JP2023176225A - Active energy ray-curable adhesive composition - Google Patents

Abstract

To provide an active energy ray-curable adhesive composition which has excellent curability even in an irradiation condition of low integrated light quantity, a cured film of which has excellent adhesive force and weatherability (light resistance and water resistance) and also has a low odor.SOLUTION: An active energy ray-curable adhesive composition comprises the following components (A), (B), and (C) as essential components. component (A): a urethane (meth)acrylate having a weight average molecular weight of 10,000 to 100,000. component (B): a compound having one ethylenic unsaturated group other than (meth)acrylamide, comprising at least component (b1) which is a compound having one ethylenic unsaturated group and an aromatic ring or an alicyclic structure. component (C): a photoinitiator comprising as essential components a photoinitiator (C-1) having a molecular weight of 300 or more except acylphosphine oxide-based compounds and/or an acylphosphine oxide-based compound (C-2).SELECTED DRAWING: None

Description

The present invention relates to an active energy ray-curable adhesive composition, which can be used for various purposes such as adhesive labels, adhesive tapes, and special adhesive films, and belongs to these technical fields.
In this specification, an acryloyl group and/or a methacryloyl group will be referred to as a (meth)acryloyl group, an acrylate and/or a methacrylate will be referred to as a (meth)acrylate, and an acrylic acid and/or a methacrylic acid will be referred to as a (meth)acrylic acid. Expressed as
In addition, in this specification, "monofunctional" means a compound having one ethylenically unsaturated group such as a (meth)acryloyl group, and "polyfunctional" means a compound having one ethylenically unsaturated group such as a (meth)acryloyl group. It means a compound having two or more sexually unsaturated groups.

Adhesives are used for various labels, tapes, etc., taking advantage of their ability to be peeled off after being applied. Adhesives are broadly classified into solvent-based adhesives, emulsion-type adhesives, and solvent-free adhesives depending on their form, but from the viewpoint of reducing solvent and energy costs, it is a type of solvent-free adhesive. A certain active energy ray-curable adhesive is attracting attention.
Unlike solvent-based adhesives and emulsion-based adhesives, active energy ray-curable adhesives have the advantage of not requiring a process to remove solvents such as solvents and water when forming an adhesive layer. In recent years, it has been used as an environmentally friendly adhesive in various fields such as image display devices, home appliances, information equipment, automobile interior and exterior parts, building materials, and labels.

As active energy ray-curable adhesives, adhesives containing (meth)acrylic polymer as a main component are known. In order to reduce the viscosity, the adhesive is often a composition containing an organic solvent, and when applying the composition to a base material to form an adhesive layer, it is necessary to remove the organic solvent by drying. There is.
However, it was difficult to eliminate residual organic solvent in the adhesive layer, which is a cured film, and there were problems with odor and safety when using it as an adhesive tape. things are wanted.

As a solvent-free composition, it consists of a (meth)acrylic polymer that is a dry resin, an unsaturated monomer having one ethylenically unsaturated group (hereinafter referred to as "monofunctional monomer"), and a polyfunctional (meth)acrylate. A composition is disclosed (Patent Document 1).
However, even if the coating film is laminated with a release film and irradiated with ultraviolet rays under air-blocking conditions, the curing properties will decrease due to the effect of polymerization inhibition due to dissolved oxygen in the coating film, and the adhesive layer of the cured film will be damaged. Because unreacted monofunctional monomers remain, there are problems with odor and safety when used as adhesive tapes.

Additionally, solvent-free compositions containing acrylic oligomers such as urethane (meth)acrylate as a main component are also known.
Patent Document 2 describes a resin composition for an ultraviolet curable adhesive containing urethane (meth)acrylate (A), (meth)acrylic monomer (B), and a photopolymerization initiator (C), A resin composition for an ultraviolet curable adhesive is disclosed in which the equivalent weight of the (meth)acryloyl group of the urethane (meth)acrylate (A) is in the range of 8,000 to 17,000. In the composition of the same document, the (meth)acrylic monomer (B) is a (meth)acrylic monomer capable of forming a homopolymer having a glass transition temperature (hereinafter referred to as "Tg") of 15°C or less. It is disclosed that a mixture of one or more monomers with one or more nitrogen atom-containing (meth)acrylic monomers capable of forming a homopolymer having a Tg higher than 15° C. is preferred.
However, the (meth)acrylic monomer having a nitrogen atom that can form a homopolymer with a Tg higher than 15°C is generally an acrylamide compound. There was a problem in that the weather resistance (light resistance and water resistance) of the material deteriorated.

Patent Document 3 discloses an active energy ray-curable adhesive composition containing urethane (meth)acrylate and an ethylenically unsaturated monomer.
Although this composition has low hydrophilicity and excellent weather resistance (light resistance and water resistance), it has the problem of odor derived from decomposition residue of the photopolymerization initiator after curing.
In addition, in active energy ray-curable adhesive compositions, high line speeds may be used for the purpose of improving productivity. In this case, it is necessary to shorten the irradiation time of the active energy rays, and the active energy rays are irradiated under irradiation conditions with a low integrated light amount (low energy), which may result in insufficient curability.

JP2007-217674A Japanese Patent Application Publication No. 2014-5368 Japanese Patent Application Publication No. 2003-155455

The present inventors have developed an active energy ray-curable adhesive that has excellent curability even under irradiation conditions of low integrated light intensity, has excellent adhesive strength and weather resistance (light resistance and water resistance) of the resulting cured film, and has low odor. They conducted extensive research to find the composition.

In order to solve the above problems, the present inventors have developed an active energy ray-curable type containing urethane (meth)acrylate having a specific weight average molecular weight, a specific monofunctional unsaturated compound, and a specific photopolymerization initiator. We discovered that the adhesive composition has excellent curability even under irradiation conditions of low integrated light intensity, and the resulting cured film has excellent adhesive strength and weather resistance (light resistance and water resistance), and has low odor. completed.
The present invention will be explained in detail below.

According to the composition of the present invention, the active energy ray cure has excellent curability even under irradiation conditions of low integrated light intensity, the resulting cured film has excellent adhesive strength and weather resistance (light resistance and water resistance), and has low odor. It can be a mold adhesive.

The present invention relates to an active energy ray-curable adhesive composition (hereinafter sometimes simply referred to as "composition") containing the following components (A), (B), and (C) as essential components.
・(A) component: Urethane (meth)acrylate with a weight average molecular weight of 10,000 to 100,000 ・(B) component: A compound having one ethylenically unsaturated group, other than (meth)acrylamide A compound containing at least the following component (b1) Component (b1): A compound having one ethylenically unsaturated group and an aromatic ring or alicyclic structure Component (C): (C-1) Acylphosphine A photopolymerization initiator with a molecular weight of 300 or more, excluding oxide compounds, or a photopolymerization initiator containing (C-2) acylphosphine oxide compounds as an essential component

The component (A) is preferably a urethane (meth)acrylate having a polyester structure, and is a reaction product of the following compounds (a), (b), and (c), and at least one of the compounds (b) is used as the component (A). Reactants obtained using polyester polyols are preferred.
・Compound (a): Compound having two isocyanate groups in one molecule ・Compound (b): Diol ・Compound (c): Hydroxyl group-containing (meth)acrylate

The component (B) preferably includes (b2) a compound having one ethylenically unsaturated group and a hydroxyl group.

The composition of the present invention contains 5 to 50% by weight of component (A) and 50 to 95% by weight of component (B) in 100% by weight of the total amount of components (A) and (B), It is preferable that the component (C) be contained in an amount of 0.1 to 15 parts by weight per 100 parts by weight of the total amount of components (A) and (B).

The composition of the present invention preferably further contains the following component (D).
・Component (D): A compound having two or more ethylenically unsaturated groups other than the component (A) In this case, the composition includes the total amount of the components (A), (B), and (D) 100 In the weight%, 5 to 50% by weight of component (A), 50 to 95% by weight of component (B), 0 to 20% by weight of component (D), (A), (B), and (D) It is preferable that the component (C) be contained in an amount of 0.1 to 15 parts by weight based on 100 parts by weight of the total amount of components ().

In the present invention, the cured film of the composition has a film thickness of 40 μm, and when a polyethylene terephthalate film is used as a base material and a glass plate is used as an adherend, the 180° peel strength at 23° C. and 50% RH is (Peeling speed: 300 mm/min) is preferably 1 to 50 N/25 mm.

The present invention also relates to an adhesive film or sheet comprising a base material and an adhesive layer comprising an active energy ray-cured film of the composition.
The present invention also relates to a method for producing an adhesive film or sheet, which comprises applying active energy rays to a substrate after coating the composition.

The components (A), (B), (C), and (D), the active energy ray-curable adhesive composition, and their uses will be described below.
In the present invention, the curable component is a component that is cured by active energy rays, and means component (A) and component (B). When combining component (D), which will be described later, component, (B) component and (D) component.

