JP2022093411A - Active energy ray-polymerizable adhesive and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray-polymerizable resin composition that can be used for an adhesive, a coating agent or the like showing excellent adhesiveness and allowing formation of a laminate excellent in high-temperature durability.

SOLUTION: The active energy ray-polymerizable resin composition comprises: a compound (A) obtained by a substitution reaction of a silane coupling agent (a1) and a photopolymerizable functional group-containing compound having a hydroxyl group (a2); and a photopolymerizable functional group-containing compound (B). The silane coupling agent (a1) contains an alkoxysilyl group and other functional groups; and the other functional groups are selected from a group consisting of a vinyl group, epoxy group, (meth)acryloyl group, mercapto group and amino group.

SELECTED DRAWING: None

COPYRIGHT: (C)2022,JPO&INPIT

Description

The present invention relates to an active energy ray-polymerizable adhesive and a laminate.

Since the active energy ray-polymerizable resin composition has a high polymerization rate and can be generally used without a solvent, it has excellent workability and excellent properties such as extremely low energy required for polymerization. As the active energy ray-polymerizable resin composition, a radically polymerizable active energy ray-polymerizable resin composition and a cationically polymerizable active energy ray-polymerizable resin composition are generally known, and an adhesive or a coat is known. It is used in a wide range of fields such as agents.

In recent years, the development and generalization of information and communication equipment including display devices such as displays has been remarkable. In these display devices, further improvement in performance and productivity of coating agents, adhesives, sealing agents, etc. are required, and various proposals using active energy ray-polymerizable resin compositions have been made. There is. Such a display device usually includes various films depending on the application, such as an antireflection film for preventing reflection from an external light source and a protective film (protective film) for preventing scratches on the surface of the display device. For example, in a liquid crystal cell member constituting a liquid crystal display (LCD), a polarizing plate and a retardation film are laminated.

Further, the flat panel display (FPD) is not only used as a display device, but may also be used as an input device by providing a touch panel function on the surface thereof. Protective films, antireflection films, ITO vapor deposition resin films, and the like are also used for touch panels.

In addition, a backlight system that illuminates the liquid crystal layer from the back surface to emit light has become widespread in the display device, and a backlight unit such as an edge light type or a direct type is equipped on the lower surface side of the liquid crystal layer. The edge light type backlight unit is basically a linear lamp as a light source, a square plate-shaped light guide plate arranged along the end of the lamp, and arranged on the surface side of the light guide plate. It is provided with a light diffusing sheet to be formed and a prism sheet arranged on the surface side of the light diffusing sheet. Recently, as a light source, a light emitting diode (LED) having excellent color reproducibility and power saving has been used instead of a cooling electrode tube (CCFL), so that the demand for heat resistance and dimensional stability is increasing. It's coming.

Such a film is attached to an adherend via an adhesive and used as a laminate for an optical element in a display device, and an active energy ray-polymerizable adhesive is used as one form.

To give a specific example of a display device, a polarizing element used for an LCD is usually produced by uniaxially stretching a polyvinyl alcohol (PVA) adsorbed with iodine or a dye. This PVA-based polarizing element is produced. The polarization performance tends to deteriorate due to shrinkage due to heat and moisture. Therefore, a laminate in which a protective film is bonded to the surface of a PVA-based polarizing element is used as a polarizing plate. As the adhesive used for this bonding, an aqueous solution of a polyvinyl alcohol-based resin (PVA-based aqueous adhesive) has been widely used. However, where the water-based adhesive requires a drying step after coating, the PVA-based polarizing element has low heat resistance, so that it needs to be dried at a low temperature for a long time, resulting in poor production efficiency. Therefore, in order to improve production efficiency, a cationic active energy ray-polymerizable adhesive using ultraviolet rays as an active energy ray is being studied instead of the water-based adhesive.

By the way, in recent years, a curved panel display has been used as a display device instead of a flat panel display.
Conventionally, curved panel displays used for indoor advertisements and the like are now used for outdoor applications such as mobile phones, and high durability is required in a wide temperature range from low temperature to high temperature. Especially under low temperature conditions, the adhesive and the base material may peel off on the curved surface, and stronger adhesive strength is required.

As the adhesive used for the display device, an adhesive containing a carboxyl group-containing vinyl polymer and a vinyl monomer (Patent Document 1) is disclosed.

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 sensitive catalyst.

JP-A-2015-110763 JP-A-2007-224235

However, when the conventional laminated body using the active energy ray adhesive is used for a curved panel display, for example, when it is stored for a long time under low temperature or high temperature conditions, there is a problem that the curved surface portion of the laminated body is peeled off.

An object of the present invention is to provide an active energy ray-polymerizable adhesive having excellent low-temperature adhesive force and high-temperature adhesive force on a curved surface portion.

The active energy ray-polymerizable adhesive of the present invention is selected from the group consisting of a hydroxyl group-containing mono (meth) acrylate monomer (A), a monomer represented by the following general formula (1), and a monomer represented by the following general formula (2). A tri or tetra (tri or tetra) selected from the group consisting of one or more di (meth) acrylate monomers (B), and the monomers represented by the following general formula (3) and the monomers represented by the following general formula (4). Meta) Contains an acrylate monomer (C).

General formula (1)

However, in the formula, R1 and R2 are methyl groups or hydrogen, P1 and P3 are alkylene groups having 2 to 4 carbon atoms, P2 is an alkylene group having 5 to 10 carbon atoms, and n1, n2 and n3 are. It is an integer from 0 to 6.

General formula (2)

However, in the formula, R3 and R4 are methyl groups or hydrogens, P4 and P5 are alkylene groups having 2 to 4 carbon atoms, and n4 and n5 are integers of 0 to 6. However, n4 and n5 do not become 0 at the same time.

General formula (3)

However, in the formula, R5, R6 and R7 are methyl groups or hydrogens, R8 is a methyl group, a hydroxyl group and an acryloyloxy group, and P6, P7 and P8 are alkylene groups having 2 to 4 carbon atoms and n6. n7 and n8 are integers of 0 to 6.

General formula (4)

However, in the formula, R9, R10, R11 and R12 are methyl groups or hydrogens, R13 and R14 are methyl groups, hydroxyl groups and acryloyloxy groups, and P9, P10, P11 and P12 are alkylenes having 2 to 4 carbon atoms. It is a group, and n9, n10, n11, and n12 are integers of 0 to 6.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an active energy ray-polymerizable adhesive having excellent low-temperature adhesive force and high-temperature adhesive force on a curved surface portion.

First, the terms used in the present specification will be described.
"Active energy ray" means an energy ray in a broad sense capable of providing the energy required for activation to cause a chemical reaction, including ultraviolet light, visible light, infrared light, electron beam (EB), and radiation. In the active energy ray-polymerizable adhesive of the present invention, the polymerization reaction proceeds by irradiation with the above-mentioned active energy rays to form a cured product such as a resin layer.
Further, "(meth) acryloyl" includes "acryloyl and methacryloyl". "(Meta) acrylic acid" includes "acrylic acid and methacrylic acid". "(Meta) acrylate" includes "acrylate and methacrylate". "(Meta) acryloyloxy" includes "acryloyloxy and methacryloyloxy". "(Meta) allyl" includes "allyl and methallyl". The "monomer" is a "monomer containing an ethylenically unsaturated bond".

Hereinafter, embodiments of the present invention will be described.
<Active energy ray-polymerizable adhesive>
The active energy ray-polymerizable adhesive of the present invention (hereinafter, may be simply referred to as “adhesive”) includes a hydroxyl group-containing mono (meth) acrylate monomer (A), a di (meth) acrylate monomer (B), and a bird. Alternatively, it is necessary to include a tetra (meth) acrylate monomer (C).

