TW201638283A - Active energy ray-curable adhesive composition for plastic film or sheet - Google Patents

Abstract

The present invention provides an active energy ray-curable adhesive composition for a plastic film, etc. The adhesive composition has low viscosity and superior curability, and whether the atmospheric humidity at the time of application and curing is low or high, the adhesive composition exhibits superior adhesion to films, etc. made of a variety of plastic materials, including (meth)acrylic resins, such as polymethyl methacrylate, and cycloolefin polymers, and also exhibits superior colorlessness and transparency. The present invention relates to an active energy ray-curable adhesive composition for a plastic film or sheet, the adhesive composition containing: ingredient (A), which is an aromatic epoxy compound having a weight-average molecular weight greater than or equal to 500; ingredient (B), which is a polyglycidyl ether of a polyol having two to ten carbon atoms; ingredient (C), which is a compound having two or more oxetanyl groups and having a molecular weight less than or equal to 500; and ingredient (D), which is a photocationic polymerization initiator. The contents of the ingredients (A) to (D) in the entire composition are: ingredient (A): 1 to 30 wt%; ingredient (B): 10 to 70 wt%; ingredient (C): 10 to 70 wt%; and ingredient (D): 0.5 to 10 wt%.

Description

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

The present invention relates to a composition of an active energy ray-curable adhesive which can be obtained by irradiating various plastic films or sheets by ultraviolet rays, visible light, or electron beam irradiation, etc., and further suitable for use in a liquid crystal display or The manufacture of various optical films or sheets used in organic electroluminescence (EL) displays and the like is preferably used in the fields of technology. In the present specification, acrylate and/or methacrylate are represented by (meth) acrylate, and propylene fluorenyl and/or methacryl fluorenyl are represented by (meth) acrylonitrile. Acrylic acid and/or methacrylic acid is represented by (meth)acrylic acid. In the following, the plastic film or sheet is collectively referred to as "plastic film or the like", and the film or sheet is collectively referred to as "film or the like".

Conventionally, in a lamination method in which a thin layer of a plastic film or the like is bonded to each other, or a thin layer of a plastic film or the like and a thin layer including the other material are bonded to the adherend, mainly as follows Dry lamination method: a solvent-based adhesive composition comprising an ethylene-vinyl acetate copolymer or a polyurethane polymer is applied to a first thin layer of a adherend and dried, and then sandwiched A second thin layer of the adherend is pressed against a nip roller or the like. In order to make the coating amount of the composition uniform, the binder composition used in this method generally contains a large amount of solvent. Therefore, a large amount of solvent vapor is volatilized during drying, and toxicity, work safety, and environmental pollution become problem. As a binder composition for solving such problems, a solventless adhesive composition is being studied.

As a solventless adhesive composition, a two-component adhesive composition and an adhesive composition which is cured by active energy rays such as ultraviolet rays or electron beams are widely used. As a two-component type adhesive composition, a so-called polyurethane-based adhesive composition mainly comprising a polymer having a hydroxyl group at its terminal as a main component and a polyisocyanate compound having an isocyanate group at its terminal as a curing agent is used. However, this composition has the disadvantage that it takes a long time to harden. On the other hand, since the active energy ray-curable adhesive composition has a high curing rate and is excellent in productivity, it has been used in recent years.

On the other hand, liquid crystal displays are widely used in mobile phones, smart phones, and tablet devices because of their thinness, light weight, and power consumption. In addition, it is also widely used in various displays of personal computers, televisions, and car navigation systems. In addition, the use of organic EL displays is also increasing around mobile devices. Active energy ray-curable adhesives are also widely used for bonding various optical films and the like used in liquid crystal displays or organic EL displays.

Examples of the optical film and the like include a hard coat film provided with functions such as anti-fingerprint or anti-glare, a front panel of a touch panel, a polarizing plate, a retardation film, a viewing angle compensation film, a brightness enhancement film, an antireflection film, and the like. A glare film, a lens sheet, a diffusion sheet, etc., which are used in various plastics.

Among these plastics, the amorphous cycloolefin polymer and polymethyl methacrylate are widely used because of their excellent optical properties such as colorless transparency and optical isotropic properties.

Recently, a large number of actions have been made due to the popularity of touch panels in the form of electrostatic capacitance. The phone has been replaced by smart phones, or new products such as tablets are gaining popularity. Also, organic EL displays are being developed due to the improvement in performance of organic EL. As such, the display of the mobile device continues to evolve until now, and there is a case where the composition of the optical film or the like is changed. At this time, there is a case where it is necessary to carry out the plastic material which completely differs in surface characteristics. For example, both cyclic olefin polymers and polymethyl methacrylate are widely used in optical applications for optical applications, but the former is non-polar and on the other hand, the latter is highly polar, and the surface characteristics of the two are completely different. There is a demand for an active energy ray-curable adhesive which is strong in adhesion to both of these different materials and which does not cause yellowing or turbidity and is excellent in transparency. Further, the adhesion reduction after the damp heat resistance test was required for the adhesive was small.

Further, in terms of mobile equipment, since thinness and weight reduction are important issues, it is required to reduce the thickness of the adhesive. In order to apply the adhesive thinner, the low viscosity of the adhesive composition becomes important. However, if the solvent-free active energy ray-curable adhesive is to be low-viscosity, the (meth)acrylic acid ethyl methacrylate used in the (meth)acrylate-based active energy ray-curable adhesive is generally used. Its viscosity is high and it is difficult to use. Therefore, it is difficult to simultaneously achieve low viscosity and strong adhesion by using a (meth) acrylate-based adhesive.

Further, in the case where at least one of the adherends is a film, a strong peeling adhesion force is required, and in order to enhance the peeling adhesion force, it is effective to increase tan δ and increase in dynamic viscoelasticity measurement of the cured product of the adhesive. The thickness of the thick adhesive (Non-Patent Document 1). In other words, it is difficult to enhance the peeling adhesion force by setting the film thickness of the adhesive to 3 μm or less.

However, a photocation-hardening type adhesive comprising a polyfunctional aliphatic epoxy monomer as a main component and comprising an alicyclic epoxy monomer and/or an oxetane monomer is disclosed, even if the thickness of the adhesive is Thinner, cycloolefin polymer or cellulose triacetate The adhesive force of the plastic material is also excellent (Patent Document 1).

