TWI488934B - Adhesive composition, adhesive and adhesive tape using the same - Google Patents

Description

Adhesive composition, adhesive and adhesive sheet using the same

The present invention relates to an adhesive composition, an adhesive, and an adhesive sheet using the same; more particularly, an adhesive having high adhesion and high cohesive force, and particularly suitable for an electronic member particularly requiring corrosion resistance Or an adhesive for optical members, and an adhesive sheet using the same.

In the adhesive, there are various types of adhesives such as a strong adhesive which adheres to the adherend for a long period of time, or a peeling type adhesive which is premised on peeling off by the adherend after being attached. The most suitable adhesives are designed and used according to various fields.

For example, an adhesive which exhibits a strong adhesive type is usually introduced with a large amount of an acidic functional group in an adhesive, or a large amount of an adhesive-imparting resin is used, thereby imparting high adhesion, and is used in various fields requiring strong adhesion. (for example, refer to Patent Document 1).

However, since these strongly adhesive adhesives are introduced with an acidic functional group, there is a case where the adherend is corroded and an outgassing from an acidic functional group occurs, and it is not suitable for bonding to an electronic member, especially Information labeling or electronic components for precision electronic components.

Therefore, it is necessary to use an adhesive which does not utilize an acid type (acid-free) for the adhesive used for such an optical use (for example, refer patent document 2).

Patent Document 1: Japanese Patent Laid-Open Publication No. 2007-217674

Patent Document 2: Japanese Patent Laid-Open Publication No. 2003-268335

In particular, an optical recording device such as an ITO transparent electrode or a PDP used in a touch panel or the like, an optical device such as an electronic display such as a metal or a metal oxide, or an optical recording disc such as a digital versatile disc is used. An adhesive used for optical applications such as (optical recording medium) is required to have excellent durability such as heat resistance in addition to corrosion resistance, and therefore it is necessary to have an adhesive having high cohesive force and high adhesion, but In the general acid-free adhesive of the patent document 2, although the corrosion resistance is excellent, since the adhesive force and the cohesive force are insufficient, the adhesive for optical use cannot be used.

Therefore, it is desired to develop an adhesive which has superior corrosion resistance and adhesive properties (adhesion, cohesion).

As described above, the present invention is directed to provide an adhesive composition for the purpose of obtaining an adhesive having high adhesion and high cohesive force and excellent corrosion resistance in the absence of an acidic group. Agent.

Therefore, the present inventors have intensively studied in view of such circumstances, and as a result, found that none consists of an acrylic resin, a monofunctional unsaturated monomer, a polyfunctional unsaturated monomer, and a photopolymerization initiator. In a solvent-type active energy ray-curable adhesive, adhesion of an ethylenically unsaturated compound having an alicyclic structure and a hydroxyl group-containing ethylenically unsaturated compound as a monofunctional unsaturated monomer can be obtained. The adhesive having a superior balance of cohesive force, 遂 completed the present invention.

That is, the gist of the present invention relates to an adhesive composition containing an acrylic resin (A), an ethylenically unsaturated compound having one ethylenically unsaturated group (B), and having two or more ethylenic groups. The saturated ethylenically unsaturated compound (C) and the photopolymerization initiator (D) are characterized by containing an alicyclic structure-containing ethylenically unsaturated compound (B1) and a hydroxyl group-containing ethylenically unsaturated compound. (B2) is an ethylenically unsaturated compound (B) having one ethylenically unsaturated group.

Furthermore, the present invention relates to an adhesive, an adhesive sheet using the same.

The present invention includes the following aspects.

[1] An adhesive composition comprising an acrylic resin (A), an ethylenically unsaturated compound (B) having one ethylenically unsaturated group, and an ethylenically unsaturated group having two or more ethylenically unsaturated groups. The compound (C) and the photopolymerization initiator (D) are characterized in that they contain an ethylenically unsaturated compound (B1) having an alicyclic structure and a hydroxyl group-containing ethylenically unsaturated compound (B2) as one. Ethylenically unsaturated ethylenically unsaturated compound (B).

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

[3] The adhesive composition according to [1] or [2] wherein the acrylic resin (A) copolymerizes a copolymerized component containing a (meth) acrylate monomer having an alicyclic structure. Acrylic resin.

[4] The adhesive composition according to any one of [1] to [3] wherein the ethylenically unsaturated compound (B) having one ethylenically unsaturated group contains an alicyclic structure-containing ethylene. The content ratio of the unsaturated compound (B1) and the hydroxyl group-containing ethylenically unsaturated compound (B2) is 10 to 70% by weight.

[5] The adhesive composition according to any one of [1] to [4] wherein the acid composition is substantially free.

[6] The adhesive composition according to any one of [1] to [5] wherein the solvent is not contained.

[7] An adhesive which is obtained by hardening an adhesive composition of any one of [1] to [6] by active energy ray irradiation.

[8] An adhesive sheet comprising an adhesive layer comprising a substrate and an adhesive of [7].

The adhesive composed of the adhesive composition of the present invention has a strong adhesive force and superior cohesive force, and therefore, peeling from the substrate is less likely to occur even in a high temperature environment, and is particularly useful as an optical member. Adhesives, adhesive sheets. In addition, since the adhesive and the cohesive force are superior even if the adhesive does not contain an acid, it is an optical device such as an electronic display or a digital versatile disc for requiring corrosion resistance to metals or metal oxides. An optical recording sheet to which an optical recording optical disk (optical recording medium) is bonded is particularly effective.

The present invention will be described in detail below, but these merely illustrate one example of a preferred embodiment.

Further, in the present invention, (meth)acrylic means acrylic acid or methacrylic acid, (meth)acryloyl group means propylene fluorenyl group or methacryl fluorenyl group, and (meth) acrylate means acrylate or nail Acrylate.

First, the adhesive composition of the present invention will be described.

The adhesive composition of the present invention contains an acrylic resin (A), an ethylenically unsaturated compound (B) having one ethylenically unsaturated group, and an ethylenically unsaturated compound having two or more ethylenically unsaturated groups ( C) and photopolymerization initiator (D).

The acrylic resin (A) contains a (meth)acrylate monomer (a1) as a main component, and optionally contains a functional group-containing copolymerizable monomer (a2) and other copolymerizable monomer (a3). The copolymerization component which is a copolymerization component is obtained by copolymerization.

The (meth) acrylate monomer (a1) (excluding (a2) to be described later) may, for example, be an alkyl (meth) acrylate monomer (a1-1) or an alicyclic structure. (Meth)acrylate monomer (a1-2) or the like.

As such an alkyl (meth)acrylate monomer (a1-1), the carbon number of the alkyl group is usually from 1 to 20, particularly preferably from 1 to 10, more preferably from 1 to 8, and most preferably from 1 to 4. For example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, (methyl) ) tert-butyl acrylate, n-propyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl acrylate, Ethyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, isostearyl acrylate, and the like. These may be used alone or in combination of two or more.

Among these alkyl (meth) acrylate monomers, ethyl (meth) acrylate (A) is preferably used from the viewpoints of copolymerizability, adhesive properties, ease of handling, and ease of obtaining raw materials. The n-butyl acrylate is preferably a n-butyl (meth) acrylate from the viewpoint of superior durability.

