KR20130129236A - Pressure-sensitive adhesive composition, pressure-sensitive adhesive, and presure-sensitive adhesive sheet using same - Google Patents

Abstract

Provided is an adhesive having high adhesive strength and cohesive force, which are cured by active energy ray irradiation. The present invention is an adhesive containing an acrylic resin (A), an ethylenically unsaturated compound (B) having one ethylenically unsaturated group, an ethylenically unsaturated compound (C) having two or more ethylenically unsaturated groups, and a photopolymerization initiator (D). It is a composition and contains an alicyclic structure containing ethylenically unsaturated compound (B1) and a hydroxyl-containing ethylenically unsaturated compound (B2) as an ethylenically unsaturated compound (B) which has one ethylenically unsaturated group, In the adhesive composition characterized by the above-mentioned. It is about.

Description

Pressure-sensitive adhesive composition, pressure-sensitive adhesive, and presure-sensitive adhesive sheet using same}

The present invention relates to a pressure-sensitive adhesive composition, a pressure-sensitive adhesive, and a pressure-sensitive adhesive sheet formed using the same, in detail, a pressure-sensitive adhesive having a high adhesive force and a high cohesive force, in particular, an adhesive suitable for an electronic member or an optical member that requires corrosion resistance, And it relates to an adhesive sheet using the same.

There exist many types of adhesives, such as a strong adhesive which aims at sticking a to-be-adhered body firmly for a long time, and a peeling-type adhesive which presupposes peeling from a to-be-adhered body after sticking, and it is an optimal adhesive for every field | area. Is designed and used.

For example, in the adhesive of the type which shows strong adhesiveness, high adhesive force is normally provided by introducing many acidic functional groups in an adhesive or using a large amount of tackifying resin, and various strong adhesiveness is needed. It is used in the field which becomes (for example, refer patent document 1).

By the way, since these strongly adhesive adhesives corrode a to-be-adhered body or generate | occur | produce the outgas derived from an acidic functional group because of the acidic functional group introduce | transduced, the information label use used for an electronic member, especially a precision electronic member, It was not suitable for the electronic member fixing use.

Therefore, it was necessary to use the adhesive (for example, refer patent document 2) of the type (acid member) which does not use an acid for the adhesive used for these optical uses.

JP 2007-217674 A JP 2003-268335 A

However, in particular, optical devices such as electronic displays in which metals such as ITO transparent electrodes used in touch panels, metal meshes used in PDPs, and the like and metal oxides are used, and optical recording discs (optical recording media) such as digital universal disks. In addition to corrosion resistance, a pressure-sensitive adhesive used for optical applications requires a strict durability such as heat resistance, so that a pressure-sensitive adhesive having a high cohesive force and a high adhesive force is required. Although it was excellent, since adhesive force and cohesion force were not enough, it could not be used as an adhesive for optical uses.

Accordingly, there has been a demand for the development of an adhesive having excellent corrosion resistance and adhesive properties (adhesive strength, cohesion).

Therefore, an object of the present invention is to provide a pressure-sensitive adhesive composition for obtaining a pressure-sensitive adhesive having high adhesion and high cohesion under such a background and containing no acidic groups and excellent in corrosion resistance.

Accordingly, the present inventors have made intensive studies in view of such circumstances, and in the active energy ray-curable pressure-sensitive adhesive of a solvent-free type consisting of an acrylic resin, a monofunctional unsaturated monomer, a polyfunctional unsaturated monomer, and a photopolymerization initiator, monofunctional unsaturated By using together an alicyclic structure containing ethylenically unsaturated compound and a hydroxyl group containing ethylenically unsaturated compound as a monomer, it discovered that the adhesive which was excellent in the balance of adhesive force and cohesion force was obtained, and completed this invention.

That is, the summary of this invention is an acrylic resin (A), the ethylenically unsaturated compound (B) which has one ethylenically unsaturated group, the ethylenically unsaturated compound (C) which has two or more ethylenically unsaturated groups, and a photoinitiator (D). A pressure-sensitive adhesive composition containing 1), containing an alicyclic structure-containing ethylenically unsaturated compound (B1) and a hydroxyl group-containing ethylenically unsaturated compound (B2) as an ethylenically unsaturated compound (B) having one ethylenically unsaturated group. It relates to an adhesive composition.

Moreover, this invention relates to an adhesive and the adhesive sheet obtained using these.

The present invention includes the following aspects.

[1] Pressure-sensitive adhesive containing acrylic resin (A), ethylenically unsaturated compound (B) having one ethylenically unsaturated group, ethylenically unsaturated compound (C) having two or more ethylenically unsaturated groups, and photopolymerization initiator (D) It is a composition and contains an alicyclic structure containing ethylenically unsaturated compound (B1) and a hydroxyl-containing ethylenically unsaturated compound (B2) as an ethylenically unsaturated compound (B) which has one ethylenically unsaturated group, The adhesive composition characterized by the above-mentioned.

[2] The pressure-sensitive adhesive composition according to [1], wherein the acrylic resin (A) is a dry resin obtained by suspension polymerization.

[3] The pressure sensitive adhesive composition according to [1] or [2], wherein the acrylic resin (A) is an acrylic resin formed by copolymerizing a copolymerization component containing an alicyclic structure-containing (meth) acrylic acid ester monomer.

[4] The content ratio of the total amount of the alicyclic structure-containing ethylenically unsaturated compound (B1) and the hydroxyl group-containing ethylenically unsaturated compound (B2) in the ethylenically unsaturated compound (B) having one ethylenically unsaturated group is 10 to 70. It is weight%, The adhesive composition in any one of [1]-[3] characterized by the above-mentioned.

[5] The pressure-sensitive adhesive composition according to any one of [1] to [4], which is substantially free of an acid.

[6] The pressure-sensitive adhesive composition according to any one of [1] to [5], wherein the adhesive composition does not contain a solvent.

[7] The pressure sensitive adhesive according to any one of [1] to [6], wherein the pressure sensitive adhesive composition is cured by active energy ray irradiation.

[8] An adhesive sheet containing a pressure-sensitive adhesive layer made of the base material and the pressure-sensitive adhesive according to [7].

The pressure-sensitive adhesive made of the pressure-sensitive adhesive composition of the present invention has strong adhesive strength and excellent cohesive force, and therefore, peeling hardly occurs from the substrate even under a high temperature environment, and is particularly useful as an adhesive for adhesive bonding to an optical member and an adhesive sheet. In addition, since the adhesive is excellent in adhesive strength and cohesion even without containing acid, optical recording disks such as an electronic display such as an electronic display requiring a corrosion resistance against metals and metal oxides, and optical recording disks such as digital universal disks (optical recording media) It is especially effective as an adhesive sheet for optics for pasting.

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated in detail, these show an example of preferable embodiment. In the present invention, (meth) acryl refers to acrylic or methacryl, (meth) acryloyl refers to acryloyl or methacryloyl, and (meth) acrylate refers to acrylate or methacrylate, respectively.

First, the adhesive composition of this invention is demonstrated.

The adhesive composition of this invention is an acrylic resin (A), the ethylenically unsaturated compound (B) which has one ethylenically unsaturated group, the ethylenically unsaturated compound (C) which has two or more ethylenically unsaturated groups, and a photoinitiator (D). It contains.

The acrylic resin (A) has a (meth) acrylic acid ester monomer (a1) as a main component as a copolymerization component and, if necessary, contains a functional group-containing copolymerizable monomer (a2) and other copolymerizable monomers (a3). It can obtain by copolymerizing a copolymerization component.