However, the composition disclosed in Patent Document 1 has a problem that the cation hardenability is poor and the energy required for hardening is large. Therefore, it is necessary to slow down the line speed of the subsequent steps or increase the number of light sources. Therefore, from the viewpoint of productivity, an active energy ray-curable adhesive which is excellent in curability is also desired, specifically, a type B ultraviolet ray (UV-B, Ultraviolet-B) (near 310 nm) at 200 mJ/cm. An active energy ray-curable adhesive which exhibits sufficient adhesion under the irradiation amount of ² or less. Further, according to the findings of the present inventors, the composition disclosed in Patent Document 1 has the following problems. That is, there is a problem that the adhesion force to the (meth)acrylic resin such as polymethyl methacrylate or alkyl (meth) acrylate polymer is insufficient. In addition to this, there is a problem that if the humidity of the environment is high when the adhesive is applied and hardened, the force is greatly lowered.

[Previous Technical Literature] [Non-patent literature]

[Non-Patent Document 1] Sandaoji Township, followed by 47 volumes, 8th, 12-15 pages (2003)

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-63397 (Application No.)

The present invention has been made in view of the above problems, and an object thereof is to provide an active energy ray-curable adhesive composition for a plastic film or the like which is low in viscosity and hard. Excellent in chemical properties, and excellent in adhesion to various plastic films including (meth)acrylic resins such as polymethyl methacrylate or cycloolefin polymers, etc., regardless of the low or high environmental humidity during coating and hardening, and Colorless transparency is also excellent. Further, it is an object of the invention to provide an adhesive composition having a small decrease in adhesion after the wet heat resistance test.

As a result of various studies conducted by the inventors of the present invention, it has been found that an aromatic epoxy compound having a weight average molecular weight of 500 or more, a polyglycidyl ether having a polyhydric alcohol having 2 to 10 carbon atoms, and one molecule are contained in a specific ratio. The active energy ray-curable adhesive composition having two or more oxetanyl groups having a molecular weight of 500 or less and a photocationic polymerization initiator can solve the above problems, and the present invention has been completed.

The present invention relates to an active energy ray-curable adhesive composition for a plastic film or sheet comprising:

(A) component: an aromatic epoxy compound having a weight average molecular weight of 500 or more

(B) component: polyglycidyl ether of a polyol having 2 to 10 carbon atoms

(C) component: a compound having two or more oxetanyl groups having a molecular weight of 500 or less in one molecule

(D) component: a photocationic polymerization initiator; and the content ratio of the above components (A) to (D) is in the entire composition,

(A) Composition: 1 to 30% by weight

(B) Composition: 10 to 70% by weight

(C) Component: 10 to 70% by weight

(D) Component: 0.5 to 10% by weight.

The content ratio of the component (B) is preferably larger than the content ratio of the component (A) In addition, it is preferable that the content ratio of the component (B) is 51 to 99% by weight based on 100% by weight of the total of the components (A) and (B).

The component (A) is preferably a compound having a weight average molecular weight of 1,000 to 20,000 and a number of epoxy groups contained in one molecule of 2 or more, and more preferably a bisphenol A type epoxy resin and/or bisphenol. F type epoxy resin. The component (B) is preferably a diglycidyl ether having a diol having 2 to 6 carbon atoms, more preferably a diglycidyl ether having an alkanediol having 4 to 6 carbon atoms. The component (C) is preferably an oxetane compound represented by the following formula (1).

As the component (D), a phosphonium salt photocationic polymerization initiator is preferred.

The content ratio of the components (A) to (D) is preferably 3 to 20% by weight of the component (A), 20 to 65% by weight of the component (B), and 20 to 60% by weight of the component (C). % and (D) components are 1 to 5% by weight. It is preferable to further contain 0.05 to 3% by weight of water in the entire composition. Further, at least one of the plastic film or sheet is preferably a cycloolefin polymer or a (meth)acrylic resin.

Further, the present invention relates to a laminate comprising a substrate, a cured film of an active energy ray-curable adhesive composition of the plastic film or sheet, and another substrate, and the substrate and the substrate Both or one of the other substrates described above is a plastic film or sheet. As the plastic film or sheet, at least one of them is preferably a cycloolefin polymer or a (meth)acrylic resin.

Moreover, the present invention relates to a method for producing a laminated body, wherein the composition is applied to a substrate, and another substrate is bonded to the coated surface, and the substrate or the substrate is coated thereon. The active energy ray is irradiated to the side of any of the other substrates, wherein either or both of the substrate and the other substrate are plastic films or sheets.

According to the present invention, it is possible to provide an active energy ray-curable adhesive composition which has low viscosity and excellent hardenability, and which is high or low in environmental humidity regardless of coating and hardening, and contains polymethyl methacrylate or the like ( Each of the plastic films of the methyl methacrylate resin has excellent adhesion and excellent colorless transparency. Therefore, it can be suitably used for manufacture of various optical films, etc. used in a liquid crystal display, an organic EL display, etc.. Further, in applications other than the display, for example, in windows, building materials, or the like, or for various applications requiring low viscosity, hardenability, adhesion, and transparency, they can be suitably used.

The present invention relates to an active energy ray-curable adhesive composition for a plastic film or sheet comprising:

(A) component: an aromatic epoxy compound having a weight average molecular weight of 500 or more

(B) component: polyglycidyl ether of a polyol having 2 to 10 carbon atoms

(C) component: a compound having two or more oxetanyl groups having a molecular weight of 500 or less in one molecule

(D) component: a photocationic polymerization initiator; and the content ratio of the above components (A) to (D) is in the entire composition,

(A) Composition: 1 to 30% by weight

(B) Composition: 10 to 70% by weight

(C) Component: 10 to 70% by weight

(D) Component: 0.5 to 10% by weight.

Hereinafter, the preferred use methods of the components (A) to (D), other components, and the composition of the present invention will be described in detail.

1. (A) component

The component (A) is an aromatic epoxy compound having a weight average molecular weight (hereinafter referred to as "Mw") of 500 or more. In the present invention, the term "aromatic epoxy compound" means an epoxy compound in which a glycidyl ether group or a glycidyl ester group is directly bonded to an aromatic ring, and a compound having a low molecular weight is conventionally referred to as "epoxy". a compound of a resin.

The component (A) has a Mw of 500 or more, preferably 500 to 50,000, more preferably 1,000 to 20,000, still more preferably 1,000 to 10,000, and particularly preferably 2,000 to 10,000. If the Mw is less than 500, the adhesion to the plastic substrate, particularly the (meth)acrylic resin, becomes lower under conditions of relatively high ambient humidity. Further, for the same reason, Mw is preferably 50,000 or less.

In the present invention, Mw means a polystyrene-converted Mw measured by gel permeation chromatography (GPC, Gel Permeation Chromatography). Further, as the epoxy compound having a low molecular weight which is not a component (A), an absolute molecular weight which can be measured by mass spectrometry can also be used.

