JP6531894B2 - Active energy ray curable composition - Google Patents

Description

The present invention relates to an active energy ray-curable composition curable by irradiation of active energy rays such as ultraviolet light, visible light, or electron beam, preferably an active energy ray-curable type capable of bonding various substrates. The present invention relates to an adhesive composition, and is further suitably used for the production of various optical films or sheets used in liquid crystal displays, organic EL displays and the like, and may be used in these technical fields. .
In the present specification, acrylate and / or methacrylate are represented as (meth) acrylate, acryloyl group and / or methacryloyl group as (meth) acryloyl group, and acrylic acid and / or methacrylic acid as (meth) acrylic acid. .

  The active energy ray-curable adhesive generally has no solvent and has an instantaneous curing property, and thus is excellent in terms of work environment, safety, production speed, energy saving and the like. For this reason, it is suitably used for manufacture of various members used for a liquid crystal display, a touch panel, a construction material, etc. Specifically, adhesives for various optical films such as polarizing plates and brightness enhancement films used in liquid crystal displays etc., adhesives for filling the gaps between touch panels and displays, optical members other than displays such as heat ray reflective films, etc. It can be mentioned.

  As active energy rays, ultraviolet rays, visible rays and electron beams are often used. Among them, ultraviolet irradiation devices are relatively inexpensive and easy to use. For this reason, active energy ray-curable adhesives are often used to bond glass and transparent films.

  As the transparent plastic film, polyethylene terephthalate, triacetyl cellulose, amorphous cycloolefin polymer, polymethyl methacrylate and polycarbonate are often used.

  The adhesive is required to have adhesiveness to various adherends, transparency of a cured product, and the like, and various studies have been made (for example, Patent Document 1).

However, in recent years, thin films may be pasted together in a large area, and in that case, in addition to adhesion and transparency, the undulation of the cured product becomes a problem.
In addition, it is necessary to increase production speed to reduce the cost of various members. For this reason, the demand for the curing speed of the adhesive has also become strict.

  From such a background, there is a demand for an active energy ray-curable adhesive which is excellent in adhesive strength, transparency and curability, and which bonds a thin film in a large area and does not cause bending.

Unexamined-Japanese-Patent No. 2001-64594 (Claims)

  The present invention has been made in view of the above problems, and provides an active energy ray-curable composition which is excellent in adhesion, transparency and curability, adheres a thin film in a large area, and does not generate deformation. The purpose is

  As a result of various studies, the present inventors have found that an active energy ray-curable composition containing a specific polymer and an epoxy compound in a specific ratio solves the above problems, and completed the present invention.

The present invention is 1 to 50% by weight of the following component (A), 1 to 98% by weight of the following component (B) and 0.5 to 10% by weight of the following component (C) based on the whole composition. The present invention relates to an active energy ray-curable composition comprising
Component (A): A polymer obtained by polymerizing a vinyl monomer at a temperature of 150 to 350 ° C. and then adding hydrogen (B) component: a compound having one or more epoxy groups in one molecule Component (C): Photocationic Polymerization Initiator Hereinafter, the present invention will be described in detail.

  According to the composition of the present invention, it is possible to provide an active energy ray-curable adhesive which is excellent in adhesive strength, transparency and curability and which bonds a thin film in a large area and does not cause deformation. For this reason, it can be used suitably for manufacture of various optical films, such as a color conversion film, a polarizing plate, a brightness improvement film, a heat ray reflective film, and a void filler. Moreover, it can use suitably for manufacture of various members and products which require smoothness other than an optical film.

The present invention is 1 to 50% by weight of the following component (A), 1 to 98% by weight of the following component (B) and 0.5 to 10% by weight of the following component (C) based on the whole composition. The present invention relates to an active energy ray-curable composition comprising
Component (A): A polymer obtained by polymerizing a vinyl monomer at a temperature of 150 to 350 ° C. and then adding hydrogen (B) component: a compound having one or more epoxy groups in one molecule Component (C): Photocationic Polymerization Initiator Hereinafter, components (A) to (C), other components, and a preferred method of using the composition of the present invention will be described in detail.
Hereinafter, the components (A) to (C) and the other components will be described in detail.

1. Component (A) Component (A) is a polymer obtained by polymerizing a vinyl monomer at a temperature of 150 to 350 ° C. and adding hydrogen to the obtained polymer.
The polymer obtained by high temperature polymerization of a vinyl monomer is used for improvement of various physical properties as a plasticizer, a tackifier and the like by being blended in an active energy ray curable composition, and the present invention Then I use it to prevent the occurrence of swell. However, when the vinyl-based monomer is polymerized at high temperature, a side reaction produces a polymer having a double bond at the molecular end. When such a polymer is blended in an active energy ray-curable composition, there is a problem that sufficient curability may not be obtained due to the influence of the double bond. In the present invention, a polymer obtained by polymerizing a vinyl monomer at a temperature of 150 to 350 is further added with hydrogen to eliminate a double bond, thereby blending the polymer. However, the curability can be excellent.

The vinyl-based monomer is a compound having one ethylenically unsaturated group, and those used in radical polymerization of a vinyl-based monomer can be used.
Specific examples of the vinyl-based monomer include (meth) acrylate, (meth) acrylic acid, styrene, α-methylstyrene, acrylonitrile, vinyl acetate and the like, and copolymerizability, mechanical properties of the cured product, (Meth) acrylate is preferred because of excellent weather resistance and water resistance.

Examples of (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (Meth) acrylate, neopentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) (Meth) acrylic acid aliphatic alkyl esters such as acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate;
Heteroatom-containing (meth) acrylates such as 2-methoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate and trifluoroethyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) Hydroxyalkyl (meth) acrylates such as acrylate, 4-hydroxybutyl (meth) acrylate, ε-caprolactone adduct of 2-hydroxyethyl (meth) acrylate, etc.
Epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate;
3-trimethoxysilylpropyl (meth) acrylate, 3-triethoxysilylpropyl (meth) acrylate, 3-triisopropoxysilylpropyl (meth) acrylate, 3-methyldimethoxysilylpropyl (meth) acrylate, 3-methyldiethoxy Silylpropyl (meth) acrylate, methyldiisopropoxysilylpropyl (meth) acrylate, 3-dimethylmethoxysilylpropyl (meth) acrylate, 3-dimethylethoxysilylpropyl (meth) acrylate, 3-dimethylisopropoxysilylpropyl (meth) And alkoxysilyl group-containing (meth) acrylates such as acrylate and 8-trimethoxysilyloctyl (meth) acrylate; and benzyl (meth) acrylate.

  Among these compounds, when importance is given to the flexibility of the cured product, it is preferable to copolymerize an alkyl (meth) acrylate having an alkyl group having 4 or more carbon atoms. When importance is given to the hardness of the cured product, it is preferable to copolymerize methyl methacrylate. When importance is attached to cationic curability, it is preferable to copolymerize a (meth) acrylate having an epoxy group.

