TWI569096B - Active energy ray-curable film for gap filling and a preparation method thereof - Google Patents

Description

Active energy ray-curable void filling film and method of producing the same

The present invention relates to an active energy ray-curable void-filling resin composition, an active energy ray-curable void-filling film or sheet obtained therefrom, a method for producing the same, and an image display device comprising the cured product of the above composition.

A liquid crystal display (hereinafter referred to as "LCD") or an organic EL (OLED) is widely used as an image display device for a portable device such as a mobile phone or a smart phone or a palm-type video game.

In recent years, there has been proposed a method in which an image display device for such a portable device exists between a surface protective layer or a display surface of a touch panel and an image display unit, or between a surface protective layer and a touch panel. The voids are filled with a transparent material having a refractive index close to the members to suppress reflection of light to improve the transparency and enhance the brightness or contrast of the image display device. Examples of the transparent material include a transparent resin sheet, a reaction-curable liquid resin, and an adhesive.

Patent Document 1 discloses a method for producing an LCD in which a transparent resin sheet containing an acrylic polymer containing a plasticizer is interposed between one or both of the transparent resin sheet and the liquid crystal display panel or the transparent protective sheet. In the state where the sheet is swollen and the volatile liquid having a viscosity of 10 cp or less is dissolved, the visible side of the liquid crystal display panel is brought into close contact with the transparent protective sheet, and then dried under heating and pressurization.

Patent Document 2 discloses a method of manufacturing an LCD, which is in a liquid Between the crystal display element and the glass plate, the reaction-curable polyoxymethylene gel of the colorless transparent elastic resin is injected in a liquid state, and then the liquid crystal display element and the glass plate are fixed by hardening.

Patent Document 3 discloses an LCD which is interposed between a liquid crystal display element and a protective plate and filled with a transparent substance. In the case of a transparent material, an unsaturated polyester is dissolved in a polymerizable monomer, and this is injected into a space between a liquid crystal display element and a protective sheet, and then cured.

Patent Document 4 discloses an adhesive composition for an optical member, which comprises a (meth)acrylic polymerization in which a (meth)acrylic acid alkyl ester and a hydroxyl group-containing (meth)acrylate are copolymerized in a specific ratio. Matter, peroxide.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 09-197387

[Patent Document 2] Japanese Patent Publication No. 06-59253

[Patent Document 3] Japanese Patent Laid-Open No. 03-204616

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2007-31506

As described above, a transparent resin sheet, a reaction-curable liquid resin, an adhesive, and the like are proposed as the transparent material for filling the gap of the image display device.

However, since the elastic modulus of the transparent resin sheet is higher than that of the liquid resin or the adhesive, there is a problem that the void filling property is poor.

Further, the reaction-curable liquid resin is produced by a process for operating a liquid The steps are complicated, and in addition, the polyoxyl gel has a problem in reliability due to low adhesion.

In contrast, since the adhesive is easy to handle, high in yield, and high in reliability, it is suitable for directly bonding the structure of the image display device and the surface protective layer.

However, the surface protective layer in the image display device has a concavo-convex shape such as a light shielding layer, and when the adhesive is adhered to the uneven surface, the adhesive is adhered to the display surface of the image display unit provided with the layer having the uneven shape. In addition, the concave and convex shapes of the holes must be filled without gaps, and the surface protective layer, the display surface of the image display unit, or the interface with the touch panel module must not be placed even under high temperature or high humidity conditions for a long time. Bubbles or flaking are also generated and must be whitened. In recent years, the thickness of the uneven shape tends to be large, and the requirements for the gap filling property and the reliability are increasing, and the void-filling resin for solving this problem is sought.

The inventors of the present invention have conducted intensive studies in order to find the following active energy ray-curable void-filling resin composition. The active energy ray-curable void-filling resin composition is excellent in void filling property and reliability, and is adhered to an article, particularly a surface protective layer of an image display device, a display surface of an image display unit, a touch panel, or the like. No bubbles are generated at the interface, and even if it is left at a high temperature and high humidity for a long time, no bubbles or flaking occurs, and it is not whitened.

The present inventors have continually studied the results in order to achieve the above object, and found that the following composition is suitable as an empty space for use in an image display device. The present invention has been achieved by a resin for gap filling. The composition comprises a composition of a polymer having an ethylenic saturated group and a hydroxyl group and a photopolymerization initiator and/or a sensitizer, and the storage modulus of the dry coating film of the composition at 25 ° C is stored at an elastic modulus G' and The 85 ° C storage elastic modulus E' of the cured product after the irradiation of the active energy ray becomes a specific value.

The present invention relates to an active energy ray-curable void-filling resin composition comprising the following (A), (B), and (E) components, a coated coating film or a dried coating film of the composition (hereinafter, etc.) The 25 ° C storage elastic modulus G' (frequency 0.0159 Hz) called "filled resin layer") is 0.001 to 0.05 MPa, and after the active energy ray irradiation, the 85 ° C storage elastic modulus E' of the cured product of the composition (Frequency 1 Hz) is 0.1 to 5000 MPa.

(A) a polymer having an ethylenically unsaturated group and a hydroxyl group [hereinafter referred to as "(A) component"]

(B) Photopolymerization initiator and/or sensitizer [hereinafter referred to as "(B) component"]

(E) Thermosetting crosslinking agent [hereinafter referred to as "(E) component"]

Further, the present invention includes an active energy ray-curable void-filling film or sheet obtained by the composition of the present invention, a method for producing the same, and a cured product of the above composition, or an image display device obtained by using the film or sheet. .

Here, the "25 ° C storage elastic modulus G'" means the storage elastic modulus at a frequency of 0.0159 Hz when the dynamic viscoelasticity measurement is performed in the shear mode; the so-called "85 ° C storage elastic modulus E' "," means the storage elastic modulus at a frequency of 1 Hz when the dynamic viscoelasticity measurement is performed in the tensile mode.

In addition, in this specification, active energy ray hardening type void filling The resin composition to be charged is simply referred to as "composition". Further, the cross-linking or hardening of the composition obtained by irradiating the active energy ray to the composition is shown as a "hardened material". Further, an acrylate or a methacrylate is represented as a (meth) acrylate.

The present invention will be described in detail below.

The active energy ray-curable void-filling resin composition of the present invention, the active energy ray-curable void-filling film or sheet obtained therefrom, is excellent in void filling property, and is placed for a long time even under high temperature and high humidity. The reliability of the bubble generation, the peeling, and the whitening is excellent. Therefore, when the surface protection layer of the image display device, the display surface of the image display unit, or the touch panel is manufactured, the above-mentioned bubbles, peeling, whitening, and the like can be produced. A high quality image display device for problems.

[Formation of the Invention]

The active energy ray-curable void-filling resin composition of the present invention comprises the above-mentioned (A), (B) and (E) components, and the 25 ° C storage elastic modulus of the coated coating film or the dried coating film of the composition. G' (frequency: 0.0159 Hz) is 0.001 to 0.05 MPa, and the active modulus cleavage type of the elastic modulus E' (frequency 1 Hz) of the cured product of the composition after the irradiation of the active energy ray is 0.1 to 5000 MPa. A resin composition for filling.

The components (A), (B) and (E) will be described below.

1. (A) component

The component (A) in the present invention is a polymer having an ethylenically unsaturated group and a hydroxyl group.

Examples of the ethylenically unsaturated group of the component (A) include a vinyl group, a (meth) acrylonitrile group, a (meth) acrylamide group, and a maleimide group, based on an active energy ray. The point which is excellent in hardenability is preferably a maleimide group and a (meth)acryl fluorenyl group.

The molecular weight of the component (A) is preferably 10,000 to 2,000,000, more preferably 50,000 to 1,500,000, based on the weight average molecular weight.

In the present invention, the number average molecular weight and the weight average molecular weight mean that the molecular weight measured by a gel permeation chromatography (hereinafter abbreviated as "GPC") is based on the molecular weight of polystyrene using tetrahydrofuran as a solvent. The value obtained by conversion.

As the component (A), as long as it is a polymer having an ethylenically unsaturated group and a hydroxyl group, various polymers can be used, but among them, it is preferred to have a maleimide group and a hydroxyl group. Polymer (A-1) [hereinafter referred to as "(A-1)"] and a polymer (A-2) having a (meth) acrylonitrile group and a hydroxyl group [hereinafter referred to as "(A-2)" ].

The components (A-1) and (A-2) will be described in detail below.

1-1. (A-1) ingredients

The component (A-1) is a polymer having a maleimide group and a hydroxyl group.

Here, as the maleimide group, it is preferably a group represented by the following formula (1) [In the formula (1), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group, or R ¹ and R ² represent a combination of a 5-membered ring or a 6-membered ring. Hydrocarbyl group].

In the case of an alkyl group, an alkyl group having 1 to 4 carbon atoms is preferred.

The alkenyl group is preferably an alkenyl group having 2 to 4 carbon atoms.

Examples of the aryl group include a phenyl group and the like.

In the case of a hydrocarbon group which forms a 5-membered ring or a 6-membered ring, the saturated hydrocarbon group may be a group -CH ₂ CH ₂ CH ₂ -, a group -CH ₂ CH ₂ CH ₂ CH ₂ -; an unsaturated hydrocarbon group may be enumerated The group -CH=CHCH ₂ -, the group -CH ₂ CH=CHCH ₂ -, and the like. Further, in the unsaturated hydrocarbon group, since the maleimide group undergoes a dimerization reaction, it is necessary to select a non-aromaticity in the finally obtained 5-membered ring or 6-membered ring. As the hydrocarbon group, a saturated hydrocarbon group is preferred.

Preferred specific examples of the maleimide group in the formula (1) are shown in the following formulas (3) to (8). Further, in the formula (7), X represents a chlorine atom or a bromine atom. Further, Ph in the formula (8) represents a phenyl group.

R ¹ and R ² are each a hydrogen atom and the other is an alkyl group having 1 to 4 carbon atoms. Both of R ¹ and R ² have a carbon number of 1 to 4 at a point where the adhesion is excellent. The alkyl group, and each of them is preferably a saturated hydrocarbon group forming a carbocyclic ring.

Further, among these, in the point that the adhesion is particularly excellent and the photodimerization of the maleimide group is easily controlled, it is more preferable to form a saturated hydrocarbon group which forms a carbocyclic ring.

The molecular weight of the component (A-1) is preferably 10,000 to 2,000,000, more preferably 50,000 to 1,500,000, based on the weight average molecular weight.

Specific examples of the component (A-1) include the following polymers.

1-1) Copolymerization of an ethylenically unsaturated compound containing a maleimide group and a hydroxyl group-containing ethylenically unsaturated compound (hereinafter referred to as "hydroxy group-containing unsaturated compound") as a necessary constituent monomer unit Things.

1-2) A polymer obtained by adding a compound having a maleimide group and an isocyanate group to a hydroxyl group-containing polymer having a hydroxyl group-containing unsaturated compound as a constituent monomer unit.

1-3) A hydroxyl group-containing unsaturated compound and a carboxyl group-containing ethylenically unsaturated compound (hereinafter referred to as "carboxyl group-containing unsaturated compound") are used as a constituent monomer unit of a hydroxyl group-containing and carboxyl group polymer. A polymer formed from a compound having a maleimide group and an epoxy group.

1-4) A hydroxyl group-containing unsaturated compound and an epoxy group-containing ethylenically unsaturated compound (hereinafter referred to as "epoxy group-containing unsaturated compound") are used as a constituent monomer unit of a hydroxyl group and an epoxy group. A polymer obtained by adding a compound having a maleimide group and a carboxyl group to the base polymer.

