TWI692515B - Active energy ray hardening type adhesive composition for plastic film or sheet - Google Patents

Abstract

The present invention provides an active energy ray-curable adhesive composition for plastic films and the like, which has a low viscosity and excellent curability, regardless of whether the environmental humidity during coating and curing is low or high. Various plastic films such as meth)acrylic resins or cycloolefin polymers are excellent in adhesion and colorless transparency.

Specifically, the present invention is an active energy ray hardening type adhesive composition for plastic films or sheets, which contains:

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

(B) Component: Polyglycidyl ether with a polyhydric alcohol having 2 to 10 carbon atoms

(C) Component: a compound with a molecular weight of 500 or less having 2 or more oxetanyl groups in 1 molecule

(D) component: photo-cationic polymerization initiator; and the content ratio of the above components (A) to (D) is in the whole composition,

(A) Ingredient: 1~30% by weight

(B) Ingredient: 10~70% by weight

(C) Ingredient: 10~70% by weight

(D) Ingredient: 0.5-10% by weight.

Description

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

The present invention relates to an active energy ray hardening type adhesive composition capable of bonding various plastic films or sheets by irradiation of active energy rays such as ultraviolet rays, visible light, or electron beams, and is furthermore suitable for use in liquid crystal displays or Manufacture of various optical films or sheets used in organic electroluminescence (EL) displays and the like, and can be preferably used in these technical fields. In addition, in this specification, acrylate and/or methacrylate are represented as (meth)acrylate, and acryl and/or methacryl are represented as (meth)acryl, and Acrylic acid and/or methacrylic acid are represented as (meth)acrylic acid. In addition, in the following, when there is no need to express specifically, the plastic film or sheet is collectively indicated as "plastic film, etc.", and the film or sheet is collectively indicated as "film, etc.".

Conventionally, in the lamination method of bonding thin-film adherends such as plastic films to each other, or laminating thin-film adherends such as plastic films and thin-layer adherends containing it and other materials, the following methods are mainly performed: Dry lamination method: A solvent-based adhesive composition containing an ethylene-vinyl acetate copolymer or a polyurethane-based polymer is applied to the first thin-layer adherend and dried, and then A second thin layer to-be-adhered body is pressed against it by a nip roller or the like. 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. Therefore, a large amount of solvent vapor will be scattered during drying, and the toxicity, operational safety and environmental pollution become problem. As an adhesive composition for solving these problems, solvent-free adhesive compositions are being studied.

As a solventless adhesive composition, a two-component adhesive composition and an adhesive composition hardened by active energy rays such as ultraviolet rays or electron beams are widely used. As the two-component adhesive composition, a so-called polyurethane-based adhesive composition mainly using a polymer having a hydroxyl group at the end as a main agent and a polyisocyanate compound having an isocyanate group at the end as a hardener is used. However, this composition has a disadvantage that it takes a long time to harden. On the other hand, the active energy ray-curable adhesive composition has a fast curing speed and is therefore excellent in productivity. Therefore, it has been increasingly used in recent years.

On the other hand, liquid crystal displays are widely used in mobile devices such as mobile phones, smart phones, and tablets due to their thinness, light weight, and power-saving features. Moreover, it is also popularized in various displays of personal computers, televisions, and car navigation systems. In addition, with mobile devices as the center, the use of organic EL displays is also increasing. Active energy ray-curable adhesives are also widely used for bonding various optical films used in liquid crystal displays or organic EL displays.

Examples of the optical film include a hard-coated film provided with functions such as anti-fingerprint or anti-glare, a touch panel front panel, a polarizing plate, a retardation film, a viewing angle compensation film, a brightness enhancement film, an anti-reflection film, and an anti-reflection film. Glare films, lens sheets and diffusers, etc., which use various plastics.

Among these plastics, amorphous cycloolefin polymers and polymethyl methacrylate are widely used because of their particularly excellent optical properties such as colorless transparency and optical isotropy.

Recently, due to the popularity of electrostatic capacitance touch panels, a large number of actions Phones are being replaced by smart phones, or new products such as tablets are becoming popular. In addition, organic EL displays are developing due to improved performance of organic EL. In this way, the display of the mobile device is still evolving until now, and there are cases where the composition of the optical film or the like needs to be changed. At this time, there are cases where it is necessary to force plastic materials with completely different surface characteristics to be adhered. For example, cycloolefin polymer and polymethyl methacrylate are both widely used plastic materials for optical applications, but the former is non-polar, while the latter is highly polar, and the surface characteristics of the two are completely different. There is a demand for an active energy ray hardening type adhesive agent which can strongly bond the two materials even if it is such a different material, and does not produce yellowing or turbidity after curing, and has excellent transparency. In addition, the adhesive requires a small decrease in adhesion after the humid heat resistance test.

Furthermore, for mobile devices, since thinness and weight reduction are important issues, it is required to reduce the thickness of the adhesive. In order to apply the adhesive thinly, it is important to reduce the viscosity of the adhesive composition. However, in order to reduce the viscosity of solvent-free active energy ray-curable adhesives, (meth)acrylate-based active energy ray-curable adhesives generally contain ethyl (meth)acrylate Its viscosity is high and difficult to use. Therefore, it is difficult to achieve both low viscosity and strong adhesion at the same time using (meth)acrylate adhesives.

In addition, when at least one of the adherends is a thin film, a stronger peeling adhesion force is often required. In order to enhance the peeling adhesion force, it is effective to increase the tan δ and increase in the dynamic viscoelasticity measurement of the adhesive hardened material. Thickness of thick adhesive (Non-Patent Document 1). In other words, if the thickness of the adhesive is 3 μm or less, it is difficult to enhance the peel adhesion.