In the production of the component (A), first, vinyl monomers are polymerized at a temperature of 150 to 350 ° C.
By controlling the polymerization temperature to 150 ° C. or higher, the control of the molecular weight becomes easy even with a small amount of initiator and without using a chain transfer agent, and the weather resistance of the cured product becomes excellent. On the other hand, by setting the polymerization temperature to 350 ° C. or less, the conversion ratio of the monomer to the polymer can be increased. Also, the problem of coloring due to decomposition products can be avoided. The preferred polymerization temperature is in the range of 170 to 300 ° C, and more preferably in the range of 180 to 250 ° C.
As the polymerization method, solution polymerization, bulk polymerization, dispersion polymerization and the like can be mentioned.
The reaction process may be any of batch system, semi-batch system and continuous polymerization, but continuous polymerization is preferable in terms of excellent uniformity of composition.

As the high temperature continuous polymerization method, known methods disclosed in JP-A-57-502171, JP-A-59-6207, JP-A-60-215007, etc. may be used.
For example, after setting a predetermined temperature under pressure in a pressurizable reactor, a monomer mixture comprising each monomer and, if necessary, a polymerization solvent is supplied to the reactor at a constant feed rate, The method of extracting the polymerization liquid of the quantity suitable for the supply amount of a monomer mixture is mentioned.
Moreover, a polymerization initiator can also be mix | blended with a monomer mixture as needed. The blending amount in the case of blending is preferably 0.001 to 3 parts by weight with respect to 100 parts by weight of the monomer mixture.
The pressure depends on the reaction temperature and the boiling point of the monomer mixture and solvent used, and does not affect the reaction, but may be a pressure that can maintain the reaction temperature.
The residence time of the monomer mixture is preferably 1 to 60 minutes. If the residence time is less than 1 minute, the monomers may not react sufficiently, and if the unreacted monomers exceed 60 minutes, the productivity may be deteriorated. The preferred residence time is 2 to 40 minutes.

As an example of the polymerization initiator used for manufacture of (A) component, if it is an initiator which generate | occur | produces a radical at predetermined | prescribed reaction temperature, all can be used.
Specifically, organic peroxides such as di-t-butyl peroxide and di-t-hexyl peroxide, and azobisisobutyronitrile, azobiscyclohexacarbonitrile, azobis (2-methylbutyronitrile ), Azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-amidinopropane) dihydrochloride, and azo compounds such as 4,4′-azobis (4-cyanovaleric acid), etc. Be

The component (A) may be produced either by solution polymerization in an organic solvent or by bulk polymerization without solvent or with a small amount of organic solvent, but bulk polymerization with no solvent or a small amount of solvent preferable.
In the case of solution polymerization, an organic hydrocarbon compound is suitable as the organic solvent, and cyclic ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbon compounds such as benzene, toluene and xylene, esters such as ethyl acetate and butyl acetate Examples thereof include ketones such as acetone, methyl ethyl ketone and cyclohexanone, and alcohols such as methanol, ethanol and isopropanol. One or more of these can be used. If the solvent does not dissolve the (meth) acrylic acid ester copolymer well, the scale tends to grow on the wall of the reactor, which tends to cause production problems in the washing step and the like.
The amount of the organic solvent used is preferably 80 parts by weight or less based on 100 parts by weight of all vinyl monomers. By setting the amount to 80 parts by weight or less, high conversion can be obtained in a short time. More preferably, it is 1 to 50 parts by weight. In addition, dehydrating agents such as trimethyl orthoacetate and trimethyl orthoformate can also be added.

The reaction liquid withdrawn from the reactor can be carried on to the next step as it is, or the polymer can be isolated by distilling off volatile components such as unreacted monomers, solvents and low molecular weight oligomers by distillation or the like. It can be released. It is also possible to return some of the unreacted monomers, solvents, and volatile components such as low molecular weight oligomers distilled off from the reaction solution back to the raw material tank or directly to the reactor, and use them again for the polymerization reaction.
Thus, the method of recycling unreacted monomers and solvents is a preferable method from the economical point of view. In the case of recycling, it is necessary to determine the mixing ratio of the newly supplied monomer mixture so as to maintain the desired monomer ratio and the desired amount of solvent in the reactor.

The polymer obtained by the above method is subjected to hydrogenation to obtain the component (A).
The method of hydrogen addition may be in accordance with a conventionally known method.
That is, after a reduction catalyst is added to the polymer reaction solution, the system is set to a hydrogen atmosphere, the pressure is normal pressure to 10 MPa, the temperature is heated to about 20 to 180 ° C., and the reaction is performed for about 2 to 20 hours.
Both homogeneous and heterogeneous catalysts can be used as the reduction catalyst.
Specific examples of homogeneous catalysts include rhodium complexes such as chlorotris (triphenylphosphine) rhodium, ruthenium complexes such as dichlorotris (triphenylphosphine) ruthenium and chlorohydrocarbonyltris (triphenylphosphine) ruthenium, and dichlorobis (triphenylphosphine). And platinum complexes such as platinum, and iridium complexes such as carbonyl bis (triphenylphosphine) iridium and the like.
On the other hand, examples of heterogeneous catalysts include solid catalysts in which transition metals such as nickel, rhodium, ruthenium, palladium and platinum are supported on carbon, silica, alumina, fibers, organic gel-like substances and the like.
The reduction catalyst is preferably a heterogeneous catalyst in that the quality is stable because the catalyst can be easily removed by filtration or the like and the expensive catalyst can be reused.
The proportion of the reduction catalyst to be added is preferably 10 to 1,000 ppm with respect to the polymer in the case of a homogeneous catalyst. In the case of heterogeneous catalysts, 1,000 to 10,000 ppm are preferred.

It is preferable to reduce the double bond concentration in the polymer to 0.2 meq / g or less by hydrogenation.
By setting the amount to 0.2 meq / g or less, the curability of the composition can be improved. More preferably, it is 0.1 meq / g or less, still more preferably 0.05 meq / g or less.
The double bond concentration of the component (A) is a signal of a double bond observed in 5 to 6.5 ppm and a methylene, methyl group adjacent to an ester observed in 3 to 4.5 ppm as measured by ¹ H-NMR. It can be calculated from the ratio of the integral value of the signal of.

As a weight average molecular weight (henceforth "Mw") of (A) ingredient, 1,000-50,000 are preferred. When it is 1,000 or more, the cured product is stably present in the system without bleeding for a long time, and when it is 50,000 or less, the viscosity becomes appropriate when formulated as a composition, and the workability Is excellent. More preferably, it is 1,500 to 20,000.
Incidentally, Mw in the present invention means a value in terms of polystyrene as measured by gel permeation chromatography (GPC).
The glass transition temperature (hereinafter referred to as "Tg") of the component (A) is preferably -80 ° C to 20 ° C. By setting the Tg to 20 ° C. or less, it becomes excellent in flexibility. More preferably, it is −10 ° C. or less.
In the present invention, Tg means a value measured by the midpoint of the endothermic peak detected in a differential scanning calorimeter.

