JP6331989B2 - Active energy ray-curable adhesive composition - Google Patents

Description

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

  The active energy ray-curable adhesive generally does not contain a solvent and has an advantage that it is instantly cured, and thus is excellent in terms of working environment, safety, production speed, energy saving, and the like. For this reason, it is used suitably for manufacture of the various members used for a liquid crystal display, a touch panel, a building material, etc. Specifically, adhesives for various optical films such as polarizing plates and brightness enhancement films used in liquid crystal displays, adhesives that fill the gap between the touch panel and the display, optical members other than displays such as heat ray reflective films, etc. Can be mentioned.

  As the active energy rays, ultraviolet rays, visible rays, and electron beams are often used. Among them, the ultraviolet irradiation device is relatively inexpensive and easy to use. For this reason, an active energy ray hardening-type adhesive agent is often used for adhesion | attachment of glass or a transparent film.

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

  Adhesives are required to have adhesive strength with various adherends and transparency of cured products, and various studies have been made (for example, Patent Document 1).

However, recently, a thin film may be bonded in a large area, and in that case, waviness of a cured product becomes a problem in addition to adhesive strength and transparency.
Moreover, it is necessary to increase the production speed in order to reduce the cost of various members. For this reason, the request | requirement with respect to the cure rate of an adhesive agent has also become severe.

  Against this background, there is a need for an active energy ray-curable adhesive that is excellent in adhesive strength, transparency, and curability, and that does not cause bending by bonding a thin film over a large area.

JP 2001-64594 A (Claims)

  The present invention has been made in view of the above problems, and is an active energy ray-curable adhesive composition that is excellent in adhesive strength, transparency, and curability, and that does not generate warping by bonding a thin film over a large area. The purpose is to provide.

  As a result of various studies, the present inventors have found that a specific polymer, a compound having one ethylenically unsaturated group, and an active energy ray containing a compound having two ethylenically unsaturated groups in a specific ratio The present inventors have found that a curable adhesive composition solves the above problems and completed the present invention.

The present invention comprises 1 to 50% by weight of the following component (A), 1 to 98% by weight of the following (B) component and 1 to 98% by weight of the following (C) component with respect to the entire composition. The present invention relates to an active energy ray-curable adhesive composition.
(A) Component: A polymer obtained by polymerizing a vinyl monomer at a temperature of 150 to 350 ° C. and then adding hydrogen (B) Component: Compound having one ethylenically unsaturated group (C ) Component: Compound having two ethylenically unsaturated groups 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 that is excellent in adhesive strength, transparency, and curability and that does not generate warpage by bonding a thin film over a large area. For this reason, it can use 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 space | gap filler. Moreover, it can use suitably for manufacture of various members and products which require smoothness other than an optical film.

The present invention comprises 1 to 50% by weight of component (A), 1 to 98% by weight of component (B) and 1 to 98% by weight of component (C) below based on the total composition. The present invention relates to a wire curable adhesive composition.
Hereinafter, components (A) to (C), other components, and preferred methods of using the composition of the present invention will be described in detail.

1. Component (A) The component (A) is a polymer obtained by polymerizing a vinyl monomer at a temperature of 150 to 350 ° C. and adding hydrogen to the resulting polymer.
A polymer obtained by polymerizing a vinyl monomer at a high temperature is used for improving various physical properties as a plasticizer, a tackifier, etc. by blending it in an active energy ray-curable composition, and the present invention. Then, it is used to prevent the occurrence of swell. However, when a vinyl monomer is polymerized at a high temperature, a polymer having a double bond at the molecular end is obtained due to a side reaction. When such a polymer is added to the 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 the double bond, thereby blending the polymer. However, it can be excellent in curability.

A vinyl-type monomer is a compound which has one ethylenically unsaturated group, and what is used by radical polymerization of a vinyl-type monomer can be used.
Specific examples of the vinyl monomer include (meth) acrylate, (meth) acrylic acid, styrene, α-methylstyrene, acrylonitrile, vinyl acetate, etc., but copolymerization, 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, and 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, 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;
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 (meta ) Acrylate, alkoxysilyl group-containing (meth) acrylates such as 8-trimethoxysilyloctyl (meth) acrylate; and benzyl (meth) acrylate.

Among these compounds, alkyl (meth) acrylates having an alkyl group having 4 or more carbon atoms are preferable because they give the cured product flexibility and are excellent in water resistance and weather resistance.
The proportion of the alkyl (meth) acrylate having an alkyl group having 4 or more carbon atoms is preferably 40% by weight or more based on the total amount of monomers used for the production of the component (A), and preferably 60% by weight or more. More preferred. If it is less than 40% by weight, the glass transition temperature of the component (A) becomes high, and the flexibility of the cured product may be insufficient.

In the production of the component (A), first, the vinyl monomer is polymerized at a temperature of 150 to 350 ° C.
By setting the polymerization temperature to 150 ° C. or higher, the molecular weight can be easily controlled even with a small amount of initiator and without using a chain transfer agent, and the weather resistance when cured is excellent. On the other hand, by setting the polymerization temperature to 350 ° C. or lower, the conversion rate from the monomer to the polymer can be increased. Further, the problem of coloring caused by the decomposition product can be avoided. The preferable polymerization temperature is in the range of 170 to 300 ° C, and more preferably in the range of 180 to 250 ° C.
Examples of the polymerization method include solution polymerization, bulk polymerization, and dispersion polymerization.
The reaction process may be any of batch type, semi-batch type, and continuous polymerization, but continuous polymerization is preferred in terms of excellent composition uniformity.

As the high-temperature continuous polymerization method, known methods disclosed in JP-A-57-502171, JP-A-59-6207, JP-A-60-215007 and the like may be used.
For example, in a pressurizable reactor, after setting a predetermined temperature under pressure, a monomer mixture composed of each monomer and, if necessary, a polymerization solvent is supplied to the reactor at a constant supply rate, The method of extracting the polymerization liquid of the quantity corresponding to the supply quantity of a monomer mixture is mentioned.
Moreover, a polymerization initiator can also be mix | blended with a monomer mixture as needed. The blending amount when blended 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, the monomer mixture used and the boiling point of the solvent, and does not affect the reaction, but may be any 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 monomer may not sufficiently react, and if the unreacted monomer exceeds 60 minutes, the productivity may deteriorate. The preferred residence time is 2 to 40 minutes.