The active energy ray-polymerizable adhesive of the present invention is used in combination with three types of (meth) acrylate monomers having a specific structure, and when used as an adhesive for curved surfaces, peeling does not occur after low temperature aging and high temperature aging. Good adhesive strength can be obtained. Therefore, the adhesive of the present invention is preferably used, for example, for a display panel having a curved surface portion.

<Hydroxy group-containing mono (meth) acrylate monomer (A)>
The hydroxyl group-containing mono (meth) acrylate monomer (A) (hereinafter, also referred to as compound (A)) may be any mono (meth) acrylate having a hydroxyl group, and is not particularly limited.
When the adhesive contains the compound (A), it forms a hydrogen bond with a substrate having a hydroxyl group such as polyvinyl alcohol, and the adhesive strength at room temperature and low temperature is further improved.

The compound (A) may be, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (. 6-Hydroxyhexyl (meth) acrylic acid, 8-hydroxyoctyl (meth) acrylic acid, cyclohexanedimethanol mono (meth) acrylic acid ester, 12-hydroxylauryl (meth) acrylic acid, ethyl-α-(meth) acrylic acid Monofunctional (meth) glycerol acrylate such as hydroxymethyl);
Fatty acid ester-based (meth) acrylic acid ester such as (meth) glycidyl lauric acid ester;

Cyclic of cyclohexanedimethanol mono (meth) acrylate, cyclohexanediethanol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-a (meth) acryloylxyethyl-2-hydroxyethyl-phthalic acid, etc. (Meta) acrylic acid ester;
A (meth) acrylic acid ester imparting a hydroxyl group to the molecular terminal by ring-opening addition of ε-caprolactone to the (meth) acrylate having a hydroxyl group;
Aliphatic (meth) acrylic acid esters such as alkylene oxide-added (meth) acrylic acid esters in which alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide are repeatedly added to the (meth) acrylate having a hydroxyl group can be mentioned. Be done.

Among these, the compound (A) has excellent adhesive strength at low temperatures, and thus contains 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate. 4-Hydroxybutyl acrylate is preferred, and 4-hydroxybutyl (meth) acrylate is preferred.

<Di (meth) acrylate monomer (B)>
The di (meth) acrylate monomer (B) (hereinafter, also referred to as compound (B)) is selected from the group consisting of the monomer represented by the following general formula (2) and the monomer represented by the following general formula (2) 1 More than a seed.

General formula (1)

However, in the formula, R1 and R2 are methyl groups or hydrogen, P1 and P3 are alkylene groups having 2 to 4 carbon atoms, P2 is an alkylene group having 5 to 10 carbon atoms, and n1, n2 and n3 are. It is an integer from 0 to 6.

General formula (2)

However, in the formula, R3 and R4 are methyl groups or hydrogens, P4 and P5 are alkylene groups having 2 to 4 carbon atoms, and n4 and n5 are integers of 0 to 6. However, n4 and n5 do not become 0 at the same time.

The method for synthesizing the monomer represented by the general formula (1) will be described by taking the following (1) and (2) as an example.
(1) A compound obtained by reacting an alkylene diol having a linear or side chain having 5 to 10 carbon atoms with a compound having a (meth) acrylate group. Here, the alkylene diol having a linear or side chain having 5 to 10 carbon atoms may be further reacted after preparing a reaction intermediate which has been reacted with an alkylene oxide group having 2 to 4 carbon atoms in advance. ..
(2) A compound obtained by reacting an alkylene diol having a linear or side chain having 5 to 10 carbon atoms with a (meth) acrylate compound having an alkylene oxide group having 2 to 4 carbon atoms.
(3) A hydroxycarboxylic acid having a linear or side chain having 5 to 10 carbon atoms is reacted with an alkylene diol having a linear or side chain having 5 to 10 carbon atoms and a compound having a (meth) acrylate group. Compound.

The method for synthesizing the monomer represented by the general formula (2) will be exemplified below.
A compound obtained by reacting a compound having an alkylene oxide unit having a linear or side chain having 2 to 4 carbon atoms repeatedly with a compound having a (meth) acrylate group.

The adhesive of the present invention contains the compound (B) to improve the adhesive strength at low temperatures.

The monomer represented by the general formula (1) is, for example, pentanediol di (meth) acrylate, 2,2-dimethylpropane-1,3-diol di (meth) acrylate, hexanediol di (meth) acrylate, heptanediol di ( A di (meth) acrylate monomer having no alkylene oxide group having 2 to 4 carbon atoms such as a meta) acrylate and a nonanediol di (meth) acrylate;
Ethylene oxide-modified pentandiol di (meth) acrylate, propylene oxide-modified pentandiol di (meth) acrylate, tetramethylene oxide-modified pentandiol di (meth) acrylate, ethylene oxide-modified 2,2-dimethylpropane-1,3-diol di ( Meta) acrylate, propylene oxide modified 2,2-dimethylpropane-1,3-diol di (meth) acrylate, tetramethylene oxide modified 2,2-dimethylpropane-1,3-diol di (meth) acrylate, hydroxypivalic acid modified 2 , 2-Dimethylpropane-1,3-diol di (meth) acrylate, ethylene oxide-modified hexanediol di (meth) acrylate, propylene oxide-modified hexanediol di (meth) acrylate, tetramethylene oxide-modified hexanediol di (meth) acrylate, Di (meth) acrylate monomers having an alkylene oxide group such as ethylene oxide-modified heptanediol di (meth) acrylate, propylene oxide-modified heptanediol di (meth) acrylate, and tetramethylene oxide-modified heptanediol di (meth) acrylate; Be done.

The monomer represented by the general formula (2) is, for example, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di ( Di (meth) acrylate monomer having one kind of alkylene glycol such as meta) acrylate and polytetramethylene glycol di (meth) acrylate;
Tylene glycol-propylene glycol di (meth) acrylate, diethylene glycol-propylene glycol di (meth) acrylate, diethylene glycol-dipropylene glycol di (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) di (meth) acrylate; etc. 2 Examples thereof include di (meth) acrylate monomers having more than one kind of alkylene oxide.

Among these, compound (B) has hexanediol di (meth) acrylate (R1 and R2 in the general formula (1) are -CH ₃ or hydrogen, P, from the aspect of improving adhesive strength at low temperature.
2 is -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH _2- , and n1, n2 and n3 are 0 compounds), ethylene oxide 2 mol-modified hexanediol di (meth) acrylate (general formula (general formula ()). In 1), R1 and R2 are -CH ₃ or hydrogen, P1 and P3 are -CH ₂ -CH _2- , P2 is -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH _2- , and n1. , N3
Is 1 and n2 is 0), propylene oxide 2 mol-modified 2,2-dimethylpropane-1,3-diol di (meth) acrylate (R1 and R2 in the general formula (1) are -CH3 or hydrogen, P1 and P3 is the structure represented by the general formula (5) or the structure represented by the general formula (6), P2 is the structure represented by the general formula (7), and n1, n3 is 1 and n2 is 0). Dipropylene glycol di (meth) acrylate (R3 and R4 in the general formula (2) are -CH3 or hydrogen, P4 and P5 are the structure represented by the general formula (5) or the structure represented by the general formula (6). n4 and n5 are 1 compounds), and tripropylene glycol di (meth) acrylate (R3 and R4 in the general formula (2) are -CH3 or hydrogen, P4 and P5 are the structures represented by the general formula (5) or the above. The structure represented by the general formula (6), a compound in which n4 is 2 and n5 is 1,) is preferable.

