unsaturated group other than the maleimide group and an ethylenically unsaturated monomer copolymerizable therewith.
As the compound having a maleimide group and an ethylenically unsaturated group other than the maleimide group, the same compounds as those described above for the component (A) can be used.
As the ethylenically unsaturated monomer having copolymerizability, those similar to the component (B) described above can be used.
The polymer M1 may be produced by the same method as described for the (CR) polymer using these monomers.

3-2-2. Polymer M2
The polymer M2 is an addition reaction product of a prepolymer having two or more isocyanate groups (hereinafter simply referred to as a urethane prepolymer) and a compound having a maleimide group and an active hydrogen group (hereinafter simply referred to as a maleimide active hydrogen compound). A maleimide active hydrogen compound is reacted for 2 moles or more per mole of urethane prepolymer.
Hereinafter, the urethane prepolymer and the maleimide active hydrogen compound will be described.

A) Urethane prepolymer As the urethane prepolymer, various compounds can be used as long as they have two or more isocyanate groups at the molecular ends.
Examples of the urethane prepolymer include a reaction product of a polyol having two or more hydroxyl groups (hereinafter simply referred to as polyol) and a polyisocyanate having two or more isocyanate groups (hereinafter simply referred to as polyisocyanate).

a1) Examples of the polyol polyol include polyether polyol, polyester polyol, and polymer polyol produced from a radical polymerizable monomer. Among these, polyether polyols and polyester polyols are preferable in that the resulting cured coating film has a low viscosity, and the resulting adhesive is excellent in water resistance in addition to adhesiveness.

a1-1) Polyether polyol As the polyether polyol, polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol and polytetramethylene glycol; ethylene glycol, propanediol, propylene glycol, tetramethylene glycol, pentamethylene glycol, Ethylene oxide modified products, propylene oxide modified products, butylene oxide modified products and tetrahydrofuran modified products of alkylene glycols such as hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane and dipentaerythritol; Copolymer of ethylene oxide and propylene oxide, propylene glycol Copolymer of ethylene and tetrahydrofuran; copolymer of ethylene glycol and tetrahydrofuran; hydrocarbon polyols such as polyisoprene glycol, hydrogenated polyisoprene glycol, polybutadiene glycol and hydrogenated polybutadiene glycol; and polytetramethylene hexaglyceryl ether ( And the like, and the like.

a1-2) Polyester polyol The polyester polyol is a random copolycondensation product of a polyvalent carboxylic acid and a polyhydric alcohol. Among these, aliphatic polyester polyols are preferable because they are excellent in curability by active energy rays of the composition.

Here, various polycarboxylic acids can be used as long as they have two or more carboxyl groups in the molecule. Specifically, succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, eicoic acid diacid, 2,6-naphthalenedicarboxylic acid, trimellitic acid, glutaric acid, 1,9 -Nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, malonic acid, fumaric acid, 2,2-dimethylglutaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid Examples include acids, itaconic acid, maleic acid, 2,5-norbornane dicarboxylic acid, 1,4-terephthalic acid, 1,3-terephthalic acid, dimer acid, and paraoxybenzoic acid.
Among these, aliphatic dicarboxylic acids are preferable, and adipic acid and sebacic acid are more preferable.

Any polyhydric alcohol can be used as long as it has two or more hydroxyl groups in the molecule. Specifically, butylethylpropanediol, 2,4-diethyl-1,5-pentanediol, 3-methyl-1,5-pentanediol and polyethylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,2-octanediol, 1,8-octanediol, 1,9-nonanediol, 1,2, decanediol, 1,10-decanediol, 2 , 2-Dimethyl-1,3-propanediol, 2,2,4-trimethyl-1,6 Hexanediol, 1,3-cyclohexanedimethanol and 1,4-cyclohexane dimethanol, etc. diol dimer acid and 2-methyl-1,8-octanediol and the like.
Among these, aliphatic diols are preferable, and butylethylpropane diol, 2,4-diethyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, dimer acid diol and 2-methyl-1, 8-octanediol is more preferable because the resulting composition has a low viscosity and is excellent in adhesiveness and water resistance.