However, it is revealed that there is a photo-cation hardening type adhesive agent which has a polyfunctional aliphatic epoxy monomer as a main component and contains an alicyclic epoxy monomer and/or an oxetane monomer, even if the thickness of the adhesive agent Thinner, for cycloolefin polymers or cellulose triacetate, etc. The adhesion of plastic materials is also excellent (Patent Document 1).

However, the composition disclosed in Patent Document 1 has a problem that the cationic curing property is poor, and the energy required for curing 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 that is also excellent in curability is desired, specifically, to use B-type ultraviolet (UV-B, Ultraviolet-B) (near 310 nm) at 200 mJ/cm Active energy ray-curable adhesives that exhibit sufficient adhesion even at irradiation doses of ² or less. Furthermore, according to the research results of the inventors, the composition disclosed in Patent Document 1 has the following problems. That is, there is a problem of insufficient adhesion to (meth)acrylic resins such as polymethyl methacrylate and alkyl (meth)acrylate polymers. In addition to this, there is also the problem that if the adhesive is applied and the humidity in the environment during curing is high, the adhesive force will be greatly reduced.

[Prior Technical Literature] [Non-patent literature]

[Non-Patent Document 1] Sandaoji Township, then, Volume 47, No. 8, pages 12-15 (2003)

[Patent Literature]

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

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

As a result of various studies conducted by the present inventors, it has been found that the polyglycidyl ether containing an aromatic epoxy compound having a weight average molecular weight of 500 or more, a polyol having 2 to 10 carbon atoms in a specific ratio, and 1 molecule The active energy ray-curable adhesive composition having a compound having two or more oxetanyl groups with a molecular weight of 500 or less and a photo-cationic polymerization initiator can solve the above-mentioned problems and complete the present invention.

The present invention relates to an active energy ray hardening type adhesive composition for plastic films or sheets, which contains:

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

(B) Component: Polyglycidyl ether with a polyhydric alcohol having 2 to 10 carbon atoms

(C) Component: a compound having two or more oxetanyl groups with a molecular weight of 500 or less in 1 molecule

(D) component: photo-cationic polymerization initiator; and the content ratio of the above components (A) to (D) is in the whole composition,

(A) Ingredient: 1~30% by weight

(B) Ingredient: 10~70% by weight

(C) Ingredient: 10~70% by weight

(D) Ingredient: 0.5-10% by weight.

The content ratio of (B) component is preferably greater than the content ratio of (A) component For example, it is preferable that the content ratio of (B) component is 51 to 99% by weight based on the total amount of (A) component and (B) component being 100% by weight.

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

The component (D) is preferably a cerium salt-based photocationic polymerization initiator.

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

In addition, the present invention relates to a laminated body composed of a base material, a cured product of the above-mentioned plastic film or active energy ray-curable adhesive composition for a sheet, and other base materials, and the base material and Two or one of the other substrates mentioned above are plastic films or sheets. As a plastic film or sheet, at least one of them is preferably a cycloolefin polymer or a (meth)acrylic resin.

In addition, the present invention relates to a method for manufacturing a laminate, which is to apply the above-mentioned composition to a substrate, and to adhere to other substrates on the coated surface, and from the substrate or above The side of any of the other substrates is irradiated with active energy rays, wherein, either or both of the above substrates and the other substrates are plastic films or sheets.

According to the present invention, it is possible to provide an active energy ray-curable adhesive composition, which has a low viscosity and excellent curability, regardless of whether the environmental humidity during coating and curing is high or low. The adhesion of various plastic films of meth)acrylic resin is excellent, and the colorless transparency is also excellent. Therefore, it can be suitably used for the production of various optical films used in liquid crystal displays, organic EL displays, and the like. In addition, it can be suitably used for applications other than displays, such as windows or building materials, or for various applications requiring low viscosity, curability, adhesion, and transparency.

The present invention relates to an active energy ray hardening type adhesive composition for plastic films or sheets, which contains:

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

(B) Component: Polyglycidyl ether with a polyhydric alcohol having 2 to 10 carbon atoms

(C) Component: a compound having two or more oxetanyl groups with a molecular weight of 500 or less in 1 molecule

(D) component: photo-cationic polymerization initiator; and the content ratio of the above components (A) to (D) is in the whole composition,

(A) Ingredient: 1~30% by weight

(B) Ingredient: 10~70% by weight

(C) Ingredient: 10~70% by weight

(D) Ingredient: 0.5-10% by weight.

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

1. (A) Ingredients

(A) The component 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 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 even a compound with a low molecular weight is commonly known as "epoxy "Resin" compound.

(A) The Mw of the component is 500 or more, preferably in the range of 500 to 50,000, more preferably in the range of 1,000 to 20,000, further preferably in the range of 1,000 to 10,000, particularly preferably in the range of 2,000 to 10,000. If the Mw is less than 500, under relatively high ambient humidity, the adhesion with the plastic substrate, especially the (meth)acrylic resin, becomes low. Also, for the same reason, Mw is preferably 50,000 or less.

In the present invention, Mw means polystyrene-converted Mw measured by gel permeation chromatography (GPC, Gel Permeation Chromatography). In addition, as the low molecular weight epoxy compound that does not belong to the component (A), an absolute molecular weight that can be measured by mass analysis can also be used.

The component (A) is preferably an aromatic epoxy compound that is solid at 25°C, and specifically, an aromatic epoxy compound having a softening point of 40°C or higher. By using an aromatic epoxy compound with a softening point of 40°C or higher, the adhesion with plastic substrates, especially (meth)acrylic resins, can be improved under relatively high ambient humidity conditions. The softening point is more preferably 50°C or higher and 200°C or lower, and further preferably 60 ℃ or more and 170°C or less, particularly preferably 70°C or more and 140°C or less. In the present invention, the so-called softening point means the measured value measured by the JIS K7234 ring and ball method.