The (meth)acrylate monomer (a1-2) having an alicyclic structure has a carbon number of 4 to 20 carbon atoms, particularly preferably 6 to 10 carbon atoms, and specifically, for example, Methyl)cyclopentyl acrylate, cyclohexyl (meth) acrylate, tricyclodecyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo(methyl) acrylate [5.2. 1.02,6]decane-8-yl ester, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, 2-dicyclopentyl epoxyethyl (meth)acrylate, ( Methyl) acrylate Ester, 4-tert-butylcyclohexyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, etc.; among these, adhesion properties and compatibility with monomers For the purpose of using (meth)acrylic acid ester.

The content of the (meth) acrylate monomer (a1) in the copolymerization component is preferably 60 to 100% by weight, particularly preferably 70 to 95% by weight, more preferably 80 to 90% by weight, if (methyl) When the content of the acrylate monomer (a1) is too small, the adhesive strength when using the adhesive tends to be insufficient.

In the case where the adhesive which cures the adhesive composition of the present invention is required to have transparency, it is preferable to use a (meth) acrylate system having an alicyclic structure from the viewpoint of suppressing the change in the haze value. The monomer is a (meth) acrylate monomer (a1).

In addition, the content ratio (parts by weight) of the (meth)acrylate monomer (a1-2) and the alkyl (meth)acrylate monomer (a1-1) having such an alicyclic structure, Preferred is (a1-2): (a1-1)=5:95~95:5, especially good (a1-2): (a1-1)=10:90~90:10, better system ( A1-2): (a1-1)=20:80~80:20.

The functional group-containing copolymerizable monomer (a2) may, for example, be a hydroxyl group-containing monomer, an oxygen-containing alkylene group monomer, a mercapto group-containing monomer, an amine group-containing monomer, a nitrogen-containing monomer, or a ring-containing ring. One type or two or more types selected from the group consisting of the above-mentioned functional group-containing monomer such as an oxypropyl group can be used.

Among these, from the viewpoint of obtaining high cohesion, it is preferred to use a hydroxyl group-containing monomer, and particularly preferably 2-hydroxyethyl (meth)acrylate.

The hydroxyl group-containing monomer may, for example, be 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate or 6-hydroxy(meth)acrylate. (meth)acrylic acid hydroxyalkane such as hexyl ester, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl (meth)acrylate Ester, caprolactone modified caprolactone modified monomer such as 2-hydroxyethyl (meth)acrylate, 2-propenyloxyethyl-2-hydroxyethyl decanoic acid, N-hydroxymethyl ( a methyl-containing monomer such as methyl acrylamide or N-hydroxyethyl (meth) acrylamide; 2-hydroxypropyl (meth) acrylate or (meth) propylene Acid 2-hydroxybutyl ester, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-(meth)acrylate A hydroxy group-containing monomer such as a phenoxypropyl ester or the like; a hydroxy group-containing monomer such as 2,2-dimethyl-2-hydroxyethyl (meth)acrylate.

Further, a polyethylene glycol derivative such as diethylene glycol (meth) acrylate or polyethylene glycol mono (meth) acrylate or a polypropylene glycol derivative such as polypropylene glycol mono (meth) acrylate may be used. , polyethylene glycol polypropylene glycol mono(meth)acrylate, poly(ethylene glycol-butanediol) mono(meth)acrylate, poly(propylene glycol-butanediol) mono(meth)acrylate The hydroxy-containing monomer modified by an alkylene group.

The oxygen-containing alkylene group monomer may, for example, be 2-methyloxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate or 3-methoxybutyl (meth)acrylate. , 2-butoxyethyl (meth)acrylate, 2-butoxyethylene glycol (meth) acrylate, methoxy diethylene glycol (meth) acrylate, methoxy triethylene glycol (Meth) acrylate, ethoxy diethylene glycol (meth) acrylate, methoxy dipropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, octyloxy Polyethylene glycol-polypropylene glycol mono(meth)acrylate, lauryloxypolyethylene glycol mono(meth)acrylic acid, stearyloxy polyethylene glycol mono(meth)acrylate, etc. (meth) acrylate, or 2-phenoxyethyl (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol - polypropylene glycol (meth) acrylate An aromatic (meth) acrylate such as an ester or a nonyl phenol ethylene oxide adduct (meth) acrylate.

Examples of the guanamine-containing monomer include acrylamide, methacrylamide, N-(n-butoxyalkyl) acrylamide, and N-(n-butoxyalkyl)methacrylamide. , N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, Acrylamide-3-methylbutylmethylamine, dimethylaminoalkyl acrylamide, dimethylaminoalkylmethacrylamide, and the like.

The amine group-containing monomer may, for example, be dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate or a tertiary compound thereof.

As the nitrogen-containing monomer, for example, an acrylonitrile group Porphyrin and the like.

Examples of the epoxy group-containing monomer include glycidyl (meth)acrylate and alkylpropylepoxypropyl ether.

The content of the functional group-containing copolymerizable monomer (a2) in the copolymerization component is preferably 0.01 to 20% by weight, particularly preferably 0.1 to 15% by weight, more preferably 0.2 to 10% by weight, if the functional group is contained. When the amount of the copolymerizable monomer (a2) is too small, the interaction between the functional groups tends to be small, and the cohesive force tends to decrease. If the amount is too large, the adhesion tends to be excessively lowered.

Examples of the other copolymerizable monomer (a3) include acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, vinyl acetate, vinyl propionate, vinyl stearate, and vinyl chloride. Dichloroethylene, alkyl vinyl ether, vinyl toluene, vinyl pyridine, vinyl pyrrolidone, dialkyl itaconate, dialkyl fumarate, allyl alcohol, chlorination Propylene group, methyl vinyl ketone, N-propylene decyl methyl methyl dimethyl ammonium chloride, allyl trimethyl ammonium chloride, dimethyl allyl ketene, and the like.

The content ratio of the other copolymerizable monomer (a3) in the copolymerization component is preferably 0 to 40% by weight, particularly preferably 3 to 30% by weight, more preferably 8 to 20% by weight, and other copolymerizable monomers ( If the content of a3) is too large, the adhesive performance tends to be lowered.

The acrylic resin (A) used in the present invention preferably contains no acidic group from the viewpoint of superior corrosion resistance.

By polymerizing the (meth) acrylate monomer (a1), the functional group-containing copolymerizable monomer (a2), and other copolymerizable monomer (a3) as a copolymerization component, When the acrylic resin (A) is produced, it can be produced by a method known to a known method such as solution radical polymerization, suspension polymerization, bulk polymerization, or emulsion polymerization at the time of the polymerization.

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

In the above polymerization, a dispersion stabilizer such as polyvinyl alcohol or a polymerization initiator such as azobisisobutyronitrile may be added as needed.

Further, the acrylic resin used for the adhesive composition is generally produced by solvent-based polymerization using an organic solvent at the time of its production. When such a solvent-based acrylic resin is used for the adhesive composition, it is necessary to dry the adhesive composition solution at a high temperature, so that a large amount of energy is required, or the organic solvent is liable to cause ignition and also cause air pollution. Therefore, a large-scale recovery device or safety device for the solvent must be provided. However, when the acrylic resin (A) which is a dry resin obtained by the above suspension polymerization is used, an adhesive composition containing no such organic solvent can be produced.