1. Component (A) Component (A) is a urethane (meth)acrylate having a weight average molecular weight (hereinafter referred to as "Mw") of 10,000 to 100,000.
By containing component (A), the composition has excellent curability and the cured film has excellent adhesive strength.
The Mw of component (A) must be 10,000 to 100,000, preferably 20,000 to 60,000.
If the Mw of component (A) is less than 10,000, the crosslinking density will be excessively high, making it impossible to obtain sufficient adhesive strength.On the other hand, if it exceeds 100,000, the viscosity will be too high and coating Workability deteriorates.
Mw in the present invention means a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

As component (A), compounds obtained by reacting the following compounds (a), (b), and (c) are preferred.
・Compound (a): Compound having two isocyanate groups in one molecule ・Compound (b): Diol ・Compound (c): Hydroxyl group-containing (meth)acrylate Hereinafter, the compound ( A) to (c) will be explained, and a method for producing component (A) will be explained.

1-1. Compound (a)
As the compound (a), various compounds can be used as long as they have two isocyanate groups in one molecule.
Specific examples of compound (a) include aromatic diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, diphenylpropane diisocyanate, triphenylmethane diisocyanate, phenylene diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, and toridine diisocyanate;
Hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, cyclohexylylene diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 4,4'-methylenebis(cyclohexyl isocyanate) , ω,ω'-diisocyanate dimethylcyclohexane, 3-isocyanatoethyl-3,5,5-trimethylcyclohexylisocyanate, and 3-isocyanatoethyl-3,5,5-triethylcyclohexylisocyanate; and
Examples include aliphatic diisocyanates such as hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and dimer acid diisocyanate.

1-2. Compound (b)
Examples of the compound (b) include low molecular weight polyols, polyether polyols, polycarbonate polyols, and polyester polyols.

Examples of low molecular weight polyols include polyols having at least two hydroxyl groups with a molecular weight of about 50 to 300, and specific examples include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, , 4-butanediol, 1,6-hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, cyclohexanedimethanol, tricyclodecane dimethanol, neopentyl glycol, 3-methyl-1 , 5-pentanediol, and neopentyl glycol hydroxypivalate.

Examples of polyether polyols include polyalkylene glycols having three or more oxyalkylene units, and specific examples include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
Examples of polycarbonate polyols include reaction products of carbonate and diol. Specific examples of carbonates include diaryl carbonates such as diphenyl carbonate, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate. Examples of the diol include the low molecular weight polyols mentioned above.

Examples of the polyester polyol include an esterification reaction product of at least one selected from the group consisting of these low molecular weight polyols, polyether polyols, and polycarbonate polyols and a dicarboxylic acid.
Various compounds can be used as dicarboxylic acids, including adipic acid, sebacic acid, succinic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, maleic acid, maleic anhydride, itaconic acid and dimer acid. etc.

As component (A) of the present invention, urethane (meth)acrylate having a polyester structure is preferable, and therefore, as compound (b), polyester diol is preferable among the above-mentioned compounds. By using urethane (meth)acrylate having a polyester structure, the adhesive layer of the resulting composition can have excellent cohesive force and flexibility.
Further, as the compound (b) of the present invention, a polyester diol having a hydroxyl value of 28 to 225 mgKOH/g [hereinafter referred to as "compound (b1)"] is preferred among the above-mentioned compounds.
The hydroxyl value of compound (b1) is preferably 37 to 115 mgKOH/g.
By setting this value to 28 mgKOH/g or more, the adhesive layer can have sufficient cohesive force, and by setting this value to 225 mgKOH/g or less, the adhesive layer can have excellent flexibility.
The raw material diol for compound (b1) may be those mentioned above, among which ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, Preferred are 1,9-nonanediol, 3-methyl-1,5-pentanediol, ethylene oxide or propylene oxide adducts of bisphenol A, and dimer diol.

1-3. Compound (c)
As the compound (c), various compounds can be used as long as they are (meth)acrylates having a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl ( meth)acrylate, hydroxypentyl (meth)acrylate, hydroxyhexyl (meth)acrylate, hydroxyalkyl (meth)acrylate such as hydroxyoctyl (meth)acrylate, ε-caprolactone (meth)acrylate [hereinafter referred to as "hydroxyl group-containing monofunctional (meth)acrylate" ) acrylate], as well as mono- or di-(meth)acrylates of glycerin, mono- or di-(meth)acrylates of trimethylolpropane, mono-, di- or tri(meth)acrylates of pentaerythritol, mono-, di- or di-(meth)acrylates of ditrimethylolpropane. Hydroxyl groups and two or more (meth)acrylates such as tri(meth)acrylate and dipentaerythritol mono, di, tri, tetra, or penta(meth)acrylate, ethylene oxide-modified isocyanuric acid mono, di, or tri(meth)acrylate, etc. Examples include compounds having an acryloyl group (hereinafter referred to as "hydroxyl group-containing polyfunctional (meth)acrylate").
Among the above-mentioned compounds, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate are preferred because they have excellent curability of the composition and adhesive strength of the cured film. preferable.

1-4. Method for producing component (A) Component (A) is preferably a compound obtained by reacting the aforementioned compounds (a), (b), and (c).
Component (A) can be produced by conventional methods, including a method of reacting compounds (a), (b) and (c), and a method of reacting compounds (a) and compound (b) to form a terminal isocyanate oligomer. After manufacturing, the isocyanate group of the compound is reacted with the hydroxyl group of the compound (c), and the compound (a) is added to a mixture of the compound (b) and the compound (c) to react. Can be mentioned.
In the production of component (A), it may be carried out in component (B) or component (D) that is included in the composition.
The obtained component (A) may be dissolved using the component (B) or component (D) that is blended in the composition.

A chain extender may be used in the production of component (A).
As chain extenders, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, 3-methyl-1,5 - Pentanediol, ethylene oxide or propylene oxide adducts of bisphenol A, and dimer diols.

In the present invention, the reaction ratio of compounds (a) to (c) is determined by the number of isocyanate group equivalents (p) of compound (a) and the total number of hydroxyl group equivalents (q) of compound (b) and compound (c). As an equivalent ratio, (p):(q) is preferably 0.8 to 1.2:1.0, more preferably 0.9 to 1.1:1.0.
Similarly, when using a chain extender, the equivalent ratio between the number of isocyanate group equivalents (p) of compound (a) and the total number of hydroxyl group equivalents (q) of compound (b), compound (c), and chain extender. , (p):(q) is preferably 0.8 to 1.2:1.0, more preferably 0.9 to 1.1:1.0.
By setting the number of isocyanate group equivalents (p) to 1 equivalent of the hydroxyl group equivalent number (q) to 0.8 or more and 1.2 or less, excellent insulation reliability can be achieved.

As component (A), a catalyst used in conventional urethanization reactions can be used. Specific examples of the urethanization catalyst include organometallic compounds and tertiary amine compounds.

Examples of organic metal compounds include organic tin compounds, organic iron compounds, organic zinc compounds, organic titanium compounds, organic aluminum compounds, organic zirconium compounds, and organic bismuth compounds.
Examples of organic tin compounds include tin carboxylates such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin diacetoacetonate, tin octylate, tin naphthenate, tin laurate, and tin ferzatic acid; Examples include reaction products of dibutyltin oxide and phthalate esters.
Examples of the organic titanium compound include titanate esters such as tetrabutyl titanate and tetrapropyl titanate, and titanium chelate compounds such as titanium tetraacetylacetonate.
Examples of the organic aluminum compound include aluminum trisacetylacetonate, aluminum trisethylacetoacetate, and diisopropoxyaluminum ethylacetoacetate.
Examples of the organic zirconium compound include zirconium chelate compounds such as zirconium tetraacetylacetonate.
Examples of the organic bismuth compound include bismuth-tris (neodecanoate), bismuth-tris (2-ethylhexoate), and bismuth octylate.
Organic iron compounds and organic zinc compounds are preferred compounds and are detailed below.

Examples of tertiary amine compounds include trialkylamines such as triethylamine; tetraalkylalkylenediamines such as tetramethylethylenediamine and tetramethylhexanediamine; pentaalkyldialkylenetriamines such as pentamethyldiethylenetriamine; trimethylaminoethylpiperazine and methylhydroxyethylpiperazine. piperazine; dialkylaminoalkyl alcohol such as dimethylaminoethoxyethanol; trialkylaminoalkyl alcohol such as trimethylaminoethylethanolamine; N-alkylimidazole such as 1,2-dimethylimidazole; bis(dimethylaminoethyl) ether; triethylenediamine [ Examples include tertiary amines such as 1,4-diazabicyclo[2,2,2]octane (DABCO); and 2,4,6-tris(dimethylaminomethyl)phenol.
Examples other than these include N-methylmorpholine and 1,8-diazabicyclo[5,4,0]undecene-7 (DBU).

In the present invention, since the metal content derived from the catalyst can be reduced in the obtained component (A) and the change in the composition over time can be reduced, organic iron compounds and organic iron compounds are used as the urethanization catalyst as the component (A). Organic zinc compounds are preferred, and those produced using a metal compound represented by the following general formula (1) as a catalyst are more preferred.
M(X)n...(1)
[In formula (1), M represents Fe or Zn, X is the same or different and represents a β-diketone, a halogen atom, an acyloxy group, or an alkoxy group, and n represents an integer of 2 or 3. ]
Since these metal compounds have excellent activity relative to conventional tin catalysts, the desired component (A) can be produced with a small amount of use.

