TW201602278A - Double-sided adhesive sheet for image display devices, and article - Google Patents

Abstract

Provided is a double-sided adhesive sheet for image display devices, said adhesive sheet being readily producible and imparting minimal damage to optical base materials, enabling optical members such as display units having good curability and adhesiveness to be obtained, and enabling optical members (touch panels) having high adhesiveness and adhesive strength with respect to base materials to be obtained. Said adhesive sheet includes: a softener component (G), and a (meth)acrylate (K) comprising at least one compound selected from the group consisting of a urethane (meth)acrylate, a (meth)acrylate having a polyisoprene skeleton, and a (meth)acrylate having a butadiene skeleton.

Description

Image display device with two-sided adhesive sheets and articles

The present invention relates to an ultraviolet curable adhesive composition for image display in which at least two optical substrates are bonded together, a double-sided adhesive sheet using the ultraviolet curable adhesive composition for image display, and a use thereof Method of optical components.

In recent years, the display device that can input screens by attaching a touch panel to a display screen of a display device such as a liquid crystal display, a plasma display, or an organic EL display has been widely used in the industry. The touch panel has a structure in which a glass plate or a resin film formed with a transparent electrode is relatively bonded with a slight gap therebetween, and a glass or resin transparent protection is attached to the touch surface as needed. board.

The bonding of the glass plate or film in which the transparent electrode is formed in the touch panel to the transparent protective plate made of glass or resin, or the bonding of the touch panel to the display unit has a technique of using a double-sided adhesive sheet. For example, Patent Document 1 proposes a transparent double-sided adhesive sheet comprising a mixture of a (meth)acrylic acid derivative, a (meth)acrylic acid derivative polymer, and a polyfunctional (meth)acrylic acid derivative. A transparent double-sided adhesive sheet that bonds a transparent protective plate such as glass or plastic to an image display device.

On the other hand, it is proposed to use a UV-curable adhesive composition to provide transparent protection. A technique in which a board is attached to an image display device (Patent Document 2). However, since the use of the transparent double-sided adhesive sheet improves the production efficiency as compared with the method of using the ultraviolet curable adhesive composition, it is more advantageous than the ultraviolet curable adhesive composition. On the other hand, when the curable component is not polymerized, when a conventional ultraviolet curable adhesive composition is used as a transparent double-sided adhesive sheet, it is difficult to form into a sheet shape, and it is difficult to obtain a desired one. Hardened physical properties.

Therefore, it has been desired to develop a transparent double-sided adhesive sheet which has a low dielectric constant and can secure cured properties such as adhesion and low shrinkage.

Patent Document 1: Japanese Laid-Open Patent Publication No. 2009-057550

Patent Document 2: Japanese Laid-Open Patent Publication No. 2012-046658

An object of the present invention is to provide an optical member such as a display unit which has less damage to an optical substrate and which has good productivity and is excellent in curability and adhesion, and has high adhesion to a substrate and can have high adhesion strength. The image display device of the optical member (touch panel or the like) has a double-sided adhesive sheet.

The inventors of the present invention have made an effort to solve the above problems, and as a result, have completed the present invention. That is, the present invention relates to the following (1) to (15).

(1) A double-sided adhesive sheet for an image display device comprising (meth) acrylate having a polyisoprene skeleton selected from urethane (meth) acrylate or At least one of a (meth) acrylate (K) and a softener component (G) having a (meth) acrylate composition of a butadiene skeleton.

(2) A two-sided adhesive sheet for an image display device obtained by drying an ultraviolet curable resin composition at 80 ° C or higher, the ultraviolet curable resin composition containing an amine ester (meth) acrylate selected from polyamino A (meth) acrylate (K) or a softener component (G) of at least one of a (meth) acrylate having a pentadiene skeleton or a (meth) acrylate having a butadiene skeleton.

(3) The image display device according to (1) or (2), wherein the (meth) acrylate is an amine ester (meth) acrylate, and the urethane (meth) acrylate is used. a polyurethane ester compound (E) obtained by reacting a compound (A) shown below with a compound (B), a compound (C) and a compound (D),

Compound (A): hydrogenated polybutadiene polyol compound

Compound (B): polyisocyanate compound

Compound (C): a (meth) acrylate compound having at least one or more hydroxyl groups

Compound (D): a diol compound other than the compound (A).

(4) A double-sided adhesive sheet for an image display device comprising the polyurethane compound (E) of (3), wherein the hydrogenated polybutadiene polyol compound (A) has an iodine value of 20 or less.

(5) A double-sided adhesive sheet for an image display device comprising the polyurethane compound (E) of (3) or (4), wherein the polyisocyanate compound (B) is an aliphatic diisocyanate compound.

(6) A double-sided adhesive sheet for a video display device comprising the polyurethane compound (E) according to any one of (3) to (5), wherein the (meth) acrylate compound having at least one or more hydroxyl groups (C) ) is 2-hydroxyethyl (meth)acrylate.

(7) A double-sided adhesive sheet for an image display device comprising the polyurethane compound (E) according to any one of (3) to (6), wherein the diol compound (D) other than the compound (A) is a polyether polyol .

(8) A double-sided adhesive sheet for an image display device comprising the polyurethane compound (E) according to any one of (1) to (7) and a polymerizable compound (F) other than (E).

(9) The double-sided adhesive sheet for an image display device according to any one of (1) to (8), which comprises a hydroxyl group-containing polymer, a terpene resin, or both thereof as a softener component (G) ).

(10) A cured product obtained by irradiating an active energy ray with a double-sided adhesive sheet according to any one of (1) to (9).

(11) A touch panel obtained by using the image display device according to any one of (1) to (9) with a double-sided adhesive sheet.

(12) A double-sided adhesive sheet for an image display device comprising (meth) acrylate selected from an amine ester (meth) acrylate, a polyisoprene skeleton, or a (meth) group having a butadiene skeleton At least one of (meth) acrylate (K) or softener component (G) in the group of acrylate compositions.

(13) A double-sided adhesive sheet for an image display device comprising (meth) acrylate selected from an amine ester (meth) acrylate, a polyisoprene skeleton, or a (meth) group having a butadiene skeleton At least one of a (meth) acrylate (K), a softener component (G), and a solvent in the group of acrylate compositions.

(14) A method of manufacturing an image display device, wherein the image display device according to any one of (1) to (9), (12) to (13) uses a double-sided adhesive sheet, and the following steps 1 and 2 are employed. The optical substrate is bonded to obtain an image display device. (Step 1) For at least one optical substrate, the image display device with the release film is provided on both sides The release film of the single side of the adhesive sheet is peeled off, and the step of arranging the image display device with the double-sided adhesive sheet is disposed; (Step 2) the image display device disposed in the step 1 is used for the remaining single-sided release film of the double-sided adhesive sheet The step of peeling off and bonding other optical substrates.

(15) A method of manufacturing an image display device, wherein the image display device according to any one of (1) to (9), (12) to (13) uses a double-sided adhesive sheet, and the following steps 1 to 3 are employed. The optical substrate is bonded to obtain an image display device, and (step 1) the image display device with the release film is peeled off from the single-sided release film of the double-sided adhesive sheet on at least one of the optical substrates, and the image is disposed. a step of using a double-sided adhesive sheet for the display device; (step 2) a step of peeling off the remaining single-sided release film from the remaining single-sided release film of the double-sided adhesive sheet in the image display device configured in the step 1; Step 3) A step of curing the cured layer by irradiating ultraviolet rays on the double-sided adhesive sheet of the image display device in the bonded optical substrate via the optical substrate having the light-shielding portion.

The cured film of the double-sided adhesive sheet of the image display device of the present invention is excellent in flexibility, high in moisture resistance, heat resistance, and light resistance, and can be effectively prevented as an image display device (especially a touch panel) with a double-sided adhesive sheet. A problem occurs in an image display device such as a touch panel.

The image display device of the present invention has a double-sided adhesive sheet containing an amine ester selected from the group consisting of (meth) acrylate (K) of at least one of a group consisting of a acrylate, a (meth) acrylate having a polyisoprene skeleton, or a (meth) acrylate having a butadiene skeleton Or softener component (G). Further, it is preferred to contain the above (meth) acrylate (K) and the softener component (G) together.

The image display device of the present invention uses a double-sided adhesive sheet using a (meth) acrylate selected from the group consisting of an amine ester (meth) acrylate, a (meth) acrylate having a polyisoprene skeleton, and a polybutadiene skeleton. Any of the constituent groups is referred to as (meth) acrylate (K). It is preferred to include at least one of an amine ester (meth) acrylate or a (meth) acrylate having a polyisoprene skeleton. Here, the (meth) acrylate compound is preferably a high molecular weight oligomer or polymer. Here, the term "polymer" refers to a high molecular weight body which does not contain a (meth)acrylic acid group, which is a high molecular weight body which is polymerized, and which has a (meth)acrylic acid group.

In the present specification, the term "(meth)acrylate" means either or both of methacrylate and acrylate. The same applies to "(meth)acrylic acid".

The amine ester (meth) acrylate which can be suitably used for the double-sided adhesive sheet of the image display device of the present invention is a hydroxy compound having at least one (meth) acryloxy group and an isocyanate compound (and further as an optional component) The (meth) acrylate obtained by the reaction of the polyol).

Specific examples of the hydroxy compound having at least one (meth) acryloxy group include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth)acrylic acid. 2-hydroxybutyl ester, 4-hydroxyethyl (meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylic acid Various (meth) acrylate compounds having a hydroxyl group such as ester, pentaerythritol tri(meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and the above-mentioned hydroxyl group ) acrylate compounds and a ring-opening reactant of ε-caprolactone or the like.

