TWI728135B - Active energy ray polymerizable adhesive for optics and laminate for optics - Google Patents

Abstract

The present invention provides a device in a wide temperature range from high temperature to low temperature Optical active energy ray polymerizable adhesive and optical laminate with excellent adhesive force. An optical active energy ray polymerizable adhesive, comprising: a (meth)acrylate monomer (A) having a molecular weight of less than 500 and having a heterocyclic ring, and a (meth)acrylate monomer having a molecular weight of less than 500 and having a hydroxyl group ( B) and (meth)acrylate monomers (C) having a molecular weight of less than 500 and having a ring structure other than a heterocyclic ring, the heterocyclic ring containing two or more selected from the group consisting of sulfur, oxygen, and nitrogen Heteroatoms are used as atoms constituting the ring.

Description

Optical active energy ray polymerizable adhesive and optical laminate body

The present invention relates to an optical active energy ray polymerizable adhesive.

In optical applications such as display devices such as displays, active energy ray polymerizable adhesives have high polymerization speed and generally can be used without solvents, so they have excellent workability and extremely low energy required for polymerization. Because of its characteristics, it is widely used. Generally, active energy ray polymerizable adhesives are known as radical polymerizable active energy ray polymerizable adhesives or cationic polymerizable active energy ray polymerizable adhesives.

In display devices such as displays, various films such as anti-reflection films to prevent reflection from external light sources or protective films to prevent damage to the surface of the display device are generally used depending on the application. For example, in the construction of liquid crystal displays ( In the liquid crystal display (LCD) cell member, a polarizing plate and a retardation film are laminated.

In addition, a flat panel display (FPD) is sometimes used not only as a display device, but also as an input device provided with a touch panel function on its surface. Protective film and anti-reflection film are also used in touch panels Or indium tin oxid (ITO) vapor-deposited resin film, etc.

In addition, in display devices, a backlight method that illuminates the liquid crystal layer from the back to make it emit light is popular, and the bottom surface of the liquid crystal layer is equipped with edge-light type, direct type, etc. backlight units. (backlight unit). The edge light type backlight unit basically includes: a linear lamp as a light source, a square plate-shaped light guide plate arranged so that the end is along the lamp, and a light arranged on the surface side of the light guide plate. A diffusion sheet and a prism sheet arranged on the surface side of the light diffusion sheet. Recently, as a light source, a light emitting diode (LED) with excellent color reproducibility or power saving has begun to replace the cold tube (cold cathode fluorescent lamp (CCFL)), which is heat resistant Or the requirements for dimensional stability have become higher.

Moreover, the display device will be used in various environments as its use expands. For example, in-vehicle-type liquid crystal display devices such as car navigation are exposed to severe high-temperature environments in summer, and therefore require adhesive strength at high temperatures. Furthermore, in cold regions in winter, adhesive strength at low temperatures is required.

As an adhesive used in a display device, an adhesive containing a carboxyl group-containing vinyl polymer and a vinyl monomer has been disclosed (Patent Document 1).

Patent Document 2 discloses an active energy ray adhesive containing an alicyclic epoxy resin, a polyol having a number average molecular weight of 400 or more, and an active energy ray induction catalyst.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2015-110763

[Patent Document 2] Japanese Patent Laid-Open No. 2007-224235

However, the display device using the conventional active energy ray adhesive agent has insufficient adhesive force in a wide temperature range from high temperature to low temperature for in-vehicle applications and the like, and particularly insufficient adhesive force at low temperatures.

The object of the problem to be solved by the present invention is to provide an optical active energy ray polymerizable adhesive having excellent adhesive force in a wide temperature range from high temperature to low temperature.

The present invention relates to an optical active energy ray polymerizable adhesive comprising: a monomer (A) containing an α,β-ethylenically unsaturated double bond group having a molecular weight of less than 500 and having a heterocyclic ring (wherein, acryloyl group) (Except morpholines), α, β-ethylenically unsaturated double bond-containing monomers (B) with a molecular weight of less than 500 and a hydroxyl group (wherein, α, β-ethylenically unsaturated double bond-containing monomers with a molecular weight of less than 500 and a heterocyclic ring Monomers (except for bond groups) and monomers (C) containing α,β-ethylenically unsaturated double bond groups with a molecular weight of less than 500 and a ring structure other than heterocycles (wherein, the molecular weight is less than 500 and has hetero Cyclic α,β-ethylenically unsaturated double bond-containing monomers (A) and hydroxy-containing α,β-ethylenically unsaturated double bond-containing monomers (B) with a molecular weight of less than 500 except for), so The heterocyclic ring includes two or more heteroatoms selected from the group consisting of sulfur, oxygen and nitrogen as the constituent ring Of the atom.

In addition, the present invention relates to the optical active energy ray polymerizable adhesive, which further comprises one or more selected from polyurethane oligomers having α, β-ethylenically unsaturated double bond groups ( D1), composed of polyester oligomer with α,β-ethylenically unsaturated double bond group (D2) and epoxy oligomer with α,β-ethylenically unsaturated double bond group (D3) The oligos in the group.

In addition, the present invention relates to the active energy ray polymerizable adhesive for optics, which contains 5 to 70% by mass of an α-containing adhesive having a molecular weight of less than 500 and a heterocyclic ring in an optical active energy ray polymerizable adhesive. , β-ethylenically unsaturated double bond group monomer (A), 20% to 80% by mass, with a molecular weight of less than 500 and having a hydroxyl group containing α, β-ethylenically unsaturated double bond group monomer (B) , 5% to 50% by mass α, β-ethylenically unsaturated double bond-containing monomer (C) with a molecular weight of less than 500 and a ring structure other than a heterocyclic ring.

In addition, the present invention relates to a laminate for optics, which includes a first substrate, a resin layer, and a second substrate, and the resin layer is a cured product of the active energy ray polymerizable adhesive for optics.

According to the present invention, it is possible to provide an optical active energy ray polymerizable adhesive having excellent adhesive force in a wide temperature range from high temperature to low temperature.

Hereinafter, embodiments of the present invention will be described.