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

Preferred specific examples of the component (A) include bisphenol A type epoxy resin with Mw of 500 or more, bisphenol F type epoxy resin, polycondensation of bisphenol A with bisphenol F and epichlorohydrin The epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin and bisphenol F novolac epoxy resin, etc.

As the component (A), bisphenol A type epoxy resin, bisphenol F type epoxy resin, epoxy resin formed by polycondensation of bisphenol A and bisphenol F, and epichlorohydrin are more preferred, and bisphenol is more preferred Phenol A type epoxy resin and bisphenol F type epoxy resin, especially bisphenol A type epoxy resin.

As the component (A), the above compounds may be used alone, or two or more kinds may be used. (A) The content ratio of the component is 1 to 30% by weight in the entire composition. If the component (A) is less than 1% by weight, the adhesion of the composition will decrease when the environmental humidity during coating and curing is high. In addition, if the content ratio of the component (A) exceeds 30% by weight, the viscosity of the composition becomes too high, and the coatability deteriorates. (A) The preferable content ratio of the component is 3 to 20% by weight in the entire composition, and more preferably 5 to 15% by weight.

2. (B) Ingredients

(B) The component 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 hydroxyl group is removed from the polyol The number of carbons in the base.

Examples of the component (B) include polyglycidyl ethers of alkane polyols, polyglycidyl ethers of naphthenic polyols, polyalkylene glycol polyglycidyl ethers, and polyglycidyl ethers of aromatic polyols. . (B) The component is preferably a diglycidyl ether having a diol having 2 to 6 carbon atoms, and more preferably a diglycidyl ether having an alkylene glycol 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, 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 triglycidyl ether Glycerol ether, pentaerythritol polyglycidyl ether and dipentaerythritol polyglycidyl ether, etc.

The component (B) is more preferably composed of ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexane Glycol diglycidyl ether, hydroquinone diglycidyl ether, resorcinol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, etc. exemplified have carbon numbers 2 to 6 The second glycidyl ether of glycol.

As the component (B), in view of the low viscosity of the obtained composition, excellent adhesion of the cured product, and further colorless and transparent, 1,4-butanediol diglycidyl ether and neopentyl are preferred Glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and the like are exemplified by diglycidyl ethers of alkylene glycols having 4 to 6 carbon atoms.

As the component (B), the above compounds may be used alone, or two the above. (B) The content ratio of the component is 10 to 70% by weight in the entire composition. If the (B) component is less than 10% by weight, the adhesion of the composition to most plastic substrates will decrease. In addition, if the content of the component (B) exceeds 70% by weight, the curability of the composition deteriorates, and the adhesion also deteriorates. (B) The preferable content ratio of the component is 20 to 65% by weight in the entire composition, and more preferably 30 to 60% by weight. In addition, the content ratio of the component (B) is preferably greater than the content ratio of the component (A) in terms of making the composition low in viscosity and excellent in adhesion. Specifically, based on a total of 100% by weight of the (A) component and (B) component, the (B) component is preferably 51 to 99% by weight, and more preferably 65 to 95% by weight.

3. (C) ingredients

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

Specific examples of the component (C) include bis[(3-ethyloxetane-3-yl)methyl]ether and bis[(3-methyloxetane-3-yl )Methyl]ether, bis[(oxetane-3-yl)methyl]ether, 1,4-bis{[(3-ethyloxetan-3-yl)methoxy] Methyl}benzene, 1,4-bis[(3-ethyloxetane-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- Tris[(3-ethyloxetan-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 and so on.

As the component (C), bis[(3-ethyloxetane-3-yl)methyl] ether, that is, an oxetane compound represented by the following formula (1) is particularly preferred.

When the molecular weight of the component (C) is 500 or less, it is preferably 150 to 400, more preferably 150 to 300, and particularly preferably the compound represented by the above formula (1). The elastic modulus 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 can be used alone, or two or more kinds can be used. (C) The content of the component is 10 to 70% by weight in the entire composition. If the (C) component is less than 10% by weight, the curability of the composition deteriorates, and the adhesion also deteriorates. In addition, if the content of the component (C) exceeds 70% by weight, the adhesion of the composition to most plastic substrates will decrease. (C) The preferable content ratio of the component is 20 to 60% by weight in the entire composition, and more preferably 25 to 55% by weight.

4. (D) ingredients

(D) The component is a photo-cationic polymerization initiator. That is, a compound that generates cations or Lewis acids by irradiation of active energy rays such as ultraviolet rays or electron beams, and initiates polymerization of cationic hardening components such as epoxy compounds and oxetane compounds. As specific examples of the component (D), there can be mentioned yak salt-based photo-cationic polymerization initiators, phosphonium salt-based photo-cationic polymerization initiators, diazonium salt-based photo-cationic polymerization initiators, and the like.

六氟銻酸鹽、7-[二(對甲苯甲醯基)二氫硫基]-2-異丙基9-氧硫

肆(五氟苯基)硼酸鹽、4-苯基羰基-4'-二苯基二氫硫-二苯硫醚六氟磷酸鹽、4-(對第三丁基苯基羰基)-4'-二苯基二氫硫基-二苯硫醚六氟銻酸鹽、4-(對第三丁基苯基羰基)-4'-二(對甲苯甲醯基)二氫硫基-二苯硫醚肆(五氟苯基)硼酸鹽等三芳基鋶鹽。 Examples of the cerium salt-based photo-cationic polymerization initiator include, for example, triphenyl arsonium hexafluorophosphate, triphenyl arsonium hexafluoroantimonate, triphenyl arsonium (pentafluorophenyl) borate, Diphenyl-4-(phenylthio) phenyl alkane hexafluorophosphate, diphenyl-4-(phenylthio) phenyl alkane hexafluoroantimonate, 4,4'-bis(diphenyl alkane Group) diphenyl sulfide bishexafluorophosphate, 4,4'-bis[bis(β-hydroxyethoxy)phenyldihydrothio]diphenyl sulfide bishexafluoroantimonate, 4,4' -Bis[bis(β-hydroxyethoxy)phenyldihydrothio]diphenyl sulfide bishexafluorophosphate, 7-[bis(p-tolylmethyl)dihydrothio]-2-isopropyl 9-oxygen