As an example of the polymerization initiator used in the production of the component (A), any initiator that generates radicals at a predetermined reaction temperature can be used.
Specifically, organic peroxides such as di-t-butyl peroxide and di-t-hexyl peroxide, azobisisobutyronitrile, azobiscyclohexacarbonitrile, azobis (2-methylbutyronitrile) ), Azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-amidinopropane) dihydrochloride, 4,4′-azobis (4-cyanovaleric acid), and the like. It is done.

The production of the component (A) may be carried out by any method of solution polymerization performed in an organic solvent and bulk polymerization including no solvent or a small amount of an organic solvent, but bulk polymerization is preferred.
In the case of solution polymerization, organic hydrocarbon compounds are suitable as the organic solvent, cyclic ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbon compounds such as benzene, toluene and xylene, and 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, and one or more of these can be used. In a solvent that does not dissolve the (meth) acrylic acid ester copolymer well, scales are likely to grow on the walls of the reactor, and production problems are likely to occur in the cleaning process.
The amount of the organic solvent used is preferably 80 parts by weight or less with respect to 100 parts by weight of the total vinyl monomer. By making it 80 parts by weight or less, a high conversion rate can be obtained in a short time. More preferably, it is 1 to 50 parts by weight. A dehydrating agent such as trimethyl orthoacetate or trimethyl orthoformate can also be added.

The reaction liquid withdrawn from the reactor proceeds to the next step as it is, or the polymer is simply removed by distilling off volatile components such as unreacted monomers, solvents and low molecular weight oligomers by distillation or the like. Can be separated. A part of the volatile components such as unreacted monomer, solvent and low molecular weight oligomer distilled off from the reaction solution can be returned to the raw material tank or directly returned to the reactor and used again for the polymerization reaction.
Thus, the method of recycling an unreacted monomer and a solvent is a preferable method from an economical viewpoint. 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.

(A) component is obtained by hydrogenating the polymer obtained by said method.
As a hydrogenation method, a conventionally known method may be followed.
That is, after the reduction catalyst is added to the polymer reaction solution, the inside of the system is put into a hydrogen atmosphere, the pressure is set to 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.
As the reduction catalyst, either a homogeneous catalyst or a heterogeneous catalyst can be used.
Specific examples of homogeneous catalysts include rhodium complexes such as chlorotris (triphenylphosphine) rhodium, ruthenium complexes such as dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorobis (triphenylphosphine) ) Platinum complexes such as platinum, and iridium complexes such as carbonylbis (triphenylphosphine) iridium.
On the other hand, examples of the heterogeneous catalyst include solid catalysts in which transition metals such as nickel, rhodium, ruthenium, palladium, and platinum are supported on carbon, silica, alumina, fibers, organic gels, and the like.
As the reduction catalyst, a heterogeneous catalyst is preferable in that the catalyst can be easily removed by filtration or the like, the quality is stable, and an expensive catalyst can be reused.
In the case of a homogeneous catalyst, the ratio of the reduction catalyst to be added is preferably 10 to 1,000 ppm with respect to the polymer. In the case of a heterogeneous catalyst, 1,000 to 10,000 ppm is preferable.

It is preferable to reduce the double bond concentration in the polymer to 0.2 meq / g or less by hydrogenation.
By setting it 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, More preferably, it is 0.05 meq / g or less.
The double bond concentration of the component (A) is determined based on the measurement of ¹ H-NMR. The double bond signal observed at 5 to 6.5 ppm and the methylene and methyl groups adjacent to the ester recognized at 3 to 4.5 ppm. It can be calculated from the ratio of the integral values of the signals.

(A) As a weight average molecular weight (henceforth "Mw") of a component, 1,000-50,000 are preferable. When it is 1,000 or more, the cured product is stably present in the system without bleed for a long time, and when it is 50,000 or less, it becomes an appropriate viscosity when blended as a composition, and workability is improved. Is better. More preferably, it is 1,500-20,000.
In addition, Mw in this invention means the value of polystyrene conversion 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 making Tg 20 degrees C or less, it will become excellent in a softness | flexibility. More preferably, it is −10 ° C. or lower.
In addition, Tg in this invention means the value | valence measured by the intermediate point of the endothermic peak detected in a differential scanning calorimeter.

As the component (A), the aforementioned compounds may be used alone or in combination of two or more.
(A) The content rate of a component is 1 to 50 weight% on the basis of the whole composition, Preferably it is 1 to 40 weight%. When the proportion of the component (A) is less than 1% by weight, the swell of the film laminate is increased. On the other hand, when it exceeds 50% by weight, curability and adhesive strength are reduced.

2. Component (B) The component (B) is a compound having one ethylenically unsaturated group.
Examples of the ethylenically unsaturated group in component (B) include vinyl groups, vinyl ether groups, (meth) acryloyl groups, and (meth) acrylamide groups.

As the component (B), various compounds can be used. Specifically, aromatic vinyl compounds such as (meth) acrylate, (meth) acrylamide, styrene and vinyltoluene, vinyl acetate, (meth) acrylic acid, N-vinylpyrrolidone, N-vinylformamide, N-vinylcaprolactam, etc. Is mentioned.
Among these compounds, (meth) acrylate, (meth) acrylamide and (meth) acrylic acid are preferable.

Specific examples of (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, and stearyl. Alkyl (meth) acrylates such as (meth) acrylates;
Cyclohexyl (meth) acrylate, tricyclodecane (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyloxyethyl (meth) Alicyclic (meth) acrylates such as acrylate, isobornyl (meth) acrylate and adamantyl (meth) acrylate;
Phenoxyethyl (meth) acrylate, o-phenylphenoxyethyl (meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, nonylphenoxyethyl (meth) acrylate, benzyl (meth) acrylate, and phenol derivatives of alkylene oxide Aromatic (meth) acrylates such as (meth) acrylates;
Alkoxyalkyl (meth) acrylates such as 2-methoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, and ethoxyethoxyethyl (meth) acrylate;
Glycidyl (meth) acrylate, 3-ethyl-3-oxetanylmethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) Cyclic ether group-containing (meth) acrylates such as acrylate, cyclohexanespiro-2- (1,3-dioxolan-4-yl) methyl (meth) acrylate;
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polycaprolactone modified product of 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl ( Hydroxyl group-containing (meth) acrylates such as (meth) acrylate, 2-hydroxy-3-butoxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate ;
Modified polycaprolactone of (meth) acrylic acid, Michael addition type multimer of (meth) acrylic acid, adduct of 2-hydroxyethyl (meth) acrylate and phthalic anhydride, 2-hydroxyethyl (meth) acrylate and succinic anhydride Carboxyl group-containing (meth) acrylates such as acid adducts;
Maleimide group-containing (meth) acrylates such as N- (meth) acryloyloxyethyl hexahydrophthalimide;
Amino group-containing (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate;
3- (trimethoxysilyl) propyl (meth) acrylate, 3- (triethoxysilyl) propyl (meth) acrylate, 3- (methyldimethoxysilyl) propyl (meth) acrylate, 3- (methyldiethoxysilyl) propyl (meth) ) Alkoxysilyl group-containing (meth) acrylates such as acrylates; and oxazolidinone ethyl (meth) acrylates.