General formula (5)

General formula (6)

General formula (7)

<Tri or tetra (meth) acrylate monomer (C)>
The tri or tetra (meth) acrylate monomer (C) (hereinafter, also referred to as compound (C)) is a monomer selected from the group consisting of the monomer represented by the general formula (3) and the monomer represented by the general formula (4). Is.

General formula (3)

However, in the formula, R5, R6 and R7 are methyl groups or hydrogens, R8 is a methyl group, a hydroxyl group and an acryloyloxy group, and P6, P7 and P8 are alkylene groups having 2 to 4 carbon atoms and n6. n7 and n8 are integers of 0 to 6.

General formula (4)

However, in the formula, R9, R10, R11 and R12 are methyl groups or hydrogens, and R13 and R14 are methyl groups, hydroxyl groups and acryloyloxy groups, and P9, P10, P11 and P1.
Reference numeral 2 is an alkylene group having 2 to 4 carbon atoms, and n9, n10, n11, and n12 are integers of 0 to 6.

The adhesive of the present invention contains the compound (C) to improve the adhesive strength at low temperatures.

The monomer represented by the general formula (3) is, for example, trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, or tetramethylene oxide-modified. Examples thereof include trimethylolpropane tri (meth) acrylate, tri (meth) acrylate such as pentaerythritol triacrylate, and the like.

The monomer represented by the general formula (4) is, for example, ditrimethylolpropane tetra (meth) acrylate, ethylene oxide-modified dimethylolpropanetetra (meth) acrylate, prolenoxide-modified dimethylolpropanetetra (meth) acrylate, or tetramethylene oxide. Examples thereof include modified dimethylolpropane tetra (meth) acrylate, pentaerythritol tetraacrylate, ethylene oxide 5 mol modified pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.

Among these, the compound (C) has trimethylolpropane tri (meth) acrylate (where R5, R6 and R7 in the general formula (3) are -CH3 or hydrogen, n6, n7 and N8 is 0), ethylene oxide 3 mol-modified trimethylolpropane tri (meth) acrylate (R5, R6 and R7 in the general formula (3) are -CH ₃ or hydrogen, P6, P7 and P8 are -CH ₂ -CH ₂ -, N6, n7
And n8 is 1), propylene oxide 3 mol-modified trimethylolpropane tri (meth) acrylate (R5, R6 and R7 in the general formula (3) are -CH ₃ or hydrogen, P6, P7 and P8 are the above general formula (5). ) Or the structure represented by the general formula (6), a compound in which n6, n7 and n8 are 1), and ditrimethylolpropane tetra (meth) acrylate (R9, R10, R11 and in the general formula (4). R
12 is -CH3 or a compound in which hydrogen, n9, n10, n11 and n12 are 0).

The adhesive of the present invention contains 10 to 80% by mass of compound (A) and 10 to 50% by mass of compound (B) in a total of 100% by mass of compound (A), compound (B) and compound (C). , The compound (C) is preferably contained in an amount of 10 to 50% by mass. When the compounds (A), (B) and (C) are contained in an appropriate amount, the adhesive strength at room temperature (23 ° C.) and the adhesive strength at low temperature are further improved. It is more preferable that the compound (A) is contained in an amount of 20 to 60% by mass, the compound (B) is contained in an amount of 20 to 40% by mass, and the compound (C) is contained in an amount of 20 to 40% by mass.

<Cation-polymerizable compound (D)>
The adhesive of the present invention preferably further contains a cationically polymerizable compound (D) (hereinafter, also referred to as compound (D)). As a result, the curing shrinkage of the resin layer due to light irradiation can be suppressed, so that the room temperature adhesive force and the low temperature adhesive force are further improved.

The compound (D) is preferably a compound having an epoxy group which is a 3-membered ring ether, a compound having an oxetanyl group which is a 4-membered ring ether, a vinyl ether compound, a cyclic carbonate compound and the like. Since the compound (D) does not have a (meth) acryloyl group, it is a compound different from the compounds (A), (B) and (C).

Examples of the compound having an epoxy group (epoxy compound) include an aromatic epoxy compound, an aliphatic epoxy compound, an alicyclic epoxy compound, and an epoxy group-containing silane coupling agent.

The aromatic epoxy compounds include, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, bisphenol A propylene oxide adduct diglycidyl ether, and phenol-novolac epoxy. , Cresol novolak epoxy, biphenyl type epoxy, resorcindiglycidyl ether, phenylglycidyl ether, phenolethylene oxide glycidyl ether, t-butylphenyl glycidyl ether and the like.

The aliphatic epoxy compound is preferably an aliphatic monoalcohol, an aliphatic polyalcohol, and a glycidyl ether as an alkylene oxide adduct thereof.
The aliphatic epoxy compound is, for example, allyl glycidyl ether, 2-ethyl-hexyl glycidyl ether, 1,4-butanjiol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl. One for aliphatic polyhydric alcohols such as ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, ethylene glycol, polypropylene glycol, and glycerin. Alternatively, polyglycidyl ether of polyether polyole obtained by adding two or more kinds of alkylene oxides (ethylene oxide or polypropylene oxide) can be mentioned.

The alicyclic epoxy compound is, for example, 1,2-epoxy-4-vinylcyclohexane, 1,2: 8,9 diepoxylimonene, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2-. (3,4-Epoxy Cyclohexyl-5,5-Spiro-3,4-Epoxy) Cyclohexane-meth-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6- Methylcyclohexylmethyl) adipate and the like can be mentioned.

Examples of the epoxy group-containing silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropylmethyldiethoxy. Examples thereof include silane, 2- (3,4-epoxycyclohexyl) ethyl-trimethoxysilane, 5,6-epoxyhexyltrimethoxysilane, 5,6-epoxyhexyltriethoxysilane and the like.

The epoxy compound has an epoxy equivalent of about 30 to 3000 g / eq, preferably 50 to 1500 g / eq. When the epoxy equivalent is 30 g / eq or more, the flexibility and adhesive strength of the resin layer are further improved. Further, when the content is 3000 g / eq or less, the curability and the adhesive strength are further improved.

Compounds having an oxetanyl group include, for example, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, and di (1-ethyl-3-oxetanyl) methyl. Ether, 3-Ethyl-3- (Phenoxymethyl) Oxetane, 3-Ethyl-3- (2-Ethyl-Hexyloxymethyl) Oxetane, Phenol-Lnovolac Oxetane, 3-Ethyl-{(3-Triethoxysilylpropoxy) Methyl} oxetane and the like can be mentioned.

The vinyl ether compound has 5 to 20 carbon atoms such as n-amyl vinyl ether, i-amyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, 2-ethyl-hexyl vinyl ether, n-dodecyl vinyl ether, stearyl vinyl ether and oleyl vinyl ether. Alcohol and alkenyl alcohol vinyl ethers;
Monoalcoholic vinyl ether having an aliphatic ring or aromatic ring such as cyclohexyl vinyl ether, 2-methylcyclohexylvinyl ether, cyclohexylmethylvinyl ether, benzylvinyl ether;
Glycerol monovinyl ether, 1,4-butanjiol monovinyl ether, 1,4-butanjiol divinyl ether, 1,6-hexanedio-ludivinyl ether, neopentyl glycol divinyl ether, pentaerythritol-ludivinyl ether, pentaerythritol Tetravinyl ether, trimethylolpropane divinyl ether, trimethylolpropane trivinyl ether, 1,4-dihydroxycyclohexanemonovinyl ether, 1,4-dihydroxycyclohexanedivinyl ether, 1,4-dihydroxymethylcyclohexanemonovinyl ether, 1,4-dihydroxy Monovinyl ethers and polyvinyl ethers of polyhydric alcohols such as methylcyclohexanedivinyl ethers; polyalkylene glycol monodivinyl ethers and divinyl ethers such as triethylene glycol divinyl ethers and diethylene glycol monobutyl monovinyl ethers; other such as glycidyl vinyl ethers and ethylene glycol vinyl ether methacrylates. Vinyl ether can be mentioned.