 As a (meth) acrylic acid ester monomer (a1) (but except (a2) mentioned later), (meth) acrylic-acid alkylester monomer (a1-1) and alicyclic structure containing (meth) acrylic acid ester monomer ( a1-2) etc. are mentioned.

As such a (meth) acrylic-acid alkylester type monomer (a1-1), carbon number of an alkyl group is 1-20 normally, Especially preferably, it is 1-10, More preferably, it is 1-8, Especially preferably, 1- 4, specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, and iso-butyl (meth) acryl Late, tert-butyl (meth) acrylate, n-propyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, iso- Octyl acrylate, nonyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, iso-stearyl acrylate, etc. Can be mentioned. These can be used individually by 1 type or in combination of 2 or more types.

Among these (meth) acrylic acid alkyl ester monomers, ethyl (meth) acrylate and n-butyl (meth) acrylate are preferably used because of the copolymerizability, adhesive properties, ease of handling and availability of raw materials. N-butyl (meth) acrylate is more preferably used in that it is excellent.

As said alicyclic structure containing (meth) acrylic-ester type monomer (a1-2), carbon number of alicyclic structure is C4-C20 normally, Especially preferably, it is 6-10, Specifically, cyclopentyl ( Meta) acrylate, cyclohexyl (meth) acrylate, tricyclodecanyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.02,6] decane-8-yl (meth) ) Acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, 4-t-butylcyclo Hexyl (meth) acrylate, 1, 4-cyclohexane dimethanol mono (meth) acrylate, etc. are mentioned, Among these, an isobornyl (meth) acrylate is used preferably because of adhesive property and compatibility with a monomer. do.

 As content in the copolymerization component of a (meth) acrylic acid ester monomer (a1), Preferably it is 60-100 weight%, Especially preferably, it is 70-95 weight%, More preferably, it is 80-90 weight%, ( When content of the meta) acrylic acid ester monomer (a1) is too small, there exists a tendency for the adhesive force at the time of using as an adhesive to run short.

When transparency is required for the adhesive obtained by hardening the adhesive composition of this invention, since a haze change can be suppressed, it is an alicyclic structure containing (meth) acrylic acid ester monomer as a (meth) acrylic acid ester monomer (a1). It is preferable to use.

Moreover, as a content ratio (weight ratio) of such a cyclic structure containing (meth) acrylic-acid ester monomer (a1-2) and a (meth) acrylic-acid alkylester monomer (a1-1), it is (a1-2): (a1- 1) = 5: 95-95: 5 are preferable, Especially preferably, (a1-2): (a1-1) = 10: 90-90: 10, More preferably, (a1-2): (a1 -1) = 20: 80 to 80:20.

Examples of the functional group-containing copolymerizable monomer (a2) include a functional group-containing monomer such as a hydroxyl group-containing monomer, an oxyalkylene group-containing monomer, an amide group-containing monomer, an amino group-containing monomer, a nitrogen-containing monomer, and a glycidyl-containing monomer. 1 type or 2 or more types are used. Among these, a hydroxyl group containing monomer is used preferably at the point which can obtain a high cohesion force, Especially preferably, it is 2-hydroxy ethyl (meth) acrylate.

As a hydroxyl-containing monomer, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth), for example (Meth) acrylic acid hydroxyalkyl esters such as acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, and (4-hydroxymethylcyclohexyl) methyl (meth) acrylate Caprolactone-modified monomers such as caprolactone-modified 2-hydroxyethyl (meth) acrylate, 2-acryloyloxyethyl-2-hydroxyethyl phthalic acid, N-methylol (meth) acrylamide, and N-hydroxy Primary hydroxyl group containing monomers, such as ethyl (meth) acrylamide; 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3- phenoxypropyl (meth) acryl Rate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2- De-hydroxy-3-phenoxypropyl (meth) secondary hydroxyl group-containing monomers such as acrylate; may be mentioned 2,2-dimethyl-2-hydroxyethyl (meth) monomers containing a tertiary hydroxyl group, such as acrylate.

Polypropylene glycol derivatives such as diethylene glycol (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol derivatives such as polypropylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol mono ( Oxyalkylene-modified hydroxyl-containing monomers, such as meta) acrylate, poly (ethylene glycol tetramethylene glycol) mono (meth) acrylate, and poly (propylene glycol tetramethylene glycol) mono (meth) acrylate, may be used.

As an oxyalkylene group containing monomer, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-butoxyethyl ( Meth) acrylate, 2-butoxydiethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate , Methoxy dipropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, octosi polyethylene glycol polypropylene glycol mono (meth) acrylate, lauoxy polyethylene glycol (meth) acrylate, stearoxy Aliphatic (meth) acrylic acid esters such as polyethylene glycol mono (meth) acrylate, 2-phenoxyethyl (meth) acrylate, phenoxy polyethyleneglycol (meth) acrylate, And the like polypropylene article refill (meth) acrylate, nonylphenol ethylene oxide adduct (meth) acrylate, aromatic (meth) acrylate of - noksi polyethylene glycol.

As an amide group containing monomer, acrylamide, methacrylamide, N- (n-butoxyalkyl) acrylamide, N- (n-butoxyalkyl) methacrylamide, N, N-dimethyl (meth), for example Acrylamide, N, N-diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, acrylamide-3-methylbutylmethylamine, dimethylaminoalkylacrylamide, dimethylaminoalkylmethacrylamide Etc. can be mentioned.

As an amino-group containing monomer, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, its quaternary cargo, etc. are mentioned, for example.

As a nitrogen containing monomer, acryloyl morpholine etc. are mentioned, for example.

As a glycidyl containing monomer, glycidyl (meth) acrylate and allyl glycidyl ether are mentioned, for example.

The content ratio in the copolymerization component of a functional group containing copolymerizable monomer (a2) becomes like this. Preferably it is 0.01-20 weight%, Especially preferably, it is 0.1-15 weight%, More preferably, it is 0.2-10 weight%, The functional group containing When there are too few copolymerizable monomers (a2), the interaction of a functional period will become small and cohesion force will fall, and when too many, adhesive force will fall too much.

Examples of the other copolymerizable monomer (a3) include acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, vinyl acetate, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, alkyl vinyl ether, vinyl toluene, and vinyl. Pyridine, vinylpyrrolidone, itaconic acid dialkyl ester, fumaric acid dialkyl ester, allyl alcohol, acryl chloride, methyl vinyl ketone, N-acrylamide methyl trimethyl ammonium chloride, allyl trimethyl ammonium chloride, dimethyl aryl vinyl ketone, etc. are mentioned. have.

The content ratio in the copolymerization component of the other copolymerizable monomer (a3) is preferably 0 to 40% by weight, particularly preferably 3 to 30% by weight, more preferably 8 to 20% by weight. When there is too much content of another copolymerizable monomer (a3), there exists a tendency for adhesive performance to fall easily.

It is preferable that acrylic resin (A) used by this invention does not contain an acidic group from the point which is excellent in corrosion resistance.

Although acrylic resin (A) is manufactured by superposing | polymerizing the said (meth) acrylic-ester type monomer (a1), a functional group containing copolymerizable monomer (a2), and other copolymerizable monomer (a3) as a copolymerization component as needed, In polymerization, it can manufacture according to well-known methods, such as solution radical polymerization, suspension polymerization, block polymerization, emulsion polymerization, and the like.

Among these, suspension polymerization is preferably used because a polymer having a large molecular weight can be obtained and isolation of the produced polymer is easy, and the acrylic resin (A) is preferably a dry resin obtained by suspension polymerization.

In the case of the said superposition | polymerization, dispersion stabilizers, such as polyvinyl alcohol, and polymerization initiators, such as azobis isobutyronitrile, can be added as needed.

