KR20140031244A - Active-energy-ray-curable adhesive composition for plastic film or sheet - Google Patents

Abstract

Provided is an active energy ray-curable adhesive composition having low viscosity, excellent curability, excellent adhesion to various plastic films or sheets, particularly hydrophilic plastic films or sheets, and excellent durability.
Active for a plastic film or sheet composed of at least a curable component and a polymerization initiator, wherein the curable component is at least composed of the following (A) component and the following (B) component, and the polymerization initiator is at least composed of the following (C) component: Energy ray curable adhesive composition.
(A) component: The aromatic epoxy compound containing 2 or more epoxy groups in a molecule | numerator.
(B) Component: At least one compound (B1) selected from the group consisting of 4-hydroxybutyl acrylate and 2-hydroxybutyl acrylate and at least one compound (B2) having two or more ethylenically unsaturated groups in the molecule Ethylenically unsaturated compounds.
(C) component: Photo cationic polymerization initiator.

Description

ACTIVE-ENERGY-RAY-CURABLE ADHESIVE COMPOSITION FOR PLASTIC FILM OR SHEET}

The present invention relates to an active energy ray-curable adhesive composition capable of adhering various plastic films or sheets by irradiation of active energy rays such as electron beams or ultraviolet rays, and the composition of the present invention relates to thin layer films such as plastic films or sheets. It is used suitably for adhesion | attachment of a complex, and is used suitably for manufacture of various optical films or sheets used for a liquid crystal display element, etc., and can be compatible in these technical fields.

In addition, in this specification, an methacrylate and / or a methacrylate are (meth) acrylate, an acryloyl group, and / or a methacryloyl group (meth) acryloyl group, acrylic acid, and / or methacrylic acid (meth) Represented by acrylic acid.

In addition, below, when it is not necessary to specify in particular, the plastic film or sheet | seat is collectively represented by "plastic film etc.", and a film or sheet is collectively represented by "film etc.".

Conventionally, in the lamination method which joins thin layer adherends, such as a plastic film, or thin layer adherends, such as a plastic film, and other materials, the solvent type adhesive agent containing an ethylene-vinyl acetate copolymer and a polyurethane-type polymer After apply | coating a composition to a 1st thin layer adherend, and drying, the dry lamination method which crimps | bonds a 2nd thin layer adherend with a nip roller etc. to this is mainly performed.

The adhesive composition used in this method generally contains a large amount of solvent in order to make the coating amount of the composition uniform. However, a large amount of solvent vapor is volatilized during drying, which causes problems of toxicity, work safety and environmental pollution. It is becoming. Moreover, the said adhesive composition has a problem that thin-layer adherends peel off in post-processing processes, such as a heat seal for adhering the obtained laminate film, and a ruled line process which lays out a groove, immediately after bonding a thin layer adherend. have.

As an adhesive composition which solves these problems, the solvent-free adhesive composition is examined.

As a solvent-free adhesive composition, the adhesive composition hardened | cured by the two-component adhesive composition and active energy rays, such as an ultraviolet-ray or an electron beam, is widely used.

As a two-component adhesive composition, what is called a polyurethane adhesive composition mainly uses the polymer which has a hydroxyl group at the terminal, and uses the polyisocyanate compound which has an isocyanate group at the terminal as a hardening | curing agent. However, the said composition has the drawback that it requires a long time for hardening, and for this reason, there exists a problem in productivity, such as being unable to enter post-processing processes, such as a ruled line process, immediately after joining a thin layer to-be-adhered body.

On the other hand, since an active energy ray hardening-type adhesive composition has a high hardening rate, it is excellent in productivity and attracts attention in recent years.

On the other hand, liquid crystal display devices are being spread to word processors, PC screens, and television receivers from small electronic devices such as automobile navigation systems, mobile phones, and PDAs due to features such as thinness, light weight, and power consumption. .

In recent years, an active energy ray hardening-type adhesive agent is used also for bonding of various optical films used for the said liquid crystal display element.

Examples of the optical film include polarizing plates, retardation films, viewing angle compensation films, brightness enhancement films, antireflection films, antiglare films, lens sheets, and diffusion sheets, and various kinds of plastics are used for these.

Among these plastics, polyvinyl alcohol and triacetyl cellulose are mentioned as being particularly used as a polarizing plate. These plastics contain hydroxyl groups, and have a feature of being extremely hydrophilic as compared with ordinary plastics.

As an active energy ray hardening-type adhesive composition for polarizing plates, the photoradical polymerization type composition using photoradical polymerization, the photocationic polymerization type composition using photocationic polymerization, and the hybrid composition which used photoradical polymerization and photocationic polymerization together are known.

As a radical photopolymerizable composition, the composition (patent document 1) etc. which contain the radically polymerizable compound containing polar groups, such as a hydroxyl group and a carboxyl group, and the radically polymerizable compound which does not contain a polar group in a specific ratio are known.

However, the composition had a large shrinkage upon curing, and it was difficult to obtain sufficient peel strength by generating stress at the interface depending on the type of adherend.

Moreover, in order to solve this problem, the composition containing urethane (meth) acrylate with a large molecular weight is examined (for example, patent document 2 etc.).

However, since the said viscosity increased, the said composition had a problem of being unable to coat thin film with a coating apparatus. In addition, although the shrinkage stress at the time of curing can be alleviated by improving the flexibility of the adhesive composition, since such a means lowers the heat resistance and water resistance of the adhesive, a defect such as peeling, foaming or cracking is required in applications requiring strict durability. There was a problem that this occurred.

As a photocationic polymerization type composition, the composition (patent document 3) which has an epoxy resin which does not contain an aromatic ring as a main component, and the composition (patent document 4) containing an aliphatic epoxy, an alicyclic epoxy, and / or oxetane are known.

The said composition has the advantage that the generation | occurrence | production of the stress at an interface can be suppressed because shrinkage at the time of hardening is comparatively small with respect to an optical radical polymerization type composition.

However, photocationic polymerization is generally known to cause polymerization inhibition by moisture or a basic substance, and it is difficult to obtain sufficient peel strength in a high humidity environment, a substrate containing a lot of moisture, and a substrate having a basic surface. did. Moreover, although it is possible to make small the influence of the curability fall by superposition | polymerization inhibition by making it the composition containing a polyfunctional epoxy resin as a main component, such a composition raises a viscosity and cannot apply thin film coating by a coating apparatus, etc. Was to have a problem.

As a hybrid composition, it has a (meth) acrylate which has an isocyanol ring skeleton, an alicyclic epoxy compound, the compound containing a hydroxyl group, and the composition containing a photo-acid generator (patent document 5), and two or more epoxy groups, Among these groups The composition containing the epoxy resin which is at least 1 alicyclic epoxy group, the epoxy resin which has 2 or more epoxy groups, and does not have an alicyclic epoxy group, a photocationic polymerization initiator, and a polymerizable monomer (patent document 6), and a (meth) acryl group The composition (patent document 7) containing the compound which has two or more, the compound which has a hydroxyl group and one (meth) acryl group, the cationically polymerizable compound which has a (meth) acryl group, an optical radical polymerization initiator, and a photocationic polymerization initiator, etc. are known. .

Although these compositions are said to solve the problems of shrinkage during curing and polymerization inhibition by moisture by hybridization, the inventors have found that there are problems shown below.

The composition disclosed in Patent Literature 5 includes a (meth) acrylate compound having an isocyanuryl ring skeleton as an essential component, but according to a study by the present inventor, the above-mentioned (meth) having two or more (meth) acryloyl groups When a large amount of acrylate is included in the composition, the shrinkage at the time of curing does not become so small, so that the generation of stress at the interface cannot be suppressed. Therefore, it is found that it is difficult to obtain sufficient peel strength from the substrate.

Although the composition disclosed by patent document 6 contains a hybridized composition as a concept, the composition disclosed by the Example is only the composition comprised only with a photocationic polymerizable monomer, and does not disclose a hybridized composition specifically.

The composition disclosed in Patent Literature 7 contains a cationically polymerizable compound having a (meth) acryl group as an essential component in a specific ratio, but according to the inventors' inventors, when a large amount of the compound is included in the composition, shrinkage upon curing is Since it does not become very small, it cannot prove that stress generation in an interface cannot be suppressed, and it turned out that it is difficult to obtain sufficient peeling strength also by a base material.