<Active energy ray polymerizable adhesive for optics>

The optical active energy ray polymerizable adhesive (hereinafter sometimes abbreviated as "adhesive") of the present invention is characterized in that it contains an α,β-ethylenically unsaturated double bond group-containing monomer having a molecular weight of less than 500 and having a heterocyclic ring. Monomers (A) (except acrylomorpholine), monomers (B) containing α,β-ethylenically unsaturated double bond groups with a molecular weight of less than 500 and a hydroxyl group (wherein, the molecular weight is less than 500 and has a heterocyclic ring Monomers containing α,β-ethylenically unsaturated double bond groups (except for A) and monomers containing α,β-ethylenically unsaturated double bond groups with a molecular weight of less than 500 and having a ring structure other than heterocycles ( C) (Among them, α,β-ethylenically unsaturated double bond-containing monomers (A) with a molecular weight of less than 500 and a heterocyclic ring and α,β-ethylenically unsaturated double bonds with a molecular weight of less than 500 and a hydroxyl group (Except for monomers (B)), the heterocyclic ring includes two or more heteroatoms selected from the group consisting of sulfur, oxygen, and nitrogen as atoms constituting the ring.

Here, the so-called "active energy ray" refers to the broad energy that includes ultraviolet rays, visible rays, infrared rays, electron beams (EB), and radiation, and can provide energy required for the activation of chemical reactions. line. The active energy ray polymerizable adhesive of the present invention undergoes polymerization reaction by irradiation of the active energy ray, and forms a cured product such as a resin layer.

In addition, in this specification, when expressed as "(meth)acryloyl", "(meth)acrylic", "(meth)acrylate", "(meth)acryloyloxy", and "( methyl) "Allyl" means "acrylic acid and/or methacrylic acid", "acrylic acid and/or methacrylic acid", and "acrylic acid ester and/or methacrylic acid ester" unless otherwise specified. , "Acryloxy and/or methacryloxy", and "Allyl and/or methallyl".

<The α,β-ethylenically unsaturated double bond-containing monomer (A) with a molecular weight of less than 500 and a heterocyclic ring>

The so-called α, β-ethylenically unsaturated double bond-containing monomer (A) (hereinafter also referred to as compound (A)) with a molecular weight of less than 500 and a heterocyclic ring means having a heterocyclic ring and α, β-ethylenicity An unsaturated double-bonded compound in which the heterocyclic ring contains two or more heteroatoms selected from the group consisting of sulfur, oxygen, and nitrogen as atoms (ring member atoms) constituting the ring.

By including the compound (A) in the adhesive, a hydrogen bond is formed between the heteroatom of the heterocyclic ring and the functional group such as the hydroxyl group on the surface of the substrate, and the adhesive force at room temperature and low temperature is improved. Furthermore, due to the ring structure, the cohesive force at high temperature increases, and the adhesive force at high temperature increases.

The heterocycles containing two or more heteroatoms selected from the group consisting of sulfur, oxygen and nitrogen as ring member atoms include: dithiolane (dithiolane) ring, dithiol (dithiol) ring, etc. Heterocycles with more than two sulfur atoms; carbonate rings, dioxolane rings, dioxane rings, and other heterocycles with more than two oxygen atoms; isocyanuric acid Ring, imidazole ring, pyrazole ring, pyrazine ring, pyrimidine ring, pyrazine ring and other heterocyclic rings with more than two nitrogen atoms; oxazole ring, isoxazole ring, oxazine ring, oxadiazole ring, oxazole ring Diazine ring and other heterocycles with oxygen atom and nitrogen atom Ring; thiazole ring, benzothiazole ring, isothiazole ring, thiazine ring, thiadiazole ring, thiadiazine ring, dithiazine ring and other heterocyclic rings having sulfur atoms and nitrogen atoms, etc.

Among these heterocyclic rings, in terms of being excellent in a wide temperature range from high temperature to low temperature, a heterocyclic ring having two or more oxygen atoms as ring member atoms is preferred, and a heterocyclic ring having two oxygen atoms as ring members is more preferred. A heterocyclic ring of ring members. In addition, in terms of polymerization reaction, monocyclic heterocycles are better than condensed heterocycles, and in terms of discoloration during the heat resistance test, aliphatic heterocycles are better than aromatic heterocycles. More specifically, particularly preferred are a dioxolane ring and a dioxane ring.

In addition, although the reason is not clear, if acrylomorpholine is contained in the optical active energy ray polymerizable adhesive, the viscosity of the adhesive will decrease during long-term storage, which is undesirable.

The number of α,β-ethylenically unsaturated double bond groups in the compound (A) is preferably 1 to 6 in terms of improved adhesion in a wide temperature range from high temperature to low temperature From the viewpoint of hardening shrinkage, one is particularly preferred.

Specific examples of the compound (A) include (2-methyl-2-ethyl-1,3-dioxolane-4-yl) (meth)methyl acrylate, (methyl) Acrylic acid 5-ethyl-1,3-dioxan-5-yl methyl ester, (meth)acrylic acid (2-oxo-1,3-dioxolane-4-yl) methyl ester, 1 ,3-Dioxan-2-one-5-yl (meth)acrylate, 1-(meth)acryl-4-methylpiperazine, (meth)acrylic acid 11-[1',3 ',3'-Trimethylspiro[3H-naphtho[2,1-b][1,4]oxazine-3,2'(3'H)-[1H]indole]-5'-yl Oxy]undecyl ester, 2,5-bis((meth)acryloyloxyethylthiomethyl)-1,4-dithiane, etc., in a wide temperature range from high to low In terms of excellent aspects, (2-methyl-2-ethyl-1,3-dioxane Pentane-4-yl) methyl (meth)acrylate, 5-ethyl-1,3-dioxan-5-yl methyl (meth)acrylate.

<The monomer (B) containing an α,β-ethylenically unsaturated double bond group with a molecular weight of less than 500 and a hydroxyl group>

As a monomer (B) containing an α,β-ethylenically unsaturated double bond group with a molecular weight of less than 500 and a hydroxyl group (hereinafter also referred to as compound (B)), as long as it is an α,β-ethylenically unsaturated monomer having a hydroxyl group The double bond compound is not particularly limited.

By including the compound (B) in the adhesive, a hydrogen bond is formed with the hydroxyl group of the substrate, etc., and the adhesive force at room temperature and low temperature is improved. In addition, by forming a hydrogen bond with the heteroatom of the heterocyclic ring of the compound (A), the cohesive force at high temperature increases, and the adhesive force at high temperature increases.