Hexafluoroantimonate, 7-[bis(p-tolylmethyl)dihydrosulfanyl]-2-isopropyl 9-oxysulfide

(Pentafluorophenyl) borate, 4-phenylcarbonyl-4'-diphenyldihydrosulfide-diphenylsulfide hexafluorophosphate, 4-(p-third butylphenylcarbonyl)-4' -Diphenyldihydrothio-diphenyl sulfide hexafluoroantimonate, 4-(p-tert-butylphenylcarbonyl)-4'-bis(p-tolylmethyl)dihydrothio-diphenyl Thiaryl ether (pentafluorophenyl) borate and other triaryl alkane salts.

基錪肆(五氟苯基)硼酸鹽、(4-甲基苯基)[4-(2-甲基丙基)苯基]-六氟磷酸鹽、二(4-壬基苯基)錪六氟磷酸鹽、二(4-烷基苯基)錪六氟磷酸鹽等二芳基錪鹽。 As examples of the photocationic polymerization initiators of the antimony salt system, for example, there can be mentioned: diphenylphosphonium (pentafluorophenyl) borate, diphenylphosphonium hexafluorophosphate, diphenylphosphonium hexafluoroantimonate, Di(4-tert-butylphenyl) hexafluorophosphate, bis(4-tert-butylphenyl) hexafluoroantimonate, tolyl

Phenylphosphonium (pentafluorophenyl) borate, (4-methylphenyl) [4-(2-methylpropyl)phenyl]-hexafluorophosphate, bis(4-nonylphenyl)phosphonium Diaryl phosphonium salts such as hexafluorophosphate, bis (4-alkylphenyl) hexafluorophosphate.

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

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

Among these, for the reason that the active energy ray is excellent in curability and colorless transparency, it is preferably a cerium salt-based photocationic polymerization initiator, and more preferably a triaryl cerium salt. As the triaryl alkoxide salt, among the above, triphenyl alkoxide hexafluorophosphate and diphenyl-4-(phenylthio)phenyl alkoxide hexafluorophosphate are preferable.

As the component (D), the above compounds can be used alone, or two or more kinds can be used.

(D) The content ratio of the component is 0.5 to 10% by weight in the entire composition, preferably 1 to 5% by weight. If the content ratio of the component (D) is less than 0.5% by weight, the hardenability of the composition becomes poor. If it exceeds 10% by weight, the adhesion of the composition decreases, or the hardened product of the composition becomes yellow.

5. Other ingredients

The composition of the present invention requires the aforementioned components (A) to (D) as essential, but various components (referred to as "other components") can be formulated according to the purpose.

As other components, a cation-curable compound (hereinafter, referred to as "other cation-curable component") other than the components (A), (B), and (C) may be contained. When other cationic hardening components are included, the total content of these components is 100% by weight of the total cationic hardening components, preferably 30% by weight or less, more preferably 20% by weight or less It is more preferably 10% by weight or less. Examples of the cationic hardening component include: (A) component and (B) component other than epoxy group-containing compound, (C) component other than oxetane group-containing compound, and vinyl ether group-containing compound Wait.

Specific examples of epoxy group-containing compounds other than the component (A) and the component (B) include: 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, caprolactone modified product of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, polycarboxylic acid Esterified with 3,4-epoxycyclohexylmethanol or caprolactone-modified product, dicyclopentadiene dioxide, huo dioxide, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy Alicyclic epoxy compounds such as silane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane and 4-ethylenecyclohexane dioxide; diglycidyl ether of bisphenol A (Mw Less than 500), diglycidyl ether of bisphenol F (Mw less than 500), diglycidyl ether of brominated bisphenol A (Mw less than 500), phenol novolac epoxy resin (Mw less than 500) , Cresol novolac epoxy resin (Mw less than 500), biphenyl epoxy resin (Mw less than 500), diglycidyl terephthalate, and diglycidyl phthalate, etc. Aromatic epoxy resin over 500; and polyethylene glycol (repeated number 6 or more) diglycidyl ether, polypropylene glycol (repeated number 4 or more) diglycidyl ether, poly 1,4-butanediol (repeated The number is 3 or more) diglycidyl ether such as diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, polybutadiene diglycidyl ether having hydroxyl groups at both ends and the like, and a diol having a carbon number of 11 or more. In addition to these, epoxidized vegetable oil, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, internal epoxy of polybutadiene Compound, epoxidized compound of a part of double bond of styrene-butadiene copolymer [for example, "EPOFRIEND" manufactured by Daicel Chemical Industry Co., Ltd.], and ethylene-butene copolymer and polyisoprene The epoxidized compound of a part of the isoprene unit of the block copolymer [for example, "L-207" manufactured by Kraton (KRATON), etc.

Specific examples of oxetane compounds other than the component (C) include alkoxyalkanes such as 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane Monofunctional oxetane, such as 3-ethyl-3-phenoxymethyloxetane, containing monofunctional oxetane, 3-ethyl-3-hydroxy Methyloxetane, novolac-type phenol-formaldehyde resin and 3-chloromethyl-3-ethyloxetane etherification modification, 3-[(3-ethyloxetane -3-yl)methoxy]propyltrimethoxysilane, 3-[(3-ethyloxetan-3-yl)methoxy]propyltriethoxysilane, 3-[( 3-ethyloxetane-3-yl)methoxy]propyltrialkoxysilane hydrolyzed condensate, 3-ethyloxetane-3-ylmethanol and silanetetraol polycondensation The product of the condensation reaction of the substance.