Moreover, generally, acrylic resin used for an adhesive composition is manufactured by solvent-type superposition | polymerization which uses the organic solvent at the time of the manufacture. When the acrylic resin of such solvent-based polymerization is used in the pressure-sensitive adhesive composition, it is necessary to dry the pressure-sensitive adhesive composition solution at a high temperature, and thus a lot of energy is required, and since the organic solvent not only ignites but also causes air pollution, Large recovery or safety devices are needed. However, when acrylic resin (A) of dry resin obtained by the said suspension polymerization is used, an adhesive composition can be manufactured without containing these organic solvents.

It is preferable that the weight average molecular weights (Mw) of acrylic resin (A) are 500,000-3 million, Especially preferably, it is 850,000-2,500,000, More preferably, it is 1 million-2 million. When the weight average molecular weight of acrylic resin (A) is too small, there exists a tendency for the cohesion force of the adhesive obtained by active energy ray irradiation to fall, and when too large, there exists a tendency for the uniformly compatible adhesive composition to become difficult to obtain.

The dispersion degree (Mw / Mn) of the acrylic resin (A) is preferably 7 or less, and more preferably 5 or less and 4 or less. When dispersion degree (Mw / Mn) of acrylic resin (A) is too big | large, there exists a tendency for the dispersion | variation by active energy ray irradiation conditions to become large about cohesion force and adhesive physical property. Moreover, as a lower limit of dispersion degree (Mw / Mn), it is 2 normally. In addition, said Mn means a number average molecular weight.

It is preferable that the glass transition temperature (Tg) of acrylic resin (A) is -70-20 degreeC, Especially preferably, -60-0 degreeC and -55-10 degreeC are still more preferable. When the glass transition temperature (Tg) of acrylic resin (A) is too low, the cohesion force tends to fall and when too high, the tendency which will lead to the brittleness of an adhesive is seen.

In addition, in this invention, a weight average molecular weight means the weight average molecular weight by conversion of a standard polystyrene molecular weight, and specifically, high performance liquid chromatography ("Waters 2695 (body)" and "Waters 2414 (detector)" by the Japan Waters company)) Column: Shodex GPC KF-806L (exclusion limit molecular weight: 2 × 10 ⁷ , separation range: 100 to 2 × 10 ⁷ , theoretical number of stages: 10,000 stages / piece, filler material: styrene-divinylbenzene copolymer It is measured by using three series of filler particle diameters: 10 micrometers). The number average molecular weight is also measured using the above-mentioned measuring apparatus.

In addition, in this invention, a glass transition temperature is computed by following formula (1) of Fox.

Tg: glass transition temperature of the copolymer (K)

Tga: glass transition temperature of homopolymer of monomer A (K) Wa: weight fraction of monomer A

TgB: glass transition temperature (K) of homopolymer of monomer B Wb: weight fraction of monomer B

Tgn: glass transition temperature (K) of homopolymer of monomer N Wn: weight fraction of monomer N

(Wa + Wb +… + Wn = 1)

It is preferable that content of acrylic resin (A) is 5-50 weight part with respect to a total of 100 weight part of acrylic resin (A) and the ethylenically unsaturated compound (B) which has one ethylenically unsaturated group mentioned later, and it is especially preferable. Preferably it is 7-45 weight part, More preferably, it is 10-40 weight part.

When there is too little content of acrylic resin (A), there exists a tendency for a viscosity to be too low and to be difficult to coat, and when too large, a viscosity will become high and it will become difficult to coat.

As an ethylenically unsaturated compound (B) which has one ethylenically unsaturated group (henceforth a "monofunctional unsaturated compound (B)"), an alicyclic structure containing ethylenically unsaturated compound (B1) and hydroxyl-containing ethylenically unsaturated It is necessary to contain the compound (B2).

In this invention, by using such (B1) and (B2) together as an essential component, especially high adhesive force by the release inhibitory effect of the adhesive derived from an alicyclic structure containing ethylenically unsaturated compound (B1), and especially hydroxyl-containing ethylenic The high cohesion force by the hydrogen bond derived from an unsaturated compound (B2) is exhibited in balance.

As an alicyclic structure containing ethylenically unsaturated compound (B1), it is preferable that it is an alicyclic structure containing (meth) acrylate type compound, As carbon number of an alicyclic structure, it is C4-C20 normally, Especially preferably, it is 6- 10. Specifically, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, tricyclodecanyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.02 , 6] decane-8-yl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-dicyclopentanyloxyethyl (meth) acrylate, isoboroyl Although (meth) acrylate, 4-t-butyl cyclohexyl (meth) acrylate, 1, 4- cyclohexane dimethanol mono (meth) acrylate, etc. are mentioned, Among these, compatibility with acrylic resin (A) is mentioned. In this outstanding point, cyclohex Sil (meth) acrylate is preferable, and cyclohexyl acrylate is particularly preferable.

As hydroxyl-containing ethylenically unsaturated compound (B2), it is preferable that it is a hydroxyl-containing (meth) acrylate type compound, For example, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate , 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxy octyl (meth) acrylate, 10-hydroxydecyl Caprolactone modification, such as (meth) acrylic-acid hydroxyalkyl esters, such as (meth) acrylate and (4-hydroxymethylcyclohexyl) methyl (meth) acrylate, and caprolactone modification 2-hydroxyethyl (meth) acrylate Primary hydroxyl group-containing ethylenically unsaturated compounds such as monomers, 2-acryloyloxyethyl-2-hydroxyethyl phthalic acid, N-methylol (meth) acrylamide, and N-hydroxyethyl (meth) acrylamide; Hydroxypropyl (meth) acrylic , 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3 Secondary hydroxyl group-containing ethylenically unsaturated compounds such as -phenoxypropyl (meth) acrylate; And tertiary hydroxyl group-containing ethylenically unsaturated compounds such as 2,2-dimethyl-2-hydroxyethyl (meth) acrylate.

Among these, a primary hydroxyl group-containing ethylenically unsaturated compound is preferable, and in particular, 4-hydroxybutyl (meth) acrylate and 2-hydroxypropyl () are preferable because of excellent viscosity and compatibility with acrylic resins and ease of obtaining. Meth) acrylate and 2-hydroxyethyl (meth) acrylate, More preferably, it is 4-hydroxybutyl (meth) acrylate.

As a monofunctional unsaturated compound (B), it has one ethylenically unsaturated group other than the said alicyclic structure containing ethylenically unsaturated compound (B1) and hydroxyl-containing ethylenically unsaturated compound (B2) in the range which does not impair the effect of this invention. Although it is preferable to use an unsaturated compound (B3) (henceforth a "monofunctional unsaturated compound (B3)"), it is preferable not to use the compound which has an acidic group from the point which is excellent in corrosion resistance.

As monofunctional unsaturated compound (B3), the C1-C30 (meth) acrylic-acid alkylester of an alkyl group is mentioned, for example, Ethyl (meth) acrylate and n-propyl (meth) acrylate specifically, are mentioned. , n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-octyl (meth) acrylate, iso-octyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, nonyl (meth) acrylate, n-disyl (meth) acrylate, iso-decyl (meth) acrylate, methyl (meth) acrylate, etc. are mentioned. Especially, Preferably, the alkyl group has 2-20 carbon atoms, Especially preferably, 4-18, More preferably, 4-10 alkyl (meth) acrylic-acid alkylester is mentioned, Especially 2-ethylhexyl (meth) is mentioned. ) Acrylate and n-butyl (meth) acrylate are used preferably.