1-5) A hydroxyl group-containing unsaturated compound having an acid anhydride group and an ethylenic unsaturated group containing an acid anhydride group (hereinafter referred to as "an acid anhydride group-containing unsaturated compound") as a constituent monomer unit of a hydroxyl group-containing and acid anhydride-based polymer A polymer obtained by adding a compound having a maleimide group and a hydroxyl group.

1-6) A polymer obtained by adding a compound having a maleimide group and a carboxyl group to a hydroxyl group-containing and epoxy group-containing polymer.

The component (A-1) is preferably a polymer of the above 1-1).

Further, in the case of the polymer of the above 1-1), it is more preferred to have a maleimide group represented by the above formula (1) and an ethylenic group other than the maleimide group. The saturated group compound (a) [hereinafter referred to as "monomer (a)"], the compound (b) having a hydroxyl group and an ethylenically unsaturated group (hereinafter referred to as "monomer (b)"), and a monomer (hereinafter) a polymer obtained by copolymerization of a compound (c) having an ethylenically unsaturated group other than a) and (b) (hereinafter referred to as "monomer (c)"] (hereinafter referred to as "polymer (A11)"] .

The monomers (a) to (c) will be described below.

1-1-1. Monomer (a)

The monomer (a) is a compound having the above-mentioned maleimide group and an ethylenically unsaturated group other than the maleimide group. By copolymerizing the monomer (a), the photosensitive group of the maleimide group can be introduced (A-1) Among the components, the photocurability, the adhesion, and the modulus of elasticity after curing can be improved.

The maleimide group is preferably a group represented by the above formula (1), and a preferred specific example is also the same as described above.

The ethylenically unsaturated group other than the maleimide group may, for example, be a (meth)acryl fluorenyl group, a vinyl group or a vinyl ether group, and is preferably a (meth) acrylonitrile group.

In the case of the monomer (a), as long as it is a compound having an ethylenically unsaturated group other than the above-mentioned maleimide group and the maleimide group, various compounds can be used, and the following formula can be used. The compound represented by (2) is preferred because it is easy to manufacture and excellent in curability.

[However, in the formula (2), R ¹ and R ² are the same as defined above. Further, R ³ represents an alkylene group, R ⁴ represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 6].

R ¹ and R ² are each a hydrogen atom and the other is an alkyl group having 4 or less carbon atoms, and both of R ¹ and R ² are an alkyl group having 4 or less carbon atoms, and each of them is formed into a single group. The compound having a saturated hydrocarbon group of a carbocyclic ring is preferred because it has excellent copolymerizability, and further, a compound which forms a saturated hydrocarbon group which forms a carbocyclic ring is more preferable because it has no problem of gelation or the like at the time of polymerization.

In the case of the alkylene group of R ³ , it may be linear or branched. More preferably, it is an alkyl group having 1 to 6 carbon atoms.

1-1-2. Monomer (b)

The monomer (b) is a compound having a hydroxyl group and an ethylenically unsaturated group. By copolymerizing the monomer (b), a hydroxyl group can be introduced into the polymer (A11), and the adhesion of the obtained composition to the substrate can be improved.

As the monomer (b), as long as it has a monomer (a) and a copolymerizable hydroxyl group, various compounds can be used, and a compound having one (meth) acryl fluorenyl group (hereinafter referred to as a monofunctional group) can be cited. Methyl) acrylate], a vinyl compound, a vinyl ester, a conjugated diene, and the like.

Examples of the ethylenically unsaturated compound having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxy-3-phenoxy (meth)acrylate. Alkyl propyl (meth) acrylate such as 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexanedimethanol mono(meth)acrylate; a polyalkylene glycol monoester of triol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and polyethylene glycol-polypropylene glycol copolymer (Meth) acrylate, hydroxyethyl (meth) acrylamide, allyl alcohol, and the like.

Among these, a monofunctional (meth) acrylate having a hydroxyl group is preferred for the reason that the composition of the copolymer and the optical film are high.

1-1-3. Monomer (c)

The monomer (c) is copolymerized for the purpose of adjusting the glass transition temperature of the polymer (A11), the physical properties such as adhesion, and adhesion. The monomer (c) may be a compound having ethylenic unsaturation other than the monomers (a) and (b) as long as it has copolymerizability with the monomers (a) and (b). Examples of the various compounds include monofunctional (meth) acrylates and vinyl compounds. Vinyl ester, conjugated diene, and (meth) acrylamide.

Examples of the monofunctional (meth) acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. N-butyl methacrylate, isobutyl (meth)acrylate, butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, (meth) acrylate Octyl ester, 2-ethylhexyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, isodecyl (meth)acrylate, n-(meth)acrylate An alkyl (meth)acrylate such as an ester, isodecyl (meth)acrylate, n-lauryl (meth)acrylate, tridecyl (meth)acrylate or n-stearate (meth)acrylate; Cyclohexyl methacrylate, (meth) acrylate Ester, adamantyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate and (methyl) An alicyclic (meth)acrylic acid alkyl ester such as tricyclodecyl acrylate; 2-methoxyethyl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate, (methyl) Alkoxy-containing (methyl) such as 2-ethylhexylcarbitol acrylate and methoxypolyethylene glycol (meth)acrylate such as methoxytriethylene glycol (meth)acrylate Acrylate; benzyl (meth) acrylate, phenol alkylene oxide modified (meth) acrylate, alkyl phenol alkylene oxide modified (meth) acrylate, p-cumyl phenol epoxide modified A (meth) acrylate having an aromatic ring such as (meth) acrylate or o-phenylphenol alkylene oxide (meth) acrylate (for the alkylene oxide, ethylene oxide and a ring are mentioned) Oxypropane, etc.; pentamethyl hexahydropiperidine (meth) acrylate, tetramethyl hexahydropiperidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate and N-(methyl) propylene Oxyloxyethylhexahydrophthalimide a heterocyclic (meth) acrylate; and a mono [2-(methyl) propylene methoxyethyl] phosphate, a mono [2-(methyl) propylene oxypropyl] phosphate, 2-(Methyl)propenyloxyethyl diphenyl phosphate, mono[3-cyclo-2-(methyl)propenyloxypropyl]phosphate, mono[(methyl)propenyloxy Ethyl]phosphate monoethanolamine salt, mono[(meth)acryloxyethyl)phosphate, [single (diethylaminoethyl (meth) acrylate) salt, mono [(methyl)) Phosphoric acid (meth) acrylate such as acryloxyethyl]phosphate or [mono(dimethylaminoethyl (meth) acrylate) salt.

Examples of the vinyl compound include styrene, vinyl toluene, acrylonitrile, methacrylonitrile, N-vinylformamide, and acrylonitrile. Porphyrin, N-vinylpyrrolidone and N-vinylcaprolactone.

Examples of the vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl chloride, trimethyl vinyl acetate, vinyl laurate, and vinyl acetate.

Examples of the conjugated diene include butadiene, isoprene, chloropentadiene, and isobutylene.

Examples of the (meth) acrylamide include (meth) acrylamide, N-methylol (meth) acrylamide, and N-methoxymethyl (meth) acrylamide. N-methoxybutyl (meth) acrylamide, N,N-dimethyl(meth) acrylamide, N,N-diethyl(meth) decylamine, 2-(methyl And acrylamide amine-2-methylpropane sulfonic acid and N-isopropyl (meth) acrylamide.

In the case of monomer (c), it may be an official other than an ethylenically unsaturated group. Specific examples of the energy base include compounds having one or more carboxyl groups and ethylenically unsaturated groups.

Examples of the compound having a carboxyl group and an ethylenically unsaturated group include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, methylene succinic acid, and methylbutylene. An unsaturated carboxylic acid such as diacid, cinnamic acid or maleic anhydride; monoethyl methylene succinate, monobutyl fumarate and monobutyl maleate; Monoalkyl ester of unsaturated dibasic acid; ω-carboxy polycaprolactone (meth) acrylate, (meth) acrylate dimer, 2-(meth) propylene methoxyethyl phthalate A carboxyl group-containing (meth) acrylate such as 2-(meth)acryloxyethyl hexahydrophthalic acid.

These monomers (c) may be used alone or in combination of two or more.

In the above-mentioned monomer (c), among the above, the (meth)acrylic acid ester having an alkyl group having 1 to 20 carbon atoms is excellent and excellent in the polymerizability of the alkyl (meth)acrylate. It is preferred because the obtained composition has a large adhesive force or a strong adhesive force and is industrially easy to obtain and inexpensive.

1-1-4. Method for producing polymer (A11)

The method for producing the polymer (A11) is not particularly limited, and it may be produced by following a usual method such as solution polymerization, emulsion polymerization, or suspension polymerization.

In the solution polymerization method, a method of producing the raw material monomer to be used in the organic solvent, and heating and stirring in the presence of a thermal polymerization initiator may be mentioned.

Further, the molecular weight of the polymer is adjusted as needed, and a chain shifting agent can be used.

As an example of the thermal polymerization initiator used, heat can be cited A peroxide, a azo compound, a redox initiator, or the like which generates a radical species.

Examples of the peroxide include benzoyl peroxide, ruthenium laurate, cumene hydroperoxide, tertiary butyl hydroperoxide, dicumyl peroxide, and the like. . Examples of the azo compound include azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, and azobis-4-methoxy-2,4-dimethylpenta Nitrile and the like. Examples of the redox initiator include hydrogen peroxide-iron (II) salt, peroxodisulfate-sodium hydrogensulfite, cumene hydroperoxide-iron (II) salt, and the like.

Examples of the organic solvent include hydrocarbon solvents such as n-hexane, benzene, toluene, xylene, ethylbenzene, and cyclohexane; methanol, ethanol, 1-propanol, 2-propanol, and 1-butanol; 2-butanol, isobutanol, 2-methoxyethanol, 2-ethoxyethanol, 2-(methoxymethoxy)ethanol, 2-isopropoxyethanol, 2-butoxyethanol, 2-isopentyloxyethanol, 2-hexyloxyethanol, 2-phenoxyethanol, 2-benzyloxyethanol, mercapto alcohol, tetrahydrofurfuryl alcohol, diethylene glycol, diethylene glycol monomethyl An alcohol solvent such as an ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, 1-methoxy-2-propanol or 1-ethoxy-2-propanol; tetrahydrofuran, two , ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, bis(2-methoxyethyl) ether, bis(2-ethoxyethyl) ether and double An ether solvent such as (2-butoxyethyl)ether; acetone, methyl ethyl ketone, methyl-n-propyl ketone, diethyl ketone, butyl methyl ketone, methyl isobutyl ketone, methyl Ketone solvents such as amyl ketone, di-n-propyl ketone, diisobutyl ketone, phorbol, isophorone, cyclohexanone and methylcyclohexanone; methyl formate, ethyl formate, propyl formate , butyl formate, isobutyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, secondary butyl acetate, amyl acetate And an ester solvent such as isoamyl acetate; nitromethane, nitroethane, 1-nitropropane, 2-nitropropane, acetonitrile, propionitrile, butyronitrile, N-methylformamide, N, Nitrogen compound solvent such as N-dimethylformamide, N,N-diethylformamide, acetamide, 2-pyrrolidone, N-methylpyrrolidone and ε-caprolactam And a sulfide solvent such as dimethyl hydrazine or cyclobutyl hydrazine.

