TW201716526A - Active-energy-ray curing adhesive composition for plastic film or plastic sheet - Google Patents

Abstract

The present invention provides an active-energy-ray curing adhesive composition for a plastic film, having low viscosity, excellent curability, excellent adhesiveness with respect to a plastic film or the like made of a cellulose-acetate-based resin, cyclo-olefin polymer, or the like, and also having excellent colorlessness and transparency. Specifically, the present invention is a composition containing components (A), (B), and (C), described below, and is an active-energy-ray curing adhesive composition for a plastic film or plastic sheet, wherein the composition as a whole contains 15 to 45 % by weight of the component (A), 10 to 75 % by weight of the component (B), and 0.5 to 10 % by weight of the component (C). The component (A) is a compound that has three or more (meth)acryloyl groups in one molecule thereof, and that has the (meth)acryloyl-group equivalent weight is equal to or less than 200 g/eq; the component (B) is polyglycidyl ether of polyol having 2 to 10 carbon atoms; and the component (C) is a photocationic polymerization initiator.

Description

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

The present invention relates to an active energy ray-curable adhesive composition which can be applied to various plastic films or sheets by irradiation with active energy rays such as ultraviolet rays, visible rays or electron beams, and is further applicable to liquid crystal displays or organic ELs ( Electroluminescence) The manufacture of optical films or sheets used in displays and the like is preferred in these technical fields.

Further, in the present specification, acrylate and/or methacrylate are represented by (meth) acrylate; propylene fluorenyl and/or methacryl fluorenyl are represented by (meth) acrylonitrile; acrylic acid and/or nail The acrylic acid is represented by (meth)acrylic acid.

In addition, in the following, the plastic film or sheet is represented by "plastic film or the like", and the film or sheet is represented by "film or the like".

Conventionally, a laminate method in which a thin layer of a plastic film or the like is adhered to each other, or a thin layer of an adherend such as a plastic film and a thin layer of a other material is adhered to, is mainly composed of ethylene-vinyl acetate. After the solvent-based adhesive composition of the copolymer or the polyurethane-based polymer is applied and dried by the first thin layer, the second thin-layer adherend is crimped by a nip roller or the like. Dry laminate method.

The adhesive composition used in such a method generally contains a large amount of solvent in order to make the coating amount of the composition uniform, so that a large amount of solvent vapor is volatilized during drying, thereby causing toxicity, work safety, and environmental pollution. Sex and other issues.

As a binder composition for solving such problems, a solvent-based adhesive composition was investigated.

As a solventless adhesive composition, a two-liquid type adhesive composition and an adhesive composition which is cured by active energy rays such as ultraviolet rays or electron beams are widely used.

The two-component type adhesive composition mainly uses 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, that is, a polyurethane-based adhesive composition. However, this composition has the disadvantage of requiring long-time hardening.

On the other hand, the active energy ray-curable adhesive composition has a high curing rate and is excellent in productivity, and has been gradually used in recent years.

On the other hand, liquid crystal displays are widely used in portable devices such as mobile phones, smart phones, and tablets because of their advantages of thinness, light weight, and power saving. In addition, it is also widely used in various displays of personal computers, televisions, and car navigation systems. Further, the organic EL display is also centered on the portable device, and the use case is gradually increasing. The active energy ray-curable adhesive is also widely used when it is bonded to various optical films used for liquid crystal displays or organic EL displays.

Examples of the optical film and the like include a hard coat film that imparts 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 an anti-reflection film. Glare films, lens sheets, diffusers, etc., which use various types of plastics.

Among these plastics, cellulose acetate-based resins such as cellulose triacetate and cycloolefin polymers are widely used because of excellent optical properties such as colorless transparency and optical isotropic properties.

Recently, due to the popularity of electrostatic capacitance type touch panels, it has become more common that most mobile phones have been replaced by new products such as smart phones and tablets. Also, organic EL displays have been growing due to the improved performance of organic ELs. As a result, displays for portable devices are now evolving, but the composition of optical films and the like will vary in this case. At this time, there is a case where the necessity of forcing the plastic material having completely different surface characteristics is followed. For example, cellulose acetate resins and cyclic olefin polymers are plastic materials widely used in optical applications, but these adhesions are completely different. Therefore, an active energy ray-curable adhesive which can strongly adhere to such a different material and which does not cause yellowing or turbidity after curing and is excellent in transparency is sought.

Further, the portable device is an important issue because of its thinness and weight reduction, and therefore the thickness of the adhesive is also required to be thin. In order to apply the adhesive thinly, 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 urethane (meth) acrylate which is generally used for the (meth) acrylate-based active energy ray-curable adhesive, Because of its high viscosity, it is difficult to use. Therefore, it is difficult for the (meth)acrylate-based adhesive to have both low viscosity and strong adhesion.

Further, when at least one of the adherends is a film, a strong peeling force is required, and the peeling force is increased to increase the tan δ of the dynamic viscoelasticity measurement of the cured material of the adhesive, and the thickening is continued. The thickness of the agent is effective (Non-Patent Document 1). In other words, when the film thickness of the adhesive is 3 μm or less, it is difficult to strengthen the peeling adhesion force.

However, a cationic photocurable adhesive containing an alicyclic epoxy monomer and/or a propylene oxide monomer having a polyfunctional aliphatic epoxy monomer as a main component is disclosed, even if the thickness of the adhesive is thin. , for cycloolefin polymer or cellulose triacetate The adhesive force of the adhesive material is still excellent (Patent Document 1).

However, the composition disclosed in Patent Document 1 has a problem that the cationic hardenability is poor and the energy required for hardening is high. For this reason, there is a need to delay the line rate of the next step, or to increase the number of light sources. In view of the viewpoint of productivity, the active energy ray-curable adhesive which is excellent in curability is specifically desired to be UV-B (near 310 nm) of 200 mJ/cm ² or less, more preferably 100 mJ/ An active energy ray-curable adhesive which exhibits sufficient adhesion under an irradiation dose of cm ² or less.

[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.)

In view of the above problems, it is an object of the present invention to provide a plastic film having excellent adhesion to a plastic film such as a cellulose acetate resin or a cycloolefin polymer, and excellent in colorless transparency. An energy ray hardening type adhesive composition.