As the component (A), the above-mentioned compounds may be used alone or two or more may be used in combination.
The content ratio of the component (A) is 1 to 50% by weight, preferably 1 to 40% by weight, based on the entire composition. When the proportion of the component (A) is less than 1% by weight, the waviness of the film laminate becomes large, while when it exceeds 50% by weight, the curability and the adhesive strength are lowered.

2. Component (B) The component (B) is a compound having one or more epoxy groups in one molecule.
As the component (B), various compounds can be used as long as they are compounds having one or more epoxy groups in one molecule, and preferred compounds are diglycidyl of diols having 2 to 10 carbon atoms. Ether [hereinafter referred to as “component (B1)”], compound having an alicyclic epoxy group [hereinafter referred to as “component (B2)]” and compound having an aromatic epoxy group [hereinafter referred to as “component (B3)” Etc. can be mentioned.
Hereinafter, the components (B1) to (B3) will be described.

2-1. (B1) component
The component (B1) is a diglycidyl ether of a diol having 2 to 10 carbon atoms.
In addition, the "carbon number" in the diol which has C2-C10 means the number of carbon which comprises the site | part which remove | eliminated the hydroxyl group from the diol.

  Specific examples of the component (B1) 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 and resorcine diglycidyl Ether etc. are mentioned.

  As the component (B1), diglycidyl ethers of alkanediols having 4 to 6 carbon atoms such as 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether and 1,6-hexanediol diglycidyl ether The composition obtained is lower in viscosity, and the cured product is more preferable in that it has excellent adhesion and is colorless and transparent.

2-2. (B2) component
The component (B2) is a compound having an alicyclic epoxy group.
Specific examples of the component (B2) include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate and 3,4-epoxycyclohexylmethyl-3,4. -Caprolactone modified product of epoxy cyclohexane carboxylate, esterified product of polyvalent carboxylic acid and 3,4-epoxycyclohexyl methyl alcohol or caprolactone modified product, 3,4,3 ', 4'-diepoxybicyclohexyl, limonene dioxide, Examples thereof include 4-vinylcyclohexene dioxide, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, silsesquioxane having an alicyclic epoxy group, and a silicone polymer having an alicyclic epoxy group.

  As the component (B2), a compound having a molecular weight of 200 to 500 having two alicyclic epoxy groups in one molecule is characterized in that the composition obtained has a low viscosity and the cured product is excellent in adhesion. The compound shown by following formula (1) is more preferable, and is especially preferable.

2-3. (B3) component
The component (B3) is a compound having an aromatic epoxy group.
Specific examples of the component (B3) include diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of brominated bisphenol A, phenol novolac epoxy resin, cresol novolac epoxy resin, biphenyl epoxy resin, Examples thereof include terephthalic acid diglycidyl ester, phthalic acid diglycidyl ester, and addition reaction products of terminal carboxylic acid polybutadiene and bisphenol A epoxy resin.

2-4. In addition, as an epoxy compound (B) component, epoxy compounds other than the said (B1)-(B3) component can also be used.
Specifically, polyethylene glycol (repetition number 6 or more) diglycidyl ether, polypropylene glycol (repetition number 4 or more) diglycidyl ether, polytetramethylene glycol (repetition number 3 or more) diglycidyl ether, hydrogenated bisphenol A diglycidyl ether And diglycidyl ethers of diols having 11 or more carbon atoms such as polybutadiene diglycidyl ethers having hydroxyl groups at both terminal groups.
Besides these, epoxidized vegetable oil, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, internal epoxidized product of polybutadiene, double bond of styrene-butadiene copolymer is partially epoxidized Compounds (for example, "Epofriend" manufactured by Daicel Chemical Industries, Ltd.), and compounds in which the isoprene unit of the block copolymer of ethylene-butylene copolymer and polyisoprene is partially epoxidized (for example, KRATON Co. And “L-207”).

As the component (B), the aforementioned compounds may be used alone or two or more may be used.
The content ratio of the component (B) is 1 to 98% by weight, preferably 1 to 60% by weight, based on the entire composition. When the proportion of the component (B) is less than 1% by weight, the curability decreases, while when it exceeds 98% by weight, the cured product is likely to be undulated.

3. Component (C) The component (C) is a cationic photopolymerization initiator. That is, the compound is a compound that generates a cation or a Lewis acid by irradiation of active energy rays such as ultraviolet rays and electron beams, and starts polymerization of cationically curable components such as epoxy compounds and oxetane compounds.
Specific examples of the component (C) include sulfonium salts, iodonium salts and diazonium salts.

As examples of sulfonium salts, for example
Triphenylsulfonium hexafluorophosphate,
Triphenylsulfonium hexafluoroantimonate,
Triphenylsulfonium tetrakis (pentafluorophenyl) borate,
Diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate,
Diphenyl-4- (phenylthio) phenylsulfonium hexafluoroantimonate,
4,4'-bis [diphenylsulfonio] diphenyl sulfide bishexafluorophosphate,
4,4'-bis [di (β-hydroxyethoxy) phenyl sulfonio] diphenyl sulfide bishexafluoroantimonate,
4,4'-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenyl sulfide bishexafluorophosphate,
7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone hexafluoroantimonate,
7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone tetrakis (pentafluorophenyl) borate
4-phenylcarbonyl-4'-diphenylsulfonio-diphenyl sulfide hexafluorophosphate,
4- (p-tert-butylphenylcarbonyl) -4′-diphenylsulfonio-diphenyl sulfide hexafluoroantimonate,
4- (p-tert-butylphenylcarbonyl) -4′-di (p-toluyl) sulfonio-diphenyl sulfide A triarylsulfonium salt such as tetrakis (pentafluorophenyl) borate is mentioned.

As examples of iodonium salts, for example
Diphenyliodonium tetrakis (pentafluorophenyl) borate diphenyliodonium hexafluorophosphate,
Diphenyliodonium hexafluoroantimonate,
Di (4-t-butylphenyl) iodonium hexafluorophosphate,
Di (4-t-butylphenyl) iodonium hexafluoroantimonate,
Tolylkamyl iodonium tetrakis (pentafluorophenyl) borate,
(4-Methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophosphate,
Di (4-nonylphenyl) iodonium hexafluorophosphate,
Di (4-alkylphenyl) iodonium hexafluorophosphate,
And the like.

Examples of diazonium salts include, for example, benzene diazonium hexafluoroantimonate,
Examples include benzenediazonium hexafluorophosphate and the like.