The component (A) is preferably an aromatic epoxy compound which is solid at 25 ° C. Specifically, an aromatic epoxy compound having a softening point of 40 ° C or higher is preferred. By using an aromatic epoxy compound having a softening point of 40 ° C or higher, the adhesion to a plastic substrate, particularly a (meth)acrylic resin, can be improved under relatively high ambient humidity conditions. The softening point is more preferably 50 ° C or more and 200 ° C or less, and further preferably 60 Above °C and below 170 °C, particularly preferably from 70 ° C to 140 ° C. In the present invention, the softening point means a measured value measured by the ring and ball method of JIS K7234.

The number of epoxy groups contained in one molecule of the component (A) is preferably 2 or more in terms of improving the adhesion to the plastic substrate. Further, for the same reason, it is more preferably a glycidyl ether group than a glycidyl ester group.

Preferred examples of the component (A) include a bisphenol A epoxy resin having a Mw of 500 or more, a bisphenol F epoxy resin, and a polycondensation of bisphenol A with bisphenol F and epichlorohydrin. Epoxy resin, phenol novolac type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolac type epoxy resin, and bisphenol F novolak type epoxy resin.

More preferably, the component (A) is a bisphenol A epoxy resin, a bisphenol F epoxy resin, an epoxy resin obtained by polycondensation of bisphenol A with bisphenol F and epichlorohydrin, and further preferably a double resin. Phenol type A epoxy resin and bisphenol F type epoxy resin, especially bisphenol A type epoxy resin.

As the component (A), the above compounds may be used singly or in combination of two or more. The content ratio of the component (A) is 1 to 30% by weight based on the entire composition. When the component (A) is less than 1% by weight, the adhesion of the composition is lowered when the ambient humidity at the time of coating and hardening is high. In addition, when the content ratio of the component (A) exceeds 30% by weight, the viscosity of the composition becomes too high, and the coatability is deteriorated. The content of the component (A) is preferably from 3 to 20% by weight, more preferably from 5 to 15% by weight, based on the total amount of the composition.

2. (B) ingredients

The component (B) is a polyglycidyl ether having a polyhydric alcohol having 2 to 10 carbon atoms. Furthermore, the "carbon number" of a polyol having 2 to 10 carbon atoms means that the hydroxy group is removed from the polyol. The number of carbons in the base.

Examples of the component (B) include a polyglycidyl ether of an alkane polyol, a polyglycidyl ether of a cycloalkanol polyol, a polyalkylene glycol polyglycidyl ether, and a polyglycidyl ether of an aromatic polyol. . The component (B) is preferably a diglycidyl ether having a diol having 2 to 6 carbon atoms, more preferably a diglycidyl ether having an alkanediol having 4 to 6 carbon atoms.

Specific examples of the component (B) include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6. - hexanediol diglycidyl ether, cyclohexane dimethylol diglycidyl ether, 1,9-nonanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether , dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, hydroquinone diglycidyl ether, resorcinol diglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane tricondensate Glycerol ether, pentaerythritol polyglycidyl ether, dipentaerythritol polyglycidyl ether, and the like.

More preferably, as the component (B), ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexyl Glycol diglycidyl ether, hydroquinone diglycidyl ether, resorcinol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, etc., having carbon number 2 to 6 Diglycidyl ether of diol.

The component (B) is preferably a 1,4-butanediol diglycidyl ether or a pentylene group because the composition obtained has a low viscosity and an excellent adhesion to a cured product, and is further colorless and transparent. A diglycidyl ether having 4 to 6 carbon atoms of alkanediol exemplified by diol diglycidyl ether and 1,6-hexanediol diglycidyl ether.

As the component (B), the above compounds may be used singly or in combination of two the above. The content ratio of the component (B) is from 10 to 70% by weight based on the entire composition. If the component (B) is less than 10% by weight, the adhesion of the composition to most of the plastic substrates may be lowered. In addition, when the content ratio of the component (B) exceeds 70% by weight, the hardenability of the composition is deteriorated, and the force is also deteriorated. The content of the component (B) is preferably from 20 to 65% by weight, more preferably from 30 to 60% by weight, based on the total amount of the composition. Further, the content ratio of the component (B) is preferably such that the composition has a lower viscosity and a higher adhesion strength than the component (A). Specifically, the component (B) is preferably 51 to 99% by weight, and more preferably 65 to 95% by weight based on 100% by weight of the total of the components (A) and (B).

3. (C) ingredients

The component (C) is a compound having two or more oxetanyl groups in one molecule and having a molecular weight of 500 or less. The component (C) is preferably a compound having a molecular weight of 150 to 400, more preferably a molecular weight of 150 to 300, in terms of a low viscosity of the composition obtained and an excellent adhesion of the cured product. range.

Specific examples of the component (C) include bis[(3-ethyloxetan-3-yl)methyl]ether and bis[(3-methyloxetan-3-yl) )methyl]ether, bis[(oxetan-3-yl)methyl]ether, 1,4-bis{[(3-ethyloxetan-3-yl)methoxy] Methyl}benzene, 1,4-bis[(3-ethyloxetan-3-yl)methoxy]benzene, 1,3-bis[(3-ethyloxetane-3) -yl)methoxy]benzene, 1,2-bis[(3-ethyloxetan-3-yl)methoxy]benzene, 4,4'-bis[(3-ethyloxa) Cyclobutane-3-yl)methoxy]biphenyl, 2,2'-bis[(3-ethyloxetan-3-yl)methoxy]biphenyl, 1,1,1- [[3-ethyloxet-3-yl)methoxymethyl]propane, 1,2-bis[(3-ethyloxetan-3-yl)methoxy] Ethane, 1,2-bis[(3-ethyloxetan-3-yl)methoxy]propane, 1,4-bis[(3-ethyloxetan-3-yl) )methoxy]butane and 1,6-bis[(3-ethyloxetan-3-yl)methoxy] Hexane, etc.

The component (C) is preferably bis[(3-ethyloxetan-3-yl)methyl]ether, that is, an oxetane compound represented by the following formula (1).

When the molecular weight of the component (C) is 500 or less, preferably 150 to 400, more preferably 150 to 300, and particularly preferably a compound represented by the above formula (1), even if the cured product of the composition is cured The modulus of elasticity can also be increased at temperatures above the glass transition temperature. Therefore, the heat resistance of the cured product of the composition can be improved.