M represents Fe or Zn, and Fe is preferable because it has better catalytic activity.
Examples of the β-diketone represented by , 2,6-dimethylheptane-3,5-dione, 4,6-nonanedione, 2,8-dimethylnonane-4,6-dione, 2,2,6,6-tetramethylheptane-3,5-dione , tridecane-6,8-dione, methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate, tert-butyl acetoacetate, methyl propionyl acetate, ethyl propionyl acetate, isopropyl propionyl acetate, tert-butyl propionyl and hexafluoroacetylacetone. Among these, acetylacetone is preferred because it is inexpensive and has excellent activity in the urethanization reaction.
Examples of the halogen atom represented by X include a chlorine atom and a bromine atom, with a chlorine atom being preferred.
As the acyloxy group represented by Examples include dodecanoyl group and octadecanoyl group.
As the alkoxy group represented by be able to.
X may be any one of the above or a combination of two or more. Among these, as X, a functional group other than a halogen atom is preferable in that the electrical properties of the cured product are particularly excellent, and acetylacetone and hexafluoroacetylacetone are more preferable. In terms of its superiority, acetylacetone is particularly preferred.

Among these, an iron β-diketone complex represented by the following formula (2) is preferable because it has particularly excellent reactivity in the urethanization reaction.
Fe(X')3...(2)
[In formula (2), X' represents β-diketone. ]
As the β-diketone represented by X', the β-diketones represented by X above can be selected.

n, which represents the number of X, is an integer of 2 or 3 and has good manufacturing stability, so when M is Fe, n is 3, and when M is Zn, n is 2.

Specific examples of metal compounds include, when X is β-diketone, tris(acetylacetonato)iron, tris(2,2,6,6-tetramethyl-3,5-heptanedionate)iron, etc. , tris(tetrafluoroacetylacetonate)iron, bis(acetylacetonate)zinc, bis(2,2,6,6-tetramethyl-3,5-heptanedionate)zinc, bis(tetrafluoroacetylacetonate) Examples include zinc. When X is a halogen atom, examples thereof include ferric chloride and zinc chloride. When X is an acyloxy group, examples thereof include iron tris(2-ethylhexanoate), iron naphthenate, zinc bis(2-ethylhexanoate), and zinc naphthenate. When X is an alkoxy group, examples thereof include triethoxyiron, triisopropoxyiron, diethoxyzinc and diisopropoxyzinc.

Among these, those in which M is Fe and n is 3 are more preferable because they have excellent catalytic activity for the urethanization reaction. Specific examples include tris(acetylacetonato)iron and ferric chloride, and tris(acetylacetonato)iron represented by formula (2) is particularly preferred because it has excellent catalytic activity.

Component (A) can be produced by heating and stirring the compounds (a), (b), and (c) in the presence of the metal compound and, if necessary, a reaction solvent to form a urethane.
In this case, compounds (a), (b) and (c) can be charged all at once and reacted (hereinafter referred to as "one-stage reaction"), and compounds (a) and (b) can be reacted to form an isocyanate group. Compound (c) can also be added after producing the containing prepolymer (hereinafter referred to as "two-stage reaction").
The proportions of compounds (a), (b) and (c) are as described above.

Incidentally, if the molecular weight of component (A) produced by this reaction becomes high, the reaction mixture becomes highly viscous and stirring may become difficult, so a reaction solvent may be blended into the reaction components.
The reaction solvent is preferably one that does not participate in the urethanization reaction, and includes, for example, aromatic compounds such as toluene and xylene, and organic solvents such as dimethylformamide.
When using an organic solvent, the amount to be blended may be appropriately determined depending on the viscosity of component (A), etc., but it is preferably set so that it is 0 to 70% by weight in the reaction solution.
Here, the reaction solution means the total amount of the raw material compounds when only the raw material compounds are used, and the total amount including these when using the reaction solvent in addition to the raw material compounds. Specifically, it is used to mean a solution containing compounds (a), (b), (c) and a reaction solvent used as necessary. same as below.

As a reaction solvent, component (B) used as a component of the composition and photopolymerizable compounds other than these (collectively referred to as curable components) may be blended together with or in place of the organic solvent. can. When a curable component is blended to perform a urethanization reaction and the resulting urethane (meth)acrylate is blended into a curable composition, unlike the case where the organic solvent is blended, the composition is applied and then dried. This is preferable because there is no need to do so.
The amount of the curable component to be added to the reaction component may be appropriately set depending on the proportion of the curable component to be finally added to the composition, but for example, 10 to 70% by weight, Furthermore, it is preferable to set the content to 10 to 50% by weight.

The amount of the urethanization catalyst may be a catalytic amount, for example, preferably 0.01 to 1,000 wtppm, more preferably 0.1 to 1,000 wtppm, based on the reaction solution.
When the amount of the metal compound is 0.01 wtppm or more, the urethanization reaction can proceed preferably, and when it is 1,000 wtppm or less, coloring of the resulting component (A) can be suppressed. .

In the case of a one-stage reaction, the urethanization catalyst can be added at the time of charging the polyol, organic polyisocyanate, and hydroxyl group-containing (meth)acrylate, and in the case of a two-stage reaction, it can be added at the time of charging the polyol and the organic polyisocyanate. .

In the urethanization reaction, a small amount of a chain extender may be added for the purpose of molecular weight adjustment.
As the chain extender, those commonly used in urethanization reactions can be used, including those similar to the above-mentioned low molecular weight polyols.

In the urethanization reaction, it is preferable to use a polymerization inhibitor for the purpose of preventing polymerization of the (meth)acryloyl group of the raw material or product, and furthermore, an oxygen-containing gas may be introduced into the reaction solution.
Examples of the polymerization inhibitor include hydroquinone, tert-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, benzoquinone, and phenothiazine. Examples include organic polymerization inhibitors such as , inorganic polymerization inhibitors such as copper chloride and copper sulfate, and organic salt polymerization inhibitors such as copper dibutyl dithiocarbamate. The polymerization inhibitors may be used alone or in any combination of two or more. The proportion of the polymerization inhibitor in the reaction solution is preferably 5 to 20,000 wtppm, more preferably 25 to 3,000 wtppm.
Examples of the oxygen-containing gas include air, a mixed gas of oxygen and nitrogen, a mixed gas of oxygen and helium, and the like.

The reaction temperature may be appropriately set depending on the raw materials used and the structure and molecular weight of the desired component (A), but is usually preferably 10 to 150°C, more preferably 30 to 120°C. The reaction time may be appropriately set depending on the raw materials used and the structure and molecular weight of the desired component (A), but is usually preferably 1 to 70 hours, more preferably 2 to 30 hours.

As component (A), only one kind of the above-mentioned compounds may be used, or two or more kinds thereof may be used in combination.
The Tg (glass transition temperature) of the homopolymer of component (A) is preferably in the range of -80 to 60°C, more preferably in the range of -60 to 40°C.
In the present invention, Tg means a value measured at a heating rate of 10°C/min using a differential scanning calorimeter (DSC), and is a value measured at a temperature increase rate of 10°C/min using a differential scanning calorimeter (DSC). means value.

2. Component (B) Component (B) is a compound having one ethylenically unsaturated group, and is a compound other than (meth)acrylamide.
When (meth)acrylamide is used, there is a problem that the water resistance of the adhesive layer decreases, and more specifically, peeling occurs after the heat and humidity resistance test. In the present invention, by not including the (meth)acrylamide as the component (B), the adhesive layer can have excellent water resistance.
Examples of compounds having one ethylenically unsaturated group in the molecule include compounds having a (meth)acryloyl group, vinyl compounds, and allyl compounds.

Examples of vinyl compounds include compounds having one vinyl group. Specifically, styrene, vinyltoluene, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinylpyridine, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, 2-hydroxyethyl vinyl ether, cyclohexanedimethanol monovinyl ether , diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, cyclohexyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, and other vinyl monomers.
Examples of allyl compounds include compounds having one allyl group. Specifically, allyl alcohol and the like can be mentioned.

Examples of the (meth)acrylate include compounds having one (meth)acryloyl group (hereinafter referred to as monofunctional (meth)acrylate). Specifically, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, alkyl (meth)acrylate having 12 to 13 carbon atoms, cetyl (meth)acrylate, ) acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, isomyristyl (meth)acrylate, methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-ethylhexyl carbitol (meth)acrylate, ethoxy Ethoxyethyl (meth)acrylate, Butoxyethyl (meth)acrylate, Methoxyethylene glycol (meth)acrylate, Ethoxydiethylene glycol (meth)acrylate, Ethoxyethyl (meth)acrylate (ethyl carbitol (meth)acrylate), Methoxytriethylene glycol ( meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 7-amino-3,7-dimethyloctyl (meth)acrylate, etc. aliphatic (meth)acrylate;
Isobornyl (meth)acrylate, Bornyl (meth)acrylate, Tricyclodecanyl (meth)acrylate, Dicyclopentanyl (meth)acrylate, 4-Butylcyclohexyl (meth)acrylate, Tetrahydrofurfuryl (meth)acrylate, Cyclohexyl (meth)acrylate ) acrylate, alicyclic (meth)acrylates such as dicyclopentenyl (meth)acrylate, adamantyl (meth)acrylate, tricyclodecane (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate,
Phenyl (meth)acrylate, (meth)acrylate of phenol derivatives, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, (meth)acrylate of alkylene oxide modified phenol, (meth)acrylate of alkylene oxide modified cresol , (meth)acrylate of alkylene oxide modified p-cumylphenol, (meth)acrylate of alkylene oxide modified nonylphenol, (meth)acrylate of alkylene oxide modified o-phenylphenol, alkylene of p-phenylphenol (meth)acrylate of oxide-modified product, (meth)acrylate of alkylene oxide-modified tribromophenol, aromatic (meth)acrylate of neopentyl glycol (meth)acrylic acid benzoate;
2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, hydroxybutyl vinyl ether, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polytetramethylene Glycol mono(meth)acrylate, polyethylene glycol-polypropylene glycol mono(meth)acrylate, polyethylene glycol-polytetramethylene glycol mono(meth)acrylate, polypropylene glycol-polytetramethylene glycol mono(meth)acrylate, 2-hydroxy-3- Phenoxypropyl (meth)acrylate, 2-hydroxy-3-butoxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, etc. hydroxyl group-containing (meth)acrylate;
(meth)acrylic acid, (meth)acrylic acid dimer, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid , carboxylic acid-containing (meth)acrylates such as ω-carboxypolycaprolactone (meth)acrylate;
Imide (meth) such as N-(meth)acryloyloxyethylhexahydrophthalimide, 2-(1,2-cyclohex-1-enedicarboximide)ethyl(meth)acrylate, Fancryl FA-502A (manufactured by Hitachi Chemical), etc. Acrylate;
Phosphoric acid (meth)acrylates such as 2-(meth)acryloyloxyethyl acid phosphate;
can be mentioned.