Moreover, as monofunctional unsaturated compound (B3), glycidyl containing unsaturated monomers, such as glycidyl (meth) acrylate and allyl glycidyl (meth) acrylate, are mentioned other than the above; t-butyl amino ethyl (meth) acryl Amino group-containing monomers such as acrylate, diethylaminoethyl (meth) acrylate and dimethylaminoethyl (meth) acrylate; acetacetyl group-containing monomers such as 2- (acetoxy) ethyl (meth) acrylate and allyl acetacetate Alkoxy (poly) alkylene glycol mono (meth) acrylates, such as 2-methoxyethyl (meth) acrylate, 3-methoxyethyl (meth) acrylate, and methoxydiethyleneglycol (meth) acrylate; Allyl compounds such as N-acrylamide methyltrimethyl ammonium chloride, aryltrimethyl ammonium chloride, and dimethylaryl vinyl ketone; N- (meth) acryloyloxymethylenesuccinimide, N- (meth) a Liloyl-2-oxydimethylene succinimide, N- (meth) acryloyl-3-oxytrimethylene succinimide, N- (meth) acryloyl-4-oxytetramethylene succinimide, N- Succinimides such as (meth) acryloyl-5-oxypentamethylene succinimide and N- (meth) acryloyl-6-oxyhexamethylene succinimide; N-vinylpyrrolidone, vinyl propionate, stearic acid Vinyl monomers, such as vinyl, vinyl chloride, vinylidene chloride, vinyl acetate, and styrene, etc. may be used.

In these monofunctional unsaturated compounds (B3), 1 type may be used individually or in combination of 2 or more types.

As content rate of an alicyclic structure containing ethylenically unsaturated compound (B1) with respect to the whole monofunctional unsaturated compound (B), Preferably it is 0.5 to 70 weight%, Especially preferably, it is 1 to 60 weight%, More preferably 3 to 50% by weight, particularly preferably 5 to 40% by weight. Even if the content rate of an alicyclic structure containing ethylenically unsaturated compound (B1) is too high or too low, there exists a tendency for adhesive force to fall.

As content rate of a hydroxyl-containing ethylenically unsaturated compound (B2) with respect to the whole monofunctional unsaturated compound (B), Preferably it is 1 to 70 weight%, Especially preferably, it is 3 to 60 weight%, More preferably, it is 5 to 50 wt%, particularly preferably 7-40 wt%. When the content ratio of the hydroxyl group-containing ethylenically unsaturated compound (B2) is too high, the cohesion force tends to be too high, and when too low, the durability tends to decrease.

As a content rate of the total amount of an alicyclic structure containing ethylenically unsaturated compound (B1) and a hydroxyl-containing ethylenically unsaturated compound (B2) with respect to the whole monofunctional unsaturated compound (B), Preferably it is 10-75 weight%, Especially preferable Preferably from 20 to 70% by weight, more preferably from 25 to 65% by weight, particularly preferably from 30 to 60% by weight. If the content ratio of the total amount of the alicyclic structure-containing ethylenically unsaturated compound (B1) and the hydroxyl group-containing ethylenically unsaturated compound (B2) is too high, the cohesion force tends to be too high, and if too low, the effect of the present invention cannot be sufficiently obtained. There is a tendency.

It is preferable that the content ratio (weight ratio) of an alicyclic structure containing ethylenically unsaturated compound (B1) and a hydroxyl group containing ethylenically unsaturated compound (B2) is (B1) :( B2) = 10: 90-90: 10, Especially Preferably, it is (B1) :( B2) = 20: 80-80: 20, More preferably, it is (B1) :( B2) = 30: 70-70: 30. When the content ratio of the alicyclic structure-containing ethylenically unsaturated compound (B1) to the hydroxyl group-containing ethylenically unsaturated compound (B2) is too high, the cohesion force tends to be low, and when too low, the adhesive force tends to decrease.

It is preferable that content of a monofunctional unsaturated compound (B) is 50-95 weight part with respect to a total of 100 weight part of acrylic resin (A) and a monofunctional unsaturated compound (B), Especially preferably, it is 55-93 weight part More preferably, it is 60-90 weight part. When there is too much content of a monofunctional unsaturated compound (B), there exists a tendency for a viscosity to be too low and to become difficult to coat, and when too low, a viscosity becomes high and it becomes difficult to coat.

As an ethylenically unsaturated compound (C) containing two or more ethylenically unsaturated groups (Hereinafter, it may be described as a "polyfunctional unsaturated compound (C).)) For example, a bifunctional (meth) acrylate type monomer , A trifunctional or higher (meth) acrylate monomer, a urethane (meth) acrylate compound, an epoxy (meth) acrylate compound, or a polyester (meth) acrylate compound can be used. Moreover, these can be used individually or in combination of 2 or more types.

As a bifunctional (meth) acrylate type monomer, what is necessary is just a monomer containing two (meth) acryloyl groups, For example, ethylene diglyfil (meth) acrylate, diethylene glycol di (meth) acrylate, Tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene Glycoldi (meth) acrylate, neopentyl glycoldi (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, 1,6-hexanediol ethylene oxide modified di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate , Ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, hydroxy pivaric acid modified neopentyl Glycol di (meth) acrylate, isocyanuric acid ethylene oxide modified diacrylate, 2- (meth) acryloyloxyethyl acid phosphate diester, and the like.

As a trifunctional or more than (meth) acrylate type monomer, what is necessary is just a monomer containing three or more (meth) acryloyl groups, For example, a trimethol propane tri (meth) acrylate and a pentaerythritol tri (meth) acryl Late, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate , Tri (meth) acryloyloxyethoxytrimetholpropane, glycerin polyglycidyl ether poly (meth) acrylate, isocyanuric acid ethylene oxide modified tri (meth) acrylate, ethylene oxide modified dipentaerythritol penta ( Meta) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, ethylene oxide modified penta Erythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol tetra (meth) acrylate, succinic acid modified pentaerythritol tri (meth) acrylate, and the like.

As a urethane (meth) acrylate type compound, it is a (meth) acrylate type compound which has a urethane bond in a molecule | numerator, The (meth) acrylic type compound containing a hydroxyl group, and polyhydric isocyanate type compound (polyol type compound as needed), What can be obtained by making it react by a well-known general method may be used, and as a weight average molecular weight, what is necessary is just to use 300-4000 normally.

As content of a polyfunctional unsaturated compound (C), it is preferable that it is 0.005-15 weight part with respect to a total of 100 weight part of acrylic resin (A) and a monofunctional unsaturated compound (B), Especially preferably, it is 0.01-13 weight part, More preferably, it is 0.1-10 weight part.

When there is too much content of a polyfunctional unsaturated compound (C), there exists a tendency for adhesive force to fall easily, and when too small, there exists a tendency for cohesion force to fall easily.

The photopolymerization initiator (D) is not particularly limited as long as it generates radicals by the action of active energy rays such as light, and an intramolecular self-cleavage type photopolymerization initiator or a hydrogen extraction type photopolymerization initiator is used.

Examples of the intramolecular self-aligned photopolymerization initiators include 4-phenoxydichloroacetphenone, 4-t-butyldichloroacetphenone, diethoxyacetphenone, 2-hydroxy-2-methyl-1-phenylpropane- 1-one, 1- (4-isopropylenephenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropane-1- On, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2- morpholino propane-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, alpha -acyroxime ester, acyl phosphine Oxide, methylphenylglyoxylate, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 4-benzoyl-4'-methyl diphenylsulfide, and the like. 2-hydroxy-2-methyl-1-phenyl propane-1- , Is very suitable for the 1-hydroxycyclohexyl phenyl ketone.