Specific examples of the isocyanate compound include p-phenylene diisocyanate, meta-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-toluene diisocyanate, and 2,6. -Aromatic diisocyanates such as toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene diisocyanate; isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-bicyclic ring An aliphatic or alicyclic diisocyanate such as hexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate or lysine diisocyanate; one or more biuret monomers of an isocyanate monomer or the above diisocyanate A polyisocyanate such as an isocyanate obtained by trimerizing a compound; a polyisocyanate obtained by an urethane reaction of the above isocyanate compound with the above polyol compound.

The polyol which can be used as an optional component is not particularly limited as long as it is known. Specific examples thereof include polyether polyols such as polyethylene glycol, polytetramethylene glycol, polytetramethylene glycol, polypropylene glycol, and polyethylene glycol, polyethylene glycol adipate, and polycondensation. Polyester polyols such as 1,4-butanediol adipate and polycaprolactone, glycols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol and neopentyl glycol, Hydroxymethylcyclohexane, polyisoprenediol, polybutadiene diol, hydrogenated bisphenol A, hydrogenated bisphenol F, alcohol containing a spiro skeleton, dimethylol tricyclodecane and dihydroxy An alicyclic alcohol such as methyl pentacyclopentadecane or an alkylene oxide adduct thereof, a branched or linear chain of a hydrogenated polyisoprene or a hydrogenated polybutadiene diol Long-chain alkyl diol, bisphenol A, bisphenol F and other bisphenols, and alkylene oxide adducts of bisphenol, trimethylolpropane, di-trimethylolpropane, pentaerythritol and dipentane A polyhydric alcohol such as a tetraol, an alkylene oxide adduct of the above polyol, and a polyester polyol obtained by reacting the polyhydric alcohol with a polybasic acid such as adipic acid. Although it is not particularly limited, in the cured product of the ultraviolet curable adhesive composition of the present invention, polyether polyols are preferably used in order to improve flexibility and compatibility.

The weight average molecular weight of the above amine ester (meth) acrylate is preferably from 5,000 to 100,000, more preferably from 10,000 to 80,000. If the weight average molecular weight is less than 5,000, the shrinkage increases, and if the weight average molecular weight is more than 100,000, the hardenability is lacking.

In the double-sided adhesive sheet for the image display device of the present invention, the amine ester (meth) acrylate can be used by mixing one or two or more kinds at any ratio. The weight ratio of the amine ester (meth) acrylate to the ultraviolet curable composition for obtaining the double-sided adhesive sheet for an image display device of the present invention is usually 20 to 80% by weight, preferably 30 to 70% by weight.

The above (meth) acrylate having a polyisoprene skeleton has a (meth) acrylonitrile group at the terminal or side chain of the polyisoprene molecule. The (meth) acrylate having a polyisoprene skeleton can be obtained in the form of "UC-203" (manufactured by Kuraray Co., Ltd.). The number average molecular weight of the (meth) acrylate having a polyisoprene skeleton in terms of polystyrene is preferably from 1,000 to 50,000, more preferably from about 25,000 to 45,000.

The weight ratio of the (meth) acrylate having a polyisoprene skeleton to the photocurable transparent adhesive composition for obtaining the double-sided adhesive sheet for an image display device of the present invention is usually 20 to 80% by weight. Good is 30~70% by weight.

The above (meth) acrylate having a polybutadiene skeleton has a (meth) acrylonitrile group at the terminal or side chain of the polybutadiene molecule. The (meth) acrylate having a polybutadiene skeleton can be "TEAI-1000 (manufactured by Japan Soda Co., Ltd.)" "TE-2000 (manufactured by Japan Soda Co., Ltd.)" "EMA-3000 (manufactured by Japan Soda Co., Ltd.)" "SPBDA" -S30 (made by Osaka Organic Chemical Industry Co., Ltd.). (meth) acrylate with polybutadiene skeleton changed with polystyrene The number average molecular weight is preferably from 1,000 to 30,000, more preferably from about 1,000 to 10,000.

The weight ratio of the (meth) acrylate having a polybutadiene skeleton to the photocurable transparent adhesive composition for obtaining the double-sided adhesive sheet for an image display device of the present invention is usually 10 to 80% by weight, preferably It is 20 to 70% by weight.

The polyurethane compound (E) which can be particularly suitably used in the present invention is characterized in that first, a hydrogenated polybutadiene polyol (A) and a diol compound (D) other than the compound (A) and a polyisocyanate compound (B) are used. The reaction (hereinafter referred to as the first reaction) is carried out, and then the (meth) acrylate compound (C) having at least one or more hydroxyl groups with respect to the residual isocyanate group is reacted (hereinafter referred to as a second reaction). The weight average molecular weight of the obtained polyurethane compound (E) is preferably from 5,000 to 100,000, more preferably from 10,000 to 80,000, particularly preferably from 30,000 to 70,000. The R value is preferably 1.1 to 2.0, more preferably 1.1 to 1.5.

The hydrogenated polybutadiene polyol (A) used in the first reaction of the present invention can be used as long as it is a hydrogenation reduction product of a usual polybutadiene polyol, especially for optical use, preferably residual. When the number of double bonds is small, the iodine value is preferably 20 or less.

The hydroxyl value is preferably 400 or less, more preferably 300 or less. The lower limit is not particularly limited, and for example, it may be 0.1 or more. Further, as for the molecular weight of (A), a generally available molecular weight distribution can be used, and in particular, when a balance between flexibility and hardenability is obtained, the weight average molecular weight is preferably from 500 to 3,000. On the other hand, as for the molecular weight of (A), a generally obtainable molecular weight distribution can be used, especially when a balance between softness and hardenability is obtained, and the number average molecular weight is preferably from 500 to 5,000. It is 500~3000.

As a commercially available hydrogenated polybutadiene polyol (A), for example, it is manufactured by Japan Soda Co., Ltd.: GI-1000, GI-2000, GI-3000, CRAY VALLEY KRASOL HLBP-H 1000, HLBP-H 2000, HLBP-H 3000, etc. manufactured. Further, those containing an alkali metal salt can be suitably used.

Specific examples of the diol compound (D) other than the compound (A) used in the first reaction of the present invention include polyethylene glycol, polytetramethylene glycol, polytetramethylene glycol, and poly Polyether polyols such as propylene glycol and polyethylene glycol, polyester polyols such as polyethylene glycol adipate, polytetramethylene glycol adipate, and polycaprolactone, ethylene glycol, a diol such as propylene glycol, butylene glycol, pentanediol, hexanediol or neopentyl glycol, dimethylol cyclohexane, polyisoprene diol, polybutadiene diol, hydrogenated bisphenol A, Hydrogenated bisphenol F, alcohol containing a spiro skeleton, alicyclic alcohol such as dimethylol tricyclodecane and dimethylol pentacyclopentadecane, and the alkylene oxide adducts thereof, hydrogenated polyisoprene Branched or linear long-chain alkyl diol such as diene or hydrogenated polybutadiene diol, bisphenol A, bisphenol F and other bisphenols, and bisphenol alkylene oxide adduct, trishydroxyl Polyols such as propane, di-trimethylolpropane, pentaerythritol and dipentaerythritol, and alkylene oxide adducts of such polyols, and further, such polyols and adipic acid Polyester obtained by reaction of polybasic acid Yuan alcohol. Although it is not particularly limited, in the cured product of the ultraviolet curable adhesive composition of the present invention, polyether polyols are preferably used in order to improve flexibility and compatibility.

Further, the molecular weight distribution of the diol compound (D) other than the compound (A) can be generally used, and in particular, when the balance between flexibility and hardenability is obtained, the number average molecular weight is preferably 50~6000, especially 100~4000.

Here, in the obtained polyurethane ester compound (E), it is dispersed by a structure derived from a diol compound (D) other than the compound (A) (particularly a polyether polyol such as polyethylene glycol) In view of introduction, and the polyethylene glycol skeleton and the hydrogenated polybutadiene skeleton are uniformly introduced, and the compatibility with the monomer is improved, the number average molecular weight of the polyethylene glycol is more preferably 2,000 or less, and particularly preferably 500 or less.

Further, in the polyurethane compound (E), the total of the hydrogenated polybutadiene polyol (A) and the diol compound (D) other than the compound (A) (preferably a polyether polyol such as polyethylene glycol) The molar amount of the diol compound (D) other than the compound (A) (preferably a polyether polyol such as polyethylene glycol) is preferably introduced in an amount of 5 to 10 mol%.

The hydroxyl value is preferably 400 or less, more preferably 300 or less. The lower limit is not particularly limited, and may be, for example, 5 or more.

As a specific example of the polyethylene glycol which is an example of the polyether polyol which can be suitably used in the first reaction of the present invention, commercially available polyethylene glycol can be used, for example, Nippon Oil Co., Ltd. can also be used. Manufactured by PEG#200T, PEG#200, PEG#300, PEG#400, PEG#600, PEG#1000, PEG#1500, PEG#1540, PEG#200, PEG#4000, PEG#4000P, PEG#6000, PEG #6000P, PEG #11000, PEG #20000, etc. or such moisture-managed amine ester grades. The moisture content is preferably 2% or less, and particularly preferably 1% or less, in order to suppress the increase in viscosity due to an increase in molecular weight.

Here, in the invention of the present invention, the hydrogenated polybutadiene polyol (A) and the diol compound (D) other than the compound (A) (preferably a polyether polyol such as polyethylene glycol) are used for the reaction. The use ratio of the hydrogenated polybutadiene (A) and the diol compound (D) other than the compound (A) (preferably a polyether polyol such as polyethylene glycol) is not particularly limited, and the component (A): The component D) is preferably 9.999:0.001 to 1:9, more preferably 9.999:0.001 to 3:7, and particularly preferably 9.999:0.001 to 4:6.

Further, the number average molecular weight of the hydrogenated polybutadiene polyol (A) used in the present invention is preferably larger than the diol compound (D) other than the compound (A) to be used (especially polyethylene The number average molecular weight of the polyether polyol such as a diol is used in combination, and it is more preferred that the hydrogenated polybutadiene polyol (A) has a diol compound (D) other than the compound (A) (especially polyethylene) a number average molecular weight of a polyether polyol such as a diol), a number average molecular weight of +500, and particularly preferably a hydrogenated polybutadiene polyol (A) having a diol compound (D) other than the compound (A) (more preferably The number average molecular weight of the polyether polyol such as polyethylene glycol (polyether polyol) is +1000.