Component (B) in the present invention is a compound having one ethylenically unsaturated group and an aromatic ring or an alicyclic structure [hereinafter referred to as " (b1) component") is required.

As specific examples of component (b1), the above-mentioned alicyclic (meth)acrylates and aromatic (meth)acrylates are preferable, and among these, isobornyl (meth)acrylate, because it can improve heat resistance and adhesiveness, Dicyclopentanyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenol Preferred are alkylene oxide-modified (meth)acrylate, N-(meth)acryloyloxyethylhexahydrophthalimide, and 2-(1,2-cyclohex-1-enedicarboximide)ethyl (meth)acrylate.

Furthermore, as the component (B) in the present invention, a compound having one ethylenically unsaturated group and a hydroxyl group [hereinafter referred to as component (b2)] is preferable. Hereinafter, the (B) component other than the (b1) and (b2) components will be referred to as the (b3) component.

As the component (b2), (meth)acrylate having one hydroxyl group is preferable, and the specific compounds are as described above, but among them, those that give the composition low viscosity and have excellent adhesive properties are preferred. Therefore, compounds with a molecular weight of less than 200 are preferred. Examples of compounds satisfying the above molecular weight include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

As the component (B), only one type of the above-mentioned compounds can be used, or two or more types can be used in combination, and the component (b1) is essential.
Furthermore, as component (B), a combination of component (b1) and component (b2) is preferred.

The content ratio of component (A) and component (B) is 5 to 50% by weight of component (A) and 50 to 95% by weight of component (B) in 100% by weight of the total amount of curable components. More preferably, it contains 10 to 40% by weight of component (A) and 60 to 90% by weight of component (B).
By setting the content ratio of component (A) to 50% by weight or less or the content ratio of component (B) to 50% by weight or more, the composition can be made to have a low viscosity and have excellent coating properties. By setting the content of component (A) to 5% by weight or more or the content of component (B) to 95% by weight or less, the cohesive force of the adhesive layer can be improved. It can be made excellent.

3. Component (C) Component (C) is a photopolymerization initiator with a molecular weight of 300 or more (hereinafter referred to as "component (C-1)"), excluding (C-1) an acylphosphine oxide compound [hereinafter referred to as "component (C-1)"] or/and (C-1) 1) A photopolymerization initiator containing an acylphosphine oxide compound [hereinafter referred to as "(C-2) component"] as an essential component.
In the present invention, by using component (C), the composition has excellent curability, and the resulting cured film has excellent low odor properties. Furthermore, component (C-1) is preferred because the cured film has excellent photostability and little coloring.

As component (C-1), an α-hydroxyketone compound is more preferable because it has excellent compatibility with components (A) and (B) in addition to the excellent performance described above.
Specific examples of α-hydroxyketone compounds include α-hydroxyketone oligomers and polymers, such as compounds represented by the following formula (1).

In formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkyl group, and n represents a number from 2 to 5. Note that n means the average number of repetitions of the above unit.
The alkyl group for R ² is preferably a lower alkyl group such as a methyl group, an ethyl group, or a propyl group.

Specific examples of the compound represented by formula (1) include oligo(2-hydroxy-2-methyl-1-(4-(1-methylvinyl)phenyl)propanone and the like.
The compounds are commercially available, and examples include ESACURE KIP 150 (manufactured by IGM Resins) and ESACURE ONE (manufactured by IGM Resins).
ESACURE KIP 150 and ESACURE ONE are compounds represented by the above formula (1), in which R ¹ is a hydrogen atom or a methyl group, R ² is a methyl group, n is a number from 2 to 3, and [(204.3×n+16 .0) or (204.3×n+30.1)].
Note that ESACURE ONE contains the same components as ESACURE KIP 150, but is a purified and highly pure product.

Examples of α-hydroxyketone compounds other than the above include 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)phenoxy]phenyl}-2-methylpropan-1-one (commercially available product) Examples include ESACURE KIP-160 manufactured by IGM Resins.Hereinafter, the words in parentheses have the same meaning.) and (2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl- Propionyl)-benzyl]-phenyl}-2-methylpropan-1-one (Irgacure 127 manufactured by BASF) and the like.

Examples of compounds other than α-hydroxyketone compounds include 2-[2-oxo-2-phenylacetoxyethoxy]ethyl ester and oxyphenylacetic acid.
The compound is commercially available, and Irgacure 754 (manufactured by BASF) is known. Irgacure 754 is a mixture of oxyphenylacetic acid, 2-[2-oxo-2-phenylacetoxyethoxy]ethyl ester and oxyphenylacetic acid, 2-(2-hydroxyethoxy)ethyl ester.
In addition, oligomer type benzophenone photopolymerization initiator SPEEDCURE 7005 (molecular weight 1200 or more, manufactured by Lambson Japan), oligomer type thioxanthone photopolymerization initiator (molecular weight 1500 or more, manufactured by Lambson Japan), etc. 1-[4-(4-Benzoylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one (ESACURE 1001M manufactured by IGM Resins), 2-benzyl-2-dimethylamino -1-(4-morpholinophenyl)butanone-1 (Irgacure 369 manufactured by BASF), and 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl) Examples include butanone-1 (Irgacure 379 manufactured by BASF).

The acylphosphine oxide type compounds of component (C-2) include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bis(2,6-dimethoxy Benzoyl)-2,4,4-trimethylpentylphosphine oxide and the like.

Component (C) has components (C-1) and (C-2) as essential components, but if necessary, photopolymerization initiators other than components (C-1) and (C-2) [ Hereinafter referred to as "component (C-3)"] can be used in combination.
Specific examples of component (C-3) include benzyl dimethyl ketal, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy) ) Phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1-[4-(methylthio)]phenyl]-2-morpholinopropan-1-one, etc. with a molecular weight of 300 less than acetophenone compounds;
Benzoin compounds such as benzoin, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether;
Benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, methyl-2-benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4 , 4'-bis(diethylamino)benzophenone and 4-methoxy-4'-dimethylaminobenzophenone;
Thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3-[3,4-dimethyl-9-oxo-9H-thioxanthon-2-yl-oxy]- Examples include thioxanthone compounds such as 2-hydroxypropyl-N,N,N-trimethylammonium chloride and fluorothioxanthone.
Examples of compounds other than those mentioned above include benzyl, ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate, methyl phenylglyoxylate, ethyl anthraquinone, phenanthrenequinone, and camphorquinone.

In addition, when it is necessary to increase the thickness of the cured film, for example, when it is necessary to increase the thickness to 50 μm or more, for the purpose of improving the curability inside the cured film, or when using UV absorbers or pigments in combination, For the purpose of improving the curability of the composition, it is preferable to use a plurality of compounds selected from thioxanthone compounds and α-aminoalkylphenone compounds in combination.
Preferred examples of compounds in this case include 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, etc. as thioxanthone compounds, and α-aminoalkylphenone compounds as such. , 2-methyl-1-[4-(methylthio)]phenyl]-2-morpholinopropan-1-one, and the like.

The content of component (C) is preferably 0.1 to 15 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total amount of curable components. By setting the proportion of component (C) to 0.1 parts by weight or more, the photocurability of the composition can be improved and the adhesion can be made excellent. By setting the proportion of component (C) to 15 parts by weight or less, the cured film can be It is possible to improve the internal curability of the material, and the adhesion to the base material can be improved.

4. (D) Component In the present invention, the above-mentioned (A) and (B) components are essential as curable components, but the following (D) component can be blended as necessary.
- Component (D): A compound having two or more ethylenically unsaturated groups other than the component (A). As a component (D), a compound having two or more (meth)acryloyl groups [hereinafter referred to as "polyfunctional ( meth)acrylate] is preferred; compounds having two (meth)acryloyl groups [hereinafter referred to as ``bifunctional (meth)acrylates'']; and compounds having three or more (meth)acryloyl groups [hereinafter referred to as ``bifunctional (meth)acrylates'']. "trifunctional or more functional (meth)acrylate compounds"].