As the component (C), the above compounds may be used singly or in combination of two or more. The content ratio of the component (C) is from 10 to 70% by weight based on the entire composition. When the component (C) is less than 10% by weight, the hardenability of the composition is deteriorated, and the force is also deteriorated. Moreover, when the content ratio of the component (C) exceeds 70% by weight, the adhesion of the composition to most plastic substrates is lowered. The content of the component (C) is preferably from 20 to 60% by weight, more preferably from 25 to 55% by weight, based on the total amount of the composition.

4. (D) ingredients

The component (D) is a photocationic polymerization initiator. In other words, it is a compound which starts polymerization of a cationically curable component such as an epoxy compound or an oxetane compound by generating a cation or a Lewis acid by irradiation with an active energy ray such as an ultraviolet ray or an electron beam. Specific examples of the component (D) include an onium salt photocationization polymerization initiator, a phosphonium salt photocationization polymerization initiator, and a diazonium salt photocationization polymerization initiator.

Examples of the onium salt-based photocationic polymerization initiator include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, and triphenylsulfonium (pentafluorophenyl) borate. Diphenyl-4-(phenylthio)phenylphosphonium hexafluorophosphate, diphenyl-4-(phenylthio)phenylphosphonium hexafluoroantimonate, 4,4'-bis(diphenylfluorene) Diphenyl sulfide dihexafluorophosphate, 4,4'-bis[bis(β-hydroxyethoxy)phenyldihydrothio]diphenyl sulfide dihexafluoroantimonate, 4,4' - bis[bis(β-hydroxyethoxy)phenyldihydrothio]diphenyl sulfide dihexafluorophosphate, 7-[bis(p-tolylmethyl)dihydrothio]-2-isopropyl 9-oxosulfur Hexafluoroantimonate, 7-[bis(p-tolylmethyl)dihydrothio]-2-isopropyl 9-oxosulfur Bis(pentafluorophenyl)borate, 4-phenylcarbonyl-4'-diphenyldihydrothio-diphenyl sulfide hexafluorophosphate, 4-(p-tert-butylphenylcarbonyl)-4' -diphenyldihydrothio-diphenyl sulfide hexafluoroantimonate, 4-(p-tert-butylphenylcarbonyl)-4'-di(p-tolylmethyl)dihydrothio-diphenyl a triarylsulfonium salt such as thioether quinone (pentafluorophenyl) borate.

Examples of the onium salt-based photocationic polymerization initiator include diphenylphosphonium (pentafluorophenyl) borate, diphenylphosphonium hexafluorophosphate, and diphenylphosphonium hexafluoroantimonate. Bis(4-t-butylphenyl)phosphonium hexafluorophosphate, bis(4-t-butylphenyl)phosphonium hexafluoroantimonate, tolyl Base (pentafluorophenyl)borate, (4-methylphenyl)[4-(2-methylpropyl)phenyl]-hexafluorophosphate, bis(4-mercaptophenyl)anthracene A diarylsulfonium salt such as hexafluorophosphate or bis(4-alkylphenyl)phosphonium hexafluorophosphate.

Examples of the diazonium salt-based photocationic polymerization initiator include diazobenzene hexafluoroantimonate and diazobenzene hexafluorophosphate.

The component (D) is commercially available, and examples thereof include Adeka Optomer SP-100, SP-150, SP-152, SP-170, SP-172 [made by ADEKA], Photo Initiator 2074 (manufactured by RHODIA), and Kayarad. PCI-220, PCI-620 [made by Nippon Kayaku Co., Ltd.], Irgacure 250 (made by Nippon Ciba Company), CPI-100P, CPI-110P, CPI-101A, CPI-200K, CPI-210S [SAN-APRO (share) manufacturing], WPI-113, WPI-116 [manufactured by Wako Pure Chemical Industries, Ltd.], BBI-102, BBI-103, TPS-102, TPS-103, DTS-102, DTS-103 [Midori Chemical Co., Ltd.] and the like.

Among these, a sulfonium-based photocationic polymerization initiator is preferred, and a triarylsulfonium salt is more preferred because it is excellent in active energy ray hardenability and excellent in colorless transparency. As the triarylsulfonium salt, preferred are triphenylsulfonium hexafluorophosphate and diphenyl-4-(phenylthio)phenylphosphonium hexafluorophosphate.

As the component (D), the above compounds may be used singly or in combination of two or more.

The content ratio of the component (D) is from 0.5 to 10% by weight, preferably from 1 to 5% by weight, based on the total amount of the composition. When the content ratio of the component (D) is less than 0.5% by weight, the hardenability of the composition is deteriorated, and if it exceeds 10% by weight, the adhesion of the composition is lowered, or the cured product of the composition is yellowed.

5. Other ingredients

The composition of the present invention is essential to the above components (A) to (D), but various components (referred to as "other components") may be blended depending on the purpose.

The other component may contain the above-mentioned (A) component, (B) component, and the cation hardening compound other than (C) component (it is hereafter called " other cation hardening component. In the case where the other cationically curable component is contained, the total content of the cationic curable components is preferably 100% by weight or less, and more preferably 20% by weight or less. Further, it is preferably 10% by weight or less. Examples of the cation-curable component include an epoxy group-containing compound other than the component (A) and the component (B), an oxetane group-containing compound other than the component (C), and a vinyl ether group-containing compound. Wait.

Specific examples of the epoxy group-containing compound other than the component (A) and the component (B) include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and a double (3,4-epoxycyclohexylmethyl) adipate, caprolactone modification of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, polycarboxylic acid Esterified or caprolactone modification with 3,4-epoxycyclohexylmethanol, dicyclopentadiene dioxide, cerium dioxide, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy An alicyclic epoxy compound such as decane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane and 4-vinylcyclohexane dioxide; bisphenol A diglycidyl ether (Mw Less than 500), bisphenol F diglycidyl ether (Mw less than 500), brominated bisphenol A diglycidyl ether (Mw less than 500), phenol novolac type epoxy resin (Mw less than 500) , cresol novolak type epoxy resin (Mw less than 500), biphenyl type epoxy resin (Mw less than 500), diglycidyl terephthalate, and diglycidyl phthalate 500% aromatic epoxy resin; and polyethylene glycol (repeated number 6 or more) diglycidyl ether, poly a diol (repeated number of 4 or more) diglycidyl ether, polytetramethylene glycol (repeated number 3 or more) diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and a polybutytidine having a hydroxyl group at both ends A diglycidyl ether of a diol having a carbon number of 11 or more, such as a diene diglycidyl ether. In addition to these, an epoxidized vegetable oil, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, and an internal epoxy of polybutadiene may also be mentioned. a compound in which a part of the double bond of the styrene-butadiene copolymer is epoxidized [for example, "EPOFRIEND" manufactured by Daicel Chemical Industries Co., Ltd.], and an ethylene-butene copolymer and polyisoprene. One of the isoprene units of the block copolymer is an epoxidized compound [for example, "L-207" manufactured by KRATON Co., Ltd., and the like.