  The component (C) is commercially available, Adeka Optomer SP-100, SP-150, SP-152, SP-170, SP-172 (manufactured by ADEKA Co., Ltd.), Photoinitiator 2074 (manufactured by Rhodia, Inc.), Kayalad PCI-220, PCI-620 [Nippon Kayaku Co., Ltd. product], Irgacure 250 (Ciba Japan Ltd. product), CPI-100P, CPI-110P, CPI-101A, CPI-200K, CPI-210S [San-Apro ( Ltd.), WPI-113, WPI-116 (Wako Pure Chemical Industries, Ltd.), BBI-102, BBI-103, TPS-102, TPS-103, DTS-102, DTS-103 (Midori Kagaku) Manufactured by Co., Ltd.] and the like.

  Among these, sulfonium salts are preferable, and triarylsulfonium salts are more preferable because they are excellent in active energy ray curability and also excellent in colorless transparency. Among the aforementioned triarylsulfonium salts, triphenylsulfonium hexafluorophosphate and diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate are preferable.

As the component (C), the aforementioned compounds may be used alone or two or more may be used.
The content ratio of the component (C) is 0.5 to 10% by weight, preferably 1 to 6% by weight in the whole composition. By setting the ratio of the component (C) to 0.5% by weight or more, the curability can be excellent, and by setting the ratio to 10% by weight or less, the cured product can be excellent in colorless transparency. .

4. Other Components The composition of the present invention essentially includes the components (A) to (C), but various components (referred to as "other components") can be blended depending on the purpose.
Preferred examples of the other components include compounds having one or more ethylenically unsaturated groups in one molecule [hereinafter referred to as “component (D)”], compounds having one or more oxetanyl groups in one molecule. [Hereafter, it is called "the (E) ingredient"] Photo radical polymerization initiator [Hereafter, it is called "the (F) ingredient"] etc. are mentioned.
Hereinafter, the components (D), (E) and (F) will be described.
4-1. Component (D) Component (D) is a compound having one or more ethylenic unsaturated groups in one molecule, and is a low molecular weight compound different from component (A), and is a compound having radical polymerization.
The proportion of the component (D) is preferably 1 to 80% by weight in the whole composition, and more preferably 10 to 50% by weight.
Examples of the component (D) include (meth) acryloyl group-containing compounds and vinyl group-containing compounds, but (meth) acryloyl group-containing compounds are preferable.
The molecular weight of these compounds can be selected variously and may be any of monomers, oligomers and polymers.

  As the (meth) acryloyl group-containing compound, a compound having one (meth) acryloyl group in the molecule [hereinafter referred to as "monofunctional (meth) acrylate"] and two or more (meth) acryloyl groups in the molecule A compound having the following formula (hereinafter referred to as "polyfunctional (meth) acrylate").

  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, n-octyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) Acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 1,4-cyclohexanedimethylol mono (meth) acrylate, dicyclopenta (Meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylate of phenol alkylene oxide adduct, p-cumylphenol alkylene oxide adduct (Meth) acrylates, (meth) acrylates of o-phenylphenol alkylene oxide adducts, (meth) acrylates of nonylphenol alkylene oxide adducts, 2-methoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, 2- (Meth) acrylate of alkylene oxide adduct of ethylhexyl alcohol, pentanediol mono (meth) acrylate, hexanediol mono (meth) acrylate, di Mono (meth) acrylate of thylene glycol, mono (meth) acrylate of triethylene glycol, mono (meth) acrylate of polyethylene glycol, mono (meth) acrylate of dipropylene glycol, mono (meth) acrylate of tripropylene glycol, polypropylene glycol Mono- (meth) acrylates, 2-hydroxy-3-phenoxypropyl (meth) acrylates, 2-hydroxy-3-butoxypropyl (meth) acrylates, tetrahydrofurfuryl (meth) acrylates, caprolactone modified tetrahydrofurfuryl (meth) acrylates , (2-ethyl-2-methyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, (2-isobutyl-2-methyl-1,3-dioxolane-4-i (1) methyl (meth) acrylate, (1,4-dioxaspiro [4,5] decan-2-yl) methyl (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, ( 3-ethyloxetan-3-yl) methyl (meth) acrylate, 2- (meth) acryloyloxyethyl isocyanate, allyl (meth) acrylate, N- (meth) acryloyloxyethyl hexahydrophthalimide, N- (meth) acryloyloxy Ethyl tetrahydrophthalimide, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl succinic acid, ω-carboxy-polycaprolactone mono (meth) acrylate, 2- (meth) acryloyloxyethyl acid Acid phosphate, 3- (meth) acryloyloxy propyl trimethoxy silane, 3- (meth) acryloyloxy propyl dimethoxy methyl silane, 3- (meth) acryloyloxy propyl triethoxysilane, and the like.

  Specific examples of the polyfunctional (meth) acrylate include di (meth) acrylate of bisphenol A alkylene oxide adduct, di (meth) acrylate of hydrogenated bisphenol A, tricyclodecane dimethylol di (meth) acrylate, alkanediol di (Meth) acrylate, polyalkylene glycol di (meth) acrylate, di- or tri (meth) acrylate of alkylene oxide adduct of isocyanuric acid, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol Tri or tetra (meth) acrylate, dipentaerythritol penta or hexa (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, and polyesters Le (meth) acrylate (excluding the di (meth) acrylate of a diol having 2 to 10 carbon atoms) and the like. The polyester (meth) acrylate may be a dendrimer type (meth) acrylate.

  Among the above compounds, as the component (D), di (meth) acrylates of diols having 2 to 10 carbon atoms (hereinafter referred to as “component (D1)”) are preferable.

  In addition, the "carbon number" in the diol which has C2-C10 means the number of carbon which comprises the site | part which remove | eliminated the hydroxyl group from the diol.

  Preferred specific examples of the component (D1) include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 6-hexanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, cyclohexane dimethylol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (Meth) acrylate, 1,9-nonanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate And esterification reaction products of neopentyl glycol, hydroxypivalic acid and (meth) acrylic acid, and the like.

  The component (D1) is more preferably a di (meth) acrylate of an alkanediol having 2 to 10 carbon atoms, and particularly preferably 1,6-hexanediol diacrylate in view of curability and adhesion.

As the component (D1), the above-mentioned compounds may be used alone or two or more may be used.
The content ratio of the component (D1) is preferably 0 to 60% by weight, more preferably 5 to 55% by weight, and still more preferably 10 to 50% by weight based on the whole composition. .

4-2. Component (E) The component (E) is a compound having one or more oxetanyl groups in one molecule.
As the component (E), various compounds can be used as long as they are compounds having one or more oxetanyl groups in one molecule, and a compound having one oxetanyl group in one molecule [hereinafter, “( And compounds having two or more oxetanyl groups in one molecule [hereinafter referred to as “component (E2)”] and the like.

  Specific examples of the component (E1) include alkoxyalkyl group-containing monofunctional oxetane such as 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, and aromatic group-containing such as 3-ethyl-3-phenoxymethyl oxetane. Mention may be made of monofunctional oxetanes, and hydroxyl group-containing monofunctional oxetanes such as 3-ethyl-3-hydroxymethyl oxetane.

  As the component (E2), a compound having a molecular weight of 500 or less having two or more oxetanyl groups in one molecule [hereinafter, referred to as “component (E2-1)]” is preferable.

