CN114854361A - Active energy ray-curable adhesive composition, cured product, and laminate - Google Patents

Active energy ray-curable adhesive composition, cured product, and laminate Download PDF

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Publication number
CN114854361A
CN114854361A CN202210111780.1A CN202210111780A CN114854361A CN 114854361 A CN114854361 A CN 114854361A CN 202210111780 A CN202210111780 A CN 202210111780A CN 114854361 A CN114854361 A CN 114854361A
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meth
acrylate
component
adhesive composition
active energy
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Chinese (zh)
Inventor
罗聪
上口恭平
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Arakawa Chemical Industries Ltd
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Arakawa Chemical Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic

Abstract

The invention provides an active energy ray-curable adhesive composition, a cured product, and a laminate. The active energy ray-curable adhesive composition provides a cured product layer having excellent heat resistance, which has adhesive force and exhibits a high storage modulus even at high temperatures. The active energy ray-curable adhesive composition comprises: a urethane (meth) acrylate (A) which is a reaction product of a polyol (a1), a polyisocyanate (a2) and a hydroxyl group-containing mono (meth) acrylate (a3-1), or a reaction product of a polyol (a1), a polyisocyanate (a2) and an isocyanate group-containing mono (meth) acrylate (a3-2), wherein the urethane (meth) acrylate (A) has an average number of (meth) acryloyl groups of 1 to 4 and a weight average molecular weight of 10000 to 90000; alkyl mono (meth) acrylate (B); a mono (meth) acrylate (C) having at least 2 aromatic rings; and a compound (D) having a secondary thiol group.

Description

Active energy ray-curable adhesive composition, cured product, and laminate
Technical Field
The present invention relates to an active energy ray-curable adhesive composition, a cured product, and a laminate.
Background
Adhesives are used for bonding optical components to each other in the manufacturing process of mobile devices such as smartphones and tablet computers, digital home appliances such as digital cameras and audio devices, communication devices such as wireless devices and modems, for example, bonding a touch sensor to a front panel in manufacturing a touch panel, bonding a touch sensor to an image display device, and the like. Such adhesives are required to have high storage modulus at high temperature (i.e., the elastic modulus changes little due to temperature change) in addition to high adhesive force, and to have excellent heat resistance.
In response to such a demand, the present applicant disclosed an ultraviolet-curable adhesive containing specific amounts of a urethane (meth) acrylate, 2 kinds of non-hydroxyl group-containing polymerizable monomers having a specific glass transition temperature, a primary hydroxyl group-containing monomer, and a photopolymerization initiator (patent document 1). However, the above adhesive has a low storage modulus at high temperatures, and there is room for further improvement in heat resistance (heat resistance retention).
In order to improve heat resistance, an aromatic ring monomer is used as a means, and as a technique thereof, for example, a heat curable adhesive composition containing an acrylic copolymer containing a specific amount of an aromatic ring monomer as a monomer unit, a polyisocyanate crosslinking agent, and an organic solvent is known (patent document 2). However, when an aromatic ring monomer is generally used, although the heat resistance is improved, the adhesive force tends to be easily lowered.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2018-039999
Patent document 2: international publication No. 2018/062288
Disclosure of Invention
Problems to be solved by the invention
The present invention addresses the problem of providing an active energy ray-curable adhesive composition that provides a layer of a cured product that has high adhesive force and exhibits a high storage modulus even at high temperatures, and that is excellent in heat resistance.
Means for solving the problems
The present inventors have conducted intensive studies and, as a result, have found that the above problems can be solved by combining various mono (meth) acrylates with urethane (meth) acrylates. That is, the present invention relates to the following active energy ray-curable adhesive composition, cured product, and laminate.
1. An active energy ray-curable adhesive composition comprising:
a urethane (meth) acrylate (A) which is a reaction product of a polyol (a1), a polyisocyanate (a2) and a hydroxyl group-containing mono (meth) acrylate (a3-1), or a reaction product of a polyol (a1), a polyisocyanate (a2) and an isocyanate group-containing mono (meth) acrylate (a3-2), the urethane (meth) acrylate (A) having an average number of (meth) acryloyl groups of 1 to 4 and a weight average molecular weight of 10000 to 90000;
alkyl mono (meth) acrylate (B);
a mono (meth) acrylate (C) having at least 2 aromatic rings; and
a compound (D) having a secondary thiol group.
2. The active energy ray-curable adhesive composition according to the preceding item 1, wherein the (a1) component comprises a polyether polyol.
3. The active energy ray-curable adhesive composition according to the aforementioned item 1 or 2, the (B) component containing a mono (meth) acrylic acid alkyl ester (B1) and/or a mono (meth) acrylic acid hydroxyalkyl ester (B2) which do not contain a hydroxyl group.
4. The active energy ray-curable adhesive composition according to any one of the preceding items 1 to 3, wherein the content ratio of the component (C) is 30 to 75% by mass relative to 100% by mass of the total of the component (A), the component (B) and the component (C).
5. The active energy ray-curable adhesive composition according to any one of the preceding items 1 to 4, wherein the component (D) is a compound having 2 or more secondary thiol groups.
6. The active energy ray-curable adhesive composition according to any one of the preceding items 1 to 5, wherein the content of the component (D) is 0.1 to 5 parts by mass based on 100 parts by mass of the total of the component (A), the component (B) and the component (C).
7. A cured product of the active energy ray-curable adhesive composition described in any one of the above items 1 to 6.
8. The cured product according to the aforementioned item 7, which has a storage modulus G 'at a temperature of 25 ℃ and a frequency of 1Hz of 0.3MPa or more, and which has a storage modulus G' at a temperature of 100 ℃ and a frequency of 1Hz of 0.1MPa or more.