Examples of the cyclic carbonate compound include ethylene carbonate and propylene carbonate.

As the compound (D), an epoxy compound is preferable in terms of excellent room temperature adhesive strength and low temperature adhesive strength, and an aliphatic epoxy compound and an epoxy group-containing silane coupling agent are more preferable.
Specifically, neopentyl glycol diglycidyl ether, 1,6-hexanedio-l diglycidyl ether, trimethylolpropane triglycidyl ether, and 3-glycidoxypropyltriethoxysilane are particularly preferable.

The compound (D) preferably contains 0.1 to 30% by mass in 100% by mass of the adhesive, and more preferably 1 to 25% by mass. When the compound (D) is contained in an appropriate amount, the room temperature adhesive force and the low temperature adhesive force are further improved.

The adhesive of the present invention further comprises a polyurethane-based (meth) acrylate oligomer (E1) (hereinafter, also referred to as compound (E1)) and a polyester-based (meth) acrylate oligomer (E2) (hereinafter, also referred to as compound (E2)). , It is preferable to contain one or more oligomers (E) selected from the group consisting of epoxy-based (meth) acrylate oligomers (E3) (hereinafter, also referred to as compound (E3)). This further improves the room temperature adhesive force and the low temperature adhesive force. The compound (E1), the compound (E2) and the compound (E3) are compounds other than the monomer (A), the monomer (B) and the monomer (C).

The weight average molecular weight of (E) is preferably 500 to 100,000. The weight average molecular weight in the present specification is a value measured by gel permeation chromatography (GPC) using polystyrene having a known weight average molecular weight as a standard substance.

<Polyurethane-based (meth) acrylate oligomer (E1)>
Compound (E1) is a compound having a urethane bond and a (meth) acryloyl group in the molecule. The compound (E1) is obtained, for example, by reacting a compound having an isocyanate group at the terminal obtained by reacting a compound having two or more isocyanate groups with a compound having a hydroxyl group with a (meth) acryloyl group having a hydroxyl group. be able to. Alternatively, it can be obtained by reacting a compound having a hydroxyl group with a compound having an isocyanate group and a (meth) acrylate group.

Compounds having at least one isocyanate group include, for example, aromatic isocyanates such as 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 1,4-phenylene bismethylene diisocyanate, and 3-isocyanate methyl-. Examples thereof include aliphatic isocyanates such as 3,5,5-trimethylcyclohexyl isocyanate and hexamethylene diisocyanate.

The compound (E1) is an aromatic polyurethane-based oligomer such as EBECRYL210, EBECRYL220 (above, manufactured by Daicel Ornex), CN9782, CN9783 (above, manufactured by SARTOMER), purple light 3000B, purple light 3700B (or more, manufactured by Daicel Ornex). Examples thereof include aliphatic polyurethane oligomers such as (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), EBECRYL230, EBECRYL270, EBECRYL8402, and EBECRYL8701 (all manufactured by Daicel Ornex).

<Polyester-based (meth) acrylate oligomer (E2)>
Compound (E2) is a compound having an ester bond and a (meth) acryloyl group in the molecule. The compound (E2) is esterified with, for example, a hydroxyl group of a polyester synthesized by polycondensing a polybasic acid and a polyhydric alcohol with a (meth) acrylate having a carboxyl group (for example, (meth) acrylic acid). It is a compound synthesized by the reaction.

The polybasic acid is an aliphatic polybase such as oxalic acid, malonic acid, succinic acid, adipic acid, sebatic acid, azelaic acid, suberic acid, maleic acid, fumaric acid, itaconic acid, succinic acid anhydride and maleic anhydride. Examples thereof include alicyclic systems such as acids, dimer acids and cyclohexanedicarboxylic acids, and aromatic systems such as isophthalic acid, terephthalic acid and biphenyldicarboxylic acid.

The polyhydric alcohol is, for example, polyethylene glycol, propylene glycol or the like, a polyol having a number average molecular weight (Mn) of 50 to 500, a polyol having a number average molecular weight (Mn) of 500 to 30,000, and trimethylolpropane, glycerin, pentaerythritol. And so on.

The compound (E2) is an aromatic polyester-based oligomer such as CN296, CN2203, CN2259, CN2261 (above, manufactured by SARTOMER), and an aliphatic such as CN294, CN2270, CN2271 (above, manufactured by SARTOMER). Examples thereof include polyester-based oligomers.

<Epoxy-based (meth) acrylate oligomer (E3)>
The compound (E3) is a compound having a (meth) accriloyl group obtained by reacting an epoxy group of a compound having an epoxy group with a compound having a carboxyl group and / or a hydroxyl group.
The compound (E3) may have an epoxy group, but is preferably a compound in which all of the epoxy groups are reacted with a carboxyl group or a hydroxyl group to be consumed.

As the epoxy compound, the epoxy compound described in the compound (D) can be used.

The compound (E3) is an aromatic epoxy oligomer such as CN104, CN110 (above, manufactured by SARTOMER), EBECRYL600, EBECRYL3701 (above, manufactured by Daicel Ornex), CN111, CN113 (above, SARTOMER) in terms of trade names. EBECRYL860 (manufactured by Daicel Ornex) and the like, and examples thereof include aliphatic epoxy-based oligomers.

The compounding amount of the compound (E1), the compound (E2) and the compound (E3) is about 1 to 30% by mass in total of the compound (E1), the compound (E2) and the compound (E3) in 100% by mass of the adhesive. Is preferable, and 3 to 20% by mass is more preferable.

The adhesive of the present invention may further contain other (meth) acrylate compound (F) (hereinafter, also referred to as compound (E)).

By containing the compound (F), the viscosity of the adhesive can be lowered to improve the coatability, and the durability such as wet and heat resistance can be further improved. The compound (F) is a (meth) acrylate monomer other than the compound (A), the compound (B), the compound (C), the compound (E1), the compound (E2) and the compound (E3).

The compound (F) is, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, n-hexyl (meth) acrylate, lauryl (meth) acrylate, and (meth). (Meta) acrylic acid alkyl esters such as stearyl acrylate;

(Meta) Acrylic acid perfluoroalkyl esters such as (meth) acrylic acid perfluoromethyl, (meth) acrylic acid 2-perfluoroethyl-ethyl, and (meth) acrylic acid 2-perfluorohexadecylethyl-;
(Meta) Acrylic Acid (methoxycarbonyl) Methyl, (Meta) Acrylic Acid 2- (ethoxycarbonyloxy) Hexyl, (Meta) Acrylic Acid 2- (Propoxycarbonyloxy) Ethyl-, and (Meta) Acrylic Acid 2- (Octyl) Oxycarbonyloxy) An aliphatic (meth) acrylic acid ester having one carbonyl group such as butyl;
2-oxobutanoylethyl (meth) acrylate, 3-oxobutanoylpropyl (meth) acrylate, 2,3-di (oxobutanoyl) butyl (meth) acrylate, 2,3- (meth) acrylate An aliphatic (meth) acrylic acid ester having two carbonyl groups such as di (oxobutanoyl) hexyl;