Japanese Patent Application Laid-Open No. 2008-009329 (claims) Japanese Patent Publication No. 2007-177169 (claims) Japanese Patent Application Laid-Open No. 2004-245925 (claims) Japanese Patent Publication No. 2008-134384 (claims) Japanese Patent Application Laid-Open No. 2008-233279 (claims) Japanese Patent Application Laid-Open No. 2008-257199 (claims) Japanese Patent Publication No. 2008-260879 (claims)

According to the inventors' investigation, when using the photocationic polymerization type composition containing an epoxy resin etc. as an adhesive agent, in addition to the said problem, the reaction advances and hardens | cures even after completion | finish of active energy ray irradiation is said to be called what is called a dark reaction. Since development advances, defects may arise depending on a use. For example, when manufacturing a laminated body using the composition of this invention for adhesion of a film-form base material, when winding up a film laminated body after irradiating an active energy ray, a dark reaction will progress and a wound shape will remain as it is, There existed a problem that marks, such as a wave and a scar of a film, were easy to generate | occur | produce.

The present invention has been made in view of the above problems, and has excellent curing properties at low viscosity, excellent adhesion to various plastic films and the like, especially hydrophilic plastic films, and the like, and durability is required even under strict conditions such as high temperature and high humidity conditions. It is an object of the present invention to provide an active energy ray-curable adhesive composition for a plastic film or sheet that exhibits sufficient performance and does not have a problem such as a wave of a film due to a dark reaction.

As a result of various studies, the inventors have found that, as a curable component, any one or both of an aromatic epoxy compound containing two or more epoxy groups in a molecule, 4-hydroxybutyl acrylate and 2-hydroxybutyl acrylate and two in the molecule The active energy ray-curable adhesive composition containing the compound having the above ethylenically unsaturated group and including the photocationic polymerization initiator as the polymerization initiator has excellent adhesion to various plastic films, especially hydrophilic plastic films and the like, and is low in viscosity. The present invention has been found to have sufficient performance even in applications requiring strict durability.

Moreover, according to the adhesive composition of this invention, the laminated body formed by laminating | stacking the base material, the hardened | cured material layer of the composition of any one of Claims 1-5, and the film or sheet made from plastics in this order, and the polyvinyl alcohol-type polarizer film Or the polarizing plate etc. which laminate | stack a sheet | seat, the hardened | cured material layer of the composition of any one of Claims 1-5, and a film or sheet made of plastics in this order are obtained.

Hereinafter, the present invention will be described in detail.

(Effects of the Invention)

Since the composition of this invention uses a specific epoxy compound and a specific ethylenically unsaturated compound as a curable component, and it can harden | cure this at least with a photocationic polymerization initiator, it is excellent in coatability at low viscosity, and especially various plastic films, etc. It is possible to maintain high reliability with respect to hydrophilic plastic films even under high temperature and high humidity conditions, and there is no problem such as wave of the film due to dark reaction, and is effective for adhesion of thin layer adherends such as various plastic films. It can use suitably for manufacture of the optical film used for etc.

The present invention is at least composed of a curable component and a polymerization initiator, wherein the curable component is at least composed of the following (A) component and the following (B) component, and the plastic film or sheet having the polymerization initiator at least composed of the following (C) component. It relates to an active energy ray curable adhesive composition.

(A) component: The aromatic epoxy compound containing two or more epoxy groups in a molecule | numerator (preferably, 10-80 weight% is contained in 100 weight% of curable components whole quantity).

(B) Component: At least one compound (B1) selected from the group consisting of 4-hydroxybutyl acrylate and 2-hydroxybutyl acrylate, and at least one compound (B2) having two or more ethylenically unsaturated groups in a molecule thereof. Composed ethylenically unsaturated compounds.

(C) component: The photocationic polymerization initiator (preferably 0.1-20 weight part is contained with respect to 100 weight part of curable components whole quantity).

Hereinafter, (A)-(C) component which is an essential component of a composition is demonstrated.

1. (A) Component

(A) component is an aromatic epoxy compound containing 2 or more epoxy groups in a molecule | numerator. Here, an aromatic epoxy compound is a compound which has an aromatic ring skeleton which has an epoxy group.

Examples of the component (A) include diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of bisphenol S, diglycidyl ether of brominated bisphenol A, and diglycides of brominated bisphenol F. Bisphenol-type epoxy resins, such as a dil ether, the diglycidyl ether of brominated bisphenol S, the bisphenol A diglycidyl ether, the bisphenol fluorene, or the di or polyglycidyl ether of its alkylene oxide adduct; Novolak-type epoxy resins, such as a phenol novolak-type epoxy resin, a cresol novolak-type epoxy resin, a brominated phenol novolak-type epoxy resin, a brominated cresol novolak-type epoxy resin, and a dicyclopentadiene phenol novolak-type epoxy resin; Naphthalene type epoxy resin; Alkyl diphenol type epoxy resins; Naphthol type epoxy resins; Biphenyl type epoxy resins; Hydroxydiglycidyl ether; Resorcin diglycidyl ether; Terephthalic acid diglycidyl ether; Phthalic acid diglycidyl ether; Epoxides of styrene-butadiene copolymers; Epoxides of styrene-isoprene copolymers; Addition reactant of terminal carboxylic acid polybutadiene and bisphenol A epoxy resin; N, N, N ', N'- tetraglycidyl-m-xylenediamine, etc. are mentioned.

In addition, two other documents, "Epoxy Resin-Recent Advancement" (Shokodo Co., Ltd.), issued in 1990, are also available. And the compounds described on pages 4 to 6, pages 9 to 16, and pages 29 to 55 of the year).

Here, an epoxy resin means the compound or polymer which has an average of 2 or more epoxy groups in a molecule | numerator, and hardens | cures by reaction. According to the practice in this field, as long as it is a compound which has 2 or more of curable epoxy groups in a molecule | numerator, even if it is a monomer, it may be called an epoxy resin.

As aromatic epoxy compounds other than these, Epicoat 5050, 5051, 1031S, 1032H60, 604, 630, 871, 872, 191P, YX310, 545, YL6810, YX8800, YL980 [above, Japan Eposy Resin Co., Ltd. Production].

As (A) component, bisphenol-type epoxy resin is preferable also in said compound, More preferably, it is the diglycidyl ether of bisphenol A.

As (A) component, using only 1 type of said compound can also use 2 or more types together.

The ratio of the component (A) and the component (B) described later in the curable component is 10 to 80% by weight of the component (A) and 20 to 90% by weight of the component (B), more preferably in 100% by weight of the curable component. 20 to 70 weight% of (A) component and 30 to 80 weight% of (B) component, More preferably, it is 30 to 60 weight% of (A) component, and 40 to 70 weight% of (B) component. . By setting the ratio of the component (A) to 10% by weight or more, the cured product is excellent in heat resistance and water resistance, and by using 80% by weight or less, the composition becomes low in viscosity and is excellent in coating property, and the cured product is excellent in adhesive force. do.

2. (B) Component

(B) component is an ethylenically unsaturated compound and is comprised at least from (B1) component and (B2) component.

According to the component (B1) of the present invention, the composition can be made low in viscosity and excellent in adhesiveness, water resistance and curability. The proportion of the component (B1) is preferably 10 to 50% by weight, more preferably 20 to 40% by weight in 100% by weight of the curable component.

By setting the ratio of the component (B1) to 10% by weight or more, the adhesive strength and curability can be improved, and by setting it to 50% by weight or less, it is possible to prevent the water resistance of the composition from being lowered.

As described above, the component (B1) is composed of one or both of 4-hydroxybutyl acrylate and 2-hydroxybutyl acrylate.

By the component (B2) of the present invention, even after the completion of the active energy ray irradiation, the reaction of the component (A) proceeds and cures, so that the above-described defects by the so-called dark reaction, specifically used for adhesion of the film-like substrate When manufacturing a laminated body, when a film laminated body is wound up after irradiation with active energy ray, the problem that the dark reaction advances and the shape wound up as it is is left, or the marks, such as a wave and a mark of a film, are easy to be solved can be solved. Moreover, heat resistance also improves because a crosslinking density becomes high.