Examples of the chain-shifting agent include cyanoacetic acid; alkyl esters having 1 to 8 carbon atoms of cyanoacetic acid; bromoacetic acid; alkyl esters having 1 to 8 carbon atoms of bromoacetic acid; anthracene, phenanthrene and anthracene; An aromatic compound such as 9-phenylindole; an aromatic nitro compound such as p-nitroaniline, nitrobenzene, dinitrobenzene, p-nitrobenzoic acid, p-nitrophenol or p-nitrotoluene a benzoquinone derivative such as benzoquinone, 2,3,5,6-tetramethyl-p-benzoquinone; a borane derivative such as tributylborane; carbon tetrabromide, 1,1,2, Halogenated hydrocarbons such as 2-tetrabromoethane, tribromoethylidene trichloroethylene, bromotrichloromethane, tribromomethane, 3-cyclo-1-propene; aldehydes such as trichloroacetaldehyde and furfural; carbon number 1 to 18 alkyl mercaptans; aromatic thiols such as thiophenol and toluene thiol; thioglycolic acid; thioglycolic acid alkyl ester having 1 to 10 carbon atoms; hydroxyalkyl group having 1 to 12 carbon atoms Mercaptans; and monoterpenes and pairs Terpenes such as dienes.

The preferred copolymerization ratio of each constituent monomer unit in the polymer (A11) is as follows.

The monomer (a) is preferably from 5 to 50% by weight, more preferably from 10 to 30% by weight.

The monomer (b) is preferably from 5 to 30% by weight, more preferably from 10 to 20% by weight.

The monomer (c) is preferably from 20 to 90% by weight, more preferably from 50 to 80% by weight.

When the copolymerization ratio of the monomer (a) is 5% by weight or more, the photocurability of the obtained composition can be made sufficient, and by 50% by weight or less, the production of the component (A-1) can be simplified. Not only is the composition of the obtained composition excellent in adhesion, but also the coloring can be reduced.

When the copolymerization ratio of the monomer (b) is 5% by weight or more, the adhesion between the composition and the adherend can be increased, and by 30% by weight or less, the moisture resistance of the composition can be maintained.

When the copolymerization ratio of the monomer (c) is 20% by weight or more, the adhesion between the composition and the adherend can be increased, and when it is 90% by weight or less, the adhesion and photocurability of the composition can be maintained.

1-2. (A-2) ingredients

The component (A-2) is a polymer having a (meth) acrylonitrile group and a hydroxyl group.

The (A-2) component can be used as long as it is a (meth)acrylonitrile group and a polymer having a hydroxyl group.

In the component (A-2), the compound (d) having a functional group and an ethylenically unsaturated group (hereinafter referred to as "monomer (d)") and an ethylenically unsaturated group other than the monomer (d) In the functional group-containing polymer of the copolymer of the monomer (e) (hereinafter referred to as "monomer (e)"), a functional group having a functional group reactive with the monomer (d) and an ethylenically unsaturated group are allowed. The polymer obtained by reacting the compound (d') (hereinafter referred to as "monomer (d')") is preferred in terms of ease of production.

The molecular weight of the component (A-2) is preferably 10,000 to 2,000,000, more preferably 50,000 to 1,500,000, based on the weight average molecular weight.

1-2-1. Monomer (d)

In the monomer (d), examples of the functional group include a hydroxyl group, a carboxyl group, an epoxy group, and an isocyanate group. That is, a hydroxyl group-containing unsaturated compound, a carboxyl group-containing unsaturated compound, an epoxy group-containing unsaturated compound, and a compound having an isocyanate group and an ethylenically unsaturated group (hereinafter referred to as "isocyanate group-containing unsaturated compound" "]Wait.

The ethylenically unsaturated group may, for example, be a (meth) acrylonitrile group, a vinyl group or a vinyl ether group, and is preferably a (meth) acrylonitrile group.

Specific examples of the monomer (d) include the following compounds.

○ Hydroxy-containing unsaturated compounds

2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate, Hydroxy (meth) acrylate such as 4-hydroxybutyl (meth) acrylate or cyclohexane dimethanol mono (meth) acrylate; glycerol mono (meth) acrylate, polyethylene glycol single Poly(alkyl) diol mono(meth) acrylate, hydroxyethyl (meth) acrylate, such as (meth) acrylate, polypropylene glycol mono (meth) acrylate, and polyethylene glycol-polypropylene glycol copolymer Indoleamine and allyl alcohol.

○ unsaturated compound containing carboxyl group

Unsaturated carboxylic acid such as (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, methylene succinic acid, methyl maleic acid, cinnamic acid and maleic anhydride Acid; monoalkyl ester of unsaturated dibasic acid such as monoethyl methylene succinate, monobutyl methacrylate and monobutyl maleate; ω-carboxy poly Lactone (meth) acrylate, (meth) acrylate dimer and 2-(meth) propylene methoxyethyl phthalate, A carboxyl group-containing (meth) acrylate such as 2-(meth)acryloxyethyl hexahydrophthalic acid.

○Opoxy group-containing unsaturated compounds

Glycidyl (meth)acrylate, vinylcyclohexene oxide, allyl glycidyl ether, and 3,4-epoxycyclohexylmethyl (meth)acrylate.

○ unsaturated compounds containing isocyanate groups

2-(Methyl)acryloxyethyl isocyanate, (meth)acrylonitrile isocyanate, 1,1-bis((meth)acryloxymethyl)ethyl isocyanate, and allyl isocyanate.

1-2-2. Monomer (d')

The monomer (d') is a compound having a functional group reactive with a functional group of the monomer (d) and an ethylenically unsaturated group.

In the monomer (d'), examples of the functional group include a hydroxyl group, a carboxyl group, an epoxy group, and an isocyanate group.

The ethylenically unsaturated group may, for example, be a (meth) acrylonitrile group, a vinyl group or a vinyl ether group, and is preferably a (meth) acrylonitrile group.

The monomer (d') is selected depending on the functional group of the monomer (d) to be used.

For example, when the monomer (d) is a hydroxyl group-containing unsaturated compound, an isocyanate group-containing unsaturated compound is selected as the monomer (d'), and when the monomer (d) is a carboxyl group-containing unsaturated compound, the isocyanate is selected. a base unsaturated compound or an epoxy group-containing unsaturated group compound as a monomer (d'), and when the monomer (d) is an epoxy group-containing unsaturated compound, a carboxyl group-containing unsaturated compound is selected as a monomer (d'), When the monomer (d) is an unsaturated compound containing an isocyanate group, a hydroxyl group-containing unsaturated compound or a carboxyl group-containing unsaturated compound is selected as the monomer (d').

As the specific example of the monomer (d'), the same compound as the monomer (d) can be used.

1-2-3. Monomer (e)

The monomer (e) is preferably copolymerized for the purpose of adjusting the glass transition temperature of the polymer (A-2) or the physical properties such as adhesion and adhesion, and as far as the monomer (e) is concerned, Any compound having an ethylenically unsaturated group other than the monomer (d) copolymerizable monomer (d) can be used, and examples thereof include a monofunctional (meth) acrylate, a vinyl compound, a vinyl ester, and a conjugate. Diene and (meth) acrylamide and the like.

Specific examples of the monomer (e) include the compounds having a carboxyl group and an ethylenically unsaturated group among the monomers (c).

1-2-4. Method for producing polymer (A-2)

The method for producing the polymer (A-2) is carried out by reacting the functional group with the functional group-containing acrylic polymer obtained by copolymerizing the monomer (d) and the monomer (e) by a conventional method. The other monomer (d) is reacted to obtain.

The above functional group-containing acrylic polymer can be copolymerized by the same method as the method for producing the polymer (A-1).

It is preferred to use the obtained functional group-containing acrylic polymer and the monomer (d) which reacts with the functional group to be modified at a normal pressure, optionally using any catalyst at 50 to 100 ° C. The temperature is about 1 to 24 hours.

In order to shorten the reaction time, a well-known catalyst can be used as needed. For example, in the case of a reaction of a hydroxyl group or a carboxyl group with an isocyanate group, an organotin compound such as dibutyltin dilaurate, triethylamine, triethanolamine, dimethylbenzylamine, trioctylamine, or 1,4-butylamine may be mentioned. Diterpene bicyclo[2.2.2]octane, 1,8-dioxinbicyclo[5.4.0]undecene-7, 1,5-dioxabicyclo[4.3.0]nonene-5, etc. a metal-based weak acid salt such as a compound of a compound, an acid weak acid salt such as acetic acid or octanoic acid, or a metal organic weak acid salt such as NACEM IRON, NACEM ZINC, etc., a metal naphthenic acid salt such as lead naphthenate or potassium acetate; a trialkylphosphine compound such as a phosphine or the like.

In addition, examples of the reaction between a carboxyl group and an epoxy group include a tertiary ammonium salt such as the above-described tertiary amine compound or tetra-n-butylammonium bromide.

The preferred copolymerization ratio and the modification ratio of each constituent monomer unit in the polymer (A-2) are as follows.

The monomer (d) is preferably from 2 to 40% by weight, more preferably from 10 to 20% by weight.

The monomer (e) is preferably from 60 to 98% by weight, more preferably from 80 to 90% by weight.

The monomer (d') varies depending on the amount of copolymerization of the monomer (d). When the total amount of the monomers (d) and (e) is 100% by weight, it is preferably 1 to 30% by weight. Good is 5~20% by weight. When it is in the above range, the residual of the unreacted component of the monomer (d') can be suppressed.

When the copolymerization ratio of the monomer (d) is 2% by weight or more, the photocurability of the obtained composition can be made sufficient, and by making it 20% by weight or less, the production of the component (A-2) can be simplified. And the adhesion of the obtained composition can be excellent.

By increasing the copolymerization ratio of the monomer (e) to 6% by weight or more, it can be improved When the adhesion between the composition and the adherend is 98% by weight or less, the photocurability of the composition can be made sufficient.

By setting the modification ratio of the monomer (d') to 1% by weight or more, the photocurability of the composition can be made sufficient, and by setting it to 20% by weight or less, the adhesion of the composition can be maintained.

2. (B) ingredients

The component (B) in the present invention is a photopolymerization initiator and/or a sensitizer. By including the component (B), the cured material can be excellent in adhesion and heat resistance.

Usually, when the ethylenically unsaturated group of the component (A) is a vinyl group or a (meth)acryl fluorenyl group or the like, the photopolymerization initiator of such a group is defined as a photopolymerization initiator, and when the component (A) When the ethylenically unsaturated group is a maleimide group, the photodimerization is promoted as a sensitizer, and since it is also a compound having both functions, it is difficult to distinguish, and is defined as "light" in the present invention. Polymerization initiator and / or sensitizer".