2-Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 3-propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, An alkoxy group-containing (meth) acrylic acid ester such as 3-butoxyethyl (meth) acrylic acid and 4-butoxyethyl (meth) acrylic acid;
An alkylene oxide-containing (meth) acrylic acid derivative such as an alkylene oxide adduct of (meth) acrylic acid;

3,3-Dicyclopropyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl- (meth) acrylate, dicyclopentanyl (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate , Tricyclodecanedimethanol di (meth) acrylate, isobonyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl ( Meta) acrylate, 2-propyl-2-adamantyl (meth) acrylate, 3,5-dihydroxy-1-adamantyl (meth) acrylate, 1,3-adamantyldiol di (meth) acrylate, 1,3,5-adamantiltli A (meth) acrylate compound having an aliphatic hydrocarbon ring of a fused ring such as (meth) acrylate and 3-hydroxy-1,5-adamantyldi (meth) acrylate;

For example, it contains hydroxyl groups such as N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide, N-hydroxyhexyl (meth) acrylamide, and N-hydroxyoctyl (meth) acrylamide. (Meta) acrylamide;

Bifunctional (meth) acrylic acid esters such as di (meth) acrylic acid bisphenol A, di (meth) acrylic acid ethylene oxide-modified bisphenol A, di (meth) acrylic acid tricyclodecanedimethanol;
Trimethylol hexane, tri (meth) acrylate, trimethylol octane, tri (meth) acrylate, 1,1,1-trishydroxymethylethane, tri (meth) acrylate, ethylene oxide-modified isocyanuric acid, tri (meth) acrylate, etc. Trifunctional (meth) acrylic acid ester;

A (meth) acrylate compound having a cationically polymerizable functional group such as glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate;
Examples thereof include (meth) acrylate compounds having a heterocycle containing one heteroatom such as tetrahydrofurfuryl (meth) acrylate.

The active energy ray-polymerizable adhesive may contain an active energy ray polymerization initiator (G) (hereinafter, also referred to as 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. Examples of commercially available products include Irgacure-184, 907, 651, 1700, 1800, 819, 369, 261, DAROCUR-TPO (above, manufactured by BASF), DaroCure-1173 (manufactured by Merck), Ezacure-KIP150, TZT (manufactured by Nippon Kayaku Co., Ltd.), Kayacure BMS, Kayacure DMBI, (all manufactured by Nippon Kayaku Co., Ltd.) and the like can be mentioned.

As the active energy ray cationic polymerization initiator (g2), a known active energy ray cationic polymerization initiator can be used. Examples of commercially available products include sulfonium salts such as UVACURE1590 (manufactured by Daicel Cytec) and CPI-110P (manufactured by San-Apro), IRGACURE250 (manufactured by BASF), WPI-113 (manufactured by Wako Pure Chemical Industries, Ltd.), and Rp. Examples thereof include iodonium salts such as 2074 (manufactured by Rhodia Japan).

As the active energy ray anionic polymerization initiator (g3), a known active energy ray anionic polymerization initiator can be used. Examples of commercially available products include WPBG-165, WPBG-018, WPBG-172, WPBG-140, WPBG-166, WPBG-027, WPBG-082, WPBG-167, WPBG-168, WPBG-266 (or more, Wako Pure Chemical Industries, Ltd.) and the like.

The compound (G) preferably contains 0.1 to 10% by mass, more preferably 0.5 to 5% by mass in 100% by mass of the adhesive.

The adhesive of the present invention may contain at least one of boric acid and boric acid derivatives in an amount of 0.1 to 20% by mass. When the base material has a hydroxyl group by containing at least one of boric acid and a boric acid derivative, a chemical bond is formed with the hydroxyl group to improve the adhesive strength.

In the present invention, the boric acid derivative is, for example, a compound having one or more B—O—H bonds in one molecule other than boric acid, hydrolyzed in the presence of water to form one or more BOH bonds. The resulting boron-containing compound is preferred.
Boric acid derivatives are boric acid oxides (eg, B ₂ O ₃ );
Derivatives obtained by reaction of boric acid with alcohol or phenol, such as trimethyl borate, triethyl borate, tri-n-propyl borate, tri-n-butyl borate, triphenyl borate, triisopropyl borate. , Tri-t-amyl borate, triphenyl borate, trimethoxyboroxin, tri-2-cyclohexylcyclohexylborate, triethanolamine borate, triisopropylamine borate, mannitol borate, glycerol borate, and borate Examples thereof include boric acid esters such as acid triisopropanolamine.
Boronic acid derivatives include derivatives of boronic acid, eg, alkyl or alkenylboronic acids such as methylboronic acid, ethyl-boronic acid, butylboronic acid, and cyclohexylboronic acid;
Examples thereof include arylboronic acids such as phenylboronic acid, naphthaleneboronic acid, and anthracemboronic acid, or substituted arylboronic acids having arbitrary substituents on these aryl groups.

In addition, examples of boric acid derivatives include oligomers and polymers containing a boron-containing moiety. For example, a boric acid ester compound obtained by reacting boric acid with an active energy ray-polymerizable compound having a hydroxyl group can be mentioned.

The active energy ray-polymerizable adhesive of the present invention further comprises a photosensitizer, an amine-based catalyst, a phosphorus-based catalyst, a filler, an antioxidant, an antioxidant, an antioxidant, an antioxidant, a tackifier, and an anti. It can contain a blocking agent, a defoaming agent, a plasticizer, a silane coupling agent, a titanium coupling agent and the like.

The adhesive of the present invention preferably contains substantially no organic solvent, and preferably does not contain any organic solvent. The adhesive is particularly preferably free of toluene. However, since the compound (G) is difficult to dissolve in a monomer or an oligomer, a small amount of an organic solvent may be contained in order to dissolve the compound (G). The content of the organic solvent in the adhesive is 5% by mass or less.

From the viewpoint of controlling the dimensional stability of the resin, the adhesive of the present invention preferably has a viscosity at 25 ° C. of 1 to 2000 mPa · s, more preferably 10 to 1500 mPa · s, and 20 to 1000 mPa · s. Is even more preferable. The viscosity is a value measured at 10 rotations / minute with a 1 ° 34'× R24 rotor using an E-type cone rotor viscometer, and is a value 1 minute after the start of rotation.

The laminate of the present invention comprises a first base material, a resin layer which is a cured product of an active energy ray-polymerizable adhesive, and a second base material.

To form the resin layer, the second base material is bonded onto the resin layer formed by coating on the first base material. Irradiation of the active energy ray is performed at an arbitrary timing. For example, the active energy rays can be irradiated at the time of applying the adhesive, at the time of laminating, and further after laminating. Among these, it is preferable to irradiate the active energy ray after laminating the second base material to cure. Therefore, it is preferable that at least one of the first base material and the second base material does not inhibit the curing reaction by the active energy ray.

As the first base material and the second base material, it is preferable to use a film-like base material. Examples of the film-like substrate include cellophane, various plastic films, and paper. Above all, it is preferable to use various transparent plastic films. Further, the film-like substrate may have a single layer or a multilayer structure in which a plurality of substrates are laminated, as long as the film is transparent.

The transparent film is a polyolefin-based film such as a polyvinyl alcohol film, a polytriacetyl cellulose film, polypropylene, polyethylene, a polycycloolefin, and an ethylene-vinyl acetate copolymer; a polyester-based film such as polyethylene terephthalate and polybutylene terephthalate; polycarbonate. Examples thereof include a based film, a polynorbornene film, a polyarylate film, a polyacrylic film, a polyphenylene sulfide film, a polystyrene film, a polyvinyl film, a polyamide film, a polyimide film, and a polyoxylan film.
As for the composition of the resin layer, for example, if a transparent film or a transparent glass plate is used for the first base material, a base material in which active energy rays are difficult to pass through as the second base material, for example, wood, a metal plate, a plastic plate, etc. A processed paper product or the like may be used.