As a (B2) component, 1, 4- butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6- hexanediol di (meth) acrylate, 3-methyl- 1, 5- pentanediol Di (meth) acrylate, 2-butyl-2-ethyl-1,3-nonanedioldiacrylate, 2-methyl-1,8-octanedioldi (meth) acrylate, 2-hydroxy-1,3 -Di (meth) acryloyloxy propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate Polyol poly (meth) acrylates;

Di (meth) acrylate of neopentyl glycol alkylene oxide adduct, di (meth) acrylate of 1,6-hexanediolalkylene oxide adduct, tri (meth) acrylate of alkylene oxide adduct of glycerin, trimethylolpropane Poly (meth) acrylates of alkylene oxide adducts of polyols such as tri (meth) acrylates of alkylene oxide adducts and tri (meth) acrylates of pentaerythritolalkylene oxide adducts;

Glycol modified polyol poly (meth) acrylates such as neopentyl glycol modified trimethylolpropanedi (meth) acrylate;

Caprolactone-modified polyol poly (meth) acrylates such as caprolactone-modified dipentaerythritol hexa (meth) acrylate;

Alkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate and tetramethylene glycoldi (meth) acrylate;

Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate;

Di (meth) acrylates of alicyclic diols such as tricyclodecanedimethylol di (meth) acrylate and dicyclopentanyldi (meth) acrylate;

Bisphenol-type compound alkylene oxide addition, such as the di (meth) acrylate of a bisphenol A alkylene oxide adduct, the di (meth) acrylate of a bisphenol F alkylene oxide adduct, and the di (meth) acrylate of a bisphenol S alkylene oxide adduct Di (meth) acrylate of water;

Di (meth) acrylates of hydrogenated bisphenol compounds such as di (meth) acrylate of alkylene oxide adducts of hydrogenated bisphenol A and di (meth) acrylate of alkylene oxide adducts of hydrogenated bisphenol F;

Poly of isocyanuric acid, such as the di (meth) acrylate of the alkylene oxide adduct of isocyanuric acid, the tri (meth) acrylate of the alkylene oxide adduct of isocyanuric acid, and the tri (meth) acrylate of the caprolactone adduct of isocyanuric acid (Meth) acrylates;

Di (meth) acrylates of ester diols such as neopentyl glycol hydroxy pivalic acid di (meth) acrylate and hydroxy pivalic acid neopentyl glycol di (meth) acrylate;

Di (meth) acrylates of caprolactone-modified ester diols such as caprolactone-modified neopentyl glycol hydroxy pivalic acid di (meth) acrylate;

Fatty acid-modified dipentaerythritol penta (meth) acrylate and fatty acid-modified dipentaerythritol tetra (meth) acrylate obtained by reacting a polyol with (meth) acrylic acid and a fatty acid having 2 to 4 carbon atoms;

Triacrylic formal; And

Aromatic polyfunctional (meth) acrylates, such as trimethylolpropane (meth) acrylic-acid benzoic acid ester, oxol EA-0200, 0500, 1000 (fluorene acrylate, the Osaka Gas Chemicla Coporation);

Examples of the alkylene oxide adducts mentioned above include ethylene oxide adducts and propylene oxide adducts.

Moreover, as an oligomer which can be used as (B2) component, polyester (meth) acrylate, epoxy (meth) acrylate, polyether (meth) acrylate, etc. are mentioned. In addition, although these oligomers are compounds which have two (meth) acryloyl groups, it describes only (meth) acrylate unless specifically mentioned according to the conventional practice.

As polyester (meth) acrylate, the dehydration condensate of polyester polyol and (meth) acrylic acid, etc. are mentioned.

Here, examples of the polyester polyols include reactants of polyols with carboxylic acids or anhydrides thereof.

Examples of the polyol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butylene glycol, polybutylene glycol, tetramethylene glycol, and hexamethylene Low molecular weight polyols, such as glycol, neopentyl glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, trimethylolpropane, glycerin, pentaerythritol and dipentaerythritol, and these Alkylene oxide adducts and the like.

Carboxylic acids or their anhydrides include dibasic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, adipic acid, succinic acid, fumaric acid, maleic acid, hexahydrophthalic acid, tetrahydrophthalic acid and trimellitic acid, or anhydrides thereof. do.

As polyester poly (meth) acrylates other than these, the compound etc. which are described in pages 74-76 of the said document "UV, EB hardening material" are mentioned.

Epoxy (meth) acrylate is a compound which (meth) acrylic acid was added and reacted with an epoxy resin, and the compound etc. which are described on pages 74-75 of the said "UV, EB hardening material" are mentioned.

Examples of the epoxy resins include aromatic epoxy resins and aliphatic epoxy resins.

Specifically as an aromatic epoxy resin, resorcinol diglycidyl ether; Di or polyglycidyl ethers of bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene or alkylene oxide adducts thereof; Novolak type epoxy resins such as phenol novolak type epoxy resin and cresol novolak type epoxy resin; Glycidyl phthalimide; o-phthalic acid diglycidyl ester and the like.

In addition to these, two documents, "Epoxy Resin-Recent Advances" (issued in Shokodo Co., Ltd. 1990), and the separate document "Polymer Processing", Volume 9, Vol. 22, Extra-Nursing Epoxy Resin [Polymer Publication, 1973] The compound described in pages 4-6 and 9-16 is mentioned.

Specific examples of the aliphatic epoxy resins include diglycidyl ethers of alkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, and 1,6-hexanediol; Diglycidyl ethers of polyalkylene glycols such as diglycidyl ether of polyethylene glycol and polypropylene glycol; Diglycidyl ether of neopentyl glycol, dibromoneopentyl glycol and alkylene oxide adduct thereof; Di or triglycidyl ethers of trimethylolethane, trimethylolpropane, glycerin and its alkylene oxide adducts, and polyhydric alcohols such as di, tri or tetraglycidyl ethers of pentaerythritol and their alkylene oxide adducts Glycidyl ethers; Di or polyglycidyl ethers of hydrogenated bisphenol A and its alkylene oxide adducts; Tetrahydrophthalic acid diglycidyl ether; Hydroquinone diglycidyl ether and the like.

In addition to these, the compound described in pages 3-6 of the said "polymer processing" annex epoxy resin is mentioned.

In addition to these aromatic epoxy resins and aliphatic epoxy resins, epoxy compounds having a triazine nucleus in the skeleton, such as TEPIC [Nissan Chemical Industries, Ltd.], Denacol EX-310 [Nagase Co., Ltd.], and the like are listed, Furthermore, the compound as described in the said "polymer processing" annex epoxy resin of page 289-296 is mentioned.

In the above, as the alkylene oxide of the alkylene oxide adduct, ethylene oxide, propylene oxide and the like are preferable.

Examples of polyether (meth) acrylate oligomers include polyalkylene glycol di (meth) acrylates, and polyethylene glycol di (meth) acrylates, polypropylene glycol di (meth) acrylates, and polytetramethylene glycol di (meth) acrylates. Rates and the like.

As a polymer which can be used as (B2) component, the (meth) acryloyl group which has a (meth) acryloyloxy group, the (meth) acryloyl group was introduce | transduced as a side chain into the (meth) acrylic-type polymer which has a functional group, The said document The compound as described in pages 78-79 of "UV / EB hardening material", etc. are mentioned.

(B2) As an alkylene oxide modified product of polyalkylene glycol di (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, and bisphenol A as a component (B2) from the point which improves prevention of the defect by a dark reaction and improves heat resistance. Di (meth) acrylate, alkylene oxide modified substance of bisphenol F Di (meth) acrylate, alkylene oxide modified substance triacrylate of isocyanuric acid are preferable. Polyalkylene glycol di (meth) acrylate and the alkylene oxide modified triacrylate of isocyanuric acid are especially preferable at the point which can maintain adhesive force with a hydrophilic plastic.

The proportion of the component (B2) is preferably 0.5 to 40% by weight, more preferably 1 to 30% by weight in 100% by weight of the curable component.