  Specific examples of the component (E2-1) include bis [(3-ethyloxetan-3-yl) methyl] ether, bis [(3-methyloxetan-3-yl) methyl] ether, bis [(oxetane-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-ethyloxetan-3-yl) methoxy] benzene, 1,2-bis [(3-ethyloxetan-3-yl) methoxy] benzene, 4,4'-bis [(3- Ethyloxetan-3-yl) methoxy] biphenyl, 2,2'-bis [(3-ethyloxetan-3-yl) methoxy] biphenyl, 1,1,1-tris [(3-ethyloxetan-3-yl) Me Toxymethyl! Propane, 1,2-bis [(3-ethyloxetan-3-yl) methoxy] ethane, 1,2-bis [(3-ethyloxetan-3-yl) methoxy] propane, 1,4-bis [ Examples include (3-ethyloxetan-3-yl) methoxy] butane and 1,6-bis [(3-ethyloxetan-3-yl) methoxy] hexane and the like.

As the component (E2-1), a compound having a molecular weight of 150 to 400 having two oxetanyl groups in one molecule is more excellent in that the composition obtained has a low viscosity and the cured product is excellent in adhesion. Preferred and even more preferred molecular weights are in the range of 150-300.
As the component (E2-1), bis [(3-ethyloxetan-3-yl) methyl] ether, that is, an oxetane compound represented by the following formula (2) is particularly preferable.

  As the component (E2) other than the component (E2-1), the etherified modified product of novolac type phenol-formaldehyde resin with 3-chloromethyl-3-ethyl oxetane, 3-[(3-ethyl oxetan-3-yl) Hydrolytic condensation of methoxy] propyltrimethoxysilane, 3-[(3-ethyloxetan-3-yl) methoxy] propyltriethoxysilane, 3-[(3-ethyloxetan-3-yl) methoxy] propyltrialkoxysilane And a condensation reaction product of 3-ethyloxetan-3-ylmethanol and a silane tetraol polycondensate.

As the component (E), the aforementioned compounds may be used alone or two or more may be used.
As for the content rate of (E) component, 1-80 weight% is preferable in the whole composition. By setting it as this ratio, even if the atmospheric humidity at the time of coating and curing is high, the adhesive strength can be made good.
The more preferable content rate of (E) component is 5 to 55 weight% in the whole composition, More preferably, it is 10 to 50 weight%.

4-3. Component (F) The component (F) is a radical photopolymerization initiator. That is, it is a compound which generates radicals by irradiation of active energy rays such as ultraviolet rays and electron beams, starts polymerization of radical curable components such as the component (D), and cures.

  The radically polymerizable component can cure the radical curable component by radicals generated when the component (C) (photocationic polymerization initiator) is decomposed by active energy rays such as light and electron beam. However, it is preferable to contain a radical polymerization initiator, which is the component (F), in order to sufficiently react with a small amount of irradiation and to obtain good adhesion.

As specific examples of the component (F), for example, the following compounds can be mentioned.
4'-phenoxy-2,2-dichloroacetophenone, 4'-tert-butyl-2,2-dichloroacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl-1- (4-methylthiophenyl)- 2-morpholinopropan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, α, α-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4- (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- ( - such as morpholinophenyl) butan-1-one, acetophenone photopolymerization initiators;
Benzoin ether based photoinitiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether;
Benzophenone-based photoinitiators such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 2,4,6-trimethylbenzophenone;
Thioxanthone photoinitiators, such as 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, and 1-chloro-4-propoxy thioxanthone;
Such as 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, bis (2, 6 dimethoxy benzoyl)-2, 4, 4- trimethyl pentyl phosphine oxide, and bis (2, 4, 6 trimethyl benzoyl) phenyl phosphine oxide , Acyl phosphine oxide photopolymerization initiators;
Oxime / ester photopolymerization initiators such as 1,2-octanedione, 1- [4- (phenylthiophenyl)]-, 2- (O-benzoyloxime);
Camphor quinone etc.

The component (F) can be used singly or in combination of two or more depending on the desired performance.
The content ratio of the component (F) is preferably 0 to 10% by weight, more preferably 0.1 to 10% by weight, and 0.5 to 5% by weight based on the whole composition. Is more preferred.

4-3. Other components besides the above In the composition of the present invention, various compounds can be blended in addition to the components (D), (E) and (F) described above.

The composition of the present invention may contain a vinyl ether group-containing compound.
When the vinyl ether group-containing compound is blended, the content thereof is preferably 40% by weight or less, and more preferably 20% by weight or less, based on the entire composition.
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, triethylene glycol divinyl ether, and cyclohexane dimethanol divinyl ether.

The composition of the present invention may contain a photocationic initiator and / or a photosensitizer for sensitizing a photoradical polymerization initiator.
The photosensitizer is preferably an anthracene-based compound such as 9,10-dibutoxyanthracene and 9,10-bis (acyloxy) anthracene. Among these, 9,10-bis (acyloxy) anthracene is particularly preferable in that both the cationic polymerization initiator and the radical polymerization initiator are sensitized and the color of the cured product is also small.
When using a photosensitizer, it is preferable to be 0.1 to 2 weight% with respect to the whole composition from the point of hardenability and low coloring.

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

Specifically, such as inorganic fillers, softeners, antioxidants, anti-aging agents, stabilizers, tackifier resins, anti-foaming agents, plasticizers, organic solvents, dyes, pigments, treating agents and ultraviolet blocking agents. Inactive ingredients can be blended. Examples of tackifying resins include rosins such as rosin acids, polymerized rosin acids and rosin esters, terpene resins, terpene phenol resins, aromatic hydrocarbon resins, aliphatic saturated hydrocarbon resins, petroleum resins and the like.
It is preferable to mix | blend these in a quantity of 20 weight% or less in a composition.
In the case of a hydrophilic plastic substrate such as polyvinyl alcohol or polyvinyl pyrrolidone, water may be blended in the composition. In this case, the water content is preferably 20% by weight or less.

8. Active Energy Ray-Curable Composition The present invention comprises 1 to 50% by weight of the component (A), 1 to 98% by weight of the component (B) below, and 0. 5% component (C) below, based on the entire composition. The present invention relates to an active energy ray-curable composition comprising 5 to 10% by weight.
As a manufacturing method of the composition of this invention, the said (A)-(C) component which is an essential component can be manufactured further by stirring and mixing other components according to a conventional method as needed.
In this case, heating can also be performed as needed. The heating temperature may be appropriately set according to the composition to be used, the substrate, the purpose and the like, but it is preferably 30 to 80 ° C.

  As a viscosity of a composition, 10-5000 mPa * s is preferable at the point which is excellent in the coating property with respect to a base material.

  As Tg of the hardened | cured material of a composition, -50-130 degreeC is preferable, More preferably, it is -20-100 degreeC.