The polyisocyanate compound (B) used in the first reaction is a compound containing two or more isocyanate groups in one molecule, and examples thereof include an aliphatic diisocyanate compound and an aromatic diisocyanate compound, and the like. Terpolymer and the like. The aliphatic diisocyanate compound referred to herein means a diisocyanate compound in which an isocyanate group is bonded to a chain carbon atom and a diisocyanate compound and an isocyanate group are bonded to a carbon atom of a cyclic saturated hydrocarbon. The aromatic diisocyanate compound is an isocyanate compound in which an isocyanate group is bonded to a carbon atom of an aromatic ring.

Examples of the aliphatic diisocyanate compound include 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated methylphenyl diisocyanate, hydrogenated deuterated diisocyanate, and hydrogenated diphenylmethane. Diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, m-tetramethylxylene diisocyanate, tetracylylene Xylylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,12-dodecylene diisocyanate, 2,2,4-trimethylcyclohexane diisocyanate, 2,4,4- Trimethylcyclohexane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, diazonic acid diisocyanate, norbornane (norbornane) diisocyanate and the like.

Examples of the aromatic diisocyanate compound include methylphenylene Isocyanate, decyl diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, 1,6-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1 a diisocyanate monomer such as 6-phenylene diisocyanate.

Among them, the aliphatic diisocyanate compound and the terpolymer of the aliphatic diisocyanate compound are preferred because they have good moisture resistance and heat resistance of the coating film. Examples of the terpolymer of the aliphatic diisocyanate compound include the above-mentioned aliphatic isocyanate-based isocyanurate-type polyisocyanate, and specific examples thereof include hexamethylene diisocyanate or isophor. Keto diisocyanate and the like. These may also be used alone or in a mixture.

In the present invention, the first reaction is added in an equivalent relationship (B/(A + D) > 1: [NCO] / [OH] molar ratio) such as residual isocyanate groups after the reaction. When the addition ratio is increased, the unreacted polyisocyanate compound (B) may be present in a large amount and may affect the flexibility of the ultraviolet curable adhesive composition. Moreover, when the addition ratio is decreased, the molecular weight is increased, and the curability of the ultraviolet curable adhesive composition is affected. Specifically, the OH group of the alcohol compound (A+D) is preferably 0.1 to 0.9 mol based on 1.0 mol of the NCO group of the polyisocyanate compound (B).

In the present invention, the first reaction can be carried out without a solvent, but the viscosity of the product is high, and in order to improve workability, it is preferably carried out in a solvent having no alcoholic hydroxyl group or in the following polymerizable compound (F). Specific examples of the solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbons such as benzene, toluene, xylene, and tetramethylbenzene; and ethylene glycol. Glycol ethers such as dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, ethyl acetate, butyl acetate, A Kesai Susu Acetate, ethyl cyproterone acetate, butyl cyproterone acetate, carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether Esters such as acid esters, dialkyl glutarate, dialkyl succinate, dialkyl adipate, cyclic esters such as γ-butyrolactone, petroleum ether, naphtha, and hydrogenated naphtha It is carried out in a separate or mixed organic solvent such as a petroleum solvent such as oil or solvent naphtha.

The reaction temperature is usually in the range of 30 to 150 ° C, preferably 50 to 100 ° C. The end point of the reaction was confirmed by a decrease in the amount of isocyanate. Further, in order to shorten the reaction time, a catalyst may be added. As the catalyst, any of an alkaline catalyst and an acidic catalyst can be used. Examples of the basic catalyst include amines such as pyridine, pyrrole, triethylamine, diethylamine, dibutylamine, and ammonia, and phosphines such as tributylphosphine and triphenylphosphine. Further, examples of the acidic catalyst include copper naphthenate, cobalt naphthenate, zinc naphthenate, aluminum tributoxide, titanium tetraisopropoxide, zirconium tetrabutoxide, aluminum chloride, tin octoate, A Lewis acid catalyst such as octyl tin laurate, dibutyl tin dilaurate or octyl tin diacetate. The amount of the catalyst added is usually 0.1 to 1 part by weight based on 100 parts by weight of the total weight of the diol compound (A+D) and the polyisocyanate compound (B).

The polyamine ester compound (E) of the present invention can be obtained by reacting (second reaction) of the (meth) acrylate compound (C) having at least one or more hydroxyl groups with respect to the residual isocyanate group after the first reaction. .

The (meth) acrylate compound (C) having at least one or more hydroxyl groups used in the second reaction is a compound having at least one hydroxyl group and one (meth) acrylate in one molecule, specifically In other words, 2-hydroxyethyl (meth)acrylate, propylene glycol mono(meth)acrylate, butanediol mono(meth)acrylate, pentanediol mono(meth)acrylate, hexanediol Mono (meth) acrylate, diethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate Ester, triethylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol Mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, ethoxylated neopentyl glycol mono (meth) acrylate, hydroxypivalic acid neopentyl glycol mono (meth) acrylate Mono(meth)acrylate of 2-alcohol such as ester; trimethylolpropane mono(meth)acrylate, ethoxylated trimethylolpropane mono(meth)acrylate, propoxylated trihydroxyl Methylpropane mono(meth)acrylate, tris(2-hydroxyethyl)isocyanuric acid mono(meth)acrylate, glycerol mono(meth)acrylate, trimethylolpropane di(meth)acrylic acid Ester, ethoxylated trimethylolpropane di(meth)acrylate, propoxylated trimethylolpropane di(meth)acrylate, tris(2-hydroxyethyl)trimeric isocyanate di(a) a methacrylate or a di(meth) acrylate of a trihydric alcohol such as acrylate or di(meth) acrylate, or a part of a hydroxyl group of the alcohol using an alkyl group or ε-caprolactone Formed Di(meth)acrylate; pentaerythritol mono(meth)acrylate, dipentaerythritol mono(meth)acrylate, di-trimethylolpropane mono(meth)acrylate, neopentyl Tetraol di(meth)acrylate, dipentaerythritol di(meth)acrylate, di-trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, Dipentaerythritol tri(meth)acrylate, di-trimethylolpropane tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, di-trimethylolpropane tetra( a polyfunctional (meth) acrylate having a methyl acrylate, dipentaerythritol hexa(meth) acrylate, or di-trimethylolpropane hexa(meth) acrylate equal to an alcohol of 4 or more A polyfunctional (meth) acrylate having a hydroxyl group or a part of a hydroxyl group of the alcohol such as an alkyl group or ε-caprolactone.

Among the (meth) acrylate compounds (C) having at least one or more hydroxyl groups, 2-hydroxyethyl (meth) acrylate is preferred from the viewpoint of excellent curability and flexibility. ester. From the viewpoint of easy work, the polymerizable compound (F) described below in the present invention may be added during the reaction.

The second reaction of the present invention is added in an equivalent relationship in which the isocyanate groups of the intermediate obtained after the first reaction disappear. Specifically, it is preferred to set the OH group of the (meth) acrylate compound (C) having at least one or more hydroxyl groups of 1.0 mol of the NCO group of the intermediate obtained after the first reaction to 1.0 to 3.0 mol. Further, it is preferably set to 1.0 to 2.0 mol.

The second reaction may be carried out without a solvent, but the viscosity of the product is high, and it is preferably carried out in the above solvent and/or the following polymerizable compound (F) in order to improve workability. Further, the reaction temperature is usually in the range of 30 to 150 ° C, preferably 50 to 100 ° C. The end point of the reaction was confirmed by a decrease in the amount of isocyanate. In order to shorten the reaction time, the above catalyst may be added.

A polymerization inhibitor such as 4-methoxyphenol is usually added to the acrylate compound used as a raw material, but a polymerization inhibitor may be added again during the reaction. Examples of such polymerization inhibitors include hydroquinone, 4-methoxyphenol, 2,4-dimethyl-6-tert-butylphenol, and 2,6-di-t-butyl- 4-cresol, 3-hydroxythiophenol, p-benzoquinone, 2,5-dihydroxy-p-benzoquinone, thiophene Wait. It is used in an amount of 0.01 to 1% by weight based on the reaction raw material mixture.

The softener component (G) is used in the double-sided adhesive sheet of the image display device of the present invention. Specific examples of the softener component that can be used include polymers or oligomers, phthalic acid esters, phosphates, glycol esters, citrate esters, and aliphatic dibasic acid esters. a fatty acid ester, an epoxy plasticizer, a castor oil, a terpene hydrogenated resin, a terpene resin, a compound having a structure represented by the following formula (1), and the like.

(In the formula, n represents an integer of 0 to 40, m represents an integer of from 10 to 50; R & lt ¹ and R ² may be identical or different; R & lt ¹ and R ² are an alkyl group having 1 to 18 carbon atoms, the carbon atoms 1 Alkenyl group ~18, alkynyl group having 1 to 18 carbon atoms, aryl group having 5 to 18 carbon atoms).

Examples of the oligomer or the polymer include an oligomer or polymer having a polyisoprene skeleton, a polybutadiene skeleton, a polybutene skeleton or a xylene skeleton, and an ester thereof, and preferably Polymers or oligomers having a polybutadiene skeleton and esterified products thereof are used as appropriate. Specific examples of the polymer or oligomer having a polybutadiene skeleton and esterified products thereof include butadiene homopolymer, epoxy modified polybutadiene, and butadiene-styrene random copolymer. Compound, maleic acid modified polybutadiene and terminal hydroxyl modified liquid polybutadiene. Further, these softener components may be used in combination of two or more kinds of the above components.

