Composition, adhesive composition, and adhesive

Abstract

To provide a composition that exhibits excellent adhesion to various components. [Solution] A composition containing a urethane (meth)acrylate compound (A) and a monofunctional ethylenically unsaturated monomer (B), wherein the monofunctional ethylenically unsaturated monomer (B) contains a monofunctional ethylenically unsaturated monomer (B1) having a glass transition temperature of 0 to 130°C and a monofunctional ethylenically unsaturated monomer (B2) having an aryl group.

Description

[Technical Field]

[0001] The present invention relates to a composition, and more particularly to a composition that exhibits good adhesiveness when formed into a pressure-sensitive adhesive, a pressure-sensitive adhesive composition, and a pressure-sensitive adhesive. [Background Art]

[0002] There are various types of pressure-sensitive adhesives, and pressure-sensitive adhesives optimized for the fields of use are designed and put into use. As said pressure-sensitive adhesives, for example, highly adhesive pressure-sensitive adhesives intended to firmly bond various adherends for a long period of time, and active energy ray-curable pressure-sensitive adhesives that exhibit their function as a pressure-sensitive adhesive when irradiated with active energy rays, are known.

[0003] As the active energy ray-curable pressure-sensitive adhesive, for example, Patent Document 1 discloses an active energy ray-curable pressure-sensitive adhesive composition containing a urethane (meth)acrylate compound obtained by reacting a hydroxyl group-containing (meth)acrylate with a terminal isocyanate group-containing compound which is a reaction product of hydrogenated polybutadiene polyol and polyisocyanate (a2), and an aliphatic or alicyclic alkyl acrylate having 6 or more carbon atoms. It is described that the active energy ray-curable pressure-sensitive adhesive composition has an excellent balance between adhesiveness to substrates and weather resistance, and is useful as a pressure-sensitive adhesive for use in various protective films. [Prior Art Literature] [Patent Literature]

[0004] [Patent Document 1] Japanese Unexamined Patent Application Publication No. 2002-309185 [Summary of the Invention] [Problem to be Solved by the Invention]

[0005] The active energy ray-curable adhesive composition disclosed in Patent Document 1 does not have sufficient adhesiveness to various members, and further improvement is required.

[0006] Therefore, against this background, the present invention aims to provide a composition that exhibits excellent adhesion to various components. [Means for solving the problem]

[0007] However, in view of these circumstances, the inventors diligently conducted research and found that the above problems can be solved by using a urethane (meth)acrylate compound in combination with a monofunctional ethylenically unsaturated monomer having a relatively high glass transition temperature and a monofunctional ethylenically unsaturated monomer having an aryl group, and thus completed the present invention.

[0008] In other words, the present invention has the following aspects. [1] A composition containing a urethane (meth)acrylate compound (A) and a monofunctional ethylenically unsaturated monomer (B), A composition in which the monofunctional ethylenically unsaturated monomer (B) contains a monofunctional ethylenically unsaturated monomer (B1) having a glass transition temperature of 0 to 130°C and a monofunctional ethylenically unsaturated monomer (B2) having an aryl group. [2] The composition according to [1], wherein the urethane (meth)acrylate compound (A) is a reaction product of a polyol (a1), a polyvalent isocyanate (a2), a hydroxyl group-containing (meth)acrylate (a3), and a monool (a4). [3] The active energy ray curable resin composition according to [2], wherein the monool (a4) is a monool having 2 or more carbon atoms. [4] The composition according to any one of [1] to [3], wherein the urethane (meth)acrylate compound (A) is a monofunctional urethane (meth)acrylate compound. [5] The composition according to any one of [1] to [4], wherein the weight-average molecular weight of the urethane (meth)acrylate compound (A) is 20,000 to 100,000. [6] The composition according to any one of [1] to [5], wherein the content of the monofunctional ethylenically unsaturated monomer (B) is 20 to 300 parts by mass per 100 parts by mass of the urethane (meth)acrylate compound (A). [7] The composition according to any one of [1] to [6], wherein the mass content ratio (B1 / B2) of a monofunctional ethylenically unsaturated monomer (B1) having a glass transition temperature of 0 to 130°C and a monofunctional ethylenically unsaturated monomer (B2) having an aryl group is 70 / 30 to 30 / 70. [8] The composition according to any one of [1] to [7], further comprising a hydrolysis inhibitor (C), wherein the content of the hydrolysis inhibitor (C) is 0.01 to 10% by mass relative to the composition. [9] The composition according to any one of [1] to [8] further contains a photopolymerization initiator (D).