Examples of the component (B) include benzyldimethylketal, benzyl, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and 1- Hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl 1,-1-propan-1-one, oligo[2-hydroxy-2-methyl-1-[4-1-(methylvinyl)phenyl]acetone, 2-hydroxy-1-{4-[ 4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, 2-methyl-1-[4-(methylthio)]phenyl ]-2- Tropicpropan-1-one, 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4- Aromatic ketone of phenyl-4-ylphenyl)-butan-1-one, ADEKA OPTOMER N-1414 (made by ADEKA), methyl phenylglyoxylate, ethyl hydrazine, phenanthrenequinone a compound; benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4- Phenylbenzophenone, 4-(methylphenylthio)phenylphenylmethane, methyl-2-benzophenone, 1-[4-(4-benzoylphenylphenyl)phenyl ]-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one, 4,4'-bis(dimethylamino)benzophenone, 4,4'-double (Diethylamino)benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone, N,N'-tetraethyl-4,4'-diamine a benzophenone compound such as benzophenone and 4-methoxy-4'-dimethylaminobenzophenone; bis(2,4,6-trimethylbenzylidene)benzene Phosphine oxide, 2,4,6-trimethylbenzimidyl diphenylphosphine oxide, ethyl (2,4,6-trimethylbenzylidene) phenylphosphinate and double a mercaptophosphine oxide compound such as (2,6-dimethoxybenzylidene)-2,4,4-trimethylpentylphosphine oxide; oxygen sulfur 2-chlorooxosulfur 2,4-diethyloxysulfide Isopropyl oxysulfide 1-cyclo-4-propyl oxysulfide , 3-[3,4-dimethyl-9-oxo-9H-oxygen sulfur -2-yl]oxy]-2-hydroxypropyl-N,N,N-trimethylammonium chloride and oxyfluoride Oxygen and sulfur a compound; an acridone compound such as acridone or 10-butyl-2-chloroacridone; 1,2-octanedione 1-[4-(phenylthio)-2-(o-phenylene)醯基肟)] and ethyl ketone 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(o-ethylindenyl), etc. Anthracene esters; 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole Polymer, 2-(o-fluorophenyl)-4,5-phenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(pair Methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4-di(p-methoxyphenyl)-5-phenylimidazole dimer and 2-(2,4-di 2,4,5-triarylimidazole dimer such as methoxyphenyl)-4,5-diphenylimidazole dimer; and 9-phenyl acridine and 1,7-bis (9,9) An acridine derivative such as '-acridinyl) heptane or the like.

These compounds may be used alone or in combination of two or more.

Among these, based on photoreactivity, adhesion, heat resistance, and coloring point, 1-hydroxycyclohexyl phenyl ketone, bis(2,4,6-trimethylbenzylidene)-phenylphosphine Oxide, 4-phenylbenzophenone, 4-(methylphenylthio)phenylphenylmethane, 2-chlorooxosulfur 2,4-diethyloxysulfide Isopropyl oxysulfide 1-cyclo-4-propyl oxysulfide Preferably.

The blending ratio of the component (B) is preferably 0.1 to 10% by weight, and more preferably 0.5 to 5% by weight based on 100 parts by weight of the total amount of the component (B).

When the blending ratio of the component (B) is 0.1% by weight or more, the composition can be cured with an appropriate amount of ultraviolet light, and the productivity can be improved. On the other hand, the cured product can be made 10% by weight or less. Excellent weather resistance or transparency.

3. (E) component

In order to impart excellent storage stability and peelability to the coating film before curing, a thermosetting crosslinking agent of the component (E) is blended in the composition of the present invention.

The (E) component may, for example, be a crosslinking agent such as a polyvalent isocyanate compound, a polyvalent epoxy compound, an amine based resin or a metal chelate compound.

Examples of the polyvalent isocyanate compound include isophorone diisocyanate, hexamethylene diisocyanate, methylphenyl diisocyanate, benzodimethyl diisocyanate, diphenylmethane-4,4'-diisocyanate, and ring a bifunctional isocyanate compound such as pentyl diisocyanate, a terpolymer of such a bifunctional isocyanate compound, a terminal isocyanate urethane prepolymer obtained by reacting a bifunctional isocyanate compound with a polyol compound, and a bifunctional isocyanate A compound, a terpolymer of a bifunctional isocyanate compound, a block of a polyvalent isocyanate compound obtained by blocking a terminal isocyanate urethane prepolymer such as phenol or an anthracene.

The polyvalent epoxy compound may, for example, be a bisphenol type epoxy such as a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol Z type epoxy resin, or a hydrogenated bisphenol type epoxy resin. Resin.

Examples of the bisphenol A type epoxy resin include those sold by the company Epikote 827 (trade name, the same applies hereinafter), Epikote 828, Epikote 1001, and Epikote 1004 manufactured by Japan Epoxy Resins Co., Ltd., and the bisphenol F type epoxy resin. For example, Epikote 806, Epikote 4004P, and the like can be cited.

Further, examples thereof include a phenol novolak resin, a novolac type epoxy resin such as a cresol novolac type epoxy resin, and a polycondensation alkyl polyol (nepentyl glycol, glycerin, etc.) polycondensation water. A glycidyl ether epoxy resin such as glyceryl ether, tetraglycidyldiamine diphenylmethane, triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, tetraglycidyl A glycidylamine epoxy resin such as benzyl-m-xylenediamine, diglycidyl phthalate, diglycidylhexahydrophthalate, diglycidyl tetrahydroortho A glycidyl ester of phthalic acid ester or the like, an epoxy group, a vinylcyclohexene oxide, a 3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexane)carboxylate a cyclic aliphatic type or triple shrinkage such as (3,4-epoxy-6-methylcyclohexylmethyl) adipate A heterocyclic epoxy resin such as glyceryl isomeric cyanurate or glycidyl glycidoxyalkyl carbendazim. Further, examples thereof include halides of such epoxy resins, polyhydric acids of such epoxy resins, polyglycidyl esters of polyester polybasic acids, and polyglycidyl ethers of polyester polyols.

Examples of the amine-based resin include a melamine resin, a guanamine resin, a urea resin, a melamine-urea co-condensation resin, a melamine-phenol co-condensation resin, and the like.

Examples of the metal crosslinking agent include aluminum ginsyl acetonate, aluminum tri-isopropylate, aluminum tri- or 2-butyrate, ethyl acetoacetate, aluminum di-isopropyl alcohol, and the like. Organoaluminum compound, titanium tetra-isopropoxide, titanium tetra-2-ethylhexanoate, triethanolamine titanium di-isopropoxide, ammonium salt of titanium lactate, tetraoctene glycol titanate, poly Organic titanium compound such as alkyl titanate, polytitanium telluride (polymer of titanium tetrabutyrate, polymer of titanium oleate), zirconium-secondary butyrate, zirconium diethoxy-three-stage An organic zirconium compound such as butyrate, another organometallic compound such as ruthenium-tertiary butyrate or ruthenium butyrate.

The proportion of the component (E) is preferably 0.01 to 3 parts by weight, more preferably 0.01 to 1 part by weight, per 100 parts by weight of the solid content of the composition.

By setting the blending ratio of the component (E) to this range, the initial adhesion of the adhesive layer of the composition does not become too low, and the storage stability is excellent.

4. Other ingredients

The components of the present invention are considered to be necessary for the components (A), (B) and (E), but may contain various components as necessary. The other components are described below.

4-1. (C) component

In order to obtain a composition exhibiting a more excellent adhesion and heat resistance, the compound (C) having one or more ethylenically unsaturated groups in the molecule may be optionally added to the composition of the present invention [hereinafter referred to as ( C) Ingredients"].

Examples of the ethylenically unsaturated group in the component (C) include a vinyl group, a vinyl ether group, a (meth) acrylonitrile group, and a (meth) acrylamide group.

The component (C) is not particularly limited, and various compounds can be used.

Specific examples of the component (C) can be the same as those of the above monomers (a) to (c).

In other words, a monofunctional (meth) acrylate, a vinyl compound, a vinyl ester, a conjugated diene, and a (meth) acrylamide may be mentioned, and specific examples thereof include the same compounds as described above. In addition, an ethylenically unsaturated compound having one or more hydroxyl groups and an ethylenically unsaturated compound having one or more carboxyl groups may be mentioned, and specific examples thereof include the same compounds as described above.

Examples of the component (C) other than the above include a compound having two or more (meth) acrylonitrile groups (hereinafter referred to as a polyfunctional (meth) acrylate).

Specific examples include butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9 -decanediol (di)acrylate, neopentyl glycol hydroxytrimethylacetic acid di(meth)acrylate, caprolactone modified neopentyl glycol hydroxytrimethylacetate di(meth)acrylate Epoxyalkylene modified neopentyl glycol II Methyl) acrylate, alkylene oxide modified 1,6-hexanediol di(meth) acrylate, neopentyl glycol modified trimethylolpropane di(meth) acrylate, polyethylene glycol Di(meth)acrylate, polypropylene glycol di(meth)acrylate, glycerol di(meth)acrylate, tricyclodecane dimethylol di(meth)acrylate, dicyclopentyldi(a) Acrylate, trimethylolpropane tri(meth)acrylate, glycerol alkylene oxide modified poly(meth)acrylate, pentaerythritol tri(meth)acrylate, carbon number 2~5 Aliphatic modified dipentaerythritol penta (meth) acrylate, aliphatic modified dipentaerythritol tetra(meth) acrylate having 2 to 5 carbon atoms, dipentaerythritol penta (methyl) Acrylate, dipentaerythritol hexa(meth) acrylate, caprolactone modified dipentaerythritol hexa(meth) acrylate, neopentyl alcohol tetra (meth) acrylate, isomeric cyanide Acid alkylene oxide modified di(meth)acrylate, iso-cyanuric acid alkylene oxide modified tri(meth)acrylate, iso-cyanuric acid caprolactone modified di(meth)acrylate, Isocyanuric acid modified caprolactone modified tris(meth)acrylate Polyfunctional (meth) acrylate such as bis(trimethylol)propane tetra(meth)acrylate and bis[2-(methyl)propenyloxyethyl]phosphate, cis (meth) propylene Phosphoric acid (meth) acrylate such as methoxyethyl phosphate.

Further, examples of the oligo group include a urethane (meth) acrylate, an epoxy (meth) acrylate, a polyester (meth) acrylate, and the like having one or more (meth) acryloyl groups in the molecule. Polymer.

Examples of the urethane (meth) acrylate include a reactant of a polyol, a polyvalent isocyanate, and a hydroxy (meth) acrylate compound, or a reactant of a polyvalent isocyanate and a hydroxy (meth) acrylate compound not using a polyol. .

In the case of a polyhydric alcohol, polypropylene glycol or polytetramethylene glycol can be cited. And a polyether polyol, a polyester polyol obtained by reacting the polyhydric alcohol with the polybasic acid, and a caprolactone dimer obtained by reacting the polyhydric alcohol with the polybasic acid and ε-caprolactone An alcohol and a polycarbonate polyol (for example, a polycarbonate polyol obtained by a reaction of 1,6-hexanediol and diphenyl carbonate) or the like.

Examples of the organic polyvalent isocyanate include isophorone diisocyanate, hexamethylene diisocyanate, methylphenyl diisocyanate, benzodimethyl diisocyanate, and diphenylmethane-4,4'-diisocyanate. Dicyclopentyl diisocyanate and the like.

A reaction product of an epoxy (meth) acrylate epoxy resin and (meth) acrylic acid.

Examples of the epoxy resin include a bisphenol type epoxy resin such as a bisphenol A type epoxy resin or a bisphenol F type epoxy resin, or a novolak type epoxy resin. Examples of the bisphenol A type epoxy resin include Epikote 827 (trade name, the same applies hereinafter), Epikote 828, Epikote 1001, and Epikote 1004 manufactured by Japan Epoxy Resins Co., Ltd., and bisphenol F type epoxy resin. Epikote 806, Epikote 4004P, etc. are mentioned. Further, examples of the novolac type epoxy resin include Epikote 152 and Epikote 154.

A reaction of a polyester (meth) acrylate polyester polyol with (meth) acrylic acid.

Polyester polyols are obtained by the reaction of a polyol with a polybasic acid.

Examples of the polyhydric alcohol include neopentyl glycol, ethylene glycol, propylene glycol, 1,6-hexanediol, trimethylolpropane, neopentyltetraol, tricyclodecane dimethylol, and bis- [Hydroxymethyl]-cyclohexane.

Examples of the polybasic acid include succinic acid, phthalic acid, hexahydrophthalic anhydride, terephthalic acid, adipic acid, sebacic acid, and tetrahydrophthalic anhydride.

As the component (C), one type or two or more types of the above compounds can be used.