By setting the ratio of the component (B2) to 0.5% by weight or more, it is possible to prevent the failure due to the dark reaction and to improve the heat resistance, and by setting it to 40% by weight or less, the shrinkage of the composition can be suppressed and the adhesive strength can be excellent.

As (B) component other than (B1) component and (B2) component, the compound which has one ethylenically unsaturated group in molecule other than (B1) component, for example, the compound which has one ethylenically unsaturated group and hydroxyl group in a molecule | numerator, molecule Compounds having an aromatic ring skeleton or alicyclic skeleton containing one ethylenically unsaturated group in them, vinyl-based compounds and allyl compounds, (meth) acrylamide compounds, aliphatic (meth) acrylates, carboxylic acid-containing (meth) acrylates , Phosphoric acid (meth) acrylate, and the like.

As a compound which has one ethylenically unsaturated group and a hydroxyl group in molecules other than (B1) component, the (meth) acrylate which has one hydroxyl group is preferable. Specifically, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexane dimethanol monoacrylate, (meth) acrylic acid adduct of cyclohexene oxide, polyethylene glycol mono (meth) Acrylate, polypropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, polyethylene glycol-polypropylene glycol mono (meth) acrylate, polyethylene glycol-polytetramethylene glycol mono (meth) acrylate , Polypropylene glycol-polytetramethylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-butoxypropyl (meth) acrylate, 2- (Meth) acryloyloxyethyl-2-hydroxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, etc. are mentioned.

Among them, a compound having a molecular weight of less than 300 is preferable in order to make the composition low viscosity and excellent in adhesiveness. As a compound which satisfy | fills the said molecular weight, the (meth) acrylic acid addition product of 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, cyclohexane dimethanol monoacrylate, and cyclohexene oxide, for example. , 2-hydroxy-3-phenoxypropyl (meth) acrylate, and the like.

A compound having an aromatic ring skeleton or an alicyclic skeleton containing one ethylenically unsaturated group in a molecule is preferable because the composition has a low viscosity and excellent heat resistance and adhesion. Specifically, alicyclic (meth) acrylate, aromatic (meth) acrylate, and imide (meth) acrylate are mentioned.

As alicyclic (meth) acrylate, isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 4-butylcyclohexyl ( Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecane (meth) acrylate , Dicyclopentenyloxyethyl (meth) acrylate, and the like.

As aromatic (meth) acrylate, (meth) acryl of phenyl (meth) acrylate, (meth) acrylate of phenol derivative, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, and alkylene oxide modified product of phenol Of the (meth) acrylate of the alkylene oxide modified product of the acrylate, the cresol, the (meth) acrylate of the alkylene oxide modified product of the p-cumylphenol, the (meth) acrylate of the alkylene oxide modified product of the nonylphenol, and the o-phenylphenol (Meth) acrylate of alkylene oxide modified product, (meth) acrylate of alkylene oxide modified product of p-phenylphenol, (meth) acrylate of alkylene oxide modified product of tribromophenol, neopentyl glycol (meth) acrylic acid Benzoic acid esters and the like.

As imide (meth) acrylate, N- (meth) acryloyloxyethyl hexahydrophthalimide, 2- (1,2-cyclohexa-1- enedicarboxyimide) ethyl (meth) acrylate, and pancrylic FA -502A (manufactured by Hitachi Chemical Co., Ltd.) and the like.

Among these, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and dicyclopentenyl (meth) acrylic acid are considered to be able to make heat resistance and adhesive force high. (Meth) acrylate, N- (meth) acrylic acid of alkylene oxide modified product of ethylene, dicyclopentenyloxyethyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenol Monooxyethyl hexahydrophthalimide, 2- (1,2-cyclohexa-1-enedicarboxyimide) ethyl (meth) acrylate, and the like are preferable.

Examples of the vinyl compound include monofunctional vinyl compounds such as styrene, vinyltoluene, N-vinylpyrrolidone, N-vinyl caprolactam, vinylimidazole, and vinylpyridine, and polyfunctional vinyl compounds such as divinylbenzene.

As an allyl compound, polyfunctional allyl compounds, such as monofunctional allyl compound, such as allyl alcohol, diallyl phthalate, triallyl isocyanurate, and triallyl cyanurate, are mentioned.

As (meth) acrylamide compound, diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N, N- dimethyl (meth) acrylamide, t-octyl (meth) acrylamide, N, N-diethyl (Meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, (meth) acryloyl morpholine, acrylamide-2-methylpropanesulfonic acid, N-isopropyl (meth) acrylamide, etc. are mentioned. .

As a specific example of aliphatic (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acryl Rate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl ( Meth) acrylate, iso octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) Acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, alkyl (meth) acrylate having 12 to 13 carbon atoms, cetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl ( Meta) acrylic , Isomyristyl (meth) acrylate, methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethylcarbitol (meth) acrylate, 2-ethylhexylcarbitol (meth) acrylic Ethoxyethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, ethoxyethyl (meth) acrylate , Methoxytriethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylic Late, 7-amino-3, 7-dimethyloctyl (meth) acrylate, and the like.

Examples of the carboxylic acid-containing (meth) acrylates include (meth) acrylic acid, (meth) acrylic acid dimer, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, and 2- (meth) Carboxylic acid containing (meth) acrylates, such as acryloyloxyethyl hexahydrophthalic acid and (omega) -carboxypolycaprolactone (meth) acrylate, are mentioned.

2- (meth) acryloyloxyethyl acid phosphate etc. are mentioned as phosphoric acid (meth) acrylate.

In addition to these, as the (B) components other than the (B1) component and the (B2) component, the compounds described on pages 53 to 56 of the document "Latest UV Curing Technology" (Printing Association of Japan, 1991) Listed.

The ratio of (B) component other than (B1) component and (B2) component becomes like this. Preferably it is 0-40 weight%, More preferably, it is 0-30 weight% in 100 weight% of curable components whole quantity. When this ratio is higher than 40 weight%, the effect of this invention may not fully be exhibited.

3. (C) component

(C) component is a photocationic polymerization initiator. That is, it is a compound which generate | occur | produces a cation or Lewis acid and a radical by irradiation of an active energy ray, and starts superposition | polymerization of (A) component which is a photocationic polymerizable compound and (B) component which is an optical radical polymerizable compound.

Specific examples of the component (C) include sulfonium salts, iodonium salts, diazonium salts, and the like.

As an example of a sulfonium salt, for example

Triphenylsulfonium hexafluorophosphate,

Triphenylsulfonium hexafluoroantimonate,

Triphenylsulfonium tetrakis (pentafluorophenyl) borate,

Diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate,

Diphenyl-4- (phenylthio) phenylsulfonium hexafluoroantimonate,

4,4'-bis [diphenylsulfonio] diphenylsulfidebishexafluorophosphate,

4,4'-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenylsulfidebishexafluoroantimonate,

4,4'-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenylsulfidebishexafluorophosphate,

7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthonehexafluoroantimonate,

7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthonetetrakis (pentafluorophenyl) borate,

4-phenylcarbonyl-4'-diphenylsulfonio-diphenylsulphidehexafluorophosphate,

4- (p-tert-butylphenylcarbonyl) -4'-diphenylsulfonio-diphenylsulfide hexafluoroantimonate,

Triarylsulfonium salts, such as 4- (p-tert- butylphenylcarbonyl) -4'-di (p-toluyl) sulfonio- diphenyl sulfide tetrakis (pentafluorophenyl) borate, are mentioned.

As an example of iodonium salt, for example

Diphenyl iodonium tetrakis (pentafluorophenyl) borate

Diphenyl iodonium hexafluorophosphate,

Diphenyl iodonium hexafluoroantimonate,

Di (4-t-butylphenyl) iodonium hexafluorophosphate,

Di (4-t-butylphenyl) iodonium hexafluoroantimonate,

Tolyl cumyl iodonium tetrakis (pentafluorophenyl) borate,

Iodonium (4-methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophosphate,

Di (4-nonylphenyl) iodonium hexafluorophosphate,

Diaryl iodonium salts, such as di (4-alkylphenyl) iodonium hexafluorophosphate, are mentioned.

As examples of the diazonium salt, for example,

Benzenediazonium hexafluoroantimonate,

Benzenediazonium hexafluorophosphate and the like.