The compositions of the present invention can be used to bond a variety of substrates, including plastics, papers, metals and the like.
As the plastic, polyethylene terephthalate, triacetyl cellulose, amorphous cycloolefin polymer, polymethyl methacrylate, polycarbonate, polystyrene, acrylic / styrene copolymer, (meth) acrylic resin, cellulose acetate butyrate, polyvinyl chloride, poly Examples include vinylidene chloride, polyethylene, polypropylene, ABS resin, polyamide, polyester, polyurethane, polyimide, polyamide, polyvinyl acetate, polyvinyl alcohol, chlorinated polypropylene, polyethylene naphthalate, polyvinyl pyrrolidone, nylon, polyvinyl butyral and the like.
Examples of paper include imitation paper, high quality paper, kraft paper, art coated paper, castor coated paper, pure white roll paper, parchment paper, water resistant paper, glassine paper, corrugated paper and the like.
As a metal foil, aluminum foil etc. are mentioned, for example.

The composition of the present invention can be preferably used as an adhesive for plastic films or sheets (hereinafter simply referred to as "plastic films"), and can be more preferably used as an adhesive for transparent plastic films.
More specifically, it can be preferably used for adhesion of plastic films, adhesion of plastic films and various other substrates (hereinafter referred to as "other substrates"). That is, it can be preferably used for adhesion of two substrates in which at least one is a plastic film. In the following, the term "substrate" simply refers to a general term for plastic films and other substrates.
As a material in a plastic film, the above-mentioned plastic can be mentioned.
Other substrates include paper, metals and the like, and the same ones as described above can be used.
Although the thickness of the substrate is not particularly limited, the thickness of the substrate is preferably 100 μm or less from the viewpoint of taking advantage of the advantage of the composition of the present invention that the laminate does not generate the waviness. And 50 μm or less.

  In addition, when a plastic film is a material with low adhesive property, before applying the composition of the present invention, one or both surfaces can be subjected to an activation treatment. Examples of the surface activation treatment include plasma treatment, corona discharge treatment, chemical treatment, surface roughening treatment and etching treatment, and flame treatment, and these may be used in combination.

9. Method of Use The composition of the present invention may be used according to a conventional method, such as a method of applying the composition to a substrate, laminating it to another substrate, and irradiating active energy rays. Be
The composition of the present invention is suitable for bonding a thin layer adherend as a substrate. The method of use in bonding the thin layer adherend may be in accordance with the method commonly used in the production of laminates. For example, the composition etc. are coated on a 1st thin layer adherend, the 2nd thin layer adherend is bonded together to this, and the method of irradiating with an active energy ray etc. is mentioned.

  Coating on a substrate may be carried out according to a conventionally known method, such as a natural coater, knife belt coater, floating knife, knife over roll, knife on blanket, spray, dip, kiss roll, squeeze roll, reverse roll, air blade And curtain flow coater, comma coater, gravure coater, microgravure coater, die coater, curtain coater and the like.

As a film thickness in the case of coating a composition with respect to a base material, what is necessary is just to set suitably according to the objective.
Specifically, it is preferably 1 to 80 μm, more preferably 2 to 30 μm.

  As the active energy ray, visible light, ultraviolet light, X-ray, electron beam and the like can be mentioned, but ultraviolet light is preferable since inexpensive devices can be used.

As a light source in the case of curing by ultraviolet light, various light sources can be used, and examples thereof include pressure or high pressure mercury lamps, metal halide lamps, xenon lamps, electrodeless discharge lamps, carbon arc lamps, and LEDs. Among these, high pressure mercury lamps and metal halide lamps are particularly preferable. The dose of ultraviolet rays is in the range of UV-A (365 nm vicinity) is preferably 100~2,000mJ / cm ^2, more preferably 200~1,500mJ / cm ^2, more preferably 300~1,000mJ It is / cm ² .

  In the case of curing by electron beam, various apparatuses can be used as EB irradiation apparatus which can be used, and examples thereof include Cockcroft-Waltsin type, Bandegraph type and resonant transformer type apparatus, etc. Those having an energy of 1000 eV are preferable, and more preferably 100 to 300 eV.

The composition of the present invention can be preferably used for producing a laminate.
Specifically, the composition described above is coated on a substrate, another substrate is bonded to the coated surface, and the active energy ray is irradiated from any side of the substrate. .
The coating method of the composition, the film thickness of the composition, the irradiation conditions of the type of active energy ray, and the like are also as described above.

The composition of the present invention can be preferably used as an adhesive for plastic films.
The method of use in this case may be the same as that described above, that is, the coating method, the coating thickness, and the irradiation condition of the active energy ray.

In the case of the adhesive for plastic films, it can be used for adhesion of plastic films, adhesion of plastic films and other substrates.
Examples of plastic films and other substrates, such as paper and metal, are as described above.
The plastic film needs to be able to transmit active energy rays, and the film thickness may be selected according to the thin layer adherend to be used and the application, but preferably the thickness is 0.2 mm or less .

Moreover, in this case, adhesion is not limited to a flat state, and bonding can also be performed in a curved state. That is, there is a method of bending the base material in a concave or convex state, applying the composition in this state, bonding the other base material, and irradiating an active energy ray.
Another method is to apply the composition of the present invention in a planar state to a substrate, bond the other substrate, fold it into a concave or convex state, and irradiate it with active energy rays to bond. It can be mentioned.
In this case, as a method of coating the composition in a planar state, the method described above may be applied. Examples of the method of applying the composition in a curved state include methods using a spray, dip, curtain flow coater, screen printing, slot die coater and the like.

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

10. Application Example The composition of the present invention can be preferably used as an adhesive composition as described above, and more preferably used as an adhesive for plastic films.
As applications of the laminate obtained from this, it can be preferably used as an optical film, and specific examples include a color conversion film, a polarizing plate, a brightness enhancement film, a heat ray reflective film, a void filler, etc. It can be preferably used for color conversion films and polarizing plates.
Specific examples of the color conversion film and the polarizing plate are shown below.

10-1. Preparation of Color Conversion Film The composition of the present invention can be used as a binder of a backlight color conversion film using an LED as a light source. That is, a phosphor that converts light of short wavelength into red or green is dispersed in the composition of the present invention, and the resulting film is used as an adhesive to bond plastic films together.
At this time, although waviness occurs in a large area, the composition of the present invention is a composition that hardly generates waviness, so the thickness of the plastic film can be reduced.

  Examples of the plastic constituting the plastic film in this case include the same polymers as those exemplified above, and polyethylene terephthalate (PET) is preferable.

  As a fluorescent substance, the thing similar to the former can be used and the inorganic compound and organic compound which show fluorescence, such as yellow, yellow + red, green + red, etc. are mentioned.

  In addition to the above, the color conversion film has at least a support and, if necessary, various functional layers such as an optical functional layer, an undercoat layer, an antireflective layer, a hard coat layer, and a lubricating layer. Can be mentioned. In this case, the binder can be used as an adhesive for each layer, for example, as an adhesive for the support and the optical functional layer.