Moreover, as a hydrogen draw type photoinitiator, benzophenone, 4-phenylbenzo phenone, hydroxy benzophenone, 3,3'- dimethyl- 4-methoxy benzophenone, 2,4, 6-trimethyl benzo, for example. Phenone, 4-methylbenzophenone, thioxanthone, 2-chlorothioxone, 2-methylthioxone, 2,4-thimethylthioxone, isopropyrthioxone, camphorquinone, di Benzosverone, 2-ethyl anthraquinone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, benzyl, 9,10-phenansrenquinone, and the like. Among them, benzophenone, methyl benzophenone and 2,4,6-trimethylbenzophenone are very suitable. These photoinitiators (D) are used 1 type or in combination or 2 or more types.

In addition to using the above-mentioned photopolymerization initiator, by using a triazine-based photopolymerization initiator, it becomes possible to reduce the amount of accumulated light required to obtain good adhesive physical properties after curing.

As a triazine type photoinitiator, 2, 4, 6-3 substituted-s-triazine represented by following General formula (1) is mentioned, for example.

[In Formula 1, R ¹ , R ² , and R ³ are each an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkenyl group, or an alkoxy group, and may be the same or different from each other, but at least one is mono halogen substituted. A methyl group, a dihalogen ring substituted methyl group, or a trihalogen substituted methyl group.]

As said alkyl group, a C1-C10 alkyl group, specifically, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, n-hexyl group etc. are mentioned, for example. Moreover, as said substituted alkyl group, a C1-C10 alkyl group substituted by the halogen atom, specifically, a trichloromethyl group, a tribromomethyl group, (alpha), (alpha), (beta)-trichloroethyl group etc. are mentioned.

As the aryl group and the substituted aryl group, for example, those having 6 to 20 carbon atoms, specifically, a phenyl group, p-methoxy phenyl group, p-methyl thiophenyl group, p-chlorophenyl group, 4-biphenyryl group, A naphthyl group, 4-methoxy-1- naphthyl group, etc. are mentioned.

Moreover, as said alkenyl group, C2-C12 things, such as a vinyl group, an allyl group, and 2-phenylethenyl group, are mentioned, for example. Moreover, as said alkoxy group, C1-C10 things, such as a methoxy group, an ethoxy group, butoxy group, are mentioned, for example.

And as said mono halogen substituted methyl group, dihalogen substituted methyl group, or trihalogen substituted methyl group, a chloromethyl group, a bromomethyl group, an iodine methyl group, a dichloromethyl group, a dibromomethyl group, a diiodine methyl group, a trichloromethyl group, a tribromomethyl group, a tribromomethyl group An iodine methyl group is mentioned. Especially, the trichloromethyl group which the chlorine atom substituted is very suitable.

Such 2,4,6-3 substituted-s-triazine represented by Formula 1 is, for example, Journal of American Chemical Society Vol. 72, pp. 3257-3528 (1950), manufactured by Journal of American Chemical Society 74, 5633-5636 (1952), Juatus Lieblgs Annalen der Chemie, 77-95 (1952).

Specifically as 2,4,6-3 substituted-s-triazine represented by the said Formula (1), 2,4,6-tris (trichloromethyl) -s-triazine, 2,4,6-tris ( Tribromomethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-methyl-s-triazine, 2,4-bis (tribromomethyl) -6-methyl-s-tri Azine, 2,4-bis (trichloromethyl) -6- (p-tolyl) -s-triazine, 2,4-bis (trichloromethyl) -6-n-propyl-s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6 -Tris (dibromomethyl) -s-triazine, 2,4,6-tris (bromomethyl) -s-triazine, 2,4,6-tris (chloromethyl) -s-triazine 2,4,6-3 substituted-s-triazine-based photopolymerization initiator having only aliphatic substituents, 2,4-bis (trichloromethyl) -6-phenyl-s-triazine, 2,4-bis (trichloromethyl ) -6- (p-methoxyphenyl) -s-triazine, 2,4-bis (trichloromethyl)- 6- (p-methylthiophenyl) -s-triazine, 2,4-bis (trichloromethyl) -6- (p-chlorophenyl) -s-triazine, 2,4-bis (trichloromethyl) -6- (2 ', 4'-dichlorophenyl) -s-triazine, 2- (p-bromophenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2, 4-bis (Tribromomethyl) -6-phenyl-s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2,4-bis (trichloromethyl) -6- [2- (p-methoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (o-methoxyphenyl) ethenyl] -s-triazine , 2- [2- (p-butoxyphenyl) ethenyl] -bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -2,4 -Bis (trichloromethyl) -s-triazine, 2- [2- (3,4,5-trimethoxyphenyl) ethenyl] -2,4-bis (trichloromethyl) -s-triazine, 2- (1-naphthyl) -2,4-bis (trichloromethyl) -s-triazine, 2- (4-biphenyryl) -2,4-bis (trichloromethyl) -s-triazine , 2- (4'-methoxy-1'-naphthyl) -2,4- S (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6- (p-methoxynaphthyl) -s-triazine, 2,4-bis (trichloromethyl)- 2,4 having aromatic substituents such as 6- (piperonyl) -s-triazine and 2,4-bis (trichloromethyl) -6- (p-methoxystyryl) -s-triazine 6-3 substituted-s-triazine type photoinitiator etc. are mentioned. These are used individually or in combination of 2 or more types.

Among these, it is preferable to use the 2,4,6-3 substituted-s-triazine type photoinitiator which has an aromatic substituent as said triazine type photoinitiator, and since it is good in compatibility with little yellowing of a coating film, it is 2 Particular preference is given to using, 4-bis (trichloromethyl) -6- (p-methoxyphenyl) -s-triazine.

Moreover, as needed, for example, as a preparation of a photoinitiator (D), a triethanol amine, a triisopropanolamine, 4,4'- dimethylamino benzophenone (mihiraketone), 4,4'- diethylamino benzophenone , 2-dimethylaminoethyl benzoic acid, 4-dimethylamino benzoic acid ethyl, 4-dimethylamino benzoic acid (n-butoxy) ethyl, 4-dimethylamino benzoic acid isoamyl, 4-dimethylamino benzoic acid 2-ethylhexyl, 2,4- It is also possible to use diethyl thioxane hands, 2,4-diisopropyl thioxane hands, etc. together.

It is preferable that content of a photoinitiator (D) is 0.1-20 weight part with respect to a total of 100 weight part of a monofunctional unsaturated compound (B) and a polyfunctional unsaturated compound (C), Especially preferably, it is 0.5-15 weight part Parts, more preferably 1 to 10 parts by weight. When the content of the photopolymerization initiator (D) is too small, a gap tends to occur in polymerization by active energy ray irradiation such as ultraviolet rays, and when too large, a certain or more addition effect may not be obtained and it may not be economical.

Moreover, when using the said triazine type photoinitiator alone as a photoinitiator (D), it is 0.01 triazine type photoinitiator with respect to a total of 100 weight part of a monofunctional unsaturated compound (B) and a polyfunctional unsaturated compound (C). It is preferable to make it contain -0.5 weight part, Especially preferably, it is 0.05-0.45 weight part, More preferably, it is 0.1-0.4 weight part, Especially preferably, it is 0.15-0.35 weight part.

In this way, although the adhesive composition of this invention containing acrylic resin (A), a monofunctional unsaturated compound (B), a polyfunctional unsaturated compound (C), and a photoinitiator (D) can be obtained, the effect of this invention is acquired, In the range which does not harm, isocyanate type, epoxy type, metal salt, metal alkoxide, aldehyde type compound, non-amino resin type amino compound, urea type, metal chelate type, melamine type, aziridine type, crosslinking agent generally used, other adhesive Tackifiers such as urethane resins, rosin, rosin esters, hydrogenated rosin esters, phenolic resins, aromatic modified terpene resins, aliphatic petroleum resins, alicyclic petroleum resins, styrene resins, xylene resins, known additives and ultraviolet rays. Or the compound which causes coloring or discoloration by irradiation can be mix | blended.