As a commercial item of (C) component, it is adeka optomer SP-100, 150, 152, 170, 172 [made by ADEKA Corporation], the photoinitiator 2074 (made by Rhodia), Kayarard PCI-220, 620 [Nippon Kayaku Co., Ltd . Production], Ilgacure 250 (manufactured by Chiba Japan Ltd.), CPI-100P, 101A, 200K, 210S (manufactured by San-Apro Ltd.), WPI-113, 116 (manufactured by Wako Pure Chemicals Co., Ltd.), BBI-102, BBI-103, TPS-102, TPS-103, DTS-102, DTS-103 [Midoro Kagaku Co., Ltd. Production].

Among these, the triarylsulfonium salt and the diaryl iodonium salt are preferable from the reason of being excellent in active energy ray hardenability, the cured film having excellent water resistance, and no coloring, and in particular, the diaryl iodonium salt is particularly excellent in curability. desirable.

As the triarylsulfonium salt, triphenylsulfonium hexafluoro phosphate and diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate are preferable among the above. Examples of the diaryl iodonium salt include tolyl cumyl iodonium tetrakis (pentafluorophenyl) borate (photoinitiator 2074; manufactured by Rhodia Japan), diphenyl iodonium hexafluorophosphate, and iodonium (4-methylphenyl) [ 4- (2-methylpropyl) phenyl] -hexafluorophosphate (monocure 250; manufactured by BASF Japan Ltd.), di (4-t-butylphenyl) iodonium hexafluorophosphate and WPI-113 (Wako Pure Chemicals Co., Ltd.) is preferred.

As (C) component, said compound may be used individually or 2 or more types may be used.

The proportion of the component (C) is preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, still more preferably 2 to 7 parts by weight based on 100 parts by weight of the curable component. By setting the ratio of the component (C) to 0.1 parts by weight or more, the active energy ray curability of the composition may be sufficient and excellent in adhesiveness. On the other hand, by setting it as 20 parts by weight or less, the internal curing properties of the adhesive layer may be good. It can be made excellent in adhesiveness.

In addition, in use of (C) component, in order to improve the photodegradation efficiency of (C) component, you may use together a sensitizer, and these are also included as (C) component.

Examples of the sensitizer include anthracene compounds, 4-methoxy-1-naphthol, fluorene, pyrene, stilbene and the like.

As an anthracene compound, for example, anthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxycanthracene, 2-ethyl-9,10-dimethoxyanthracene, 2-ethyl- 9,10-diethoxyanthracene, 2-ethyl-9,10-dipropoxycanthracene, 4'-nitrobenzyl-9,10-dimethoxyanthracene-2-sulfonate, 4'-nitrobenzyl-9,10- Diethoxyanthracene-2-sulfonate, 4'-nitrobenzyl-9,10-dipropoxycanthracene-2-sulfonate, and the like.

Among these, 9,10- dimethoxy anthracene, 9,10- diethoxy anthracene, and 9,10-dipropoxy anthracene are preferable from the point which the solubility to a composition is excellent and the sensitization effect of (C) component is high. .

Commercially available products of these sensitizers include anthracure UVS-1331, 1221, 1101, and ET-2111 [KAWASAKI KASEI CHEMICALS. Production] is enumerated.

The proportion of the sensitizer is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight based on 100 parts by weight of the curable component.

It is preferable to use an anthracene compound together as a sensitizer when the ultraviolet absorption of the plastic which is a to-be-adhered body is large and a sulfonium salt is used as (C) component.

4. (D) component

(D) component is an optical radical polymerization initiator. The polymerization initiator of this invention may contain the said (D) component as desired other than the said (C) component.

(D) component is a compound which generate | occur | produces a radical by irradiation of an active energy ray, and starts superposition | polymerization of (B) component which is a compound which has an ethylenically unsaturated group. Moreover, depending on the kind of (D) component, it may function as a sensitizer which accelerates photolysis of (C) component.

Specific examples of the component (D) are benzyl dimethyl ketal, benzyl, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexylphenyl ketone, and 2-hydroxy-2-methyl -1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, oligo [2-hydroxy -2-methyl-1- [4-1- (methylvinyl) phenyl] propanone, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -Phenyl} -2-methylpropan-1-one, 2-methyl-1- [4- (methylthio)] phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one Aromatic ketone compounds such as adeka optomer N-1414 (manufactured by Asahi denka), phenylglyoxylic acid methyl ester, ethylanthraquinone and phenanthrenequinone;

Benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 4- (methylphenylthio) phenylphenylmethane, methyl-2 -Benzophenone, 1- [4- (4-benzoylphenylsulfanyl) phenyl] -2-methyl-2- (4-methylphenylsulfonyl) propan-1-one, 4,4'-bis (dimethylamino) benzo Phenone, 4,4'-bis (diethylamino) benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone, N, N'-tetraethyl-4,4'-diaminobenzo Benzophenone compounds such as phenone and 4-methoxy-4'-dimethylaminobenzophenone;

Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl- (2,4,6-trimethylbenzoyl) phenylphosphinate and bis ( Acylphosphine oxide compounds such as 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide;

Thioxanthone, 2-chlorothioxanthone, 2,4-diethyl thioxanthone, isopropyl thioxanthone, 1-chloro-4-propyl thioxanthone, 3- [3,4-dimethyl-9-oxo Thioxanthone compounds such as -9H- thioxanthone-2-yl] oxy] -2-hydroxypropyl-N, N, N-trimethylammonium chloride and fluorothioxanthone;

Acridon compounds such as acridon and 10-butyl-2-chloroacridone;

1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3 Oxime esters such as -yl] -1- (O-acetyl oxime), 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4, 5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-phenylimidazole dimer, 2- (o-methoxyphenyl) -4,5- Diphenyl imidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer And 2,4,5-triarylimidazole dimers such as 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer; And

Acridine derivatives, such as 9-phenylacridine and 1,7-bis (9,9'-acridinyl) heptane, etc. are mentioned.

Among these, a thioxanthone type compound is preferable because it has a high sensitizing effect of (C) component. Among the thioxanthone compounds, 2,4-diethyl thioxanthone and isopropyl thioxanthone are more preferable because of excellent active energy ray curability and small coloring of the cured film.

As (D) component, said compound may be used independently, or 2 or more types may be used.

The proportion of the component (D) is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the curable component. By setting the ratio of the component (D) to 0.1 part by weight or more, the active energy ray curability of the composition may be sufficient, and the adhesiveness may be excellent. On the other hand, the content of 10 parts by weight or less may improve the internal curing property of the adhesive layer, thereby making the adhesiveness good. This can be made excellent.

5. Other ingredients

Moreover, as a preferable component which can be used by this invention, the compound other than the (A) component which has 1 or more cationically polymerizable group in a molecule | numerator is mentioned. The compound has one or more epoxy groups in the molecule, at least one of which is an alicyclic epoxy group (here, an alicyclic epoxy group represents an alicyclic group which forms an epoxide between two adjacent carbon atoms constituting the ring) , "It is called an alicyclic epoxy compound"), A compound other than the said "alicyclic epoxy compound" which has two or more epoxy groups in a molecule, and does not contain an aromatic ring (henceforth "aliphatic epoxy compound"), oxetane The compound and vinyl ether compound are mentioned.

Examples of the alicyclic epoxy compound include dicyclopentadiene dioxide, limonene dioxide, 4-vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, bis (3,4-epoxy Cyclohexylmethyl) adipate, 3, 4- epoxycyclohexyl methyl (meth) acrylate, etc. are mentioned.

In addition, besides these, two pieces of literature "epoxy resin-recent advance" (issued by Shokodo Co., Ltd.) and the separate document "polymer processing" volume 9, volume 22 issue issue epoxy resin (polymer publication, 1973 publication) The compound described on page 7 and pages 18-20 is mentioned.

