JP7030263B2 - Active energy ray-curable adhesives and laminates - Google Patents

Description

The present invention relates to active energy ray-curable adhesives and laminates.

A display such as a liquid crystal display or an organic EL display is used as a laminate in which optical members such as an antireflection film, a retardation film, a polarizing plate, and a liquid crystal cell (or an organic EL layer) are bonded with an adhesive or an adhesive. There is.

In addition to being used as a television or monitor, the display is widely used as a touch panel with a transparent electrode layer on its surface and an input function, for mobile terminals such as smartphones and tablet terminals, and for in-vehicle applications such as car navigation. ing.
In smartphones and the like, curved displays are used in which the display is extended to the outer periphery (curved surface) of the smartphone in order to expand the display area within a limited size. Furthermore, smartphones are increasingly being used in automobiles as car navigation systems that utilize apps to take advantage of their high functionality.

However, general displays for in-vehicle use are directly affected by temperature changes and temperature / humidity changes in winter and summer. Therefore, an active energy ray-curable adhesive that takes into consideration low temperature and heat resistance has been used for the display.

Patent Document 1 discloses an active energy ray-curable adhesive containing isocyanuric acid ethylene oxide-modified polyfunctional acrylate, benzyl metallicate, 2-hydroxyethyl methacrylate and the like.

Patent Document 2 discloses an active energy ray-curable adhesive containing a polyfunctional urethane acrylate, an orthophenylphenol acrylate, a hydroxybutyl acrylate, and a hydroxyethyl methacrylate.

International Publication No. 2011/145524 International Publication No. 2006/110878

However, since the various optical members used in the display have different dimensional change rates due to temperature changes, when a curved display using a conventional active energy ray-curable adhesive is used for in-vehicle use, each optical member can be used. The bonded adhesive layer could not cope with the temperature change and temperature / humidity change at the curved surface of the display where the stress change due to the difference in the dimensional change rate was the largest, and the optical members sometimes floated or peeled off from each other. ..

An object of the present invention is to provide an active energy ray-curable adhesive and a laminate capable of forming an adhesive layer having low temperature suitability, high temperature suitability, and high temperature and high humidity suitability even when used on a curved surface portion.

The active energy ray-curable adhesive of the present invention is a monomer (A) having one methacryloyl group having a glass transition temperature of a homopolymer having a glass transition temperature of 25 ° C. or less, and a hydroxyl group-containing radically polymerizable monomer (B) (however, the above one). (Excluding the monomer (A) having a methacryloyl group), a polyfunctional radically polymerizable monomer (C) (however, excluding the monomer (A) having one methacryloyl group and the hydroxyl group-containing radically polymerizable monomer (B)) , And a photopolymerization initiator.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an active energy ray-curable adhesive and a laminate capable of forming an adhesive layer having low temperature suitability, high temperature suitability, and high temperature and high humidity suitability even when used 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-curable adhesive of the present invention, the polymerization reaction proceeds by irradiation with the above active energy rays to form a cured product such as an adhesive 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".
The radically polymerizable monomer is a monomer having a radically polymerizable functional group such as a vinyl group or an acryloyl group.
Polyfunctional means that the number of functional groups of the ethylenically unsaturated group is 2 or more in one molecule, and bifunctional or trifunctional means that the number of functional groups of the ethylenically unsaturated group is 2 or 3 in one molecule. Indicates that there is.

The active energy ray-curable adhesive (hereinafter, may be simply referred to as “adhesive”) herein is a monomer (A) having a single methacryloyl group having a glass transition temperature of a homopolymer having a glass transition temperature of 25 ° C. or lower. It contains a hydroxyl group-containing radically polymerizable monomer (B), a polyfunctional radically polymerizable monomer (C), and a photopolymerization initiator (G).

The adhesive of the present specification is preferably used as an adhesive layer for adhering a base material to a base material, which is cured by active energy rays.

The adhesive of the present specification can be used for all purposes of bonding two substrates to each other, a purpose of forming a polarizing plate (hereinafter referred to as a polarizing plate forming), and an optical member including a polarizing plate are bonded together. It is preferable to use it for various purposes (hereinafter referred to as optical member applications).

The adhesive of the present specification contains a monomer (A) having one methacryloyl group having a glass transition temperature of a homopolymer having a glass transition temperature of 25 ° C. or lower, so that an appropriate curing rate that is neither too fast nor too slow can be obtained. Therefore, in addition to being able to suppress the curing shrinkage of the adhesive layer, the adhesive strength immediately after irradiation with the active energy ray (hereinafter referred to as the initial adhesive strength) is good because the adhesiveness to the substrate is improved. As a result, the adhesion to the curved surface of the display can be ensured, and the stress on the optical member due to temperature changes and temperature / humidity changes can be alleviated. Can be formed.