The weight average molecular weight (Mw) of the acrylic resin (A) is preferably from 500,000 to 3,000,000, particularly preferably from 850,000 to 2.5 million, more preferably from 1,000,000 to 2,000,000. When the weight average molecular weight of the acrylic resin (A) is too small, the cohesive force of the adhesive obtained by irradiation with active energy rays tends to decrease, and if it is too large, it tends to be difficult to obtain a uniformly compatible adhesive composition.

The degree of dispersion (Mw/Mn) of the acrylic resin (A) is preferably 7 or less, particularly preferably 5 or less, more preferably 4 or less. When the degree of dispersion (Mw/Mn) of the acrylic resin (A) is too large, the fluctuation due to the active energy ray irradiation conditions tends to increase in the cohesive force or the adhesive property. Further, the lower limit of the degree of dispersion (Mw/Mn) is usually 2. Further, the above Mn means a number average molecular weight.

The glass transition temperature (Tg) of the acrylic resin (A) is preferably -70 to 20 ° C, particularly preferably -60 to 0 ° C, more preferably -55 to -10 ° C. When the glass transition temperature (Tg) of the acrylic resin (A) is too low, the cohesive force tends to decrease, and if it is too high, the adhesive tends to be brittle.

In addition, the weight average molecular weight in the present invention means a weight average molecular weight converted from a standard polystyrene molecular weight, and specifically, a high-speed liquid chromatograph ("Waters 2695 (body), manufactured by Waters Corporation, Japan"). With "Waters 2414 (detector)", use the column: Shodex GPC KF-806L (excluding the limit molecular weight: 2 × 10 ⁷ , separation range: 100 ~ 2 × 10 ⁷ , theoretical number of stages: 10,000 segments / root, filler The material was measured by three series of materials: styrene-divinylbenzene copolymer and filler particle diameter: 10 μm. The number average molecular weight was also measured in the same manner as described above.

In addition, the glass transition temperature in this invention is calculated by the following Fox formula.

[Number 1]

Tg: glass transition temperature of copolymer (K)

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

Tgb: glass transition temperature (K) of homopolymer of monomer B

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

Wa: the weight fraction of monomer A

Wb: the weight fraction of monomer B

Wn: the weight fraction of monomer N

(Wa+Wb+...+Wn=1)

The content of the acrylic resin (A) is preferably from 5 to 50 parts by weight based on 100 parts by weight of the total of the acrylic resin (A) and the ethylenically unsaturated compound (B) having one ethylenically unsaturated group described later. It is preferably 7 to 45 parts by weight, more preferably 10 to 40 parts by weight.

When the content of the acrylic resin (A) is too small, the viscosity tends to be too low to be easily applied, and if it is too large, the viscosity tends to be high and it tends to be difficult to apply.

The ethylenically unsaturated compound (B) having one ethylenically unsaturated group (hereinafter sometimes referred to as "monofunctional unsaturated compound (B)") must contain an ethylenically unsaturated compound having an alicyclic structure. (B1) and a hydroxyl group-containing ethylenically unsaturated compound (B2).

In the present invention, by using (B1) and (B2) as essential components, the release suppressing effect of the adhesive derived from the alicyclic structure-containing ethylenically unsaturated compound (B1) can be favorably balanced. High adhesion, high cohesion caused by hydrogen bonding from the hydroxyl group-containing ethylenically unsaturated compound (B2).

The ethylenically unsaturated compound (B1) having an alicyclic structure preferably contains a (meth) acrylate compound having an alicyclic structure, and has a carbon number of 4 to 20 as an alicyclic structure. Particularly preferred are 6 to 10, and specific examples thereof include cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, tricyclodecyl (meth)acrylate, and 2-methylcyclopropene (meth)acrylate. Ester, tricyclo [5.0.1.02,6]decane-8-yl ester, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, (meth)acrylic acid 2-dicyclopentyloxyethyl ester, (meth)acrylic acid Ester, 4-tert-butylcyclohexyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, etc.; among these, from the acrylic resin (A) From the viewpoint of excellent solubility, cyclohexyl (meth)acrylate and cyclohexyl acrylate are preferred.

The hydroxyl group-containing ethylenically unsaturated compound (B2) is preferably a hydroxyl group-containing (meth) acrylate type compound, and examples thereof include 2-hydroxyethyl (meth)acrylate and 2-hydroxyl (meth)acrylate. Propyl ester, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, (methyl) a hydroxyalkyl (meth) acrylate such as 10-hydroxy decyl acrylate, (4-hydroxymethylcyclohexyl)methyl (meth) acrylate, or a 2-hydroxy propyl (meth) acrylate modified by caprolactone Caprolactone modified monomer such as ester, 2-propenyloxyethyl-2-hydroxyethyl decanoic acid, N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (methyl) An ethylenically unsaturated compound containing a hydroxy group of acrylamide or the like; 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-benzene (meth)acrylate a 2-hydroxy group-containing ethylenically unsaturated compound such as oxypropyl ester, 3-chloro-2-hydroxypropyl (meth)acrylate or 2-hydroxy-3-phenoxypropyl (meth)acrylate; 3-hydroxyl group, such as 2,2-dimethyl-2-hydroxyethyl methacrylate The ethylenically unsaturated compound.

Among these, an ethylenically unsaturated compound containing a hydroxyl group is preferred, and 4-hydroxybutyl (meth)acrylate is particularly preferred from the viewpoints of excellent viscosity and compatibility with an acrylic resin and easy availability. The ester, 2-hydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, more preferably 4-hydroxybutyl (meth)acrylate.

The monofunctional unsaturated compound (B) preferably uses the above-mentioned alicyclic structure-containing ethylenically unsaturated compound (B1) and a hydroxyl group-containing ethylenically unsaturated compound insofar as the effects of the present invention are not impaired. An unsaturated compound (B3) having one ethylenically unsaturated group other than (B2) (hereinafter sometimes referred to as "monofunctional unsaturated compound (B3)"), but from the viewpoint of superior corrosion resistance, It is preferred not to use a compound having an acidic group.

The monofunctional unsaturated compound (B3) may, for example, be an alkyl (meth)acrylate having an alkyl group having 1 to 30 carbon atoms, and specific examples thereof include ethyl (meth)acrylate and (meth)acrylic acid. N-propyl ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, methyl (meth)acrylate, and the like. Among them, an alkyl (meth)acrylate having a carbon number of 2 to 20, particularly preferably 4 to 18, more preferably 4 to 10 is preferred, and 2-ethylhexyl (meth)acrylate is particularly suitable. , n-butyl (meth)acrylate.

Further, as the monofunctional unsaturated compound (B3), in addition to the above, a glycidyl group containing (meth)acrylic acid propyl acrylate or (meth) acrylallyl propyl propyl acrylate may be used. Saturated monomer; amine-containing monomer such as tert-butylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, etc. (Ethyl ethyl ethoxide-containing monomer such as 2-(ethoxymethyl ethoxy) ethyl (meth) acrylate or allyl acetate; 2-methoxyethyl (meth) acrylate; 3-methoxyethyl (meth)acrylate; alkoxy (poly)alkylene glycol mono(meth)acrylates such as methoxydiethylene glycol (meth)acrylate; N-propylene oxime Allyl compounds such as amine methyltrimethylammonium chloride, allyltrimethylammonium chloride, dimethylallyl vinyl ketone, etc.; N-(methyl) propylene decyloxymethylene Amber succinimide, N(methyl) propylene decyl-2-oxydimethylene succinimide, N-(methyl) propylene decyl-3-oxy trimethylene succinimide, N -(Meth)acryloyl-4-oxytetramethylene succinimide, N-(methyl) propylene Amber quinone imines such as mercapto-5-oxypentamethylene succinimide, N-(methyl) propylene fluorenyl-6-oxyhexamethylene succinimide; N-vinyl A vinyl monomer such as pyrrolidone, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, vinyl acetate or styrene.