As a method for producing the polyester polyol, a general esterification reaction may be followed, and examples thereof include a method in which a polyvalent carboxylic acid and a polyhydric alcohol are heated with stirring in the presence of a catalyst.
As said catalyst, the catalyst normally used by esterification reaction can be used, A base catalyst, an acid catalyst, a metal alkoxide, etc. are mentioned.
What is necessary is just to set suitably as reaction temperature and time in esterification reaction according to the objective. As reaction temperature, 80-220 degreeC is preferable.

a1-3) Polymer polyol A polymer polyol produced from a radically polymerizable monomer includes a polymer having an ethylenically unsaturated group and a monomer having a hydroxyl group as essential components. More specifically, those obtained by polymerizing hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate, and other radical polymerizable monomers such as (meth) acrylate, etc. It is done.
Examples of the method for producing the polymer polyol include a method for producing a radical polymerizable monomer by solution polymerization or high temperature continuous polymerization.

a2) Various polyisocyanates can be used as long as they have two or more isocyanate groups in the molecule. Specifically, p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, 4,4′-diphenylene diisocyanate, 1,5-octylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexa Methylene diisocyanate, pentamethylene diisocyanate, 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methyl 2,4-cyclohexane diisocyanate, methyl 2,6-cyclohexane diisocyanate, diphenylmethane Diisocyanate, 1,4-bis (isocyanatemethyl) cyclohexane, 1,3-bis (isocyanatemethyl) cyclohexane, Examples include sophorone diisocyanate and carbodiimide-modified 4,4′-diphenylmethane diisocyanate.
Among these, alicyclic or aliphatic isocyanates are preferable in that they are excellent in curability by active energy rays of the composition and weather resistance of the cured product. As the alicyclic or aliphatic isocyanate, hexamethylene diisocyanate and isophorone diisocyanate are preferable.
Polyisocyanate can use 2 or more types together as needed.
In the present invention, the amount of the polyisocyanate with respect to the polyol in producing the urethane prepolymer is preferably in a range where the equivalent ratio of group-NCO / group-OH is 1.8 to 3, more preferably 2 to 2. .5.

a3) Method for Producing Urethane Prepolymer The urethane prepolymer may be produced by a conventional method. For example, a method of heating a polyol and a polyisocyanate in the presence of a catalyst can be mentioned.
As a catalyst, the catalyst used by a general urethanation reaction can be used, for example, a metal compound, an amine, etc. are mentioned. Examples of the metal compound include tin catalysts such as dibutyltin laurate and tin dioctylate, lead catalysts such as lead dioctylate, zirconium catalysts, aluminum catalysts, and titanate catalysts such as tetra 2-ethylhexyl titanate. Examples of the amine include triethylamine, N, N-dimethylbenzylamine, triphenylamine, and triethylenediamine.
In the production of the urethane prepolymer, a general radical polymerization inhibitor such as hydroquinone and triethylamine can be used as necessary for the purpose of preventing gelation during the reaction.

B) Maleimide active hydrogen compound As the maleimide active hydrogen compound, an alcohol having a maleimide group (hereinafter referred to as maleimide alcohol) is preferable. Specifically, a compound in which a maleimide group and a hydroxyl group are linked by an alkylene group can be exemplified.

C) Manufacturing method (A) As a manufacturing method of a component, what is necessary is just to manufacture a urethane prepolymer and a maleimide active hydrogen compound according to a general urethanation reaction. Specific examples of the urethanization reaction include the same methods as described above.
In the production of the component (A), it is preferable to react in the presence of an antioxidant in order to prevent discoloration of the resulting maleimide compound.
Antioxidants include phenolic, phosphite triesters and amine antioxidants that are commonly used.