9. A laminate comprising a cured product according to item 7 or 8 above on at least one surface of a substrate.
ADVANTAGEOUS EFFECTS OF INVENTION
The active energy ray-curable adhesive composition of the present invention (hereinafter, simply referred to as "adhesive composition") provides a layer of a cured product having high adhesive force and excellent heat resistance that exhibits a high storage modulus. In addition, the layer of the cured product has excellent moist heat resistance.
Detailed Description
The adhesive composition of the present invention contains a specific urethane (meth) acrylate (a) (hereinafter, referred to as component (a)), a mono (meth) acrylic acid alkyl ester (B) (hereinafter, referred to as component (B)), a mono (meth) acrylic acid ester (C) (hereinafter, referred to as component (C)) having at least 2 aromatic rings, and a compound (D) having a secondary thiol group (hereinafter, referred to as component (D)).
The component (A) of the present invention is a reaction product of a polyol (a1) (hereinafter referred to as a component (a 1)), a polyisocyanate (a2) (hereinafter referred to as a component (a 2)), and a hydroxyl group-containing mono (meth) acrylate (a3-1) (hereinafter referred to as a component (a 3-1)) or an isocyanate group-containing mono (meth) acrylate (a3-2) (hereinafter referred to as a component (a 3-2)).
(a1) The component (b) is an alcohol having 2 or more hydroxyl groups, and is used for the purpose of imparting excellent adhesion to a cured product. As the component (a1), a polyol or a polymer polyol of a single compound may be used, or a crystalline polyol or an amorphous polyol may be used. The crystalline polyol is a polyol having a crystal structure preferably at 20 to 60 ℃, more preferably at 20 to 40 ℃.
The polyhydric alcohol as the single compound is not particularly limited, and examples thereof include aliphatic diols such as ethylene glycol, diethylene glycol, propylene glycol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 2-methyl-1, 3-propanediol, 1, 5-pentanediol, neopentyl glycol, 1, 6-hexanediol, 3-methyl-1, 5-pentanediol, 2-diethyl-1, 3-propanediol, 1, 9-nonanediol, 1, 10-decanediol, butylethylpropanediol, butylethylpentanediol and the like; alicyclic diols such as 1, 4-cyclohexanedimethanol; trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, dimer diol, hydrogenated dimer diol, triol, hydrogenated trimer triol, castor oil-based modified polyol, and alkylene oxide adduct of bisphenol compound or its derivative. These may be used alone, or 2 or more of them may be used in combination.
The polymer polyol is not particularly limited, and examples thereof include polyether polyol, polyester polyol, poly (meth) acrylic polyol, polyolefin polyol, polycaprolactone polyol, polycarbonate polyol, and the like. These may be used alone, or 2 or more of them may be used in combination. The term (meth) acrylic acid means acrylic acid or methacrylic acid.
Among them, polymer polyols are preferred in that the cured product exhibits high adhesive force. Specific polymer polyols are listed below.
The polyether polyol is not particularly limited, and examples thereof include polyalkylene glycols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, and (alkylene oxide-other alkylene oxide) copolymers containing a plurality of alkylene oxides as monomer components such as ethylene oxide-propylene oxide copolymers. These may be used alone, or 2 or more of them may be used in combination.
Commercially available polyether polyols include "Adeka Polyester P-400", "Adeka Polyester G-400", "Adeka Polyester T-400", "Adeka Polyester AM-302", "Adeka Polyester P1000" and "Adeka Polyester P2000" (manufactured by ADEKA Co., Ltd.); "polyethylene glycol # 1540" (manufactured by NACALII TESSQUE Co., Ltd.); "dipropylene glycol" and "polypropylene glycol 400" (manufactured by genuine chemical Co., Ltd.); "PTMG 650", "PTMG 1000", "PTMG 2000" and "PTMG 3000" (manufactured by Mitsubishi Chemical Co., Ltd.).
The polyester polyol is not particularly limited, and examples thereof include condensation polymers of a polyol and a polycarboxylic acid; ring-opening polymers of cyclic esters (lactones); trihydric reaction products of polyhydric alcohols, polycarboxylic acids, and cyclic esters, and the like.
The polyol is not particularly limited, and examples thereof include the polyols listed as the above-mentioned single compound polyol; triols such as glycerin, trimethylolpropane and trimethylolethane; cyclohexanediols such as 1, 2-cyclohexanediol, 1, 3-cyclohexanediol and 1, 4-cyclohexanediol; cyclohexanedimethanol such as 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol and 1, 4-cyclohexanedimethanol; bisphenols such as bisphenol a and bisphenol F; xylitol, sorbitol and other sugar alcohols, they can be used alone, also can be combined with more than 2.
The polycarboxylic acid is not particularly limited, and examples thereof include aliphatic dicarboxylic acids such as malonic acid, maleic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; alicyclic dicarboxylic acids such as 1, 4-cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, 2, 6-naphthalenedicarboxylic acid, and trimellitic acid, and the like, and these may be used alone or in combination of 2 or more.
The cyclic ester is not particularly limited, and examples thereof include propiolactone, β -methyl- δ -valerolactone, and ∈ -caprolactone, and these may be used alone or in combination of 2 or more.
Commercially available polyester polyols include "POLYLITE RX-4800", "POLYLITE OD-X-2523", "POLYLITE OD-X-2547", "POLYLITE OD-X-2420", "POLYLITE OD-X-2692" and "POLYLITE OD-X-2108" (available from DIC corporation); "Kuraray Polyol P-510", "Kuraray Polyol P-1010", "Kuraray Polyol P-2010", "Kuraray Polyol F-510" (manufactured by Kuraray Co., Ltd.).