<Monomer (A) having one methacryloyl group having a glass transition temperature of homopolymer of 25 ° C. or less>
A monomer (A) having a single methacryloyl group having a homopolymer glass transition temperature of 25 ° C. or lower (hereinafter, also referred to as monomer (A)) has a homopolymer glass transition temperature (hereinafter referred to as Tg) of 25 ° C. or lower. The monomer (A) has one methacryloyl group.
Since the Tg of the monomer (A) is 25 ° C. or lower, the adhesive layer does not become excessively hard and the flexibility is improved, and since the monomer (A) has a methacryloyl group, the adhesive as a whole is appropriate. The curing speed can be easily obtained, and not only the curing shrinkage of the adhesive layer can be suppressed, but also the curing strain can be suppressed. This makes it possible to form an adhesive layer having good low temperature suitability, high temperature suitability, and high temperature and high humidity suitability. The Tg of the monomer (A) is preferably 0 ° C. or lower. The lower limit of Tg of the monomer (A) is not limited as long as the problem can be solved as a whole of the adhesive, but it is about −70 ° C. if it is strongly mentioned.

The monomer (A) may be, for example, normal butyl methacrylate (Tg: 20 ° C.), normal hexyl methacrylate (Tg: −5 ° C.), lauryl methacrylate (Tg: −65 ° C.), normal decyl methacrylate (Tg: −70 ° C.), or the like. (Tg is the value listed in the Polymer Handbook).
Further, as the monomer (A), methacrylate having a hydroxyl group or an alkyleneoxy group is also preferable. Examples of the alkyleneoxy group include an ethyleneoxy group, a propyleneoxy group, a butyleneoxy group, and a pentyleneoxy group. A methacrylate having an alkyleneoxy group can have one or more alkyleneoxy groups (also referred to as "addition"; the number of alkyleneoxy groups is also referred to as the number of moles of addition). The alkyleneoxy group may be used as long as the adhesive of the present specification can solve the problem, and the upper limit of the number of added moles is not particularly limited, but is about 30. Further, as the type of the alkyleneoxy group of the monomer (A), one type or two or more types may be added.

Examples of commercially available methacrylates having an alkyleneoxy group include Blemmer PME-100 (Tg: -26 ° C, number of moles of added ethyleneoxy group 2) and Blemmer PME-200 (Tg: -59 ° C, number of moles of ethyleneoxy group added). Average 4), Blemmer PME-400 (Tg: -60 ° C, average number of moles of ethylenedioxy groups added 9), Blemmer PME-1000 (Tg: -52 ° C, average number of moles of ethyleneoxy groups added 23), Blemmer PSE-1300 (Tg) : -51 ° C Ethyleneoxy group addition mole number average 23), the above can be mentioned by Nichiyu Co., Ltd. Commercially available products of methacrylate having a hydroxyl group and an alkyleneoxy group include Bremmer PE-90 (Tg: -20 ° C, number of moles of ethyleneoxy group added 2) and Bremmer PE-200 (Tg: -53 ° C, number of moles of ethyleneoxy group added). Average 4.5), Blemmer PE-350 (Tg: -58 ° C, number of moles of ethyleneoxy groups added, average 8), Blemmer PP-1000 (Tg: -49 ° C, number of moles of propyleneoxy groups added 4 to 6), Blemmer PP- 500 (Tg: -57 ° C, average number of moles of propyleneoxy group added 4.5), Blemmer PP-800 (Tg: -62 ° C, average number of moles of propyleneoxy group added 8), Blemmer 50 PEP-300 (Tg: -60 ° C ethylene) Average number of moles of oxy groups added 3 and average number of moles of propyleneoxy groups 2), Blemmer 50PEP-300B (Tg: -60 ° C, average number of moles of ethyleneoxy groups added 5, average number of moles of propyleneoxy groups 2) or more, Manufactured by Nichiyu Co., Ltd .; Propene FM1 or higher, manufactured by Daisel Co., etc. can be mentioned. The Tg associated with the compound name is a homopolymer Tg.

Among these, the monomer (A) is preferably methacrylate having a hydroxyl group and an alkyleneoxy group. In methacrylate having a hydroxyl group and an alkyleneoxy group, the hydroxyl group easily forms a hydrogen bond with some functional group or bond unit of the base material, and in addition to improving the adhesion (adhesive strength), the presence of the alkyleneoxy group causes the methacrylate. The adhesive layer is easy to relieve stress. Thereby, the adhesive of the present specification can form an adhesive layer that more highly satisfies low temperature aptitude, high temperature aptitude, and high temperature and high humidity aptitude.

The monomer (A) can be used alone or in combination of two or more.

The monomer (A) is preferably contained in an amount of 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, in 100% by mass of the adhesive. When the monomer (A) is used in an appropriate amount, the low temperature aptitude, the high temperature aptitude, and the high temperature and high humidity aptitude are further improved.

<Hydroxy group-containing radical polymerizable monomer (B)>
The hydroxyl group-containing radically polymerizable monomer (B) (hereinafter, also referred to as a monomer (B)) is a monomer other than the above-mentioned monomer (A) containing a hydroxyl group.

Examples of the hydroxyl group-containing radical polymerizable monomer (B) include a hydroxyl group-containing (meth) acrylic acid alkyl ester and a hydroxyl group-containing (meth) acrylic acid cyclic ester.
The hydroxyl group-containing (meth) acrylic acid alkyl ester is, for example, (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 3-hydroxypropyl, (meth) acrylic acid 4-. Examples thereof include hydroxybutyl, (meth) acrylic acid 6-hydroxyhexyl, (meth) acrylic acid 8-hydroxyoctyl, cyclohexanedimethanol mono (meth) acrylic acid ester, and (meth) acrylic acid 12-hydroxylauryl.
The hydroxyl group-containing (meth) acrylic acid cyclic ester is, for example, chlorhexanedimethanol mono (meth) acrylate, cyclohexanediethanol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-a (meth). Acryloyl xyethyl-2-hydroxyethyl-phthalic acid and the like can be mentioned.
Other examples include fatty acid ester-based (meth) acrylic acid esters such as meth) acrylic acid glycidyl lauric acid ester.