3-2-3. Polymer M3
The polymer M3 is an esterification reaction product from a prepolymer having two or more hydroxyl groups (hereinafter simply referred to as a polyol prepolymer) and a carboxylic acid having a maleimide group (hereinafter referred to as a maleimide carboxylic acid).
Examples of the polyol prepolymer include the same polyols.
As the maleimide carboxylic acid, various compounds can be used, and examples thereof include compounds in which a maleimide group and a carboxyl group are linked by an ethylene group.
The polyol prepolymer, maleimide carboxylic acid, and esterification reaction method may follow the same method as described above.

3-2-4. Polymer M4
The polymer M4 is an esterification reaction product of a prepolymer having two or more carboxyl groups at the terminal (hereinafter simply referred to as carboxylic acid prepolymer) and a maleimide active hydrogen compound.
Examples of the carboxylic acid prepolymer include those produced using the same polycarboxylic acid and polyol or polyhydric alcohol as described above.
Examples of the maleimide active hydrogen compound include those described above.
The esterification reaction method with the carboxylic acid prepolymer and the maleimide active hydrogen compound may follow the same method as described above.

4). Other components The composition of the present invention essentially comprises the above-mentioned components, but various components can be blended as necessary within the range not impairing the object of the present invention.

The composition of the present invention is cross-linked and cured by irradiation with active energy rays, but in the case of curing with ultraviolet rays and visible rays, a photopolymerization initiator [hereinafter referred to as component (D)] is blended. In the case of curing with an electron beam, it is not always necessary to add the component (D).
In the composition of the present invention, the maleimide group in the component (A) is subjected to photodimerization by irradiation with active energy rays, so that a photopolymerization initiator is unnecessary or can be used in a smaller amount than usual.

  The photopolymerization initiator of component (D) is not particularly limited as long as it generates radicals by the action of light, and an intramolecular self-cleavage photopolymerization initiator or a hydrogen abstraction photopolymerization initiator is used. It is done.

Examples of the intramolecular self-cleaving photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one 1- (4-Isopropylenephenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2 -Hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, benzoin, Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether , Benzoin isobutyl ether, benzyldimethyl ketal, α-acyloxime ester, acylphosphine oxide, methylphenylglyoxylate, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 4-benzoyl -4'-methyldiphenyl sulfide and the like. Among them, 2-hydroxy-2-methyl-1-phenylpropan-1-one and 1-hydroxycyclohexyl phenyl ketone are preferable.

Examples of the hydrogen abstraction type photopolymerization initiator include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 2,4,4, 6-trimethylbenzophenone, 4-methylbenzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, camphorquinone, dibenzosuberone, 2-ethylanthra Examples include quinone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, benzyl, 9,10-phenanthrenequinone, among which benzophenone, methylbenzophenone, 2,4,6- Trimethylbenzo Enon is preferred.
These components (D) are used alone or in combination of two or more.

  Further, if necessary, triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michler's ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid as an auxiliary for component (D) Ethyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2 , 4-Diisopropylthioxanthone can also be used in combination.

The proportion of component (D) may be appropriately set according to the purpose, but is preferably 0.1 to 10% by weight, more preferably 0.2 to 5% by weight in the composition.
By making the proportion of component (D) 0.1% by weight or more, it is possible to prevent variation in polymerization due to irradiation of active energy rays such as ultraviolet rays, and to make it 10% by weight or less. Odor can be prevented and coloring of the cured product can be prevented.

  As crosslinking agents, generally used crosslinking agents such as isocyanate-based, epoxy-based, metal salts, metal alkoxides, aldehyde-based compounds, non-amino resin-based amino compounds, urea-based, metal chelate-based, melamine-based, aziridin-based, etc. Can be mentioned.

  Further, in the present invention, rosin, rosin ester, hydrogenated rosin ester, phenol resin, aromatic modified terpene resin, aliphatic petroleum resin, alicyclic petroleum resin, styrene resin as long as the effects of the present invention are not impaired. In addition, a tackifier such as a xylene-based resin, a known additive, and a compound that causes coloration or discoloration upon irradiation with ultraviolet rays or radiation can be added.