Moreover, in addition to the said compounding agent, what contained a small amount of impurities etc. which are contained in the manufacturing raw materials of the component of an adhesive composition, etc. may be sufficient. What is necessary is just to set the compounding quantity of these compounding agents suitably so that a desired physical property may be obtained.

The pressure-sensitive adhesive composition is preferable in that it is excellent in corrosion resistance substantially free of acid, and the acid value of the pressure-sensitive adhesive composition is substantially 1 mg KOH / g or less, preferably 0.5 mg KOH, without substantially including acid. / g or less, particularly preferably 0.

It is preferable that the adhesive composition obtained by this invention does not contain solvents, such as water, an aqueous solvent, or an organic solvent substantially, and an acrylic resin (A), a polyfunctional unsaturated compound (C), and a photoinitiator (D) are further needed. The other component mix | blended with will be in the state melt | dissolved or uniformly disperse | distributed in a monofunctional unsaturated compound (B). Such an adhesive composition is an acrylic resin (A), a monofunctional unsaturated compound (B), a polyfunctional unsaturated compound (C), a photoinitiator (D), and the other component mix | blended as needed to normal temperature or about 60 degreeC It can prepare by mixing after heating.

In this way, although the adhesive composition of this invention is obtained, such an adhesive composition can harden | cure by active energy ray irradiation and can obtain the adhesive of this invention.

As the active energy ray, in addition to electromagnetic waves such as ultraviolet rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, X rays, and γ rays, electron rays, floton rays, neutron rays, and the like can be used. In view of ease, price and the like, curing by ultraviolet irradiation is advantageous.

High-pressure mercury lamps, ultra-high pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps and the like that emit light in the wavelength range of 150 to 450 nm can be used for ultraviolet irradiation.

As an irradiation amount of an active energy ray, it is preferable that it is 500 mJ / cm <2> or more, Furthermore, it is preferable that it is 1000 mJ / cm <2> or more, Especially 1500 mJ / cm <2> or more. If the amount of such irradiation is too small, there is a tendency for a gap to easily occur in polymerization by active energy ray irradiation. In addition, the upper limit of irradiation amount is 10000mJ / cm <2> normally, and when there is too much irradiation amount, it exists in the tendency which is not economical in terms of apparatus and cost.

It is very suitable to use the adhesive of this invention as an adhesive sheet. As a manufacturing method of an adhesive sheet, after apply | coating [I] adhesive composition on a base material, irradiating an active energy ray to make an adhesive layer, the method of sticking a release sheet, and apply | coating a [II] adhesive composition on a base material, and a release sheet After attaching, the method of performing an active energy ray irradiation to form an adhesive layer, the method of apply | coating a [III] adhesive composition on a release sheet and irradiating an active energy ray to make an adhesive layer, and then sticking a base material or a release sheet, [IV] A pressure-sensitive adhesive composition is applied onto a release sheet, and a base material or a release sheet is pasted, followed by active energy ray irradiation to form an adhesive layer.

When the base material or the release sheet is applied after the active energy ray irradiation, it is more preferable to irradiate the active energy ray under an inert gas atmosphere in order to exclude the polymerization inhibitory factor due to oxygen at the time of active energy ray irradiation. It is also possible to balance the physical properties by adjusting the irradiation conditions in consideration of the polymerization inhibition factor.

Examples of the substrate include metal foils such as aluminum, copper, and iron; polyester resins such as polyethylene naphthalate, polyethylene terephthalate, polybutylene terephthalate and polyethylene terephthalate / isophthalate copolymer; polyethylene, polypropylene, Polyolefin resins such as polymethylpentene; polyfluorinated ethylene resins such as polyvinyl fluoride, polyvinylidene fluoride, and polyfluoride; polyamides such as nylon 6 and nylon 66; polyvinyl chloride, polyvinyl chloride / vinyl acetate copolymer , Vinyl aggregates such as ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyvinyl alcohol, vinylon; cellulose resins such as cellulose triacetate and cellophane; methyl polymethacrylate, polyethyl methacrylate, polyacrylic acid Acrylic resins such as ethyl and butyl polyacrylate; polystyrene and polycarbonate And monolayers or multilayers selected from synthetic resin films or sheets such as polyarylate and polyimide, paper such as high-quality paper and glassine paper, glass fibers, natural fibers, synthetic fibers and the like. Moreover, it is also possible to use it for uses, such as a double-sided tape, using a nonwoven fabric, a foam base material, etc. as a base material sheet.

Although the thickness of the said base material is not specifically limited, Usually, it is 500 micrometers or less, Preferably it is 5-300 micrometers, More preferably, it is 10-200 micrometers.

As a release sheet, the thing which carried out the mold release process to the various synthetic resin sheets, paper, cloth, nonwoven fabric etc. which were illustrated by the said support base material can be used, for example.

As a coating method of an adhesive composition, if it is a general coating method, it will not specifically limit, For example, methods, such as roll coating, die coating, gravure coating, comma coating, screen printing, are mentioned.

Moreover, although the thickness of the said adhesive layer formed on a base material after active energy ray irradiation is suitably set according to a use, it is 5-300 micrometers normally, Preferably it is 10-250 micrometers. If the thickness of the pressure-sensitive adhesive layer is too thin, the sticking property tends to be difficult to stabilize, and if it is too thick, there is a tendency to easily cause pull marks.

At the time of use of the adhesive sheet in this invention, as a kind of to-be-adhered body, For example, the article which has a various metal surface; Polyester resins such as polyethylene naphate, polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate / isophthalate copolymer; polyolefin resins such as polyethylene, polypropylene, polymethylpentene; polyvinyl fluoride, polyvinyl fluoride Polyfluorinated ethylene resins such as lithium and polyfluoride; polyamides such as nylon 6 and nylon 66; polyvinyl chloride, polyvinyl chloride / vinyl acetate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, poly Vinyl aggregates such as vinyl alcohol and vinylon; cellulose resins such as cellulose triacetate and cellophane; acrylic resins such as polymethyl methacrylate, polyethyl methacrylate, ethyl polyacrylate, and butyl polyacrylate; polystyrene, polycarbonate, and polya Synthetic resin film, sheet such as related, polyimide It may include a plate or the like.

The article which has the said metal surface has a metal surface, and the said adhesive sheet may be stuck at least partly or whole surface directly to this metal surface. In the article which has these metal surfaces, as an adherend to which the said adhesive sheet sticks (it may be called a "metal surface containing adherend"), if it has a metal surface at least partially, it will not specifically limit. In these metal surface containing to-be-adhered bodies, the site | part in which the metal surface is formed is not specifically limited if it is a site | part which can directly stick the said adhesive sheet, The outer side may be sufficient, and an inner side etc. may be sufficient as it. In the case where a plurality of metal surfaces are formed on one metal surface-containing adherend, the plurality of metal surfaces may be surfaces formed of the same metal material or may be surfaces formed of different metal materials.

The metal surface in the said metal surface containing adherend may be the surface of the metal surface containing adherend formed of the metal material, and the metal layer surface (especially a metal thin film layer) formed in the surface of the base material (or the structure) formed of various materials. Surface). The metal surface may be any surface made of a metal material anyway.

Metal layers, such as the said metal thin film layer, can be formed in the predetermined | prescribed site | part of the surface of the base material (or structure) comprised with various materials. In these metal layers, as a thickness of a metal thin film layer, it can select suitably according to the kind of metal surface containing adherend, for example, 0.1 micrometer or more may be sufficient. The upper limit of the thickness of the metal thin film layer is not particularly limited as long as the thickness is generally regarded as a thin film layer.