Specific examples of vinyl ether compounds include cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, and triethylene dioxide. Alcohol divinyl ether, cyclohexane dimethanol divinyl ether, etc.

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

The composition of the present invention may contain a radical hardening component. When a radical hardening component is included, the total amount of these is preferably 120 parts by weight or less relative to 100 parts by weight of the total amount of the cationic hardening component, more preferably 100 parts by weight or less, and further preferably 50 Below parts by weight. Examples of other radical-curable components include compounds containing (meth)acryloyl groups. In addition, as these molecular weights, various molecular weights may be selected, and may be any of monomers, oligomers, and polymers.

Examples of the compound containing (meth)acryloyl group include compounds having one (meth)acryloyl group in the molecule [hereinafter, referred to as "monofunctional (meth)acrylate"] and two in the molecule. The above (meth)acryloyl compound [hereinafter, referred to as "multifunctional (meth)acrylate"].

酯、1,4-環己烷二甲醇單(甲基)丙烯酸酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯基氧基乙酯、(甲基)丙烯酸苄酯、苯酚環氧烷加成物之(甲基)丙烯酸酯、對

基苯酚環氧烷加成物之(甲基)丙烯酸酯、鄰苯基苯酚環氧烷加成物之(甲基)丙烯酸酯、壬基苯酚環氧烷加成物之(甲基)丙烯酸酯、2-(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙氧基乙酯、2-乙基己醇之環氧烷加成物之(甲基)丙烯酸酯、戊二醇單(甲基)丙烯酸酯、己二醇單(甲基)丙烯酸酯、二乙二醇之單(甲基)丙烯酸酯、三乙二醇之單(甲基)丙烯酸酯、四乙二醇之單(甲基)丙烯酸酯、聚乙二醇之單(甲基)丙烯酸酯、二丙二醇之單(甲基)丙烯酸酯、三丙二醇之單(甲基)丙烯酸酯、聚丙二醇之單(甲基)丙烯酸酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯、(甲基)丙烯酸2-羥基-3-丁氧基丙酯、(甲基)丙烯酸四氫呋喃甲酯、己內酯改質(甲基)丙烯酸四氫呋喃甲酯、(甲基)丙烯酸(2-乙基-2-甲基-1,3-二氧雜環戊烷-4-基)甲酯、(甲基)丙烯酸(2-異丁基-2-甲基-1,3-二氧雜環戊烷-4-基)甲酯、(甲基)丙烯酸(1,4-二氧雜螺[4,5]癸烷-2-基)甲酯、(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸3,4-環氧環己基甲酯、(甲基)丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯、異氰酸2-(甲基)丙烯醯氧基乙酯、(甲基) 丙烯酸烯丙酯、N-(甲基)丙烯醯氧基乙基六氫鄰苯二甲醯亞胺、N-(甲基)丙烯醯氧基乙基四氫鄰苯二甲醯亞胺、六氫鄰苯二甲酸2-(甲基)丙烯醯氧基乙酯、琥珀酸2-(甲基)丙烯醯氧基乙酯、ω-羧基-聚己內酯單(甲基)丙烯酸酯、酸式磷酸2-(甲基)丙烯醯氧基乙酯、3-(甲基)丙烯醯氧基丙基三甲氧基矽烷、3-(甲基)丙烯醯氧基丙基二甲氧基甲基矽烷、3-(甲基)丙烯醯氧基丙基三乙氧基矽烷等。於上述環氧烷加成物中，作為環氧烷，可列舉環氧乙烷及環氧丙烷等。 Specific examples of monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, ( Butyl meth)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)acrylic acid Cyclohexyl, (meth)acrylic acid

Ester, 1,4-cyclohexanedimethanol mono(meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyl (meth)acrylate Oxyethyl ester, benzyl (meth)acrylate, (meth)acrylic acid ester of phenol alkylene oxide adduct,

(Meth) acrylate of alkylphenol alkylene oxide adduct, (meth)acrylate of o-phenylphenol alkylene oxide adduct, (meth)acrylate of nonylphenol alkylene oxide adduct , (Meth)acrylic acid 2-(meth)acrylate, (meth)acrylic acid ethoxyethoxyethyl, 2-ethylhexanol alkylene oxide adduct (meth)acrylate, pentan Glycol mono(meth)acrylate, hexylene glycol mono(meth)acrylate, diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, tetraethylenedioxide Mono(meth)acrylate of alcohol, mono(meth)acrylate of polyethylene glycol, mono(meth)acrylate of dipropylene glycol, mono(meth)acrylate of tripropylene glycol, mono(meth)acrylate of polypropylene ( Methacrylate), 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-butoxypropyl (meth)acrylate, methyl tetrahydrofuran (meth)acrylate, hexyl Modification of lactone tetrahydrofuran methyl (meth)acrylate, (2-ethyl-2-methyl-1,3-dioxol-4-yl) methyl (meth)acrylate, (methyl ) (2-isobutyl-2-methyl-1,3-dioxolane-4-yl) methyl acrylate, (meth)acrylic acid (1,4-dioxaspiro[4,5 ] Decane-2-yl) methyl ester, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl methyl (meth) acrylate, (3-ethyl oxetane) (meth) acrylic acid Alkyl-3-yl)methyl ester, 2-(meth)acryloyloxyethyl isocyanate, allyl (meth)acrylate, N-(meth)acryloyloxyethyl hexahydrophthalate Dimethyimine, N-(meth)acryloyloxyethyltetrahydrophthalimide, hexahydrophthalic acid 2-(meth)acryloyloxyethyl, succinic acid 2 -(Meth)acryloyloxyethyl ester, ω-carboxy-polycaprolactone mono(meth)acrylate, 2-(meth)acryloyloxyethyl acid phosphate, 3-(methyl) Acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyldimethoxymethylsilane, 3-(meth)acryloyloxypropyltriethoxysilane, etc. In the above-mentioned alkylene oxide adduct, examples of the alkylene oxide include ethylene oxide and propylene oxide.