One type of these monofunctional unsaturated compounds (B3) may be used alone or two or more types may be used in combination.

The content ratio of the ethylenically unsaturated compound (B1) having an alicyclic structure is preferably 0.5 to 70% by weight, particularly preferably 1 to 60% by weight, more preferably 3, based on the entire monofunctional unsaturated compound (B). ~50% by weight, preferably 5~40% by weight. When the content ratio of the ethylenically unsaturated compound (B1) having an alicyclic structure is too high or too low, the adhesive strength tends to decrease.

The content of the hydroxyl group-containing ethylenically unsaturated compound (B2) is preferably from 1 to 70% by weight, particularly preferably from 3 to 60% by weight, more preferably from 5 to 50% by weight based on the total of the monofunctional unsaturated compound (B). %, the best 7~40% by weight. When the content ratio of the hydroxyl group-containing ethylenically unsaturated compound (B2) is too high, the cohesive force tends to be too high, and if it is too low, the durability tends to be lowered.

The content ratio of the alicyclic structure-containing ethylenically unsaturated compound (B1) and the hydroxyl group-containing ethylenically unsaturated compound (B2) to the total amount of the monofunctional unsaturated compound (B) is preferably 10 ~75% by weight, particularly preferably 20 to 70% by weight, more preferably 25 to 65% by weight, most preferably 30 to 60% by weight. When the content ratio of the ethylenically unsaturated compound (B1) having an alicyclic structure and the ethylenically unsaturated compound (B2) having a hydroxyl group is too high, the cohesive force tends to be too high; if it is too low, there is a tendency The tendency of the effect of the present invention is not sufficiently obtained.

The content ratio (weight ratio) of the ethylenically unsaturated compound (B1) having an alicyclic structure to the hydroxyl group-containing ethylenically unsaturated compound (B2) is preferably (B1): (B2) = 10:90 to 90: 10. Excellent system (B1): (B2) = 20: 80 ~ 80: 20, better system (B1): (B2) = 30: 70 ~ 70: 30. When the content ratio of the ethylenically unsaturated compound (B1) having an alicyclic structure to the hydroxyl group-containing ethylenically unsaturated compound (B2) is too high, the cohesive force tends to be lowered, and if it is too low, there is adhesion. The tendency of the force to be easily lowered.

The content of the monofunctional unsaturated compound (B) is 100 parts by weight, preferably 50 to 95 parts by weight, particularly preferably 55 to 93, based on 100 parts by weight of the total of the acrylic resin (A) and the monofunctional unsaturated compound (B). Parts by weight, more preferably 60 to 90 parts by weight.

When the content of the monofunctional unsaturated compound (B) is too large, the viscosity tends to be too low to be easily applied, and if it is too low, the viscosity tends to be high and it is difficult to apply.

As the ethylenically unsaturated compound (C) having two or more ethylenically unsaturated groups (hereinafter sometimes referred to as "polyfunctional unsaturated compound (C)"), for example, a bifunctional (meth) acrylate can be used. Monomer, trifunctional or higher (meth) acrylate ester monomer, urethane (meth) acrylate compound, (meth) acrylate epoxy compound, polyester (methyl ) an acrylate compound. Further, these may be used alone or in combination of two or more.

The bifunctional (meth) acrylate monomer may be a monomer containing two (meth) acrylonitrile groups, and examples thereof include ethylene glycol di(meth) acrylate and 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, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide modified bisphenol A type di(meth)acrylic acid Ester, propylene oxide modified bisphenol A type di(meth) acrylate, 1,6-hexanediol di(meth) acrylate, 1,6-hexane diol oxirane modification II Acrylate, glycerol di(meth)acrylate, pentaerythritol di(meth)acrylate, ethylene glycol diepoxypropyl ether di(meth)acrylate, diethylene glycol diepoxypropyl ether Di(meth)acrylate, diepoxypropyl phthalate di(meth)acrylate, hydroxytrimethylacetate modified neopentyl glycol di(meth)acrylate, isomeric cyanuric acid epoxy Ethyl modified diacrylate, 2-( Yl) Bing Xixi oxyethyl acid phosphate diesters.

The trifunctional or higher (meth)acrylate monomer may be a monomer containing three or more (meth) acrylonitrile groups, and examples thereof include trimethylolpropane tri(meth)acrylate. Pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol Hexa(meth)acrylate, tris(meth)acryloxyethoxyethoxytrimethylolpropane, glycerol polyepoxypropyl ether poly(meth)acrylate, trimeric isocyanate ethylene oxide Modified tris(meth)acrylate, ethylene oxide modified dipentaerythritol penta (meth) acrylate, ethylene oxide modified dipentaerythritol hexa(meth) acrylate, ethylene oxide modified pentaerythritol III (Meth) acrylate, ethylene oxide modified pentaerythritol tetra(meth) acrylate, succinic acid modified pentaerythritol tri (meth) acrylate, and the like.

The ethyl urethane (meth) acrylate type compound is a (meth) acrylate type compound having a urethane bond in a molecule, and is a (meth) acrylate type compound containing a hydroxyl group. The polyisocyanate compound (a polyol compound if necessary) may be obtained by a known general method, and a weight average molecular weight of usually 300 to 4,000 may be used.

The content of the polyfunctional unsaturated compound (C) is preferably from 0.005 to 15 parts by weight, particularly preferably 0.01%, based on 100 parts by weight of the total of the acrylic resin (A) and the monofunctional unsaturated compound (B). ~13 parts by weight, more preferably 0.1 to 10 parts by weight.

When the content of the polyfunctional unsaturated compound (C) is too large, the adhesive strength tends to be lowered, and if it is too small, the cohesive force tends to be lowered.

The photopolymerization initiator (D) is not particularly limited as long as it generates radicals by the action of an active energy ray such as light, and a self-cracking photopolymerization initiator or a dehydrogenation type can be used. Photopolymerization initiator.

As a photopolymerization initiator of the self-cracking type in the molecule, for example, 4-phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, diethoxyacetophenone, 2- Hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylpropyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-Ten Diphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)one, 1-hydroxycyclohexyl Phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2- Lolinylpropan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal,醯-mercaptopurine, fluorenylphosphine oxide, methylphenylglyoxylate, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 4-benzyl Indole-4'-methyldiphenyl sulfide or the like; among them, 2-hydroxy-2-methyl-1-phenylpropan-1-one and 1-hydroxycyclohexyl phenyl ketone are preferred.

Further, examples of the photopolymerization initiator of the dehydrogenation type include diphenyl ketone, 4-phenyl diphenyl ketone, hydroxy diphenyl ketone, and 3,3'-dimethyl-4-methoxy Diphenyl ketone, 2,4,6-trimethyldiphenyl ketone, 4-methyldiphenyl ketone, 9-oxosulfur 2-chloro 9-oxosulfur 2-methyl 9-oxosulfur 2,4-dimethyl 9-oxosulfur Isopropyl 9-oxosulfur , camphorquinone, cycloheptanone, 2-ethylhydrazine, 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)diphenyl ketone, benzyl, 9,10-phenanthrenequinone, etc. Among them, preferred are diphenyl ketone, methyl benzodiphenyl ketone, and 2,4,6-trimethyldiphenyl ketone. These photopolymerization initiators (D) may be used alone or in combination of two or more.