Specific examples of bifunctional (meth)acrylates include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, and nonanediol di(meth)acrylate. Alkylene glycol di(meth)acrylates such as acrylates;
Polyalkylene glycol di(meth)acrylates such as polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and polytetramethylene glycol di(meth)acrylate; and di(meth) of alkylene oxide adducts of bisphenol A. Examples include acrylate, bisphenol-based compounds such as di(meth)acrylate of alkylene oxide adduct of bisphenol F, and di(meth)acrylate of alkylene oxide adduct.

As the bifunctional (meth)acrylate, oligomers can also be used, such as urethane (meth)acrylate with Mw of less than 10,000, epoxy (meth)acrylate, polyester (meth)acrylate, and polyether poly(meth)acrylate. etc.

As the urethane (meth)acrylate having an Mw of less than 10,000, one manufactured such that the Mw of component (A) is less than 10,000 can be used. The raw materials and structure of this are the same as those of component (A) described above.

It is also possible to use urethane (meth)acrylate produced from compounds (a) and (c), which were the essential raw materials for component (A). This compound is called a urethane adduct.

Among urethane adducts, compound (a) is preferably hexamethylene diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, and trimethyl cyclohexyl isocyanate, since they are excellent in reducing the viscosity of the composition and in the adhesive strength of the cured film. Diisocyanates are preferred, and compound (c) includes 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, ε-caprolactone (meth)acrylate, and glycerin monomers. Alternatively, di(meth)acrylate, mono-, di- or tri-(meth)acrylate of pentaerythritol, and mono-, di- or tri(meth)acrylate of ethylene oxide-modified isocyanuric acid are preferred.

Another preferred compound of the urethane adduct is a reaction product of an organic polyisocyanate having three or more isocyanate groups and a hydroxyl group-containing monofunctional (meth)acrylate.
Examples of the hydroxyl group-containing monofunctional (meth)acrylate in the compound include the same compounds as the above-mentioned compounds.
Examples of organic polyisocyanates having three or more isocyanate groups include the aforementioned hexamethylene diisocyanate trimer and isophorone diisocyanate trimer, trimethylolpropane adduct of hexamethylene diisocyanate, and trimethylolpropane adduct of tolylene diisocyanate. etc. can be mentioned.

Epoxy (meth)acrylate is a reaction product of epoxy resin and (meth)acrylic acid.
Examples of the epoxy resin include bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, and novolac type epoxy resins. Examples of bisphenol A-type epoxy resins include Epicote 827 (product name, same hereinafter) manufactured by Japan Epoxy Resins, Epicote 828, Epicote 1001, and Epicote 1004, and examples of bisphenol F-type epoxy resins include Epicote 806 and Epicote 4004P. etc. Further, examples of the novolac type epoxy resin include Epikot 152 and Epicoat 154.

Polyester (meth)acrylate is a reaction product of polyester polyol and (meth)acrylic acid.
Polyester polyols are obtained by reacting polyhydric alcohols with polybasic acids.
Examples of the polyhydric alcohol include neopentyl glycol, ethylene glycol, propylene glycol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, tricyclodecane dimethylol, and bis-[hydroxymethyl]-cyclohexane.
Examples of polybasic acids include succinic acid, phthalic acid, hexahydrophthalic anhydride, terephthalic acid, adipic acid, azelaic acid, and tetrahydrophthalic anhydride.

Examples of trifunctional or more functional (meth)acrylate compounds include various compounds having three or more (meth)acryloyl groups, such as glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate , tri- or tetra(meth)acrylate of diglycerin, tri- or tetra(meth)acrylate of pentaerythritol, tri- or tetra(meth)acrylate of ditrimethylolpropane and tri-, tetra-, penta- or hexa(meth)acrylate of dipentaerythritol. polyol poly(meth)acrylate such as;
Tri- or tetra(meth)acrylates of pentaerythritol alkylene oxide adducts, tri- or tetra(meth)acrylates of ditrimethylolpropane alkylene oxide adducts, tri-, tetra-, penta- or hexa(meth)acrylates of dipentaerythritol alkylene oxide adducts and tri(meth)acrylate of isocyanuric acid alkylene oxide adducts.

Examples of alkylene oxide adducts in the compounds exemplified above include ethylene oxide adducts, propylene oxide adducts, and ethylene oxide and propylene oxide adducts.

Component (D) may be used alone or in combination of two or more.
The Tg of the homopolymer of component (D) is preferably in the range of -80 to 60°C, more preferably in the range of -60 to 40°C.

The content of component (D) is preferably 0 to 20% by weight, more preferably 5 to 18% by weight based on 100% by weight of the total amount of curable components. By controlling the content of component (D) to 20% by weight or less, the peel strength can be made sufficiently high.

5. Active energy ray curable adhesive composition The present invention provides an active energy ray curable adhesive composition in which the above components (A), (B), and (C) are essential components, and component (D) may optionally be blended. The present invention relates to a drug composition.
Further, the composition of the present invention has excellent coating properties and curability, and the cured film has excellent adhesive strength, so that it can be preferably used as an active energy ray-curable adhesive composition for repeeling.
The peel strength when used for re-peeling purposes is 50% at 23°C when the cured film of the composition has a thickness of 40 μm, a polyethylene terephthalate film is used as the base material, and a glass plate is used as the adherend. It is preferable that the 180° peel strength (peel speed: 300 mm/min) under RH conditions is 1 to 50 N/25 mm. A composition having a peel strength within this range is less likely to peel off due to environmental changes after pasting, and has excellent durability.

The viscosity of the composition is preferably 20 to 500,000 mPa·s, more preferably 50 to 50,000 mPa·s.
In the present invention, viscosity means a value measured at 25° C. using an E-type viscometer (cone-plate viscometer).

The composition of the present invention has the above-mentioned components (A), (B), and (C) as essential components, and optionally contains component (D), but various other components may be added depending on the purpose. can do.
Other components include organic solvents, sensitizers, polymerization inhibitors, antioxidants, ultraviolet absorbers, silane coupling agents, surface modifiers, and plasticizers.
The other components will be explained below.
In addition, as for the other components to be described later, only one type of the exemplified compounds may be used, or two or more types may be used in combination.

5-1. Organic Solvent The composition of the present invention is most preferably solvent-free, but may contain an organic solvent for the purpose of improving coatability on a substrate.

Specific examples of organic solvents include aromatic compounds such as benzene, toluene, and xylene; ester compounds such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; and ketone compounds such as methyl ethyl ketone and methyl isobutyl ketone.
Among these, aromatic compounds are more preferred since they have excellent solubility of components (A) and (B).

The content ratio of the organic solvent is preferably 0 to 1,000 parts by weight, more preferably 0 to 500 parts by weight, and 0 to 300 parts by weight based on 100 parts by weight of the total amount of curable components. It is more preferable that Within the above range, the composition can have a viscosity suitable for coating, and can be easily coated by a known coating method described later.

5-2. Sensitizer A sensitizer is blended for the purpose of further increasing the photoreactivity of the composition.
Examples of the sensitizer include aliphatic amines and aromatic amines such as diethylaminophenone, ethyl dimethylaminobenzoate, and isoacyl dimethylaminobenzoate. Moreover, in order to reduce migration from the coating film after curing, a high molecular weight type amine can also be used.
The content of the sensitizer is preferably 0 to 5 parts by weight, more preferably 0 to 3 parts by weight, based on 100 parts by weight of the solid content of the composition.

5-3. Polymerization Inhibitor A polymerization inhibitor is blended for the purpose of increasing the thermal stability and photoreactivity of the composition.
Specific examples of the polymerization inhibitor include organic polymerization inhibitors, inorganic polymerization inhibitors, and organic salt polymerization inhibitors. Specific examples of organic polymerization inhibitors include phenol compounds such as hydroquinone, tert-butylhydroquinone, and hydroquinone monomethyl ether, quinone compounds such as benzoquinone, galvinoxyl, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4 -Hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl and other stable radicals, phenothiazine, N-nitroso-N-phenylhydroxylamine ammonium, and the like. Specific examples of inorganic polymerization inhibitors include copper chloride, copper sulfate, and iron sulfate. Specific examples of organic salt-based polymerization inhibitors include nitroso compounds such as N-nitroso-N-phenylhydroxylamine aluminum salt, ammonium N-nitrosophenylhydroxylamine, and copper dibutyldithiocarbamate.

Among these, stable radicals and nitroso compounds are preferred because they cause little coloring of the adhesive and can prevent the composition from thickening or gelling, thereby increasing stability.
The proportion of the polymerization inhibitor in the curable component is 0.0001 to 1% by weight, more preferably 0.0005 to 0.5% by weight. By setting the proportion of the polymerization inhibitor to 0.0001% by mass or more, the thermal stability and photostability of the composition can be improved, and by setting the proportion of the polymerization inhibitor to 1% by mass or less, the photocurability of the composition can be improved. It becomes something.