[10] An adhesive composition comprising any of the compositions described in [1] to [9].

[11] An adhesive obtained by curing the adhesive composition described in

[10] . [Effects of the Invention]

[0009] The composition of the present invention exhibits excellent adhesion to various substrates. Therefore, the composition of the present invention can be applied to various uses such as coatings, paints, inks, and adhesives, and is particularly suitable for use as an adhesive. [Modes for carrying out the invention]

[0010] The present invention will be described below based on examples of embodiments for carrying out the present invention. However, the present invention is not limited to the embodiments described below.

[0011] In this specification, "x and / or y (where x, y are any configuration)" means at least one of x and y, and can mean x only, y only, or x and y. In this specification, when "X~Y" (where X and Y are any numbers) is used, unless otherwise specified, it means "X or greater and Y or less," and also includes the meanings of "preferably greater than X" or "preferably less than Y." In this specification, when we use the expressions "X or more" (where X is any number) or "Y or less" (where Y is any number), we also mean "preferably greater than X" or "preferably less than Y." In this specification, the numerical ranges described in stages may be arbitrarily combined with the upper or lower limits of the numerical ranges in any stage. Furthermore, in the numerical ranges described herein, the upper or lower limits may be replaced with the values ​​shown in the examples.

[0012] In this specification, "(meth)acrylic" means acrylic and / or methacrylic, "(meth)acryloyl" means acryloyl and / or methacryloyl, and "(meth)acrylate" means acrylate and / or methacrylate. In this specification, "film" includes "tape" and "sheet."

[0013] A composition according to one embodiment of the present invention (hereinafter referred to as "the Composition") contains a urethane (meth)acrylate compound (A) and a monofunctional ethylenically unsaturated monomer (B). Furthermore, this composition is curable by irradiation with active energy rays. In other words, this composition can be suitably used as an active energy ray curable resin composition.

[0014] <Urethane (meth)acrylate compound (A)> The urethane (meth)acrylate compound (A) is not particularly limited as long as it is a compound having a urethane bond formed by reacting an isocyanate group with a hydroxyl group and a (meth)acryloyl group.

[0015] From the viewpoint of adhesion to an adherend, the number of (meth)acryloyl groups contained in the urethane (meth)acrylate compound (A) is preferably 1 to 6, more preferably 1 to 4, and particularly preferably 1. That is, from the viewpoint of adhesion to an adherend, the urethane (meth)acrylate compound (A) is preferably a monofunctional urethane (meth)acrylate compound.

[0016] The weight average molecular weight of the urethane (meth)acrylate compound (A) is preferably 20,000 to 100,000, more preferably 22,000 to 80,000, still more preferably 24,000 to 50,000, particularly preferably 26,000 to 40,000, and most preferably 28,000 to 35,000. When the weight average molecular weight of the urethane (meth)acrylate compound (A) falls within the above range, the adhesion to an adherend tends to be excellent.

[0017] The weight average molecular weight of the urethane (meth)acrylate compound (A) is a weight average molecular weight in terms of standard polystyrene molecular weight, and is measured using a high performance liquid chromatograph (manufactured by Showa Denko K.K., "Shodex GPC system-11"), with Shodex GPC KF-806L (exclusion limit molecular weight: 2×10 7 , separation range: 100 to 2×10 7 , theoretical plate number: 10,000 plates / column, filler material: styrene-divinylbenzene copolymer, filler particle size: 10 μm) connected in series in three columns.

[0018] The viscosity of the urethane (meth)acrylate compound (A) is usually 1,000 to 1,000,000 mPa·s, preferably 2,000 to 800,000 mPa·s, and more preferably 3,000 to 600,000 mPa·s. When the viscosity of the urethane (meth)acrylate compound (A) falls within the above range, the handleability tends to be excellent, and the coatability also tends to be excellent. The viscosity of the urethane (meth)acrylate compound (A) is measured at 60°C using an E-type viscometer.