Among these, the monomer (B) is preferably 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. , 4-Hydroxybutyl (meth) acrylate is more preferred. The use of these monomers further improves low temperature aptitude.

The monomer (B) can be used alone or in combination of two or more.

The monomer (B) is preferably contained in an amount of 5 to 60% by mass, more preferably 10 to 40% by mass, in 100% by mass of the adhesive. When an appropriate amount of the monomer (B) is used, the low temperature aptitude and the high temperature and high humidity aptitude are further improved.

<Polyfunctional radically polymerizable monomer (C))>
The polyfunctional radically polymerizable monomer (C)) (hereinafter, also referred to as a monomer (C)) is a monomer other than the monomer (A) and the monomer (B) having two or more radically polymerizable functional groups. When the adhesive of the present specification contains the monomer (C), the cohesive force of the adhesive layer is improved, so that the high temperature suitability and the high temperature and high humidity suitability are further improved. Further, the monomer (C) is a compound having a weight average molecular weight or a formula weight of less than 1000.

The monomer (C) is preferably a bifunctional radically polymerizable monomer, a trifunctional radically polymerizable monomer, or a tetrafunctional or higher functional radically polymerizable monomer, and is selected from the group consisting of a bifunctional radically polymerizable monomer and a trifunctional radically polymerizable monomer. One or more of them are more preferable.
Examples of the bifunctional radically polymerizable monomer include di (meth) acrylate, alkyleneoxy group-containing di (meth) acrylate, and polyol ester-based di (meth) acrylate. Examples of the trifunctional radically polymerizable monomer include tri (meth) acrylate. Examples of the tetrafunctional or higher functional radical polymerizable monomer include tetrafunctional or higher (meth) acrylates.

The di (meth) acrylate is, for example, pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 2,2-dimethylpropane-1, Examples thereof include 3-diol di (meth) acrylate, hexanediol di (meth) acrylate, heptanediol di (meth) acrylate, and nonanediol di (meth) acrylate.
The alkyleneoxy group-containing di (meth) acrylate is, for example, ethylene oxide-modified pentandiol di (meth) acrylate, propylene oxide-modified pentandiol di (meth) acrylate, tetramethylene oxide-modified pentandiol di (meth) acrylate, or ethylene oxide-modified. 2,2-Dimethylpropane-1,3-diol di (meth) 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, ethylene oxide-modified hexanediol di (meth) acrylate, propylene oxide-modified hexanediol di (meth) acrylate, tetramethylene oxide-modified hexanediol di (meth) acrylate, ethylene oxide-modified heptanediol di (meth) acrylate. ) Acrylate, propylene oxide modified heptanediol di (meth) acrylate, tetramethylene oxide modified heptanediol di (meth) acrylate, ethylene glycol-propylene glycol di (meth) acrylate, diethylene glycol-propylene glycol di (meth) acrylate, diethylene glycol-di Propylene glycol di (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) di (meth) acrylate, isocyanuric acid ethylene oxide-modified di (meth) acrylate, isocyanuric acid propylene oxide-modified di (meth) acrylate, isocyanuric acid butyl oxide-modified Examples thereof include di (meth) acrylate and isocyanuric acid butyl oxide-modified di (meth) acrylate.
Examples of the polyol ester-based di (meth) acrylate include neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, and propylene glycol di (meth) acrylate. ) Acrylate, tetramethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate and the like can be mentioned.

The tri (meth) acrylate is, for example, trimethylol propanetri (meth) acrylate, ethylene oxide-modified trimethylol propanetri (meth) acrylate, propylene oxide-modified trimethylol propanetri (meth) acrylate, and tetramethylene oxide-modified trimethylol propanetri. (Meta) acrylate, propylene oxide 2 mol-modified 2,2-dimethylpropane-1, ethylene oxide 3 mol-modified trimethylol propanetri (meth) acrylate, propylene oxide 3 mol-modified trimethylol propanetri (meth) acrylate, pentaerythritol tri (meth) Acrylate, propylene oxide 3 mol-modified glycerin (meth) acrylate, isocyanuric acid ethylene oxide-modified tri (meth) acrylate, isocyanuric acid propylene oxide-modified tri (meth) acrylate, isocyanuric acid butyl oxide-modified tri (meth) acrylate, isocyanuric acid butyl oxide-modified Examples thereof include tri (meth) acrylate.

The tetrafunctional or higher functional (meth) acrylate is, for example, dimethylolpropanetetra (meth) acrylate, ethylene oxide-modified dimethylolpropanetetra (meth) acrylate, prolenoxide-modified dimethylolpropanetetra (meth) acrylate, or tetramethyleneoxide-modified. Examples thereof include dimethylolpropane tetra (meth) acrylate, dimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

Among these, the monomer (C) is neopentyl glycol diacrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, propylene oxide 2 mol-modified 2,2-dimethylpropane- 1, Tripropylene glycol di (meth) acrylate, trimethylolpropane triacrylate, isocyanuric acid ethylene oxide-modified tri (meth) acrylate, and isocyanuric acid ethylene oxide-modified di (meth) acrylate are preferable. The use of these monomers further improves high temperature aptitude and high temperature and high humidity aptitude.