Specific examples of polyfunctional (meth)acrylates 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- Di(meth)acrylates of aliphatic diols such as butyl-2-ethyl-1,3-propanediol di(meth)acrylate and 1,9-nonanediol di(meth)acrylate; Di(meth)acrylates of alicyclic diols such as hexane dimethylol di(meth)acrylate and tricyclodecane dimethylol di(meth)acrylate; diethylene glycol di(meth)acrylate Alkylene glycol di(meth)acrylates such as meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate and tripropylene glycol di(meth)acrylate ; Esterification reaction product of neopentyl glycol with hydroxytrimethylacetic acid and (meth)acrylic acid; alkylene oxide addition of bisphenol compounds such as bisphenol A alkylene oxide adduct Bis(meth)acrylate of the product; bis(meth)acrylate of hydrogenated bisphenol compounds such as hydrogenated bisphenol A bis(meth)acrylate; trimethylolpropane tri(meth)acrylate , Di-trimethylolpropane tetra (meth) acrylate, pentaerythritol tri or tetra (meth) acrylate, di pentaerythritol penta or hexa (meth) acrylate and other polyol poly (meth) acrylate; three Hydroxymethyl propane alkylene oxide adduct (trimethyl) propane Enoic acid ester, tetra-(meth)acrylate of di-trimethylolpropane alkylene oxide adduct, tri- or tetra(meth)acrylate of dipentaerythritol alkylene oxide adduct, dipentaerythritol alkylene oxide addition Poly(meth)acrylates of polyol alkylene oxide adducts such as penta or hexa(meth)acrylates; urethane (meth)acrylates; epoxy (meth)acrylates; And polyester (meth) acrylate and so on. The polyester (meth)acrylate may be a dendrimer type (meth)acrylate. In the above-mentioned alkylene oxide adduct, examples of the alkylene oxide include ethylene oxide and propylene oxide.

When the composition of the present invention contains a radical hardening component, it is preferable to contain 0.1 to 10% by weight of a photo radical polymerization initiator based on the entire composition. As a photo radical polymerization initiator, those which can usually be obtained can be used.

In addition to these, the composition of the present invention may contain various additives other than the hardening component within the range that does not impair the effect of the present invention. Examples of various additives include thermal cationic polymerization initiators, photosensitizers, ultraviolet absorbers, light stabilizers, antioxidants, polymerization inhibitors, silane coupling agents, polyol compounds, polymers, adhesion-imparting agents, fillers, and metals Fine particles, metal oxide fine particles, ion trapping agents, defoamers, leveling agents, pigments and pigments, etc.

Examples of the polymer include poly(meth)acrylate, polyvinyl acetate, polystyrene, polyether, and polyester. As the polymer, those containing cationic polymerizable groups such as epoxy groups, oxetanyl groups, and vinyl ether groups in the molecule can also be used. In addition, those containing a radical polymerizable group such as (meth)acryloyl group or vinyl group in the molecule can also be used.

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

The present invention relates to thin plastics containing the above components (A) to (D) as essential components Active energy ray hardening type adhesive composition for film or sheet.

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

The method for producing the composition of the present invention may be a conventional method, and it may be produced by stirring and mixing the above-mentioned components (A) to (D) and other components as necessary according to a conventional method. In this case, it may be heated or heated as necessary.

The viscosity of the composition of the present invention may be appropriately set according to the purpose of use. In order to obtain a coating surface that can be used in a manufacturing process using a laminate with a plastic film, etc., and is excellent in smoothness even if it is a film, the viscosity at 25°C is preferably 1,000 mPa‧s or less, and more The best is 10~500mPa‧s, and the best is 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 adhering plastic films and the like, and adhering plastic films and other various substrates (hereinafter, referred to as "other substrates"). In other words, it can be used to bond at least one of two types of substrates such as plastic films. In addition, in the following, when only referred to as "substrate", it means the general term for plastic films and other substrates. Examples of other substrates include glass, metal oxides, metals, wood, and paper.

Examples of materials for plastic films include cycloolefin polymers, (meth)acrylic resins, polystyrene, acrylic/styrene copolymers, cellulose triacetate, cellulose acetate butyrate, polyvinyl chloride, Polyvinylidene chloride, polyethylene, polypropylene, acrylonitrile-butadiene-styrene (ABS) Resin, polyamide, polyester, polycarbonate, polyurethane, chlorinated polypropylene, etc. Examples of (meth)acrylic resins include polymethyl methacrylate, (meth)acrylic resin which is a copolymer containing methyl methacrylate as a main component, and methyl methacrylate is not included as a polymer (Meth)acrylic resins such as monomers. Among these plastic films and the like, the composition of the present invention can be preferably applied to cycloolefin polymers and (meth)acrylic resins.

Examples of metal oxides include tin oxide, indium oxide, titanium oxide, and zinc oxide. Examples of the metal include gold, silver, copper, aluminum, iron, nickel, and titanium. Among these, when the transparent film formed by vapor deposition or sputtering is the base material, since the transparency which is one of the characteristics of the composition of the present invention is required in many cases, it can be more preferably applied .

Furthermore, in the case where plastic films and other materials are difficult to adhere to, one or both surfaces may be activated before coating the composition of the present invention. Examples of the surface activation treatment include plasma treatment, corona discharge treatment, chemical treatment, roughening treatment, etching treatment, flame treatment, etc., and these may be used in combination.

7. How to use

As a method for using the composition of the present invention, a conventional method may be used, and a method of applying a composition to a substrate and bonding it to another substrate and irradiating an active energy ray, etc. may be mentioned. The composition of the present invention is suitable for a case where a thin layer adherend is used as a base material. The method of use in the case where the thin-layer adherend is to be adhered may be a method generally performed in the manufacture of lamination. For example, a method of applying the composition to the first thin-layer adherend, bonding the second thin-layer adherend to it, and irradiating the active energy ray, etc.