[0019] Specific examples of urethane (meth)acrylate compounds (A) include, for example, urethane (meth)acrylate compounds (A1) which are reaction products of polyol (a1), polyvalent isocyanate (a2), hydroxyl group-containing (meth)acrylate (a3), and monool (a4); urethane (meth)acrylate compounds which are reaction products of polyol (a1), polyvalent isocyanate (a2), and hydroxyl group-containing (meth)acrylate (a3); and urethane (meth)acrylate compounds which are reaction products of polyvalent isocyanate (a2) and hydroxyl group-containing (meth)acrylate (a3). Among these, urethane (meth)acrylate compounds (A1) which are reaction products of polyol (a1), polyvalent isocyanate (a2), hydroxyl group-containing (meth)acrylate (a3), and monool (a4) are preferred due to their excellent adhesion to the adherend. The following describes a preferred urethane (meth)acrylate compound (A1), but other urethane (meth)acrylates can also be obtained using known reaction methods with polyols (a1), polyvalent isocyanates (a2), and hydroxyl group-containing (meth)acrylates (a3), which will be described later.

[0020] [Urethane (meth)acrylate compound (A1)] As mentioned above, the urethane (meth)acrylate compound (A1) is a reaction product of a polyol (a1), a polyvalent isocyanate compound (a2), a hydroxyl group-containing (meth)acrylate compound (a3), and a monool (a4).

[0021] [Polyol (a1)] The polyol (a1) can be any compound containing two or more hydroxyl groups, such as aliphatic polyols, alicyclic polyols, polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, polybutadiene polyols, polyisoprene polyols, (meth)acrylic polyols, and polysiloxane polyols. These may be used individually or in combination of two or more.

[0022] Examples of the aliphatic polyols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, dimethylolpropane, neopentyl glycol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-tetramethylenediol, 1,3-tetramethylenediol, 2-methyl-1,3-trimethylenediol, 1,5-pentamethylenediol, 1, Examples include aliphatic alcohols containing two hydroxyl groups, such as 6-hexamethylenediol, 3-methyl-1,5-pentamethylenediol, 2,4-diethyl-1,5-pentamethylenediol, pentaerythritol diacrylate, 1,9-nonanediol, and 2-methyl-1,8-octanediol; sugar alcohols such as xylitol and sorbitol; and aliphatic alcohols containing three or more hydroxyl groups, such as glycerin, trimethylolpropane, and trimethylolethane.

[0023] Examples of the alicyclic polyols include cyclohexanediols such as 1,4-cyclohexanediol and cyclohexyldimethanol, hydrogenated bisphenols such as hydrogenated bisphenol A, and tricyclodecanedimethanol.

[0024] Examples of the polyether polyol include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, polypentamethylene glycol, and polyhexamethylene glycol, as well as random or block copolymers of these polyalkylene glycols.

[0025] Examples of the aforementioned polyester polyols include condensation polymers of polyhydric alcohols and polyhydric carboxylic acids; ring-opening polymers of cyclic esters (lactones); and reaction products of three components: polyhydric alcohols, polyhydric carboxylic acids, and cyclic esters. Examples of the aforementioned polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylenediol, 1,3-tetramethylenediol, 2-methyl-1,3-trimethylenediol, 1,5-pentamethylenediol, neopentyl glycol, 1,6-hexamethylenediol, 3-methyl-1,5-pentamethylenediol, 2,4-diethyl-1,5-pentamethylenediol, glycerin, trimethylolpropane, trimethylolethane, cyclohexanediols (such as 1,4-cyclohexanediol), bisphenols (such as bisphenol A), sugar alcohols (such as xylitol and sorbitol), and the like. Examples of the aforementioned polycarboxylic acids include aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedionic acid; alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; and aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid, and trimellitic acid. Examples of the cyclic esters mentioned above include propiolactone, β-methyl-δ-valerolactone, and ε-caprolactone.