Specific examples of the oxetane compound other than the component (C) include an alkoxyalkyl group such as 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane. Monofunctional oxetane, such as 3-ethyl-3-phenoxymethyl oxetane, aromatic group-containing monofunctional oxetane, 3-ethyl-3-hydroxyl Etherified modified product of methyloxetane, novolac type phenol-formaldehyde resin and 3-chloromethyl-3-ethyloxetane, 3-[(3-ethyloxetane) 3-yl)methoxy]propyltrimethoxydecane, 3-[(3-ethyloxetan-3-yl)methoxy]propyltriethoxydecane, 3-[( Hydrolyzed condensate of 3-ethyloxetane-3-yl)methoxy]propyltrialkoxydecane, polycondensation of 3-ethyloxetane-3-ylmethanol with decanetetraol a condensation reaction product or the like.

Specific examples of the vinyl ether compound include cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, lauryl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, and triethylene glycol. Alcohol divinyl ether, cyclohexane dimethanol divinyl ether and the like.

The composition of the present invention preferably contains 0.05 to 3% by weight of water in the entire composition. By setting the water content ratio to 0.05% or more, it is possible to prevent the cation hardening from becoming too fast and the force to be lowered. On the other hand, by setting the water content ratio to 3% by weight or less, the hardenability and the adhesion of the composition can be improved.

The composition of the present invention may also contain a radical curable component. In the case of containing a radical curable component, the total amount of these is preferably 120 parts by weight or less, more preferably 100 parts by weight or less, even more preferably 100 parts by weight or less based on 100 parts by total of the total amount of the cationically curable components. Parts by weight or less. Examples of the other radical curable component include a compound containing a (meth) acrylonitrile group. Further, as the molecular weights, various molecular weights may be selected, and any of a monomer, an oligomer, and a polymer may be used.

Examples of the compound containing a (meth) acrylonitrile group include a compound having one (meth) acryl fluorenyl group in the molecule (hereinafter referred to as "monofunctional (meth) acrylate)" and two molecules in the molecule. The compound of the above (meth) acrylonitrile group (hereinafter referred to as "polyfunctional (meth) acrylate"].

Specific examples of the monofunctional (meth) acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and isopropyl (meth)acrylate. Methyl)butyl acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, (meth)acrylic acid Lauryl ester, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) acrylate Cyclohexyl ester, (meth)acrylic acid Ester, 1,4-cyclohexanedimethanol mono(meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyl (meth)acrylate Ethyloxyethyl ester, benzyl (meth)acrylate, (meth)acrylate of phenol alkylene oxide adduct, pair (meth) acrylate of a phenol phenol alkylene oxide adduct, a (meth) acrylate of an o-phenylphenol alkylene oxide adduct, a (meth) acrylate of a nonyl phenol alkylene oxide adduct , (meth) acrylate of 2-methoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, alkylene oxide of 2-ethylhexanol, pentane Diol mono(meth)acrylate, hexanediol mono(meth)acrylate, mono(meth)acrylate of diethylene glycol, mono(meth)acrylate of triethylene glycol, tetraethylene Mono (meth) acrylate of alcohol, mono (meth) acrylate of polyethylene glycol, mono (meth) acrylate of dipropylene glycol, mono (meth) acrylate of tripropylene glycol, single of polypropylene glycol ( Methyl) acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-butoxypropyl (meth)acrylate, tetrahydrofuran methyl (meth)acrylate, The lactone is modified with tetrahydrofuran methyl (meth)acrylate, (2-ethyl-2-methyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, (methyl) ) (2-isobutyl-2-methyl-1,3-dioxolan-4-yl)methyl acrylate (Meth)acrylic acid (1,4-dioxaspiro[4,5]decane-2-yl)methyl ester, glycidyl (meth)acrylate, 3,4-epoxy ring of (meth)acrylic acid Hexylmethyl ester, (3-ethyloxetane-3-yl)methyl (meth)acrylate, 2-(methyl)propenyloxyethyl isocyanate, (meth)acrylic acid allyl Ester, N-(methyl)propenyloxyethylhexahydrophthalate, N-(methyl)propenyloxyethyltetrahydrophthalimide, hexahydroortylene 2-(methyl)propenyloxyethyl dicarboxylate, 2-(methyl)propenyloxyethyl succinate, ω-carboxy-polycaprolactone mono(meth)acrylate, acid phosphate 2 -(Meth) propylene methoxyethyl ester, 3-(meth) propylene methoxy propyl trimethoxy decane, 3-(methyl) propylene methoxy propyl dimethoxy methyl decane, 3 -(Methyl)acryloxypropyltriethoxydecane, and the like. In the above alkylene oxide adduct, examples of the alkylene oxide include ethylene oxide and propylene oxide.

Specific examples of the polyfunctional (meth) acrylate include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and 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- a di(meth)acrylate of an aliphatic diol such as butyl-2-ethyl-1,3-propanediol di(meth)acrylate or 1,9-nonanediol di(meth)acrylate; Di(meth) acrylate of alicyclic diol such as hexane dihydroxymethyl di(meth) acrylate or tricyclodecane dimethylol di(meth) acrylate; diethylene glycol bis ( Alkyl diol di(meth) acrylate such as methyl acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tripropylene glycol di (meth) acrylate An esterification reaction product of neopentyl glycol with hydroxytrimethylacetic acid and (meth)acrylic acid; an alkylene oxide compound of a bisphenol compound such as bis(A) alkylene oxide adduct Di(meth)acrylate; hydrogenated bisphenol A di(methyl) Di(meth)acrylate of a hydrogenated bisphenol compound such as an enoate; trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, pentaerythritol three or four Polyol (meth) acrylate such as (meth) acrylate, dipentaerythritol penta or hexa (meth) acrylate; tris(meth) propyl trimethylolpropane alkylene oxide adduct Terephthalate, di-trimethylolpropane alkylene oxide adduct tetrakis (meth) acrylate, pentaerythritol alkylene oxide adduct tris or tetra (meth) acrylate, dipentaerythritol alkylene oxide plus a poly(meth)acrylate of a polyol alkylene oxide adduct such as a five or six (meth) acrylate; an ethyl methacrylate; an epoxy (meth) acrylate; And polyester (meth) acrylate and the like. The polyester (meth) acrylate may be a dendrimer type (meth) acrylate. In the above alkylene oxide adduct, examples of the alkylene oxide include ethylene oxide and propylene oxide.