10-2. Production of Polarizing Plate The composition of the present invention can be used for adhesion of a polarizer and a protective film, and adhesion of a polarizing plate and a retardation film.

The polarizer has a function of selectively transmitting in one direction linear polarized light from natural light.
Specific examples of the polarizer include an iodine-based polarizer in which iodine is adsorbed and oriented in a polyvinyl alcohol-based film, a dye-based polarizer in which a dichroic dye is adsorbed and oriented in a polyvinyl alcohol-based film, and (lyotropic) liquid crystal The coating type polarizer etc. which coated the pigment | dye of the state, and were orientated and fixed are mentioned.
These iodine-based polarizers, dye-based polarizers, and coating-type polarizers have a function of selectively transmitting linearly polarized light in one direction from natural light and absorbing linearly polarized light in the other direction, and absorbing them. Type polarizer.

  In the above-mentioned iodine type polarizer and dye type polarizer, although a protection layer is usually provided in the single side or both sides, a composition of the present invention can be used for adhesion of a polarizer and a protective film.

As a protective film, for example, cellulose acetate resin film such as triacetyl cellulose and diacetyl cellulose, acrylic resin film, polyester resin film, polyarylate resin film, polyether sulfone resin film, cyclic olefin such as norbornene and monomers Cyclic polyolefin resin film and the like.
In this case, the moisture permeability of the protective film, preferably has the following 150g / m ² / 24h.

Next, the composition of the present invention can also be used to bond a polarizing plate and a retardation film.
In this case, as the polarizing plate, one having a protective layer on one side or both sides can be used. In this case, the protective layer may be one obtained by bonding the protective film or a protective film formed by coating. In the polarizing plate provided with a protective layer only on one side, the surface to be adhered to the retardation film may be a surface with a protective layer or a surface without a protective layer.

  As the retardation film, various films can be used, and an optical film subjected to processing such as uniaxial or biaxial stretching, or a liquid crystalline compound or the like is applied to a substrate, and processed to be oriented and fixed. An optical film or the like may be mentioned, and the magnitude relationship (refractive index ellipsoid) of the three-dimensional refractive index is controlled in accordance with the use conditions. It is mainly used to compensate for the coloring of the liquid crystal layer of the liquid crystal display and to compensate for the change in retardation due to the viewing angle.

Specific examples of retardation films include, as materials of optical films to which processing such as stretching is applied, polyethylene, polypropylene, polyolefin such as cyclic polyolefin, polycarbonate, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polyarylate And polyamide etc.
The cyclic polyolefin described above is a general term for resins obtained from cyclic olefins such as norbornene, tetracyclododecene and derivatives thereof. For example, JP-A-3-14882 and JP-A-3-122137 And the like.
Specifically, ring-opening polymers of cyclic olefins, addition polymers of cyclic olefins, random copolymers of cyclic olefins and α-olefins such as ethylene and propylene, and modifying these with unsaturated carboxylic acids and their derivatives, etc. The modified graft body etc. can be illustrated. Furthermore, these hydrides can be mentioned. Examples of the product include Zeonex made by Nippon Zeon Co., Ltd., Zeonor, Arton made by JSR Co., Ltd., torus made by TICONA, and the like.

  Moreover, as a film for optics which apply | coated the liquid crystalline compound etc. to the base material, and processed orientation and fixation, "WV film" (made by Fuji Photo Film Co., Ltd.), "LC film", "NH film" [All are Nippon Nippon Oil Co., Ltd. products] etc. are mentioned.

The manufacturing method of a polarizing plate or a polarizing plate with a retardation film is demonstrated using the composition of this invention.
As the said manufacturing method, the method containing following process [1]-[3] is mentioned.
[1] A step of applying the composition of the present invention to an adherend (base material) selected from a polarizer to be adherend, a polarizing plate, a protective film, a protective film, a retardation film, and a retardation film ,
[2] The other adherend selected from a polarizer, a polarizing plate, a protective film, a protective film, a retardation film, and a retardation film is attached to the adherend (base material) coated with the composition Combining process, and
[3] A step of irradiating the bonded adherend (laminate) with an active energy ray, particularly a step of irradiating the composition with an active energy ray through the bonded adherend (laminate).
When pasting a protective film or a retardation film only on one side, a polarizing plate or a polarizing plate with a retardation film can be manufactured by the above-mentioned procedure, but when pasting on both sides, a process [1] and [2 ] May be performed twice, or step [3] may be performed, or steps [1], [2] and [3] may be repeated twice.

The coating method in the step [1] and the active energy ray irradiation method in the step [3] may be performed by the same method as described above.
Further, as described above, it is also possible to bond in a curved surface state using the above-mentioned manufacturing method.

When a polarizing plate with retardation film is used as a circularly polarizing plate, a retardation film with different retardations is further attached to the retardation film side of the polarizing plate with retardation film in order to obtain circular polarization over a wide band. It can also be fitted.
Specifically, there is a method of bonding a retardation film having a half wavelength to each wavelength to a polarizing film, and further bonding a retardation film having a quarter wavelength to each wavelength. . In this case, step [3] may be performed after steps [1] and [2] are repeated three times, or steps [1], [2] and [3] may be repeated three times.

The present invention will be described more specifically by the following Examples and Comparative Examples. However, the present invention is not limited by these examples.
In the following description, "parts" means parts by weight, and the numerical values indicating the proportions in the table mean% by weight.

  Each component used for preparation of a composition in an Example and a comparative example is as follows, and is abbreviated as follows hereafter.

Component (A) Component A-1: A polymer obtained in Production Example 2 described later.
Component (A ') [polymer other than component (A)]
A'-1: The polymer obtained in Production Example 1 described later.

(B) Component · HD-DGE: 1,6-hexanediol diglycidyl ether (distilled and purified product), "Epo-Gose HD (D)" manufactured by Yokkaichi Gosei Co., Ltd.
CEL-2021: 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, "Celloxide 2021 P" manufactured by Daicel Chemical Industries, Ltd.

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

(D) Component OXT-221: bis [(3-ethyloxetan-3-yl) methyl] ether, "Aron oxetane OXT-221" manufactured by Toagosei Co., Ltd.

(E) Component HDDA: 1,6-hexanediol diacrylate, "Biscoat # 230" manufactured by Osaka Organic Chemical Industry Co., Ltd.
(F) Component I-184: 1-hydroxy-cyclohexyl-phenyl-ketone, "IRGACURE 184" manufactured by BASF.
TPO: 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, "Darocur TPO" manufactured by BASF
(Others)
UVS-581: 9,10-bis (octanoyloxy) anthracene, "Anthracure UVS-581" manufactured by Kawasaki Kasei Kogyo Co., Ltd.