[0026] Examples of the polycarbonate polyol include the reaction product of a polyhydric alcohol and phosgene; and ring-opening polymers of cyclic carbonate esters (such as alkylene carbonates). Examples of the polyhydric alcohol include the polyhydric alcohols exemplified in the description of the polyester polyol, and examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, and hexamethylene carbonate. The polycarbonate polyol is any compound having a carbonate bond in its molecule and a hydroxyl group at its terminal end, and may also have an ester bond in addition to the carbonate bond.

[0027] Examples of the aforementioned polyolefin polyols include those having a homopolymer or copolymer of ethylene, propylene, butene, etc. as a saturated hydrocarbon backbone, and having hydroxyl groups at the molecular ends.

[0028] Examples of the polybutadiene polyols include those having a butadiene copolymer as the hydrocarbon backbone and having hydroxyl groups at the molecular ends. The polybutadiene-based polyol may also be a hydrogenated polybutadiene polyol in which all or part of the ethylenically unsaturated groups contained in its structure are hydrogenated.

[0029] Examples of the polyisoprene polyol include those having an isoprene copolymer as a hydrocarbon backbone and having hydroxyl groups at the molecular termini. The polyisoprene-based polyol may also be a hydrogenated polyisoprene polyol in which all or part of the ethylenically unsaturated groups contained in its structure are hydrogenated.

[0030] Examples of the (meth)acrylic polyol include polymers or copolymers of (meth)acrylic acid esters that have at least two hydroxyl groups in the molecule. Examples of such (meth)acrylic acid esters include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, and octadecyl (meth)acrylate.

[0031] Examples of the polysiloxane polyols include dimethylpolysiloxane polyol and methylphenylpolysiloxane polyol.

[0032] Among these, aliphatic polyols and alicyclic polyols are preferred in terms of cost, polyester polyols, polyether polyols, and polycarbonate polyols are preferred in terms of versatility, and polyester polyols are particularly preferred in terms of excellent adhesion to the substrate.

[0033] The number of hydroxyl groups in the polyol (a1) is preferably 2 to 5, more preferably 2 to 3, and particularly preferably 2.

[0034] The hydroxyl value of the polyol (a1) is typically 10 to 500 mg KOH / g, preferably 20 to 300 mg KOH / g, and more preferably 40 to 200 mg KOH / g. When the hydroxyl value of the polyol (a1) is within this range, it tends to exhibit excellent flexibility and adhesion to the adherend. The hydroxyl value of polyol (a1) is measured in accordance with JIS K 1557-1.

[0035] The number-average molecular weight of the polyol (a1) is preferably 60 to 10,000, particularly preferably 100 to 5,000, and even more preferably 200 to 4,000. When the number-average molecular weight of the polyol (a1) is within this range, it tends to exhibit excellent flexibility and adhesion to the adherend. The number-average molecular weight of the polyol (a1) can be calculated from the hydroxyl value.

[0036] [Polyvalent isocyanate (a2)] For example, the polyvalent isocyanate (a2) is: Examples include aromatic polyvalent isocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate; aliphatic polyvalent isocyanates such as pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate; alicyclic polyvalent isocyanates such as isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, norbornene diisocyanate, etc.; trimer compounds or polymer compounds of these polyvalent isocyanates; allophanate-type polyvalent isocyanates, biuret-type polyvalent isocyanates, etc. These may be used individually or in combination of two or more types.

[0037] In particular, aliphatic polyvalent isocyanates and alicyclic polyvalent isocyanates are preferred due to their low yellowing, and more preferably pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, and norbornene diisocyanate. Furthermore, alicyclic diisocyanates are preferred in terms of their excellent reactivity and versatility, more preferably isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated xylylene diisocyanate, and even more preferably isophorone diisocyanate and hydrogenated diphenylmethane diisocyanate in terms of their excellent adhesive properties.

[0038] [Hydroxyl group-containing (meth)acrylate (a3)] Examples of hydroxyl group-containing (meth)acrylates (a3) ​​include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxyhexyl (meth)acrylate; 2-hydroxyethyl acryloyl phosphate, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone-modified 2-hydroxyethyl (meth)acrylate, dipropylene glycol (meth)acrylate, fatty acid-modified glycidyl (meth)acrylate, and polyethylene glycol mono(meth)acrylate. Examples include methyl acrylate, polypropylene glycol mono(meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate, glycerin di(meth)acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, pentaerythritol tri(meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate, ethylene oxide-modified pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol penta(meth)acrylate, and ethylene oxide-modified dipentaerythritol penta(meth)acrylate. These may be used individually or in combination of two or more.