As the compound (B), for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-(meth)acrylate Hydroxybutyl ester, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, cyclohexanedimethanolmono(meth)acrylic ester, (methyl) ) Monofunctional glycerol (meth)acrylate such as 12-hydroxylauryl acrylate and ethyl-α-(hydroxymethyl) (meth)acrylate; aliphatic (meth)acrylate glycidyllaurate and other aliphatic Ester (meth)acrylate; cyclohexanedimethanolmono(meth)acrylate, cyclohexanedimethanolmono(meth)acrylate, 2-hydroxy-3-phenoxy Propyl(meth)acrylate, 2-(meth)acryloyloxyethyl phthalate Cyclic (meth)acrylates such as -2-hydroxyethyl ester; the (meth)acrylate having a hydroxyl group is subjected to the ring-opening addition of ε-caprolactone to impart a hydroxyl-containing (meth) acrylate to the molecular end Base) acrylate; alkylene oxide addition (meth)acrylic acid formed by repeated addition of ethylene oxide, propylene oxide, butylene oxide and other alkylene oxides to the (meth)acrylate having a hydroxyl group Aliphatic (meth)acrylates such as esters; N-hydroxyethyl (meth)acrylamide (N-hydroxyethyl (meth)acrylamide (N-hydroxyethyl (meth)acrylamide) and N-hydroxyethylmethacrylamide are collectively referred to as "N -Hydroxyethyl (meth)acrylamide], N-hydroxypropyl (meth)acrylamide, N-hydroxybutyl (meth)acrylamide, N-hydroxyhexyl (meth)acrylamide Hydroxyl-containing (meth)acrylamides such as amines, N-hydroxyoctyl (meth)acrylamides, and the like.

In terms of excellent adhesion at low temperatures, the compound (B) is preferably 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate. Ester, 4-hydroxybutyl (meth)acrylate, particularly preferably 4-hydroxybutyl (meth)acrylate.

<α,β-ethylenically unsaturated double bond-containing monomer (C) having a molecular weight of less than 500 and having a ring structure other than a heterocyclic ring>

The so-called α,β-ethylenically unsaturated double bond-containing monomer (C) (hereinafter also referred to as compound (C)) having a molecular weight of less than 500 and having a ring structure other than a heterocyclic ring refers to a hydrocarbon containing a heterocyclic ring The α,β-ethylenically unsaturated double bond compound of the ring (aromatic hydrocarbon ring or aliphatic hydrocarbon ring). The compound (C) is preferably an α,β-ethylenically unsaturated double bond compound containing a hydrocarbon ring (aromatic hydrocarbon ring or aliphatic hydrocarbon ring) that does not contain a heterocyclic ring. By including The compound (C) can obtain an optical active energy ray polymerizable adhesive having excellent adhesive force at high temperatures.

As the compound (C), for example, benzyl (meth)acrylate, phenoxy (meth)acrylate, ethylene oxide modified phenoxy (meth)acrylate, bisphenol A di( Meth) acrylate, alkylene oxide modified bisphenol A di(meth)acrylate, bisphenol F di(meth)acrylate, alkylene oxide modified bisphenol F di(meth)acrylate, ortho (Meth)acrylate compounds having aromatic hydrocarbon rings such as 2-(meth)acryloyloxyethyl phthalate, neopentyl glycol-acrylic acid-benzoate, etc.; hydrogenated bisphenol A bis(methyl) (Meth)acrylate compounds having one or more aliphatic hydrocarbon rings, such as acrylate, 2-(meth)propenoxyethyl hexahydrophthalate, and cyclohexyl methacrylate; 3 , 3-Dicyclopropyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, dicyclopentyl (methyl) )Acrylate, dimethylol dicyclopentane di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, isobornyl (meth)acrylate, 3-hydroxy-1- Adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, 2-propyl-2 -Adamantyl (meth)acrylate, 3,5-dihydroxy-1-adamantyl (meth)acrylate, 1,3-adamantyldiol di(meth)acrylate, 1,3 , 5-adamantyl tri(meth)acrylate, 3-hydroxy-1,5-adamantyl di(meth)acrylate, and other (meth)acrylate compounds having condensed aliphatic hydrocarbon rings, etc. .

Regarding the number of α,β-ethylenically unsaturated double bond groups in compound (C), In terms of the increase in the adhesive force in a wide temperature range from high temperature to low temperature, 1 to 6 are preferable, and from the viewpoint of hardening shrinkage, 1 is preferable.

As the compound (C), an α,β-ethylenically unsaturated double bond compound having a condensed aliphatic hydrocarbon ring is preferred in terms of excellent adhesion at high temperatures. Specifically, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentyl (meth)acrylate, tricyclodecane are preferred. Alkyl dimethanol di(meth)acrylate and isobornyl (meth)acrylate, particularly preferably tricyclodecane dimethanol di(meth)acrylate and isobornyl (meth)acrylate.

Regarding the content of the compound (A), the compound (B), and the compound (C) in the optical active energy ray polymerizable adhesive, it is preferable that the compound (A) is 5 mass% to 70 mass%, and the compound (B) 20 mass% to 80 mass%, compound (C) is 5 mass% to 50 mass%, more preferably compound (A) is 10 mass% to 70 mass%, and compound (B) is 30 mass% to 70 mass% , The compound (C) is 5% to 40% by mass. In addition, it is preferable that the total amount of the compound (A), the compound (B), and the compound (C) in the optical active energy ray polymerizable adhesive is 70% by mass or more.

The optical active energy ray polymerizable adhesive of the present invention further comprises one or more selected from polyurethane oligomers (D1) having α, β-ethylenically unsaturated double bond groups (hereinafter also referred to as Is compound (D1)), polyester-based oligomer (D2) with α,β-ethylenically unsaturated double bond group (hereinafter also referred to as compound (D2)), has α,β-ethylenically unsaturated double bond group The bond-based epoxy-based oligomer (D3) (hereinafter also referred to as compound (D3)) in the group of oligomers has improved adhesion at room temperature, In this respect, it is better.

The weight average molecular weight of the compound (D1), the compound (D2), and the compound (D3) is preferably 500 to 100,000. In addition, the weight average molecular weight in this specification is a value obtained by measuring polystyrene with a known weight average molecular weight as a standard substance using gel permeatioh chromatography (GPC).

<Polyurethane oligomer with α,β-ethylenically unsaturated double bond group (D1)>

Polyurethane oligomer with α,β-ethylenically unsaturated double bond group (D1) (compound (D1)) means having a urethane bond and α,β-ethylene in the molecule Compounds with unsaturated double bond groups. For example, it can be obtained by reacting an α,β-ethylenically unsaturated double bond group having a hydroxyl group with a compound having an isocyanate group at the end. The compound having an isocyanate group at the end is a compound having one or more isocyanate groups and a compound having an isocyanate group. The hydroxyl compound is obtained by reaction.