Examples of the polycarbonate polyol include a reaction product of a polyol and phosgene; and ring-opened polymers of cyclic carbonates (alkylene carbonates, etc.). Examples of the polyol include the above-mentioned polyols. The alkylene carbonate is not particularly limited, and examples thereof include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, and hexamethylene carbonate. As a commercially available product of a polycarbonate Polyol, "Kuraray Polyol C-590" (manufactured by Kuraray Co., Ltd.); "NIPPOLAN 4002", "NIPPOLAN 4009" and "NIPPOLAN 981" (manufactured by Tosoh corporation); "DURANOL T6002" and "DURANOL T5652" (manufactured by Asahi Kasei corporation).
Examples of the poly (meth) acrylic polyol include homopolymers and copolymers of acrylic monomers having 1 or more hydroxyl groups, and poly (meth) acrylic polyols obtained by copolymerizing these copolymers with other monomers, and these can be used alone or in combination of 2 or more.
As a commercially available product of a poly (meth) acrylic polyol, "ARUFON UH-2041" (manufactured by Toyo Kabushiki Kaisha); "acrylic polyol # 6000" (manufactured by TAISEI FINE CHEMICAL K); "acrylic polyol PC # 5984" (manufactured by Tohony chemical Co., Ltd.), and the like.
The polyolefin polyol is not particularly limited, and examples thereof include polybutadiene having 2 or more hydroxyl groups, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene, and chlorides thereof. These may be used alone, or 2 or more of them may be used in combination. Examples of commercially available products include "NISSO-PB GI-1000", "NISSO-PB GI-2000" and "NISSO-PB GI-3000" (manufactured by Nippon Caoda Co., Ltd.).
The polycaprolactone polyol is not particularly limited, and examples thereof include polycaprolactone diol, polycaprolactone triol, and polycaprolactone tetraol, and these can be used alone or in combination of 2 or more. Examples of commercially available products include "POLYLITE OD-X-2155" (available from DIC Co., Ltd.); "Praxel 200", "Praxel 205", "Praxel 300", and "Praxel 400" (manufactured by DAICEL, Inc., above), and the like.
Among these polymer polyols, polyether polyols, polyester polyols and polycaprolactone polyols are preferred, and polyether polyols are more preferred, from the viewpoint that a cured product thereof exhibits high adhesion and excellent heat resistance and moist heat resistance.
(a1) The physical properties of the component (A) are not particularly limited, and for example, the number average molecular weight (polystyrene equivalent value by gel permeation chromatography (GPC method)) is usually about 700 to 10000, preferably about 1000 to 4000, from the viewpoint that the cured product exhibits high adhesion and excellent moist heat resistance.
The average number of hydroxyl groups per 1 molecule of the component (a1) (hereinafter also simply referred to as "average number of hydroxyl groups") is usually about 1.5 to 3, preferably about 2 to 3, from the viewpoint that the cured product exhibits high adhesive force.
(a1) The average number of hydroxyl groups per 1 molecule of the component (a1) is the average number of hydroxyl groups present in 1 molecule of the component (a). For example, ethylene glycol has 2 hydroxyl groups in 1 molecule, and thus the average number of hydroxyl groups is "2". When a plurality of components (a1) having different numbers of hydroxyl groups are used, for example, when 0.4 mol of ethylene glycol (number of hydroxyl groups: 2) and 0.6 mol of trimethylolpropane (number of hydroxyl groups: 3) are used, the average number of hydroxyl groups can be determined by weighted average.
(formula 1) [ (average number of hydroxyl groups per 1 molecule of component a1) ]
＝(2×0.4+3×0.6)/(0.4+0.6)＝2.6
The component (a2) is not particularly limited, and examples thereof include aromatic diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1, 4-cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated toluene diisocyanate. These may be used alone, or 2 or more of them may be used in combination. Further, as the component (a2), a urethane, adduct or biuret thereof can be used. Among them, aliphatic diisocyanates are preferable in that the cured product exhibits high adhesive force.
(a1) The ratio of the component (a) to the component (a2) is not particularly limited, and is usually determined by the number of moles of isocyanate groups (NCO) in the component (a2) (a2) ) The number of moles (OH) of the hydroxyl group(s) of the component (a1) (a1) ) Ratio of (NCO) (a2) /OH (a1) ) Preferably about 1.01 to 2.
The component (a3-1) is not particularly limited, and examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 8-hydroxyoctyl (meth) acrylate, and these may be used alone or in combination of 2 or more. Among them, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable because the cured product exhibits high adhesive force. The term (meth) acrylate refers to acrylate or methacrylate.
The component (a3-2) is not particularly limited, and various known mono (meth) acrylates can be used. Examples thereof include 2-isocyanatoethyl (meth) acrylate, 1-bis (acryloyloxymethyl) ethyl isocyanate, and 2- (o- [ 1' -methylpropyleneamino ] carboxyamino) ethyl methacrylate, and these may be used alone or in combination of 2 or more.
(A) The component (b) is not particularly limited, and can be produced by various known methods. Hereinafter, the component (a1) (hereinafter, referred to as component (a 1)) obtained by using the component (A3-1) as the component (A3) and the component (a2) (hereinafter, referred to as component (a 2)) obtained by using the component (A3-2) as the component (A3) will be separately described.