From the viewpoint of ensuring adhesion, low shrinkage, and maintaining the shape of the sheet, it is preferable to use a softener component which is a solid at room temperature (25 ° C) as a double-sided adhesive sheet for an image display device. More preferably, a solid softener component having a melting point of 80 ° C or higher is used, and a solid softener component having a melting point of 100 ° C or higher is particularly preferably used. Specific examples include aromatic modified terpene resins and the like. Here, two or more types of solid softener components may be mixed and used.

The weight ratio of the softener component to the ultraviolet curable adhesive composition for obtaining the double-sided adhesive sheet for an image display device is usually 10 to 80% by weight, preferably 10 to 70% by weight.

The ultraviolet curable resin composition for obtaining the double-sided adhesive sheet for an image display device of the present invention usually contains the above (meth) acrylate (K), a softener component (G), and an organic solvent.

The organic solvent that can be used is not particularly limited, and examples thereof include alcohols such as methanol, ethanol, and isopropyl alcohol, dimethyl hydrazine, dimethyl hydrazine, tetrahydrofuran, and Alkane, toluene, xylene, and the like.

The double-sided adhesive sheet for the image display device of the present invention may contain a (meth) acrylate monomer as an optional component.

As the (meth) acrylate monomer, a (meth) acrylate having one (meth) acrylonitrile group in the molecule can be suitably used.

Here, the (meth) acrylate monomer means (meth) acrylate other than the above-mentioned amine ester (meth) acrylate, the following epoxy (meth) acrylate, and the above (meth) acrylate having a polyisoprene skeleton. (Meth) acrylate other than ester.

Examples of the (meth) acrylate having one (meth) acrylonitrile base in the molecule include isobutyl (meth)acrylate, isoamyl (meth)acrylate, and (methyl). Lauryl acrylate, isodecyl (meth) acrylate, stearyl (meth) acrylate, cetyl (meth) acrylate, isomyristyl (meth) acrylate, tridecyl (meth) acrylate An alkyl (meth)acrylate having a carbon number of 5 to 20, such as an ester, preferably an alkyl (meth)acrylate having a carbon number of 10 to 20, and more preferably having a carbon number of 10 to 20 A branched alkyl (meth) acrylate having a carbon number of 10 to 20, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, propylene fluorenyl Porphyrin, phenylglycidyl (meth)acrylate, tricyclodecyl (meth)acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl (meth)acrylate, (meth)acrylic acid Isodecyl ester, dicyclopentanyl (meth)acrylate, 1-adamantyl acrylate, 2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl acrylate, acrylic acid 1 - adamantyl methyl ester, polypropylene oxide modified (meth) methacrylate acrylate, (meth) acrylate dicyclopentadienyloxyethyl ester (meth) acrylate having a cyclic skeleton, (meth) 2-hydroxypropyl acrylate, 4-hydroxybutyl (meth) acrylate, etc., alkyl (meth) acrylate having a hydroxyl group of 1 to 5, ethoxy diethylene glycol (methyl) Acrylate, polypropylene glycol (meth) acrylate, polypropylene oxide modified polyalkylene glycol (meth) acrylate such as nonylphenyl (meth) acrylate, ethylene oxide modified phenoxy The phosphorylated (meth) acrylate, the ethylene oxide modified butoxylated phosphoric acid (meth) acrylate, and the ethylene oxide modified octoxylated phosphoric acid (meth) acrylate. Among them, preferred are alkyl (meth)acrylates having a carbon number of 10 to 20, 2-ethylhexylcarbitol acrylate, and acrylonitrile groups. Porphyrin, 4-hydroxybutyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isostearyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, polyepoxy Propane-modified decyl phenyl (meth) acrylate, especially from the viewpoint of flexibility of the resin, preferably an alkyl (meth) acrylate having a carbon number of 10 to 20 and a bicyclo(meth) acrylate. Pentenyloxyethyl ester, polypropylene oxide modified nonylphenyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate.

On the other hand, from the viewpoint of improving the adhesion to the glass, an alkyl (meth)acrylate having a carbon number of 1 to 5 and a propylene group are preferred. Porphyrin Porphyrin.

Here, the (meth) acrylate monomer means an amine ester (meth) acrylate, an epoxy (meth) acrylate, or a (meth) acrylate having a polyisoprene skeleton ( Methyl) acrylate.

In the composition of the present invention, a (meth) acrylate other than the (meth) acrylate having one (meth) acrylonitrile group can be contained without impairing the characteristics of the present invention. For example, tricyclodecyl dimethylol di (meth) acrylate, two Alkylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, alkylene oxide modified bisphenol A type di(methyl) Acrylate, caprolactone modified hydroxypivalic acid neopentyl glycol di(meth) acrylate and ethylene oxide modified di(meth) acrylate, trimethylolpropane tri (meth) acrylate Trimethylol C2~C10 alkane tri(meth) acrylate such as ester, trimethylol octane tri(meth) acrylate, trimethylolpropane polyethoxy tri(meth) acrylate, three Trimethylol C2~C10 alkane polyalkoxy tris (hydroxymethylpropane) polypropoxy tri(meth)acrylate, trimethylolpropane polyethoxypolypropoxy tri(meth)acrylate Acrylate, tris((meth)acryloxyethyl) isocyanurate, neopentyl tris(tri) methacrylate, ethylene oxide modified trimethylolpropane III Methyl) acrylate, propylene oxide modified trimethylolpropane tri(meth) acrylate, etc., alkylene oxide modified trimethylolpropane tri(meth) acrylate, neopentyl alcohol polyethoxylate Tetra(meth)acrylate, new Tetraol polypropoxy tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(methyl) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

In the present invention, in the case of use in combination, in order to suppress hardening shrinkage, it is preferred to use a 1- or 2-functional (meth) acrylate.

In the ultraviolet curable adhesive composition, the (meth) acrylate monomer components can be used by mixing one or two or more kinds at any ratio. The weight ratio of the (meth) acrylate monomer to the photocurable transparent adhesive composition of the present invention is usually 5 to 70% by weight, preferably 10 to 50% by weight. If it is less than 5% by weight, the curing property is lacking, and if it is more than 70% by weight, the shrinkage is increased.

The ultraviolet curable adhesive composition contains (i) at least one of an amine ester (meth) acrylate or a (meth) acrylate having a polyisoprene skeleton, and (ii) (methyl) In the aspect of the acrylate monomer, the total content of both (i) and (ii) is usually 25 to 90% by weight, 40 to 90% by weight, based on the total amount of the resin composition. Good is 40~80% by weight.

In the image display device of the present invention, the two-sided adhesive sheet can be used without damaging the hair Epoxy (meth) acrylate is used in the range of characteristics. The epoxy (meth) acrylate has a function of improving hardenability or increasing the hardness or hardening speed of the cured product. Epoxy (meth) acrylate is a general term for (meth) acrylate obtained by reacting an epoxy resin having a monofunctional or higher epoxy group with (meth)acrylic acid. The (meth)acrylic acid is reacted at a ratio of 0.9 to 1.5 moles, more preferably 0.95 to 1.1 moles, per equivalent of the epoxy group of the epoxidized epoxy type epoxy compound. The reaction temperature is preferably from 80 to 120 ° C, and the reaction time is from about 10 to 35 hours. In order to promote the reaction, it is preferred to use a catalyst such as triphenylphosphine, TAP, triethanolamine or tetraethylammonium chloride. Further, in the reaction, in order to prevent polymerization, for example, p-methoxyphenol or methyl hydroquinone may be used as a polymerization inhibitor. Specific examples of the epoxy resin which is a raw material of the epoxy (meth) acrylate include hydroquinone diglycidyl ether, catechol diglycidyl ether, and resorcinol epoxide. Phenyl diglycidyl ether such as propyl ether; bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, 2,2-bis(4-hydroxyphenyl)-1, Bisphenol type epoxy compound such as 1,1,3,3,3-hexafluoropropane epoxy compound; hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, hydrogenated bisphenol S type epoxy Hydrogenated bisphenol type epoxy compound such as epoxy resin compound of hydrogenated 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane; brominated bisphenol A type Halogenated bisphenol epoxy compound such as epoxy resin or brominated bisphenol F epoxy resin; alicyclic diglycidyl ether compound such as cyclohexane dimethanol digoxifen ether compound; 1,6-hexane Aliphatic diglycidyl ether compounds such as alcohol diglycidyl ether, 1,4-butanediol diglycidyl ether, diethylene glycol diglycidyl ether; polysulfide diglycidyl ether and other polysulfide Type diglycidyl ether compound; phenolic novolak type epoxy resin, cresol novolac Lacquer type epoxy resin, trihydroxyphenylmethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, biphenol type epoxy resin, bisphenol A novolac type epoxy resin, epoxy containing naphthalene skeleton Resin, heterocyclic epoxy resin, etc.

The epoxy (meth) acrylate which can be suitably used in the present invention is a bisphenol A type epoxy (meth) acrylate obtained from an epoxy compound of a bisphenol A type. The weight average molecular weight of the epoxy (meth) acrylate is preferably 500 to 10,000.

The weight ratio of the epoxy (meth) acrylate to the ultraviolet curable adhesive composition of the present invention is usually from 1 to 80% by weight, preferably from 5 to 30% by weight.

The content ratio of the (meth) acrylate in the ultraviolet curable resin composition for obtaining the double-sided adhesive sheet for an image display device of the present invention is 25 to 90 by weight based on the total amount of the ultraviolet curable adhesive composition. %, preferably 40 to 90% by weight, more preferably 40 to 80% by weight.

The ultraviolet curable adhesive composition preferably contains a (meth) acrylate selected from the above amine ester (meth) acrylate, the above polyisoprene skeleton, and the above (meth) acrylate single At least one of the group of the body composition is (meth) acrylate, and the content of the amine ester (meth) acrylate is 20 to 80% by weight, preferably 30 to 70% by weight, and the above has a poly The content ratio of the (meth) acrylate of the isoprene skeleton is 20 to 80% by weight, preferably 30 to 70% by weight, and the content ratio of the (meth) acrylate monomer is 5 to 70% by weight. More preferably, it is 10 to 50% by weight.