  Specific examples of (meth) acrylamide include N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl ( (Meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide and N- Examples include acryloylmorpholine.

As the component (B), the aforementioned compounds may be used alone or in combination of two or more.
As the component (B), among these compounds, a compound having a hydrophilic group and one ethylenically unsaturated group (hereinafter referred to as “hydrophilic unsaturated compound”) is excellent in adhesion to various substrates. This is preferable.
Examples of the hydrophilic group in the hydrophilic unsaturated compound include a hydroxyl group, a carboxyl group, an amino group, an imide group, and an amide group.
Specific examples of the hydrophilic unsaturated compound include a hydroxyl group-containing (meth) acrylate as an example of a compound having a hydroxyl group,
Examples of the compound having a carboxyl group include (meth) acrylic acid and carboxyl group-containing (meth) acrylate,
As an example of the compound having an amino group, an amino group-containing (meth) acrylate can be mentioned,
Examples of compounds having an imide group include maleimide group-containing (meth) acrylates,
Examples of the compound having an amide group include (meth) acrylamide.
Specific examples of these compounds are as described above.
Among these compounds, hydroxyl-containing (meth) acrylate and (meth) acrylamide are preferable as the hydrophilic unsaturated compound.

(B) The content rate of a component is 1 to 98 weight% on the basis of the whole composition, Preferably it is 20 to 70 weight%. (B) When the ratio of a component is less than 1 weight%, adhesive force will fall, and when it exceeds 98 weight%, sclerosis | hardenability will fall.
(B) As a content rate of the hydrophilic unsaturated compound in a component, 10-100 weight% is preferable on the basis of the whole (B) component, More preferably, it is 20-80 weight%.

3. Component (C) The component (C) is a compound having two ethylenically unsaturated groups.
(C) As an ethylenically unsaturated group in a component, a vinyl group, a vinyl ether group, and a (meth) acryloyl group are mentioned, A (meth) acryloyl group is preferable.

Examples of the (meth) acrylate having two (meth) acryloyl groups (hereinafter referred to as “bifunctional (meth) acrylate”) include ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and Di (meth) acrylates of aliphatic diols such as nonanediol di (meth) acrylate and neopentyl glycol di (meth) acrylate;
Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, etc. Of polyalkylene glycol di (meth) acrylates;
Polyol di (meth) such as glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, di (meth) acrylate of pentaerythritol, di (meth) acrylate of ditrimethylolpropane and di (meth) acrylate of dipentaerythritol ) Acrylate;
Di (meth) acrylate of glycerol alkylene oxide adduct, di (meth) acrylate of pentaerythritol alkylene oxide adduct, di (meth) acrylate of ditrimethylolpropane alkylene oxide adduct, di (meth) of dipentaerythritol alkylene oxide adduct ) Di (meth) acrylates of polyol alkylene oxide adducts such as acrylates;
Di (meth) acrylate of an isocyanuric acid alkylene oxide adduct;
Di (meth) acrylates of alicyclic diols such as tricyclodecane dimethylol di (meth) acrylate;
Examples include di (meth) acrylates of alkylene oxide adducts of bisphenol compounds such as di (meth) acrylates of alkylene oxide adducts of bisphenol A and di (meth) acrylates of alkylene oxide adducts of bisphenol F.
In addition, as an example of the above-mentioned alkylene oxide adduct, an ethylene oxide adduct, a propylene oxide adduct, ethylene oxide, a propylene oxide adduct, etc. are mentioned.

  An oligomer may be used as the bifunctional (meth) acrylate. Examples of the oligomer include urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, and polyether (meth) acrylate. These oligomers are compounds having two (meth) acryloyl groups, but are simply referred to as (meth) acrylates unless otherwise specified.

  Examples of the urethane (meth) acrylate having two (meth) acryloyl groups include a reaction product of a diol, an organic diisocyanate, and a hydroxyl group-containing (meth) acrylate.

As the diol, a low molecular weight diol, a diol having a polyester skeleton, a diol having a polyether skeleton, and a diol having a polycarbonate skeleton are preferable.
Examples of the low molecular weight diol include ethylene glycol, propylene glycol, cyclohexanedimethanol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, and the like.
Examples of the diol having a polyester skeleton include an esterification reaction product of a diol component such as the low molecular weight diol or polycaprolactone diol and an acid component such as dicarboxylic acid or its anhydride.
Examples of the dicarboxylic acid or anhydride thereof include adipic acid, succinic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid and terephthalic acid, and anhydrides thereof.
Examples of the polyether diol include polyethylene glycol, polypropylene glycol, and polyetramethylene glycol.
Examples of the polycarbonate diol include a reaction product of the low molecular weight diol or / and bisphenol such as bisphenol A and a dialkyl ester carbonate such as ethylene carbonate and dibutyl ester carbonate.

  Organic diisocyanates include tolylene diisocyanate, 1,6-hexane diisocyanate, 4,4′-diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, Examples include paraphenylene diisocyanate, 1,5-naphthalene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, and isophorone diisocyanate.

  As the hydroxyl group-containing (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate and hydroxyoctyl And hydroxyalkyl (meth) acrylates such as (meth) acrylates.

Examples of the polyester (meth) acrylate include a dehydration condensate of polyester diol and (meth) acrylic acid.
Here, examples of the polyester diol include a reaction product of a diol and a dicarboxylic acid or an anhydride thereof.
Diols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butylene glycol, polybutylene glycol, tetramethylene glycol, hexamethylene glycol, neo Examples thereof include low molecular weight diols such as pentyl glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol and 1,6-hexanediol, and alkylene oxide adducts thereof.
Examples of the dicarboxylic acid or its anhydride include orthophthalic acid, isophthalic acid, terephthalic acid, adipic acid, succinic acid, fumaric acid, maleic acid, hexahydrophthalic acid, tetrahydrophthalic acid and trimellitic acid, and these An anhydride etc. are mentioned.