In the case where the composition of the present invention contains a radical curable component, it is preferred to contain 0.1 to 10% by weight of the photoradical polymerization initiator based on the entire composition. As the photoradical polymerization initiator, those which are usually available can be used.

In addition to these, the composition of the present invention may contain various additives other than the curable component insofar as the effects of the present invention are not impaired. As various additives, examples thereof include a thermal cationic polymerization initiator, a photosensitizer, an ultraviolet absorber, a light stabilizer, an antioxidant, a polymerization inhibitor, a decane coupling agent, a polyol compound, a polymer, an adhesion-imparting agent, a filler, and a metal. Microparticles, metal oxide microparticles, ion trapping agents, antifoaming agents, leveling agents, pigments, pigments, and the like.

Examples of the polymer include poly(meth)acrylate, polyvinyl acetate, polystyrene, polyether, and polyester. As the polymer, a cationically polymerizable group such as an epoxy group, an oxetane group, or a vinyl ether group may be used in the molecule. Further, a radical polymerizable group such as a (meth)acryl fluorenyl group or a vinyl group may be used in the molecule.

6. Active energy ray hardening type adhesive composition for plastic film or sheet

The present invention relates to a plastic thin film comprising the above components (A) to (D) as essential components. The film or sheet is composed of an active energy ray-curable adhesive composition.

The composition of the present invention preferably has a total chlorine content of 0.1% by weight or less in the composition. As a method of reducing the total chlorine content in the composition, for example, a method in which a distilled refined product is used as all or a part of the component (B) and/or the component (C) can be mentioned.

The method for producing the composition of the present invention may be carried out according to a conventional method, and the components (A) to (D) and, if necessary, other components may be stirred and mixed according to a conventional method. In this case, heating or heating may be performed as needed.

The viscosity of the composition of the present invention may be appropriately set depending on the purpose of use. In order to obtain a coating surface which can be used in a production step using a laminate having a plastic film or the like, and a coating surface which is excellent in smoothness even for a film, the viscosity at 25 ° C is preferably 1,000 mPa ‧ s or less. Good for 10~500mPa‧s, especially for 20~100mPa‧s. In the present invention, the viscosity of the composition means the measured value measured by an E-type viscometer.

The composition of the present invention can be used for the subsequent bonding of plastic films and the like, and various substrates other than plastic films (hereinafter referred to as "other substrates"). That is, it can be used for at least one of two types of substrates such as a plastic film. In the following, the term "base material" means a general term for a plastic film or the like and other substrates. Examples of the other substrate include glass, metal oxide, metal, wood, paper, and the like.

Examples of the material of the plastic film or the like include a cycloolefin polymer, a (meth)acrylic resin, polystyrene, an acrylic acid/styrene copolymer, cellulose triacetate, cellulose acetate butyrate, polyvinyl chloride, and the like. Polyvinylidene chloride, polyethylene, polypropylene, acrylonitrile-butadiene-styrene (ABS) Resins, polyamides, polyesters, polycarbonates, polyurethanes, and chlorinated polypropylenes. Examples of the (meth)acrylic resin include polymethyl methacrylate, a (meth)acrylic resin which is a copolymer of methyl methacrylate as a main component, and no methyl methacrylate as a polymerization. A monomeric (meth)acrylic resin or the like. Among the plastic films and the like, the composition of the present invention can be preferably applied to a cycloolefin polymer and a (meth)acrylic resin.

Examples of the metal oxide include tin oxide, indium oxide, titanium oxide, and zinc oxide. Examples of the metal include gold, silver, copper, aluminum, iron, nickel, titanium, and the like. In the case where the transparent film formed by vapor deposition, sputtering, or the like is used as the substrate, since transparency which is one of the features of the composition of the present invention is required, it can be more preferably applied. .

Further, in the case where the plastic film or the like is a material having difficulty in adhesion, the surface of one or both of them may be activated before the composition of the present invention is applied. Examples of the surface activation treatment include plasma treatment, corona discharge treatment, chemical liquid treatment, roughening treatment, etching treatment, flame treatment, and the like, and these may be used in combination.

7. How to use

The method of using the composition of the present invention may be a conventional method, and examples thereof include a method in which a composition is applied to a substrate, and then bonded to another substrate, and an active energy ray is irradiated. The composition of the present invention is suitable for the case where a thin layer is carried out as a substrate by a substrate. The method of using the thin layer to be carried out in the subsequent step may be carried out in accordance with a method generally carried out in the production of lamination. For example, a method in which a composition is applied to a first thin layer adherend, a second thin layer adherend is bonded thereto, and an active energy ray is irradiated is exemplified.

The coating of the substrate may be carried out according to a conventional method, and examples thereof include a natural coater, a knife belt coater, a floating knife method, and a roll lining blade ( Knife-over-roll method, knife-on-blanket method, spray, dipping method, contact roll method, squeeze roll method, reverse roll method, air blade method, A method such as a curtain coater, a notch coater, a gravure coater, a micro gravure coater, a die coater, and a curtain coater.

Further, the coating thickness of the composition of the present invention may be selected depending on the substrate to be used and the use, and is preferably 0.1 to 10 μm, more preferably 1 to 5 μm.

Examples of the active energy ray include visible light rays, ultraviolet rays, X-rays, and electron beams. In order to use an economical device, ultraviolet rays are preferable.

As a light source in the case of curing by ultraviolet rays, various light sources can be used, and examples thereof include pressurized or high pressure mercury lamps, metal halide lamps, xenon lamps, electrodeless discharge lamps, carbon arc lamps, and light emitting diodes (LED, Light). Emitting Diode) and so on. Among these, high pressure mercury lamps and metal halide lamps are particularly preferred. The amount of ultraviolet radiation, to UV-B region (the vicinity of 310 nm), preferred is 10 ~ 1,000mJ / cm ^2, more preferably 20 ~ 500mJ / cm ^2, further preferably 50 ~ 200mJ / cm ^2.

In the case of hardening by an electron beam, as an electron beam (EB) irradiation device that can be used, various devices can be used, and for example, a Cockcroft-Walton type can be cited. The Van de Graaff type and the resonance transformer type device, etc., as the electron beam, preferably have an energy of 50 to 1000 eV, more preferably 100 to 300 eV.

8. Manufacturing method of laminated body

The composition of the present invention can be preferably used in the manufacture of a laminate. As a laminate The structure is a laminate comprising a substrate, a cured product of the above composition, and another substrate, wherein either or both of the substrate and the other substrate are plastic films or sheets. As a plastic film or the like, at least one of them is preferably a cycloolefin polymer or a (meth)acrylic resin. Specific examples of the method for producing the laminate include a method of applying the above-described composition to a substrate, bonding another substrate to the coated surface, and using any of the substrate or the other substrate. The side of the person illuminates the active energy ray. In this case, a plastic film or the like is used as a substrate or at least one substrate of both the substrate and the other substrate. Specific examples and preferred examples of the substrate are as described above. The coating method of the composition, the film thickness of the composition, and the irradiation conditions of the types of the active energy ray are also as described above.