As a result of various studies to solve the above problems, the inventors of the present invention found that three or more (meth)acryl fluorenyl groups in one molecule and a (meth) acrylonitrile group equivalent of 200 g/eq or less are contained in a specific ratio. Compound, with 2 to 10 carbon atoms The polyepoxypropyl ether of a polyhydric alcohol and the active energy ray-curable adhesive composition of a cationic photopolymerization 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, which composition contains the following components (A), (B) and (C), and the composition is a whole (A) The component is 15 to 45% by weight, the component (B) is 10 to 75% by weight, and the component (C) is 0.5 to 10% by weight.

(A) component: a compound having three or more (meth)acrylonyl groups in one molecule and having a (meth)acrylonitrile group equivalent of 200 g/eq or less; (B) component: having 2 to 10 carbon atoms a polyepoxypropyl ether of a polyhydric alcohol; (C) component: a cationic photopolymerization initiator.

The component (A) is preferably a compound having 3 to 6 (meth)acrylonyl groups in one molecule and having a (meth)acrylonitrile group equivalent of 150 g/eq or less.

The component (B) is preferably a diglycidyl ether having a diol having 2 to 10 carbon atoms, more preferably a diglycidyl ether having a diol having 2 to 6 carbon atoms.

As the component (C), a phosphonium salt cationic photopolymerization initiator is preferred.

In the composition of the present invention, the component (D) preferably contains 0.1 to 10% by weight of a radical photopolymerization initiator. Further, the component (E) preferably contains 1 to 40% by weight of an epoxy compound having two or more aromatic rings and two or more epoxy groups in one molecule. Further, the component (F) preferably contains 1 to 40% by weight of a compound having two or more oxetanyl groups in one molecule and having a molecular weight of 500 or less.

As the component (D), a hydrogen scavenging type radical photopolymerization initiator is preferred.

As the component (E), a bisphenol epoxy resin is preferred.

The component (F) is preferably a compound represented by the following formula (1).

Further, it is preferable to 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 cellulose acetate resin or a cycloolefin polymer.

Moreover, the present invention relates to a laminated body comprising a base material, a cured product of an active energy ray-curable adhesive composition of the above-mentioned plastic film or sheet, and a laminate of the other substrate, and the base Both or one of the other materials described above are plastic films or sheets.

As the plastic film or sheet, at least one of them is preferably a cellulose acetate resin or a cycloolefin polymer.

Furthermore, the present invention relates to a method for producing a laminate, which comprises applying the above composition to a substrate, bonding another substrate to the coated surface, and from either the substrate or the other substrate. The active energy ray is irradiated, and 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 is excellent in adhesion to a plastic film such as cellulose acetate or a cycloolefin polymer and excellent in colorless transparency, and is excellent in low viscosity and hardenability. Therefore, it can be applied to the manufacture of an optical film used for a liquid crystal display or an organic EL display. Further, applications other than the display, such as windows, building materials, and the like, are also applicable to various applications requiring low viscosity, hardenability, adhesion, and transparency.

The present invention relates to an active energy ray-curable adhesive composition for a plastic film or sheet, which comprises the following components (A), (B) and (C), and contains the entire composition (A) The component is 15 to 45 wt%, the component (B) is 10 to 75 wt%, and the component (C) is 0.5 to 10 wt%.

(A) component: a compound having three or more (meth)acrylonyl groups in one molecule and having a (meth)acrylonitrile group equivalent of 200 g/eq or less; (B) component: having 2 to 10 carbon atoms a polyepoxypropyl ether of a polyhydric alcohol; (C) component: a cationic photopolymerization initiator.

Hereinafter, the components (A) to (C) will be described. Next, the preferred blending components (D) to (F), other components, and preferred methods of using the compositions of the present invention will be described in detail.

1. (A) component

The component (A) is a compound having three or more (meth)acrylonyl groups in one molecule and having a (meth)acrylonitrile group equivalent of 200 g/eq or less.

When the component (A) is blended in an appropriate amount, it has an effect of improving the adhesion of the cellulose acetate-based substrate or the adhesion of the cycloolefin polymer after the corona treatment.

Even a compound having three or more (meth) acrylonitrile groups in one molecule and a compound having a (meth) acrylonitrile group equivalent of more than 200 g/eq have a decrease in adhesion to a cellulose acetate-based substrate or the like. problem.

The (meth) acrylonitrile group equivalent in the present invention means (meth) propylene fluorenyl group per 1 mole The weight (g/eq) of the component (A) refers to the value obtained by calculation based on the molecular weight of the component (A) and the amount of the (meth)acrylon group in one molecule.

The component (A) is preferably a compound having 3 to 6 (meth)acrylonyl groups in one molecule and having a (meth)acrylonitrile group equivalent of 150 g/eq or less, more preferably (meth)acryl. A compound having a thiol equivalent of 80 to 150 g/eq. Further, a compound having 3 to 4 (meth)acrylonyl groups in one molecule and having a (meth)acrylonitrile group equivalent of 80 to 150 g/eq is more preferable.

Further, as the component (A), a compound having no amine group and urethane bond is preferable because the cation hardenability of the component (B) is deteriorated.

Specific examples of the component (A) include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, and glycerin tris(A). Polyol (meth) acrylate such as acrylate, diglycerol tetra(meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate; trishydroxyl Tris(meth)acrylate of an alkylene oxide adduct of a propane, tetra(meth)acrylate of an alkylene oxide adduct of pentaerythritol, and hexa(methyl) of an alkylene oxide adduct of dipentaerythritol Alkylene oxide addition of a polyhydric alcohol such as an acrylate, a tris(meth) acrylate of an alkylene oxide adduct of glycerol, or an alkylene oxide adduct of a diglycerol Poly(meth)acrylate; tris(meth)acrylate of isomeric cyanide alkylene oxide adduct; and polyester (meth)acrylic acid having 3 or more (meth)acrylonitrile groups Ester and the like.

The alkylene oxide adduct is preferably ethylene oxide or propylene oxide as the alkylene oxide. Further, a poly(meth) acrylate having an alkylene oxide adduct of a polyhydric alcohol and a polyester (meth) acrylate having three or more (meth) acrylonitrile groups, and a (meth) acrylonitrile group An equivalent of 200 g/eq or less is necessary.

Preferable examples of the component (A) include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, and glycerin tri ( Methyl) acrylate.

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 15 to 45% by weight based on the entire composition.