Examples of compounds having at least one isocyanate group include aromatics such as 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 1,4-phenylene bis-methylene diisocyanate, etc. Isocyanates; aliphatic isocyanates such as 3-isocyanatemethyl-3,5,5-trimethylcyclohexyl isocyanate, hexamethylene diisocyanate, etc.

Specific examples of the compound (D1) include: EBECRYL 210, EBECRYL 220 (the above are manufactured by Daicel-Allnex), CN9782, CN9783 (above for Aromatic polyurethane-based oligomers such as SARTOMER (manufactured by SARTOMER); Ziguang 3000B, Ziguang 3700B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), BECRYL 230, Abacli (BECRYL) 270, BECRYL 8402, BECRYL 8701 (the above are made by Daicel-Allnex) and other aliphatic polyurethane oligomers .

<Polyester-based oligomer with α,β-ethylenically unsaturated double bond group (D2)>

The polyester-based oligomer (D2) (compound (D2)) having an α,β-ethylenically unsaturated double bond group is a compound having an ester bond and an α,β-ethylenically unsaturated double bond group in the molecule. For example, the end of a polyester obtained by polycondensation of a polybasic acid and a polyhydric alcohol in the main chain skeleton, or the hydroxyl group in the polyester chain, and (meth)acrylic acid, etc. have one or more carboxyl groups in the molecule. -Obtained by the esterification reaction of an ethylenically unsaturated double bond compound.

Examples of the polybasic acid include: oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, suberic acid, maleic acid, fumaric acid, itaconic acid, butyric acid Aliphatic polybasic acids such as diacid anhydride and maleic anhydride; alicyclic polybasic acids such as dimer acid and cyclohexane dicarboxylic acid; aromatics such as isophthalic acid, terephthalic acid and biphenyl dicarboxylic acid Department of polybasic acid.

Examples of polyalcohols include relatively low molecular weight polyols with a number average molecular weight (Mn) of 50 to 500, or relatively high molecular weight polyols with a number average molecular weight (Mn) of 500 to 30,000. .

Specific examples of the compound (D2) include: CN296, CN2203, CN2259, CN2261 (above are made by SARTOMER) and other aromatic polyester-based oligomers; CN294, CN2270, CN2271 (above are sand Aliphatic polyester-based oligomers such as Duowei (manufactured by SARTOMER).

<Epoxy-based oligomer with α,β-ethylenically unsaturated double bond group (D3)>

The epoxy-based oligomer (D3) (compound (D3)) having an α,β-ethylenically unsaturated double bond group refers to the reaction between the epoxy group of the epoxy compound and the compound having a carboxyl and/or hydroxyl group The resulting partial structure and α,β-ethylenically unsaturated double bond group compound.

Examples of the epoxy compound include aromatic epoxy compounds such as bisphenol epoxy resins, aliphatic epoxy compounds such as diglycidyl ethers of diols having 2 to 20 carbon atoms, and alicyclic epoxy compounds.

Specific examples of the compound (D3) include: CN104, CN110 (the above are manufactured by SARTOMER), BECRYL 600, and BECRYL 3701 (the above is Daicelo (Manufactured by Daicel-Allnex) and other aromatic epoxy-based oligomers; CN111, CN113 (manufactured by SARTOMER), BECRYL 860 (BECRYL) (Daicel-Allnex) and other aliphatic epoxy-based oligomers.

Regarding the content of the compound (D1), the compound (D2), and the compound (D3) in the optical active energy ray polymerizable adhesive, the compound is preferably The total of (D1), compound (D2), and compound (D3) is 1% by mass to 30% by mass, more preferably 3% by mass to 20% by mass.

The optical active energy ray polymerizable adhesive of the present invention may also include other α, β other than compound (A), compound (B), compound (C), compound (D1), compound (D2), and compound (D3) -Ethylene unsaturated double bond compound (E) (hereinafter also referred to as compound (E)) or cationically polymerizable compound (F) (hereinafter also referred to as compound (F)).

By including the compound (E), the viscosity of the optical active energy ray polymerizable adhesive can be reduced to improve coating properties, or further improve durability such as moisture and heat resistance.

Examples of the compound (E) include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, n-hexyl (meth)acrylate, and lauryl (meth)acrylate , And alkyl (meth)acrylates such as stearyl (meth)acrylate; (meth)allyl (meth)acrylate, 1-butenyl (meth)acrylate, (meth) ) Acrylic acid 3,7-dimethyloct-6-en-1-yl, acrylic acid 2-(2-vinyloxyethoxy) ethyl, and (meth)acrylic acid vinyl ester and other unsaturated Base (meth)acrylate; perfluoromethyl (meth)acrylate, 2-perfluoroethyl ethyl (meth)acrylate, 2-perfluorohexadecylethyl (meth)acrylate, etc. Perfluoroalkyl (meth)acrylate; (methoxycarbonyl)methyl (meth)acrylate, 2-(ethoxycarbonyloxy)hexyl (meth)acrylate, 2-(meth)acrylate (Propoxycarbonyloxy) ethyl and (meth) propylene 2-(octyloxycarbonyloxy)butyl ester and other aliphatic (meth)acrylates with one carbonyl group; 2-oxobutyryl ethyl (meth)acrylate, 3-oxobutyryl (meth)acrylate Propyl ester, 2,3-bis(oxobutanoyl)butyl (meth)acrylate, 2,3-bis(oxobutanoyl)hexyl (meth)acrylate, etc. aliphatic (methyl) with two carbonyl groups Acrylate; 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-propoxyethyl (meth)acrylate, 3-propane (meth)acrylate Alkoxy ethyl, 2-butoxyethyl (meth)acrylate, 3-butoxyethyl (meth)acrylate, 4-butoxyethyl (meth)acrylate and other alkoxy-containing (Meth)acrylate; (meth)acrylic acid derivatives containing alkylene oxide such as alkylene oxide adducts of (meth)acrylic acid; di(meth)acrylate glycol, di(meth)acrylate tri Ethylene glycol, tetraethylene glycol di(meth)acrylate, 2,2-dimethylpropyl diol di(meth)acrylate, hydroxytrimethylacetoxyhydroxytrimethyldi(meth)acrylate Acetate, 2,5-hexanediol di(meth)acrylate, 1,2-octanediol di(meth)acrylate, 2,2-diethyl-1,3-di(meth)acrylate Difunctional (meth)acrylates such as propylene glycol and 2,5-dimethyl-2,5-hexanediol di(meth)acrylate; 1,2,3-propanetriol tri(meth)acrylate, Tri(meth)acrylate trimethylolhexane, tri(meth)acrylate trimethyloloctane, and tri(meth)acrylate 1,1,1-trihydroxymethylethane and other trifunctional (meth) Base) acrylate; pentaerythritol tetra(meth)acrylate, 2,2-bis(hydroxymethyl)-1,3-propanediol tetra(meth)acrylate, and di-2,2-bis(meth)acrylate (Hydroxymethyl)-1,3-propanedi Polyfunctional (meth)acrylates such as alcohols; glycidyl α,β-ethylenically unsaturated double bond compounds, 3,4-epoxycyclohexylmethyl α,β-ethylenically unsaturated double bond compounds, etc. have cations Α,β-ethylenically unsaturated double-bond compounds with polymerizable functional groups; α,β-ethylenically unsaturated compounds with heterocyclic rings containing one heteroatom such as tetrahydrofurfuryl α,β-ethylenically unsaturated double-bond compounds Double bond compounds and so on.