In the ultraviolet curable adhesive composition described above, the (meth) acrylate containing the above amine ester (meth) acrylate or having a polyisoprene skeleton is used as the (meth) acrylate, and the content ratio thereof is 20 It is preferably 80% by weight, preferably 30 to 70% by weight, and further preferably contains a (meth) acrylate monomer in a proportion of 5 to 70% by weight, preferably 10 to 50% by weight.

In addition, as a compound containing a maleimide group which is used for the double-sided adhesive sheet for the image display device of the present invention, for example, N-n-butylbutyleneimine, N -hexyl succinimide, 2-m-butylene imine ethyl-ethyl carbonate, 2-m-butylenediamine ethyl-propyl carbonate, N-ethyl-( Monofunctional aliphatic maleimide such as 2-m-butylenediamine ethyl)carbamate; alicyclic monofunctional cis-butyl such as N-cyclohexylmethyleneimine Alkene diimine; N,N-hexamethylenebis-synylene diimide, polypropylene glycol-bis(3-maleoximeimidopropyl) ether, bis(2-cis-butene) Aliphatic bis-butenylene diamines such as dimethyleneimine ethyl carbonate; 1,4-dimethyleneimine cyclohexane, isophorone bis- carbazate An alicyclic di-n-butylene iminoimide such as N-ethyl maleimide; an ester obtained by esterifying maleic acid imide with acetic acid and polytetramethylene glycol An enediquinone imine compound, a cis-butane compound such as a maleimide compound produced by esterification of a maleic acid hexanoic acid hexanoic acid with a tetraethylene oxide adduct of neopentyl alcohol a (poly)ester (poly) maleimide compound obtained by esterifying an enediamine derivative with various (poly) alcohols , but not limited to these. The content ratio is 25 to 90% by weight, preferably 40 to 90% by weight, and more preferably 40 to 80% by weight based on the total amount of the ultraviolet curable adhesive composition.

As the (meth) acrylamide compound which can be used in the double-sided adhesive sheet for the image display device of the present invention, for example, an acrylonitrile group can be mentioned. Monofunctional (meth) acrylamide such as phenyl or N-isopropyl (meth) acrylamide; polyfunctional (meth) acrylamide such as methylene bis(meth) acrylamide . The content ratio is 25 to 90% by weight, preferably 40 to 90% by weight, more preferably 40 to 80% by weight based on the total amount of the ultraviolet curable adhesive composition for obtaining the double-sided adhesive sheet for an image display device. %.

The photopolymerization initiator contained in the double-sided adhesive sheet for the image display device of the present invention is not particularly limited, and a fluorenylphosphine oxide compound is preferably used. For example, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, 2,4,6-trimethylbenzimidylphenylethoxy oxidation Phosphine, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl- Pentylphosphine oxide. When the ultraviolet curable resin after application is irradiated with ultraviolet rays to obtain a cured layer having a hardened portion existing on the side of the optical substrate and an uncured portion existing on the side opposite to the side of the optical substrate, it is easy to form an uncrystallized layer. From the viewpoint of the transparency of the hardened portion and the cured resin layer, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide is particularly preferable.

As another photopolymerization initiator, 1-hydroxycyclohexyl phenyl ketone (Irgacure-184; manufactured by BASF), 2-hydroxy-2-methyl-[4-(1-methylvinyl)phenyl group is exemplified. ]propanol oligomer (Esacure ONE; manufactured by Lamberti), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (Irgacure) -2959; manufactured by BASF), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl]-phenyl}-2-methyl-propane-1 -ketone (Irgacure-127; manufactured by BASF), 2,2-dimethoxy-2-phenylacetophenone (Irgacure-651; manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl- Propane-1-one (Darocure 1173; manufactured by BASF), 2-methyl-1-[4-(methylthio)phenyl]-2- Lolinylpropan-1-one (Irgacure-907; manufactured by BASF), oxy-phenyl-acetic acid 2-[2-oxo-2-phenyl-ethyloxy-ethoxy]-ethyl ester and oxygen a mixture of 2-phenyl-2-acetic acid 2-[2-hydroxy-ethoxy]-ethyl ester (Irgacure-754; manufactured by BASF), 2-benzyl-2-dimethylamino-1-(4- Polinylphenyl)-butan-1-one, 2-chloro 9-oxosulfur 2,4-dimethyl 9-oxosulfur 2,4-diisopropyl 9-oxosulfur Isopropyl 9-oxosulfur An α-hydroxyketone polymer or the like.

In the double-sided adhesive sheet for an image display device of the present invention, an α-hydroxyketone polymer (manufactured by ESACURE Co., Ltd.) is preferably used from the viewpoint of suppressing volatilization when heat is applied to obtain a sheet. KIP150).

In the double-sided adhesive sheet for a video display device of the present invention, one or two or more kinds of photopolymerization initiators can be used in combination at any ratio. The weight ratio of the photopolymerization initiator to the photocurable resin composition for obtaining the double-sided adhesive sheet for an image display device of the present invention is usually 0.2 to 5% by weight, preferably 0.3 to 3% by weight. If it is more than 5% by weight, when the cured layer having the hardened portion and the uncured portion existing on the side opposite to the side of the optical substrate is obtained, the uncured portion or the cured layer of the resin is not formed. The difference is worse.

Further, it may be a tertiary amine such as triethanolamine or methyldiethanolamine, a benzoic acid derivative such as ethyl N,N-dimethylaminobenzoate or isoamyl N,N-dimethylaminobenzoate. A promoter or the like is used in combination. The amount of the accelerator to be added is preferably 100% by weight or less based on the photopolymerization initiator.

In addition to the above (meth) acrylate and the photopolymerization initiator, the double-sided pressure-sensitive adhesive sheet for image display device of the present invention may contain, as other components, the following photopolymerization initiation aid, the following additives, and the like. The content ratio of the other component to the total amount of the ultraviolet curable adhesive composition of the present invention is the total amount obtained by subtracting the total amount of the above (meth) acrylate and the photopolymerization initiator from the total amount. . Specifically, the total amount of the other components is from 0 to 74% by weight, preferably 5, based on the total amount of the ultraviolet curable adhesive composition for obtaining the double-sided adhesive sheet for an image display device of the present invention. ~70% by weight or so.

Further, an amine or the like which can be used as a photopolymerization initiation aid may be used in combination with the above photopolymerization initiator. Examples of the amines and the like which can be used include 2-dimethylaminoethyl benzoate, dimethylaminoacetophenone, ethyl p-dimethylaminobenzoate or p-dimethylaminobenzene. Isoamyl formate and the like. In the case of using a photopolymerization starter such as an amine, the content of the resin composition for use in obtaining the double-sided adhesive sheet for an image display device of the present invention is usually 0.005 to 5 by weight. % is preferably 0.01 to 3% by weight.

In the double-sided adhesive sheet for the image display device of the present invention, an antioxidant, an organic solvent, a decane coupling agent, a polymerization inhibitor, a leveling agent, an antistatic agent, a surface lubricant, a fluorescent whitening agent, or the like may be added as needed. An additive such as a light stabilizer (for example, a hindered amine compound) or a filler.

Specific examples of the antioxidant include BHT and 2,4-bis-(n-octylsulfo)-6-(4-hydroxy-3,5-di-t-butylanilinyl)-1,3. 5-three , tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoic acid pentaerythritol], bis[3-(3,5-di-t-butyl-4-hydroxybenzene) Base) propionic acid 2,2-thiodiethyl ester], triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1 ,6-hexanediol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 3-(3,5-di-t-butyl-4- Octadecyl hydroxyphenyl)propionate, N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-phenylpropanamide), 1,3,5-trimethyl -2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tris-(3,5-di-t-butyl-4-hydroxybenzyl)-polyisocyanate , octylated diphenylamine, 2,4-bis[(octylthio)methyl-O-cresol, 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid Octyl ester, dibutylhydroxytoluene, and the like.

Specific examples of the organic solvent include alcohols such as methanol, ethanol, and isopropanol, dimethyl hydrazine, dimethyl hydrazine, tetrahydrofuran, and Alkane, toluene, xylene, and the like.

Specific examples of the decane coupling agent include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, and 3-glycidoxypropyl group. Dimethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, N-(2-aminoethyl) 3-aminopropylmethyldimethoxydecane, Γ-巯propyltrimethoxyfluorene Alkane, N-(2-aminoethyl) 3-aminopropylmethyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, vinyl trimethyl Oxydecane, N-(2-(vinylbenzylamino)ethyl)-3-aminopropyltrimethoxydecane hydrochloride, 3-methylpropenyloxypropyltrimethoxydecane, a decane coupling agent such as 3-chloropropylmethyldimethoxydecane or 3-chloropropyltrimethoxydecane; isopropyl (N-ethylaminoethylamino) titanate, isopropyl Triisostearyl decyl titanate, bis(dioctylpyrophosphate) oxyacetic acid titanium, tetraisopropylbis(dioctyl phosphite) titanate, neoalkoxy III (for N- Titanium coupling agent such as (β-aminoethyl)aminophenyl) titanate; zirconium acetonate, zirconium methacrylate, zirconium propionate, neoalkoxy zirconate, neoalkoxy Mercapto zirconate, neoalkoxytris(dodecanoyl)benzenesulfonyl zirconate, neoalkoxytris(ethylideneethylamine)zirconate, neoalkoxy Zirconium, such as tris(m-aminophenyl)zirconate, zirconium ammonium carbonate, aluminum acetonate, aluminum methacrylate, aluminum propionate, or aluminum Mixture, etc.

Specific examples of the polymerization inhibitor include p-methoxyphenol and methyl hydroquinone.