When the content ratio of the component (A) is less than 15% by weight or, conversely, more than 45% by weight, the adhesion of the cellulose acetate or the corona-treated cycloolefin polymer to the plastic film is lowered. From this point of view, the component (A) is preferably contained in an amount of 15 to 40% by weight.

2. (B) ingredients

The component (B) is a polyepoxypropyl ether having a polyhydric alcohol having 2 to 10 carbon atoms.

Further, the "carbon number" in the polyol having 2 to 10 carbon atoms means the number of carbon atoms formed by the portion after removing the hydroxyl group from the polyol.

When the component (B) is blended in an appropriate amount, it has an effect of improving the adhesion of the cellulose acetate-based substrate or the adhesion of the cycloolefin polymer after the corona treatment.

The component (B) is preferably a diepoxypropyl ether having a diol having 2 to 10 carbon atoms, from the viewpoint that the composition is low in viscosity and excellent in adhesion between the composition and the plastic substrate. More preferably, it is a diglycidyl ether of a diol having 2 to 6 carbon atoms, more preferably a diglycidyl ether of an alkanediol having 2 to 6 carbon atoms.

In addition, as a component (B), the total chlorine content is preferably 1% or less, more preferably 0.5% or less, further preferably 0.2% or less, from the viewpoint that the composition is excellent in curability and adhesion. It is 0.1% or less.

The above total chlorine amount can be measured by quartz tube combustion-ion chromatography.

Specific examples of the component (B) include ethylene glycol diepoxypropyl ether, propylene glycol diepoxypropyl ether, 1,4-butanediol diepoxypropyl ether, and neopentyl glycol II. Epoxypropyl ether, 1,6-hexanediol diepoxypropyl ether, cyclohexane dimethylol diepoxypropyl ether, 1,9-nonanediol diepoxypropyl ether, diethyl Glycol diepoxypropyl ether, triethylene glycol diepoxypropyl ether, dipropylene glycol diepoxypropyl ether, tripropylene glycol diepoxypropyl ether, hydroquinone diepoxypropyl ether, Hydroquinone diepoxypropyl ether, glycerol diepoxypropyl ether, trimethylolpropyl diglycidyl ether, trimethylolpropyl triepoxypropyl ether, pentaerythritol three or four A epoxidized propyl ether, and a di- or tri-epoxypropyl ether of an isomeric cyanuric acid ethylene oxide adduct.

Preferable examples of the component (B) include ethylene glycol diepoxypropyl ether, propylene glycol diepoxypropyl ether, 1,4-butanediol diepoxypropyl ether, and neopentyl glycol. Diepoxypropyl ether, 1,6-hexanediol diepoxypropyl ether, and the like.

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

The content ratio of the component (B) is 10 to 75% by weight based on the entire composition.

When the content ratio of the component (B) is less than 10% by weight, the adhesion of the composition is lowered for many plastic substrates. In addition, when the component (B) exceeds 75% by weight, the hardenability of the composition is deteriorated, and the force is also deteriorated.

The content ratio of the component (B) is preferably from 15 to 60% by weight, more preferably from 15 to 50% by weight, based on the total amount of the composition.

3. (C) ingredients

The component (C) is a cationic photopolymerization initiator. That is, via ultraviolet light or electrons A compound in which a cationic or Lewis acid is generated by irradiation with an active energy ray, and a cationically curable component such as an epoxy compound or an oxetane compound other than the component (A) or a component (A) described later is polymerized.

Specific examples of the component (C) include a phosphonium salt cationic photopolymerization initiator, a phosphonium salt cationic photopolymerization initiator, and a diazonium salt cationic photopolymerization initiator.

Examples of the onium salt-based cationic photopolymerization initiator include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, and triphenylsulfonium (pentafluorophenyl) borate. Diphenyl-4-(phenylthio)phenylphosphonium hexafluorophosphate, diphenyl-4-(phenylthio)phenylphosphonium hexafluoroantimonate, 4,4'-bis[diphenylsulfonate Disulfide diphenyl bis hexafluorophosphate, 4,4′-bis[bis(β-hydroxyethoxy)benzenesulfonyl]sulfide diphenyl bis hexafluoroantimonate, 4,4′-double [Bis(β-hydroxyethoxy)benzenesulfonyl]diphenylbishexafluorophosphate, 7-[bis(p-toluene)sulfonyl]-2-isopropyl 9-oxosulfur Hexafluoroantimonate, 7-[bis(p-toluene)sulfonyl]-2-isopropyl 9-oxosulfide Bis(pentafluorophenyl)borate, 4-phenylcarbonyl-4'-diphenylsulfonyl-diphenylphosphonium sulfide, 4-(p-tert-butylphenylcarbonyl)-4'-diphenyl Sulfosyl-diphenyl hexafluoroantimonate, 4-(p-tert-butylphenylcarbonyl)-4'-bis(p-toluene)sulfonyl-diphenylphosphonium(pentafluorophenyl)borate Triaryl sulfonium salt such as salt.

Examples of the onium salt-based cationic photopolymerization initiator include diphenylphosphonium (pentafluorophenyl) borate, diphenylphosphonium hexafluorophosphate, and diphenylphosphonium hexafluoroantimonate. Bis(4-t-butylphenyl)phosphonium hexafluorophosphate, bis(4-t-butylphenyl)phosphonium hexafluoroantimonate, tolylpyridinium (pentafluorophenyl)boronic acid Salt, (4-methylphenyl)[4-(2-methylpropyl)phenyl]-hexafluorophosphate, bis(4-mercaptophenyl)phosphonium hexafluorophosphate, di(4-alkane) Diarylsulfonium salt such as phenyl) quinone hexafluorophosphate.

As an example of the diazonium salt cationic photopolymerization initiator, an example is exemplified. Such as: diazobenzene hexafluoroantimonate, diazobenzene hexafluorophosphate and the like.

The component (C) is commercially available, and examples thereof include ADEKA OPTOMER SP-100, SP-150, SP-152, SP-170, SP-172 (made by ADEKA), and Photoinitiator 2074. (made by RHODIA), KAYARAD PCI-220, PCI-620 (made by Nippon Chemical Co., Ltd.), IRGACURE250 (made by Chiba‧Japan), CPI-100P, CPI-110P, CPI-101A, CPI-200K, CPI -210S (San-Apro), WPI-113, WPI-116 (made 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, the sulfonium-based cationic photopolymerization initiator, more preferably a triarylsulfonium salt, is preferred because it is excellent in storage stability as an adhesive, excellent in active energy ray curability, and excellent in colorless transparency. . As the triarylsulfonium salt, among the above articles, triphenylsulfonium hexafluorophosphate and diphenyl-4-(phenylthio)phenylphosphonium hexafluorophosphate are preferred.