Furthermore, in addition to the above photopolymerization initiator, by using three By using a photopolymerization initiator, the amount of accumulated light required for obtaining good adhesion properties after hardening can be reduced.

As three The photopolymerization initiator may, for example, be a 2,4,6-trisubstituted-s-three represented by the following general formula (a). .

[Chemical 1]

(In the above formula (a), 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, at least one of which is Monohalogen substituted methyl, dihalo substituted methyl or trihalogen substituted methyl.)

The alkyl group may, for example, be an alkyl group having 1 to 10 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, and a n-hexyl group. Further, the substituted alkyl group may, for example, be an alkyl group having 1 to 10 carbon atoms which is substituted by a halogen atom, and specifically, such as trichloromethyl, tribromomethyl, α, α, β-trichloroethyl, etc. .

Further, examples of the aryl group and the substituted aryl group include a carbon number of 6 to 20, specifically, a phenyl group, a p-methoxyphenyl group, a p-methylthiophenyl group, a p-chlorophenyl group, and a 4-linked group. Phenyl, naphthyl, 4-methoxy-1-naphthyl and the like.

Further, examples of the alkenyl group include a carbon number of 2 to 12 such as a vinyl group, an allyl group or a 2-phenylvinyl group. In addition, examples of the alkoxy group include those having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, and a butoxy group.

Further, examples of the monohalogen-substituted methyl group, the dihalogen-substituted methyl group or the trihalogen-substituted methyl group include a chloromethyl group, a bromomethyl group, an iodomethyl group, a dichloromethyl group, a dibromomethyl group, and a diiodomethyl group. Base, trichloromethyl, tribromomethyl, triiodomethyl. Among them, a trichloromethyl group substituted with a chlorine atom is preferred.

Such a 2,4,6-trisubstituted-s-three represented by the general formula (a) For example, in Journal of American Chemical Society, Vol. 72, pp. 3257~3528 (1950), Journal of American Chemical Society, Vol. 74, pp. 5633~5636 (1952), Juatus Lieblgs Annalen der Chemie, Vol. 577, No. 77 The method described in ~95 pages (1952) was synthesized.

2,4,6-trisubstituted-s-three as shown in the above general formula (a) Specifically, for example, 2,4,6-gin (trichloromethyl)-s-three , 2,4,6-parade (tribromomethyl)-s-three 2,4-bis(trichloromethyl)-6-methyl-s-three 2,4-bis(tribromomethyl)-6-methyl-s-three , 2,4-bis(trichloromethyl)-6-(p-tolyl)-s-three 2,4-bis(trichloromethyl)-6-n-propyl-s-three , 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-three , 2,4,6-gin (dichloromethyl)-s-three , 2,4,6-parade (dibromomethyl)-s-three , 2,4,6-para (bromomethyl)-s-three , 2,4,6-para (chloromethyl)-s-three 2,4,6-trisubstituted-s-three having only aliphatic substituents Photopolymerization initiator; 2,4-bis(trichloromethyl)-6-phenyl-s-three 2,4-bis(trichloromethyl)-6-(p-methoxyphenyl)-s-three , 2,4-bis(trichloromethyl)-6-(p-methylthiophenyl)-s-three 2,4-bis(trichloromethyl)-6-(p-chlorophenyl)-s-three , 2,4-bis(trichloromethyl)-6-(2',4'-dichlorophenyl)-s-three , 2-(p-bromophenyl)-4,6-bis(trichloromethyl)-s-three 2,4-bis(tribromomethyl)-6-phenyl-s-three 2,4-bis(trichloromethyl)-6-styryl-s-three , 2,4-bis(trichloromethyl)-6-[2-(p-methoxyphenyl)vinyl]-s-three , 2,4-bis(trichloromethyl)-6-[2-(o-methylphenyl)vinyl]-s-three ,2-[2-(p-butoxyphenyl)vinyl]-bis(trichloromethyl)-s-three ,2-[2-(3,4-dimethoxyphenyl)vinyl]-2,4-bis(trichloromethyl)-s-three ,2-[2-(3,4,5-Trimethoxyphenyl)vinyl]-2,4-bis(trichloromethyl)-s-three ,2-(1-naphthyl)-2,4-bis(trichloromethyl)-s-three , 2-(4-biphenyl)-2,4-bis(trichloromethyl)-s-three , 2-(4'-methoxy-1'-naphthyl)vinyl]-2,4-bis(trichloromethyl)-s-three , 2,4-bis(trichloromethyl)-6-(p-methoxynaphthyl)-s-three , 2,4-bis(trichloromethyl)-6-(sunflower based)-s-three , 2,4-bis(trichloromethyl)-6-(p-methoxystyryl)-s-three 2,4,6-trisubstituted-s-three having an aromatic substituent A photopolymerization initiator or the like.

These may be used alone or in combination of two or more.

Among these, as the above three a photopolymerization initiator, preferably a 2,4,6-trisubstituted-s-three having an aromatic substituent It is a photopolymerization initiator, and further, from the viewpoint of less yellowing of the coating film and good compatibility, 2,4-bis(trichloromethyl)-6-(p-methoxyphenyl) is particularly preferred. )-s-three .

Further, as an auxiliary agent of the photopolymerization initiator (D), for example, triethanolamine, triisopropanolamine, 4,4'-dimethylaminodiphenyl ketone (michlerone) may be used in combination. 4,4'-diethylaminodiphenyl ketone, 2-dimethylaminoethyl benzoic acid, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid (positive Butoxy)ethyl ester, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethyl 9-oxosulfur 2,4-diisopropyl 9-oxosulfur Wait.

The content of the photopolymerization initiator (D) is 100 parts by weight, preferably 0.1 to 20 parts by weight, particularly preferably 0.5, based on the total of the monofunctional unsaturated compound (B) and the polyfunctional unsaturated compound (C). ~15 parts by weight, more preferably 1 to 10 parts by weight.

When the content of the photopolymerization initiator (D) is too small, there is a tendency that the polymerization is carried out by an active energy ray such as ultraviolet rays, and if it is too large, the effect of adding a certain amount or more may not be obtained, and it is not economical. .

In addition, use the above three separately When the photopolymerization initiator is used as the photopolymerization initiator (D), it is preferably contained in an amount of 100 parts by weight based on 100 parts by weight of the total of the monofunctional unsaturated compound (B) and the polyfunctional unsaturated compound (C). The photopolymerization initiator is 0.01 to 0.5 parts by weight, particularly preferably 0.05 to 0.45 parts by weight, more preferably 0.1 to 0.4 parts by weight, most preferably 0.15 to 0.35 parts by weight.