Specific examples of the aliphatic epoxy compound include diglycidyl ethers of alkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol; Diglycidyl ethers of polyalkylene glycols such as diglycidyl ether of polyethylene glycol and polypropylene glycol; Diglycidyl ether of neopentyl glycol, dibromoneopentyl glycol and alkylene oxide adduct thereof; Di or triglycidyl ethers of trimethylolethane, trimethylolpropane, glycerin and its alkylene oxide adducts, and polyhydric alcohols such as di, tri or tetraglycidyl ethers of pentaerythritol and their alkylene oxide adducts Glycidyl ethers; Di or polyglycidyl ethers of hydrogenated bisphenol A and its alkylene oxide adducts; Tetrahydrophthalic acid diglycidyl ether; Hydroquinone diglycidyl ether and the like.

In addition to these, the compound described in pages 3-6 of the said "polymer processing" annex epoxy resin is mentioned.

As aliphatic epoxy compounds other than these, Denarex R-45EPT (manufactured by Nagase Chemtex Corporation), epofriend AT501, CT310, eporide PB3600 [above, Daicel Chemical Industries, Ltd.]. Production], KL-630 [Kuraray Co., Ltd.] Production], Tetrad C [Mitsubishi Gas Chemical Company, Inc.]. Production), TEPIC [Nissan Chemical Industries, Ltd. Production].

An oxetane compound is a compound which has one or more oxetane rings in a molecule | numerator. Specifically, various oxetane compounds described in Japanese Patent Application Laid-Open No. Hei 8-85775, Japanese Patent Application Laid-Open No. Hei 8-134405 and the like are listed, and among these, a compound having one or a plurality of oxetanyl groups is preferable. Examples of monofunctional oxetane include 3-ethyl-3- (hydroxymethyl) oxetane, 3-ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (chloromethyl) oxetane and the like are listed. Examples of the bifunctional oxetane include 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, bis {[1-ethyl (3-oxetanyl)] methyl} ether, and the like.

The vinyl ether compound is a compound having at least one vinyl ether group in a molecule. Specifically, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, 2-hydroxyethyl vinyl ether, cyclohexane dimethanol monovinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether Such as cyclohexyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate Polyfunctional vinyl ether, such as a functional vinyl ether, 1, 4- butanediol divinyl ether, cyclohexane dimethanol divinyl ether, diethylene glycol divinyl ether, and triethylene glycol divinyl ether, is mentioned.

As a compound other than the (A) component which has one or more cationically polymerizable group in a molecule | numerator, a low molecular weight compound is preferable, for the reason that adhesiveness can be made high and low viscosity is possible, specifically, molecular weight 2,000 or less Compounds of are preferred. Particularly preferred examples include limonene dioxide, 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, 3-ethyl-3- (hydroxymethyl) oxetane, 3-ethyl-3-[(phenoxy Ci) methyl] oxetane and bis (3-ethyl-3-oxetanylmethyl) ether are listed.

In addition to the above, the composition of the present invention may be blended with other components usually used in the adhesive composition.

Specifically, inert components such as silane coupling agents, inorganic fillers, softeners, antioxidants, anti-aging agents, stabilizers, tackifying resins, leveling agents, antifoaming agents, plasticizers, organic solvents, dyes, pigments, treatment agents and sunscreen agents can be blended. have. As tackifying resin, rosin, such as rosin acid, polymeric rosin acid, and rosin acid ester, terpene resin, terpene phenol resin, aromatic hydrocarbon resin, aliphatic saturated hydrocarbon resin, petroleum resin, etc. are mentioned, for example.

As the silane coupling agent, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltri Ethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyltri Ethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3 -Aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy sisilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N -Phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and the like. A silane coupling agent can also use 2 or more types together using only 1 type of said compound.

6. Active for plastic films or sheets Energy line  Curable Adhesive Composition

This invention is an active energy ray hardening-type adhesive composition for plastic films or sheets containing said (A)-(C) component.

As a manufacturing method of a composition, the said (A)-(C) component can be manufactured by stirring and mixing other components according to a conventional method as needed.

In this case, you may heat as needed. As heating temperature, what is necessary is just to set suitably according to the composition to be used, a base material, an objective, etc., but 30-80 degreeC is preferable.

As a viscosity of a composition, 10-1000 mPa * s is preferable at the point which is excellent in the coating property with respect to a base material.

The composition of this invention can be used for adhesion | attachment of various base materials (henceforth other base materials) other than adhesion of a plastic film, etc., a plastic film, etc.

In addition, in this invention, when only "substrate" is described, the generic term of a plastic film etc. and other base material is meant.

Other substrates include paper and metals.

The usage method of the composition of this invention should follow a conventional method, As a specific example, after apply | coating to a base material, the method of joining with another base material, and irradiating an active energy ray etc. are mentioned.

As a material in a plastic film etc., for example, polyvinyl chloride resin, polyvinylidene chloride, cellulose resin, polyethylene, polypropylene, polystyrene, ABS resin, polyamide, polyester, polycarbonate, polyurethane, polyvinyl alcohol , Triacetyl cellulose, cycloolefin polymer, polymethyl methacrylate, acrylic / styrene resin, ethylene-vinyl acetate copolymer, chlorinated polypropylene and the like.

Examples of the paper include imitation paper, fine paper, kraft paper, art coated paper, caster coated paper, white rolled paper, parchment paper, water resistant paper, glassine paper and corrugated paper.

As metal foil, aluminum foil etc. are mentioned, for example.

Coating on the substrate is in accordance with conventionally known methods, natural coater, knife belt coater, floating knife, knife over roll, knife-on blanket, spray, dip, kiss roll, squeeze roll, reverse roll, air blade, curtain flow coater , Comma coater, gravure coater, micro gravure coater, die coater and curtain coater.

Moreover, what is necessary is just to select the coating thickness of the composition of this invention according to the base material and a use to use, Preferably it is 0.1-100 micrometers, More preferably, it is 1-25 micrometers.

Examples of the active energy rays include visible rays, ultraviolet rays, X rays, electron beams, and the like, but ultraviolet rays are preferable because inexpensive devices can be used.

As a light source in the case of hardening by ultraviolet rays, various things can be used, for example, a pressurized or high pressure mercury lamp, a metal halide lamp, a xenon lamp, an electrodeless discharge lamp, a carbon arc lamp, LED, etc. are mentioned.

In the case of curing by an electron beam, various apparatuses can be used as the EB irradiation apparatus that can be used. For example, Cocroft-Walton type, Van de Graaf type, and resonant transformer type devices can be used. Enumerated, it is preferable to have an energy of 50-1000 eV as an electron beam, More preferably, it is 100-300 eV.

The composition of the present invention is preferred for adhering a thin layer adherend as a substrate.

The use method at the time of adhering a thin layer to-be-adhered body may follow the method normally performed in manufacture of a laminate.

For example, after coating a composition to a 1st thin layer to-be-adhered body and drying it as needed, the method of joining a 2nd thin layer to-be-adhered body to this, and irradiating an active energy ray etc. are mentioned.

As a thin layer to-be-adhered body, paper, metal foil, etc., such as a plastic film, are mentioned.

The plastic film or the like needs to be capable of transmitting an active energy ray, and the film thickness may be selected depending on the thin layer adherend to be used and the use thereof, but the thickness is preferably 0.2 mm or less.

The composition of this invention can be used suitably for adhesion | attachment of a plastic film etc. among these thin layer adherends, and also a hydrophilic plastic, specifically, a thing made from polyvinyl alcohol or triacetyl cellulose can be used preferably.

In addition, before adhering a to-be-adhered body, an activation process can be performed to one or both surfaces in order to enlarge interlayer adhesive force. Examples of the surface activation treatment include plasma treatment, corona discharge treatment, chemical treatment, roughening treatment and etching treatment, flame treatment, and the like.

Coating to a thin layer to-be-adhered body should follow the method known conventionally, The same method as the above is enumerated.

Moreover, what is necessary is just to select the coating thickness of the composition of this invention according to the thin layer to-be-adhered body to be used, and a use, but the same coating thickness as above is preferable.

In this case, the bonding can be performed not only in a planar state but also in a curved state.

That is, the method of bending a base material in a concave state or convex state, coating a composition in this state, bonding another base material, and irradiating an active energy ray is mentioned.

As another method, the method of apply | coating the composition of this invention in a planar state, bonding the other base material, bending in concave state or convex state, and irradiating and bonding an active energy ray is mentioned.