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 0.5 to 10% by weight, preferably 1 to 7% by weight based on the entire composition. When the content ratio of the component (C) 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 is yellowed.

4. Other ingredients

In the composition of the present invention, the components (A) to (C) described above are essential, but various components (hereinafter referred to as "other components") may be blended for the purpose.

As a preferable example of other components, for example, radical photopolymerization An initiator (hereinafter referred to as "(D) component)", an epoxy compound having two or more aromatic rings and two or more epoxy groups in one molecule (hereinafter referred to as "(E) component)", in one molecule A compound having two or more oxetanyl groups and having a molecular weight of 500 or less (hereinafter referred to as "(F) component").

Hereinafter, the components (D), (E), and (F) will be described.

4-1. (D) component

The radically curable component such as the component (A) contained in the composition of the present invention is capable of utilizing the radical sclerosis generated when the component (C) is decomposed by light, but sufficient reaction is obtained in order to obtain a small amount of irradiation. The ratio is preferably a compound (D) (radical photopolymerization initiator).

Specific examples of the component (D) include, for example, 4'-phenoxy-2,2-dichloroacetophenone, 4'-t-butyl-2,2-dichloroacetophenone, and 2, 2-dimethoxy-2-phenylacetophenone, 2-methyl-1-(4-methylphenylthio)-2- Orolinyl propan-1-one, 1-hydroxycyclohexyl phenyl ketone, α,α-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methylpropan-1-one, and 2-benzyl-2-dimethylamino-1-(4- An acetophenone photopolymerization initiator such as phenylphenyl phenyl-butan-1-one; benzoin ether, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether Polymerization initiator; diphenyl ketone, methyl phthalic acid benzoate, 4-phenyl diphenyl ketone, 4-benzylidene-4'-methyl diphenyl sulfide, and 2,4,6 a diphenyl ketone photopolymerization initiator such as trimethyldiphenyl ketone; 2-isopropyl 9-oxosulfur 2,4-diethyl 9-oxosulfur 2,4-dichloro 9-oxosulfur And 1-chloro-4-propoxy 9-oxosulfur 9-oxosulfur Photopolymerization initiator; 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl Phosphate-based phosphine-based photopolymerization initiators such as pentylphosphine oxide and bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide; 1,2-octanedione, 1-[ 4-(phenylthiophenyl)]-, 2-(o-benzamide) and the like 肟 ester photopolymerization initiator; and camphorquinone.

The component (D) may be used singly or in combination of two or more kinds in combination with desired properties.

As component (D), 9-oxosulfur A hydrogen-trapping type radical polymerization initiator such as a photopolymerization initiator or a diphenylketone-based photopolymerization initiator is preferred because it has an effect of improving the adhesion to a plastic substrate. Among these, 9-oxosulfur It is particularly preferable that the photopolymerization initiator has a higher effect of improving the adhesion.

In the case where the component (D) is blended, the content ratio thereof is preferably 0.1 to 10% by weight, and more preferably 0.1 to 5% by weight based on the entire composition. When the content of (D) is 0.1% by weight or more, the curability is excellent, and when it is 10% by weight or less, yellowing of the cured product can be prevented.

4-2. (E) component

The component (E) is an epoxy compound having one or more aromatic rings and two or more epoxy groups in one molecule. However, the (E) component in the present invention, the polyepoxypropyl ether of a polyhydric alcohol having 10 or less carbon atoms such as di-epoxypropyl ether of naphthalenediol is not included in the component (E).

When the component (E) is blended in an appropriate amount, the effect of improving the adhesion to the cellulose acetate-based substrate or the cycloolefin polymer after the corona treatment is enhanced.

Specific examples of the component (E) include bisphenol A epoxy resin, bisphenol F epoxy resin, brominated bisphenol A epoxy resin, bisphenol A, bisphenol F, and epoxy chloride. Epoxy resin, novolak type epoxy resin, cresol A novolac type epoxy resin, a bisphenol A novolak type epoxy resin, a bisphenol F novolak type epoxy resin, and a biphenyl type epoxy resin.

Here, the epoxy resin refers to a compound or a polymer having an average of two or more epoxy groups in the molecule and hardened by a reaction. According to the practice in this field, in the present specification, if there are two or more hardening epoxy groups in the molecule, even a monomer is called an epoxy resin.

As the component (E), a bisphenol epoxy resin such as a bisphenol A epoxy resin or a bisphenol F epoxy resin is particularly preferable from the viewpoint of adhesion. In addition, as the component (E), the total chlorine content is preferably 0.5% or less, more preferably 0.3% or less, and still more preferably 0.2% or less from the viewpoint of adhesion.

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

In the case where the component (E) is blended, the content ratio thereof is preferably from 1 to 40% by weight, more preferably from 5 to 30% by weight, even more preferably from 10 to 30% by weight based on the entire composition.

4-3. (F) component

The component (F) is a compound having two or more oxetanyl groups in one molecule and having a molecular weight of 500 or less. By blending the component (F) in an appropriate amount, the hardenability of the composition can be improved, and the adhesion between the cured product of the composition and the plastic substrate can be improved.

Specific examples of the component (F) include bis[(3-ethyloxetan-3-yl)methyl]ether and bis[(3-methyloxetane-3-) 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-ethyl) Oxetane-3-yl)methoxy]benzene, 1,2-bis[(3-ethyloxetan-3-yl)methoxy]benzene, 4,4'-double [ (3-ethyloxetan-3-yl)methoxy]biphenyl, 2,2'-bis[(3-ethyloxetan-3-yl)methoxy]biphenyl 1,1,1-para[(3-ethyloxetan-3-yl)methoxymethyl]propane, 1,2-bis[(3-ethyloxetane-3) -yl)methoxy]ethane, 1,2-bis[(3-ethyloxetan-3-yl)methoxy]propane, 1,4-bis[(3-ethyloxa) Cyclobutane-3-yl)methoxy]butane and 1,6-bis[(3-ethyloxetan-3-yl)methoxy]hexane and the like.