<Cationically polymerizable compound (F)>

As the compound (F), a compound having an epoxy group as a 3-membered cyclic ether, a compound having an oxetanyl group as a 4-membered cyclic ether, a vinyl ether compound, a cyclic ester compound, and a cyclic condensate are preferred. Formaldehyde compounds, cyclic carbonate compounds, fluorine-containing cyclic compounds, etc. Among these compounds, none of the compounds having a ring has an α,β-ethylenically unsaturated double bond group, and is therefore different from the compound (A), the compound (B), and the compound (C).

By containing the compound (F), the curing shrinkage of the adhesive is reduced, and the adhesive force at room temperature is improved.

As a compound (epoxy compound) having an epoxy group, an aromatic epoxy compound, an aliphatic epoxy compound, an alicyclic epoxy compound, etc. are preferable.

As the aromatic epoxy compound, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, diglycidyl ether of bisphenol A propylene oxide adduct, Phenol novolac epoxy resin, cresol novolac epoxy resin, biphenyl type epoxy resin, resorcinol diglycidyl ether, phenyl glycidyl ether, phenol ethylene oxide glycidyl ether, tertiary butyl Phenyl glycidol Ether and so on.

The aliphatic epoxy compound is preferably an aliphatic monool, an aliphatic polyol, and the glycidyl ether of an alkylene oxide adduct thereof. Examples of the aliphatic epoxy compound include: allyl glycidyl ether, 2-ethylhexyl glycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, Diglycidyl ether of 6-hexanediol, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, through Polyglycidyl ether of polyether polyol obtained by adding one or two or more alkylene oxides (ethylene oxide or propylene oxide) to aliphatic polyols such as glycol, polypropylene glycol, and glycerin.

As the alicyclic epoxy compound, for example, 1,2-epoxy-4-vinylcyclohexane, 1,2:8,9-diepoxylimonene, 3,4-epoxycyclohexylmethyl -3,4-epoxycyclohexane carboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, bis( 3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, etc.

The epoxy equivalent of the epoxy compound is generally preferably about 30 g/eq to 3000 g/eq, and more preferably 50 g/eq to 1500 g/eq. When the epoxy equivalent is 30 g/eq or more, the flexibility of the cured sheet is excellent, and the adhesive force is also improved. In addition, if it is 3000 g/eq or less, the curability is excellent and the adhesive force is improved.

Examples of the compound having oxetanyl group include 3-ethyl-3-hydroxymethyloxetane and 1,4-bis[(3-ethyl-3-oxetanyl group) Methoxymethyl)benzene, bis(1-ethyl-3-oxetanyl) methyl ether, 3-ethyl-3-(phenoxymethyl)oxa Cyclobutane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, phenol novolac oxetane, 3-ethyl-{(3-triethoxy Silylpropoxy)methyl}oxetane and the like.

Examples of vinyl ether compounds include n-pentyl vinyl ether, isopentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, 2-ethylhexyl vinyl ether, and n-dodecane. Vinyl ether, stearyl vinyl ether, oleyl vinyl ether and other C5-20 alkyl alcohols and vinyl ethers of alkenyl alcohol; cyclohexyl vinyl ether, 2-methylcyclohexyl ethylene Vinyl ether, cyclohexyl methyl vinyl ether, benzyl vinyl ether and other mono-alcohol vinyl ethers with aliphatic or aromatic rings; glycerol monovinyl ether, 1,4-butanediol monovinyl ether , 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, neopentyl glycol divinyl ether, pentaerythritol divinyl ether, pentaerythritol tetravinyl ether, trimethylol Propane divinyl ether, trimethylolpropane trivinyl ether, 1,4-dihydroxycyclohexane monovinyl ether, 1,4-dihydroxycyclohexane divinyl ether, 1,4-dihydroxy Monovinyl ether and polyvinyl ether of polyhydric alcohols such as methylcyclohexane monovinyl ether and 1,4-dihydroxymethylcyclohexane divinyl ether; triethylene glycol divinyl ether, diethyl Polyalkylene glycol monovinyl ether and divinyl ether such as glycol monobutyl monovinyl ether; other vinyl ethers such as glycidyl vinyl ether and ethylene glycol vinyl ether methacrylate.

As a cyclic ester compound, lactone etc. are mentioned, for example. As cyclic carbonic acid Examples of the ester compound include ethylene carbonate, propylene carbonate, and the like. Examples of the cyclic formal compound include dioxolane, dioxane, trioxane, and the like. The compound (F) can be used alone or in combination of two or more kinds.

The compound (F) is preferably a compound having an epoxy group and a compound having an oxetanyl group. Among the epoxy-containing compounds and the oxetanyl-containing compounds, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, bis(3,4-epoxy ring) Hexyl methyl) adipate, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, and diglycidyl ether of 1,6-hexanediol are preferred because they are particularly excellent in reactivity.