Examples of the metal material for forming the metal surface include metal materials such as aluminum, silver, gold, copper, iron, titanium, platinum, nickel, and the like, metal materials; gold alloys (for example, gold-copper alloys). Copper alloys (eg, copper-zinc alloys (brass), copper-aluminum alloys, etc.), aluminum alloys (eg, aluminum-molybdenum alloys, aluminum-tantalum alloys, aluminum-cobalt alloys, aluminum-chromium) Metal materials by various alloys such as alloys, aluminum-titanium alloys, aluminum-platinum alloys), nickel alloys (for example, nickel-chromium alloys, copper-nickel alloys, zinc-nickel alloys, etc.), tin alloys, and stainless steels. Etc. can be mentioned. These metal materials can be used individually or in combination of 2 or more types.

The metal material may be a metal material containing only a metal element, or a metal material containing a non-metal element together with the metal element (for example, an oxide, a hydroxide, a halide (chloride, etc.) of a metal, an oxate (nitrate, Metal compounds such as lactates, phosphates, carbonates, and the like].

Specifically, as the metal surface-containing adherend, for example, a window member having at least a metal surface (metal thin film layer surface, etc.), a member for constituting the window member, or an electromagnetic shield layer formed of the metal thin film layer may be used. The optical product which has, or the member for composing this optical product, etc. are mentioned. As an optical product which has the said electromagnetic shield layer, optical instruments, such as an electronic display (plasma display etc.), and optically recordable discs (optical recording disc), such as a digital universal disk, etc. are mentioned, for example.

Hereinafter, although an Example demonstrates this invention still more concretely, this invention is not limited to a following example, unless the summary is exceeded. In addition, "part" and "%" mean a basis of weight in an Example.

[Production of Acrylic Resin (A)]

300 parts of water was put into the four round bottom flask with a stirrer, 0.7 parts of polyvinyl alcohols were melt | dissolved as a dispersion stabilizer, n-butylacrylate (a1) 87.8, stirring at 300 rpm with a stirring blade. Part, a monomer mixture consisting of 7.2 parts of acrylonitrile (a3) and 5 parts of 2-hydroxyethyl methacrylate (a2) and 0.9 part of N, N'-azobisisobutyronitrile as a polymerization initiator were added in a batch to prepare a suspension. It was.

The suspension was continuously stirred to raise the temperature in the reaction system to 68 ° C, and was kept constant for 4 hours to react. Thereafter, it was cooled to room temperature (about 25 ° C). Subsequently, the reaction product was solid-liquid separated, and it fully wash | cleaned with water, and it dried at 70 degreeC for 12 hours using the dryer, and obtained the bulk acryl-type resin (A-1). The weight average molecular weight (Mw) of obtained acrylic resin (A-1) was 4.6, and dispersion degree (Mw / Mn) was 4.6 and glass transition temperature was -47 degreeC.

[Production of Acrylic Resin (A-2)]

51 parts of n-butyl acrylates (a1) were put into 300 parts of flasks with four round mouths of glass-equipped glass with a stirrer, dissolving 0.7 parts of polyvinyl alcohols as a dispersion stabilizer, and stirring at 300 rpm with a stirring blade. A suspension was prepared by adding a monomer mixture consisting of 44 parts of isobornyl acrylate (a1) and 5 parts of 2-hydroxyethyl methacrylate (a2) and 0.9 part of N, N'-azobisisobutyronitrile as a polymerization initiator. .

The suspension was continuously stirred to raise the temperature in the reaction system to 68 ° C, and was kept constant for 4 hours to react. Thereafter, it was cooled to room temperature (about 25 ° C). Subsequently, the reaction product was solid-liquid separated, and after wash | cleaning enough with water, it dried at 70 degreeC for 12 hours using the dryer, and obtained the bulk acryl-type resin (A-2). The weight average molecular weight (Mw) of obtained acrylic resin (A-2) was 950,000, dispersion degree (Mw / Mn) was 3.5, and the glass transition temperature was -5 degreeC.

[Example 1]

12 parts of acrylic resin (A-1) as acrylic resin (A), 18 parts of 4-hydroxybutyl acrylate (HBA: (B2)) as a monofunctional unsaturated compound (B), cyclohexyl acrylate (CHA: (B1 )) 20 parts, 2-ethylhexyl acrylate (2 EHA: (B3)) 50 parts, 0.3 parts of trimetholpropane triacrylate (TMPTA) as a polyfunctional unsaturated compound (C) in a container with a stirrer for 24 hours The mixture was stirred and dissolved. To this solution, 2-hydroxy-2-methyl-1-phenyl-propane-1-one (brand name: "Darocure 1173"; product of Chiba Specialty Chemicals, Inc.) as a photoinitiator (D) ( The pressure-sensitive adhesive composition was obtained by mixing 1 part of HMPP).

The adhesive composition obtained above was coated on the 100-micrometer-thick polyethylene terephthalate (PET) base material so that it might be 130 micrometers in thickness. The release surface was coated with the release surface so that the release surface was in contact with the coating surface. Then, the pressure-sensitive adhesive layer obtained by curing the pressure-sensitive adhesive composition by irradiating ultraviolet rays so that the amount of accumulated light becomes 2400 mJ / cm 2 with a high-pressure mercury lamp adjusted to an irradiation intensity of 200 mW / cm 2 using an ultraviolet irradiation device shown below. An adhesive sheet having was obtained.

<Ultraviolet rays irradiation device>

Igland Daisy ECS-301 G1 Type (I Graphics)

<Irradiation conditions>

80 W / cm (high pressure mercury lamp) × 18 cm H, irradiation intensity 200 mW / cm 2

[Examples 2 to 8]

In Example 1, except that the compounding ratio of 4-hydroxybutyl acrylate (HBA), cyclohexyl acrylate (CHA) and 2-ethylhexyl acrylate (2 EHA) was changed as shown in Table 1 below In the same manner as in Example 1, an adhesive composition and an adhesive sheet were obtained.

EXAMPLE 9

In Example 1, except using acrylic resin (A-1) instead of acrylic resin (A-1), and changing the compounding ratio of the other components like Table 2 below, it carried out similarly to Example 1 An adhesive composition and an adhesive sheet were obtained.

[Comparative Examples 1 to 3]

In Example 1, except for changing the compounding ratio of 4-hydroxy butyl acrylate (HBA), cyclohexyl acrylate (CHA) and 2-ethyl hexyl acrylate (2 EHA) as shown in the following table In the same manner as in 1, an adhesive composition and an adhesive sheet were obtained.

In Example 1, the composition of the pressure-sensitive adhesive composition was 14.6 parts of acrylic resin (A-1), 39.4 parts of 2-ethylhexyl acrylate (2 EHA), 39.4 parts of butyl acrylate (BA), 6.6 parts of acrylic acid (AAc), trimes 0.3 part of tyrol propane triacrylate (TMPTA), 2-hydroxy-2-methyl-1- phenyl- propane- 1-one (brand name: "Tarocure 1173", Chiba Specialty Chemicals Co., Ltd. product HMPP) Except having made it 1 part, it carried out similarly to Example 1, and obtained the adhesive composition and the adhesive sheet.

About the adhesive composition used by the said Example and the comparative example, the compounding ratio of each said component material is shown in following Table 1.

About the adhesive sheet obtained by the said Example and the comparative example, the gel fraction, adhesive force, holding force (cohesion force), and corrosion resistance of an adhesive layer were measured and evaluated by the following method, and the result is shown in following Table 2 together.