In the case of the component (C), among the above-mentioned compounds, among the above-mentioned compounds, it is preferred that the isocyanuric acid alkylene oxide is modified with di- or tri(meth)acrylate or an amine group. Formate (meth) acrylate.

Further, in the case of a urethane (meth) acrylate, it is produced by using a polyether polyol, a polyester polyol or a polycarbonate polyol as a raw material polyol, in weather resistance, transparency, and adhesion. Good point is better. Further, the raw material organic polyisocyanate is preferably produced from isophorone diisocyanate, hexamethylene diisocyanate or xylene diisocyanate in terms of excellent weather resistance.

The ratio of the component (C) may be appropriately set depending on the purpose, and is preferably from 1 to 100% by weight, and more preferably from 5 to 80% by weight, based on 100 parts by weight of the component (A).

4-2. (D) component

The composition of the present invention preferably contains an organic solvent as the component (D) for the purpose of improving the coating property to the substrate and the like. In the case of the organic solvent, the organic solvent used in the production of the component (A) may be used as it is, or may be added separately. Specific examples of the component (D) include organic solvents which have been used in the production of the component (A) described above.

The proportion of the component (D) is preferably set as appropriate, but is preferably from 10 to 90% by weight, more preferably from 30 to 80% by weight, based on the composition.

4-3. Other ingredients

In addition to the above, other components described later may be blended in the composition of the present invention as needed. Specific examples thereof include an inorganic material, a leveling agent, a decane coupling agent, a polymerization inhibitor or/and an antioxidant, a light resistance improving agent, an organic solvent, and/or water.

These components are described below.

●Photopolymerization start aid

In order to further increase the reactivity, a photopolymerization initiation adjuvant may also be added to the composition of the present invention.

The photopolymerization initiation auxiliary agent may, for example, be an aromatic amine such as an aliphatic amine or diethylaminobenzophenone, dimethylaminobenzoic acid ethyl ester or dimethylaminobenzoic acid isoamyl ester. .

The compounding ratio of the photopolymerization initiation aid is preferably from 0 to 10% by weight, and more preferably from 0 to 5% by weight, based on 100 parts by weight of the solid content of the composition.

●Inorganic materials

The inorganic material may be formulated for the purpose of alleviating the deformation at the time of hardening the composition and improving the force.

Examples of the inorganic material include colloidal cerium oxide, cerium oxide, aluminum oxide, talc, clay, and the like.

The blending ratio of the inorganic material is preferably from 0 to 50% by weight, more preferably from 0 to 30% by weight, still more preferably from 0 to 10% by weight, based on 100 parts by weight of the solid content of the composition.

● leveling agent

Examples of the leveling agent include polyfluorene-based compounds and fluorine-based compounds. Things and so on.

The blending ratio of the leveling agent is preferably 0.5% by weight or less based on 100 parts by weight of the solid content of the composition, which is preferable because the adverse effect on the subsequent properties is small.

● decane coupling agent

A decane coupling agent may be added for the purpose of improving the adhesion property to an inorganic substance such as glass, metal, or metal oxide.

The decane coupling agent is a compound having one or more alkoxyalkyl groups and one or more organic functional groups in one molecule, and the organic functional group is preferably a (meth) acryl fluorenyl group, an epoxy group or an amine group. And a thiol group, more preferably a (meth) acrylonitrile group.

The blending ratio of the decane coupling agent is preferably 5% by weight or less based on 100 parts by weight of the solid content of the composition based on the point at which the exhaust gas is reduced.

● Polymerization inhibitors or / and antioxidants

Addition of a polymerization inhibitor or/and an antioxidant to the composition of the present invention can improve the storage stability of the composition of the present invention and the photocurable filler resin sheet, which is preferable.

As the polymerization inhibitor, preferred are hydroquinone, hydroquinone monomethyl ether, 2,6-di-tertiary butyl-4-methylphenol, and various phenolic antioxidants, and sulfur-based anti-oxidants may be added. A secondary oxidizing agent, a phosphorus-based secondary oxidizing agent, a propylene-based antioxidant, or the like.

The total blending ratio of these polymerization inhibitors or/and antioxidants is preferably 0.001 to 3% by weight, and more preferably 0.01 to 0.5% by weight, based on 100 parts by weight of the solid content of the composition.

●Lightfastness enhancer

In the composition of the present invention, a light-resistant enhancer such as an ultraviolet absorber or a light stabilizer may be added depending on the application.

Examples of the ultraviolet absorber include three of TINUVIN 400, TINUVIN 405, TINUVIN 460, and TINUVIN 479 manufactured by BASF Corporation. It is a UV absorber and a benzotriazole-based UV absorber such as TINUVIN 900, TINUVIN 928, and TINUVIN 1130.

Examples of the photostabilizer include a hindered amine light stabilizer and the like. Examples of commercially available products include TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, and TINUVIN 5100 manufactured by BASF Corporation.

The blending ratio of the light fastness improving agent is preferably from 0 to 10% by weight, and more preferably from 0 to 5% by weight, based on 100 parts by weight of the solid content of the composition.

5. Reactive resin composition for active energy ray-hardening void filling

The composition of the present invention is considered to be necessary for the components (A), (B) and (E).

The method for producing the composition of the present invention may be carried out by following the usual method, and the components (A), (B) and (E) may be stirred and mixed with other components as needed. The mixing time can be shortened by heating as needed.

Further, regarding this composition, the 25 ° C storage elastic modulus G' (frequency: 0.0159 Hz) (hereinafter referred to simply as "G'") of the filled resin layer (coated coating film or dried coating film) of the composition must be The storage modulus E' (frequency 1 Hz) (hereinafter referred to as "E'") of the cured product of the composition after 0.001 to 0.05 MPa and after the irradiation of the active energy ray must be 0.1~ 5000MPa.

In addition, the coating film refers to a coating film obtained by coating a solventless composition containing no component (D) (organic solvent), and the term "dry coating film" means that (D) is contained. After coating the composition of the component (organic solvent), it is heated and dried to obtain a coating film.

The G'-based void filling property of the filled resin layer of the composition is a particularly important factor.

In the case where the G' of the filled resin layer before the irradiation of the active energy ray is less than 0.001 MPa, the filled resin layer leaks when adhered to the adherend, which causes inconvenience in the production of the laminated body. On the other hand, when G' exceeds 0.05 MPa, when a film containing a resin-filled layer is bonded to an adherend having an uneven surface of about 10 to 20 μm, display defects or display unevenness of the image display device may occur. G' is 0.001 to 0.05 MPa, preferably 0.002 to 0.02 MPa.

Further, G' of the filled resin layer before curing can be adjusted by appropriately changing the type, molecular weight, and composition ratio of each component in the composition.

G' before the active energy ray irradiation is filled with a resin layer to form a sample having a predetermined thickness, and then obtained by measuring the dynamic viscoelasticity in the shear mode in accordance with JIS K7244-6. The thickness of the sample is appropriately selected depending on the elastic modulus of the sample, the amount of warpage imparted thereto, and the like.

In the present invention, G' refers to a value obtained by measuring at a temperature of 100 μm, a warpage of 0.2%, a measurement frequency of 0.0159 Hz, and a temperature increase rate of 2 ° C/min, and measuring at 25 °C.

Further, when the E' of the cured product of the composition after the active energy ray irradiation is less than 0.1 MPa, the water resistance or heat resistance of the cured product is lowered, and if When the pressure exceeds 5000 MPa, the force is lowered, and as a result, an image display device having excellent reliability cannot be obtained. E' is from 0.1 to 5,000 MPa, preferably from 2 to 100 MPa.

The E' of the cured product of the composition can be adjusted by appropriately changing the type, molecular weight, and composition ratio of each component in the composition.

E' of the cured product of the composition after the irradiation of the active energy ray is formed by laminating a resin layer and preparing a sample having a predetermined thickness, and then irradiating the active energy ray to cure the sample to obtain a cured product. It was determined by measuring the dynamic viscoelasticity in the tensile mode in accordance with JIS K7244-4. The thickness of the sample is appropriately selected depending on the elastic modulus of the sample, the width of the sample, the amount of warpage imparted, and the like.

In the present invention, E' refers to a sample obtained by curing a thickness of 100 μm and an ultraviolet light cumulative amount of 36 J/cm ² (365 nm light), and is measured at a warpage of 0.5%, a frequency of 1 Hz, and a temperature increase rate of 2 ° C/min. The value obtained by measurement at 85 ° C.

6. Active energy ray hardening type void filling film or sheet

The composition of the present invention is used in the production of a film or sheet for active energy curing type void filling (AE hardening film).

The AE-curable film is a resin-filled layer having the above composition on a substrate.

The base material may be a material for subsequent use (hereinafter referred to as "adhered matter"), or may be a peelable substrate (hereinafter referred to as "release material") irrespective of the adherend.

Specific examples of the material of the substrate include a metal such as glass or aluminum, a vapor deposited film of a metal or a metal oxide, a ruthenium, a polymer, and the like.

Examples of the polymer include polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyamines, polyimines, polycarbonates, epoxy resins, and polyamines. Acid ester, polylactic acid, polyethylene, polypropylene, cycloolefin polymer, acrylic resin, methacrylic resin, polystyrene, methacrylic acid/styrene, polyvinyl acetate, polyvinyl alcohol, triethyl Mercapto cellulose, cellulose acetate butyrate, hydroxypropyl cellulose, polyether oxime, copolymer of the above polymer, liquid crystal polymer, fluororesin, and the like.

In the case of a polymer, it is preferably a sheet or a film.

When the substrate is an adherend, a member made of the above-described material may be mentioned, and a member used in a video display device or the like is preferable.

The release material may be a film-form or sheet-like substrate (hereinafter referred to as "release film") and a release-treated surface untreated film or sheet-like substrate (hereinafter referred to as a release material). "surface untreated film").

Examples of the release treatment of the release-treated film include polyoxane treatment, long-chain alkyl treatment, and fluorine treatment. Specific examples thereof include a release-treated polyethylene terephthalate (hereinafter referred to as "PET") film, a polyolefin film, a cycloolefin polymer, and the like. A preferred embodiment is a polyfluorene-treated PET film or the like.

Examples of the surface untreated film having releasability include a surface untreated PET film, a surface untreated polyolefin film such as a surface untreated OPP (stretched polypropylene) film, a surface untreated cycloolefin polymer, and the like.

In the case of a release material, it is preferred to release the film.

The AE-curable film may, for example, be a film of the following form.

‧ AE hardened film B2: substrate / filled resin layer / release material

‧ AE hardened film B3: release material / filled resin layer / release material

The AE-curable film is preferably a film of the above B3, and among the films of the above B3, a film of the film obtained by using a release-treated film is more preferably used as a release material.

Release film/filled resin layer/release film

The film thickness of the filled resin layer is preferably from 0.5 to 500 μm, more preferably from 70 to 200 μm.

When the film thickness of the filled resin layer is 70 μm or more, when the film thickness of the uneven shape is large, the film thickness can be filled without a gap, and when the film thickness is 200 μm or less, it is possible to prevent deformation in the storage, and the solvent is easy to dry. Residual issues.

In the AE-curable film B3, when the film thickness of the filled resin layer is relatively thin, when the release material is peeled off during use, it can be easily peeled off without residual glue or the like.

On the other hand, when the film thickness of the filled resin layer of the AE-curable film B3 is preferably 70 to 200 μm, the filled resin layer is easily deformed when the release material is peeled off during use. Therefore, even if it is peeled off without a residual glue, the force required for peeling becomes large, and when it adheres to the large-sized adherend, the mold release material may break in the middle, and it may become peeling.