The component (F) preferably has two oxetanyl groups and a molecular weight of from 150 to 400 in terms of a low viscosity of the obtained composition and an excellent adhesion of the cured product. The compound, more preferably, has a molecular weight in the range of from 150 to 300.

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

The adhesion of the cellulose acetate-based resin or the cycloolefin polymer after the corona treatment becomes more powerful by appropriately blending the component (F). Further, the hardenability of the composition is also improved, and the amount of the cationic photopolymerization initiator is also small, which is sufficient.

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

When the component (F) is blended, the proportion of the component is based on the entire composition. It is preferably 1 to 40% by weight, more preferably 5 to 35% by weight, still more preferably 10 to 30% by weight.

4.4 Other ingredients than the above

Although the components (D) to (F) which are preferred examples of the other components have been described above, various components other than these may be blended for the purpose of blending.

The other component may contain the cation curable compound (hereinafter referred to as "other cation curable component") other than the above (B) component, (E) component, and (F) component. In the case of the other cation-hardening component, the total content of the components is preferably 30% by weight or less, more preferably 20% by weight or less, and still more preferably 10% by weight or less based on the total amount of the composition. Examples of the other cation-curable component include an epoxy group-containing compound other than the component (B) and the component (E), an oxetane group-containing compound other than the component (F), and a vinyl ether-containing compound. .

Specific examples of the epoxy group-containing compound other than the component (B) and the component (E) include, for example, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate. a caprolactone modification of bis(3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, Esterified or caprolactone modification of polycarboxylic acid and 3,4-epoxycyclohexylmethyl alcohol, dicyclopentadiene dioxide, limonyl dioxide, 2-(3,4-epoxycyclohexyl An alicyclic epoxy compound such as ethyl trimethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltriethoxy decane, and 4-vinylcyclohexene dioxide; and polyethylene glycol (repeated number 6 or more) diepoxypropyl ether, polypropylene glycol (repeated number 4 or more) diepoxypropyl ether, polytetramethylene glycol (repeated number 3 or more) diepoxypropyl ether, both ends A diglycidyl ether of a diol having a carbon number of 11 or more, such as a polybutadiene diepoxypropyl ether of a hydroxyl group.

Other examples of such are: epoxidized vegetable oil, 3-glycidoxypropyltrimethoxy decane, 3-glycidoxypropylmethyldimethoxy decane, and internal epoxide of polybutadiene. Wait.

Specific examples of the oxetane other than the component (F) include an alkoxyalkyl group such as 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane. A monofunctional oxetane, 3-ethyl-3-hydroxymethyl group containing an aromatic group such as a monofunctional oxetane or a 3-ethyl-3-phenoxymethyloxetane Oxetane, etherified modified product of 3-chloromethyl-3-ethyloxetane derived from novolac type phenol formaldehyde resin, 3-[(3-ethyloxetane- 3-yl)methoxy]propyltrimethoxy decane, 3-[(3-ethyloxetan-3-yl)methoxy]propyltriethoxy decane, 3-[(3-ethyl Hydrodegradation condensate of oxetane-3-yl)methoxy]propyltrialkoxydecane (molecular weight over 500), 3-ethyloxet-3-ylmethanol and decane IV A condensation reaction product of an alcohol polycondensate or the like.

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

In the composition of the present invention, it is preferred that the composition contains 0.05 to 3% by weight of water as a whole. The adhesion can be increased by the content ratio of water being 0.05% by weight or more. On the other hand, when the content ratio of water is 3% by weight or less, the hardenability of the composition can be prevented from decreasing.

The composition of the present invention may contain a radical curable component other than the component (A) (hereinafter referred to as "other radical curable component").

Examples of the other radical curable component include a compound containing a (meth) acrylonitrile group. Further, as the molecular weight of the above, various types may be selected, and monomers may be used. Any of an oligomer and a polymer.

The compound containing a (meth) acrylonitrile group may, for example, be a compound having one (meth) acryl fluorenyl group in the molecule (hereinafter referred to as "monofunctional (meth) acrylate"), and have two molecules in the molecule. (meth)acryloyl group-based compound (hereinafter referred to as "difunctional (meth) acrylate"), and having three or more (meth) acrylonitrile groups in the molecule and (meth) acryl oxime equivalents exceeding 200 g /eq compound (hereinafter referred to as "polyfunctional (meth) acrylate other than (A) component).

Specific examples of the monofunctional (meth) acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and propyl (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, hydroxypropyl 2-(meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) acrylate Cyclohexyl ester, (meth)acrylic acid Ester, 1,4-cyclohexanedimethylol mono(meth)acrylate, dicyclopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl B Oxy (meth) acrylate, benzyl (meth) acrylate, (meth) acrylate of phenol alkylene oxide adduct, (meth) acrylate of p-isopropylphenol alkylene oxide adduct, (Meth) acrylate of o-phenylphenol alkylene oxide adduct, (meth) acrylate of nonylphenol alkylene oxide adduct, 2-methoxyethyl (meth) acrylate, B Oxyethoxyethyl (meth) acrylate, (meth) acrylate of 2-alkylhexanol alkylene oxide adduct, pentylene glycol mono (meth) acrylate, hexane diol (Meth) acrylate, mono(meth) acrylate of diethylene glycol, mono (meth) acrylate of triethylene glycol, mono (meth) acrylate of tetraethylene glycol, polyethylene glycol Mono (meth) acrylate, mono (meth) acrylate of dipropylene glycol, mono (meth) acrylate of tripropylene glycol, mono (meth) acrylate of polypropylene glycol, 2-hydroxy-3- phenyloxy Propyl (meth) acrylate, 2-hydroxy-3-butoxypropyl ( Yl) acrylate, (meth) acrylate, tetrahydrofurfuryl methacrylate, caprolactone-modified (meth) acrylate, tetrahydrofurfuryl methacrylate, (2-ethyl-2-methyl-1,3- Pentane-4-yl)methyl(meth)acrylate, (2-isobutyl-2-methyl-1,3-di Pentane-4-yl)methyl(meth)acrylate, (1,4-dioxaspiro[4,5]decane-2-yl)methyl(meth)acrylate, (methyl) Glycidyl acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, (3-ethyloxetan-3-yl)methyl (meth) acrylate, 2- (Meth) propylene oxiranyl ethyl isocyanate, allyl (meth) acrylate, 2-vinyloxyethyl (meth) acrylate, 2-vinyloxy ethoxyethyl (meth) acrylate Ester, N-(methyl)propenyloxyethylhexahydrophthalimide, N-(methyl)propenyloxyethyltetrahydrophthalimide, 2-(A) Acryloxyethylhexahydrophthalic acid, 2-(methyl)propenyloxyethyl succinic acid, ω-carbonyl-polycaprolactone mono(meth)acrylate, 2-(A) Base) propylene methoxyethyl phosphate, 3-(meth) propylene methoxy propyl trimethoxy decane, 3-(methyl) propylene methoxy propyl dimethoxy methyl decane, 3- (Meth) propylene methoxy propyl triethoxy decane, and the like.