In this case, the above-mentioned method may be followed as a method of coating the composition in a planar state. As a method of coating a composition in a curved state, the method of using a spray, a dip, a curtain flow coater, a screen printing, a slot die coater, etc. is mentioned.

In the above method, a laminate composed of a plastic film / cured product of the composition of the present invention / plastic film, a laminate composed of a plastic film / cured product of the composition of the present invention / other substrate is produced.

Since laminated bodies, such as a laminated film obtained from the composition of this invention, are excellent in the adhesive force under high temperature and high humidity conditions, they can be used suitably for optical films, such as a polarizing plate used for a liquid crystal display device, a protective film, and a retardation film.

Especially the composition of this invention can be used suitably for manufacture of a polarizing plate and a polarizing plate with retardation film. Hereinafter, the manufacturing method of a polarizing plate is demonstrated.

In addition, in this specification, a polarizer shows the thing of the film or film which has a polarizing function mentioned later, and a polarizing plate shows the thing of the polarizer with a protective layer which protected one side or both sides of a polarizer with a film or a film. In addition, the polarizing plate with retardation film means what bonded the retardation film to a polarizer or a polarizing plate, or formed the film which has a retardation function by coating.

As mentioned above, the composition of this invention can be used suitably for adhesion | attachment of a hydrophilic plastic, and polyacetyl alcohol used as a polarizer and triacetyl cellulose used as a protective film of a polarizer correspond to a hydrophilic plastic in manufacture of a polarizing plate. .

The composition of this invention can be used for adhesion | attachment of a polarizer and a protective film, and adhesion | attachment of a polarizing plate and retardation film.

The polarizer has a function of selectively transmitting linear polarization in any one direction from natural light.

Specific examples of the polarizer include coating an iodine polarizer in which iodine is adsorbed and oriented on a polyvinyl alcohol film, a dye polarizer in which a dichroic dye is adsorbed and oriented on a polyvinyl alcohol film, and a pigment in a (liotropic) liquid crystal state. , Orientation, immobilized coated polarizer, and the like.

These iodine type polarizers, dye type polarizers and coating type polarizers have a function of selectively transmitting linearly polarized light in any one direction from natural light and absorbing linearly polarized light in the other direction, and are called absorption type polarizers.

In the said iodine type polarizer and dye type polarizer, although a protective layer is normally formed in one or both surfaces, the composition of this invention can be used for adhesion | attachment of a polarizer and a protective film.

As a protective film used as a protective layer, For example, cellulose acetate resin films, such as a triacetyl cellulose and a diacetyl cellulose, an acrylic resin film, a polyester resin film, a polyarylate resin film, a polyether sulfone resin film, norbornene The cyclic polyolefin resin film etc. which make such a cyclic olefin a monomer are mentioned.

Next, the composition of this invention can also be used for adhesion | attachment of a polarizing plate and retardation film.

In this case, as a polarizing plate, what has a protective layer in the one side or both sides can be used.

In this case, the protective layer may be a laminate of the above protective films or a protective film formed by coating.

The polarizing plate in which the protective layer is provided only on one side may be a surface with a protective layer or may be a surface without a protective layer.

Various types can be used as retardation film, The optical film etc. which processed the film for optical processing, such as uniaxial or biaxial stretching, or liquid crystalline compound etc. to the base material, and processed the orientation, fixation, etc. are listed. Then, the magnitude (refractive index ellipsoid) of the three-dimensional refractive index is controlled according to the use conditions. It is mainly used in order to compensate for the compensation by the coloring of the liquid crystal layer of a liquid crystal display, or the change of phase difference by a viewing angle.

Specific examples of the retardation film include, for example, polyolefins and polycarbonates such as polyethylene, polypropylene, cyclic polyolefins, polycarbonates, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polyarylate, and the like. Polyamide and the like can be exemplified.

Said cyclic polyolefin is a general generic name of resin obtained from cyclic olefins, such as norbornene, tetracyclo dodecene, and derivatives thereof, For example, Unexamined-Japanese-Patent No. 3-14882, Unexamined-Japanese-Patent No. 3-122137. Listed in the publication etc. are listed.

Specifically, ring-opening polymers of cyclic olefins, addition polymers of cyclic olefins, random copolymers of cyclic olefins with α-olefins such as ethylene and propylene, or graft modified bodies modified with unsaturated carboxylic acids or derivatives thereof, and the like It can be illustrated. In addition, these hydrides are listed. Examples of the product include Zeonex manufactured by ZEON CORPORATION, Zeonoa, Atom manufactured by JSR Corporation, Tow Pass manufactured by TICONA, and the like.

Moreover, as an optical film which apply | coated a liquid crystalline compound etc. to the base material, and processed the orientation and fixation, "WV film" [made by FUJIFILM CORPORATION], "LC film", "NH film" [all JX Nippon Oil & Energy Corporation] Production].

The method of manufacturing a polarizing plate or a polarizing plate with retardation film using the composition of this invention is demonstrated below.

As said manufacturing method, the method containing following process [1]-[3] is included.

[1] a step of coating the composition of the present invention on any one of a polarizer, a polarizing plate, a protective film, a protective film, a retardation film, and a retardation film to be an adherend;

[2] a step of bonding any one of a polarizer, a polarizing plate, a protective film, a protective film, a retardation film, and a retardation film to be the other adherend to the film coated with the composition;

[3] A step of irradiating an active energy ray with the film between the coated substrates of the composition of the present invention.

In the case where the protective film or the retardation film is bonded only to one side, the polarizing plate or the polarizing plate with the retardation film can be produced by the above procedure. ] May be performed, and process [1], [2], and [3] may be repeated twice.

What is necessary is just to perform the coating method in the said process [1], and the active energy ray irradiation method in the said process [3] by the same method as the above.

Moreover, as above-mentioned, it can also adhere | attach in a curved state.

When using the polarizing plate with retardation film as a circularly polarizing plate, in order to make circularly polarized state over broadband, the retardation film from which retardation differs may further be bonded to the retardation film side of the polarizing plate with retardation film.

Specifically, there is a method of bonding a retardation film having 1/2 wavelength to each wavelength and bonding a retardation film having 1/4 wavelength to each wavelength to the polarizer film. In this case, after repeating process [1] and [2] three times, process [3] may be performed and process [1], [2], and [3] may be repeated three times.

(Example)

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, "part" in each following example means a weight part.

(Manufacture example 1 of a polarizer)

0.05 mass part of iodine and 0.5 mass part of potassium iodide were dissolved in 100 mass parts of water, and the dyeing liquid was prepared. This dyeing solution was heated at 55 degreeC, the PVA film (Kuraray Co., Ltd. make, vinylon film VF-PS, 75 micrometers) was immersed for 1 minute, and the film was stretched 6 times in one direction. Further, washing after dyeing was performed in an aqueous solution in which 4 parts by mass of boric acid and 6 parts by mass of potassium iodide were dissolved in 90 parts by mass of water, followed by drying to prepare a polarizer having a film thickness of 30 µm.

(Manufacture example 1 of a polarizing plate)

Corona treatment (NAVISTA CO., LTD. Produced polydyne 1) as an easy-adhesive treatment on a triacetyl cellulose film (trade name Fuji-Taek, Fujifilm Corporation, hereinafter referred to as "UVA-TAC") containing a UV absorber having a thickness of 80 µm. , Output 0.1 kW, processing speed 1 second / cm) was performed.

Next, the active energy ray hardening-type adhesive composition was apply | coated to the polarizer obtained by the manufacture example 1 in thickness of 5 micrometers with the bar coater. After laminating | stacking UVA-TAC which performed corona treatment to this, it reversed and performed the coating of active-energy-ray-curable adhesive composition and UVA-TAC which corona-treated similarly. Thereafter, ultraviolet rays were irradiated and cured by one pass for each front and back using an 80 W / cm condensing metal halide lamp. Then, it cured at room temperature for 12 hours or more, and manufactured the TAC polarizing plate which is a test body. The ultraviolet ray intensity was 250 mW / cm ² and the accumulated light amount was 300 mJ / cm ² (both at 365 nm).