<Active energy ray polymerization initiator (G)>

The active energy ray polymerizable adhesive agent for optics may contain an active energy ray polymerization initiator (G) (hereinafter also referred to as a compound (G)). Examples of the compound (G) include an active energy ray radical polymerization initiator (g1), an active energy ray cationic polymerization initiator (g2), and an active energy ray anionic polymerization initiator (g3).

As the active energy ray radical polymerization initiator (g1), a known active energy ray radical polymerization initiator can be used. If a commercially available product is listed, for example, IRGACURE-184, 907, 651, 1700, 1800, 819, 369, 261, DAROCUR-TPO (the above are made by BASF) ; DAROCUR-1173 (manufactured by Merck); Esacure KIP150, TZT (manufactured by Nihon Siber Hegner, Japan); Kayacure BMS, Kayacure DMBI (manufactured by Nippon Kayaku Co., Ltd.), etc.

As the active energy ray cationic polymerization initiator (g2), known The active energy line cationic polymerization initiator. If a commercially available product is listed, for example, UVACURE 1590 (manufactured by Daicel Cytec), CPI-110P (manufactured by San-Apro), etc., or Yanjia IRGACURE 250 (manufactured by BASF), WPI-113 (manufactured by Wako Pure Chemical Industries, Ltd.), and Rp-2074 (manufactured by Rhodia Japan Co., Ltd.).

As the active energy ray anionic polymerization initiator (g3), a known active energy ray anionic polymerization initiator can be used. If commercially available products are listed, for example: WPBG-165, WPBG-018, WPBG-172, WPBG-140, WPBG-166, WPBG-027, WPBG-082, WPBG-167, WPBG-168, WPBG-266 ( The above is made by Wako Pure Chemical Industries, Ltd.) etc.

The compound (G) is preferably blended in the range of 0.1% by mass to 10% by mass in 100% by mass of the optical active energy ray polymerizable adhesive, more preferably 0.5% by mass to 5% by mass.

The optical active energy ray polymerizable adhesive of the present invention may further contain a photosensitizer, an amine-based catalyst, a phosphorus-based catalyst, a filler, an antistatic agent, an anti-aging agent, an antioxidant, an adhesion imparting agent, and an anti-blocking agent as necessary. Agent, defoamer, plasticizer, silane coupling agent, titanium coupling agent, etc.

The optical active energy ray polymerizable adhesive of the present invention preferably contains substantially no organic solvent, and more preferably contains no organic solvent at all. However, many of the compounds (G) are hardly soluble in polymerizable components, so in order to dissolve the compound (G), a small amount of organic solvent may be included. The content of the organic solvent in the adhesive is preferably 5% by mass or less.

From the viewpoint of controlling the smoothness of the coating film or the dimensional stability of the cured resin, the viscosity of the optical active energy ray polymerizable adhesive of the present invention at 25° C. is preferably 1 mPa. s~2000mPa. s, more preferably 10mPa. s~1500mPa. s, further preferably 20mPa. s~1000mPa. s.

When the optical active energy ray polymerizable adhesive is used as the adhesive layer of the optical laminate (hereinafter sometimes referred to as "laminate"), the thickness of the adhesive layer is preferably 0.1 μm to 6 μm, more preferably 0.1μm~3μm. If the thickness of the adhesive layer is within the above range, the adhesive strength is further improved.

A well-known coating device can be used to coat the substrate with the adhesive. Examples include: wire rods, applicators, brushes, sprayers, rollers, gravure coaters, die coaters, micro gravure coaters, lip coaters, corner wheel coaters, curtain coaters, doctor blades Type coater, reverse coater, spin coater, etc.

The active energy rays used in the curing of the adhesive are preferably light including ultraviolet rays, and the wavelength in this case is preferably 150 nm to 550 nm. Examples of light sources of active energy rays include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, chemical lamps, backlight lamps, microwave-excited mercury lamps, LED lamps, xenon lamps, metal halide lamps, and the like.

The irradiation intensity of active energy rays is preferably 10 mW/cm ² to 500 mW/cm ² . The cumulative irradiation amount expressed as the product of irradiation intensity and irradiation time is preferably 10 mJ/cm ² to 5000 mJ/cm ² , more preferably 30 mJ/cm ² to 4000 mJ/cm ² .

The optical laminate of the present invention includes a resin layer formed of an optical active energy ray polymerizable adhesive, an adhesive layer, and a substrate.

The polymerization reaction of the adhesive is carried out by irradiating active energy rays at the time of application or lamination of the adhesive, and further after lamination. It is preferable to irradiate the active energy rays after lamination of the substrate to advance the polymerization reaction. At this time, in order to carry out the polymerization reaction by irradiation of active energy rays, it is preferable that at least one of the first substrate and the second substrate is made of a material that easily transmits active energy rays. Specifically, it is preferably Transparent film, plastic lens, transparent glass plate, etc. For example, if a transparent film or a transparent glass plate is used as the first substrate, a substrate that hardly transmits active energy rays, such as wood, metal plate, plastic board, paper processed products, etc., can also be used as the second substrate.

In the laminate of the present invention, it is preferable to use a film-like substrate as the substrate. Examples of the film-like substrate include cellophane, various plastic films, paper, and the like. Among them, various transparent plastic films are preferably used. In addition, as long as the film-like substrate is transparent, it may have a single layer or a multilayer structure in which a plurality of substrates are laminated.

Hereinafter, a more specific embodiment of the optical laminate of the present invention will be described using a transparent film as a base material as an example.

The laminate of the present invention may be, for example, a sheet-like multilayer film obtained by laminating multiple transparent films such as transparent film/adhesive layer/transparent film, or transparent film/adhesive layer/transparent film/adhesive layer/transparent film. In addition, it is also preferable to have a structure in which a sheet-like multilayer film is bonded to other optical members such as glass or optical sheets. The laminate can be obtained by irradiating active energy rays from one or both sides of the film to polymerize and harden the optical active energy ray polymerizable adhesive, thereby hardening the adhesive layer.

Examples of the transparent film include: polyvinyl alcohol film, polytriacetyl cellulose film, polypropylene, polyethylene, polycycloolefin, and ethylene-vinyl acetate copolymer Polyolefin-based films such as materials; polyester-based films such as polyethylene terephthalate and polybutylene terephthalate; polycarbonate-based films, polynorbornene-based films, polyarylate-based films, poly Acrylic film, polyphenylene sulfide film, polystyrene film, polyvinyl film, polyamide film, polyimide film, polyethylene oxide (polyoxirane) film, etc.