<Gel fraction>

After cutting the obtained adhesive sheet to 50 mm x 50 mm, after sticking the adhesive layer side of this adhesive sheet to the mesh sheet avoiding the center part of the longitudinal direction of the 60 * 100 mm SUS mesh sheet (200 mesh), a mesh sheet The test piece was produced by wrapping the adhesive sheet at the center part. The test piece is immersed in 23 degreeC x 24 hours in the sealed container which contained 180 g of toluene, and makes the gel fraction the weight% of the insoluble adhesive component which remained in the mesh sheet. At this time, the weight of the base material is omitted.

<Adhesion>

Adhesive force was measured according to JISZ-0273.

That is, after cutting the obtained adhesive sheet into 25 mm x 100 mm, it is made to reciprocate twice to the stainless plate (SUS304BA board) as a to-be-adhered body using 2 kg rubber ruler in the atmosphere of 23 degreeC, and 50% of relative humidity. The test piece was produced by crimping | bonding. After leaving this test piece for 30 minutes in the same atmosphere, 180 degree peeling test was done by the peeling rate 0.3m / min, and adhesive force (N / 25mm) was measured.

 (Evaluation standard)

○ ... 10N / 25mm or more

× 10 ... less than 10N / 25mm

<Holding force (cohesion force)>

In accordance with JIS Z-0273, SUS 304 was used as the adherend, and the resultant was pasted with an attached area of 25 mm x 25 mm, and then subjected to a load of 1 kg and measured for evaluation after leaving at 80 ° C for 20 minutes.

 (Evaluation standard)

It did not fall even after being left for 24 hours.

△ · · gap after 24 hours left within 1 mm

The gap after leaving for 24 hours is 1 mm or more or falls

<Corrosion Resistance>

After obtaining the obtained adhesive sheet to copper foil (thickness: 130 micrometers), it preserve | saved for 250 hours in 60 degreeC x 90% RH atmosphere. Then, the surface of the copper foil was observed visually from the film side made of polyethylene terephthalate, and the presence or absence of the corrosion of the surface of the copper foil which an adhesive sheet can stick was confirmed.

 (Evaluation standard)

○ ... no corrosion

× ...

* CHA: cyclohexyl acrylate

4HBA: 4-hydroxybutyl acrylate

2EHA: 2-ethylhexyl acrylate

BA: butyl acrylate

AAc: Acrylic acid

TMPTA: trimethylolpropane triacrylate

HMPP: 2-hydroxy-2-methyl-1-phenyl-propan-1-one

-The number of (A)-(D) in a table means that a weight part does not mix | blend.

In the table, N. C represents Non Creep.

The pressure-sensitive adhesives of Examples 1 to 9, which consist of pressure-sensitive adhesive compositions containing both an alicyclic structure-containing ethylenically unsaturated compound and a hydroxyl group-containing ethylenically unsaturated compound, are excellent in adhesion and cohesion (holding force) in balance. Since it does not contain, it turns out that it is excellent also in corrosion resistance.

On the other hand, the pressure-sensitive adhesive of Comparative Example 1 which does not contain both of the alicyclic structure-containing ethylenically unsaturated compound and the hydroxyl group-containing ethylenically unsaturated compound is inferior to both the adhesive force and the cohesive force (holding force), and the alicyclic structure-containing ethylenic compound. The pressure-sensitive adhesive of Comparative Example 2 which does not contain an unsaturated compound was inferior in adhesive force, and the pressure-sensitive adhesive of Comparative Example 3 which did not contain a hydroxyl group-containing ethylenically unsaturated compound was inferior to cohesive force (holding force). Moreover, although the adhesive of Comparative Example 4 which consists of an adhesive composition which mix | blended acrylic acid which has an acidic group was excellent in adhesive force and cohesion force (holding force), it was inferior to corrosion resistance.

Moreover, about the adhesive sheet of Example 9, transparency (haze) was measured by the following method. The results are shown in Table 3.

<Hayes>

Preparation of sample for haze measurement

The obtained pressure-sensitive adhesive sheet was cut out to 3 cm x 4 cm, the release mold release sheet was peeled off, and the pressure-sensitive adhesive layer side was pressed on an alkali-free glass plate (manufactured by Corning, Eagle XG), followed by an autoclave (50 ° C, 0.5 MPa x 20). min) was treated to obtain a sample for haze measurement.

Haze value measurement

The haze of the said sample for haze measurement was measured on each of the following conditions.

Initial haze: We measure after sample making for haze measurement.

-Moist heat haze 1: After making sample for haze measurement, it measures after standing for 100 hours on 60 degreeC x 90% RH conditions.

-Moist heat haze 2: After making a sample for haze measurement, after standing still for 100 hours on 60 degreeC x 90% RH conditions, it measures after standing still for 3 hours at room temperature.

Haze measured the diffusivity and total light transmittance using HAZE MATER NDH2000 (made by Nihon Denshoku Kogyo Co., Ltd.). In addition, this apparatus is based on JISK7361-1.

The haze was computed by substituting the obtained diffuse transmittance and the total light transmittance into the following formula. Haze value (%) = (diffusion transmittance / total light transmittance) x 100

* The value of () is the rate of change from the initial haze

The adhesive of Example 9 which consists of an adhesive composition using the acrylic resin (A-2) obtained by copolymerizing an alicyclic structure containing (meth) acrylic acid ester monomer, has little change of a haze even in wet heat conditions, and is excellent also in moisture heat resistance. Able to know.

Although this invention was detailed also demonstrated with reference to the specific embodiment, it is clear for those skilled in the art that various changes and correction can be added without deviating from the mind and range of this invention.

This application is based on the JP Patent application (Japanese Patent Application No. 2010 # 271653) of December 6, 2010, The content was described here as a reference.

 (Industrial availability)

In order to have a strong adhesive force and the outstanding cohesion force, the adhesive which consists of an adhesive composition of this invention is hard to produce peeling from a base material even in a high temperature environment, It is especially useful as an adhesive for adhesives and an adhesive sheet for an optical member, and an acid is used in an adhesive. The adhesive sheet for optics for attaching optical devices such as an electronic display requiring corrosion resistance to metals and metal oxides, or optical recording discs (optical recording media) such as digital universal discs, because adhesive properties can be satisfied without Useful as

Claims (8)

It is an adhesive composition containing acrylic resin (A), the ethylenically unsaturated compound (B) which has one ethylenically unsaturated group, the ethylenically unsaturated compound (C) which has two or more ethylenically unsaturated groups, and a photoinitiator (D), The pressure-sensitive adhesive composition containing an alicyclic structure-containing ethylenically unsaturated compound (B1) and a hydroxyl group-containing ethylenically unsaturated compound (B2) as an ethylenically unsaturated compound (B) having one ethylenically unsaturated group. The method according to claim 1,
Acrylic resin (A) is a dry resin obtained by suspension polymerization. The method according to claim 1 or 2,
Acrylic resin (A) is an adhesive resin characterized by copolymerizing the copolymerization component containing an alicyclic structure containing (meth) acrylic acid ester monomer. The method according to any one of claims 1 to 3
The content rate of the total amount of an alicyclic structure containing ethylenically unsaturated compound (B1) and hydroxyl-containing ethylenically unsaturated compound (B2) in the ethylenically unsaturated compound (B) which has one ethylenically unsaturated group is 10-70 weight% Adhesive composition, characterized in that. 5. The method according to any one of claims 1 to 4,
Pressure-sensitive adhesive composition, characterized in that substantially no acid. 6. The method according to any one of claims 1 to 5,
It does not contain a solvent, The adhesive composition characterized by the above-mentioned. The pressure-sensitive adhesive composition according to any one of claims 1 to 6 is cured by active energy ray irradiation. Description and claim The adhesive sheet containing the adhesive layer which consists of adhesives.