(A1) Component (b) is not particularly limited, and is obtained, for example, by reacting component (a1) with component (a2) to produce an isocyanate-terminated urethane prepolymer (hereinafter referred to as component (a1 '), and then reacting component (a 1') with component (A3-1). The reaction conditions are not particularly limited, but the temperature is usually about 70 to 85 ℃ and the time is usually about 1 to 5 hours. In addition, the ratio of the component (a1) to the component (a2) is not particularly limitedThe number of moles of isocyanate group (NCO) in the component (a2) (a2) ) The number of moles (OH) of the hydroxyl group(s) of the component (a1) (a1) ) Ratio of (NCO) (a2) /OH (a1) ) Usually, the range is about 1.01 to 2. The ratio of the component (A1') to the component (a3-1) is not particularly limited, and the molar number of isocyanate groups (NCO) in the former is not particularly limited (A1’) ) Number of moles (OH) of hydroxyl group with the latter (a3-1) ) Ratio of (NCO) (A1’) /OH (a3-1) ) Usually, the range is about 0.25 to 1.
Component (a2) may be prepared by reacting component (a1) with component (a2) to obtain a hydroxyl-terminated urethane prepolymer (hereinafter referred to as component (a2 '), and then reacting component (a 2') with component (A3-2). The reaction temperature and the reaction time were the same as those of the component (A1). The ratio of the component (a1) to the component (a2) is not particularly limited, and the NCO content is not particularly limited (a2) /OH (a1) ) Usually, the range is about 0.50 to 0.99. The ratio of the component (A2') to the component (a3-2) is not particularly limited, and the number of moles of isocyanate groups (NCO) in the latter is not particularly limited (a3-2) ) Number of moles of hydroxyl group (OH) of the former (A2’) ) Ratio of (NCO) (a3-2) /OH (A2’) ) Usually, the range is about 0.5 to 1.
The production of these (a1) component and (a2) component can be carried out in the presence of an organic solvent described later, but is preferably carried out in the absence of a solvent from the viewpoint of reducing environmental load. In addition, in the production thereof, the reaction may be carried out in the presence of the component (B) described later.
The weight average molecular weight of the component (A) is 10000-90000. When the weight average molecular weight is less than 10000, the adhesive force of the cured product cannot be sufficiently exhibited, and when it exceeds 90000, the storage modulus of the cured product at high temperature is lowered, and the heat resistance is also lowered. In addition, from the same tendency, the weight average molecular weight of the component (A) is preferably 20000 to 80000, more preferably 20000 to 60000. The weight average molecular weight is a value measured by gel permeation chromatography (GPC method) using polystyrene as a standard substance.
The average (meth) acryloyl group number per 1 molecule of the component (A) (hereinafter also simply referred to as "average (meth) acryloyl group number") is 1 to 4. When the average (meth) acryloyl group number is in this range, the cured product has high adhesive force. In addition, from the same tendency, the average number of (meth) acryloyl groups is preferably 1 to 3, and more preferably 1 to 2. The term (meth) acryloyl means acryloyl or methacryloyl.
(A) The average number of (meth) acryloyl groups per 1 molecule of the component (a) means the average number of (meth) acryloyl groups present per 1 molecule of the component (a). For example, when 1 mol of ethylene glycol, 2 mol of diisocyanate as the component (a2), and 2 mol of the component (a3-1) are reacted, the average (meth) acryloyl number is "2" when the component (a3-1) is a mono (meth) acrylate, and the average (meth) acryloyl number is "6" when the component (a3-1) is a tri (meth) acrylate.
The component (a) may contain 2 or more kinds of substances having the same or different average (meth) acryloyl groups, or may be mixed, and the average (meth) acryloyl group number in this case may be determined by a weighted average. For example, the case where the component (a) contains 0.2 mol of the component (a) having an average (meth) acryloyl group number of 1 and 0.8 mol of the component (a) having an average (meth) acryloyl group number of 2 is as follows.
(formula 2) [ (a) component has an average (meth) acryloyl group number per 1 molecule ] (1 × 0.2+2 × 0.8)/(0.2+0.8) ═ 1.8
The content of the component (a) is, in terms of exhibiting high adhesive force and excellent heat resistance, usually 10 to 49 mass%, preferably 15 to 49 mass%, more preferably 25 to 49 mass% of the total of the components (a), (B) and (C) as 100 mass% of the solid content (hereinafter the same).
(B) The component (b) is a component for imparting high adhesive force to a cured product, and various known components can be used. Specifically, there may be mentioned a mono (meth) acrylic acid alkyl ester (B1) (hereinafter referred to as component (B1)) containing no hydroxyl group and/or a mono (meth) acrylic acid hydroxyalkyl ester (B2) (hereinafter referred to as component (B2)).
Examples of the component (B1) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, aliphatic mono (meth) acrylic acid alkyl esters such as 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, tri-n-decyl (meth) acrylate, n-lauryl (meth) acrylate, n-myristyl (meth) acrylate, n-palmityl (meth) acrylate, n-stearyl (meth) acrylate, and isostearyl (meth) acrylate;
alicyclic mono (meth) acrylates such as cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, and tricyclodecane dimethylol di (meth) acrylate;
aromatic mono (meth) acrylates such as phenyl (meth) acrylate, benzyl (meth) acrylate, 2-phenylethyl (meth) acrylate, and nonylphenoxypolyethylene glycol (meth) acrylate. These may be used alone, or 2 or more of them may be used in combination. Among them, from the viewpoint that the adhesive layer exhibits high adhesive force, aliphatic mono (meth) acrylate is preferable, and 2-ethylhexyl (meth) acrylate is more preferable.
Examples of the component (B2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 8-hydroxyoctyl (meth) acrylate. These may be used alone, or 2 or more of them may be used in combination. Among them, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable from the viewpoint that the adhesive layer exhibits excellent moist heat resistance.