Thus, the adhesive composition of the present invention comprising the acrylic resin (A), the monofunctional unsaturated compound (B), the polyfunctional unsaturated compound (C), and the photopolymerization initiator (D) can be obtained. However, an isocyanate type, an epoxy type, a metal salt, a metal alkoxide, an aldehyde type compound, a non-amino resin type amine compound, a urea type, and a metal chimera can be blended in the range which does not impair the effect of this invention. Commonly used cross-linking agents such as melamine, aziridine, etc., other adhesives, urethane resin, rosin, rosin ester, hydrogenated rosin ester, phenol resin, aromatic modified resin, fat An adhesion-imparting agent such as a family petroleum resin, an alicyclic petroleum resin, a styrene resin, or a xylene resin, or a known additive or a compound which develops color or discolors by ultraviolet rays or radiation. In addition to the above-mentioned compounding agent, impurities and the like contained in the raw material for production of the constituent components of the adhesive composition may be contained in a small amount. The blending amount of these formulating agents can be appropriately set to obtain desired physical properties.

The above-mentioned adhesive composition is preferably substantially free of acid from the viewpoint of superior corrosion resistance, and substantially does not contain an acid, and means that the acid value of the adhesive composition is usually 1 mgKOH/g or less. It is preferably 0.5 mgKOH/g or less, and particularly preferably 0.

The adhesive composition obtained by the present invention is preferably a solvent which does not substantially contain water, an aqueous solvent or an organic solvent, an acrylic resin (A), a polyfunctional unsaturated compound (C), or a photopolymerization initiator ( D) and, if necessary, other components are in a state of being dissolved or uniformly dispersed in the monofunctional unsaturated compound (B). Such an adhesive composition is prepared by dispersing an acrylic resin (A), a monofunctional unsaturated compound (B), a polyfunctional unsaturated compound (C), a photopolymerization initiator (D), and optionally The other components are prepared by mixing at room temperature or after heating to about 60 ° C.

Thus, the adhesive composition of the present invention can be obtained, which is hardened by active energy rays to obtain the adhesive of the present invention.

As the active energy ray, an ultraviolet ray, an ultraviolet ray, a near ultraviolet ray, an infrared ray, an electromagnetic wave such as an X-ray or a gamma ray, an electron beam, a proton ray, a neutral ray, or the like can be used, and the curing speed and the easiness of the irradiation device can be easily obtained. In terms of price and the like, hardening by ultraviolet irradiation is advantageous.

In the case of ultraviolet irradiation, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless discharge lamp, or the like which emits light in a wavelength region of 150 to 450 nm can be used.

The irradiation amount of the active energy ray is preferably 500 mJ/cm ² or more, more preferably 1000 mJ/cm ² or more, and particularly preferably 1500 mJ/cm ² or more. If the amount of irradiation is too small, there is a tendency that variation occurs in polymerization by irradiation with active energy rays. Further, the upper limit of the irradiation amount is usually 10000 mJ/cm ² , and if the amount of irradiation is too large, the relationship between the apparatus and the cost tends to be uneconomical.

The adhesive of the present invention is suitably used as an adhesive sheet.

Examples of the method for producing the pressure-sensitive adhesive sheet include: [I] a method in which an adhesive composition is applied onto a substrate, and an active energy ray is applied as an adhesive layer, and then the release sheet is bonded; [II] an adhesive is applied. a method in which a composition is applied onto a substrate, and after the release sheet is bonded, an active energy ray is irradiated to form an adhesive layer; [III] the adhesive composition is applied onto the release sheet, and the active energy ray is irradiated to form an adhesive. After the agent layer, a method of bonding the substrate or the release sheet; [IV] applying the adhesive composition to the release sheet, bonding the substrate or the release sheet, and performing active energy ray irradiation to form an adhesive layer Method etc.

Further, in the case where the substrate or the release sheet is bonded after the irradiation of the active energy ray, in order to eliminate the cause of polymerization inhibition by oxygen during the irradiation of the active energy ray, it is more preferable to irradiate the active energy ray in an inert gas atmosphere. It is considered that the polymerization condition due to oxygen is adjusted to adjust the irradiation conditions to obtain a physical balance.

Examples of the substrate include metal foils such as aluminum, copper, and iron; polyethylene naphthalene, polyethylene terephthalate, polybutylene terephthalate, and polyethylene terephthalate/isophthalic acid. Polyester resin such as acid ester copolymer; polyolefin resin such as polyethylene, polypropylene or polymethylpentene; polyvinyl fluoride such as polyvinyl fluoride, polydifluoroethylene or polyfluorinated ethylene Resin; nylon 6, nylon 6,6, etc. polyamine; polyvinyl chloride, polyvinyl chloride / vinyl acetate copolymer, ethylene - vinyl acetate copolymer, ethylene - vinyl alcohol copolymer, polyvinyl alcohol, Vinyl polymers such as Vinylon; cellulose resins such as cellulose triacetate and celecin; acrylic acid such as polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, polybutyl acrylate, etc. Resin; synthetic resin film or sheet of polystyrene, polycarbonate, polyarylate, polyimine, etc., paper such as Daolin paper, cellophane, glass fiber, natural fiber, synthetic fiber, etc. Layer or stratified body. Further, a non-woven fabric, a foamed substrate or the like can be used as the substrate sheet, and it can be used for a double-sided film or the like.

The thickness of the substrate is not particularly limited, and is usually 500 μm or less, preferably 5 to 300 μm, more preferably 10 to 200 μm.

As the release sheet, for example, various synthetic resin sheets exemplified for the above-mentioned support base material, paper, cloth, non-woven fabric, and the like can be used for release treatment.

The coating method of the adhesive composition is not particularly limited as long as it is a general coating method, and examples thereof include a method such as roll coating, die coating, gravure coating, blade coating, and screen printing.

Further, the thickness of the above-mentioned pressure-sensitive adhesive layer formed on the substrate after the irradiation with the active energy ray is appropriately set depending on the application, but is usually 5 to 300 μm, preferably 10 to 250 μm. When the thickness of the pressure-sensitive adhesive layer is too small, the adhesiveness tends to be unstable, and if it is too thick, the paste tends to be prone to stickiness.

In the case of using the pressure-sensitive adhesive sheet of the present invention, examples of the type of the adherend include articles having various metal faces; polyethylene naphthalene, polyethylene terephthalate, polybutylene terephthalate, and poly Polyester resin such as ethylene terephthalate/isodecanoate copolymer; polyolefin resin such as polyethylene, polypropylene, polymethylpentene; polyvinyl fluoride, polydifluoroethylene, Polyfluorinated vinyl resin such as polyvinyl fluoride; polyamine which is nylon 6, nylon 6,6, etc.; polyvinyl chloride, polyvinyl chloride/vinyl acetate copolymer, ethylene-vinyl acetate copolymer, ethylene - vinyl alcohol copolymer, polyvinyl alcohol, vinyl polymer such as vinylon; cellulose acetate resin such as cellulose triacetate or celecoxib; polymethyl methacrylate, polyethyl methacrylate, polyacrylic acid Acrylic resin such as ethyl ester or polybutyl acrylate; synthetic resin film, sheet or plate of polystyrene, polycarbonate, polyarylate or polyimine.

The article having the metal surface has a metal surface, and the adhesive sheet is directly bonded to at least a part or the entire surface of the metal surface. In such a metal-coated article, the adherend to be bonded to the adhesive sheet (sometimes referred to as "metal-containing surface adherend") is not particularly limited as long as it has at least partially a metal surface. In the metal-containing surface adherend, the portion on which the metal surface is formed is not particularly limited as long as it can directly adhere the adhesive sheet, and may be the outer surface or the inner surface. Further, when a plurality of metal faces are formed on a metal-containing surface adherend, the plurality of metal faces may be faces formed of the same metal material, or may be faces formed of dissimilar metal materials.