5). Production / Use Method The composition of the present invention is produced by using the essential components (A) to (C) and further using other desired components as necessary, followed by stirring and mixing according to a conventional method. can do.
In this case, it can be heated or heated as necessary, and is preferably 60 ° C. or lower.
The composition of the present invention is preferably substantially free of a solvent. A composition in which each constituent component is uniformly compatible is preferable.

The composition of the present invention can be used for various applications, and examples thereof include pressure-sensitive adhesives, adhesives, inks, coating agents, resists and molding agents.
The composition of the present invention can be preferably used as an adhesive.
When using the composition of this invention as an adhesive, what makes Tg of hardened | cured material become -90--10 degreeC is preferable.

  As a method of using the composition of the present invention, a conventional method may be used, and examples include a method of irradiating active energy rays after applying the composition to a substrate.

As a base material, what is necessary is just to set suitably according to the objective, and paper, wood, a plastics, ceramics, metal foil, etc. can be mentioned.
Examples of plastics include polyolefins such as polyethylene, polypropylene, and cyclic polyolefins (resins obtained from cyclic olefins such as norbornene and tetracyclododecene and their derivatives); polyvinyl chloride resins, polyvinylidene chloride, chlorinated polypropylene, and the like Chlorinated plastics; polystyrene; cellulose resins such as triacetyl cellulose (TAC); acrylonitrile-butadiene-styrene resin (ABS resin); polymethyl methacrylate; polyamide; polyimide; polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc. Polyester; Polycarbonate; Polyurethane; Polyvinyl alcohol; and ethylene-vinyl acetate copolymer. Depending on the intended use, it is also possible to use a material whose surface is subjected to treatment such as metal vapor deposition.
Examples of ceramics include oxides, composite oxides, and nitrides of various metals such as silicon, aluminum, zinc, indium, tin, titanium, barium, zirconium, cerium, and yttrium.
Examples of the metal include iron, aluminum, copper, zinc, and stainless steel.
The plastic is preferably a sheet or film.
Examples of the release material include non-surface-treated OPP film (polypropylene), silicone-treated polyethylene terephthalate (PET) film, and paper whose surface is silicone-treated.
When the polymer is adhered, an activation treatment can be performed on one or both surfaces in order to increase the interlayer adhesion. Examples of the surface activation treatment include plasma treatment, corona discharge treatment, chemical treatment, surface roughening treatment, etching treatment, and flame treatment, and these may be used in combination.

  The coating method may be appropriately set depending on the purpose, and includes conventionally known roll coating, die coating, knife coating, and the like.

The active energy ray may be appropriately set depending on the purpose, and includes rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, electromagnetic waves such as X-rays and γ rays, electron beams, proton rays, neutron rays, and the like. Ultraviolet rays are preferable from the viewpoints of curing speed, availability of an irradiation device, price, and the like.
For the ultraviolet irradiation, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless discharge lamp, an ultraviolet LED, or the like that emits light in a wavelength range of 150 to 450 nm can be used.

Although the composition of this invention can be used for various uses as above-mentioned, it can be preferably used as an adhesive.
The method of using the composition of the present invention as a pressure-sensitive adhesive includes a method of applying the composition of the present invention to a base material, pasting it with another base material, and irradiating active energy rays. Can be mentioned.
In this case, the active energy ray may be irradiated from either the original base material side or the other base material side. However, either the original substrate or the other substrate needs to be transparent.