The thickness of the substrate is usually 5 to 50,000 μm.

For coating, a known coating device can be used. For example, minor bar, appliqué, brush, spray, roller, gravure coater, die coater, micro gravure coater, lip coater, comma coater, Examples thereof include a cartridge coater, a knife coater, a river coater, and a spin coater.

The active energy ray preferably has a wavelength or light including ultraviolet rays, and more preferably 150 to 550 nm. Examples of the light source of the active energy ray include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, a black light lamp, a microwave excited mercury lamp, an LED lamp, a xenon lamp, and a metal halide lamp. ..

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

The thickness of the resin layer is preferably 0.1 to 6 μm, more preferably 0.1 to 3 μm. When the thickness of the resin layer is within the above range, the adhesive strength is further improved.

Examples of the embodiment of the laminated body include a sheet shape obtained by laminating a plurality of transparent films such as a transparent film / adhesive layer / transparent film or a transparent film / adhesive layer / transparent film / adhesive layer / transparent film. Multilayer film is preferred. In another embodiment, a sheet-like multilayer film such as a transparent film / adhesive layer / transparent film / adhesive layer / transparent film / adhesive layer / transparent film is bonded to another optical member such as glass or an optical sheet. The configuration is also preferable. In these laminates, the active energy ray-polymerizable adhesive cures the adhesive layer that irradiates the active energy ray from one side or both sides of the base material.

Further, the laminate of the present invention is preferably used for optical purposes, and more preferably used as a polarizing plate.

The optical application is an application used for a liquid crystal display device, a PDP module, a touch panel module, an organic EL module, and the like. An optical laminate is used for this purpose. The optical laminate uses an optical film on at least one of a first substrate and a second substrate. The optical film may be, for example, a hard coat film, an antistatic coat film, an antiglare coat film, a polarizing film, a retardation film, an elliptical polarizing film, an antireflection film, a light diffusing film, a brightness improving film, or a prism film (prism film). -Also referred to as a light film), a decorative film (meaning a filling sheet for a touch panel), a light guide film (also referred to as a light guide plate), and the like.

In the polarizing plate, the first base material is a polarizing element, and a protective film is used as the second base material. Further, the polarizing plate may be provided with a third substrate via a resin layer on the opposite surface of the first substrate on the second substrate side. A protective film is used as the third substrate.

As the splitter, a polyvinyl alcohol film or the like is usually used. The thickness of the stator is usually about 2 to 200 μm.

The protective film is, for example, a polytriacetyl cellulose-based protective film (hereinafter referred to as “TAC film”) which is a polyacetyl cellulose-based film, a polycycloolefin-based film which is a polynorbornene-based film, a polyacrylic film, a polycarbonate-based film, and the like. Examples include polyester films.
The thickness of the protective film is usually about 5 to 200 μm.

An example of a method for manufacturing a polarizing plate will be described below.

(1) An active energy ray-polymerizable adhesive is applied to one surface of a protective film, which is a first transparent film, to form a first resin layer, and one of the protective films, which is a second transparent film. An active energy ray-polymerizable adhesive is applied to the surface of the film to form a second resin layer.

Next, each surface of the polyvinyl alcohol-based polarizing element is superposed on the first resin layer and the second resin layer surface simultaneously or in order, and then irradiated with active energy rays to irradiate the first resin layer and the second resin layer surface. A method for producing by polymerizing and curing the resin layer of 2.

(2) An active energy ray-polymerizable adhesive is applied to one surface of a polyvinyl alcohol-based polarizing element to form a first resin layer, and the surface of the formed first resin layer is a transparent film. A second resin layer formed by covering with a first protective film and then applying an active energy ray hard polymerizable adhesive to the other surface of the polyvinyl alcohol-based polarizing element to form a second resin layer. A method of producing by covering the surface of the resin with a second protective film, irradiating the surface with active energy rays, and polymerizing and curing the first resin layer and the second resin layer.

(3) The end portion where the protective film which is the first transparent film and the polyvinyl alcohol-based polarizing element are overlapped, and the end portion of the second protective film which is laminated on the surface of the polyvinyl alcohol-based polarizing element where the first protective film is not present. After the active energy ray-polymerizable adhesive is applied to the film, it is passed between the rolls and the adhesive is spread between the layers. Next, there is a method of producing by irradiating with active energy rays and polymerizing and curing the active energy ray-polymerizable adhesive, but the present invention is not particularly limited.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. In addition, "part" is "part by weight", and "%" represents "% by weight". The blending amount in the table is a part by weight.

[Production example of polyvinyl alcohol-based polarizing element]
A staining solution was prepared by dissolving 20 parts by weight of boric acid, 0.2 parts by weight of iodine, and 0.5 part by weight of potassium iodide in 480 parts by weight of water. A PVA film (Vinylon film # 40, manufactured by Aicello Corporation) was immersed in this dyeing solution for 30 seconds, and then the film was stretched twice in one direction and dried to obtain a PVA splitter having a thickness of 30 μm.

[Example 1]
<Production example of active energy ray-polymerizable adhesive>
In a light-shielded glass bottle with a capacity of 300 mL, 50 parts of 4-hydroxybutyl acrylate as compound (A), 20 parts of 1,6-hexanediol diacrylate (trade name Miramer M200 manufactured by MIWON) as compound (B), and compound (C). ), 28 parts of trimethylolpropane triacrylate (trade name Miramer M300 manufactured by MIWON) and 2 parts of Irgacure 184 (photoradical polymerization initiator manufactured by BASF) are added, and the mixture is sufficiently stirred and defoamed to be active energy ray-polymerizable. Obtained an adhesive.

[Examples 2 to 26, Comparative Examples 1 to 6]
Examples 2 to 26 and Comparative Examples 1 to 6, respectively, were subjected to the same procedure as in Example 1 except that the raw materials of Example 1 and the blending amounts thereof were changed as shown in Tables 1 to 4. An active energy ray-polymerizable adhesive was obtained.
However, Examples 28, 29, 31, and 32 are reference examples.

The following laminates A and B were prepared using the active energy ray-polymerizable adhesives obtained in Examples 1 to 26 and Comparative Examples 1 to 6, respectively.

<Manufacturing example of laminated body A>
As the transparent film, an acrylic film HBD-022 manufactured by Mitsubishi Rayon Corporation and a polynorbornene-based film (thickness 100 μm) manufactured by Nippon Zeon Corporation containing no ultraviolet absorber were used. The surface of one side of the two transparent films was subjected to corona treatment at a discharge rate of 300 W / min / m ² . Within 1 hour thereafter, the above-mentioned active energy ray-polymerizable adhesive was applied onto the corona-treated surface of the acrylic film HBD-022 using a wire bar coater so as to have a thickness of 4 μm. A resin layer was formed. Further, a polynorbornene-based film containing no ultraviolet absorber was layered, and the acrylic film was fixed to the tin plate with cellophane tape on all sides so that the acrylic film was in contact with the tin plate.

Maximum illuminance of 500 mW / cm ² with an active energy ray irradiation device (high-pressure mercury lamp manufactured by Toshiba),
A laminated body A was prepared by irradiating ultraviolet rays having an integrated light intensity of 500 mJ / cm ² from the side of a polynorbornene-based film manufactured by Zeon Corporation that does not contain an ultraviolet absorber.