The content of the component (B) is, in terms of the adhesive layer exhibiting high adhesive force and excellent moist heat resistance, 100 mass%, usually 10 to 35 mass%, preferably 10 to 30 mass%, more preferably 10 to 20 mass% of the total of the components (a), (B) and (C).
The content of the component (B1) and the component (B2) is preferably (B1)/(B2) 1/3 to 2/1, more preferably 1/3 to 1/1, and further preferably 1/2 to 1/1 in terms of a solid content mass ratio, from the viewpoint that the adhesive layer exhibits high adhesive force and excellent moisture and heat resistance.
(C) The component (a) is a mono (meth) acrylate having at least 2 aromatic rings, and is a component which exhibits excellent heat resistance of the pressure-sensitive adhesive layer when incorporated in the pressure-sensitive adhesive composition. Examples of the component (C) include o-phenylphenoxyethyl (meth) acrylate, m-phenylphenoxyethyl (meth) acrylate, p-phenylphenoxyethyl (meth) acrylate, o-phenoxybenzyl (meth) acrylate, m-phenoxybenzyl (meth) acrylate, p-phenoxybenzyl (meth) acrylate, ethoxylated-o-phenylphenol (meth) acrylate, ethoxylated-m-phenylphenol (meth) acrylate, ethoxylated-p-phenylphenol (meth) acrylate, ethylene oxide-modified o-cumylphenol (meth) acrylate, ethylene oxide-modified m-cumylphenol (meth) acrylate, ethylene oxide-modified p-cumylphenol (meth) acrylate, and triphenylmethyl (meth) acrylate. These may be used alone, or 2 or more of them may be used in combination. Among them, o-phenylphenoxyethyl (meth) acrylate, m-phenylphenoxyethyl (meth) acrylate, and p-phenylphenoxyethyl (meth) acrylate are preferable from the viewpoint that the adhesive layer exhibits high adhesive force and excellent heat resistance.
The content of the component (C) is, in terms of the binder exhibiting excellent heat resistance, preferably 40 to 75% by mass, more preferably 45 to 75% by mass, and still more preferably 50 to 75% by mass, based on 100% by mass of the total of the component (a), the component (B), and the component (C).
(D) The component (a) is a compound having at least 1 secondary thiol group, and is a component which exhibits high adhesive force of the adhesive layer by being incorporated in the adhesive composition. The secondary thiol group is a group having a thiol group (-SH) bonded to a secondary carbon atom (-C (H)) -.
Examples of the component (C) include compounds having one secondary thiol group, such as 2-octanethiol, 2-nonanethiol, 2-decanethiol, 1, 2-propanedithiol, 1, 2-butanedithiol, 1, 3-butanedithiol, and 1,2, 3-propanetrithiol;
compounds having two secondary thiol groups, such as 1, 4-bis (3-mercaptobutyryloxy) butane and tetraethylene glycol bis (2-mercaptopropionate);
compounds having three secondary thiol groups, such as trimethylolpropane tris (2-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), 1,3, 5-tris (3-mercaptobutyryloxyethyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione;
and compounds having four secondary thiol groups such as pentaerythritol tetrakis (2-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate). These may be used alone, or 2 or more of them may be used in combination.
Examples of commercially available products of component (D) include "Carnlz (Karenz) MT D1", "Carnlz (Karenz) MT TPMB", "Carnlz (Karenz) MT NR 1" and "Carnlz (Karenz) MT PE 1" (manufactured by Showa Denko K.K.).
Among the above-mentioned (D) components, from the viewpoint that the adhesive layer exhibits excellent heat resistance, a compound having two or more secondary thiols is preferable, and trimethylolpropane tris (3-mercaptobutyrate), 1,3, 5-tris (3-mercaptobutyryloxyethyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, pentaerythritol tetrakis (2-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate) are more preferable.
The content of the component (D) is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass, based on 100 parts by mass of the total of the components (a), (B) and (C), in terms of the mass of the solid content, from the viewpoint that the adhesive layer exhibits high adhesive force and excellent heat resistance.
The adhesive composition of the present invention may further comprise a polyfunctional monomer in view of the fact that the adhesive layer exhibits a high storage modulus at high temperatures. Examples thereof include (meth) acrylates such as hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and urethane (meth) acrylate. These can be used alone, also can be used in combination of more than 2. The amount of the polyfunctional monomer used is also not particularly limited, and is usually 10 parts by mass or less, preferably 5 parts by mass or less, per 100 parts by mass of the pressure-sensitive adhesive composition of the present invention.
The adhesive composition of the present invention may contain various known additives as needed. The additives are not particularly limited, and examples thereof include a surface conditioner, a surfactant, an ultraviolet absorber, an antioxidant, a light stabilizer, an inorganic filler, a silane coupling agent, colloidal silica, a defoaming agent, a wetting agent, and a rust preventive. These can be used alone, also can be used in combination of more than 2.
The adhesive composition of the present invention is obtained by mixing the component (a), the component (B), the component (C), and the component (D), and the above-mentioned polyfunctional monomer and additives as required. The mixing method and the mixing order are not particularly limited. When the component (a) is diluted with the component (B), the component (C) and the component (D), and the monomer and the additive as required may be mixed in a solution of the component (B) of the component (a).
The adhesive composition of the present invention is substantially solvent-free, but may contain an organic solvent if the content is less than 1 mass%, preferably less than 0.1 mass%. The organic solvent here includes, for example, aromatic hydrocarbons such as benzene, toluene, ethylbenzene, n-propylbenzene, tert-butylbenzene, o-xylene, m-xylene, p-xylene, tetrahydronaphthalene, decahydronaphthalene, and aromatic naphtha; aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane, isooctane, and n-decane; alicyclic hydrocarbons such as cyclohexane; esters such as ethyl acetate, n-butyl acetate, n-pentyl acetate, 2-hydroxyethyl acetate, 2-butoxyethyl acetate, 3-methoxybutyl acetate, and methyl benzoate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone, and methylcyclohexanone; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, and tert-butanol.