The monomer (C) can be used alone or in combination of two or more.

The monomer (C) is preferably contained in an amount of 5 to 80% by mass, more preferably 10 to 60% by mass, in 100% by mass of the adhesive. When an appropriate amount of the monomer (C) is used, the cohesive force of the adhesive layer is further improved, and the high temperature suitability and the high temperature and high humidity suitability are further improved.

<Polyfunctional radically polymerizable oligomer (D)>
The adhesives herein can further include the polyfunctional radically polymerizable oligomer (D). The polyfunctional radically polymerizable oligomer (D) (hereinafter referred to as oligomer (D)) is a compound having two or more radically polymerizable functional groups and having a weight average molecular weight of 1000 or more. By containing the oligomer (D) in the adhesive, the low temperature suitability and the high temperature and high humidity suitability of the adhesive layer are further improved. The oligomer (D) is a compound other than the monomer (A), the monomer (B), and the monomer (C). The oligomer (D) may have an upper limit of the weight average molecular weight as long as it can solve the problem as a whole adhesive, but it is about 100,000 if it is strongly mentioned. The weight average molecular weight is more preferably 1000 to 100,000, and even more preferably 1500 to 50,000. 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.

The oligomer (D) is preferably one or more selected from the group consisting of polyurethane oligomers, polyester oligomers, and epoxy oligomers.

The polyurethane oligomer is a compound having a urethane bond and a radically polymerizable functional group. The polyurethane oligomer can be 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. can. Alternatively, it can be synthesized by reacting a compound having a hydroxyl group with a compound having an isocyanate group and a (meth) acrylate group.

Compounds having two or more isocyanate groups include aromatic isocyanates such as 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, and 1,4-phenylene bismethylene diisocyanate; 3-isocyanatemethyl-3. , 5,5-trimethylcyclohexyl isocyanate, aliphatic isocyanate such as hexamethylene diisocyanate, etc. may be mentioned.

Polyurethane oligomers are aromatic polyurethane oligomers such as EBECRYL210, EBECRYL220 (above, manufactured by Dycel Ornex), CN9782, CN9783 (above, manufactured by SARTOMER), etc.; Examples thereof include aliphatic polyurethane oligomers such as EBECRYL230, EBECRYL270, EBECRYL8402, and EBECRYL8701 (all manufactured by Daicel Ornex).

The polyester oligomer is a compound having an ester bond and a radically polymerizable functional group. The compound (D2) esterifies, 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 can be synthesized by 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. Acids; examples include alicyclic acids such as dimer acid and cyclohexanedicarboxylic acid, and aromatic acids 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.

Examples of the polyester oligomer include aromatic polyester oligomers such as CN296, CN2203, CN2259, and CN2261 (above, manufactured by SARTOMER); aliphatic polyester oligomers such as CN294, CN2270, CN2271 (above, manufactured by SARTOMER). Be done.

The epoxy oligomer is a compound having a radically polymerizable functional group obtained by reacting an epoxy group of a compound having an epoxy group with a compound having a carboxyl group or a hydroxyl group. The epoxy oligomer may have a small amount of epoxy group remaining.

Epoxy oligomers are aromatic epoxy oligomers such as CN104, CN110 (above, manufactured by SARTOMER), EBECRYL600, EBECRYL3701 (above, manufactured by Dycel Ornex), CN111, CN113 (above, manufactured by SARTOMER). , EBECRYL860 (manufactured by Daicel Ornex) and the like, and examples thereof include aliphatic epoxy oligomers.

The oligomer (D) can be used alone or in combination of two or more.

The oligomer (D) is preferably 1 to 30% by mass, more preferably 2 to 20% by mass in 100% by mass of the adhesive. When an appropriate amount of the oligomer (D) is used, appropriate adhesion is easily obtained in the adhesive layer, and low temperature suitability and high temperature suitability are further improved.

<Alkoxysilane (E)>
The adhesive herein further preferably contains alkoxysilane (E) (hereinafter, also referred to as compound (E)).

The alkoxysilane (E) is, for example, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltributoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyl. A silane compound having a methacryloxy group such as methyldiethoxysilane and two alkyl and alkoxy groups; acryloxy such as γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, and γ-acryloxypropylmethyldimethoxysilane. A silane compound having two groups, an alkyl group and an alkoxy group;
A silane compound having three (meth) acryloxyalkyl groups and an alkoxy group, such as γ-methacryloxymethyltrimethoxysilane and γ-acryloxymethyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane. , Alkoxysilane having a vinyl group such as vinylmethyldimethoxysilane;
Silane compounds having an alkyl group and an alkoxy group such as 5-hexenyltrimethoxysilane, 9-decenyltrimethoxysilane, and styryltrimethoxysilane;
Silane compounds having aminoalkyl groups and alkoxy groups such as γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane;
γ-Mercaptopropyltrimethoxysilane, γ-Mercaptopropyltriethoxysilane, γ-Mercaptopropylmethyldimethoxysilane, γ-Mercaptopropylmethyldiethoxysilane, β-Mercaptomethylphenylethyltrimethoxysilane, Mercaptomethyltrimethoxysilane, 6 -A silane compound having a mercapto group and an alkoxy group such as mercaptohexyltrimethoxysilane, 10-mercaptodecyltrimethoxysilane;
Tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane;
3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltrimethoxysilane, 2- (3,4-epylcyclohexyl) ethyltriethoxysilane, 5,6-epoxyhexyltrimethoxysilane, 5,6-epoxyhexyltriethoxysilane and other silanes having an oxylan ring and an alkoxy group. Compound;
In addition, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, phenyltrimethoxysilane, hexamethylsilazane, diphenyldimethoxysilane, 1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate, vinyltris. (2-Methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-isoxapropyltriethoxysilane, etc. Can be mentioned.