Further, when the release material is peeled off, if the substrate is caught by the peeling during the peeling, the film is strongly peeled off and the film is vibrated between the high peeling force and the low peeling force (referred to as a viscous sliding phenomenon). Filled resin layer will accommodate Easy to deform and leave traces.

In order to prevent this, it is preferred to use a release-treated film as a release material, and further use a release strength (tensile speed of 300 mm/min) of the release-treated film and the filling resin layer before the active energy ray irradiation to be 0.01 N. /mm or less. By setting the value to 0.01 N/mm or less, it is possible to prevent the release film from being peeled off without slipping and leaving a mark, and the occurrence of a problem such as a positional deviation of the AE-curable film.

Examples of the release-treated film that satisfies the peel strength include Fujimori Industrial Co., Ltd., FILMBYNA HTA, KF, BD, DG-2, and the like.

Further, in this case, the relationship between the film thickness of the filled resin layer and the film thickness of the two release treated films is also important.

In this case, the film thickness of the filled resin layer and the film thickness of the two release-treated films are preferably AE-curable films having a value of the following formula (A) of 1 or less, and the value of the following formula (A) is 0.1. The ~1 system is more preferable, and the value of the following formula (A) is further preferably from 0.4 to 0.9.

(film thickness of the filled resin layer) / (total film thickness of the two release treated films) ... (A)

The AE-curable film having a value of the formula (A) of 1 or less can prevent the AE-curable film from wrinkles or tunnel-like defects during storage.

The AE-curable film of the present invention can achieve sufficient void filling property before bonding, and has sufficient adhesion and reliability after curing.

By using an AE hardening type film having such a sufficient void filling property, even when applied to an image display unit display surface provided with a surface protective layer having a concave-convex shape or a layer having a concave-convex shape (for example, a polarizing plate), Absorbing the irregularities and filling the voids, as far as the results are concerned, The occurrence of display defects on the image display device is prevented. Further, when the thickness of the film itself is scattered, it also has sufficient flexibility, so that it can be bonded to the surface of the adherend without a gap, and the occurrence of display unevenness on the image display device can be prevented.

6-1. Method for manufacturing AE hardened film

As for the method of producing the AE-curable film, various methods of use can be employed depending on the purpose.

Specifically, a method of applying the composition of the present invention to a substrate to form a coating film or, if necessary, drying the film to form a dry coating film, and further bonding the other substrate, and the like may be mentioned. .

A more specific manufacturing method will be described based on Fig. 1 .

Fig. 1 is a view showing an example of a preferred production method of the AE-curable film B2 composed of a substrate/filled resin layer/release material.

In Fig. 1, (1) means a substrate, and (3) means a release material.

When the composition is a solventless type (Fig. 1 : A1), the composition is applied to a substrate [Fig. 1 : (1)]. When the composition contains an organic solvent or the like (Fig. 1 : A2), the composition is applied onto a substrate [Fig. 1 (1)], dried, and the organic solvent or the like is evaporated (Fig. 1 : 1) -1).

By this method, a filling resin layer [Fig. 1 (2)] is formed on a substrate to produce an AE-curable film (Fig. 1 : B1).

In the AE-curable film B1, it is preferable to laminate a release material (3) as a protective film on the filling resin layer as needed (first drawing: B2).

In the above, when the release material is used as the substrate (1), the AE-curable film B3 composed of the release material/filled resin layer/release material can be produced.

The coating amount of the composition of the present invention is as long as it is used. Alternatively, it may be preferably applied so that the filled resin layer has the above-mentioned preferable film thickness.

The coating method may be appropriately set as the purpose may be, and coatings such as conventionally known bar coating, blade coating, knife coating, notch wheel coating, reverse roll coating, die coating, gravure coating, and micro gravure coating may be mentioned. method.

When the composition contains an organic solvent or the like, it is dried after coating, and an organic solvent or the like is evaporated.

The drying conditions may be appropriately set depending on the organic solvent to be used, etc., and a method of heating to a temperature of 40 to 120 ° C may be mentioned.

After the production of the AE-curable film, as described above, it is preferable to laminate a release material [Fig. 1 (3)] as a protective film (Fig. 1 : B2) on the filled resin layer, and it is also possible to use The release material is used as a substrate, and a form of a release material is further laminated on the filled resin layer.

6-2. How to use AE hardened film

The AE-curable film of the present invention can be suitably used for the production of a laminate.

Specifically, the filling of the voids for various articles having voids (hereinafter simply referred to as "articles") can be suitably used for the production of recording media such as image display devices and Blu-ray discs, and nanoimprint materials, and is more suitable. Used in the manufacture of image display devices.

In the method of filling the voids of the article, at least one of the substrate or the adherend of the AE-curable film is used as a transparent material, and these are bonded together, and the active energy ray is irradiated from the side of the transparent material. The method of hardening, etc.

Examples of the active energy ray include ultraviolet rays, visible rays, X-rays, and electron beams. Since an inexpensive device can be used, it is preferable to use violet. For the light source when the outer line or/and the visible light is hardened by ultraviolet rays or/and visible rays, various light sources can be used. Preferred examples of the light source include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a UV electrodeless lamp, and an LED that emits ultraviolet rays and/or visible light.

The irradiation conditions such as the irradiation intensity when the active energy ray is irradiated may be appropriately set depending on the composition to be used, the substrate, the purpose, and the like.

A more specific method of manufacturing a laminated body will be described with reference to FIGS. 2 and 3 .

Fig. 2 shows an example in which an active energy ray is irradiated from a sheet-like substrate side by using an AE-curable film laminated with a release material. In the AE-curable film B2 of Fig. 2, (1) means a substrate, (2) means a filled resin layer, and (3) means a release material.

In Fig. 2, the release material is released from the AE-curable film immediately before use (Fig. 2: 2-1), and the filled resin layer is adhered to the adherend (4) (Fig. 2) :2-2) The active energy ray (Fig. 2: 2-3) is irradiated from the substrate side to produce a product of a laminate (Fig. 2: 2-4).

Fig. 3 shows an example in which an AE-curable film B3 formed by laminating two sheets of a release material is used, and two sheets of adherends are subsequently produced to produce a laminate. In the AE-curable film B3 of Fig. 3, (2) means a filled resin layer, and (3) means a release material.

In Fig. 3, the release material is released from the AE-curable film (Fig. 3-1) immediately before use, and the filled resin layer is adhered to the adherend [Fig. 2: (5)] ( Fig. 3: 3-2), the other release material is released (Fig. 3-3), and the filled resin layer is adhered to other adherends [Fig. 2: (4)] (Fig. 3) : 3-4), the active energy ray (Fig. 3: 3-5) is irradiated from the side of the adherend (1) to produce an article of a laminate (Fig. 3: 3-6).

7. Image display device including touch panel

As described above, the article manufactured by the AE-curable film of the present invention may, for example, be an image display device, a recording medium, or a nanoimprint material, and is preferably an image display device, and more preferably includes a touch panel. The image display device (hereinafter referred to as "touch panel type image display device").

The touch panel type image display device will be described below.

The touch panel type image display device is mainly composed of a surface protection layer, a touch panel and an image display unit.

The AE hardened film of the present invention can be mainly used for filling a surface protective layer or a gap between a touch panel and an image display unit, a gap between a surface protective layer and a touch panel.

The image forming apparatus of the present invention is preferably a cured product of the active energy ray-curable void-filling resin composition of the present invention, which is selected from the group consisting of a touch panel module, a surface protective layer, and an image display unit. At least 1 fixed.

The surface protective layer is disposed on the outermost layer when disposed on the image display device.

Even if the surface protective layer is composed only of a polymer film or glass, it can form a plurality of layers together with other layers.

The surface protective layer may be a user who has been conventionally used as a protective film for an image display device, and may be, for example, an acrylic resin such as polymethyl methacrylate (PMMA), a polycarbonate resin, or glass. The thickness of the surface protective layer is preferably 0.1 to 5 mm.

When the surface protective layer is a laminated body composed of a plurality of layers, it can be provided on the observer side of the image display device to impart wear resistance, scratch resistance, antifouling property, antireflection property, and antistatic property. The function of the ‧ characteristics layer

For example, abrasion resistance and scratch resistance can be obtained by forming a coating. Further, the hard coat layer may be provided with antistatic properties, antifouling properties, and the like.

Further, when the surface protective layer is a laminated body composed of a plurality of layers, an additional layer such as a printed layer, a hard coat layer, or a vapor deposited layer may be included in the surface protective layer on the opposing surface of the observer side or Part of the area.

When the layer thus added is formed in a partial region of the surface protective layer, the surface protective layer becomes a surface having an uneven shape. The thickness of the surface protective layer at this time is preferably 0.1 to 6 mm as a whole.

When the filling resin is bonded to the surface protective layer having the uneven shape at the tip end portion, in the case where the filling resin is bonded to the display surface of the image display unit provided with the layer having the uneven shape at the tip end portion, the uneven shape It must also be filled without gaps, and even if it is left for a long time under high temperature or high humidity conditions, the surface protection layer, the display surface of the image display unit, or the interface with the touch panel module does not generate bubbles or peeling off, and Albino. By bonding using the composition of the present invention, no air bubbles are generated at the interface, and even if it is left at a high temperature and high humidity for a long period of time, no bubbles or peeling occurs, and it is not whitened, and a high-quality image display device can be obtained.

Examples of the touch panel include various methods such as a resistive film method, a surface type electrostatic capacitance method, and a projection type electrostatic capacitance method.

Examples of the image display unit include a transmissive or reflective liquid crystal display unit, a plasma display unit, an organic EL (OLED) unit, and an image display unit such as electronic paper.

On the display surface of the image display unit, an additional functional layer (one or more layers) such as a polarizing plate or the like can be provided. Moreover, the touch panel may exist on the display surface of the image display unit.

The touch panel type image display device can be used for various electronic devices.

Specific examples of the electronic device include a mobile phone, a smart phone, a portable information terminal, a palm-type video game, an e-book, a navigation system, a portable music player, a watch, a desktop computer, Cameras, video players, digital cameras, global positioning system (GPS) devices, and personal computers (PCs).

[Examples]

The present invention will be more specifically described below by way of examples and comparative examples. In the following description, "parts" means parts by weight, and "%" means % by weight.

The meaning of the code used in the production example is as follows.

‧THPI: a compound represented by the following formula (11) [monomer (a)]

The meaning of the code used in the production example is as follows.

EHMA: 2-ethylhexyl methacrylate

BA: butyl acrylate

HEA: 2-hydroxyethyl acrylate

AMBN: 2,2'-azobis(2-methylbutyronitrile)

BuAc: n-butyl acetate

AOI: 2-propenyloxyethyl isocyanate

BHT: Dibutylhydroxytoluene

DBTDL: Dibutyltin dilaurate

○Manufacturing Example 1 [Production of component (A-1)]

In a flask equipped with a stirrer, a thermometer, and a cooler, the following compound was placed in the following amounts at room temperature (25 ° C, the same applies hereinafter), and nitrogen was blown at a flow rate of 50 mL/min. Dissolve evenly. THPI: 15.0 g, EHMA: 45.0 g, BA: 60.0 g, HEA: 30.0 g, BuAc: 190 g, AMBN: 0.3 g

While continuously blowing nitrogen gas, the temperature was raised, and after stirring at 85 ° C for 30 minutes, the temperature was raised to 90 ° C, and the following mixture was dropped for 3 hours, followed by stirring for 5 hours.

THPI: 15.0 g, EHMA: 45.0 g, BA: 60.0 g, HEA: 30.0 g, BuAc: 190 g, AMBN: 1.2 g

The resulting copolymer solution had a nonvolatile content of 42.0%, Mn 20,000, and Mw 294,000.