The coating of the substrate may be performed according to a conventional method, and examples include natural coater, knife belt coater, floating knife method, and roller liner blade ( knife-over-roll method, knife-on-blanket method, spraying, dipping method, contact roll method, squeeze roll method, reverse roll method, air blade method, The methods of curtain coating machine, corner wheel coating machine, gravure coating machine, micro gravure coating machine, die coating machine and curtain coating machine.

In addition, the coating thickness of the composition of the present invention may be selected according to the base material and application to be used, preferably 0.1 to 10 μm, more preferably 1 to 5 μm.

Examples of active energy rays include visible rays, ultraviolet rays, X-rays, and electron beams. In order to be able to use economical devices, ultraviolet rays are preferred.

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

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

8. Manufacturing method of laminate

The composition of the present invention can be preferably used in the production of laminates. As a laminate The structure is a laminate composed of a base material, a hardened product of the above-mentioned composition, and other base materials, wherein both or one of the above-mentioned base materials and other base materials are plastic films or sheets. As the plastic film or the like, at least one of them is preferably a cycloolefin polymer or a (meth)acrylic resin. As a method of manufacturing the laminate, specifically, the following methods may be mentioned: the above composition is applied to a substrate, another substrate is bonded to the coated surface, and either of the above substrate or the other substrate is used The side of the person is irradiated with active energy rays. In this case, a plastic film or the like is used as the substrate or at least one substrate of both the above 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, the irradiation conditions of the type of active energy rays, etc. are also as described above.

Examples of applications of the obtained laminate include various optical films used in liquid crystal displays, organic EL displays, and the like, and specific examples include hard coating films provided with 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, etc.

[Example]

The present invention will be described more specifically below with examples and comparative examples. However, the present invention is not limited by these examples. In addition, in the following, the so-called "parts" means parts by weight, and the numerical value in the table indicating the blending ratio means% by weight.

In the examples and comparative examples, the components used in the preparation of the composition are as follows, and the following is abbreviated as follows.

(A) Ingredients

‧J-1004: Bisphenol A type solid epoxy resin (Mw: 4,500, softening point 97℃), "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) Ingredients

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) Ingredients

‧OXT-221: bis[(3-ethyloxetan-3-yl)methyl] ether, "ARONE OXETANE OXT-221" manufactured by Toyasei Corporation

(D) Ingredients

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

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

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

‧Polymer X: copolymer of glycidyl methacrylate, methyl methacrylate, and styrene

(Other) [other ingredients]

‧2N-220S: Polyester diol (quantity average molecular weight 2,000, melting point 0°C), "HS2N-220S" manufactured by Feng Guo 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℃), "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), Kuraray (Share) Manufactured "Clarity LA1114"

1. Manufacturing Example 1) Manufacturing example 1

The temperature of the jacket of the 1000 mL pressurized stirred tank reactor equipped with an oil jacket was maintained at 190°C. Then, while keeping the pressure of the reactor fixed, the process started to contain glycidyl methacrylate (30 parts), methyl methacrylate (45 parts), styrene (25 parts), and methyl ethyl as a polymerization solvent. The monomer mixture of base ketone (18 parts) and di-tertiary butyl peroxide (0.25 parts) as the polymerization initiator was continuously fed from the raw material tank at a fixed supply rate (48 g/min; residence time: 12 minutes) Supply to the reactor, And the reaction liquid corresponding to the supply amount of the monomer mixture is continuously drawn from the outlet. Immediately after the start of the reaction, after the reaction temperature was temporarily lowered, it was confirmed that the temperature was increased due to the heat of polymerization. By controlling the temperature of the oil jacket, the internal temperature of the reactor was maintained at 192 to 194°C. The time point after 36 minutes from the stabilization of the internal temperature of the reactor was taken as the starting point for the reaction liquid to be taken, and the reaction was continued for 25 minutes from this time point. As a result, 1.2 kg of the monomer mixed liquid was supplied, and 1.2 kg of the reaction was recovered. liquid. Thereafter, the reaction liquid was introduced into a thin-film evaporator, and volatile components such as unreacted monomers were separated, and volatile components such as unreacted monomers were removed to obtain a polymer "Polymer X". The measurement result of GPC is that the polystyrene-equivalent number average molecular weight (Mn) is 3,500, Mw is 9,900, and Tg [Differential Scanning Calorimetry (DSC, Differential Scanning Calorimetry) measurement, heating rate 10°C/min] is 65°C.

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

The components shown in Table 1 and Table 2 are prepared in respective proportions, and stirred and mixed according to a conventional method to prepare an active energy ray-curable adhesive composition. For the obtained composition, the viscosity at 25° C. was measured with an E-type viscometer manufactured by Toki Industry Co., Ltd.

2) Manufacturing of laminates

Cycloolefin polymer with a thickness of 100 μm [trade name ZEONOR ZF-14, manufactured by Japan Ruion Co., Ltd., hereinafter referred to as “ZEONOR”], and an acrylic resin with a thickness of 75 μm added with a UV absorber [trade name HI50- 75KT-UV, manufactured by Kuraray Co., Ltd., hereinafter referred to as "acrylic resin"] is subjected to corona treatment as an easy adhesion treatment. Then, on the corona-treated surface of the acrylic resin, the obtained composition was applied to a thickness of 3 μm using a bar coater, and then ZEONOR was laminated. At this time, the arrangement is such that the corona treatment surface of ZEONOR is in contact with the coating surface. Finally, an ultraviolet irradiation device (using a metal halide lamp) with a conveyor belt manufactured by EYE GRAPHICS Co., Ltd. irradiates ultraviolet rays from the surface of ZEONOR 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 for 1 day under the condition of 23° C. and a relative humidity of 50%, the colorless transparency and adhesion were evaluated according to the following method. First, apply and cure the adhesive under the conditions of 23°C and 70% relative humidity. The obtained laminate was evaluated according to the evaluation method described later. The results are shown in Table 1 and Table 2. Here, a test piece was also prepared under the conditions of 23° C. and a relative humidity of 30% for a composition with good adhesion, and the same evaluation was performed. The results are shown in Table 3.