1. Production example
1) Production Example 1
The jacket temperature of a 1000 mL pressurized stirred tank reactor equipped with an oil jacket was maintained at 245 ° C. Then, while keeping the pressure in the reactor constant, 2-ethylhexyl acrylate (75 parts), methyl methacrylate (25 parts), methyl ethyl ketone (4.6 parts) as a polymerization solvent, di-t-butylperme as a polymerization initiator Continuously supply the monomer mixture consisting of oxides (0.77 parts) from the raw material tank to the reactor at a constant feed rate (48 g / min, residence time: 12 minutes), and supply the monomer mixture The reaction solution corresponding to was continuously withdrawn from the outlet. Immediately after the start of the reaction, once the reaction temperature decreased, a temperature increase due to heat of polymerization was observed, but the internal temperature of the reactor was maintained at 240 to 242 ° C. by controlling the oil jacket temperature. 36 minutes after the internal temperature of the reactor became stable was taken as the collection start point of the reaction liquid, and as a result of continuing the reaction for 25 minutes from this, 1.2 kg of monomer mixture was supplied, 1.2 kg of The reaction solution was recovered.
Thereafter, the reaction solution was introduced into a thin-film evaporator to separate volatile components such as unreacted monomers, and volatile components such as unreacted monomers were removed to obtain a polymer A′-1.
As a result of measuring GPC of polymer A'-1, as a polystyrene equivalent number average molecular weight (hereinafter referred to as "Mn") is 1,500, Mw (weight average molecular weight) is 2,400, viscosity at 25 ° C is And 3,600 mPas. The Tg was −64 ° C., and the double bond concentration was 0.63 meq / g.

2) Production Example 2
Polymer A'-1 (700 g) and dried 5% palladium carbon (3.5 g) were placed in a 1,000 mL pressurized, pressure-stirred tank reactor equipped with an oil jacket, and the atmosphere was evacuated, The internal temperature was heated to 130 ° C. and pressurized to about 1.5 MPa with hydrogen. In this state, the mixture was stirred for 8 hours.
After the pressure was purged, it was filtered using diatomaceous earth "Radiolite # 100" manufactured by Showa Chemical Industry Co., Ltd. as a filter aid to obtain a polymer A-1.
The double bond concentration of the polymer A-1 was below the lower limit of detection (0.01 meq / g) by ¹ H-NMR.

2. Example 1, Comparative Example 1
1) Preparation of Composition The components shown in Table 1 were blended in respective proportions and mixed by stirring according to a conventional method to prepare an active energy ray-curable adhesive composition.

2) Production of laminate 100 μm thick cycloolefin polymer (trade name: Zeonor ZF-14, manufactured by Nippon Zeon Co., Ltd., hereinafter referred to as “Zeonor”), and UV absorber-containing acrylic resin having a thickness of 75 μm (trade name: HI50) Corona treatment was carried out on -75 KT-UV, manufactured by Kuraray Co., Ltd., hereinafter referred to as "acrylic resin" as an easy adhesion treatment.
Next, the resulting composition was coated to a thickness of 15 μm with a bar coater on a corona-treated surface of an acrylic resin, and then Zeonoa was laminated. At this time, the corona-treated surface of Zeonor was placed in contact with the coated surface.
Finally, UV radiation with integrated light quantity 500mJ / cm2 (UV-B) or 250mJ / cm2 (UV-A) from the surface of Zeonoa with UV radiation device with belt conveyor (using metal halide lamp) manufactured by Eye Graphics Co., Ltd. To cure the adhesive composition.
Moreover, after leaving the obtained laminated body on 23 degreeC and the conditions of 50% of relative humidity for 1 day, it evaluated according to the following method.

3. Evaluation method
1) Evaluation of colorless transparency The obtained laminate was visually observed and judged according to the following criteria.
A: No turbidity or yellowing was felt at all B: A slight turbidity or yellowing was felt C: A haze or yellowing was clearly felt

2) Evaluation of swell The swell of the obtained laminate was visually observed and judged according to the following criteria.
A: I can not recognize swell at all.
B: Swelling can hardly be recognized.
C: I can recognize a small swell.
D: We can recognize clear swell.

3) Evaluation of Adhesive Strength The obtained laminate was cut out into a width of 1 inch and a length of 10 cm, and the peel adhesive strength was evaluated by a T-peel test and a peeling speed of 200 mm / min. However, when the adhesive was uncured and liquid, the adhesive strength was not evaluated because there was no meaning in the adhesive strength measurement. Moreover, when the base material was destroyed and the adhesive force can not be evaluated, it was described as "material breakage" in the table.

Example 1 which is the composition of the present invention showed good adhesion even with a small amount of ultraviolet radiation,
In Comparative Example 1 in which the component (A) was changed to the component (A ′), the adhesive strength became weak when the ultraviolet irradiation amount was small.

  The composition of the present invention can be preferably used as an adhesive for the adhesion of various substrates, in particular by the adhesion of plastic films. Further, the composition of the present invention can be suitably used for the production of a laminate, and in particular, can be suitably used for the production of a laminate for an optical film used for a liquid crystal display or an organic EL display.

Claims (11)

Active energy containing 1 to 50% by weight of the following component (A), 1 to 98% by weight of the following component (B) and 0.5 to 10% by weight of the following component (C) based on the whole composition Radiation curable composition.
Component (A): a polymer obtained by polymerizing a monomer mixture containing an alkyl (meth) acrylate having an alkyl group having 4 or more carbon atoms, and having a double bond concentration of 0.2 meq / g or less Polymer (B) Component: Compound having two or more epoxy groups in one molecule (C) Component: Photocationic polymerization initiator   The active energy ray-curable composition according to claim 1, wherein the weight average molecular weight of the component (A) is 1,000 to 50,000. The active energy according to claim 1 or 2 , further comprising 1 to 80% by weight of a compound having one or more ethylenically unsaturated groups in one molecule as component (D) with respect to the entire composition. Radiation curable composition. The compound according to any one of claims 1 to 3 , further comprising 1 to 80% by weight of a compound having one or more oxetanyl groups in one molecule as component (E) with respect to the whole composition. Active energy ray-curable composition. The active energy ray curable composition according to any one of claims 1 to 4 , wherein the component (B) contains a diglycidyl ether of a diol having 2 to 10 carbon atoms. The active energy ray curable composition according to any one of claims 1 to 5 , wherein the component (B) contains a compound having an alicyclic epoxy group. The active energy ray curable composition according to any one of claims 3 to 6 , wherein the component (D) contains a di (meth) acrylate of a diol having 2 to 10 carbon atoms. Furthermore, the active energy ray curable composition according to any one of claims 1 to 7 , further comprising a photo radical polymerization initiator as the component (F). An active energy ray-curable adhesive composition for plastic films or sheets comprising the composition according to any one of claims 1 to 8 . A laminate comprising a plastic film or sheet, a cured product of the composition according to claim 9 , and another substrate or a plastic film or sheet. A method for producing a laminate, comprising adhering two substrates, at least one of which is a plastic film or sheet, using the composition according to claim 9 , and irradiating the substrate with active energy rays.