Specific examples of the difunctional (meth) acrylate include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and 1,4-butanediol di(meth)acrylic acid. Ester, neopentyl glycol di(meth) acrylate, 1,6-hexanediol di(meth) acrylate, 3-methyl-1,5-pentanediol di(meth) acrylate, ring Hexane dimethylol di(meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth) acrylate, 1,9-nonanediol di(meth)acrylic acid Ester, diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol Esterification reaction product with hydroxytrimethylacetic acid and (meth)acrylic acid, bis(meth)acrylate of bisphenol A alkylene oxide adduct, hydrogen addition bisphenol Abis (meth) acrylate, tricyclodecane dimethylol di(meth) acrylate, addition reaction of bisphenol A epoxy resin with (meth)acrylic acid, bisphenol F type Addition reaction product of epoxy resin and (meth)acrylic acid

Specific examples of the polyfunctional (meth) acrylate other than the component (A) include polyester (meth) acrylate or dendrimer having a (meth) acrylonitrile equivalent of more than 200 g/eq. Type (meth) acrylate, etc.

The composition of the present invention may contain various additives other than the curable component, in addition to the effects of the present invention. Examples of the various additives include a thermal cationic polymerization initiator, a photosensitizer, an ultraviolet absorber, a photosetter, an antioxidant, a polymerization inhibitor, a decane coupling agent, a polyol compound, a polymer, an adhesion-imparting agent, and a filler. , metal fine particles, metal oxide fine particles, ion trapping agents, antifoaming agents, leveling agents, pigments and pigments.

The polymer may, for example, be poly(meth)acrylate, polyvinyl acetate, polystyrene, polyether or polyester.

As the polymer, a cationically polymerizable group such as an epoxy group, an oxetane group, or a vinyl ether group can be used for the molecule. Further, a radical polymerizable group containing a (meth)acryl fluorenyl group or a vinyl group can be used in the molecule.

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

The present invention relates to an active energy ray-curable adhesive composition for a plastic film or sheet, which comprises the above (A) to (C) components as essential components, preferably also containing (D) to (F) components. .

The composition of the present invention preferably has a total chlorine content of 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 refined product or the like as the component (B), the component (E), and/or the component (F) is used.

The method for producing the composition of the present invention may be carried out according to a usual method, and may be produced by stirring and mixing the respective components in accordance with a usual method. In this case, it can be heated or warmed as needed.

The viscosity of the composition of the present invention may be appropriately set in accordance with the purpose of use. In order to obtain a coating surface which can be used when a laminate production process using a plastic film or the like is used, and a coating surface which is excellent in film smoothness, the viscosity is preferably 200 mPa ‧ or less at 25 ° C, more preferably 10~100mPa‧s, especially good 20~70mPa‧s.

In the present invention, the viscosity of the composition means a measured value measured by an E-type viscometer.

The composition of the present invention can be used for the adhesion of plastic films and the like, plastic films, and the like to various substrates other than these (hereinafter referred to as "other substrates"). That is, it is possible to use at least one of the two substrates which are a plastic film or the like. In the following, the case of "base material" alone refers to the general term for plastic film and other substrates. Examples of the other substrate include glass, metal oxide, metal, wood, paper, and the like.

Examples of the material in the plastic film or the like include cellulose triacetate, cellulose acetate butyrate, cycloolefin polymer, (meth)acrylic resin, polystyrene, acrylic acid/styrene copolymer, and polyvinyl chloride. , polyvinylidene chloride, polyethylene, polypropylene, ABS resin, polyamide, polyester, polycarbonate, polyurethane, and chlorinated polypropylene. The (meth)acrylic resin may, for example, be a (meth)acrylic acid tree of polymethyl methacrylate or a copolymer of methyl methacrylate as a main component. A (meth)acrylic resin which does not contain methyl methacrylate as a polymerization monomer.

The composition of the present invention is preferably a cycloolefin polymer or a cellulose acetate-based resin among these plastic films and the like.

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. Among these, when a transparent film formed by evaporation or sputtering is used as a substrate, one of the characteristics of the composition of the present invention requires more transparency, and thus can be more preferably applied. .

Further, when a plastic film or the like is a material which is difficult to bond, 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 a plasma treatment, a corona discharge treatment, a chemical liquid treatment, a surface roughening treatment, an etching treatment, a flame treatment, and the like, and these may be used in combination.

6. How to use

The method of using the composition of the present invention may be a conventional method, and for example, a method in which a composition is applied onto a substrate, and then bonded to another substrate, and then irradiated with an active energy ray.

The composition of the present invention is suitably used as a substrate and then a thin layer is adhered. The method of using the thin layer after being adhered to the layer is followed by a method generally performed in the manufacture of the laminate. For example, a method in which a composition is applied onto a first thin layer adherend, and a second thin layer is adhered thereto, and then subjected to active energy ray irradiation is used.

The coating of the substrate may be carried out according to a conventionally known method, and examples thereof include natural coating, knife coating, floating knife coating, doctor roll coating, liner coating, spray coating, and dipping. Coating, contact top coat coating, squeeze roll coating, reverse roll coating, Air knife coating, curtain flow coating, angle wheel coating, gravure coating, micro gravure coating, die coating, and curtain coating.

Further, the coating thickness of the composition of the present invention can be selected in accordance with the substrate to be used and the use thereof, but is preferably 0.1 to 10 μm, more preferably 1 to 5 μm.

Examples of the active energy ray include visible light, ultraviolet light, X-ray, and electron beam. In order to use a relatively inexpensive device, ultraviolet light is preferred.