Examples of the use of the obtained laminated body include various optical films used in liquid crystal displays, organic EL displays, and the like, and specific examples thereof include hard coating films having functions such as anti-fingerprint and anti-glare. Touch panel front panel, polarizing plate, retardation film, viewing angle compensation film, brightness enhancement film, anti-reflection film, anti-glare film, lens sheet and diffusion sheet.

[Examples]

The present invention will be more specifically described below by way of examples and comparative examples. However, the invention is not limited by the examples. In the following, the term "parts" means parts by weight, and the numerical value in the table indicating the ratio of the proportions means % by weight.

In the examples and comparative examples, the components used in the preparation of the composition were as follows, and the following are briefly described as follows.

(A) component

‧J-1004: Bisphenol A type solid epoxy resin (Mw: 4,500, softening point 97 ° C), "jER-1004" manufactured by Mitsubishi Chemical Corporation

‧J-1007: bisphenol A type solid epoxy resin (Mw: 7,000, softening point 128 ° C), "jER-1007" manufactured by Mitsubishi Chemical Corporation

(B) component

‧BD-DGE: 1,4-butanediol diglycidyl ether (distilled refined product), "SR-14BJ" manufactured by Sakamoto Pharmaceutical Co., Ltd.

‧HD-DGE: 1,6-hexanediol diglycidyl ether (distilled refined product), "Epogosey HD (D)" manufactured by Yokkaichi Synthetic Co., Ltd.

‧NPG-DGE: Neopentyl glycol diglycidyl ether (distilled refined product), "NPG-DEP(D)" manufactured by Yokkaichi Synthetic Co., Ltd.

(C) component

‧OXT-221: bis[(3-ethyloxetan-3-yl)methyl]ether, "ARONE OXETANE OXT-221" manufactured by East Asia Synthetic Co., Ltd.

(D) component

‧110P: Triaryl hexafluorophosphate (100% active ingredient), "CPI-110P" manufactured by SAN-APRO Co., Ltd.

(A) '[Aromatic epoxy resin other than (A) component]

‧J-828: Bisphenol A type liquid epoxy resin (Mw: 370), "jER-828" manufactured by Mitsubishi Chemical Corporation

‧850CRP: Distillate refined product of bisphenol A epoxy resin (molecular weight 340), "EDCLON 850-CRP" manufactured by DIC

(A) "Epoxy resin other than [(A) component]

‧Polymer X: a copolymer of the product of Production Example 1 glycidyl methacrylate, methyl methacrylate, and styrene

(other) [other ingredients]

‧2N-220S: Polyester diol (quantitative average molecular weight 2,000, melting point 0 °C), "HS2N-220S" manufactured by Fengguo Oil Co., Ltd.

‧V240: Amorphous polyester resin (number average molecular weight 15,000, glass transition temperature 60 ° C), "Vylon 240" manufactured by Toyobo Co., Ltd.

‧BR-83: Polymethyl methacrylate (Mw: 40,000, glass transition temperature 105 ° C), "Dianal BR-83" manufactured by Mitsubishi Rayon Co., Ltd.

‧LA-1114: block copolymer of polybutyl acrylate and polymethyl methacrylate (the main component of the monomer unit is butyl acrylate) (Mw: 80,000, liquid at room temperature), Kura "Clarity LA1114" manufactured by (share)

Manufacturing example 1) Manufacturing Example 1

The sheath temperature of the pressurized stirred tank reactor having a capacity of 1000 mL of oil jacket was maintained at 190 °C. Then, while maintaining the pressure of the reactor, the glycidyl methacrylate (30 parts), methyl methacrylate (45 parts), styrene (25 parts), and methyl ethyl bromide as a polymerization solvent were started. The monomer mixture of the ketone (18 parts) and the third tert-butyl peroxide (0.25 parts) as a polymerization initiator was continuously supplied from the raw material tank at a fixed supply rate (48 g/min; residence time: 12 minutes). Supply to the reactor, The reaction liquid corresponding to the supply amount of the monomer mixture was continuously withdrawn from the outlet. Immediately after the start of the reaction, the reaction temperature was temporarily lowered, and the temperature rise due to the heat of polymerization was confirmed. The temperature of the oil jacket was controlled to maintain the internal temperature of the reactor at 192 to 194 °C. The time point 36 minutes after the internal temperature of the reactor was stabilized was taken as the starting point of the reaction liquid, and the reaction was continued for 25 minutes from the time point. As a result, 1.2 kg of the monomer mixture was supplied, and 1.2 kg of the reaction was recovered. liquid. Thereafter, the reaction liquid is introduced into a thin film evaporator, and volatile components such as unreacted monomers are separated to remove volatile components such as unreacted monomers, thereby obtaining a polymer "polymer X". As a result of measurement by GPC, the number average molecular weight (Mn) in terms of polystyrene was 3,500, Mw was 9,900, and Tg [measured by Differential Scanning Calorimetry (DSC), and the temperature rise rate was 10 ° C/min] was 65 °C.

2. Example 1 to Example 3, Comparative Example 1 to Comparative Example 9 1) Fabrication of the composition

Each of the components shown in Tables 1 and 2 was formulated in a ratio of each of them, and stirred and mixed in accordance with a conventional method to prepare an active energy ray-curable adhesive composition. For the obtained composition, the viscosity at 25 ° C was measured by an E-type viscometer manufactured by Toki Sangyo Co., Ltd.

2) Manufacturing of laminates

A cycloolefin polymer having a thickness of 100 μm [trade name: ZEONOR ZF-14, manufactured by Japan's Ryan (hereinafter), hereinafter referred to as "ZEONOR"], and an acrylic resin having a thickness of 75 μm to which a UV absorber is added [trade name HI50- 75KT-UV, manufactured by Kuraray Co., Ltd., hereinafter referred to as "acrylic resin", was subjected to corona treatment as an easy-to-continue treatment. Then, on the corona-treated surface of the acrylic resin, the obtained composition was applied to a thickness of 3 μm by a bar coater, and then ZEONOR was laminated. At this time, the corona-treated surface of ZEONOR is placed in contact with the coated surface. Finally, an ultraviolet irradiation device with a conveyor belt manufactured by EYE GRAPHICS (using a metal halide lamp) irradiates ultraviolet rays from the surface of the ZIONOR with a cumulative light amount of 100 mJ/cm ² (UV-B) to harden the adhesive composition. . After the obtained laminate was allowed to stand at 23 ° C and a relative humidity of 50% for one day, colorless transparency and adhesion were evaluated by the following methods. First, application and hardening of the adhesive were carried out under conditions of 23 ° C and a relative humidity of 70%. The obtained laminate was evaluated in accordance with the evaluation method described later. The results are shown in Tables 1 and 2. Here, the test piece was produced under conditions of 23 ° C and a relative humidity of 30% for the composition having good adhesion, and the evaluation was performed in the same manner, and the results are shown in Table 3.