The metal surface of the metal-containing surface adherend may be a surface of the metal-containing surface formed by the metal material, or may be on the surface of the substrate (or structure) formed of various materials. The surface of the metal layer formed (especially the surface of the metal film). The metal surface may be any surface obtained from a metal material.

The metal layer such as the metal thin film layer can be formed on a predetermined portion of the surface of the substrate (or structure) composed of various materials. In the metal layer, the thickness of the metal thin film layer can be appropriately selected in accordance with the type of the metal-containing surface adherend, and can be, for example, 0.1 μm or more. Further, the upper limit of the thickness of the metal thin film layer is not particularly limited as long as it is generally regarded as the thickness of the thin film layer.

Examples of the metal material for forming the metal surface include a metal material of a metal monomer such as aluminum, silver, gold, copper, iron, titanium, platinum, or nickel; a gold alloy (for example, a gold-copper alloy), Copper alloy (such as copper-zinc alloy (brass), copper-aluminum alloy, etc.), aluminum alloy (such as aluminum-molybdenum alloy, aluminum-bismuth alloy, aluminum-cobalt alloy, aluminum-chromium alloy, aluminum-titanium alloy, aluminum - a platinum alloy or the like), a nickel alloy (for example, a nickel-chromium alloy, a copper-nickel alloy, a zinc-nickel alloy, etc.), a tin alloy, a stainless steel, or the like, and a metal material of various alloys. These metal materials may be used alone or in combination of two or more.

Further, 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 of a metal, a hydroxide, a halide (chloride), or the like) a metal compound such as an acid salt (nitrate, sulfate, phosphate, carbonate, etc.).

Specifically, as the metal-containing surface adherend, for example, a window material having a metal surface (metal thin film layer or the like) at least partially or a member for constituting the window material, or a metal thin film layer may be used. An optical article of the electromagnetic wave shielding layer formed or a member for constituting the optical article. The optical product having the electromagnetic wave shielding layer may, for example, be an optical device such as an electronic display (such as a plasma display) or an optical disk (optical recording disk) such as a digital versatile optical disk that can be optically recorded.

(Example)

The present invention will be specifically described by the following examples, but the present invention is not limited to the following examples, and is not limited to the following examples. In the example, "part" and "%" refer to the weight basis.

(Manufacture of acrylic resin (A))

300 parts of water was placed in a glass four-necked round bottom flask equipped with a stirrer, and 0.7 parts of polyvinyl alcohol as a dispersion stabilizer was dissolved, and while stirring was carried out at 300 rpm by a stirring blade, n-butyl acrylate (a1) was once charged. 87.8 parts, a mixture of acrylonitrile (a3) 7.2 parts, 2 parts of 2-hydroxyethyl methacrylate (a2), and N,N'-azobisisobutyronitrile as a polymerization initiator 0.9 parts, making a suspension.

The suspension was heated to 68 ° C in the reaction system while stirring, and allowed to react for 4 hours. Thereafter, it was cooled to room temperature (about 25 ° C). Then, the reaction product was subjected to solid-liquid separation, and sufficiently washed with water, and then dried at 70 ° C for 12 hours using a dryer to obtain a bulk acrylic resin (A-1). The obtained acrylic resin (A-1) had a weight average molecular weight (Mw) of 1.3 million, a degree of dispersion (Mw/Mn) of 4.6, and a glass transition temperature of -47 °C.

(Manufacture of acrylic resin (A-2))

300 parts of water was placed in a glass four-necked round bottom flask equipped with a stirrer, and 0.7 parts of polyvinyl alcohol as a dispersion stabilizer was dissolved, and while stirring was carried out at 300 rpm by a stirring blade, n-butyl acrylate (a1) was once charged. ) 51 parts, acrylic acid a monomer mixture of 44 parts of ester (a1) and 5 parts of 2-hydroxyethyl methacrylate (a2), and 0.9 parts of N,N'-azobisisobutyronitrile as a polymerization initiator Turbidity.

The suspension was heated to 68 ° C in the reaction system while stirring, and allowed to react for 4 hours. Thereafter, it was cooled to room temperature (about 25 ° C). Then, the reaction product was subjected to solid-liquid separation, and sufficiently washed with water, and then dried at 70 ° C for 12 hours using a dryer to obtain a bulk acrylic resin (A-2). The obtained acrylic resin (A-2) had a weight average molecular weight (Mw) of 950,000, a degree of dispersion (Mw/Mn) of 3.5, and a glass transition temperature of -5 °C.

(Example 1)

12 parts of the acrylic resin (A-1) as the acrylic resin (A), 18 parts of 4-hydroxybutyl acrylate (HBA: (B2)) as the monofunctional unsaturated compound (B), and cyclohexyl acrylate 20 parts of ester (CHA: (B1)), 50 parts of 2-ethylhexyl acrylate (2EHA: (B3)), trimethylolpropane triacrylate (TMPTA) as polyfunctional unsaturated compound (C) 0.3 part was placed in a container equipped with a stirrer, and stirred and mixed for 24 hours to dissolve. In this solution, 2-hydroxy-2-methyl-1-phenyl-propan-1-one as a photopolymerization initiator (D) was mixed (trade name: "DAROCUR 1173"; Ciba Specialty Chemicals Co., Ltd. (HMPP) 1 part, whereby an adhesive composition was obtained.

The adhesive composition obtained above was applied to a polyethylene terephthalate (PET) substrate having a thickness of 100 μm so as to have a thickness of 130 μm. Further, the release-treated PET substrate was used to coat the coated surface so that the release-treated surface was in contact with the coated surface. Then, by using an ultraviolet irradiation device shown below, a high-pressure mercury lamp adjusted to have an irradiation intensity of 200 mW/cm ² was irradiated with ultraviolet rays so as to have a cumulative light amount of 2400 mJ/cm ² , thereby obtaining an adhesive composition. The adhesive sheet of the obtained adhesive layer is hardened.

<UV irradiation device>

EYE Grandage ECS-301G1 (EYE GRAPHICS)

<Irradiation conditions>

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

[Examples 2 to 8]

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

[Embodiment 9]

In the first embodiment, the acrylic resin (A-2) was used instead of the acrylic resin (A-1), and the blending ratio of the other components was changed as in the following Table 2, and the same procedure as in Example 1 was carried out. The adhesive composition and the adhesive sheet were obtained.

[Comparative Examples 1 to 3]

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

[Comparative Example 4]

In Example 1, except that the composition of the adhesive composition was 14.6 parts of acrylic resin (A-1), 39.4 parts of 2-ethylhexyl acrylate (2EHA), 39.4 parts of butyl acrylate (BA), and acrylic acid. (AAc) 6.6 parts, trimethylolpropane triacrylate (TMPTA) 0.3 parts, 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name: "DAROCUR1173"; Ciba Specialty Chemicals The adhesive composition and the adhesive sheet were obtained in the same manner as in Example 1 except for one part (HMPP).

With respect to the adhesive compositions used in the above examples and comparative examples, the blending ratios of the above respective component materials are shown in Table 1 below.

With respect to the adhesive sheets obtained in the above examples and comparative examples, the gel fraction, adhesion, retention (cohesion), and corrosion resistance of the adhesive layer were evaluated by the following method, and the results were combined and described later. Table 2.