As a light source used for curing by ultraviolet rays, various light sources can be used, and examples thereof include a pressurized or high-pressure mercury lamp, a metal halide lamp, a xenon lamp, an electrodeless discharge lamp, a carbon arc lamp, and an LED. Among them, high-pressure mercury lamps and metal halide lamps are particularly preferred. The amount of ultraviolet rays to be irradiated is in the UV-B region (near 310 nm), preferably 10 to 500 mJ/cm ² , more preferably 20 to 300 mJ/cm ² , still more preferably 30 to 200 mJ/cm ² .

When hardened by an electron beam, various devices can be used as an EB (Electron Beam) irradiation device that can be used, and for example, Cockcroft Walton type, van de Graf (van de The Graaff type and the resonance transformer type device preferably have an energy of 50 to 1000 eV, more preferably 100 to 300 eV, as the electron beam.

7. Manufacturing method of laminated body

The composition of the present invention can be preferably used in the manufacture of a laminate. The laminated body has a base material, a cured product of the above composition, and a laminated body composed of another base material, and either or both of the base material and the other base material are plastic film or sheet.

It is preferable that at least one of a plastic film or the like is a cellulose acetate-based resin or a cycloolefin polymer.

Specific examples of the method for producing the laminate include, for example, coating the substrate with the composition, and bonding the coated surface to another substrate, and then from either the substrate or the other substrate. A method of irradiating an active energy ray or the like.

In this case, a plastic film or the like is used as the substrate of the substrate and the other substrate, or at least one of the substrates. 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 the active energy ray, and the like are also as described above.

Examples of the use of the laminated body to be obtained include various optical films used for liquid crystal displays, organic EL displays, and the like, and specific examples thereof include hard coating films which are provided with functions such as anti-fingerprint or anti-glare. The front panel of the touch panel, the polarizing plate, the retardation film, the viewing angle compensation film, the brightness enhancement film, the antireflection film, the anti-glare film, the lens sheet, and the diffusion sheet.

[Examples]

The present invention will be specifically described below by way of examples and comparative examples. However, the invention is not limited by such examples.

In the following, "parts" means parts by weight, "%" means % by weight, and the values indicated by the proportions in the table refer to % by weight.

In the examples and comparative examples, the components used for the preparation of the composition are as follows, and are roughly described below.

(A) component

‧M-305: a mixture of pentaerythritol triacrylate (acrylic equivalent of 99g/eq) and pentaerythritol tetraacrylate (acrylic equivalent of 88g/eq), manufactured by East Asia Synthetic Co., Ltd. "Aronix M-305".

(B) component

‧ BD-DGE: 1,4-butanediol diepoxypropyl ether (distilled refined product, total chlorine content: 0.1% by weight or less), "SR-14BJ" manufactured by Sakamoto Pharmaceutical Co., Ltd.

‧HD-DGE: 1,6-hexanediol diglycidyl ether (distilled product, total chlorine content: 0.1% by weight or less), "Epogosey HD (D)" manufactured by Yokkaichi Synthetic Co., Ltd.

(C) component

‧110P: Triarylsulfonium hexafluorophosphate (active ingredient: 100%), "CPI-110P" manufactured by San-Apro Co., Ltd.

‧100P-net: an active ingredient in a solution of triaryl hexafluorophosphate propylene carbonate (hereinafter referred to as "PC") [50% active ingredient, "CPI-100P" manufactured by San-Apro Co., Ltd.]. It is almost the same component as the above "110P". The PC in CPI-100P is separately described in the table as will be described later.

(D) component

‧DETX: 2,4-diethyl 9-oxosulfur (Catch hydrogen-type radical photopolymerization initiator), "DETX-S" manufactured by Nippon Kayaku Co., Ltd.

(E) component

‧J-828US: Bisphenol A type epoxy resin (low chlorine grade, total chlorine content 0.1~0.2% by weight), "jER-828US" manufactured by Mitsubishi Chemical Corporation.

(F) component

‧ OXT-221: bis[(3-ethyloxetan-3-yl)methyl]ether (molecular weight 214), "Aron Oxetane OXT-221" manufactured by East Asia Synthetic Co., Ltd.

(A') component [not belonging to the (meth) acrylate compound in the component (A)]

‧4HBA: 4-hydroxybutyl acrylate (monofunctional acrylate), "4-HBA" manufactured by Osaka Organic Chemical Industry Co., Ltd.

‧HDDA: 1,6-hexanediol diacrylate (difunctional acrylate), "Viscoat #230" manufactured by Osaka Organic Chemical Industry Co., Ltd.

‧M-321: Triacrylate of propylene oxide 6 molar additive of trimethylolpropane (acrylic acid equivalent: 215 g/eq), "ARONIX M-321" manufactured by Toagosei Co., Ltd.

(other) [other ingredients]

‧ PC: propylene carbonate containing CPI-100P.

‧ Water: ion exchange water.

[Example 1 to Example 4, Comparative Example 1 to Comparative Example 6] 1. Composition manufacturing

The components shown in Tables 1 and 2 were formulated in accordance with their respective ratios, and the active energy ray-curable adhesive composition was prepared by stirring and mixing according to a usual method.

For the obtained composition, the viscosity at 25 ° C was measured using an E-type viscometer manufactured by Toki Sangyo Co., Ltd. The results are shown in Tables 1 and 2.

2. Manufacturing of laminates

A cycloolefin polymer film having a thickness of 100 μm [trade name: ZEONOR ZF-14, manufactured by Japan ZEON Co., Ltd., hereinafter referred to as "ZEONOR"], and a cellulose acetate resin film having a thickness of 80 μm [product name FujiTAC, Fujifilm (Stock) manufacturing, hereinafter referred to as "TAC", is implemented as a corona treatment which is easy to handle.

Next, the obtained composition was applied to a corona-treated surface of TAC by a bar coating method to a thickness of 3 μm, and ZEONOR was laminated. At this time, the corona treatment surface of ZEONOR is disposed so as to adhere to the coated surface.

Finally, an ultraviolet irradiation device (using a metal halide lamp) equipped with a belt conveyor manufactured by iGrafx (shares) is used to irradiate ultraviolet rays from the surface of the ZIONOR with a cumulative light amount of 70 mJ/cm ² (UV-B) to harden the adhesive composition. (at 23 ° C 50% environment). Here, the end of the laminate was peeled off by hand immediately after the ultraviolet irradiation, and the hardenability was evaluated by the following criteria. Further, the obtained laminate was allowed to stand at 23 ° C and a relative humidity of 50% for one day, and the colorless transparency and adhesion were evaluated in accordance with the following methods. The results of these are shown in Tables 1 and 2.