The adhesive composition of the present invention is mixed with a photopolymerization initiator when irradiated with active energy rays. The photopolymerization initiator is not particularly limited, and examples thereof include photopolymerization initiators such as benzoin compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, thioxanthone compounds and oxime ester compounds, and photosensitizers such as amines and quinones, and more specifically include 2, 2-dimethoxy-1, 2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one and 1- [4- (2-hydroxyethoxy) -phenyl ] propane-1-one]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl]Phenyl radical]-2-methyl-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl]-1- [4- (4-morpholinyl) phenyl]-1-butanone, diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide, bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, bis (. eta. 5 -2, 4-cyclopentadien-1-yl) -bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 1, 2-octanedione 1- [4- (phenylthio) -2- (o-benzoyloxime)]Ethanone 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-1- (o-acetyloxime), and the like. These may be used alone, or 2 or more of them may be used in combination.
The content of the photopolymerization initiator is not particularly limited, and is usually about 0.1 to 10 parts by mass, preferably about 0.1 to 3 parts by mass, and more preferably about 0.1 to 2 parts by mass, based on 100 parts by mass of the total of the components (a) to (D), from the viewpoint of exhibiting excellent heat resistance of the pressure-sensitive adhesive layer.
The cured product of the present invention is obtained by curing the above adhesive composition.
The cured product of the present invention is obtained by applying the above adhesive composition to a substrate and then irradiating the substrate with an active energy ray.
Examples of the substrate include, but are not particularly limited to, polyethylene terephthalate (PET), cycloolefin polymer (COP), polypropylene, polybutene, polybutadiene, polymethylpentene, polyvinyl chloride, vinyl chloride copolymer, polyethylene naphthalate, polybutylene terephthalate, polyurethane, ethylene vinyl acetate, ionomer resin, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, polystyrene, polycarbonate, polyimide, and fluorine-based resin. In addition, a crosslinked film or a laminated film thereof may also be used. Any of untreated films, films subjected to light to heavy peeling treatment, and films having an easy-adhesion layer can be used as the films.
The coating method is not particularly limited, and examples thereof include an applicator, a bar coater, a roll coater, a die coater, a comma coater, a knife coater, and a gravure coater. The coating amount of the active energy ray-curable adhesive composition is not particularly limited, and the coating is usually performed so that the film thickness of the cured product becomes 10 to 500. mu.m, preferably 25 to 250. mu.m.
The active energy ray is not particularly limited, and examples thereof include light rays such as ultraviolet rays, infrared rays, and visible rays, electron beams, X rays, α rays, β rays, γ rays, and neutron beams. In the present invention, light is preferable, and ultraviolet rays are more preferable.
The light source of ultraviolet rays is not particularly limited, and examples thereof include xenon lamps, high-pressure mercury lamps, metal halide lamps, and UV-LEDs. The cumulative quantity of ultraviolet light and the transmission speed are not particularly limited, and the cumulative quantity of ultraviolet light is usually 100 to 3000mJ/cm 2 The conveying speed is usually about 5 to 50 m/min.
The physical properties of the resulting cured product have a storage modulus G' of 0.3MPa or more, preferably 0.5MPa or more at a temperature of 25 ℃ and a frequency of 1 Hz.
The storage modulus G' of the cured product at a temperature of 100 ℃ and a frequency of 1Hz is 0.1MPa or more, preferably 0.12MPa or more.
The laminate of the present invention has the cured product on at least one surface of a substrate. The substrate, coating method, irradiation conditions, and the like used are the same as those described above.
[ examples ] A method for producing a compound
The present invention will be specifically described below by way of examples and comparative examples. Needless to say, the technical scope of the present invention is not limited to these. In the examples, "parts" and "%" are by mass unless otherwise specified.
Production example 1
Into a reaction apparatus equipped with a condenser, a stirrer and a nitrogen inlet tube, 870 parts of polypropylene glycol (trade name: "Adeka Polyester P-2000", manufactured by ADEKA Co., Ltd.), 113 parts of isophorone diisocyanate (hereinafter, IPDI), 0.4 parts of P-hydroxyanisole (Japanese text: メトキノン, hereinafter, MQ) and 0.1 parts of stannous octoate were charged, and the temperature was raised to 70 ℃ and maintained for 3 hours to obtain an isocyanate group-terminated urethane prepolymer as an intermediate. Subsequently, 17 parts of 2-hydroxyethyl acrylate (hereinafter, referred to as HEA) was added, the mixture was incubated at 70 ℃ for 2 hours, and the NCO value was measured to confirm completion of the reaction, whereby a component (A-1) having a weight average molecular weight of 39000 and an average number of acryloyl groups of 2 was obtained. The NCO value was measured in accordance with JIS K1603-1 (the same applies hereinafter).
Production example 2
884 parts of P-2000, 106 parts of IPDI, 0.4 part of MQ and 0.1 part of stannous octoate were charged into the same reaction apparatus as in production example 1, and after heating to 70 ℃ and holding for 3 hours, an isocyanate group-terminated urethane prepolymer as an intermediate was obtained. Then, 10 parts of 4-hydroxybutyl acrylate (hereinafter, referred to as 4-HBA) was added thereto, and the mixture was incubated at 70 ℃ for 2 hours to determine the NCO value and confirm the completion of the reaction, thereby obtaining a component (A-2) having a weight average molecular weight of 70000 and an average number of acryloyl groups of 2.