  Epoxy (meth) acrylate is a compound obtained by adding (meth) acrylic acid to an epoxy resin. Examples of the epoxy resin include aromatic epoxy resins and aliphatic epoxy resins.

  Specific examples of the aromatic epoxy resin include resorcinol diglycidyl ether, hydroquinone diglycidyl ether; diglycidyl ether of bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene or an alkylene oxide adduct thereof; a phenol novolac type epoxy resin, and Examples thereof include novolak type epoxy resins such as cresol novolac type epoxy resins; glycidyl phthalimide; o-phthalic acid diglycidyl ester and the like.

Specific examples of the aliphatic epoxy resin include diglycidyl ethers of alkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol; diglycidyl ethers of polyethylene glycol and polypropylene glycol, etc. Diglycidyl ethers of polyalkylene glycols; diglycidyl ethers of neopentyl glycol, dibromoneopentyl glycol and its alkylene oxide adducts; diglycidyl ethers of hydrogenated bisphenol A and its alkylene oxide adducts; tetrahydrophthalic acid diglycidyl esters, etc. Is mentioned.
In the above, the alkylene oxide of the alkylene oxide adduct is preferably ethylene oxide or propylene oxide.

  Examples of the polyether (meth) acrylate oligomer include polyalkylene glycol (meth) diacrylate, and examples thereof include polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and polytetramethylene glycol di (meth) acrylate. .

As the component (C), the aforementioned compounds may be used alone or in combination of two or more.
As the component (C), urethane (meth) acrylate is preferable among the above-mentioned compounds because it is excellent in adhesive force and hardly causes undulation of the film laminate.

  (C) The content rate of a component is 1 to 98 weight% on the basis of the whole composition, Preferably it is 5 to 50 weight%. When the proportion of the component (C) is less than 1% by weight, the curability is lowered. On the other hand, when it exceeds 98% by weight, the adhesive strength is lowered.

4). Other components Although the composition of this invention contains the said (A)-(C) component as an essential component, according to the objective, another component can be mix | blended.
Preferred other components include a radical photopolymerization initiator (hereinafter referred to as “component (D)”), a compound having three or more ethylenically unsaturated groups (hereinafter referred to as “component (E)”), a base material Leveling agent (hereinafter referred to as component (F)) and / or silane coupling agent (hereinafter referred to as component (G)) in order to improve the surface smoothness of the blended liquid and the heat resistance, water resistance, and adhesiveness. Etc.
Hereinafter, the components (D) to (G) will be described.
In addition, the compound etc. which were mentioned as another component in the postscript may be used individually, or may use 2 or more types together.

4-1. (D) Component (D) A component is a radical photopolymerization initiator.
Component (D) is a compound that generates radicals by irradiation with active energy rays and initiates polymerization of a compound having an ethylenically unsaturated group. When an electron beam is used as the active energy ray, it is not always necessary to add the component (D).

Specific examples of the component (D) include benzyl dimethyl ketal, benzyl, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane- 1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, oligo [2-hydroxy-2-methyl-1- [4-1] -(Methylvinyl) phenyl] propanone, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl] -2-methylpropan-1-one, 2- Methyl-1- [4- (methylthio)] phenyl] -2-morpholinopropane-1-o 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) ) -Butane-1-one, Adekaoptomer N-1414 (manufactured by ADEKA), phenylglyoxylic acid methyl ester, ethyl anthraquinone, phenanthrenequinone, and other aromatic ketone compounds;
Benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 4- (methylphenylthio) phenylphenylmethane, methyl-2-benzophenone, 1- [4- (4-Benzoylphenylsulfanyl) phenyl] -2-methyl-2- (4-methylphenylsulfonyl) propan-1-one, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis ( Benzophenone compounds such as diethylamino) benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone and 4-methoxy-4′-dimethylaminobenzophenone ;
Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl- (2,4,6-trimethylbenzoyl) phenylphosphinate and bis (2, Acylphosphine oxide compounds such as 6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide;
Thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3- [3,4-dimethyl-9-oxo-9H-thioxanthone-2-yl] oxy]- Thioxanthone compounds such as 2-hydroxypropyl-N, N, N-trimethylammonium chloride and fluorothioxanthone;
Acridone compounds such as acridone, 10-butyl-2-chloroacridone;
1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)] and ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] Oxime esters such as -1- (O-acetyloxime);
2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-phenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2 2,4,5-triarylimidazole such as 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer and 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer Dimer; and acridine derivatives such as 9-phenylacridine and 1,7-bis (9,9'-acridinyl) heptane.
These compounds may be used alone or in combination of two or more.

  (D) The content rate of a component is 20 weight% or less on the basis of the whole composition, Preferably it is 0.1-10 weight%. (D) By making the ratio of a component 20 weight% or less, problems derived from initiators, such as yellowing of a hardened material, outgas, and insufficient strength, can be suppressed.

4-2. Component (E) The component (E) is a compound having 3 or more ethylenically unsaturated groups.
Examples of the compound having three or more (meth) acryloyl groups include glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri- or tetra (meth) acrylate, ditrimethylolpropane tri- or Polyol (meth) acrylates such as tetra (meth) acrylate and dipentaerythritol, such as tri, tetra, penta or hexa (meth) acrylate;
Tri (meth) acrylate of glycerol alkylene oxide adduct, tri or tetra (meth) acrylate of pentaerythritol alkylene oxide adduct, tri or tetra (meth) acrylate of ditrimethylolpropane alkylene oxide adduct, dipentaerythritol alkylene oxide adduct Poly (meth) acrylates of polyol alkylene oxide adducts such as tri, tetra, penta or hexa (meth) acrylates of
Urethane which is a reaction product of an organic polyisocyanate and a tri (meth) acrylate of an isocyanuric acid alkylene oxide adduct; and a compound having two or more (meth) acryloyl groups having a hydroxyl group such as pentaerythritol tri (meth) acrylate A (meth) acrylate etc. can be mentioned.
Examples of the alkylene oxide adduct include ethylene oxide adduct, propylene oxide adduct, ethylene oxide and propylene oxide adduct, and the like.
Examples of the organic polyisocyanate include tolylene diisocyanate, 1,6-hexane diisocyanate, 4,4′-diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, 1,6-hexane diisocyanate trimer, hydrogenated tolylene diisocyanate, Hydrogenated 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, paraphenylene diisocyanate, tolylene diisocyanate dimer, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate mutual adduct, 4,4′- Dicyclohexylmethane diisocyanate, trimethylolpropane tris (tolylene diisocyanate) adduct, isophorone diisocyanate, etc. That.