Further, when a flexible base material (hereinafter referred to as “flexible base material”) such as a plastic film is used as the base material, it can be bonded not only in a flat state but also in a curved surface state. .
That is, there is a method in which a flexible base material is bent into a concave state or a convex state, the composition is applied in this state, the other flexible base material is bonded, and active energy rays are irradiated.
As another method, the composition of the present invention is applied in a flat state on a flexible substrate, the other flexible substrate is bonded together, bent into a concave state or a convex state, and irradiated with active energy rays. And bonding them.
In this case, as a method for applying the composition in a planar state, the above-described method may be followed. Examples of the method of coating the composition in a curved surface include a method using a spray, dip, curtain flow coater, screen printing, slot die coater and the like.

When using the composition of this invention as an adhesive, it is preferable to use as an adhesive sheet especially.
In the case of producing an adhesive sheet using the composition of the present invention, it is preferable to use a release sheet in addition to the base sheet.
Examples of the manufacturing method in this case include the following four manufacturing methods.
(1) Method of irradiating active energy ray after applying composition on substrate sheet and pasting release sheet on cured film (2) After applying composition on release sheet, active Method of irradiating energy rays and pasting base sheet or release sheet on cured film (3) After applying composition on base sheet, release sheet is pasted and irradiated with active energy rays Method (4) Method of applying the composition on the release sheet, bonding the release sheet, and irradiating this with active energy rays In this case, the irradiation of the active energy rays is performed on the base sheet side or the release sheet. It can be from either side. However, either the base sheet or the release sheet needs to be transparent.

  When pasting after irradiation with active energy rays, it is more preferable to irradiate active energy rays in an inert gas atmosphere in order to eliminate polymerization inhibition factors due to oxygen during irradiation with active energy rays. It is also possible to bond a release sheet or a base sheet for the purpose of blocking oxygen, or to balance the physical properties by adjusting the irradiation conditions in consideration of the polymerization inhibition factor due to oxygen.

Examples of the active energy ray include the same as described above.
In the present invention, the exposure dose of the actinic energy ray is preferably at 500 mJ / cm ² or more, more preferably 1000 mJ / cm ² or more, particularly more preferably 1500 mJ / cm ² or more. By setting the irradiation amount to 500 mJ / cm ² or more, it is possible to prevent variations in polymerization due to active energy ray irradiation. The upper limit of the irradiation amount is usually 10,000 mJ / cm ² . If the irradiation amount is too large, it is not practical due to the device and cost.

  What is necessary is just to set suitably the thickness of the composition hardened | cured material layer of an adhesive sheet according to a use, 3-200 micrometers is preferable, Furthermore, 5-50 micrometers is preferable. By making this thickness 3 μm or more, the performance can be stabilized, and by making it 200 μm or less, it is possible to reach an active energy ray to the deep part of the composition, and the resulting cured film has heat resistance. Can be excellent.

Similarly to the above, in the production of the pressure-sensitive adhesive sheet, when a flexible base material is used, it can be bonded not only in a flat state but also in a curved surface state. In this case, both the adherend and the release sheet need to be flexible substrates.
The bonding method in this case may include the same method as described above. The flexible base material is folded into a concave state or a convex state, and after applying the composition in this state, the other flexible base material is attached. The method of bonding and irradiating an active energy ray is mentioned.
As another method, the composition of the present invention is applied in a flat state on a flexible substrate, the other flexible substrate is bonded together, bent into a concave state or a convex state, and irradiated with active energy rays. And bonding them.
In this case, the method similar to the above is mentioned as a method of applying a composition in a planar state and a method of applying a composition in a curved surface state.

The pressure-sensitive adhesive sheet of the present invention can be used for applications such as decorative sheets, optical sheets, and pressure-sensitive adhesive tapes by designing each component.
More specifically, various adhesives such as packaging adhesive tape, office adhesive tape, medical adhesive product, agricultural adhesive product, electrical insulating tape, masking tape or sheet, adhesive label, double-sided adhesive tape and special adhesive tape. Can be used for processed agents.
In addition, in applications that require particularly high adhesive performance, in addition to bonding metals and glass used in automobiles, etc., adhesive tapes, adhesive labels, special adhesive tapes, polarizing plates used for electrical and electronic parts. It can be used for adhesive tapes or sheets for optical parts such as, adhesive labels and the like.
Furthermore, it can be used for the production of automobile parts, the production of electricity and electronic parts, and the production of optical parts such as polarizing plates.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples.
In the following description, “parts” and “%” mean weight basis unless otherwise specified.