Specific examples of the photostabilizer include 1,2,2,6,6-pentamethyl-4-piperidinol and 2,2,6,6-tetramethyl-4-piperidinol. 1,2,2,6,6-pentamethyl-4-piperidyl (meth)acrylate (manufactured by Adico Co., Ltd., LA-82), four (1,2,2,6,6- Pentamethyl-4-piperidinyl-1,2,3,4-butanetetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidinyl)-1,2 , 3,4-butane tetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9- Mixed esterified product of bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, azelaic acid bis(2,2,6 ,6-tetramethyl-4-piperidinyl) sebacate, bis(1-undecyloxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, A 2,2,6,6-tetramethyl-4-piperidinyl acrylate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, azelaic acid bis ( 1,2,2,6,6-pentamethyl-4-piperidinyl), 4-benzylideneoxy-2,2,6,6-tetramethylpiperidine, 1-[2-[ 3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoxy]ethyl]-4-[3-(3,5-di-t-butyl-4-hydroxyphenyl) Propyloxy]-2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate , bis(1,2,2,6,6-pentamethyl-4-piperidinyl) malonate [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl) ]methyl]butyl ester, bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidyl) sebacate, 1,1-dimethylethyl Reaction product of hydrogen peroxide and octane, N, N', N", N'''-tetra-(4,6-bis-(butyl-(N-methyl-2,2,6,6-four) Methylpiperidin-4-yl)amino)-three -2-yl)-4,7-diazadecane-1,10-diamine, dibutylamine-1,3,5-three -N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl) Polycondensate of phenyl-4-piperidyl)butylamine, poly[[6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-tri -2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imido]hexamethylene[(2,2,6,6-tetramethyl- 4-piperidinyl)imido]], dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol polymer, 2, 2, 4, 4 -tetramethyl-20-(β-lauryloxycarbonyl)ethyl-7-oxa-3,20-diazaspiro[5-1-11-2]eicosane-21-one, --alanine, N-(2,2,6,6-tetramethyl-4-piperidinyl)-dodecyl ester/tetradecyl ester, N-acetamido-3-dodecane 1-(2,2,6,6-tetramethyl-4-piperidinyl)pyrrolidine-2,5-dione, 2,2,4,4-tetramethyl-7-oxa- 3,20-diazabispiro-[5,1,11,2]-eicosane-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20- Diazabicyclo-[5,1,11,2]-docosane-20-propionic acid lauryl ester/tetradecyl ester, malonic acid-[(4-methoxyphenyl) )-methylene]-bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester, advanced 2,2,6,6-tetramethyl-4-piperidinol Fatty acid ester, 1,3-phenyldicarboxyguanamine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl) and other hindered amine systems, diphenyl benzophenone and the like Methyl ketone compound, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2-hydroxy-5-methyl Phenyl)benzotriazole, 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimido-methyl)-5-methylphenyl]benzotriene Oxazole, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-t-pentylphenyl) a reaction product of benzotriazole, methyl 3-(3-(2H-benzotriazol-p-yl)-5-t-butyl-4-hydroxyphenyl)propanoate and polyethylene glycol, 2 a benzotriazole compound such as (2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol, 2,4-di-t-butylphenyl-3,5- a benzoate such as di-tert-butyl-4-hydroxybenzoate, 2-(4,6-diphenyl-1,3,5-three -2-yl)-5-[(hexyl)oxy]phenol, etc. A compound or the like is particularly preferably a hindered amine compound.

Specific examples of the filler include, for example, crystalline cerium oxide, molten cerium oxide, aluminum oxide, zircon, calcium silicate, calcium carbonate, cerium carbide, cerium nitride, boron nitride, zirconia, magnesium. Powders such as olivine, talc, spinel, titanium oxide, and talc, or beads obtained by spheroidizing the particles.

In the case of being present in the composition of various additives, the weight ratio of the various additives to the photocurable transparent adhesive composition for obtaining the double-sided adhesive sheet for an image display device is 0.01 to 3% by weight, preferably 0.01. ~1% by weight, more preferably 0.02 to 0.5% by weight.

The ultraviolet curable adhesive composition for obtaining the double-sided adhesive sheet for an image display device of the present invention can be obtained by mixing and dissolving the above components at a normal temperature of -80 ° C, and if necessary, the inclusions can be handled by filtration or the like. Remove. In view of coatability, the resin composition for subsequent use of the present invention is preferably such that the blend ratio of the components is appropriately adjusted so that the viscosity at 25 ° C is in the range of 300 to 15000 mPa ‧ s.

Next, an image display device is obtained from the ultraviolet curable adhesive composition described above. A method of manufacturing a sheet of a double-sided adhesive sheet will be described.

The ultraviolet curable adhesive composition containing the (meth) acrylate (K) and the softener component (G) usually further contains the above organic solvent. Further, the ultraviolet curable adhesive composition can be applied to a substrate (usually a release film) so as to have a constant film thickness, and after drying, the release film can be bonded to obtain a release film. The film image display device uses a two-sided sheet.

The drying conditions are not particularly limited as long as they are necessary for removing the solvent. For example, they can be used for drying at a temperature of from 50 ° C to 300 ° C (for example, 50 to 150 ° C in the case of using a release film) for several minutes to several minutes. Ten minutes (for example, about 1 to 60 minutes). The sheet thus obtained exhibited a form in which no solvent was present or only a small amount remained. Here, the amount of the residual solvent is preferably 5,000 ppm or less, more preferably 1,000 ppm or less, and still more preferably 100 ppm or less.

Further, the type of the release film is not particularly limited, and for example, a PET film can be used.

The double-sided adhesive sheet for the image display device thus obtained has a configuration in which the (meth) acrylate is polymerized without crosslinking, and the (meth) acryl fluorenyl group is directly left to be laminated.

The double-sided adhesive sheet of the image display device of the present invention is suitably used for bonding at least one optical substrate having an optical substrate having a light-shielding portion to produce a touch panel.

The cured product of the double-sided adhesive sheet of the image display device of the present invention preferably has a curing shrinkage ratio of 3.0% or less, and particularly preferably 2.0% or less. Thereby, when the ultraviolet curable adhesive composition is cured, the internal stress accumulated in the cured resin can be reduced, and the base material and the cured product of the ultraviolet curable adhesive can be effectively prevented from being formed. The interface at the layer produces strain.

Further, when the substrate such as glass is thin, since the warpage at the time of hardening increases when the hardening shrinkage ratio is large, the display performance is greatly adversely affected, so From the viewpoint, it is also preferred that the hardening shrinkage rate is small.

Next, a preferred manufacturing form of the manufacturing process of the optical member using the double-sided adhesive sheet using the image display device of the present invention will be described.

In the method for producing an optical member of the present invention, it is preferred to bond at least two optical substrates according to the following (Step 1) to (Step 3). Furthermore, when it is judged that sufficient adhesion strength can be ensured in the stage of (step 2), it can be omitted (step 3).

(Step 1): For at least one optical substrate, the image display device with the release film is peeled off by a single-sided release film of the double-sided adhesive sheet, and the step of attaching the double-sided adhesive sheet to the image display device is performed; (Step 2) The image display device disposed in step 1 is peeled off by the remaining single-sided release film of the double-sided adhesive sheet, and the other optical substrate is bonded; (step 3) is passed through the optical substrate having the light-shielding portion, The image display device in the bonded optical substrate is a step of curing the cured layer by irradiating ultraviolet rays with the double-sided adhesive sheet.

Hereinafter, a specific embodiment of the method for producing an optical member of the present invention which has been subjected to the steps 1 to 3 will be described by taking a bonding between a liquid crystal display unit and a transparent substrate having a light shielding portion as an example.

(Production form of image display device)

This method is a method of obtaining an optical member by laminating a liquid crystal display unit and a transparent substrate.

The liquid crystal display unit is one in which a liquid crystal material is sealed between one of the electrodes and the substrate, and a polarizing plate, a driving circuit, a signal input cable, and a backlight unit are provided.

The transparent substrate is transparent to glass plates, polymethyl methacrylate (PMMA) plates, polycarbonate (PC) plates, alicyclic polyolefin polymer (COP) plates, acrylic resins, polyethylene terephthalate, etc. Substrate. Regarding the transparent substrate, it is also possible to apply a hard coating treatment or an anti-reflection treatment to one side or both surfaces.

Here, as the transparent substrate, a light-shielding portion having a black frame shape on the surface of the transparent substrate can be suitably used, and the light-shielding portion is formed by adhesion of a tape or coating or printing of a paint. Further, in the present invention, it is also possible to apply to a case where the light-shielding portion is not provided. However, in the following description of the embodiment, a case where the light-shielding portion is provided will be described as a specific example. When the light-shielding portion is not provided, if the "transparent substrate having the light-shielding portion" is replaced with the "transparent substrate", it is considered to be an example in which the light-shielding portion is not provided.

(step 1)

First, after peeling off the single-sided release film with the double-sided adhesive sheet with the double-sided release film, the adhesive surface is disposed on the surface of the liquid crystal display unit or the surface of the transparent substrate having the light-shielding portion on which the light-shielding portion is formed.

The film thickness of the double-sided adhesive sheet of the image display device is adjusted such that the cured resin layer is 50 to 500 μm, preferably 50 to 350 μm, and more preferably 100 to 350 μm.

(Step 2)

Next, after the remaining image display device is peeled off by the release film of the double-sided adhesive sheet, the liquid crystal display unit is bonded to the transparent substrate having the light-shielding portion in the opposite direction. It can be carried out in any of the atmosphere and in a vacuum.

Here, in order to prevent generation of bubbles at the time of bonding, it is preferable to bond them in a vacuum.

The bonding can be carried out by pressing, pressing, or the like.

(Step 3)

Next, the optical member obtained by laminating the transparent substrate and the liquid crystal display unit is irradiated with ultraviolet rays from the transparent substrate side having the light shielding portion, and the image display device is cured by the double-sided adhesive sheet.