Production example 3
883 parts of P-2000, 108 parts of dicyclohexylmethane diisocyanate, 0.4 part of MQ and 0.1 part of stannous octoate were charged into the same reaction apparatus as in production example 1, and after heating to 70 ℃ and holding for 3 hours, a hydroxyl-terminated urethane prepolymer as an intermediate was obtained. Next, 9 parts of 2-isocyanatoethyl (meth) acrylate (trade name: "Carrenz (Karenz) MOI") (hereinafter, referred to as "Carrenz (Karenz) MOI") were added thereto, and the mixture was incubated at 70 ℃ for 2 hours to determine the NCO value and confirm the completion of the reaction, thereby obtaining a component (A-3) having a weight-average molecular weight of 45000 and an average number of acryloyl groups of 2.
Production example 4
918 parts of P-2000, 72 parts of hexamethylene diisocyanate, 0.4 part of MQ and 0.1 part of stannous octoate were charged into the same reaction apparatus as in production example 1, and after heating to 70 ℃ and holding for 3 hours, a hydroxyl-terminated urethane prepolymer as an intermediate was obtained. Next, 9 parts of Carrenz (Karenz) MOI was added, the mixture was incubated at 70 ℃ for 2 hours, and the NCO value was measured to confirm completion of the reaction, whereby a component (A-4) having a weight average molecular weight of 45000 and an average number of acryloyl groups of 2 was obtained.
Comparative production example 1
Into the same reaction apparatus as in production example 1 were charged 732 parts of P-2000, 163 parts of IPDI, 0.4 part of MQ and 0.1 part of stannous octoate, and the temperature was raised to 70 ℃ and maintained for 3 hours to obtain an isocyanate group-terminated urethane prepolymer as an intermediate. Next, 105 parts of 4-HBA was added, the mixture was incubated at 70 ℃ for 2 hours, and the reaction was confirmed by measuring the NCO value to obtain a (G-1) component having a weight-average molecular weight of 8000 and an average number of acryloyl groups of 2.
Comparative production example 2
A polyether polyol (trade name: "PREMINOL S4103F", manufactured by AGC Co., Ltd.) having a number average molecular weight of 12000, 972 parts, 22 parts of IPDI, 0.4 part of MQ and 0.1 part of stannous octoate were charged into the same reaction apparatus as in production example 1, and after raising the temperature to 70 ℃ and maintaining the temperature for 3 hours, an isocyanate group-terminated urethane prepolymer as an intermediate was obtained. Subsequently, 6 parts of 4-HBA was added, the mixture was incubated at 70 ℃ for 2 hours, and the reaction was confirmed by measuring the NCO value to obtain a (G-2) component having a weight average molecular weight of 100000 and an average acryloyl number of 2.
Example 1
An active energy ray-curable adhesive composition was obtained by mixing component (A-1), 2-ethylhexyl acrylate as component (B1), 4-hydroxybutyl acrylate as component (B2), o-phenylphenoxyethyl acrylate as component (C), and pentaerythritol tetrakis (3-mercaptobutyrate) as component (D) at the mixing ratios shown in Table 1, and further mixing 1 part of 1-hydroxycyclohexylphenyl ketone (trade name: "Omnirad 184", manufactured by IGM Resins) as a photopolymerization initiator.
Examples 2 to 12 and comparative examples 1 to 6
By changing the composition and the content ratio shown in table 1, an active energy ray-curable adhesive composition was obtained in the same manner as in example 1. Since the adhesive composition of comparative example 4 was poor in storage stability, the following items were not evaluated.
< production of laminate >
The adhesive compositions of examples and comparative examples were applied to a 75 μm thick heavy release treated polyester film (product name "SP-PET-03-75 BU" manufactured by PANAC) so that the cured film thickness became 100 μm, and the release treated surface of a 38 μm thick light release treated polyester film (product name "SP-PET-01-38 BU" manufactured by PANAC) was bonded to the applied layer.
Next, in the atmosphere, a high-pressure mercury lamp (100 mW/cm) was used 2 ，900mJ/cm 2 ) The pre-laminate (light-release treated polyester film/cured product/heavy-release treated polyester film) was produced by irradiating with ultraviolet light.
Next, the light release treated polyester film was peeled from the above-mentioned pre-laminate, and instead, a 50 μm thick polyester film (product name "Cosmoshine A-4300" available from Toyo Boseki) was bonded to the pre-laminate with a 2kg roller and left for 2 hours. Then, a test piece of 8cm × 8cm was cut therefrom, and the heavy-release treated polyester film was peeled off to obtain a single-sided adhesive sheet (Cosmoshine a-4300/cured product).
A laminate (Cosmoshine A-4300/cured product/glass) was prepared by bonding a 2kg roller to a glass plate and leaving the laminate at a temperature of 25 ℃ and a humidity of 50% for 24 hours. In the adhesive composition of comparative example 1, the adhesive layer was peeled off from the glass plate, and the following items were not evaluated.
< adhesion >
The adhesive strength (N/25mm) of the cured product was measured by peeling the glass plate from the laminate at a speed of 300mm/min in the 180 ℃ direction using a commercially available tester (Tensilon Universal Material testing machine, manufactured by A & D). The thickness exceeding 10N/25mm is preferable. The results are shown in Table 1.
< Damp-heat resistance >
After each laminate was allowed to stand in a constant temperature and humidity bath at a temperature of 85 ℃ and a humidity of 85% for 500 hours, the wet heat resistance of the cured product was evaluated according to the following criteria.