[Production Example 1: Production of polymer having maleimide group (polymer M1)]
In a flask equipped with a stirrer, thermometer, and condenser, at room temperature, 13.0 g of a compound represented by the following formula (9) (hereinafter referred to as THPI), 81.0 g of butyl acrylate (hereinafter referred to as BA), acrylic 5.0 g of acid (hereinafter referred to as AA), 1.0 g of hydroxyethyl acrylate (hereinafter referred to as HEA), 100 g of ethyl acetate and 0.5 g of 2,2′-azobis (2-methylbutyronitrile) (hereinafter referred to as AMBN) ) And uniformly dissolved.
Thereafter, the temperature was raised and the mixture was stirred at 78 ° C. for 8 hours. Subsequently, the system was depressurized to remove ethyl acetate and unreacted substances. Mw of the obtained copolymer was about 500,000. The obtained copolymer is referred to as P3.

[Production Example 2: Production of polymer having maleimide group (polymer M2)]
In a flask equipped with a stirrer, a thermometer and a cooler, polyester polyol Kyowapol 5000PA [polyester diol, a reaction product of 2,4-diethyl-1,5-pentanediol and adipic acid, Kyowa Hakko Kogyo Co., Ltd. )] Was added, the temperature was raised to 120 ° C. with stirring, and the mixture was dehydrated under reduced pressure for 1 hour.
After dehydration, the mixture was cooled to 80 ° C., 22.8 g of isophorone diisocyanate was added thereto and mixed for 1 hour, and then 0.050 g of di-n-butyltin dilaurate was added and reacted for 2 hours. Further, 15.9 g of 2-hydroxyethyl citracimide was charged and reacted for 2 hours to obtain a polymer.
The viscosity of this polymer at 25 ° C. was 600,000 mpa · S, and Mw was about 50,000. This polymer is referred to as P4.

[ Reference Example 1]
○ Production of composition As component (A), 10 parts of THPI, as component (B), 78.0 parts of BA and 2.0 parts of HEA, as component (C), 10.0 parts of Baymac G shown below As the component (D), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name: “Darocur 1173”; manufactured by Ciba Specialty Chemicals Co., Ltd., hereinafter referred to as DC) Was put into a container equipped with a stirrer, stirred and mixed for 24 hours to dissolve, and an active energy ray-curable composition was obtained.
● Baymac G: DuPont brand name. Ethylene acrylic rubber with the following constituent monomer units. Mw: about 290,000. Tg: about -29 ° C. Hereinafter referred to as P1.
Ethylene / methyl acrylate / acrylic acid = 70 / 29.2 / 0.8 (weight ratio)
The viscosity of the obtained composition was 3,000 mPa · s / 25 ° C.

○ Manufacture of pressure-sensitive adhesive sheet The composition obtained above was bubbled with nitrogen for 30 minutes, and after dissolved oxygen reached the lower limit of detection with a dissolved oxygen meter B-505 manufactured by Iijima Electronics Co., Ltd., the untreated thickness Was coated in a nitrogen-substituted glove book so that the thickness of the film was 25 μm on a 60 μm OPP substrate. Further, a biaxially stretched polypropylene (OPP) base material having a thickness of 60 μm subjected to the release treatment was used and bonded so that the release treatment surface was in contact with the coated surface.
Thereafter, a chemical light having an irradiation intensity of 40 mW / cm ² was used for 30 minutes of ultraviolet irradiation for photopolymerization to obtain an adhesive sheet.
A part of this pressure-sensitive adhesive sheet was cut out, and the extract obtained by soaking in THF (tetrahydrfuran) for 7 days at room temperature was analyzed. As a result, the unreacted BA was less than 0.1%.
The following (1)-(3) was evaluated using the obtained adhesive sheet. The evaluation results are shown in Table 3.