Alkoxysilane (E) can be used alone or in combination of two or more.

Among these, alkoxysilane (E) is preferably a silane compound having an oxylan ring and an alkoxy group in terms of particularly excellent wet and heat durability. Silane compounds having an oxylan ring and an alkoxy group include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and 5,6-epoxyhexyltrimethoxy. Silane is particularly preferred.

The alkoxysilane (E) preferably contains 0.1 to 30% by mass in 100% by mass of the adhesive, and more preferably 1 to 20% by mass. When an appropriate amount of alkoxysilane (E) is used in the adhesive of the present invention, for example, the alkoxysilyl group is appropriately crosslinked with the hydrophilic functional group on the surface of the substrate, so that the high temperature and high humidity suitability is often further improved.

The adhesive herein preferably contains a compound (F) having an epoxy group. As a result, the curing shrinkage of the adhesive layer due to the active energy rays can be suppressed, so that the initial adhesive strength and low temperature suitability are further improved. The compound (F) having an epoxy group is a compound other than the alkoxysilane (E).

Examples of the compound (F) having an epoxy group include aromatic epoxy compounds, aliphatic epoxy compounds, and alicyclic epoxy compounds.

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, resorcin diglycidyl ether, phenyl glycidyl ether, phenol ethylene oxide glycidyl ether, t-butyl phenyl glycidyl ether and the like.

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.

Among these, neopentyl glycol diglycidyl ether, 1,6-hexanedio-l diglycidyl ether, and trimethylol propantriglycidyl ether are preferable.

The compound (F) having an epoxy group has an epoxy equivalent of about 30 to 3000 g / eq, preferably 50 to 1500 g / eq. Adjusting the epoxy equivalent to an appropriate range will further improve the adhesion to the substrate.

The compound (F) having an epoxy group can be used alone or in combination of two or more.

The compound (F) having an epoxy group preferably contains 0 to 30% by mass in 100% by mass of the adhesive, and more preferably 1 to 25% by mass. When an appropriate amount of the compound (F) having an epoxy group is contained, the adhesiveness, the adhesive strength at 25 ° C., and the low temperature aptitude are further improved.

<Photopolymerization initiator (G)>
The photopolymerization initiator (G) is a compound that triggers a polymerization reaction by an active energy ray, and examples thereof include a photoradical polymerization initiator, a photocationic polymerization initiator, and a photoanionic polymerization initiator.
Examples of commercially available photo-radical polymerization initiators include OMNIRAD 184, 907, 651, 1700, 1800, 819, 369, 261 and TPO (above, manufactured by IGM Resin), DaroCure-1173 (manufactured by Merck), and 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.

Examples of commercially available photocationic polymerization initiators include sulfonium salts such as UVACURE1590 (manufactured by Dycel Cytec) and CPI-110P (manufactured by San-Apro), OMINICAT250 (manufactured by IGM Resin), and WPI-113 (Jun Wako). Examples thereof include iodonium salts (manufactured by Yakuhin Kogyo Co., Ltd.) and Rp-2074 (manufactured by Rhodia Japan).

Examples of commercially available photoanionic polymerization initiators include WPBG-165, WPBG-018, WPBG-172, WPBG-140, WPBG-166, WPBG-027, WPBG-082, WPBG-167, WPBG-168, etc. WPBG-266 (all manufactured by Wako Pure Chemical Industries, Ltd.) and the like can be mentioned.

The photopolymerization initiator (G) can be used alone or in combination of two or more.

The photopolymerization initiator (G) preferably contains 0.1 to 15% by mass, more preferably 0.5% by mass or more and 10% by mass in 100% by mass of the adhesive.

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

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

By containing the compound (H), 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 (H) is a (meth) acrylate monomer other than the monomer (A), the monomer (B), the monomer (C), and the oligomer (D).

Compound (H) may be, for example, (meth) such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, n-hexyl acrylate, lauryl acrylate, and stearyl acrylate. Acrylic acid alkyl ester;

(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, Alkoxy group-containing (meth) acrylic acid esters such as (meth) acrylic acid 3-butoxyethyl and (meth) acrylic acid 4-butoxyethyl;
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 and the like can be mentioned.

The adhesives herein can contain at least one of boric acid and boric acid derivatives in an amount of 0.1-20% 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 further 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.