  As a content rate of (E) component, 1 to 40 weight% is preferable on the basis of the whole composition, More preferably, it is 1 to 25 weight%. When the ratio of the component (E) is 1% by weight or more, the curability can be improved, and when it is 40% by weight or less, the adhesive strength can be improved.

4-3. Component (F) Component (F) is a leveling agent, and is a compound that, when added to the composition, reduces the surface tension of the composition and improves the surface smoothness of the composition. is there.

  Specific examples of the component (F) include polyacrylate polymers such as polyalkyl acrylate; polyvinyl ether polymers such as polyalkyl vinyl ether; dimethylpolysiloxane, methylphenylpolysiloxane, polyether, polyester, aralkyl, etc. Examples thereof include silicone polymers such as organically modified polysiloxane, among which it is preferable to add a leveling agent such as fluorine or silicone.

The leveling agent may or may not have a polymerizable reactive group such as a (meth) acryloyl group.
A commercially available leveling agent can also be used. Examples of commercially available leveling agents that can be used in the present invention include the following.

As a commercially available leveling agent which does not have a polymerizable reactive group, Megafac series (MCF350-5, F472, F476, F445, F444, F443, F178, F470, F475, F479, F477, F482, manufactured by DIC Corporation, F486, TF1025, F478, F178K, etc.); X22-3710, X22-162C, X22-3701E, X22160AS, X22170DX, X224015, X22176DX, X22-176F, X224272, KF8001, X22-2000, etc. manufactured by Shin-Etsu Chemical Co., Ltd. ; FM4421, FM0425, FMDA26, FS1265, etc. manufactured by Chisso Corporation; BY16-750, BY16880, BY16848, SF8427, SF8421, S manufactured by Toray Dow Corning Corporation; 3746, SH8400, SF3771, SH3749, SH3748, SH8410, etc .; TSF series manufactured by Momentive Performance Materials Japan (TSF4460, TSF4440, TSF4445, TSF4450, TSF4446, TSF4453, TSF4452, TSF4730, TSF4770, etc.) ILF Series (SILWETL77, SILWETL2780, SILWETL7608, SILWETL7001, SILWETL7002, SILWETL7087, SILWETL7200, SILWETL7210, SILWETL7220, SILWETL7230, SILWETL7510, SILWETL7500, SILWETL7510, SILWETL7510 02, SILWETL7604, SILWETL7604, SILWETL7605, SILWETL7607, SILWETL7622, SILWETL7644, SILWETL7650, SILWETL7657, SILWETL8500, SILWETL8600, SILWETL8610, SILWETL8620, SILWETL720) and the like.
Also, Neos's Fantent Series (FTX218, 250, 245M, 209F, 222F, 245F, 208G, 218G, 240G, 206D, 240D, etc.) and KB series, BYK333, manufactured by BYK Japan, Inc., 300, etc., Kyoeisha Chemical Co., Ltd. KL600 etc. are also mentioned.

As those having a polymerizable reactive group, X22-163A, X22-173DX, X22-163C, KF101, X22164A, X24-8201, X22174DX, X22164C, X222426, X222245, X222457, X222245, manufactured by Shin-Etsu Chemical Co., Ltd. , X221602, X221603, X22164E, X22164B, X22164C, X22164D, TM0701, etc .; Chisso Corporation Silaplane series (FM0725, FM0721, FM7725, FM7721, FM7726, FM7727, etc.); Toray Dow Corning S 84 SF8413, BY16-152D, BY16-152, BY16-152C, 8388A and the like; SU made by Shin-Nakamura Chemical Co., Ltd. 1900L10, SUA1900L6, etc .; Ebecryl 1360, Ebecryl 350, KRM7039, KRM7734, etc., manufactured by Daicel-Cytec Co., Ltd .; TEGO Rad2100, 2200N, 2500, 2600, 2700, etc., manufactured by Evonik Degussa Japan Co., Ltd .; ;
Mitsubishi Chemical Corporation H512X, H513X, H514X, etc .; Daikin Industries, Ltd. OPTOOL DAC; Nippon Gosei Co., Ltd. UT3971, UT4315, UT4313; DIC Corporation Defenser series (TF3001, TF3000, TF3004, TF3028, TF3027, TF3026, TF3025, etc.), RS series (RS71, RS101, RS102, RS103, RS104, RS105, etc.); BYK3500 manufactured by BYK Japan Japan Co., Ltd .; Light Procoat AFC3000 manufactured by Kyoeisha Chemical Co., Ltd. ; KNS5300 manufactured by Shin-Etsu Silicone; UVHC1105 and UVHC8550 manufactured by Momentive Performance Materials Japan; ACS-1122 manufactured by Nippon Paint Co., Ltd. It can be exemplified's like.

  (F) As addition amount of a component, 0 to 3 weight% is preferable with respect to the total solid of a composition, 0 to 1 weight% is more preferable, 0.01 to 0.5 weight% is further more preferable.

4-4. Component (G) The component (G) is a silane coupling agent that can improve the interfacial adhesive strength between the adhesive layer and the hydrophilic plastic. The silane coupling agent used in the present invention is not particularly limited as long as it can contribute to improvement in adhesion to the substrate.

  Specifically, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane 3- (meth) acryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, N-2 -(Aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3- Aminopropyltrimethoxysilane, 3-aminop Pyrtriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltri And methoxysilane.

  Among these silane coupling agents, 3- (meth) acryloxypropylmethyldimethoxysilane and 3- (meth) acryloxypropyltrimethoxysilane are preferable from the viewpoint of storage stability and adhesive strength of the composition.

(G) A component can use only 1 type of an above described compound, and can also use 2 or more types together.
When (G) component is included in a composition, 0.1-20 weight% is preferable in a composition, and, as for the ratio of (G) component, More preferably, it is 1-10 weight%. By making the ratio of the component (G) 0.1% by weight or more, the effect of improving the adhesive strength of the composition is made sufficient, and by making it 20% by weight or less, the storage stability of the composition is excellent. Can be.