<gel fraction>

After the obtained adhesive sheet was cut into 50 mm × 50 mm, the adhesive sheet layer side of the adhesive sheet was attached to the mesh sheet in a 60×100 mm SUS mesh sheet (200 mesh) while avoiding the central portion in the longitudinal direction. On the material, the mesh sheet was then folded back from the center portion and wrapped in an adhesive sheet to prepare a test piece. The test piece was placed in a sealed container of 180 g of toluene, and immersed at 23 ° C for 24 hours to obtain a gel fraction of the weight % of the insoluble adhesive component remaining in the mesh sheet. At this time, the weight of the substrate is first subtracted.

<adhesion>

The adhesion was measured in accordance with JIS Z-0273. That is, after the obtained adhesive sheet was cut into 25 mm × 100 mm, it was placed on a stainless steel plate (SUS304BA plate) as a adherend, and a 2 kg rubber roller was used in an environment of 23 ° C and a relative humidity of 50%. The test piece was made by pressing it. After the test piece was allowed to stand in the same environment for 30 minutes, a 180-degree peeling test was performed at a peeling speed of 0.3 m/min, and the adhesive force (N/25 mm) was measured.

(evaluation benchmark)

○: 10N/25mm or more

╳: less than 10N/25mm

<Retention force (aggregation power)>

The obtained adhesive sheet was attached to SUS304 as a adherend according to JIS Z-0273, and attached to an attachment area of 25 mm × 25 mm, and then subjected to measurement and evaluation by applying a load of 1 kg to a person who was placed at 80 ° C for 20 minutes.

(evaluation benchmark)

○: Do not fall after 24 hours

△: The offset after being placed for 24 hours is within 1 mm

╳: After shifting for 24 hours, the offset is 1mm or more or falling.

<Corrosion resistance>

The obtained adhesive sheet was bonded to a copper foil (thickness: 130 μm), and then stored in an environment of 60 ° C × 90% RH for 250 hours. Thereafter, the surface of the copper foil was observed from the side of the film made of polyethylene terephthalate, and it was confirmed whether or not there was corrosion on the surface of the copper foil to which the adhesive sheet was bonded.

○: no corrosion

╳: Corrosive

It is understood that the adhesives of Examples 1 to 9 composed of an adhesive composition containing both an alicyclic structure-containing ethylenically unsaturated compound and a hydroxyl group-containing ethylenically unsaturated compound are adhesion and cohesive force (maintaining The force balance is excellent and the corrosion resistance is superior because it does not contain acid.

On the other hand, the adhesive of Comparative Example 1 which does not contain both the alicyclic structure-containing ethylenically unsaturated compound and the hydroxyl group-containing ethylenically unsaturated compound is inferior in adhesion and cohesive force (holding force). The adhesive of Comparative Example 2 which does not contain the ethylenically unsaturated compound having an alicyclic structure is inferior in adhesion, and the adhesive strength (retention force) of Comparative Example 3 which does not contain the hydroxyl group-containing ethylenically unsaturated compound Bad.

Further, the adhesive of Comparative Example 4 composed of the adhesive composition containing acrylic acid having an acidic group was superior in adhesion and cohesive force (holding force), but was inferior in corrosion resistance.

Further, with respect to the adhesive sheet of Example 9, the transparency (fog value) was measured by the following method. The results are shown in Table 3.

<Fog value> ‧Manufacture of samples for measuring fog value

The obtained adhesive sheet was cut out to 3 cm × 4 cm, the release release sheet was peeled off, and the adhesive layer side was pressed to an alkali-free glass plate (EAGLE XG, manufactured by Corning Co., Ltd.), and then autoclaved (50 ° C, 0.5 MPa ×). After 20 min), a sample for measuring the haze value was obtained.

‧ Determination of fog value

The haze value of the sample for measuring the haze value was measured under the following conditions.

‧ Initial fog value: Measured after the sample for measuring the fog value is prepared.

‧ Wet heat fog value 1: After the sample for measuring the haze value was prepared, it was allowed to stand at 60 ° C × 90% RH for 100 hours, and then measured.

‧ Wet heat fog value 2: After the sample for measuring the haze value was prepared, it was allowed to stand at 60 ° C × 90% RH for 100 hours, and then allowed to stand at room temperature for 3 hours, and then measured.

The haze value was measured by using HAZE MATER NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.) for the diffusion transmittance and the total light transmittance. Moreover, this machine is based on JIS K7361-1.

The value of the obtained diffusion transmittance and total light transmittance was substituted into the following formula to calculate the haze value.

Fog value (%) = (diffusion transmittance / total light transmittance) × 100

The adhesive of Example 9 which is composed of an adhesive composition using an acrylic resin (A-2) obtained by copolymerizing a (meth)acrylate monomer having an alicyclic structure is used. Even under hot and humid conditions, the haze value is still less, and the heat and humidity resistance is superior.

The present invention has been described in detail above with reference to the specific embodiments thereof, and it will be understood by those skilled in the art that various changes or modifications can be made without departing from the spirit and scope of the invention.

The present application is based on Japanese Patent Application No. 2010-271653, filed on Dec.

(industrial availability)

Since the adhesive composed of the adhesive composition of the present invention has strong adhesive force and superior cohesive force, peeling from the substrate is less likely to occur even in a high temperature environment, and is particularly useful as an optical member. The adhesive and the adhesive sheet are used, and even if the adhesive does not contain an acid, the adhesive property can be satisfied, so that it can be used as an optical device for bonding an electronic display such as a metal or a metal oxide which requires corrosion resistance. Or optical adhesive sheets for optical recording discs (optical recording media) such as digital versatile discs.

Claims (8)

An adhesive composition comprising an acrylic resin (A), an ethylenically unsaturated compound (B) having one ethylenically unsaturated group, and an ethylenically unsaturated compound having two or more ethylenically unsaturated groups (C) And a photopolymerization initiator (D) characterized in that it contains an ethylenically unsaturated compound (B1) having an alicyclic structure and a hydroxyl group-containing ethylenically unsaturated compound (B2) as having one ethylenicity. The ethylenically unsaturated compound (B) having a saturated group; the content ratio of the ethylenically unsaturated compound (B1) having an alicyclic structure with respect to the entire ethylenically unsaturated compound (B) having one ethylenically unsaturated group The content of the hydroxyl group-containing ethylenically unsaturated compound (B2) is from 1 to 70% by weight based on the total amount of the ethylenically unsaturated compound (B) having one ethylenically unsaturated group. The adhesive composition according to claim 1, wherein the acrylic resin (A) is a dry resin obtained by suspension polymerization. The adhesive composition according to claim 1 or 2, wherein the acrylic resin (A) is obtained by copolymerizing a copolymerization component containing a (meth) acrylate monomer having an alicyclic structure. Acrylic resin. An adhesive composition according to claim 1 or 2, wherein the ethylenically unsaturated compound (B1) having an alicyclic structure in the ethylenically unsaturated compound (B) having one ethylenically unsaturated group The content ratio of the total amount of the hydroxyl group-containing ethylenically unsaturated compound (B2) is from 10 to 70% by weight. An adhesive composition according to claim 1 or 2, wherein the acid composition is substantially free. An adhesive composition according to claim 1 or 2, wherein the solvent is not contained. An adhesive which is obtained by hardening an adhesive composition according to any one of claims 1 to 6 by active energy ray irradiation. An adhesive sheet comprising a substrate and an adhesive layer composed of the adhesive of claim 7 of the patent application.