< evaluation Standard >
O: the peeling of the substrate, the position deviation of the adhesive layer, the air bubbles in the adhesive layer and the damage of the adhesive layer are not generated
X: at least 1 defect of peeling of the substrate, displacement of the position of the adhesive layer, air bubble in the adhesive layer, and damage of the adhesive layer is generated
< Heat resistance >
After a 2.5cm × 2.5cm test piece was cut from the above-mentioned pre-laminate, the light release treated polyester film was peeled off, and instead, a 50 μm thick polyester film (2.5cm × 8cm) was bonded to the surface of the adhesive layer of the test piece with a 2kg roller, and left to stand for 2 hours.
Subsequently, after obtaining a single-sided adhesive sheet (Cosmoshine a-4300/cured product) by peeling off the re-peeling treated polyester film, the adhesive layer side of the adhesive sheet was bonded to a stainless steel plate (2.5cm × 8cm) with a 2kg roller, and left to stand at 25 ℃ and 50% RH for 24 hours.
According to JISZ-1524, a load of 1kg was applied to one end of the single-sided adhesive sheet in the vertical direction, and the time until the adhesive tape deviated and peeled was measured under a condition of 100 ℃ in a retention force tester with a thermostatic bath (testnasandyo corporation, creep tester (thermostatic bath)). The evaluation criteria are shown below.
O: the time required for the adhesive tape to fall off is 240 hours or more
X: the time until the adhesive tape falls off is less than 240 hours
< storage modulus >
After a test piece of 1cm × 1cm was cut from the pre-laminate, the light release treated polyester film and the heavy release treated polyester film were peeled off to obtain an adhesive sheet.
An adhesive layer having a film thickness of 1mm was prepared by stacking 10 sheets of the obtained adhesive sheet, and the dynamic viscoelasticity was measured under the following conditions using a commercially available measuring machine (product name "MCR 302", manufactured by anton paar corporation). Then, the storage modulus G' (unit: MPa) at 25 ℃ and 100 ℃ was determined from the measurement results.
(measurement conditions)
Deformation mode: torsion
Measuring frequency: 1Hz
Strain: 0.01-1% automatic setting
Temperature rise rate: 3 ℃ per minute
Measuring temperature: -50 to 100 DEG C
Shape: parallel plates 8.0mm phi
[ TABLE 1 ]
Figure BDA0003495309860000301
In addition, the method is as follows: the content of the thiol compound is represented by a mass part based on 100 mass parts of the total of the solid components of the component (a), the component (B) and the component (C).
The symbols and abbreviations of table 1 refer to the following compounds.
< polyurethane (meth) acrylate >
A-1: preparation example 1 urethane acrylate
A-2: preparation example 2 urethane acrylate
A-3: preparation example 3 urethane acrylate
A-4: preparation example 4 urethane acrylate
G-1: urethane acrylate of comparative production example 1
G-2: urethane acrylate of comparative production example 2
Alkyl mono (meth) acrylates
B-1: 2-ethylhexyl acrylate
B-2: acrylic acid 4-hydroxybutyl ester
< Mono (meth) acrylate having aromatic ring >
C-1: o-phenylphenoxyethyl acrylate (having 2 aromatic rings)
C-2M-Phenoxybenzyl acrylate (having 2 aromatic rings)
E-1: benzyl acrylate (having 1 aromatic ring)
< thiol Compound >
D-1: pentaerythritol tetrakis (3-mercaptobutyrate), trade name: "Karenz MT PE 1" manufactured by Showa Denko K.K.
F-1: pentaerythritol tetrakis (3-mercaptopropionate)

Claims (9)

1. An active energy ray-curable adhesive composition comprising:
a urethane (meth) acrylate (A) which is a reaction product of a polyol (a1), a polyisocyanate (a2) and a hydroxyl group-containing mono (meth) acrylate (a3-1), or a reaction product of a polyol (a1), a polyisocyanate (a2) and an isocyanate group-containing mono (meth) acrylate (a3-2), wherein the urethane (meth) acrylate (A) has an average number of (meth) acryloyl groups of 1 to 4 and a weight average molecular weight of 10000 to 90000;
alkyl mono (meth) acrylate (B);
a mono (meth) acrylate (C) having at least 2 aromatic rings; and
a compound (D) having a secondary thiol group.
2. The active energy ray-curable adhesive composition according to claim 1, wherein the component (a1) comprises a polyether polyol.
3. The active energy ray-curable adhesive composition according to claim 1 or 2, wherein the component (B) contains a mono (meth) acrylic acid alkyl ester (B1) containing no hydroxyl group and/or a mono (meth) acrylic acid hydroxyalkyl ester (B2).
4. The active energy ray-curable adhesive composition according to any one of claims 1 to 3, wherein the content ratio of the component (C) is 30 to 75% by mass based on 100% by mass of the total of the components (A), (B) and (C).
5. The active energy ray-curable adhesive composition according to any one of claims 1 to 4, wherein the component (D) is a compound having 2 or more secondary thiol groups.
6. The active energy ray-curable adhesive composition according to any one of claims 1 to 5, wherein the content of the component (D) is 0.1 to 5 parts by mass based on 100 parts by mass of the total of the component (A), the component (B) and the component (C) in terms of the mass of the solid component.
7. A cured product of the active energy ray-curable adhesive composition according to any one of claims 1 to 6.
8. The cured product according to claim 7, which has a storage modulus G 'at a temperature of 25 ℃ and a frequency of 1Hz of 0.3MPa or more, and which has a storage modulus G' at a temperature of 100 ℃ and a frequency of 1Hz of 0.1MPa or more.
9. A laminate comprising the cured product according to claim 7 or 8 on at least one surface of a substrate.
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