Boric acid derivatives also include oligomers and polymers containing boron-containing moieties. 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 adhesive of the present invention preferably contains substantially no organic solvent, and more preferably does not contain any organic solvent. The adhesive is particularly preferably free of toluene. However, since the photopolymerization initiator (G) is difficult to dissolve in the monomer or oligomer, a small amount of organic solvent may be contained in order to dissolve the photopolymerization initiator (G). In that case, the content of the organic solvent in the adhesive is preferably 5% by mass or less.

Boric acid and boric acid derivatives can be used alone or in combination of two or more.

The adhesive of the present specification may contain other additives as long as the problem can be solved. Other additives include, for example, photosensitizers, amine catalysts, phosphorus catalysts, fillers, antistatic agents, antioxidants, antioxidants, tackifiers, antiblocking agents, defoamers, plasticizers, etc. Examples include titanium coupling agents.

The adhesive of the present specification preferably has a viscosity at 25 ° C. of 1 to 2000 mPa · s, more preferably 10 to 1500 mPa · s, because the surface of the adhesive layer is smooth and facilitates thickness control. -1000 mPa · s is 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 adhesive of the present specification can be produced by blending and stirring the materials described above.

The laminate of the present specification comprises a first substrate, an adhesive layer which is a cured product of an active energy ray-curable adhesive, and a second substrate.

For the formation of the adhesive layer, it is preferable to bond the second base material on the adhesive 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 bonding, and further after bonding. 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. The first substrate and the second substrate may be the same or different.

The first base material and the second base material may be plate materials, but it is preferable to use a film-like base material. Examples of the film-like substrate include cellophane, a plastic film, paper and the like. Of these, a transparent plastic film is preferable. Further, the film-like substrate may be a single layer or a multilayer structure in which a plurality of substrates are laminated, as long as the film is transparent.

Plastic films are, for example, polyolefin films such as polyvinyl alcohol films, polytriacetyl cellulose films, polypropylene, polyethylene, polycycloolefins, and ethylene-vinyl acetate copolymers; polyester films such as polyethylene terephthalates and polybutylene terephthalates; Examples thereof include polycarbonate-based films, polynorbornene-based films, polyarylate-based films, polyacrylic films, polyphenylene sulfide-based films, polystyrene-based films, polyvinyl-based films, polyamide-based films, polyimide-based films, and polyoxylan-based films.

The composition of the laminate is such that if a transparent film or a transparent glass plate is used for the first base material, a base material that is difficult for active energy rays to pass through as the second base material, for example, wood, metal, plastic, or paper processing. Goods may be used.

The thickness of the base material is usually about 5 to 50,000 μm.

For coating, a known coating device can be used. Examples thereof include a Meyer bar, an applicator, a brush, a spray, a roller, a gravure coater, a die coater, a micro gravure coater, a lip coater, a comma coater, a curtain coater, a knife coater, a reverse coater, a spin coater and the like.

The active energy ray preferably has a wavelength or light including ultraviolet rays, and more preferably a wavelength of 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 , more preferably 30 to 4000 mJ / cm ² .

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

Examples of the embodiment of the laminate include a sheet 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. A shape-like multilayer film is preferable. 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-curable adhesive cures the adhesive layer that irradiates the active energy ray from one side or both sides of the base material.

A polarizing plate is mentioned as a preferable embodiment of the laminated body of this specification. Examples of the polarizing plate include a configuration in which a protective film is bonded to both sides of a polarizing element via an adhesive layer.

Examples of the polarizing element include a polyvinyl alcohol film. The thickness of the stator is usually about 2 to 200 μm.

Examples of the protective film include polytriacetyl cellulose film (hereinafter referred to as "TAC film") which is a polyacetyl cellulose-based film, polycycloolefin film which is a polynorbornene film, polyacrylic film, polycarbonate-based film, and polyester-based film. Can be mentioned. The thickness of the protective film is usually about 5 to 200 μm.

As for the polarizing plate, for example, it is preferable that 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 an adhesive layer on the opposite surface of the first substrate on the second substrate side. It is preferable to use a protective film as the third base material.

The polarizing plate can be used, for example, in a liquid crystal display or an organic EL display.

The adhesive of the present specification is preferably used for bonding to an optical member including a polarizing plate, to each other, and to a member other than the optical member.

The optical member is, for example, a member used for a liquid crystal display, a plasma display panel module, a touch panel module, an organic EL element, an organic EL module, and the like.
The optical member is a film having some kind of optical function and is also called an optical film. Examples of the optical film include 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 diffusion film, a brightness improving film, and a prism film (also referred to as a prism sheet). ), 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.

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% 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 parts by weight of potassium iodide in 480 parts by weight of water. After immersing a polyvinyl alcohol (PVA) film (Vinylon film # 40, manufactured by Aicello Corporation) in this dyeing solution for 30 seconds, the film is stretched twice in one direction and dried to obtain a PVA polarizing element having a thickness of 30 μm. Got

[Example 1]
<Production example of active energy ray-curable adhesive>
In a light-shielded glass bottle with a capacity of 300 mL, normal butyl methacrylate 5% by weight as the monomer (A) (trade name Light Ester NB manufactured by Kyoeisha Chemical Co., Ltd.) and 4-hydroxybutyl acrylate (trade name manufactured by Osaka Organic Chemical Industry Co., Ltd.) as the monomer (B). 4-HBA) 30% by weight, Neopentyl glycol diacrylate (trade name: Light Acrylate NP-A manufactured by Kyoeisha Chemical Co., Ltd.) as monomer (C) 40% by weight, Isocyanic acid ethylene oxide-modified triacrylate (trade name: Aronix manufactured by Toa Synthetic Co., Ltd.) M315) 20% by weight, OMINIRAD TPO (photoradical polymerization initiator manufactured by IGM Resins) 2% by weight, and CPI-110P (manufactured by San Apro, trade name CPI-110P) 3% by weight added as a photopolymerization initiator (G). After sufficient stirring and defoaming, an active energy ray-curable adhesive was obtained.