4-5. Other components other than the above In addition to the above, other components usually used in the adhesive composition can be added to the composition of the present invention.

Specifically, such as inorganic fillers, softeners, antioxidants, anti-aging agents, stabilizers, tackifier resins, antifoaming agents, plasticizers, organic solvents, dyes, pigments, treating agents and UV blockers Inactive ingredients can be blended. Examples of the tackifying resin include rosins such as rosin acid, polymerized rosin acid and rosin acid ester, terpene resin, terpene phenol resin, aromatic hydrocarbon resin, aliphatic saturated hydrocarbon resin, and petroleum resin.
These are preferably blended in the composition in an amount of 20% by weight or less.
Moreover, in the case of hydrophilic plastic base materials, such as polyvinyl alcohol and polyvinylpyrrolidone, you may mix | blend water with a composition. In this case, the water content is preferably 20% by weight or less.

5. Active energy ray-curable adhesive composition The present invention comprises 1 to 50% by weight of component (A), 1 to 98% by weight of component (B) and 1 to 1% of the following component (C) with respect to the entire composition. The present invention relates to an active energy ray-curable adhesive composition containing 98% by weight.
As a manufacturing method of the composition of this invention, it can manufacture by stirring and mixing the said (A)-(C) component which is an essential component, and another component as needed according to a conventional method.
In this case, heating can be performed as necessary. The heating temperature may be appropriately set according to the composition to be used, the substrate, the purpose, etc., but 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 composition of the present invention can be used for bonding various substrates, and examples thereof include plastic, paper, and metal.
Plastics include 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, and polyvinyl butyral.
Examples of the paper include imitation paper, fine paper, craft paper, art coated paper, caster coated paper, pure white roll paper, parchment paper, water resistant paper, glassine paper, and corrugated paper.
Examples of the metal foil include aluminum foil.

The composition of the present invention can be preferably used as an adhesive for plastic films or sheets (hereinafter simply referred to as “plastic film”), and more preferably as an adhesive for transparent plastic films.
More specifically, it can be preferably used for adhesion between plastic films and adhesion between a plastic film and various other substrates (hereinafter referred to as “other substrates”). That is, it can be preferably used for adhesion of two substrates, at least one of which is a plastic film. In the following, the simple expression “base material” means a general term for plastic films and other base materials.
Examples of the material for the plastic film include the above-described plastics.
Other examples of the substrate include paper and metal, and the same materials as described above can be used.
The thickness of the substrate is not particularly limited, but it is preferable that the thickness of the substrate is 100 μm or less from the viewpoint that the advantage of the composition of the present invention that does not cause undulation of the laminate can be utilized. More preferably, it is 50 μm or less.

  When the plastic film is a hardly adhesive material, one or both surfaces can be activated before the composition of the present invention is applied. 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.

6). Method of use As a method of using the composition of the present invention, it is sufficient to follow a conventional method, and after applying the composition to a substrate, it is bonded to the other substrate and irradiated with an active energy ray. It is done.
The composition of the present invention is suitable for bonding a thin layer adherend as a substrate. The method of use for adhering the thin-layer adherend may be in accordance with a method usually used in the production of laminates. For example, a method in which the composition is applied to a first thin-layer adherend, a second thin-layer adherend is bonded to the composition, and irradiation with active energy rays is performed.

  Coating on the substrate may be performed by a conventionally known method, natural coater, knife belt coater, floating knife, knife over roll, knife on blanket, spray, dip, kiss roll, squeeze roll, reverse roll, air blade , Curtain flow coater, comma coater, gravure coater, micro gravure coater, die coater and curtain coater.

What is necessary is just to set suitably as a film thickness in the case of coating a composition with respect to a base material according to the objective.
Specifically, 1-80 micrometers is preferable, More preferably, it is 2-30 micrometers.

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

Various light sources can be used as the light source when cured by ultraviolet rays, 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 these, a high pressure mercury lamp and a metal halide lamp 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 / Cm ² .

  In the case of curing with an electron beam, various devices can be used as an EB irradiation device that can be used, such as a Cockloft-Waltsin type, a bandegraph type, and a resonance transformer type device. What has the energy of 1000 eV is preferable, More preferably, it is 100-300 eV.

The composition of this invention can be preferably used for manufacture of a laminated body.
Specifically, the above-described composition is applied to a substrate, another substrate is bonded to the coated surface, and an active energy ray is irradiated from either 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, etc. are also as described above.

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

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

In this case, the bonding can be performed not only in a flat state but also in a curved surface state. That is, there is a method in which the base material is folded into a concave state or a convex state, the composition is applied in this state, the other base material is bonded, and active energy rays are irradiated.
As another method, there is a method in which the composition of the present invention is applied in a planar state, the other substrate is bonded, folded into a concave state or a convex state, and irradiated with active energy rays to adhere. Can be mentioned.
In this case, as a method for applying the composition in a planar state, the above-described method may be followed. Examples of the method for coating the composition in a curved surface include a method using a spray, a dip, a curtain flow coater, screen printing, a 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 and a laminate composed of a plastic film / cured product of the composition of the present invention / other substrates are produced. The

7). Application Examples The composition of the present invention can be preferably used as an adhesive for plastic films as described above.
As a use of the laminate obtained from this, it can be preferably used as an optical film, specifically, a color conversion film, a polarizing plate, a brightness enhancement film, a heat ray reflective film, a void filler and the like can be mentioned, It can be preferably used for a color conversion film and a polarizing plate.
Specific examples of the color conversion film and the polarizing plate are shown below.

7-1. Production of Color Conversion Film The composition of the present invention can be used as a binder for a color conversion film of a backlight having an LED as a light source. That is, a phosphor that converts short-wavelength light into red or green is dispersed in the composition of the present invention, and this is used as an adhesive to bond the plastic films together.
At this time, undulation occurs in a large area, but the composition of the present invention is a composition that hardly generates undulation, and therefore 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 preferred.

  As a fluorescent substance, the same thing as the past can be used, and the inorganic compound and organic compound which emit fluorescence, such as yellow, yellow + red, green + red, 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 antireflection layer, a hard coat layer, and a lubricating layer. Can be mentioned. In this case, as the adhesive of each layer, for example, the binder can be used as an adhesive between the support and the optical functional layer.

7-2. Production of Polarizing Plate The composition of the present invention can be used for adhesion between a polarizer and a protective film and adhesion between a polarizing plate and a retardation film.