5-4. Antioxidant The antioxidant is blended for the purpose of improving the durability of the cured film, such as heat resistance and weather resistance.
Examples of the antioxidant include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like.
Examples of the phenolic antioxidant include hindered phenols such as 2,6-di-t-butylhydroxytoluene. Commercially available products include AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, and AO-80 manufactured by Adeka Corporation.
Examples of phosphorus-based antioxidants include phosphines such as trialkylphosphines and triarylphosphines, trialkyl phosphites, and triaryl phosphites. Commercially available derivatives of these include, for example, Adekastab PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, 3010 manufactured by Adeka Co., Ltd. etc.
Examples of the sulfur-based antioxidant include thioether-based compounds, and commercially available products include AO-23, AO-412S, and AO-503A manufactured by Adeka Corporation.
These may be used alone or in combination of two or more. Preferred combinations of these antioxidants include combinations of phenolic antioxidants and phosphorus antioxidants, and combinations of phenolic antioxidants and sulfur antioxidants.
The content ratio of the antioxidant may be appropriately set depending on the purpose, and is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the total amount of curable components. It is.
By setting the content of the antioxidant to 0.1 parts by weight or more, the durability of the composition can be improved, while by setting it to 5 parts by weight or less, curability and adhesion can be improved. be able to.

5-5. Ultraviolet absorber The ultraviolet absorber is blended for the purpose of improving the light resistance of the cured film.
Examples of the ultraviolet absorber include triazine ultraviolet absorbers such as TINUVIN400, TINUVIN405, TINUVIN460, and TINUVIN479 manufactured by BASF, and benzotriazole ultraviolet absorbers such as TINUVIN900, TINUVIN928, and TINUVIN1130.
The content ratio of the ultraviolet absorber may be appropriately set depending on the purpose, and is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the total amount of curable components. It is. By setting the content ratio of the ultraviolet absorber to 0.01 parts by weight or more, the light resistance of the cured film can be made good, while by setting the content ratio to 5 parts by weight or less, the curability of the composition can be improved. It can be made excellent.

5-6. Silane coupling agent The silane coupling agent is blended for the purpose of improving the interfacial adhesive strength between the cured film and the base material.
The silane coupling agent is not particularly limited as long as it can contribute to improving adhesiveness with the base material.

Specific examples of the silane coupling agent include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane. Glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3 -aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like.

The content ratio of the silane coupling agent may be appropriately set depending on the purpose, and is preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the total amount of curable components. .
By setting the content of the silane coupling agent to 0.1 parts by weight or more, the adhesive strength of the composition can be improved, while by setting it to 10 parts by weight or less, changes in adhesive strength over time can be prevented. be able to.

5-7. Surface modifier A surface modifier may be added to the composition of the present invention for the purpose of increasing the leveling property during application, the slipperiness of the cured film, and the like.
Examples of the surface modifier include surface conditioning agents, surfactants, leveling agents, antifoaming agents, slippery agents, antifouling agents, and the like, and these known surface modifiers can be used. .
Among them, silicone-based surface modifiers and fluorine-based surface modifiers are preferably mentioned. Specific examples include silicone polymers and oligomers having silicone chains and polyalkylene oxide chains, silicone polymers and oligomers having silicone chains and polyester chains, and fluorine polymers having perfluoroalkyl groups and polyalkylene oxide chains. and oligomers, and fluorine-based polymers and oligomers having perfluoroalkyl ether chains and polyalkylene oxide chains.
Furthermore, for the purpose of increasing the durability of slipperiness, a surface modifier having an ethylenically unsaturated group, preferably a (meth)acryloyl group, in the molecule may be used.

The content of the surface modifier is preferably 0.01 to 1.0 parts by weight based on 100 parts by weight of the total amount of curable components. Within the above range, the surface smoothness of the coating film will be excellent.

5-8. Plasticizer The composition of the present invention may be blended as necessary for the purpose of adjusting the tackiness of the cured film.

Examples of plasticizers include phthalic acid esters such as dimethyl phthalate, diethyl phthalate and dioctyl phthalate; aliphatic dibases such as dimethyl adipate, dibutyl adipate, dioctyl adipate, dimethyl sebacate, diethyl sebacate, dibutyl sebacate and diethyl succinate; acid esters and aliphatic polybasic acid esters such as acetyl tributyl citrate; orthophosphoric acid esters such as trimethyl phosphate, triethyl phosphate, triphenyl phosphate and tricresyl phosphate; glyceryl triacetate and 2-ethylhexyl acetate, etc. Acetate esters; Phosphite esters such as triphenyl phosphite and dibutylhydrodiene phosphite; Natural resins such as rosin resins and terpene resins and their derivatives; and polyesters and acrylic polymers (for example, Toagosei Co., Ltd.) Examples include inert compounds such as Alfon UP-1000), polyethers, and petroleum resins.

The content of the plasticizer may be appropriately set depending on the purpose, but it is preferably 1 to 90% by weight, more preferably 5 to 80% by weight in the composition.

6. Method of Use The composition of the present invention may be used in any conventional manner.
Specifically, examples include a method in which the composition is coated on a base material and cured by irradiating the composition with active energy rays, and a method in which the composition is bonded to another base material and then further irradiated with active energy rays to cure the composition.
Further, the coating range for the base material may be appropriately selected depending on the purpose, and may be partially coated or entirely coated.

The base material may be a material intended for adhesion (hereinafter referred to as "adherent"), or a sheet or film having mold releasability (hereinafter referred to as "mold release material").

Examples of the material of the adherend include polymers, paper, glass, ceramics, metals such as steel plates and aluminum, vapor-deposited films of metals and metal oxides, and silicon.
Polymers include cellophane, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyamides, polyimides, polycarbonates, urea/melamine resins, epoxy resins, polyurethane, polylactic acid, polyethylene, polypropylene, cycloolefin polymers, acrylic resins, methacrylic resins, and polyesters. Examples include vinyl chloride, polystyrene, polyvinyl acetate, polyvinyl alcohol, triacetyl cellulose, hydroxypropyl cellulose, polyether sulfone, copolymers of the above polymers, liquid crystal polymers, and fluororesins. The shape of these polymers is preferably a film or sheet.
Examples of paper include high-quality paper, coated paper, art paper, imitation paper, thin paper, and cardboard.

Examples of the mold release material include materials obtained by subjecting the polymers mentioned above as the adherend to mold release treatment. Specific mold release treatments include silicone treatment, fluorine treatment, and long-chain alkyl treatment. It is also possible to use polymers with low surface free energy untreated, and specific examples include polyethylene, polypropylene, cycloolefin polymers, and fluororesins.

The coating method can be set as appropriate depending on the purpose, and can be set as appropriate depending on the purpose. Examples include coating methods using a coater, reverse roll coater, die coater, lip coater, gravure coater, microgravure coater, inkjet, and the like.

Examples of active energy rays for curing the composition of the present invention include ultraviolet rays, visible rays, and electron beams, but ultraviolet rays are preferred.
Examples of the ultraviolet irradiation device include a high-pressure mercury lamp, a metal halide lamp, an ultraviolet electrodeless lamp, and an ultraviolet light emitting diode (UV-LED).
The irradiation energy may be set appropriately depending on the type of active energy ray and the composition, and will vary depending on the thickness of the coating film, illuminance, etc., but for example, when using a high-pressure mercury lamp, the irradiation energy in the UV-A region 10 to 2,000 mJ/cm ² is preferable, and 10 to 1,000 mJ/cm ² is more preferable.
The composition of the present invention has excellent curability even under irradiation conditions of low integrated light intensity (low energy). In this case, the cumulative amount of light (irradiation energy) is preferably 10 to 500 mJ/cm ² , more preferably 10 to 200 mJ/cm ² .

7. Adhesive sheet The composition of the present invention can be preferably used for producing an adhesive sheet.
The pressure-sensitive adhesive sheet may be produced by a conventional method, for example, by applying the composition to a base material and then irradiating it with active energy rays.

When the composition is solvent-free, the composition is applied to a substrate. If the composition contains an organic solvent, etc., the composition is applied to a base material and then dried to evaporate the organic solvent.
By irradiating active energy rays to a sheet having a composition layer formed on a base material, a pressure-sensitive adhesive sheet composed of a base material/cured film can be obtained. The active energy rays are usually irradiated from the composition layer side, but can also be irradiated from the base material side.

The coating amount of the composition of the present invention may be appropriately selected depending on the intended use, but it is preferable that the film thickness after drying the organic solvent etc. is 1 to 100 μm, preferably 5 to 50 μm. It is more preferable that there be.

When the composition contains an organic solvent, etc., it is dried after coating to evaporate the organic solvent.
Drying conditions may be appropriately set depending on the organic solvent used, and examples include a method of heating to a temperature of 40 to 150°C.

Irradiation conditions such as irradiation energy in active energy ray irradiation may be appropriately set depending on the composition, substrate, purpose, etc. to be used, and may follow the same conditions as described above.

8. Applications The adhesive sheet formed from the composition of the present invention can be used in various applications such as adhesive labels, adhesive tapes, and special adhesive films.

Specific examples of adhesive labels include trademark labels, quality display labels, content display labels, returnable labels, product display such as name plates, measurement labels, hand labels, price display such as price tags and nameplates, instruction manual labels, and inspection labels. Explanation/guarantee labels such as certification labels, warranty labels, tamper-proof labels, power distribution diagram labels, scale plate labels, PL Law warning labels, etc., stickers (for windows, vehicles, storefronts, etc.), marks/decorative labels, stamps. , stickers, patches, posters, multilayer labels, etc. for advertising and sales promotions, form labels, computer labels, POS labels, process/inventory management labels, etc. management, double-sided/single-sided shipping labels, address labels, delivery slips. For tags and addresses such as labels, seals for seals, seals for caps, etc., for information and signs such as information sign labels, traffic sign labels, facility sign labels, toiletry-related labels, labels for home appliances, labels for OA equipment, etc. For recycling, other index labels (for stationery, Blu-ray discs, etc.), color sample labels, toys (stickers), educational materials, etc.