<Manufacturing example of laminated body B (polarizing plate)>
As the first transparent film, a polytriacetyl cellulose-based film containing an ultraviolet absorber manufactured by Fuji Film Co., Ltd .: trade name "Fujitac: 80 μm" (thickness 80 μm) is used, and as the second transparent film, ultraviolet rays manufactured by Nippon Zeon Co., Ltd. are used. A polynorbornne-based film (thickness 100 μm) containing no absorbent was used. The surface of one side of the first and second transparent films is corona-treated with a discharge amount of 300 W · min / m ² , and within 1 hour thereafter, the active energy ray-polymerizable adhesive is applied onto the corona-treated surface of each film. Was coated with a wire bar coater so as to have a thickness of 4 μm to form a resin layer. A polyvinyl alcohol-based polarizing element is sandwiched between the resin layers formed on the first and second transparent films, and the laminate is composed of the first transparent film / resin layer / PVA-based polarizing element / resin layer / second transparent film. I got a body. The four sides of this laminated body were fixed with cellophane tape so that the first transparent film was in contact with the tin plate, and fixed to the tin plate.

Maximum illuminance of 500 mW / cm ² with an active energy ray irradiation device (high-pressure mercury lamp manufactured by Toshiba),
^The laminated body B (
Polarizer) was created.

The obtained laminated bodies A and B were evaluated for curved surface room temperature adhesive strength, curved surface high temperature adhesive strength, and curved surface low temperature adhesive strength. The results are shown in Tables 1 to 4.

《Curved surface room temperature adhesive strength》
The obtained laminates A and B were wound around a metal cylinder having a diameter of 8 cm, and the ends of the laminates were fixed with commercially available cellophane tape and stored at 23 ° C. and a relative humidity of 50% RH for 1 month. After that, the laminate was peeled off from the metal cylinder, and the adhesive strength was measured.
Adhesive strength was measured according to Japanese Industrial Standards (JIS) K6854-4 Adhesive-Peeling Adhesive Strength Test Method-Part 4: Floating Roller Method. That is, the obtained laminate was cut into a size of 25 mm × 150 mm using a cutter to obtain a measurement sample. A double-sided adhesive tape (DF8712S manufactured by Toyokem Co., Ltd.) was attached to the polynorbornene film surface of the measurement sample and fixed on a metal plate using a laminator. The laminating body for measurement is provided with a peeling kick in advance between the transparent films, and the laminating body for measurement is placed at a speed of 300 mm / min and 90 ° under the conditions of 23 ° C. and a relative humidity of 50%. The adhesive force was measured at the angle of. As for the adhesive strength, the acrylic film HBD-022 was peeled off in the case of the laminated body A, and the first transparent film / resin layer / PVA-based polarizing element was peeled off in the case of the laminated body B, and the adhesive strength was measured. This adhesive strength was evaluated on a 4-point scale. If the evaluation criteria are ⊚, ◯, and Δ, there is no problem in practical use.
◎: Cannot be peeled off or destroys the base material (extremely good)
◯: Peeling force is 2.0 (N / 25 mm) or more (good)
Δ: Peeling force is 1.0 (N / 25 mm) or more and less than 2.0 (N / 25 mm) (usable)
×: Peeling force is less than 1.0 (N / 25 mm) (cannot be used)

《Curved surface high temperature adhesive strength》
The adhesive strength was measured in the same manner as the curved surface room temperature adhesive force, except that the storage condition of the laminate fixed to the metal cylinder in the curved surface room temperature adhesive force was changed from 23 ° C. to 80 ° C. This adhesive strength was evaluated on a 4-point scale. If the evaluation is ◎, ○, △, there is no problem in practical use.
⊚: Peeling force is 1.5 (N / 25 mm) or more (extremely good)
◯: Peeling force is 1.0 (N / 25 mm) or more and less than 1.5 (N / 25 mm) (good)
Δ: Peeling force is 0.5 (N / 25 mm) or more and less than 1.0 (N / 25 mm) (usable)
×: Peeling force is less than 0.5 (N / 25 mm) (cannot be used)

《Curved surface low temperature adhesive strength》
The adhesive strength was measured in the same manner as the curved surface room temperature adhesive strength, except that the storage condition of the laminate fixed to the metal cylinder in the curved surface room temperature adhesive strength was changed from 23 ° C. to −30 ° C. This adhesive strength was evaluated on a 4-point scale. If the evaluation is ◎, ○, △, there is no problem in practical use.
◎: Cannot be peeled off or destroys the base material (extremely good)
◯: Peeling force is 1.0 (N / 25 mm) or more (good)
Δ: Peeling force is 0.5 (N / 25 mm) or more and less than 1.0 (N / 25 mm) (usable)
×: Peeling force is less than 0.5 (N / 25 mm) (cannot be used)

Hereinafter, the materials used in the examples and their abbreviations are shown.
<Compound (B)>
Ethyleneoxide 2 mol-modified 1,6-hexanediol diacrylate (Mir Omar M202 manufactured by MIWON, R1 and R2 in the general formula (1) are hydrogen, P1 and P3 are -CH ₂ -CH _2- , P2 is -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -C
Compounds with H _2- , n1 and n3 of 1)
Propylene oxide 2 mol-modified neopentyldiol diacrylate (Mir Omar M216 manufactured by MIWON, R1 and R2 in the general formula (1) are hydrogen, P1 and P3 are the structures represented by the general formula (5) or the general formula (6). ), P2 is the structure represented by the general formula (7), and n1 and n3 are 1 compounds).
Dipropylene glycol diacrylate (Mir Omar M222 manufactured by MIWON, R3 and R4 in the general formula (2) are hydrogen, and P4 and P5 are the general formula (5).
(Structure represented by the above formula or the structure represented by the general formula (6), a compound in which n4 and n5 are 1) 1,6-hexanediol dimethacrylate (Mir Omar M201 manufactured by MIWON, R1 and R2 in the general formula (1) Is -CH ₃ , P2 is -CH ₂ -CH ₂ -C
H ₂ -CH ₂ -CH ₂ -CH _2- , compound in which n1 and n3 are 0)
Polyethylene Glycol 200 Diacrylate (MIWON Product Item Mir Omar
M282 (R3 and R4 in the general formula (2) are hydrogen, P4 is -CH ₂ -CH _2- , and n4 = 4, n5 = 0 compound))

<Compound (C)>
Trimethylolpropane triacrylate (MIWON product Mir omer)
M300, a compound in which R5, R6 and R7 in the general formula (3) are hydrogen, and n6, n7 and n8 are 0).
Ethylene oxide 3 mol-modified trimethylolpropane triacrylate (MIWON product Miromer M3130, R5, R6 and R7 in the general formula (3) are hydrogen, P6, P7 and P8 are _{-CH2 -} CH2-, n6, n7 and Compound with n8 of 1)
Propylene oxide 3 mol-modified trimethylolpropane triacrylate (Mir Omar M360 manufactured by MIWON, R5, R6 and R7 in the general formula (3) are hydrogen, P6, P7 and P8 are the structures represented by the general formula (5) or the above. Structure represented by the general formula (6), a compound in which n6, n7 and n8 are 1)
Ditrimethylolpropane tetraacrylate (Mir Omar M410, manufactured by MIWON, a compound in which R9, R10, R11, and R12 in the general formula (4) are hydrogen, and n9, n10, n11, and n12 are 0).
Trimethylolpropane Trimethacrylate (MIWON product Mir omer)
M301, a compound in which R5, R6 and R7 in the general formula (3) are -CH ₃ , n6, n7 and n8 are 0)
Ethylene oxide 9 mol-modified trimethylolpropane triacrylate (MIWON product Miromer M3190, R5, R6 and R7 in the general formula (3) are hydrogen, P6, P7 and P8 are _{-CH2 -} CH2-, n6, n7 and Compound with n8 of 3)