3. Evaluation method 1) Evaluation of hardenability

Immediately after the ultraviolet irradiation, the end of the laminate was peeled off by hand and judged by the following criteria. In addition, if it is judged by B or more, it is evaluated that there is no problem in actual use.

A: The adhesive is non-liquid and is not weak enough to be easily peeled off.

B: The adhesive is not liquid, but is weak to the extent that it is easily peeled off.

C: The adhesive is in the form of a liquid.

2) Evaluation of colorless transparency

Five sheets of the obtained laminated body were superimposed and visually observed, and the judgment was made based on the following criteria.

A: I don't feel turbid or yellow.

B: I feel a little turbid or yellow.

C: Obvious turbidity or yellowing is felt.

3) Evaluation of the force

The obtained laminate was cut into a width of 1 inch and a length of 15 cm, and the TAC was attached to the aluminum plate with a double-sided tape. Next, the ZEONOR was peeled off at a peeling speed of 180 mm/min of 180°, and the adhesion was measured. At this time, the adhesion was very strong, and the film was broken, and those who could not be measured were evaluated as "material breakage".

The compositions of Examples 1 to 4 belonging to the composition of the present invention are low in viscosity, colorless in transparency, and excellent in adhesion. Among these, the hardenability of the composition of Example 1 was B and was slightly lower. However, it is considered that the adhesive agent is not liquid immediately after the ultraviolet ray is irradiated, and the hardenability is lower, so that there is no problem in use.

In Example 2, in which a part of the component (B) in the composition of Example 1 was replaced with the component (E), the hardenability was improved as compared with Example 1. This adhesion is not "material broken", but it is 9.5 N / inch, and strong.

In the third embodiment, a part of the component (B) of the composition of Example 2 was replaced with the component (F), and the force was increased as compared with the example 2, and the material was broken.

The composition of Example 4 was slightly changed in composition of the composition of Example 3, and had the same excellent curability, colorless transparency, and adhesion as Example 3. At the same time, the viscosity is further lowered.

On the other hand, the composition of Comparative Example 1 containing the component (A) exceeding 45% by weight of the present invention had a significantly lower adhesion force than the compositions of Examples 1 to 4.

The composition of Comparative Example 2 which does not contain the component (A) has poor hardenability and a low adhesive force.

The majority of M-305 in the composition of Example 3 was replaced with 4HBA, and the composition of Comparative Example 3 in which the component (A) was less than 15% by weight of the lower limit of the present invention, and the force was extremely low.

The composition of Comparative Example 4 in which the M-305 in the composition of Example 3 was replaced with HDDA which is not the component (A), and the composition of Comparative Example 5 which was replaced with M-321 which does not belong to the component (A), The strength of both is very low.

The component (B) was a composition of Comparative Example 6 which was less than 10% by weight of the lower limit of the present invention, and the force was relatively low.

(industrial availability)

The composition of the present invention can be used as an adhesive for a plastic film or the like, and is particularly suitable for use in an optical film used in a liquid crystal display or an organic EL display.

Claims (16)

An active energy ray-curable adhesive composition for a plastic film or sheet, which comprises the following components (A), (B) and (C), and contains (A) a component in the entire composition 15 to 45% by weight, (B) component 10 to 75% by weight, and (C) component 0.5 to 10% by weight; (A) component: 3 or more (meth)acryl fluorenyl groups in 1 molecule, and (A) a compound having a propylene oxime equivalent of 200 g/eq or less; a component (B): a polyepoxypropyl ether having a polyhydric alcohol having 2 to 10 carbon atoms; and a component (C): a cationic photopolymerization initiator. The active energy ray-curable adhesive composition for a plastic film or sheet according to claim 1, wherein the component (A) has 3 to 6 (meth) acrylonitrile groups in one molecule, and (A) A compound having an acrylonitrile equivalent of 150 g/eq or less. The active energy ray-curable adhesive composition for a plastic film or sheet according to claim 1 or 2, wherein the component (B) is a diglycidyl ether having a diol having 2 to 10 carbon atoms. The active energy ray-curable adhesive composition for a plastic film or sheet according to claim 3, wherein the component (B) is a diglycidyl ether having an alkylene glycol having 2 to 6 carbon atoms. 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 (C) is a sulfonium-based cationic photopolymerization initiator. The active energy ray-curable adhesive composition for a plastic film or sheet according to any one of claims 1 to 5, further comprising 0.1 to 10% by weight of a radical photopolymerization initiator as a whole of the composition (D) ingredient. The active energy ray-curable adhesive composition for a plastic film or sheet according to claim 6, wherein the component (D) is a hydrogen-trapping type radical photopolymerization initiator. The active energy ray-curable adhesive composition for a plastic film or sheet according to any one of claims 1 to 7, further comprising two or more of one molecule containing 1 to 40% by weight of the entire composition. An aromatic ring and an epoxy compound of two or more epoxy groups are used as the component (E). The active energy ray-curable adhesive composition for a plastic film or sheet according to claim 8, wherein the component (E) is a bisphenol epoxy resin. 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 1 to 40% by weight of one molecule and has two or more molecules. A compound having an oxetane group and a molecular weight of 500 or less is used as the component (F). The active energy ray-curable adhesive composition of the plastic film or sheet according to claim 10, wherein the component (F) is a 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 11, wherein the 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 any one of claims 1 to 11, wherein at least one of the plastic film or sheet is a cellulose acetate resin or a ring Olefin polymer. A laminate comprising a base material, a plastic film or a sheet of the active energy ray-curable adhesive composition of any one of claims 1 to 12, and a laminate of the other substrate. Further, either or both of the substrate and the other substrate are plastic films or sheets. The laminate according to claim 14, wherein at least one of the plastic film or sheet is a cellulose acetate resin or a cycloolefin polymer. A method for producing a laminate, which is characterized in that the substrate is coated with the composition according to any one of claims 1 to 12, and the other substrate is bonded to the coated surface, and the substrate and the other substrate are not used. A method for producing a laminate in which an active energy ray is irradiated on one side, and either or both of the substrate and the other substrate are plastic films or sheets.