Adhesive tapes include name plate tapes, tapes for metal construction materials, surface protection tapes for automobiles, tapes for semiconductor manufacturing processes, tapes for transporting electronic components, tapes for protection and masking, tapes for fixing and adhesives, and electrical insulation. For electrical/electronic equipment such as tape, binding/repair tape, conductive tape, for displaying and sealing EPS (expanded polystyrene bead fused products) cases, for general masking such as painted masking tape, curing masking tape, etc. , for sealing and packaging cardboard packaging tape, office use, other automotive decorative tapes, photolithography tapes, splicing tapes, etc., and for general binding and fixing purposes such as double-sided tapes, cellophane tapes, OPP tapes, etc. Can be mentioned.

Special adhesive films include outdoor advertising films, automotive stripes, marking films for outdoor durability, posters, interior films, general wall coverings such as interior materials, elevator interior films, counter decoration films, furniture decoration films, and vehicle interior films. , for interior decoration such as vending machine decorative film, cash corner decorative film, table decorative film, etc., for short-term decoration such as window display film, stickers, and marking film, for internally illuminated signage such as outdoor durable film, and for building solar shading and scattering prevention. Films, security reflective films (for automobiles, shoes, helmets, etc.), window films that are applied to automobiles etc. while wet with water or soapy water, and other applications such as prisms, hologram films, phosphorescent films, and luminescent films. etc.

EXAMPLES Below, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

1. Manufacture of urethane acrylate
1) Production example 1 [Production of component (A)]
In a 0.5 L flask equipped with a stirrer, thermometer, and 5% ON piping, 22.86 g (0.103 mol) of isophorone diisocyanate [manufactured by Evonik Japan Co., Ltd.: IPDI] and dibutyl hydroxytoluene [Kawaguchi Chemical Industry Co., Ltd.] were added. 0.10 g of Antige BHT (product name)] and isobornyl acrylate (product name: Osaka Organic Chemical Industry Co., Ltd.: IBXA (product name)) used as a diluent. 193.55 g of ``IBXA''] was charged.
The contents were stirred while blowing 5% ON to bring the inside of the flask to 70°C.
Add 0.002 g of tris(acetylacetonato)iron (manufactured by Nihon Kagaku Sangyo Co., Ltd.: Naseem ferric iron (trade name)), and then add neopentyl with a hydroxyl value of 55 mg KOH/g (molecular weight 2,040). Glycol and a polyester diol derived from adipic acid [Polylite OD-X-2044 (trade name) manufactured by DIC Corporation] were gradually added. Finally, 167.23 g (0.082 mol) of polyester diol was charged. Thereafter, 0.93 g (0.010 mol) of 1,4-butanediol was added, and the temperature inside the flask was raised to 80°C.
2-Hydroxyethyl acrylate [manufactured by Toagosei Co., Ltd.] was added when the Mw of the contents exceeded 28,000 as determined by molecular weight measurement by GPC. 4.32 g (0.037 mol) of HEA (hereinafter referred to as "HEA") was added. At this time, 0.002 g of Naseem was also added again.
Subsequent IR measurement confirmed that the isocyanate group had disappeared, and the synthesis was completed.
The resulting reaction mixture was a mixture containing 50% by weight of polyester urethane acrylate (hereinafter referred to as "A-1") whose Mw was 31,000 as determined by molecular weight measurement by GPC, and 50% by weight of IBXA. .
In addition, GPC was measured according to the following measurement conditions.

◆GPC measurement conditions GPC (manufactured by Tosoh Corporation: HLC-8120, column: TSKgel-GMHxl x 2, eluent: tetrahydrofuran (THF) 1 mL/min, detector: differential refractometer (RI)) The weight average molecular weight (Mw) in terms of polystyrene was measured.

2) Production Example 2 [Production of component (A)]
Instead of OD-X-2044, 3-methyl-1,5-pentanediol with a hydroxyl value of 55 mgKOH/g (molecular weight 2,040) and an ester diol derived from adipic acid [manufactured by Kuraray Co., Ltd.: Kuraray Polyol P-] 2010 (trade name)] was used in an amount of 167.23 g (0.082 mol).
The resulting reaction mixture was a mixture containing 50% by weight of a urethane acrylate oligomer (hereinafter referred to as "A-2") with a molecular weight of 32,000 as measured by GPC and 50% by weight of IBXA.

3) Production Example 3 [Production of component (A)]
Instead of IBXA, use nonylphenoxyethyl acrylate [manufactured by Toagosei Co., Ltd.: Aronix M-111 (trade name). The same operation as in Production Example 1 was performed except that 82.0 g of ``M111'' (hereinafter referred to as "M111") was used.
The resulting reaction mixture was a mixture containing 70% by weight of a urethane acrylate oligomer (hereinafter referred to as "A-3") with a molecular weight of 31,000 as measured by GPC and 30% by weight of M111.

4) Production example 4 [Production of component (A)]
The same operation as in Production Example 3 was performed except that HEA was added at the stage when the Mw of the contents exceeded 48,000 as determined by molecular weight measurement by GPC.
The resulting reaction mixture was a mixture containing 70% by weight of a urethane acrylate oligomer (hereinafter referred to as "A-4") with a molecular weight of 52,000 as measured by GPC and 30% by weight of M111.

5) Production Example 5 [Production of component (A)]
The same operation as in Production Example 3 was carried out, except that HEA was added when the Mw of the contents exceeded 13,000 as determined by molecular weight measurement by GPC.
The resulting reaction mixture was a mixture containing 70% by weight of a urethane acrylate oligomer (hereinafter referred to as "A-5") with a molecular weight of 15,000 as measured by GPC and 30% by weight of M111.

6) Production Example 6 [Production of component (A)]
The same operation as in Production Example 3 was carried out, except that 4.32 g of glycerin di/triacrylate [Toagosei Co., Ltd.: Aronix M-920 (trade name), hydroxyl value = 240 mg KOH/g] was charged instead of HEA. went.
The resulting reaction mixture was a mixture containing 70% by weight of a urethane acrylate oligomer (hereinafter referred to as "A-6") with a molecular weight of 68,000 as measured by GPC and 30% by weight of M111.

7) Production Example 7 [Production of component (A)]
Instead of M111, use ethoxyethoxyethyl acrylate [manufactured by Osaka Organic Industry Co., Ltd.: Viscoat #190 (trade name). The same operation as in Production Example 3 was performed except that 82.0 g of EEEA (hereinafter referred to as "EEEA") was used.
The resulting reaction mixture was a mixture containing 70% by weight of a urethane acrylate oligomer (hereinafter referred to as "A-7") with a molecular weight of 30,000 as measured by GPC and 30% by weight of EEEA.

8) Comparative Production Example 1 [Production of component (A')]
The same operation as in Production Example 3 was carried out, except that 1,4-butanediol was not used and HEA was added at a stage when the Mw of the contents exceeded 4,000 as determined by molecular weight measurement by GPC.
The resulting reaction mixture was a mixture containing 70% by weight of a urethane acrylate oligomer (hereinafter referred to as "A'-1") whose Mw was 0.5 million as determined by molecular weight measurement by GPC, and 30% by weight of M111. .

2. Production of active energy ray-curable adhesive composition
1) Examples 1 to 10, Comparative Examples 1 to 4
The reactants obtained in Production Examples 1 to 7 and Comparative Production Example 1 and the compounds shown in Table 1 were stirred and mixed in the proportions shown in Table 1 to produce an active energy ray-curable adhesive composition. .
Since the reaction product obtained in the production example is a mixture of components (A) and (B), Table 2 lists the reaction product obtained in the production example separately for the (A) and (B) components. .
Note that the numbers in Tables 1 and 2 mean the number of copies.
Moreover, the abbreviations in Tables 1 and 2 mean the following.

(1) (A) Component UN6304: Non-yellowing polyether skeleton urethane acrylate (Mw13,000), urethane acrylate "Art Resin UN-6304" manufactured by Negami Kogyo Co., Ltd.

(2) (B) component
(2-1) (b1) Component M111: Nonylphenol ethylene oxide modified (n=1) acrylate, "Aronix M-111" (trade name) manufactured by Toagosei Co., Ltd.
・M113: Nonylphenol ethylene oxide modified (n=4) acrylate, “Aronix M-113” (trade name) manufactured by Toagosei Co., Ltd.
・IBXA: Isobornyl acrylate, “IBXA” (trade name) manufactured by Osaka Organic Chemical Industry Co., Ltd.
・TMCHA: 3,3,5-trimethylcyclohexyl acrylate, “Viscoat” #196” manufactured by Osaka Organic Chemical Industry Co., Ltd. (product name)
・CTFA: Cyclic trimethylolpropane formal acrylate, "Viscoat"#200" manufactured by Osaka Organic Chemical Industry Co., Ltd. (product name)

(2-2) (b2) Component /4HBA: 4-Hydroxybutyl acrylate, “4-HBA” (product name) manufactured by Osaka Organic Chemical Industry Co., Ltd.

(2-3) (b3) Component /EEEA: Ethoxyethoxyethyl acrylate, “Viscoat #190” (product name) manufactured by Osaka Organic Chemical Industry Co., Ltd.