<Evaluation test of adhesive sheet>
(1) Adhesive strength test The obtained adhesive tape was measured for 180 ° peel strength according to JIS Z-0273. As the adherend, a SUS304 plate subjected to BA treatment (bright heat treatment and skin pass after cold rolling) was used.

(2) Holding power test According to JIS Z-0273, the obtained adhesive tape was applied with BA-treated SUS304 as an adherend, stuck at a sticking area of 25 mm x 25 mm, left at 60 ° C for 20 minutes, and then 1 kg. The following load was measured and evaluated as follows.
○ ・ ・ ・ Don't fall even after being left for 24 hours. Δ ・ ・ ・ Deviation within 1 mm after being left for 24 hours.

(3) Adhesive stability The adhesive tape was prepared three times by changing the working days by the methods of the above Examples and Comparative Examples, and the adhesive strength was measured for each of the obtained three levels of the adhesive tape, and the average value was obtained. When all three levels of adhesive tape have adhesive strength within 10% error, it is evaluated as ◯ when 1 level is within 10% error, and x when 2 level or more is within 10% error. did.

[ Reference Examples 2 and 3, Examples 1 to 3, Comparative Examples 1 and 2]
A composition was produced in the same manner as in Example 1 except that the types and blending ratios of the components were changed to Tables 1 and 2 below.
Using the obtained composition, a pressure-sensitive adhesive sheet was produced in the same manner as in Examples, and the results are shown in Table 3.
It was.

Abbreviations in Table 1 mean the following, except for those defined above.
・ EMA: Ethyl methacrylate (THPI and Tg are almost the same)
P2: polybutyl acrylate, Mw of about 410,000 TMPTA: trimethylolpropane triacrylate L-45: polyfunctional polyisocyanate, Nippon Polyretane Kogyo Co., Ltd. Coronate L45

Abbreviations in Table 2 mean the following, except for those defined above.
P5: LumiCure MIA200 [trade name, manufactured by DIC Corporation, polyether bismaleimide acetate represented by the following formula (10)]

The composition of this invention can be used for various uses, such as an adhesive, an adhesive agent, ink, a coating agent, a resist, and a molding agent, and can be preferably used especially as an adhesive. Furthermore, the composition of the present invention can be used for various applications by forming a cured film on a substrate, and can be particularly preferably used as an adhesive sheet.

Claims (9)

Compound (A) having an ethylenically unsaturated group other than a maleimide group and a maleimide group, a compound other than the component (A), a compound having an ethylenically unsaturated group having a molecular weight of 300 or less, and an alkyl (meth) acrylate A composition containing (B) and a polymer (C) containing a polymer having a maleimide group, wherein the component (A) is added in an amount of 0.1 based on the total amount of the components (A) to (C). An active energy ray-curable composition comprising -15% by weight, 45 to 97.9% by weight of component (B), and 2 to 40% by weight of component (C).   The active energy ray-curable composition according to claim 1, which does not contain an organic solvent. The active energy ray-curable composition according to claim 1 or 2 , wherein the component (C) is a polymer having a weight average molecular weight of 10,000 or more. Furthermore, the active energy ray hardening-type composition in any one of Claims 1-3 containing a photoinitiator (D). The active energy ray hardening-type composition of Claim 4 which contains 0.1-10 weight% of photoinitiators (D) in a composition. The active energy ray hardening-type adhesive composition containing the composition in any one of Claims 1-5 . The adhesive sheet containing the cured film of the composition in any one of Claims 1-6 on a base material. The manufacturing method of the sheet | seat which irradiates an active energy ray after coating the composition in any one of Claims 1-6 on a base material. The manufacturing method of the adhesive sheet which irradiates an active energy ray after applying the composition in any one of Claims 1-6 to a base material.