[Examples 2-34, Comparative Examples 1-4]
Examples 2 to 34 and Comparative Examples 1 to 4, respectively, were subjected to the same procedure as in Example 1 except that the components of Example 1 and the blending amounts thereof were changed as shown in Tables 1 to 5. An active energy ray-curable adhesive was obtained.

The following laminates A and B were prepared using the active energy ray-curable adhesives obtained in Examples 1 to 34 and Comparative Examples 1 to 4, respectively.

<Manufacturing example of laminated body A>
As the transparent film, an acrylic film HBD-022 (thickness 50 μm, 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 obtained energy ray-curable adhesive was applied onto the corona-treated surface of the acrylic film HBD-022 using a wire bar coater to a thickness of 4 μm to form an adhesive layer. did. 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.

An active energy ray irradiator (high-pressure mercury lamp manufactured by Toshiba Corporation) irradiates ultraviolet rays with a maximum illuminance of 500 mW / cm ² and an integrated light intensity of 500 mJ / cm ² from the side of a polynorbornene film manufactured by Zeon Corporation that does not contain an ultraviolet absorber. , 25 ° C.-50% environment was stored for 1 day or more to prepare a laminated body A.

<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 a second transparent film, ultraviolet rays manufactured by Nippon Zeon Co., Ltd. are used. A polynorbornene-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, an active energy ray-curable 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 an adhesive layer. A laminate composed of a first transparent film / adhesive layer / PVA-based polarizing element / adhesive layer / second transparent film with a polyvinyl alcohol-based polarizing element sandwiched between the adhesive layers formed on the first and second transparent films. Got 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.

With an active energy beam irradiator (high-pressure mercury lamp manufactured by Toshiba), irradiate ultraviolet rays with a maximum illuminance of 500 mW / cm ² and an integrated light intensity of 500 mJ / cm ² from the second transparent film side, and in a 25 ° C-50% environment for one day. The above storage was performed to prepare a laminated body B (polarizing plate).

The initial adhesive strength, curved surface high temperature adhesive strength, curved surface low temperature adhesive strength, and curved surface wet heat adhesive strength were evaluated for the obtained laminated bodies A and B. The results are shown in Tables 1 to 5.

《Initial adhesive strength》
Adhesive strength was measured according to JIS K6 854-4 Adhesive-Peeling Adhesive Strength Test Method-Part 4: Floating Roller Method. That is, the obtained laminates A and B were cut into a size of 25 mm in width × 150 mm in length using a cutter to prepare a sample for measurement. A double-sided adhesive tape (DF8712S manufactured by Toyochem Co., Ltd.) was attached to one side of the sample and adhered onto 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 strength was measured at the angle of. As for the adhesive strength, the laminated body A was measured by peeling off the acrylic film HBD-022. Further, in the laminated body B, the first transparent film / adhesive layer / PVA-based polarizing element was peeled off and the adhesive strength was measured. This adhesive strength was evaluated in the following four stages. 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)

《High temperature adhesive force on curved surface》
The high temperature suitability was evaluated by the following adhesive strength.
The obtained laminated body A is wound around a metal cylinder (made of SUS304) having a diameter of 8 cm, the end portion of the laminated body A is fixed with cellophane tape, stored at 80 ° C. and a relative humidity of 50% RH for 1 month, and then laminated. After removing the body from the metal cylinder, the adhesive strength of the laminated body A was measured. The adhesive force conforms to the method for measuring the initial adhesive force. The laminated body B was also evaluated in the same manner as in the case of the laminated body A. The adhesive strength was evaluated in the following four stages. 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)

《Low temperature adhesive force on curved surface》
The low temperature suitability was evaluated by the following adhesive strength.
The adhesive strength was measured in the same manner as the high temperature adhesive strength of the curved surface portion, except that the storage condition of the laminated body fixed to the metal cylinder was changed to −20 ° C. as in the case of the high temperature adhesive strength of the curved surface portion. The adhesive strength was evaluated based on the same criteria as the high temperature adhesive strength of the curved surface portion.

《Wet and heat adhesive force on curved surface》
The high temperature and high humidity suitability was evaluated by the following adhesive strength.
The adhesive strength was measured in the same manner as the curved surface high temperature adhesive force, except that the storage condition of the laminated body fixed to the metal cylinder was changed to 60 ° C.-90% as in the curved surface high temperature adhesive force. The adhesive strength was evaluated based on the same criteria as the high temperature adhesive strength of the curved surface portion.