3. Evaluation method 1) Evaluation of colorless transparency

The laminate obtained by the five sheets was superimposed and visually observed, and judged by the following criteria.

A: I don't feel turbid or yellow at all.

B: Slightly turbid or yellowish

C: Clearly feel turbid or yellow

2) Evaluation of the force

○ After storage at room temperature

The obtained laminate was cut into a width of 1 inch and a length of 15 cm, and a polymethyl methacrylate film (PMMA) was coated with a double-sided tape. The side is attached to the aluminum plate. Then, ZEONOR was peeled at 90° at a peeling speed of 200 mm/min, and the adhesion was measured. At this time, the film was immediately broken and the unmeasured person was evaluated as "material cracking". In the case where peeling was possible, the peeling was stopped at 5 cm, and the moist heat resistance test shown below was performed.

○ After the damp heat test

The test piece after the measurement of the adhesion after storage at normal temperature was placed in a constant temperature and humidity chamber of 85% at 85 ° C for 2 days, and then the adhesion was measured in the same manner as the measurement after "keeping after normal temperature".

The compositions of Examples 1 to 3 of the present invention were coated or cured at 70% of 23 ° C or cured at 23 ° C and 30%, and exhibited strong adhesion to both ZEONOR and PMMA. It was then maintained at 85 ° C for 85% and did not decay after 2 days. On the other hand, the composition of Comparative Example 1 to Comparative Example 4 in which the component (A) was replaced with the bisphenol A type liquid epoxy resin which does not belong to the component (A) was coated at 70 ° C and 70%. The adhesion to PMMA is very low. The adhesive force of the composition of Comparative Example 5 in which the component (A) of Example 1 was changed to the polymer X having an epoxy group was strong at the case of hardening at 70 ° C and 70%, and was maintained at 85 ° C and 85%. There was no decline after 2 days. However, in the case of coating and hardening at 30% at 23 ° C, the adhesion at room temperature was strong, but it was lowered to 6.5 N/inch after 2 days at 85% at 85 °C. Next, the composition of Comparative Example 6 to Comparative Example 9 in which the component (A) of Example 1 was changed to various polymers will be described. The composition of Comparative Example 8 using BR-83 was relatively good after 2 days at 85% at 85 ° C, but was inferior to the compositions of Example 1 and Comparative Example 5. The composition of Comparative Example 6 and Comparative Example 9 had a lower adhesion after storage at room temperature, and the composition of Comparative Example 7 had a lower adhesion after 2 days at 85 ° C and 85%.

(industrial availability)

The composition of the present invention can be used as an adhesive for a plastic film or the like, and can be suitably used for light used in a liquid crystal display or an organic EL display. Learn the film.

Claims (14)

An active energy ray-curable adhesive composition for a plastic film or sheet comprising: (A) component: an aromatic epoxy compound having a weight average molecular weight of 500 or more (B) component: having 2 to 10 carbon atoms Polyglycidyl ether (C) component of a polyhydric alcohol: a compound (D) having two or more oxetanyl groups in one molecule and having a molecular weight of 500 or less: a photocationic polymerization initiator; and the above (A) The content of the component (D) is in the entire composition, (A) component: 1 to 30% by weight (B) Component: 10 to 70% by weight (C) Component: 10 to 70% by weight (D) Component: 0.5 to 10% by weight. The active energy ray-curable adhesive composition for a plastic film or sheet according to claim 1, wherein the content of the component (B) is based on 100% by weight of the total of the components (A) and (B). , 51 to 99% by weight. The active energy ray-curable adhesive composition of the plastic film or sheet according to claim 1 or 2, wherein the component (A) has a weight average molecular weight of 1,000 to 20,000 and the number of epoxy groups contained in one molecule It is a compound of 2 or more. The active energy ray-curable adhesive composition for a plastic film or sheet according to any one of claims 1 to 3, wherein the component (A) is a bisphenol A epoxy resin and/or a bisphenol F ring Oxygen resin. The active energy ray-curable adhesive composition for a plastic film or sheet according to any one of claims 1 to 4, wherein the component (B) is a diol having 2 to 6 carbon atoms. Diglycidyl ether. The active energy ray-curable adhesive composition for a plastic film or sheet according to any one of claims 1 to 5, wherein the component (B) is diglycidyl having an alkylene glycol having 4 to 6 carbon atoms. ether. The active energy ray-curable adhesive composition for a plastic film or sheet according to any one of claims 1 to 6, wherein the component (C) is an oxetane compound represented by the following formula (1) : The active energy ray-curable adhesive composition for a plastic film or sheet according to any one of claims 1 to 7, wherein the component (D) is a sulfonium salt-based photocationic polymerization initiator. The active energy ray-curable adhesive composition for a plastic film or sheet according to any one of claims 1 to 8, wherein the composition contains 3 to 20% by weight of the component (A) and (B) 20 to 65% by weight, (C) component 20 to 60% by weight, and (D) component 1 to 5% by weight. The active energy ray-curable adhesive composition for a plastic film or sheet according to any one of claims 1 to 9, wherein the composition contains 0.05 to 3% by weight of water as a whole. The active energy ray-curable adhesive composition for a plastic film or sheet according to any one of claims 1 to 10, wherein at least one of the plastic film or sheet is a cycloolefin polymer or (meth) Acrylic resin. A laminate comprising a substrate, a cured film of a plastic optical film or sheet of any one of claims 1 to 11 and a cured product of an active energy ray-curable adhesive composition, and other substrate, wherein Both or one of the above substrate and the other substrate is a plastic film or sheet. The laminate according to claim 12, wherein at least one of the plastic film or sheet is a cycloolefin polymer or a (meth)acrylic resin. A method for producing a laminate, which comprises applying the composition according to any one of claims 1 to 11 to a substrate, bonding another substrate to the coated surface, and using any of the substrate or the other substrate One side of the active energy ray is irradiated, wherein either or both of the substrate and the other substrate are plastic films or sheets.