When a transparent film is used as the base material, the laminate of the present invention can be suitably used for optical applications.

The thickness of the transparent film can be appropriately determined. Generally, from the viewpoints of film strength, workability, and thin layer properties, it is preferably 1 μm to 500 μm, more preferably 1 μm to 300 μm, and still more preferably 5 μm to 200 μm. In addition, when used for optical purposes, the thickness of the transparent film is preferably 5 μm to 150 μm.

The laminated body for optical elements as an example of the embodiment of the laminated body for optics of the present invention preferably uses an optical film mainly used for optical applications as a transparent film.

Examples of optical films include hard coating films, antistatic coating films, anti-glare coating films, polarizing films, retardation films, elliptically polarizing films, anti-reflection films, light diffusion films, brightness enhancement films, and prism films (also called prism films). Sheets), decorative films (including filling sheets for touch panels), light guide films (also called light guide plates), and the like.

Using the optical active energy ray polymerizable adhesive of the present invention, liquid crystal display devices, plasma display (PDP) modules, touch panel modules, organic electroluminescence (EL) modules, etc. can be formed Layered body.

[Example]

Hereinafter, examples are shown to describe the present invention more specifically, but the present invention is not limited by these examples. In addition, "parts" means "mass%", and "%" means "mass%".

<Weight average molecular weight>

The weight-average molecular weight is measured by using GPC (gel permeation chromatograph) "Shodex GPC System-21" manufactured by Showa Denko Corporation as a measuring device, and two pieces manufactured by Showa Denko Corporation Shodex GPC LF-604 was used as the column, and tetrahydrofuran (THF) was used as the developing solvent, and the measurement was performed under the conditions of a flow rate of 0.6 ml/min and a column temperature of 40°C. The weight average molecular weight is determined based on a standard curve prepared using polystyrene with a known weight average molecular weight as a standard substance.

[Example 1]

<Production example of active energy ray polymerizable adhesive>

Add (2-methyl-2-ethyl-1,3-dioxolane-4-yl)methyl acrylate (Osaka Organic Chemical Industry Co., Ltd.) as compound (A) to a 300 mL glass bottle with a light-shielding capacity. Manufactured by the company, trade name: MEDOL-10, molecular weight: 208) 40 parts, 40 parts of 4-hydroxybutyl acrylate as compound (B), and dicyclopentenyl acrylate as compound (C) (Manufactured by Hitachi Chemical Company, trade name: Fancryl FA511AS, molecular weight: 204) 18 parts, IRGACURE 184 (photo-radical polymerization initiator manufactured by BASF) 2 parts, sufficient Stirring and degassing are carried out to obtain an active energy ray polymerizable adhesive. Picking up The viscosity (initial viscosity) measured under the following conditions immediately after the preparation of the adhesive was 8mPa. s.

"Viscosity over time"

After storing the obtained active energy ray polymerizable adhesive at 40°C for one month, the viscosity with time was measured under the following conditions. In addition, if the viscosity change rate calculated by Equation 1 is within ±20%, it is an adhesive that can be used.

<Formula 1> Viscosity change rate (%)=((Viscosity with time-initial viscosity)/initial viscosity)×100

<Viscosity measurement conditions>

Use E-type viscometer (manufactured by Toki Sangyo Co., Ltd., TV-22), with 1.2 mL of active energy ray polymerizable adhesive as a measurement sample, under the conditions of 23°C, rotation speed 0.5 rpm to 100 rpm, and 1 minute rotation The viscosity is measured.

<Production example of laminated body>

As the transparent film, a UV absorber-containing polytriacetate-based cellulose film manufactured by Fujifilm Co., Ltd.: trade name "Fujitac: 80μm" (thickness 80μm), and ZEON ) Polynorbornene film (thickness 100μm) made by the company without ultraviolet absorber. To the surface of one side of two transparent films, use 300W. The discharge amount of min/m ^{2 is corona treated.} After that, within 1 hour, on the corona-treated surface of the polytriacetyl cellulose film containing the ultraviolet absorber, use a wire bar coater to coat the active energy ray polymerizable layer with a thickness of 4 μm. Adhesive. Furthermore, a polynorbornene film containing no ultraviolet absorber was laminated, and the polytriacetyl cellulose film containing the ultraviolet absorber was in contact with the tinplate, and cellophane tape was used to The four sides are fixed on the tin plate.

Using an active energy ray irradiation device (manufactured by Toshiba Corporation, high-pressure mercury lamp), a polynorbornene-based film without ultraviolet absorber manufactured by ZEON, Japan, was used to irradiate the maximum illuminance 500mW/cm ² and the cumulative light intensity 1000mJ/ cm ² of ultraviolet rays to produce a laminate.

Regarding the obtained laminate, the room temperature adhesive force, the high temperature adhesive force, and the low temperature adhesive force were determined according to the following methods, and the results are shown in Table 1.

"Temperature Adhesion at Room Temperature"

The adhesion force is measured in accordance with Japanese Industrial Standards (JIS) K6854-4 Adhesive-Peel Adhesion Strength Test Method-Part 4: Floating Roll Method. That is, the obtained laminate was cut into a size of 25 mm×150 mm using a cutter to prepare a sample for measurement. A double-sided adhesive tape (DF8712S manufactured by TOYO CHEM) was attached to the polynorbornene-based film surface of the sample without an ultraviolet absorber, and it was fixed on a metal plate using a laminator. For the laminated body for measurement, a preset part for peeling is set in advance between the transparent films. For the laminated body for measurement, under the conditions of 23°C and 50% relative humidity, at a speed of 300mm/min, 90° The polytriacetate-based cellulose film containing the ultraviolet absorber was peeled off at an angle of, and the adhesive force was measured. The adhesive force was evaluated on 4 levels. If the evaluation is ⊚, ◯, and △, it is a practically no problem level.

◎: Do not peel off, or the substrate is damaged (very good)

○: Peeling force is 2.0 (N/25mm) or more (good)

△: The peeling force is 1.0 (N/25mm) or more and less than 2.0 (N/25mm) (usable)

×: Peeling force is less than 1.0 (N/25mm) (unavailable)

"High Temperature Adhesive Force"

In the room temperature adhesive force evaluation method, the adhesive force was measured in the same manner as the room temperature adhesive force except that the temperature was changed from 23°C to 60°C. The adhesive force was evaluated on 4 levels. If the evaluation is ⊚, ◯, and △, it is a practically no problem level.