<Compound (D)>
2021P: 3,4-Epoxycyclohexylmethyl (3,4-epoxy) cyclohexylcarboxylate, manufactured by Daicel, trade name Serokiside 2021P
EX212L: 1,6-Hexanediol diglycidyl ether (low chlorine grade), manufactured by Nagase Chemitex, trade name Denacol EX212L
KBE-403: 3-glycidoxypropyltriethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd. Product name KBE-403)

<Compound (E1)>
UV3000B: Polyurethane-based acrylate oligomer, weight average molecular weight 18,000, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name Shikou UV3000 cationically polymerizable compound B
PU3701: Polyurethane-based methacrylate oligomer, weight average molecular weight 15000, manufactured by MIWON, trade name Miramer PU3701

<Compound (E2)>
EBECRYL525: Polyester-based acrylate oligomer (containing 40% by mass of tripropylene glycol diacrylate), weight average molecular weight 40,000, manufactured by Daicel Ornex, trade name EBECRYL525
EBECRYL884: Polyester-based acrylate oligomer, weight average molecular weight 300
0, manufactured by Daicel Ornex, trade name EBECRYL884

<Compound (E3)>
KAYARAD R-9485: Epoxy acrylate oligomer, weight average molecular weight 5000, manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD R-9485
EBECRYL860: Epoxy acrylate oligomer, weight average molecular weight 1200, manufactured by Daicel Ornex, trade name EBECRYL860

<Compound (F)>
THFA: Tetrahydrofurfuryl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name Viscoat # 150
M315: Isocyanuric acid ethylene oxide-modified triacrylate manufactured by Toagosei Co., Ltd. Product name Aronix M315
Polyethylene Glycol 600 Diacrylate (MIWON Product Item Mir Omar
M280 (R3 and R4 in the general formula (2) are hydrogen, P4 is -CH ₂ -CH _2- , and n4 = 14, n5 = 0 compound))
ABE300: Ethylene oxide 3 mol-modified bisphenol A diacrylate (trade name NK ester ABE300 manufactured by Shin-Nakamura Chemical Co., Ltd.)

<Compound (G)>
Irgacure 184: 1-Hydroxycyclohexyl-phenyl-ketone, manufactured by BASF, trade name Irgacure 184
CPI-100P: Active energy ray cationic polymerization initiator, manufactured by San-Apro, trade name CPI-100P

From the results in the table, Examples 1 to 32 are clearly superior to Comparative Examples 1 to 6 in terms of the curved surface room temperature adhesive force, the curved surface high temperature adhesive force, and the curved surface low temperature adhesive force.

[Example 1]
<Production example of active energy ray-polymerizable adhesive>
In a light-shielded glass bottle with a capacity of 300 mL, 50 parts of 4-hydroxybutyl acrylate as compound (A), 20 parts of 1,6-hexanediol diacrylate (trade name Miramer M200 manufactured by MIWON) as compound (B), and compound (C). ), 28 parts of trimethylolpropane triacrylate (trade name Miramer M300 manufactured by MIWON) and 2 parts of Irgacure 184 (photoradical polymerization initiator manufactured by BASF) are added, and the mixture is sufficiently stirred and defoamed to be active energy ray-polymerizable. Obtained an adhesive.
However, Example 1 is a reference example.

[Examples 2 to 26, Comparative Examples 1 to 6]
Examples 2 to 26 and Comparative Examples 1 to 6, respectively, were subjected to the same procedure as in Example 1 except that the raw materials of Example 1 and the blending amounts thereof were changed as shown in Tables 1 to 4. An active energy ray-polymerizable adhesive was obtained.
However, Example 2 is a reference example.

Claims (8)

A di (meth) acrylate selected from the group consisting of a hydroxyl group-containing mono (meth) acrylate monomer (A), a monomer represented by the following general formula (1), and a monomer represented by the following general formula (2). Active energy comprising the monomer (B) and the tri or tetra (meth) acrylate monomer (C) selected from the group consisting of the monomer represented by the following general formula (3) and the monomer represented by the following general formula (4). Linear polymerizable adhesive.
General formula (1)

(However, in the formula, R1 and R2 are methyl groups or hydrogens, P1 and P3 are alkylene groups having 2 to 4 carbon atoms, P2 is an alkylene group having 5 to 10 carbon atoms, and n1, n2 and n3. Is an integer from 0 to 6)
General formula (2)

(However, in the formula, R3 and R4 are methyl groups or hydrogens, P4 and P5 are alkylene groups having 2 to 4 carbon atoms, and n4 and n5 are integers of 0 to 6. However, n4 and n5 are simultaneous. It can never be 0.)
General formula (3)

(However, in the formula, R5, R6 and R7 are methyl groups or hydrogens, R8 is a methyl group, a hydroxyl group and an acryloyloxy group, and P6, P7 and P8 are alkylene groups having 2 to 4 carbon atoms and n6. , N7, n8 are integers from 0 to 6).
General formula (4)

(However, in the formula, R9, R10, R11, R12 are methyl groups or hydrogens, R13 and R14 are methyl groups, hydroxyl groups and acryloyloxy groups, and P9, P10, P11 and P12 have 2 to 4 carbon atoms. It is an alkylene group, and n9, n10, n11, and n12 are integers of 0 to 6). 10-80% by mass of hydroxyl group-containing mono (meth) acrylate monomer (A), 10-50% by mass of di (meth) acrylate monomer (B), tri or tetra (meth) in the active energy ray-polymerizable adhesive. The active energy ray-polymerizable adhesive according to claim 1, which contains 10 to 50% by mass of the acrylate monomer (C). The di (meth) acrylate monomer (B) is hexanediol di (meth) acrylate, ethylene oxide 2 mol-modified hexanediol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, propylene oxide 2 mol-modified 2,2. Claim 1 or 2 which is one or more selected from the group consisting of -dimethylpropane-1,3-diol di (meth) acrylate, dipropylene glycol di (meth) acrylate, and tripropylene glycol di (meth) acrylate. The active energy ray polymerizable adhesive according to the above. The tri or tetra (meth) acrylate monomer (C) is trimethylol propanetri (meth) acrylate, ethylene oxide 3 mol modified trimethylol propanetri (meth) acrylate, propylene oxide 3 mol modified trimethylol propanetri (meth) acrylate, pentaerythritol. One or more selected from the group consisting of triacrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetraacrylate, ethylene oxide 5 mol-modified pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate. , The active energy ray-polymerizable adhesive according to any one of claims 1 to 3. The active energy ray-polymerizable adhesive according to any one of claims 1 to 4, further comprising 0.1 to 30% by mass of the cationically polymerizable compound (D). Further, one or more selected from the group consisting of a polyurethane-based (meth) acrylate oligomer (E1), a polyester-based (meth) acrylate oligomer (E2), and an epoxy-based (meth) acrylate oligomer (E3) (however, the above-mentioned monomer). The active energy ray-polymerizable adhesive according to any one of claims 1 to 5, which comprises (A), the monomer (B) and the monomer (C)). A laminate comprising a first base material, a resin layer which is a cured product of the active energy ray-polymerizable adhesive according to any one of claims 1 to 6, and a second base material. The laminate according to claim 7, wherein the first base material is a polarizing element and the second base material is a protective film.