○Manufacturing Example 2 [Production of component (A-1)]

The following compound was placed in the same manner as in Production Example 1 to uniformly dissolve it.

THPI: 45.0 g, EHMA: 30.0 g, BA: 45.0 g, HEA: 30.0 g of dodecyl mercaptan: 0.60 g, BuAc: 190 g, AMBN: 0.3 g

Then, the temperature was raised, and after the stirring, the following mixing was carried out in the same manner and under the same conditions as in Production Example 1, followed by stirring.

THPI: 45.0 g, EHMA: 30.0 g, BA: 45.0 g, HEA: 30.0 g of dodecyl mercaptan: 0.60 g, BuAc: 190 g, AMBN: 1.2 g

The nonvolatile content of the obtained copolymer solution was 41.1%, Mn 13,900, and Mw 200,600.

○Manufacturing Example 3 [Production of component (A-2)]

In the same flask as in Production Example 1, the following compound was placed at room temperature in the following amounts, and the nitrogen was blown in at a flow rate of 50 mL/min while being uniformly dissolved.

EHMA: 52.5g, BA: 67.5g, HEA: 30.0g, BuAc: 290g, AMBN: 0.15g

While continuously blowing nitrogen gas, the temperature was raised, and after stirring in the same manner and under the same conditions as in Production Example 1, the following mixture was dropped and then stirred.

EHMA: 52.5g, BA: 67.5g, HEA: 30.0g, BuAc: 100g, AMBN: 0.6g

After temporarily cooling to room temperature, BHT: 0.1 g and DBTDL: 0.1 g were added while blowing a 5% oxygen/95% nitrogen mixed gas at a flow rate of 50 mL/min, and the mixture was uniformly dissolved. Then, the temperature was raised to 80 ° C, and after maintaining for 1 hour, AOI: 30.0 g was placed in total, and the mixture was reacted at 80 ° C for 2 hours to obtain a copolymer solution containing an ethylenically unsaturated group.

The obtained copolymer solution had a nonvolatile content of 45.3%, Mn 41,000, and Mw 142,000.

○Manufacturing Example 4 [Production of component (A-2)]

The following compound was placed in the same manner as in Production Example 3 to be uniformly dissolved.

EHMA: 52.5g, BA: 67.5g, HEA: 30.0g, BuAc: 190g, AMBN: 0.15g

While continuously blowing nitrogen gas, the temperature was raised, and after stirring at 85 ° C for 30 minutes, the temperature was raised to 90 ° C, and the following mixture was dropped for 3 hours, followed by stirring for 5 hours.

EHMA: 52.5g, BA: 67.5g, HEA: 30.0g, BuAc: 190g, AMBN: 0.6g

After temporarily cooling to room temperature, BHT: 0.1 g and DBTDL: 0.1 g were added while blowing a 5% oxygen/95% nitrogen mixed gas at a flow rate of 50 mL/min, and the mixture was uniformly dissolved. Then, the temperature was raised to 80 ° C, and after maintaining for 1 hour, AOI: 15.0 g was placed in total, and the mixture was reacted at 80 ° C for 2 hours to obtain a copolymer solution containing an ethylenically unsaturated group.

The obtained copolymer solution had a nonvolatile content of 43.5%, Mn 14,000, and Mw of 127,000.

○Manufacturing Example 5 [Production of a polymer other than the component (A)]

The following compound was placed in the same manner as in Production Example 1 to uniformly dissolve it.

EHMA: 52.5g, BA: 67.5g, HEA: 30.0g, BuAc: 190g, AMBN: 0.3g

Then, the temperature was raised, and after the stirring, the following mixing was carried out in the same manner and under the same conditions as in Production Example 1, followed by stirring.

EHMA: 52.5g, BA: 67.5g, HEA: 30.0g, BuAc: 190g, AMBN: 1.2g

The obtained copolymer solution had a nonvolatile content of 41.5%, Mn18,000, and Mw of 63,000.

Regarding the polymers other than the component (A) and the component (A) obtained in Production Examples 1 to 5, the monomers and other components used are summarized in Table 1. In addition, in Table 1, the number of parts is represented by the total amount of the monomers (a), (b), and (c) used as 100 parts.

Moreover, regarding these polymers, the nonvolatile content and molecular weight were measured by the following methods. The results of these are shown in Table 1.

(1) Non-volatile components (%)

The obtained copolymer solution was dried under the conditions of 150 ° C for 1 hour, and the nonvolatile matter was calculated from the weight before and after drying of the sample.

(2) Molecular weight

The molecular weight in terms of polystyrene was measured using GPC (manufactured by TOSOH: HLC-8120, column: TSKgel-GMHx 1 × 2, eluent: THF 1 mL/min, detector: RI). Mw represents a weight average molecular weight, and Mn represents a number average molecular weight.

○Example 1 to Example 7, Comparative Example 1 to Comparative Example 4 (manufacture of composition)

The compound shown in the following Table 2 was placed in a stainless steel container at a ratio shown in Table 2, and stirred at room temperature with a magnetic stirrer until it was uniformly dissolved to obtain an active energy-hardening type void-filling resin. Things.

The code numbers in Table 2 are as follows.

‧M1200: Polyester urethane acrylate, East Asian synthetic (stock) ARONIX M-1200

‧M313: Isophthalic acid ethylene oxide modified di- and triacrylate, East Asian synthetic (stock) ARONIX M-313

‧OT2501: Acrylic acid adduct of bisphenol A type epoxy resin, ARONIX OT-2501 made by East Asia Synthetic Co., Ltd.

‧S-1511: Acrylic adhesive, East Asian synthetic (stock) Arontack S-1511 (X) Solid content 40wt% (ethyl acetate, toluene solution)

‧Irg184: 1-hydroxycyclohexyl phenyl ketone, Ciba Specialty Chemicals, IRGACURE 184

‧PBZ: 4-phenylbenzophenone

‧CO-L: 3-functional isocyanate compound, CORONATE L made by NIPPON POLYURETHANE

Further, in the column of (A) + (D), the upper half means the blending ratio of the copolymer solution, and the lower half means the blending ratio of each component.

○Examples F1 to F7, Comparative Example F1 to Comparative Example F4 (Production of AE-curable film)

The film was coated with a TORAY ADVANCED FILM (manufactured by TORAY ADBANCED FILM) film having a width of 300 mm × 300 mm and a length of 38 μm. The resulting composition was dried at 100 ° C for 20 minutes using a hot air dryer. Then, a release film of "Cerapeel BK" (polyoxylized PET film, thickness: 38 μm) of TORAY ADVANCED FILM Co., Ltd. having a width of 300 mm × 300 mm was laminated on the resin layer to obtain an AE-curable film.

The AE hardened film obtained was evaluated by the following method. The results of these are shown in Table 3.

(1) Resin layer bulge

The AE-curable film obtained in the examples and the comparative examples was cut into a size of 100 mm × 50 mm, and the upper and lower sides were formed into a sandwich sandwich structure using a glass plate of a size of 100 mm × 100 mm. Then, under a state of carrying a weight of 1 kg of load, heating with a hot air dryer at 50 ° C for 24 hours, using visual inspection The degree of swelling of the resin layer from the tip end portion of the sheet was observed, and the results were determined by the following three levels.

○: There is no resin bulge.

△: Although there is a little resin transfer on the glass, there is no residue.

×: The resin of the bulge is transferred to the glass.

(2) Demoulding

When the release-treated film on one side of the AE-curable film obtained in the examples and the comparative examples was peeled off, the release-treated film on the peeled side was visually observed for the presence or absence of residual glue, and the following three levels were used to determine the results. The result.

○: No residue.

△: The residual gel was confirmed to have an area of 5% or less.

×: The residual gel was confirmed, and the area was 5% or more.

(3) Storage modulus before hardening G' (25 ° C)

The AE-curable film obtained in the examples and the comparative examples was laminated to prepare a sample having a thickness of 500 μm.

The dynamic viscoelasticity (frequency: 0.0159 Hz, temperature increase rate: 2 ° C/min) of this AE-curable film was measured in accordance with JIS K7244-4, and the storage elastic modulus G' at 25 ° C in the shear mode was calculated.

(4) Storage elastic modulus E' after hardening (85 ° C)

The AE-curable film obtained in the examples and the comparative examples was laminated to prepare an elongated sample having a width of 5 mm × a length of 50 mm and a thickness of 100 μm.

Then, the cured product was produced by ultraviolet irradiation (illuminance of 365 nm light of 100 mW/cm ² and cumulative light amount of 36 J/cm ² ) derived from a metal halide lamp. The mechanical properties (frequency 1 Hz, temperature increase rate 2 ° C/min) of the cured material of the adhesive were measured in accordance with JIS K7244-4, and the storage elastic modulus E' at 85 ° C in the tensile mode was calculated.

(5) Peel strength

The single-sided release-treated film of the AE-curable film was peeled off and adhered to a polyethylene terephthalate film having a film thickness of 50 μm which was easily treated (trade name "COSMOSHINE A-4300" Toyobo Co., Ltd.) system).

The other release-treated film was peeled off and adhered to the glass slide, and four sweeps were passed at a conveying speed of 5 m/min under a concentrating high-pressure mercury lamp (120 W/cm, single lamp, lamp height 30 cm). The ultraviolet ray was irradiated (the illuminance of 365 nm light was 200 mW/cm ² , and the cumulative light amount per one sweep was 500 mJ/cm ² ).

The laminate was subjected to a 90-degree peeling test under the conditions of a peel width of 25 mm, 23 ° C, and 50% RH in accordance with JIS K-6854-1 to obtain peel strength.

(6) Reliability test (foaming, peeling, whitening)

The AE-curable film and the release film of the adhesive sheet which were evaluated were peeled off on one side, and adhered to a 1 mm-thick acrylic plate by an adhesive roller so as not to allow air to enter. Then, the release-treated film on the other side was peeled off, and pressed against a 1 mm-thick float glass using a rubber roller. With respect to [Examples 1 to 6] [Comparative Examples 1 to 4], a laminate of (acrylic plate/filled resin layer/glass) obtained by a condensed high-pressure mercury lamp (120 W/cm, single lamp, The lamp height was 30 cm), and four ultraviolet rays were irradiated at a conveying speed of 5 m/min, and ultraviolet rays were irradiated from the glass plate side (illuminance of 365 nm light was 200 mW/cm ² , and integrated light amount per one sweep was 500 mJ/cm ² ).

After adjusting for 12 hours at room temperature, (a) 100 ° C × 100 small In the environmental test at (b) 60 ° C / 90% RH × 100 hours, the change in appearance of the laminate was visually confirmed. If an abnormality such as foaming, peeling, or whitening is observed, it is determined as ×: unqualified, and if there is no abnormality, it is determined as ○: pass.

(7) Void filling

A rectangular film having a length of 50 mm, a width of 5 mm, and a thickness of 20 μm was formed by a photolithography method using a solder resist film ("SRF-8000" manufactured by Toagosei Co., Ltd., 25 μm) on a smooth glass plate (100 mm × 100 mm). Concave shape. The AE hardened film and the adhesive film are adhered to the entire surface of the bump. At this time, the presence or absence of air accumulation (gas) at the edge of the uneven shape was confirmed by an optical microscope (100 times magnification). If it can be bonded without gas, it is set to ○: pass, otherwise it is set to ×: unqualified.

In the compositions of Examples 1 to 4 of the composition of the present invention, the resin layer in the storage state before the active energy ray irradiation is not embossed, and the release property of the release film is also good, and the void filling property of the filling gap is good. The peel strength or reliability after the active energy ray irradiation is also excellent.