(Manufacture example 2 of a polarizing plate)

A polarizing plate was produced in the same manner as in Manufacturing Example 1 of the polarizing plate except for using a triacetylcellulose film (hereinafter referred to as "TAC" produced by LOFO) that did not contain a UV absorber having a thickness of 100 µm in place of the UVA-TAC. .

Examples 1 to 7, Comparative Examples 1 to 7

The components (A) to (D) shown in the following Table 1 and other components were dissolved by heating and stirring at 60 ° C for 1 hour to prepare an active energy ray-curable adhesive composition.

The numbers in Table 1 mean copies. In addition, the symbol in Table 1 is as follows.

1) (A) Component

JER828: Diglycidyl ether of bisphenol A, Japan Epoxy Resin Co., Ltd. Production jER-828 (brand name)

2) (B1) Component

4HBA: 4-hydroxybutyl acrylate, Osaka Organic Chemical Industry Ltd. Production biscot 4-HBA (brand name)

2HBA: 2-hydroxybutyl acrylate, Koyeisha Chemical Co., Ltd. Production light acrylate HOB-A (brand name)

3) (B2) Component

M270: polypropylene glycol (n ≒ 12) diacrylate, Toagosei Co., Ltd. Production Aronix M-270 (brand name)

M313: isocyanuric acid EO modified di / triacrylate, Toagosei Co., Ltd. Production aronix M-313 (brand name)

4) Other (B) Ingredients

PEA: Phenoxyethyl acrylate, Koyeisha Chemical Co., Ltd. Production light acrylate PO-A (brand name)

THFA: tetrahydrofurfuryl acrylate, Osaka Organic Chemical Industry Ltd. Production biscotti # 150 (brand name)

HEA: 2-hydroxyethyl acrylate, Toagosei Co., Ltd. Production aronix HEA (brand name)

HPA: 2-hydroxypropyl acrylate, Koyeisha Chemical Co., Ltd. Production light ester HOP-A (brand name)

M5700: 2-hydroxy-3-phenoxypropylacrylate, Toagosei Co., Ltd. Aronix M-5700 (brand name)

5) (C) component

Irg: Iodonium salt type photo cationic initiator, BASF Japan Co., Ltd. Production monocure 250 (brand name)

CPI: 50 wt% propylene carbonate solution of sulfonium salt-based photo cationic initiator, San-Apro Ltd. Production CPI-100P (brand name)

DBA: 9,10-dibutoxyanthracene, Kawasaki Kasei Chemicals. Production anthracure UVS-1331 (brand name)

6) (D) component

DETX: 2,4-diethyl thioxanthone, produced by Nippon Kayaku Co., Ltd.DETX-S (brand name)

7) Other Ingredients

CEL2021: 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate, Daicel Chemical Industries, Ltd. Production Celoxide 2021P (brand name)

YX: Diglycidyl ether of hydrogenated bisphenol A, Japan Epoxy Resin Co., Ltd. Production YX-8000 (brand name)

evaluation

The obtained composition was evaluated according to the following test method. The results are shown in Table 2.

(25 ℃ viscosity)

The viscosity of the active energy ray hardening-type adhesive composition in 25 degreeC was measured using the E-type viscosity meter. Since the 25 degreeC viscosity is so preferable at the time of thin film coating in a coater, it determined by the following reference | standard.

(Circle): less than 100 mPa * s, (triangle | delta): 100-200 mPa * s, x: exceeding 200 mPa * s

(Peel strength)

The test body obtained in the manufacture example 1 or 2 of the said polarizing plate was bonded to glass through the double-sided tape, and peeling strength of UVA-TAC or TAC and a polarizer was measured on condition of the following.

Tensile Tester: Instron Japan Company Limited, Instron 5564

Test piece: 25mm × 100mm

Test method: 90 ° peeling

Peeling Speed: 200mm / min

(Humidity resistance)

The test body obtained by the manufacture example 1 or 2 of the said polarizing plate was thrown into the thermo-hygrostat of 60 degreeC / 90% RH for 500 to 1000 hours, and the appearance change was observed.

○: no discoloration

△: Some discoloration is seen

×: almost completely discolored

(Film curl)

The test body obtained by the manufacture example 1 or 2 of the said polarizing plate was cut out to width 50mm x length 100mm, and was bonded to the 3 inch paper pipe using the cello tape (registered trademark). Then, after leaving at room temperature for 24 hours, the film was removed and placed on a horizontal desk to observe the appearance of the film. The curl height of the edge part of four corners of a film was measured by normality, and the average value was measured. Smaller is better.

○: bending height of film end is less than 1 cm

X: The bending height of the film edge part is 1 cm or more

From Table 2, the composition of this invention was low viscosity, was excellent in peeling strength and the appearance after a high humidity test, and the curl of the film derived from the dark reaction after UV hardening was also suppressed.

On the other hand, it does not contain the composition (Comparative Examples 1-4) which do not contain the (B1) component of this invention, the composition (Comparative Example 5) which does not contain the (B2) component of this invention, and (A) component of this invention. The composition (Comparative Examples 6-7) which did not have sufficient viscosity, peeling strength, the external appearance after a high humidity test, and film curl.

(Industrial availability)

The composition of the present invention can be used as an adhesive such as various plastic films, and in particular, as an adhesive such as hydrophilic plastic, and can be suitably used particularly for the production of optical films such as liquid crystal displays, in particular for the production of polarizing plates.

Claims (12)

At least a curable component and a polymerization initiator, The curable component is at least composed of the following (A) component and the following (B) component, The polymerization initiator is at least composed of the following (C) component Or active energy ray-curable adhesive composition for sheet.
(A) component: The aromatic epoxy compound containing 2 or more epoxy groups in a molecule | numerator.
Component (B): at least one compound (B1) selected from the group consisting of 4-hydroxybutyl acrylate and 2-hydroxybutyl acrylate, and at least one compound (B2) having two or more ethylenically unsaturated groups in a molecule thereof. Composed ethylenically unsaturated compounds.
(C) component: Photo cationic polymerization initiator. The method of claim 1,
The said (A) component is a bisphenol-type epoxy resin, The active-energy-ray-curable adhesive composition for plastic films or sheets characterized by the above-mentioned. 3. The method according to claim 1 or 2,
It contains 10 to 80 weight% of (A) component and 20 to 90 weight% of (B) component in 100 weight% of curable components whole quantity,
(C) Component is contained in the ratio of 0.1-20 weight part with respect to 100 weight part of curable components whole quantity, The active energy ray curable adhesive composition for plastic films or sheets characterized by the above-mentioned. 4. The method according to any one of claims 1 to 3,
An active energy ray curable adhesive composition for plastic films or sheets, comprising (B1) component at 10 to 50% by weight and (B2) component at a ratio of 0.5 to 40% by weight in 100% by weight of the curable component. 5. The method according to any one of claims 1 to 4,
The polymerization initiator is an active energy ray-curable adhesive composition for a plastic film or sheet, characterized in that it further comprises a (D) radical photopolymerization initiator. The method of claim 5, wherein
(D) component is contained in 0.1-10 weight part with respect to 100 weight part of curable components whole quantity, The active energy ray curable adhesive composition for plastic films or sheets characterized by the above-mentioned. 7. The method according to any one of claims 1 to 6,
The component (B) further comprises a compound having an aromatic ring skeleton or an alicyclic skeleton containing one ethylenically unsaturated group in a molecule, wherein the active energy ray-curable adhesive composition for a plastic film or sheet. The method according to any one of claims 1 to 7,
Adhesive film for polarizing plate manufacture characterized by the plastic film or sheet being a hydrophilic plastic film or sheet. The method of claim 8,
The hydrophilic plastic film or sheet is a polyvinyl alcohol polarizer film, the adhesive composition for producing a polarizing plate. The base material, the hardened | cured material layer of the active energy ray hardening-type adhesive composition for plastic films or sheets of any one of Claims 1-7, and a plastic film or sheet are laminated | stacked in this order, The laminated body characterized by the above-mentioned. . 11. The method of claim 10,
The substrate is a laminate, characterized in that the plastic film or sheet. A polyvinyl alcohol polarizer film or sheet, a cured product layer of the active energy ray-curable adhesive composition for a plastic film or sheet according to any one of claims 1 to 7, and a plastic film or sheet are laminated in this order A polarizing plate made of.