A polarizer has a function of selectively transmitting linearly polarized light in one direction from natural light.
Specific examples of polarizers include iodine polarizers in which iodine is adsorbed and oriented on a polyvinyl alcohol film, dichroic dyes in which dichroic dye is adsorbed and oriented on a polyvinyl alcohol film, and (lyotropic) liquid crystal Examples thereof include a coating type polarizer coated with a dye in a state, oriented and fixed.
These iodine-based polarizers, dye-based polarizers, and coating-type polarizers have the function of selectively transmitting one direction of linearly polarized light from natural light and absorbing the other direction of linearly polarized light. It is called a type polarizer.

  In the iodine-based polarizer and the dye-based polarizer, a protective layer is usually provided on one side or both sides thereof, but the composition of the present invention can be used for bonding the polarizer and the protective film.

Examples of the protective film include cellulose acetate resin films such as triacetyl cellulose and diacetyl cellulose, acrylic resin films, polyester resin films, polyarylate resin films, polyether sulfone resin films, and cyclic olefins such as norbornene. And a cyclic polyolefin resin film.
In this case, the moisture permeability of the protective film, preferably has the following 150g / m ² / 24h.

Next, the composition of this invention can also be used for adhesion | attachment of a polarizing plate and retardation film.
In this case, a polarizing plate 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 a polarizing plate provided with a protective layer only on one side, the surface to be bonded to the retardation film may be a surface with a protective layer or a surface without a protective layer.

  Various types of retardation films can be used. Optical films that have been subjected to processing such as uniaxial or biaxial stretching, or liquid crystal compounds are applied to a substrate, and processed to be oriented and fixed. An optical film or the like is used, 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 coloration of the liquid crystal layer of a liquid crystal display and to compensate for changes in phase difference due to viewing angle.

Specific examples of retardation films include optical film materials that are subjected to processing such as stretching, such as polyolefins such as polyethylene, polypropylene, and cyclic polyolefins, polycarbonate, polyvinyl alcohol, polystyrene, polymethyl methacrylate, and polyarylate. And polyamide.
The above-mentioned cyclic polyolefin is a general generic name for resins obtained from cyclic olefins such as norbornene, tetracyclododecene, and derivatives thereof. For example, JP-A-3-14882 and JP-A-3-122137. Etc. are mentioned.
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 these are modified with unsaturated carboxylic acids or their derivatives. Examples of such graft-modified products can be given. Furthermore, these hydrides are mentioned. Examples of the products include ZEONEX and ZEONOR manufactured by Nippon Zeon Co., Ltd., Arton manufactured by JSR Corporation, and TOPAS manufactured by TICONA.

  In addition, as optical films coated with liquid crystalline compounds, etc., and oriented and fixed, "WV film" (Fuji Photo Film Co., Ltd.), "LC film", "NH film" “[All manufactured by Nippon Oil Corporation]” and the like.

The manufacturing method of a polarizing plate or a polarizing plate with a retardation film will be described using the composition of the present invention.
Examples of the production method include a method including the following steps [1] to [3].
[1] A process of applying the composition of the present invention to an adherend (base material) selected from a polarizer, a polarizing plate, a protective film, a protective film, a retardation film, and a retardation film to be an adherend. ,
[2] On the adherend (base material) coated with the composition, another adherend selected from a polarizer, a polarizing plate, a protective film, a protective film, a retardation film, and a retardation film is attached. The process of combining, and
[3] A step of irradiating the bonded adherend (laminate) with active energy rays, particularly a step of irradiating the composition with active energy rays through the bonded adherend (laminate).
When the protective film or retardation film is bonded to only one side, a polarizing plate or a polarizing plate with a retardation film can be produced by the above procedure, but when bonding to both sides, the steps [1] and [2 ] May be repeated after repeating step [3], 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.
Moreover, it can also adhere | attach in a curved surface state as mentioned above using said manufacturing method.

When using a polarizing plate with a retardation film as a circularly polarizing plate, in order to obtain a circularly polarized state over a wide band, a retardation film having a different retardation is further pasted on the retardation film side of the polarizing plate with a retardation film. It can also be combined.
Specifically, there is a method in which a retardation film having a ½ wavelength with respect to each wavelength is bonded to a polarizing film, and a retardation film having a ¼ wavelength is bonded 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.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples.
In the following description, “part” means part by weight, and the numerical value indicating the blending ratio in the table means weight%.

  In the examples and comparative examples, each component used for preparing the compositions is as follows, and is abbreviated as follows.

(A) component * A-1: The polymer obtained by manufacture example 2 mentioned later.
Component (A ′) [polymer other than component (A)]
A′-1: a polymer obtained in Production Example 1 described later.

(B) Component / HBA: 4-hydroxybutyl acrylate, “4-HBA” manufactured by Osaka Organic Chemical Industry Co., Ltd.
IBXA: Isobornyl acrylate, “IBXA” manufactured by Osaka Organic Chemical Industry Co., Ltd.
# 190: Ethyl carbitol acrylate, "Biscoat # 190" manufactured by Osaka Organic Chemical Industry Co., Ltd.

(C) component * UN9200: Polycarbonate diol type bifunctional urethane acrylate, "Art Resin UN-9200A" manufactured by Negami Kogyo Co., Ltd.

(D) Component I-184: 1-hydroxy-cyclohexyl-phenyl-ketone, “Irgacure 184” manufactured by BASF.
TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, “Darocur TPO” manufactured by BASF.

(E) Component M309: Trimethylolpropane triacrylate, “Aronix M-309” manufactured by Toagosei Co., Ltd.