3. Evaluation method 1) Evaluation of colorless transparency

The laminates obtained by stacking 5 sheets were visually observed and judged by the following criteria.

A: No turbidity or yellowing at all

B: Cloudiness or yellowing is slightly felt

C: Cloudiness or yellowing is clearly felt

2) Evaluation of adhesion

○After storage at room temperature

Cut the obtained laminate into a width of 1 inch and a length of 15 cm, and use a double-sided tape to form a polymethyl methacrylate (PMMA) film The side is attached to the aluminum plate. Next, ZEONOR was peeled at a peeling speed of 200 mm/min at 90°, and the adhesive force was measured. At this time, those who could not measure the film immediately were evaluated as "material fracture". When peeling is possible, the peeling is stopped at 5 cm, and the humidity and heat resistance test shown below is performed.

○After humidity and heat resistance test

After putting the test piece with the measured adhesion after normal temperature storage into a constant temperature and humidity bath at 85°C and 85% for 2 days, the adhesion was measured in the same manner as the measurement after "normal temperature storage".

The composition of Example 1 to Example 3 of the present invention exhibits strong adhesion to ZEONOR and PMMA regardless of whether coating at ‧ 70% at 23°C, curing or coating at 23% at 30% ‧ curing Its adhesive force did not decline after being kept at 85°C 85% for 2 days. On the other hand, the components of Comparative Examples 1 to 4 in which the (A) component was replaced with a bisphenol A type liquid epoxy resin that was not the (A) component were applied at 23°C 70% and cured , Adhesion to PMMA is very low. The adhesive strength of the composition of Comparative Example 5 in which the component of Example 1 (A) is changed to the polymer X having an epoxy group is hardened at 23°C 70%, it is strong, and it is maintained at 85°C 85% It did not decline after 2 days. However, in the case of coating and curing at 23°C and 30%, although the adhesion at room temperature is strong, it is reduced to 6.5N/inch after 8 days at 85°C and 85%. Next, the composition of Comparative Examples 6 to 9 in which the component of Example 1 (A) is changed to various polymers will be described. The composition of Comparative Example 8 using BR-83 at 85° C. 85% after 2 days also had relatively good adhesion, but it was inferior to the compositions of Example 1 and Comparative Example 5. The adhesion of the compositions of Comparative Example 6 and Comparative Example 9 after storage at room temperature was also low, and the adhesion of the composition of Comparative Example 7 after 85 days at 85% at 85% was low.

(Industry availability)

The composition of the present invention can be used as an adhesive for plastic films and the like, and is particularly suitable for light used in liquid crystal displays or organic EL displays Then learn the film.

Claims (14)

An active energy ray-curable adhesive composition for plastic films or sheets, comprising: (A) component: 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 polyhydric alcohol: Compound (D) component having two or more oxetanyl groups and a molecular weight of 500 or less in one molecule: photocationic polymerization initiator; and (A) above The content ratio of ~(D) component is in the whole composition, (A) component: 1~30 wt% (B) component: 10~70 wt% (C) component: 10~70 wt% (D) component: 0.5~10% by weight. The active energy ray-curable adhesive composition for plastic films or sheets according to claim 1, wherein the content ratio of (B) component is based on the total amount of 100% by weight of (A) component and (B) component , 51 to 99% by weight. The active energy ray-curable adhesive composition for plastic films or sheets according to claim 1, wherein (A) component is a weight average molecular weight of 1,000 to 20,000 and the number of epoxy groups contained in 1 molecule is 2 The above compounds. The active energy ray-curable adhesive composition for plastic films or sheets according to claim 1, wherein (A) component is bisphenol A epoxy resin and/or bisphenol F epoxy resin. The active energy ray-curable adhesive composition for plastic films or sheets as claimed in claim 1, wherein component (B) is diglycidol having a diol having 2 to 6 carbon atoms ether. The active energy ray-curable adhesive composition for plastic films or sheets according to claim 1, wherein the component (B) is a diglycidyl ether having an alkylene glycol having 4 to 6 carbon atoms. The active energy ray-curable adhesive composition for plastic films or sheets according to claim 1, wherein component (C) is an oxetane compound represented by the following formula (1):

The active energy ray hardening type adhesive composition for plastic films or sheets according to claim 1, wherein the component (D) is a photo salt cationic polymerization initiator. The active energy ray-curable adhesive composition for plastic films or sheets according to claim 1, which contains (A) component 3 to 20% by weight and (B) component 20 to 65% by weight in the entire composition, (C) The component is 20 to 60% by weight, and (D) the component is 1 to 5% by weight. The active energy ray hardening type adhesive composition for a plastic film or sheet according to claim 1, wherein the entire composition contains 0.05 to 3% by weight of water. The active energy ray-curable adhesive composition for a plastic film or sheet according to claim 1, 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 product of an active energy ray-curable adhesive composition for a plastic film or sheet according to any one of claims 1 to 11, and other substrates, wherein, Two or one of the above substrates and the other substrates are plastic films or sheets. The laminate according to claim 12, wherein at least one of the plastic film or sheet is a cycloolefin polymer or (meth)acrylic resin. A method for manufacturing a laminate, which is to apply the composition of any one of claims 1 to 11 to a substrate, and to adhere the other substrate to the coated surface, and from the above substrate or any of the above other substrates One side is irradiated with active energy rays, wherein both or one of the above-mentioned substrate and the above-mentioned other substrate are plastic films or sheets.