In the compositions of Examples 5 to 6, the resin layer was raised, the mold release property, the void filling property, and the reliability were good, but the peel strength was slightly lower.

On the other hand, a composition of Comparative Example 1 containing no component (C) or a polymer different from the component (A) of the present invention, that is, a comparative example containing a hydroxyl group-containing polymer having no ethylenically unsaturated group The composition of 2, the reliability test is low. Further, the composition of Comparative Example 3 containing no (E) component had poor resin layer bulging and mold release property. The reliability test and the void filling property of Comparative Example 4 using a commercially available acrylic pressure-sensitive adhesive were used.

○Example SF1 to Example SF7, Comparative Example SF1 to Comparative Example SF8 (Manufacture of AE-curable film)

Using a coater consisting of a film take-up mechanism, a coating unit (die coating), a hot air dryer, a laminator, and a take-up mechanism, the release-treated film shown in Table 4 having a width of 300 mm was dried. The film thickness was a composition obtained by coating the thickness as shown in Table 4, and dried at 100 ° C for 10 minutes using a hot air dryer. Then, a release-treated film shown in Table 4 having a width of 300 mm was laminated on the dried coating film, and a roll-shaped AE-curable film having a length of 100 m was obtained by winding. The tension of the roll-out was set to 30 N, and the build-up condition was room temperature ‧0.3 MPa.

The calculation results of the values of the following formula (A) of the obtained AE hardening type film are shown in Tables 4 and 5.

(film thickness of the filled resin layer) / (total film thickness of the two release treated films) ... (A)

Further, the obtained AE-curable film was evaluated by the following method. The results of these are shown in Table 5.

The symbols in Table 4 have the following meanings.

‧HTA: release film, polyfluorene-treated polyethylene terephthalate film made by Fujimori Industrial Co., Ltd., trade name; FILMBYNA HTA (75μm)

‧KF: De-modeling film, polyoxyethylene polyethylene terephthalate film made by Fujimori Industrial Co., Ltd., trade name; FILMBYNA KF (50μm)

‧BX8: release film, polyfluorinated polyethylene terephthalate film made of TORAY ADVANCED FILM, trade name; Cerapeel BX8 (38μm)

‧BKE: release film, polyfluorinated polyethylene terephthalate film made of TORAY ADVANCED FILM, trade name; Cerapeel BKE (38μm)

(1) Appearance

The roll-shaped AE hardening film having a length of 100 m was stored under the conditions of 23° C. and 50% RH for one month, and the change in appearance was visually observed, and the evaluation was carried out by the following three levels.

○: Wrinkles, tunnel-like defects, and bulging of the resin at the film end were not observed on the film.

△: A tunnel-like defect and a bulge of the resin at the film end were not observed on the film, but wrinkles were observed.

X: Wrinkles, tunnel-like defects, or ridges of the resin at the end of the film were observed on the film.

(2) release treatment film peelability

The AE-curable film or the release-treated film on one side of the adhesive film was peeled off, and T was carried out in accordance with JIS K-6854-3 under the conditions of a peel width of 25 mm, 23 ° C, 50% RH, and a tensile speed of 300 mm/min. The peeling test was determined as the release film peelability (1).

Next, on the AE-curable film or the adhesive film from which the release-treated film on the other side is peeled off, a polyethylene terephthalate film having a film thickness of 50 μm which is easily treated is adhered (trade name "COSMOSHINE A-4300" "Toyobo Co., Ltd.", peeling off another release film and putting it on The T-peel test was carried out under the measurement conditions, and the release film peeling property (2) was determined.

Further, in the evaluation of the peeling property, the AE-curable film or the adhesive film was cut into a size of 15 cm square, and the release-treated film on one side was peeled off with a finger, and bonded to the film which was easily treated by using an adhesive roller. Polyethylene terephthalate film (manufactured by COSMOSHINE A-4300, manufactured by Toyobo Co., Ltd.) having a thickness of 188 μm. Further, another release-treated film was similarly peeled off with a finger and adhered to a 20 cm square type glass slide. The appearance of the sample prepared in this continuous operation was judged by the following three levels.

○: The release-treated film was smoothly peeled off, and no trace of the eye was observed on the adhesive layer.

△: There are 1 to 5 traces of straight lines visible on the adhesive layer.

×: There are six or more linear traces visible on the adhesive layer.

(3) Storage elastic modulus G' (25 ° C) before hardening, storage elastic modulus E' (85 ° C) after hardening, peel strength, reliability test (foaming, peeling, whitening), void filling

Both were carried out in the same manner as described above.

In the examples SF1 to SF7 of the more preferable AE-cured film of the present invention, there is no problem of occurrence of tunnel-like defects or wrinkles or swelling of the resin layer during storage under the roll shape before the irradiation of the active energy ray. The release property of the mold-treated film is also good, and the void filling property of the filling gap and the peeling strength or reliability after the irradiation of the active energy ray are also excellent.

In the AE hardened film of SF5 to SF6, the defects in the state of no storage were good, and the mold release property, void filling property, and reliability were good, but the peel strength was slightly low.

On the other hand, in Comparative Examples SF1 to SF3, a comparative example of an AE-cured film produced by using a composition of the composition of the present invention and a release-treated film having excellent mold release property was used. The AE-cured film produced from the composition of Comparative Example 1 containing no component (C) had good appearance, mold release property, and drop filling property, but was inferior in reliability test. AE hardened film produced from the composition of Comparative Example 2 containing a polymer different from the component (A) in the present invention, that is, a hydroxyl group-containing polymer having no ethylenically unsaturated group, appearance, mold release property, height difference Although the compliance is also good, the reliability test is poor. In addition, the AE-cured film produced from the composition of Comparative Example 3 containing no component (E) had a good reliability test and void filling property, but was inferior in appearance and mold release property.

Next, Comparative Examples SF4 to SF7 were comparative examples in which an AE-cured film produced by using a release-treated film having no release property was used as a composition of the composition of the present invention. The AE-cured film produced from the composition of Comparative Example 1 had poor appearance, insufficient mold release property, and poor reliability test. The AE hardened film produced from the composition of Comparative Example 2 was poor in appearance, mold release property, and reliability test. The AE hardened film produced from the composition of Comparative Example 3 was inferior in appearance and mold release property. The AE-cured film produced from the composition of Comparative Example 4 which is a commercially available acrylic pressure-sensitive adhesive has poor appearance, insufficient mold release property, and poor reliability test and void filling property.

Finally, Comparative Examples SF8 to SF10 are comparative examples using an AE-cured film produced by using the composition of the present invention and using a mold release-treated film having a release property. The AE hardened film of Comparative Example SF8 to SF9 was inferior in appearance and mold release property. Further, since the AE-cured film of Comparative Example 10 in which the film thickness of the filled resin layer was thin, the film thickness was thin, and the appearance and the mold release property were not bad, but they were insufficient, and the void filling property was poor.

[Industrial availability]

The active energy ray-curable void-filling resin composition of the present invention can be suitably used for the production of an active energy ray-curable void-filling film or sheet, and can be suitably used for the production of a laminate using the same. More specifically, the laminated body can be suitably used for the manufacture of an image display device which is characterized by fixing any or all of the touch panel module, the surface protective layer, and the image display unit.

(1) ‧‧‧Substrate

(2) ‧‧‧filled resin layer

(3) ‧‧‧Removable materials

(4) ‧ ‧ affixed objects

Fig. 1 shows an example of production of an active energy ray-curable void-filling film or sheet (hereinafter referred to as "AE-curable film") which is obtained by using the composition of the present invention.

Fig. 2 shows an example of production of a laminate obtained by using the AE-curable film of the present invention.

Fig. 3 shows another example of production of a laminate obtained by using the AE-curable film of the present invention.

Claims (12)

An active energy ray-curable void-filling film which is formed in the following order: a film-form substrate which has been subjected to release treatment (hereinafter referred to as "release film"), a resin-filled layer, and a release-treated film in which filling The film thickness of the resin layer is 70 to 200 μm, and the peel strength (stretching speed 300 mm/min) before the active energy ray of the release resin film and the filling resin layer is greater than 0 N/mm and less than 0.01 N/mm. The filled resin layer is formed of an active energy ray-curable void-filling resin composition containing the following components (A), (B), and (E), and is a coating film or a dried coating film of the composition. The 25 ° C storage elastic modulus G' (frequency 0.0159 Hz) of the filled resin layer is 0.001 to 0.05 MPa, and the elastic modulus E' (frequency 1 Hz) of the cured product of the composition after irradiation with the active energy ray is 85 ° C. The relationship between the film thickness of the filled resin layer and the film thickness of the two release-treated films is from 0.1 to 5000 MPa, and the value of the following formula (A) is 0.4 to 1, (A) having an ethylenically unsaturated group and a hydroxyl group. Polymer (B) photopolymerization initiator and/or sensitizer (E) thermosetting crosslinking agent. (film thickness of the filled resin layer) / (total film thickness of the two release treated films) ‧ ‧ (A) The active energy ray-curable void-filling film according to the first aspect of the invention, wherein the film (B) is contained in an amount of 0.1 to 10% by weight based on 100 parts by weight of the total amount of the component (B). The active energy ray-curable void-filling film according to the first aspect of the invention, wherein the component (A) has a maleimide group represented by the following formula (1) as an ethylenically unsaturated group. , [In the formula (1), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group, or R ¹ and R ² represent a combination of a 5-membered ring or a 6-membered ring. Hydrocarbyl group]. The active energy ray-curable void-filling film according to the third aspect of the invention, wherein the component (A) is a copolymer obtained by copolymerizing the following monomers (a) to (c) in the following ratio (A-1) Monomer (a): a compound having a maleimide group represented by the above formula (1) and an ethylenically unsaturated group other than the maleimide group: 5 to 50% by weight (b): a compound having a hydroxyl group and an ethylenically unsaturated group: 5 to 30% by weight of the monomer (c): a compound having an ethylenically unsaturated group other than the monomers (a) and (b): 20 to 90 weight%. The active energy ray-curable void-filling film according to the fourth aspect of the invention, wherein the monomer (a) is a compound represented by the following formula (2), [In the formula (2), R ¹ and R ² are the same as defined above; further, R ³ represents an alkylene group, R ⁴ represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 6]. The active energy ray-curable void-filling film according to the first aspect of the invention, wherein the component (A) is a polymer having a (meth)acryl fluorenyl group as an ethylenically unsaturated group. The active energy ray-curable void-filling film according to the first aspect of the invention, further comprising (C) a compound having one or more ethylenically unsaturated groups in the molecule. The active energy ray-curable void-filling film according to claim 7, wherein the film (C) is contained in an amount of from 1 to 100% by weight based on 100 parts by weight of the component (A). The active energy ray-curable void-filling film according to claim 1, further comprising (D) an organic solvent. The active energy ray-curable void-filling film according to claim 1, wherein the film (E) is contained in an amount of 0.01 to 3% by weight based on 100 parts by weight of the solid content of the composition. An image display device comprising: a cured product of an active energy ray-curable void-filling film according to claim 1 of the patent application, which is selected from the group consisting of a touch panel module, a surface protective layer, and an image display unit. At least one of the groups is fixed. A method for producing an active energy ray-curable void-filling film according to the first aspect of the invention, comprising: coating the composition on a release-treated film to form a coating film, or coating the film as needed a step of heating the coating film and drying to form a dry coating film, and The step of bonding another release-treated film to the surface of the filling resin layer (coating the coating film or drying the coating film).