Hereinafter, the components used in the examples and their abbreviations are shown.
<Monomer (A)>
n-BMA: Normal butyl methacrylate, Tg 20 ° C (trade name: Light Ester NB manufactured by Kyoeisha Chemical Co., Ltd.)
n-LMA: Normal lauryl methacrylate, Tg-65 ° C (trade name: Light Ester L manufactured by Kyoeisha Chemical Co., Ltd.)
PME-100: Methoxypolyethylene glycol monomethacrylate, Tg-26 ° C (trade name Blemmer PME-100 manufactured by NOF CORPORATION)
PP-1000: Polypropylene glycol monomethacrylate, Tg-49 ° C
(Product name Blemmer PP-1000 manufactured by NOF Corporation)
PE-200: Polyethylene glycol monomethacrylate, Tg-26 ° C.
(Product name Blemmer PE-200 manufactured by NOF Corporation)
FM1: Unsaturated fatty acid hydroxyalkyl ester modified ε-caprolactone
(Product name made by Daicel, Inc. Praxel FM1)

<Monomer (B)>
4-HBA: 4-Hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
HPA: 2-Hydroxypropyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
HEA: 2-Hydroxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)

<Monomer (C)>
NP-A: Neopentyl glycol diacrylate (trade name: Light Acrylate NP-A manufactured by Kyoeisha Chemical Co., Ltd.)
M220: Tripropylene glycol diacrylate (trade name Miramer M220 manufactured by MIWON)
M-215: Ethylene oxide-modified diacrylate of isocyanuric acid (trade name: Aronix M215 manufactured by Toagosei Co., Ltd.)
M-315: Ethylene oxide-modified triacrylate of isocyanuric acid (trade name: Aronix M315 manufactured by Toagosei Co., Ltd.)
M300: Trimethylolpropane triacrylate (trade name Miramer M200 manufactured by MIWON)
M410: Ditrimethylolpropane tetraacrylate (trade name: Miramer M410, manufactured by MIWON)
DPHA: Zipene erythritol hexaacrylate (trade name Miramer M600 manufactured by MIWON)

<Oligomer (D)>
UV3000B: Polyurethane-based acrylate oligomer, weight average molecular weight 18,000, (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
EBECRYL884: Polyester-based acrylate oligomer Weight average weight 3000 (manufactured by Daicel Ornex)
EBECRYL860: Epoxy acrylate oligomer, weight average molecular weight 1200
(Manufactured by Daisel Ornex)

<Alkoxysilane (E)>
KBE-403: 3-glycidoxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
KBM-303: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
KBE-5103: 3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

<Compound (F)>
EX-830: Polyethylene glycol diglycidyl ether (trade name Denacol EX-830 manufactured by Nagase ChemteX)
EX-212: 1,6-hexanediol diglycidyl ether (trade name: Denacol EX-212 manufactured by Nagase ChemteX Corporation)

<Photopolymerization initiator (G)>
OMNIRAD TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (manufactured by IGM Resins)
CPI-110P: p-Phenylthiophenyldiphenylsulfonium hexafluolofusphate (manufactured by San Apro)
OMNICAT 250: 4-isobutylphenyl (4-methylphenyl) iodonium hexafluorophosphate (manufactured by IGM Resins)

<Sensitizer>
DETX-S: 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd.)

<Other monomers>
EMA: Ethyl methacrylate (monomer having one methacryloyl group having Tg 65 ° C. light ester ETg of 25 ° C. or higher, manufactured by Kyoeisha Chemical Co., Ltd.)

From the results of Tables 1 to 5, the adhesives of Examples 1 to 34 can form an adhesive layer having low temperature aptitude, high temperature aptitude, and high temperature and high humidity aptitude.

Claims (7)

A monomer (A) having a methacryloyl group having a glass transition temperature of 0 ° C. or lower, an alkyleneoxy group, an alkyleneoxy group, and a hydroxyl group, and a hydroxyl group-containing radically polymerizable monomer (B) (however, the above-mentioned one). Monomer (A) having a methacryloyl group), polyfunctional radically polymerizable monomer (C) (however, excluding the monomer (A) having one methacryloyl group and the hydroxyl group-containing radical polymerizable monomer (B)). And 0. An active energy ray-curable adhesive containing 1 to 15% by mass , a hydroxyl group-containing radically polymerizable monomer (B) in an amount of 5 to 60% by mass, and a polyfunctional radically polymerizable monomer (C) in an amount of 5 to 80% by mass . The active energy ray-curable adhesion according to claim 1, wherein the polyfunctional radically polymerizable monomer (C) is at least one selected from the group consisting of a bifunctional radically polymerizable monomer and a trifunctional radically polymerizable monomer. Agent. Further, a polyfunctional radically polymerizable oligomer (D) (excluding the monomer (A) having one methacryloyl group, the hydroxyl group-containing radically polymerizable monomer (B), and the polyfunctional radically polymerizable monomer (C)). The active energy ray-curable adhesive according to claim 1 or 2, which comprises. The active energy ray-curable adhesive according to any one of claims 1 to 3, further comprising an alkoxysilane (E). The active energy ray-curable according to any one of claims 1 to 4, wherein the photopolymerization initiator (G) is at least one selected from the group consisting of a photoradical polymerization initiator and a photocationic polymerization initiator. glue. A laminate comprising a first base material, an adhesive layer which is a cured product of the active energy ray-curable adhesive according to any one of claims 1 to 5, and a second base material. A laminate comprising a polarizing element, an adhesive layer which is a cured product of the active energy ray-curable adhesive according to any one of claims 1 to 5, and a protective film.