1. Production example
1) Production Example 1
The jacket temperature of a 1,000 ml capacity pressurized stirred tank reactor equipped with an oil jacket was kept at 245 ° C. Next, 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, and di-t-butyl perfluoroethylene as a polymerization initiator. The monomer mixture consisting of oxide (0.77 parts) was continuously fed from the raw material tank to the reactor at a constant feed rate (48 g / min, residence time: 12 minutes). The reaction solution corresponding to was continuously extracted from the outlet. Immediately after the start of the reaction, once the reaction temperature decreased, a temperature increase due to the heat of polymerization was observed. By controlling the oil jacket temperature, the internal temperature of the reactor was maintained at 240 to 242 ° C. The time point after 36 minutes from the stabilization of the reactor internal temperature was taken as the starting point for collecting the reaction liquid, and the reaction was continued for 25 minutes. As a result, 1.2 kg of the monomer mixture was supplied, The reaction solution was collected.
Thereafter, the reaction solution was introduced into a thin film evaporator to separate volatile components such as unreacted monomers and remove volatile components such as unreacted monomers to obtain a polymer A′-1.
As a result of measuring GPC of the polymer A′-1, the polystyrene-equivalent number average molecular weight (hereinafter referred to as “Mn”) is 1,500, the Mw (weight average molecular weight) is 2,400, and the viscosity at 25 ° C. 3,600 mPas. 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 stirred tank reactor equipped with an oil jacket, and the atmosphere was evacuated. The internal temperature was heated to 130 ° C. and pressurized with hydrogen to about 1.5 MPa. In this state, the mixture was stirred for 8 hours.
After purging pressure, it filtered using diatomaceous earth "Radiolite # 100" by Showa Chemical Co., Ltd. for the filter aid, and obtained polymer A-1.
The double bond concentration of the polymer A-1 was not more than the lower limit of detection (0.01 meq / g) by ¹ H-NMR.

2. Example 1, Example 2, Comparative Examples 1-5
1) Manufacture of composition Each component shown in Table 1 was blended in respective proportions and stirred and mixed according to a conventional method to prepare an active energy ray-curable adhesive composition.

2) Production of laminates 20 cm wide, 30 cm long, 50 μm thick untreated surface polyethylene terephthalate film [trade name Lumirror 50 T-60, manufactured by Toray Industries, Inc., hereinafter referred to as “PET”] is shown in Table 1. After coating the composition with a bar coater to a thickness of 15 μm, PET was laminated. Subsequently, the adhesive composition was cured by irradiating ultraviolet rays with an integrated light amount of 1,000 mJ / cm ² (UV-A) by an ultraviolet irradiation device with a belt conveyor (using a metal halide lamp) manufactured by Eye Graphics Co., Ltd. .

3. Evaluation method
1) Immediately after curable ultraviolet irradiation, the end of the laminate was peeled off by hand and judged according to the following criteria.
◯: Cured and had an adhesive strength of at least an extent that the adherends were not displaced.
(Triangle | delta): Although it was not liquid, it was a semi-hardened state, it was the weak adhesive force of the grade which adherends slip | deviated, or it was in the state which has adhesiveness like an adhesive.
X: It was liquid.

2) Evaluation of colorless transparency The obtained laminate was visually observed and judged according to the following criteria.
○: No turbidity or yellowing is felt △: Turbidity or yellowing is slightly felt ×: Turbidity or yellowing is clearly felt

3) Evaluation of waviness The obtained laminate was visually observed for waviness and judged according to the following criteria.
A: Swell is not recognized at all.
○: Swell is hardly recognized.
Δ: A small swell can be recognized.
X: A clear swell can be recognized.

4) Evaluation of adhesive strength The obtained laminate was cut into a 1 inch width and a length of 10 cm, and the peel adhesive strength was evaluated by a T-shaped peeling test and a peeling speed of 200 mm / min. However, when the adhesive was uncured and in liquid form, the adhesive strength was not evaluated because there was no meaning in measuring the adhesive strength.

The compositions of Example 1 and Example 2 corresponding to the present invention were excellent in curability, colorless transparency and adhesive strength, and were excellent in that undulation was small or no undulation was generated.
On the other hand, the compositions of Comparative Example 1 and Comparative Example 2 in which the component (A) was changed to the component (A ′) had poor curability. Moreover, the composition of Comparative Example 3 not containing the component (A) caused undulations in the obtained laminate. The composition of Comparative Example 4 not containing the component (C) and the component (E) had poor curability. The composition of Comparative Example 5 containing the component (E) but not the component (C) not only generated undulations in the resulting laminate, but also had low adhesion.

  The composition of the present invention can be used as an adhesive for bonding various substrates, and can be particularly preferably used for bonding a plastic film. Moreover, the composition of this invention can be used conveniently for manufacture of a laminated body, and can be used especially suitably for manufacture of the laminated body for optical films used for a liquid crystal display or an organic electroluminescent display.

Claims (12)

Active energy ray curing containing 1 to 50% by weight of the following (A) component, 1 to 98% by weight of the following (B) component, and 1 to 98% by weight of the following (C) component with respect to the entire composition. Mold adhesive composition.
(A) Component: A polymer obtained by polymerizing a vinyl monomer at a temperature of 150 to 350 ° C. and then adding hydrogen (B) Component: Compound having one ethylenically unsaturated group (C ) Component: Compound having two ethylenically unsaturated groups The active energy ray-curable adhesive composition according to claim 1, wherein the component (A) has a weight average molecular weight of 1,000 to 50,000. The active energy ray-curable adhesive composition according to claim 1 or 2, wherein the vinyl monomer in component (A) contains an alkyl (meth) acrylate having an alkyl group having 4 or more carbon atoms. (A) The double bond density | concentration of a component is 0.2 meq / g or less, The active energy ray hardening-type adhesive composition of any one of Claims 1-3. (B) The active energy ray hardening-type adhesive composition in any one of Claims 1-4 in which a component contains the compound which has a hydrophilic group and one ethylenically unsaturated group. 6. The activity according to claim 5, wherein in the compound having the hydrophilic group and one ethylenically unsaturated group, the hydrophilic group is a compound selected from a hydroxyl group, a carboxyl group, an amino group, an imide group and / or an amide group. Energy ray curable adhesive composition. (C) The active energy ray hardening-type adhesive composition of any one of Claims 1-6 in which a component contains urethane (meth) acrylate. Furthermore, the active energy ray hardening-type adhesive composition of any one of Claims 1-7 which contain the following (D) component in the ratio of 0-20 weight% with respect to the whole composition.
Component (D): radical photopolymerization initiator Furthermore, the active energy ray hardening-type adhesive composition of any one of Claims 1-8 which contain the following (E) component in the ratio of 1 to 40 weight% with respect to the whole composition.
(E) Component: Compound having 3 or more ethylenically unsaturated groups The active energy ray hardening-type adhesive composition for plastic films or sheets containing the composition of any one of Claims 1-9. A laminate comprising a plastic film or sheet, a cured product of the composition according to claim 10, and other substrates or plastic films or sheets. The manufacturing method of the laminated body which sticks two base materials whose at least one is a plastic film or sheet | seat using the composition of Claim 10, and irradiates this with an active energy ray.