UV exposure accumulated light amount of good care of about 100 ~ 4000mJ / cm ^2, particularly preferably about 200 ~ 3000mJ / cm ^2. The light source used for hardening caused by ultraviolet to near-ultraviolet light is a light source that illuminates ultraviolet to near-ultraviolet light, regardless of the light source. For example, a low pressure, high pressure or ultra high pressure mercury lamp, a metal halide lamp, a (pulse) xenon lamp, or an electrodeless lamp can be cited.

In this way, an optical member can be obtained.

Preferably, the cured product of the double-sided adhesive sheet of the image display device of the present invention has a transmittance of from 400 nm to 800 nm of 90% or more. The reason for this is that light is difficult to transmit when the transmittance is less than 90%, and visibility is lowered when used in a display device.

Further, when the transmittance of the cured product is high at 400 to 450 nm, the visibility can be further improved. Therefore, the transmittance of 400 to 450 nm is preferably 90% or more.

The double-sided adhesive sheet for an image display device of the present invention can be suitably used as an adhesive for bonding a plurality of optical substrates to produce an optical member.

Examples of the optical substrate used in the method for producing an optical member of the present invention include a transparent plate, a sheet, a touch panel, and a display unit.

In the present invention, the term "optical substrate" means both an optical substrate having no light-shielding portion on its surface and an optical substrate having a light-shielding portion on its surface. In the production of the optical member of the present invention, an optical substrate having a light-shielding portion in at least one of a plurality of optical substrates to be used is suitably used.

The position of the light shielding portion of the optical substrate having the light shielding portion is not particularly limited. As a preferable aspect, a band-shaped light-shielding portion having a width of 0.05 to 20 mm, preferably about 0.05 to 10 mm, more preferably about 0.1 to 6 mm, may be formed in the peripheral portion of the optical substrate. The light-shielding portion on the optical substrate can be formed by attaching a tape or coating or printing a coating or the like.

As the material of the optical substrate used in the present invention, various materials can be used. Specific examples thereof include resins such as PET, PC, PMMA, a combination of PC and PMMA, glass, COC, COP, and plastic (acrylic resin). As the optical substrate used in the present invention, for example, a transparent plate or a sheet, a film or a sheet obtained by laminating a plurality of films or sheets such as a polarizing plate, or a film or sheet laminated with an unlaminated polarizing plate can be used. A sheet or a transparent plate, and a transparent plate made of inorganic glass (an inorganic glass plate and a processed product thereof, for example, a lens, a crucible, or an ITO glass). Further, the optical substrate used in the present invention includes the above-described polarizing plate or the like, and a touch panel (touch panel input sensor) or a display unit such as the following, which is composed of a plurality of functional boards or sheets. Body (hereinafter also referred to as "functional laminate").

Examples of the sheet which can be used as the optical substrate used in the present invention include an icon sheet, a decorative sheet, and a protective sheet. A plate (transparent plate) which can be used in the method for producing an optical member of the present invention includes a decorative plate and a protective plate. As a material of these sheets or sheets, it can be applied as a material of a transparent board.

Examples of the material of the surface of the touch panel which can be used as the optical substrate used in the present invention include glass, PET, PC, PMMA, a composite of PC and PMMA, COC, and COP.

The thickness of the plate-like or sheet-shaped optical substrate such as a transparent plate or a sheet is not particularly limited, and is usually from about 5 μm to about 5 cm, preferably from about 10 μm to about 10 mm, more preferably from about 50 μm to about 3 mm.

The preferred touch panel used in the present invention is a plate-like or sheet-like transparent optical substrate having a light-shielding portion and a cured product of the ultraviolet-curable adhesive composition for a touch panel of the present invention. The optical member in which the above functional laminated body is bonded.

Further, by using a display unit such as a liquid crystal display device as one of optical substrates, and using light Learning Functional Materials As other optical substrates, a display unit (hereinafter also referred to as a display panel) with an optical functional material can be manufactured. Examples of the display unit include a display device such as an LCD, an EL display, an EL illumination, an electronic paper, or a plasma display to which a polarizing plate is attached to glass. Further, examples of the optical functional material include a transparent plastic plate such as an acrylic plate, a PC plate, a PET plate, and a PEN plate, a tempered glass, and a touch panel input sensor.

In the case of being used as a bonding material for bonding an optical substrate, in order to improve visibility, when the refractive index of the cured product is 1.45 to 1.55, the visibility of the displayed image is further improved, which is preferable.

If it is within the range of the refractive index, the difference in refractive index from the substrate used as the optical substrate can be reduced, and diffuse reflection of light can be suppressed to reduce optical loss.

The optical member including the display unit obtained by the manufacturing method of the present invention and the optical substrate having the light shielding portion can be incorporated, for example, into an electronic device such as a television, a mini game machine, a mobile phone, or a personal computer.

In the image display device of the present invention, the double-sided adhesive sheet is excellent in flexibility, and has high moisture resistance, heat resistance, and light resistance, and is an air gap of a display device such as a liquid crystal display device, an organic EL display device, or a touch panel type image display device. Useful applications such as fillers.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples.

(Synthesis Example 1)

GI-2000 manufactured by Japan Soda Co., Ltd. as a hydrogenated polybutadiene diol compound in a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature regulating device (Iodine value: 12.2, hydroxyl value: 46.8 mg ‧ KOH/g) 545.99 g (0.23 mol), Exenol 3020 (polypropylene glycol, hydroxyl value: 35.9 mg ‧ KOH/g) manufactured by Asahi Glass Co., Ltd. as a diol compound 7.19 g (0.0023 mol) and 208 g of toluene were stirred until uniform, and the internal temperature was set to 50 °C. Then, 61.35 g (0.28 mol) of isophorone diisocyanate as a polyisocyanate compound was added, and it reacted at 80 ° C until it became the target NCO content. Next, 0.37 g of 4-methoxyphenol as a polymerization inhibitor was added, and the mixture was stirred until uniform, and it was added by Osaka Organic Chemical Industry Co., Ltd. as a (meth) acrylate compound having at least one or more hydroxyl groups. 11.00 g (0.095 mol) of 2-hydroxyethyl acrylate, 0.20 g of tin octylate as an amine esterification reaction catalyst, and reacted at 80 ° C, and when the NCO content is just 0.1% or less, it is used as an end point of the reaction to obtain a polyurethane. Compound (E-1). The weight average molecular weight of the obtained polyurethane compound was 66,700.

(Synthesis Example 2)

GI-2000 manufactured by Japan Soda Co., Ltd. as a hydrogenated polybutadiene diol compound was added to a reactor equipped with a reflux condenser, a stirrer, a thermometer, and a temperature regulating device (iodine value: 12.2, hydroxyl value: 46.8 mg) ‧ KOH / g) 522.50g (0.22mol), Exenol 3020 (polypropylene glycol, hydroxyl value: 35.9mg ‧ KOH / g) manufactured by Asahi Glass Co., Ltd. as a diol compound, 6.88g (0.0022mol), 73.4g of toluene, Stirring was carried out until it became uniform, and the internal temperature was set to 50 °C. Then, 88.9 g (0.40 mol) of isophorone diisocyanate as a polyisocyanate compound was added, and it reacted at 80 ° C until it became the target NCO content. Next, 0.37 g of 4-methoxyphenol as a polymerization inhibitor was added, and the mixture was stirred until uniform, and it was added by Osaka Organic Chemical Industry Co., Ltd. as a (meth) acrylate compound having at least one or more hydroxyl groups. 41.80g (0.36mol) of 2-hydroxyethyl acrylate as an amine esterification catalyst 0.20 g of tin octylate was reacted at 80 ° C, and when the NCO content was just 0.1% or less, the end point of the reaction was obtained to obtain a polyurethane compound (E-2). The weight average molecular weight of the obtained polyurethane compound was 15,000.

(Example 1)

109 parts of E-1 (polyamine compound) of Synthesis Example 1 and 18 parts of Clearon TO-125 (aromatically modified terpene resin) manufactured by Anwara Chemical Co., Ltd., and KIP150 (α-hydroxyketone polymer) manufactured by ESACURE 5 parts were mixed and dissolved in 40 parts of toluene to obtain a resin composition. The resin composition obtained was uniformly applied to a PET film (thickness: 50 μm) treated with a lanthanide release agent by a ruproid coater so that the thickness of the resin composition layer after drying became 100 μm. The mold-removed surface was dried at 120 ° C for 3 minutes, and after drying, the release-treated surface of the PET film treated with the oxime-based release agent was applied to the resin composition layer to obtain the present invention. (Construction: release-treated PET/resin composition layer/release-treatment PET) resin composition sheet.

(Example 2)

100 parts of E-1 (polyamine compound) of Synthesis Example 1, 2 parts of Blemmer LA (lauryl acrylate) manufactured by Nippon Oil Co., Ltd., and Clearon M-105 (Aromatic modified hydrogenated hydrazine) manufactured by Anhara Chemical Co., Ltd. 18 parts of olefin resin, 5 parts of GI-2000 (1,2-hydrogenated polybutadiene diol) manufactured by Japan Soda Co., Ltd., SPEEDCURE TPO (2,4,6-trimethylbenzamide) manufactured by LAMBSON 0.4 parts of bisphenylphosphine oxide and 2 parts of KIP150 (α-hydroxyketone polymer) manufactured by ESACURE were mixed and dissolved in 42 parts of toluene to obtain a resin composition.

The obtained resin composition was applied in the same manner as in Example 1 and dried to obtain a resin composition sheet.

(Example 3)

100 parts of E-1 (polyamine compound) of Synthesis Example 1, 2 parts of Blemmer LA (lauryl acrylate) manufactured by Nippon Oil Co., Ltd., and Clearon M-105 (Aromatic modified hydrogenated hydrazine) manufactured by Anhara Chemical Co., Ltd. 18 parts of olefin resin, 5 parts of polybutene manufactured by Jikun Nippon Mining & Energy Co., Ltd., SPEEDCURE TPO (2,4,6-trimethylbenzoguanidinophenylphosphine oxide) manufactured by LAMBSON 0.4 parts and 2 parts of KIP150 (α-hydroxyketone type polymer) manufactured by ESACURE were mixed and dissolved in 42 parts of toluene to obtain a resin composition.