(2) (B)' Ingredient ACMO: Acryloylmorpholine, "ACMO" (product name) manufactured by KJ Chemicals

(4) (C) component
(4-1) (c1) component・E-ONE: Poly{2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one}, “ESACURE” manufactured by IGM Resins ONE” (product name)
(4-2) (c2) component
・TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide, “Omnirad TPO” (product name) manufactured by IGM Resins

(5) Photopolymerization initiator other than component (C) - O-184: 1-hydroxycyclohexylphenyl ketone, "Omnirad 184" (trade name) manufactured by IGM Resins

(6) Component (D) M930: Glycerin triacrylate, “Aronix M-930” manufactured by Toagosei Co., Ltd. (trade name)

2) Method for evaluating compositions The compositions obtained in Examples 1 to 10 and Comparative Examples 1 to 4 were used to perform the evaluations described below. The results are shown in Table 3.
(1) Viscosity at 25℃
The viscosity of the obtained composition was measured at 25°C using an E-type viscometer.

3) Evaluation method of cured film
◆Production of Adhesive Sheet The obtained composition was coated with a polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., Cosmoshine A4300 (thickness: 50 μm) having a width of 300 mm and a length of 300 mm so as to have a film thickness of 40 μm). Hereinafter referred to as "PET"] was applied with an applicator to form a coating film. This is called "test body 0."
A release PET film of 300 mm width x 300 mm length [manufactured by Toray Film Kako Co., Ltd., Therapel BKE (thickness 38 μm)] was applied to this coating film. Hereinafter referred to as "release PET"] was laminated.
Next, a conveyor-type ultraviolet irradiation device (160 W/cm high-pressure mercury lamp, lamp height 10 cm, irradiation intensity in the UV-A region 1,200 mW/cm ² (UV POWER PUCK, manufactured by Heraeus Co., Ltd.) manufactured by Eye Graphics Co., Ltd. By passing through a conveyor at a speed of 14 m/min, ultraviolet rays were irradiated from the release PET side with an irradiation energy of 100 mJ/cm ² in the UV-A region to obtain an adhesive sheet. "Body 1".
Using the obtained test specimen 0 (composition before curing) and test specimen 1 (adhesive sheet), the curability, adhesive strength, odor, 100°C E', light resistance, and water resistance described below were evaluated. Ta. Note that light resistance and water resistance are tests performed to evaluate weather resistance.

(1) Curability The acryloyl group reactivity of Test Body 0 (composition before curing) and Test Body 1 (cured film cured with ultraviolet rays) was measured by infrared absorption spectroscopy [μ-ATR method]. Spectrum 100 manufactured by PerkinElmer Japan Co., Ltd. was used as an infrared absorption spectrum measuring device.
Using the obtained ultraviolet absorption spectrum, the acryloyl group reaction rate was calculated using the following formula (1).
Acryloyl group reaction rate = {1-(B2/A2)/(B1/A1)]×100...(1)
A1: Peak height of 1724 cm ^-1 derived from -C=O of the composition B1: Peak height of 1405 cm ^-1 derived from -CH=CH ₂ of the composition A2: Originated from -C=O of the cured film ^{B2: Peak height of 1405 cm -1 derived} from -CH=CH ₂ of the cured film Acryloyl group reaction rate of the cured film cured under irradiation condition 2 according to the same method as above. It was measured.
If the acryloyl group reaction rate calculated here was 95% or more, it was determined to be "○", and if it was less than 95%, it was determined to be "x".

(2) Adhesive Strength Test Using Sample 1, adhesive strength was measured in accordance with JIS Z 0237:2009.
Specifically, using a glass plate as an adherend, 180° peel strength (peel speed: 300 mm/min) was measured at 23° C. and 50% RH.
The peel strength was measured using a universal material testing machine Instron 5564 manufactured by Instron Japan Company Limited.

(3) Using odor test specimen 1, the glass plate after measuring the adhesive force in (2) above was peeled off, the adhesive layer was smelled, and evaluation was made on the following three levels.
○: No odor felt at all.
△: There is a slight odor.
×: There is a strong odor.

(4) 100℃E'
Test specimen 0 (composition before curing) was irradiated with light at an illuminance of 200 mW/cm ² , an integrated light amount of 2 J/cm ² (365 nm), and a film thickness of 1 mm to obtain a cured product.
The mechanical properties of this cured product were measured according to JIS K7244-4 (frequency: 1 Hz, heating rate: 2° C./min), and the tensile storage modulus E' at 100° C. in tensile mode was calculated.

(5) Light resistance Test Sample 1 was used to conduct a light resistance test using a fade meter, and the cured film after 96 hours of irradiation was visually evaluated on the following four levels.
◎: Almost no change in color tone ○: Slight change in color tone is observed △: Slightly yellowish ×: Significant discoloration

(6) Humid and heat resistance test specimen 1 was placed in a constant temperature and humidity chamber at 60°C and 90% RH, and the appearance was observed after 100 hours to evaluate whether peeling had occurred and evaluated using the following 4 levels. .
◎: No peeling at all 〇: Less than 10 small peelings are seen △: Peeling is seen on less than 10% of the area ×: Peeling is seen on 10% or more of the area

4) Evaluation Results As is clear from the results of Examples 1 to 10, the composition of the present invention has low odor and excellent curability, and the resulting cured film has excellent adhesive strength, weather resistance, and heat and humidity resistance. It was something.
In addition, Example 9 containing M930 as component (D) and Example 10 using M920 containing bifunctional acrylate as component (c), which is the raw material for component (A), had a 100% ℃E' was improved, and therefore the composition also had better heat and humidity resistance.
On the other hand, the composition of Comparative Example 1 which did not contain component (A) had excellent curability and low odor, but the cured film had low adhesive strength and poor heat and humidity resistance. Further, in the composition of Comparative Example 2 using a photopolymerization initiator other than component (C), the cured film had a significant odor. Furthermore, the composition of Comparative Example 3 containing ACMO, which is (meth)acrylamide, had poor moist heat resistance. Furthermore, the composition of Comparative Example 4, which did not contain the component (b1), was inferior in curability, adhesive strength, odor, weather resistance, and heat and humidity resistance.

The active energy ray-curable adhesive composition of the present invention can be used for various purposes such as adhesive labels, adhesive tapes, and special adhesive films.More specifically, image display devices, home appliances, information equipment, It can be used in various fields such as automobile interior and exterior parts, building materials, and labels.

Claims (10)

An active energy ray-curable adhesive composition containing the following components (A), (B), and (C) as essential components.
・(A) component: Urethane (meth)acrylate with a weight average molecular weight of 10,000 to 100,000 ・(B) component: A compound having one ethylenically unsaturated group, other than (meth)acrylamide A compound containing at least the following component (b1) Component (b1): A compound having one ethylenically unsaturated group and an aromatic ring or alicyclic structure Component (C): (C-1) Acylphosphine A photopolymerization initiator with a molecular weight of 300 or more, excluding oxide compounds, or a photopolymerization initiator containing (C-2) acylphosphine oxide compounds as an essential component The active energy ray-curable adhesive composition according to claim 1, wherein the component (A) is a urethane (meth)acrylate having a polyester structure. Component (A) is a reactant of the following compounds (a), (b), and (c), and is a reactant obtained by using at least one polyester polyol as compound (b). 2. The active energy ray-curable adhesive composition according to item 2.
・Compound (a): Compound having two isocyanate groups in one molecule ・Compound (b): Diol ・Compound (c): Hydroxyl group-containing (meth)acrylate The active energy ray-curable adhesive composition according to any one of claims 1 to 3, wherein the component (B) contains (b2) a compound having one ethylenically unsaturated group and a hydroxyl group. In the total amount of 100% by weight of the above (A) and (B) components, 5 to 50% by weight of the (A) component and 50 to 95% by weight of the (B) component are included, and (A) and (B) The active energy ray-curable adhesive composition according to any one of claims 1 to 4, containing 0.1 to 15 parts by weight of the component (C) based on 100 parts by weight of the total amount of the components. The active energy ray-curable adhesive composition according to any one of claims 1 to 5, further comprising the following component (D).
・(D) component: a compound having two or more ethylenically unsaturated groups other than the above-mentioned (A) component In the total amount of 100% by weight of the above (A), (B), and (D) components, 5 to 50% by weight of the (A) component, 50 to 95% by weight of the (B) component, and the (D) component. 7. The composition according to claim 6, wherein the component (C) is contained in an amount of 0.1 to 15 parts by weight based on 100 parts by weight of the total amount of components (A), (B), and (D). Active energy ray curable adhesive composition. The cured film of the composition has a film thickness of 40 μm, and when a polyethylene terephthalate film is used as the base material and a glass plate is used as the adherend, 180° peel strength (peel speed: 300 mm) under the conditions of 23 ° C. and 50% RH. The active energy ray-curable adhesive composition according to any one of claims 1 to 7, wherein the active energy ray-curable pressure-sensitive adhesive composition has a pressure of 1 to 50 N/25 mm. An adhesive film or sheet comprising a base material and an adhesive layer comprising an active energy ray-cured film of the composition according to any one of claims 1 to 8. A method for producing an adhesive film or sheet, which comprises coating a base material with the composition according to any one of claims 1 to 8, and then irradiating the composition with active energy rays.