◎: The peeling force is 1.5 (N/25mm) or more (very good)

○: The peeling force is 1.0 (N/25mm) or more and less than 1.5 (N/25mm) (good)

△: The peeling force is 0.5 (N/25mm) or more and less than 1.0 (N/25mm) (usable)

×: Peeling force is less than 0.5 (N/25mm) (unavailable)

"Low Temperature Adhesion"

In the room temperature adhesive force evaluation method, the adhesive force was measured in the same manner as the room temperature adhesive force except that the temperature was changed from 23°C to 0°C. The adhesive force was evaluated on 4 levels. If the evaluation is ⊚, ◯, and △, it is a practically no problem level.

◎: Do not peel off, or the substrate is damaged (very good)

○: The peeling force is 1.0 (N/25mm) or more (good)

△: The peeling force is 0.5 (N/25mm) or more and less than 1.0 (N/25mm) (usable)

×: Peeling force is less than 0.5 (N/25mm) (unavailable)

[Example 2 to Example 28, Comparative Example 1 to Comparative Example 5]

Except for changing the materials and compositions shown in Tables 1 to 4, the active energy ray polymerizable adhesive and laminate were produced in the same manner as in Example 1, and the viscosity, time-dependent viscosity, viscosity change rate, and room The warm adhesive strength, high temperature adhesive strength and low temperature adhesive strength were evaluated. The evaluation results are shown in Tables 1 to 4.

The materials used in the examples and their abbreviations are shown below.

<Compound (A)>

MEDOL-10: (2-Methyl-2-ethyl-1,3-dioxolane-4-yl) methyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name: MEDOL- 10

Biscoat200: 5-ethyl-1,3-dioxan-5-yl methyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name: Biscoat #200

<Compound (C)>

FA511AS: Dicyclopentenyl acrylate, manufactured by Hitachi Chemical Co., Ltd., trade name: Fancryl FA511AS

IBXA: Isobornyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name: IBXA

A-DCP: Tricyclodecane dimethanol diacrylate, manufactured by Shinnakamura Chemical Industry Co., Ltd., trade name: NK ester (NK ester) A-DCP

BPE-80N: Ethoxylated bisphenol A dimethacrylate, manufactured by Shinnakamura Chemical Industry Co., Ltd., trade name: NK ester (NK ester) BPE-80N

<Compound (D1)>

UV3000B: Urethane acrylate oligomer, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: Ziguang UV3000B

EBECRYL210: Urethane acrylate oligomer, manufactured by Daicel-Allnex Corporation, trade name: EBECRYL 210

<Compound (D2)>

EBECRYL525: Polyester acrylate oligomer (containing 40% by mass of tripropylene glycol diacrylate), manufactured by Daicel-Allnex, trade name: EBECRYL 525

EBECRYL884: Polyester acrylate oligomer, manufactured by Daicel-Allnex, trade name: EBECRYL 884

<Compound (D3)>

KAYARAD R-9485: Epoxy acrylate oligomer, manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD R-9485

BAEM-100: Epoxy methacrylate oligomer, manufactured by KSM, trade name: BAEM-100

<Compound (E)>

THFA: Tetrahydrofurfuryl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name: Biscoat #150

<Compound (F)>

2021P: 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexyl carboxylate, manufactured by Daicel Corporation, trade name: Celloxide 2021P

EX212L: 1,6-hexanediol diglycidyl ether (low chlorine grade), manufactured by Nagase ChemteX, trade name: Denacol EX212L

<Compound (G)>

IRGACURE184: 1-hydroxy-cyclohexyl-phenyl-ketone, manufactured by BASF, trade name: IRGACURE 184

CPI-100P: Active energy ray cationic polymerization initiator, manufactured by San-Apro, trade name: CPI-110P

It can be seen that the active energy ray polymerizable adhesive of the present invention has excellent storage stability, and furthermore, compared with the laminates of Comparative Examples 1 to 5, the laminates using the active energy ray polymerizable adhesive of the present invention (implementation Examples 1 to 28) are more excellent in room temperature adhesion, high temperature adhesion, and low temperature adhesion.

Claims (4)

An optical active energy ray polymerizable adhesive, comprising: a mono(meth)acrylate monomer (A) having a molecular weight of less than 500 and having a heterocyclic ring containing two or more oxygen atoms as ring members (A) (wherein, acrylic acid Except for morpholine), α,β-ethylenically unsaturated double bond group-containing monomers (B) with a molecular weight of less than 500 and a hydroxyl group (wherein, the molecular weight is less than 500 and has two or more oxygen atoms as the ring Mono-(meth)acrylate monomers (except for heterocyclic ring members (A)) and monomers containing α,β-ethylenically unsaturated double bond groups with a molecular weight of less than 500 and having a ring structure other than the heterocyclic ring (C ) (Wherein the mono(meth)acrylate monomer (A) having a molecular weight of less than 500 and having a heterocyclic ring containing two or more oxygen atoms as ring member atoms (A) and the α-containing monomer having a molecular weight of less than 500 and having a hydroxyl group , excluding β-ethylenically unsaturated double bond monomers (B)). The optical active energy ray polymerizable adhesive described in the first item of the scope of patent application, which further includes one or more selected from polyurethane oligomers having α, β-ethylenically unsaturated double bond groups (D1), polyester-based oligomers with α,β-ethylenically unsaturated double bond groups (D2), and epoxy-based oligomers with α,β-ethylenically unsaturated double bond groups (D3) The oligomers in the group. The active energy ray polymerizable adhesive agent for optics as described in item 1 or item 2 of the scope of patent application, wherein the active energy ray polymerizable adhesive agent for optics contains 5 mass% to 70 mass% of the Mono(meth)acrylate monomer (A) having a molecular weight of less than 500 and having a heterocyclic ring containing two or more oxygen atoms as ring member atoms, 20% by mass to 80% by mass of the molecular weight less than 500 and having a hydroxyl group Contain α, β-ethylenically unsaturated double bond group monomer (B), 5 mass% to 50 mass% of the α, β-ethylenically unsaturated double bond containing α, β-ethylenically unsaturated double bond with a molecular weight of less than 500 and having a ring structure other than a heterocyclic ring The monomer of the bond group (C). A laminated body for optics, comprising: a first base material, a resin layer, and a second base material, the resin layer being the optical active energy ray according to any one of items 1 to 3 in the scope of the patent application Cured product of polymerizable adhesive.