The obtained resin composition was applied in the same manner as in Example 1 and dried to obtain a resin composition sheet.

(Example 4)

67 parts of E-1 (polyamine ester compound) of Synthesis Example 1, 28 parts of E-2 (polyamine compound) of Synthesis Example 2, 2 parts of Blemmer LA (lauryl acrylate) manufactured by Nippon Oil Co., Ltd., and Anyuan Chemical Co., Ltd. 18 parts of Clearon M-105 (aromatically modified hydrogenated terpene resin) manufactured by the company, 5 parts of GI-2000 (1,2-hydrogenated polybutadiene diol) manufactured by Japan Soda Co., Ltd., SPEEDCURE manufactured by LAMBSON 0.4 parts of TPO (2,4,6-trimethylbenzimidyldiphenylphosphine oxide) and 2 parts of KIP150 (α-hydroxyketone polymer) manufactured by ESACURE were mixed and dissolved in 47 parts of toluene to obtain Resin composition.

The obtained resin composition was applied in the same manner as in Example 1 and dried to obtain a resin composition sheet.

Examples 1 to 4 are shown in Table 1, and the following evaluations were carried out.

[Table 1]

(refractive index measurement)

The resin composition of the present invention via the release-treated PET sheet using a high pressure mercury lamp (120W / cm, ozone free) irradiation integrated light quantity of 3000mJ / cm ² of ultraviolet rays, the resin composition layer is cured.

The refractive index (20 ° C) of the resin layer after hardening was measured by RX-7000CX (manufactured by Ai Co., Ltd.).

(rigid modulus measurement)

The resin composition of the present invention via the release-treated PET sheet using a high pressure mercury lamp (120W / cm, ozone free) irradiation integrated light quantity of 3000mJ / cm ² of ultraviolet rays, the resin composition layer is cured.

The rigid modulus (30 ° C) of the cured resin layer was measured by ARES (TA Instruments).

(transmittance measurement)

The release-treated PET of the resin composition sheet of the present invention was peeled off and bonded to a glass plate having a thickness of 1 mm (constitution: 1 mm glass plate/resin composition layer/1 mm glass plate) to prepare a test piece.

The test piece produced was irradiated with ultraviolet light having a cumulative light amount of 3000 mJ/cm ² through a glass using a high-pressure mercury lamp (120 W/cm, no ozone) to cure the resin composition layer.

The transmittance of the obtained resin-hardened test piece was measured by a spectrophotometer UV-3600 (manufactured by Shimadzu Corporation). As a result, the transmittance at 380 nm to 780 nm was 95% or more.

(Haze measurement)

The release-treated PET of the resin composition sheet of the present invention was peeled off and bonded to a glass plate having a thickness of 1 mm (constitution: 1 mm glass plate/resin composition layer/1 mm glass plate) to prepare a test piece.

The test piece produced was irradiated with ultraviolet light having a cumulative light amount of 3000 mJ/cm ² through a glass using a high-pressure mercury lamp (120 W/cm, no ozone) to cure the resin composition layer.

The haze value of the obtained resin-hardened test piece was measured by a haze meter TC-HIII DPK (manufactured by Tokyo Electrochromic Color Co., Ltd.). As a result, the haze value was 0.5 or less and was relatively transparent.

(close contact test)

The release-treated PET on one side of the resin composition sheet of the present invention was peeled off, bonded to a 100 μm COP film (manufactured by Jen Japan Co., Ltd.), and cut into a strip having a width of 25 mm. The other release-treated PET was peeled off, and one of the cut strip-shaped films was half-attached to the glass plate, and the cumulative light amount was 3000 mJ/cm ² from the glass plate side using a high-pressure mercury lamp (120 W/cm, no ozone). Ultraviolet rays harden the resin composition layer. The obtained resin-hardened test piece was subjected to an adhesion test (180° peeling, peeling speed 300 mm/min) using EZ-Test (manufactured by Shimadzu Corporation).

(durability)

The release-treated PET of the resin composition sheet of the present invention was peeled off and bonded to a glass plate having a thickness of 1 mm (constituting a 1:1 mm glass plate/resin composition layer/1 mm glass plate) to prepare a test piece (constituted 2:1 mm). Glass plate / resin composition layer / polarizing film / acrylic adhesive layer / 1mm glass plate).

The test piece produced was irradiated with ultraviolet light having a cumulative light amount of 3000 mJ/cm ² through a glass using a high-pressure mercury lamp (120 W/cm, no ozone) to cure the resin composition layer.

Using the obtained resin-hardened test piece, a 85 ° C heat resistance test and a 60 ° C 90% RH moisture heat resistance test were performed for 100 hours. As a result, the cured resin test piece after the end of the durability test was visually confirmed, but the peeling from the glass plate and the polarizing film was not observed.

From the above results, it was confirmed that the double-sided adhesive sheet of the image display device of the present invention has high transmittance and a low haze value, and is excellent in adhesion, heat resistance, and moist heat resistance.

The present invention has been described in detail above with reference to the specific embodiments thereof. It is understood that various modifications and changes can be made without departing from the spirit and scope of the invention.

Furthermore, the present application is based on a Japanese patent application filed on June 11, 2014 (2014-120621) and a Japanese patent application filed on June 3, 2015 (2015-112948), the entire contents of which are incorporated by reference. Was cited. Again, all references cited herein are incorporated as a whole.

[Industrial availability]

The double-sided adhesive sheet for an image display device of the present invention is useful as an optical member because of its high transparency, excellent adhesion and durability. Further, the resin group of the present invention The product sheet is useful as an adhesive for bonding a transparent display substrate.

Claims (15)

An image display device uses a double-sided adhesive sheet containing a (meth) acrylate having a polyisoprene skeleton or a butadiene skeleton selected from the group consisting of urethane (meth) acrylate. At least one of a (meth) acrylate (K) and a softener component (G) in a group of (meth) acrylate. An image display device obtained by drying a UV-curable resin composition containing a double-sided adhesive sheet containing an amine ester (meth) acrylate and having a polyisoprene skeleton (A) A (meth) acrylate (K) or a softener component (G) of at least one of a group consisting of an acrylate or a (meth) acrylate having a butadiene skeleton. The image display device according to claim 1 or 2, wherein the (meth) acrylate is an amine ester (meth) acrylate, and the amine ester (meth) acrylate is as follows The polyurethane compound (E) obtained by reacting the compound (A) with the compound (B), the compound (C) and the compound (D), and the compound (A): a hydrogenated polybutadiene polyol compound (B) : Polyisocyanate Compound (C): (meth) acrylate compound (D) having at least one or more hydroxyl groups: a diol compound other than the compound (A). An image display device comprising a double-sided adhesive sheet comprising the polyurethane compound (E) of claim 3, wherein the hydrogenated polybutadiene polyol compound (A) has an iodine value of 20 or less. An image display device using a double-sided adhesive sheet containing the third or fourth item of the patent application scope An amine ester compound (E) in which the polyisocyanate compound (B) is an aliphatic diisocyanate compound. An image display device comprising a double-sided adhesive sheet comprising the polyurethane compound (E) according to any one of claims 3 to 5, wherein the (meth) acrylate compound (C) having at least one or more hydroxyl groups is 2-Hydroxyethyl (meth)acrylate. An image display device comprising a double-sided adhesive sheet comprising the polyurethane compound (E) according to any one of claims 3 to 6, wherein the diol compound (D) other than the compound (A) is a polyether polyol. An image display apparatus comprising a double-sided adhesive sheet comprising the polymerizable compound (F) other than the polyurethane compound (E) and (E) according to any one of claims 1 to 7. The double-sided adhesive sheet for an image display device according to any one of claims 1 to 8, which comprises a hydroxyl group-containing polymer, a terpene resin or both of them as a softener component (G). A cured product obtained by irradiating an active energy ray with a double-sided adhesive sheet of the image display device according to any one of claims 1 to 9. A touch panel is formed by using an adhesive image on both sides of an image display device according to any one of claims 1 to 9. An image display device uses a double-sided adhesive sheet comprising a (meth) acrylate selected from an amine ester (meth) acrylate, a polyisoprene skeleton or a (meth) acrylate having a butadiene skeleton. At least one of (meth) acrylate (K) or softener component (G) in the group. An image display device using a double-sided adhesive sheet containing an amine ester (meth)acrylic acid (meth)acrylate (K), softener of at least one of an ester, a (meth) acrylate having a polyisoprene skeleton or a (meth) acrylate having a butadiene skeleton Ingredient (G) and solvent. A method of manufacturing an image display device, wherein the optical display substrate is pasted by the double-sided adhesive sheet of the image display device according to any one of claims 1 to 9, 12 to 13 by the following steps 1 and 2 The image display device is obtained in combination (step 1), for at least one optical substrate, the image display device with the release film is peeled off from the single-sided release film of the double-sided adhesive sheet, and the double-sided adhesive sheet for the image display device is disposed. Step (Step 2) The step of bonding the other optical substrates by peeling off the remaining single-sided release film of the double-sided adhesive sheet in the image display device disposed in the step 1. A method of manufacturing an image display device, wherein the optical display substrate is attached to the image display device according to any one of claims 1 to 9, 12 to 13 by the following steps 1 to 3; The image display device is obtained in combination (step 1), for at least one optical substrate, the image display device with the release film is peeled off from the single-sided release film of the double-sided adhesive sheet, and the double-sided adhesive sheet for the image display device is disposed. (Step 2) The step of peeling off the remaining single-sided release film of the image display device disposed in the step 1 and bonding the other optical substrates; (Step 3) The optical substrate of the portion is a step of curing the cured layer by irradiating ultraviolet rays on the double-sided adhesive sheet of the image display device in the bonded optical substrate.