[0039] Among these, hydroxyl group-containing (meth)acrylates having one ethylenically unsaturated group are preferred in terms of excellent adhesion to the adherend, and more preferably hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxyhexyl (meth)acrylate. In terms of excellent reactivity and versatility, 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate are even more preferred.

[0040] [Monoall (a4)] The monool (a4) is not particularly limited as long as it is a compound having one hydroxyl group in its molecule. Examples of the monool (a4) include aliphatic monools, aromatic monools, alicyclic monools, and polyoxyalkylene glycol monoalkyl ethers. These may be used individually or in combination of two or more.

[0041] Examples of the aliphatic monools include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 1-hexanol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 1-octanol, 2-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol, 1 Examples include linear saturated aliphatic monools such as nonadecanol, 1-eicosanol, 1-hexacosanol, 1-heptatriconol, and 2-octyldodecanol; linear unsaturated aliphatic monools such as 1-oleyl alcohol; and branched saturated aliphatic monools such as 2-ethylhexanol, 2-hexyldecanol, isohexadecanol, isooctadecanol, 3,5-dimethyl-1-hexanol, 2,2,4-trimethyl-1-pentanol, and 2,6-dimethyl-4-heptanol.

[0042] Examples of the aromatic monools include phenol, cresol, and benzyl alcohol.

[0043] Examples of the alicyclic monool include cyclohexanol and methylcyclohexanol.

[0044] Examples of the polyoxyalkylene glycol monoalkyl ether include reaction products of the aliphatic monool and polyoxypropylene glycol, specifically, polyoxypropylene methyl ether, polyoxypropylene ethyl ether, polyoxypropylene butyl ether, polyoxypropylene-2-ethylhexyl ether, polyoxypropylene oleyl ether, polyoxypropylene-2-octyldodeca ether, and the like.

[0045] The monool (a4) is preferably a C2 or more, more preferably an aliphatic monool having C2 to C10, and even more preferably a linear saturated aliphatic monool having C2 to C10, particularly preferably 2-propanol, due to its excellent adhesion to the adherend.

[0046] The urethane (meth)acrylate compound (A1) is, for example, (1) A method of charging polyol (a1), polyvalent isocyanate (a2), hydroxyl group-containing (meth)acrylate (a3), and monool (a4) into a reactor together or separately and carrying out the reaction. (2) A method of reacting the isocyanate group in a compound (X) containing isocyanate groups at both ends, which is a reaction product of a polyol (a1) and a polyvalent isocyanate (a2), with the hydroxyl group of a hydroxyl group-containing (meth)acrylate (a3) ​​and a monool (a4). (3) A method of reacting a terminal isocyanate-containing compound (Y), which is a reaction product of a polyvalent isocyanate (a2) and a hydroxyl-containing (meth)acrylate (a3), a terminal isocyanate-containing compound (Z), which is a reaction product of a polyvalent isocyanate (a2) and a monool (a4), and a compound (W) containing both terminal hydroxyl groups, which is a reaction product of a polyol (a1) or a polyol (a1) and a polyvalent isocyanate (a2). It can be obtained by the following means. Among these, method (2) is preferred in terms of reaction stability and reduction of by-products. The method described in (2) below will be explained in detail.

[0047] In the method described in (2) above, known reaction methods can be used for the reaction between the polyol (a1) and the polyvalent isocyanate (a2). In this case, for example, by setting the molar ratio [hydroxyl group:isocyanate group] of the hydroxyl group in the polyol (a1) to the isocyanate group in the polyvalent isocyanate (a2) to approximately (2n-2):2n (where n is an integer of 2 or more), a compound (X) containing isocyanate groups at both ends with residual isocyanate groups can be obtained.

[0048] In the aforementioned molar ratio, n is usually 4 or more, preferably 5 or more, and more preferably 6 or more. The upper limit is usually 10 or less, preferably 9 or less, more preferably 8 or less, and even more preferably 7 or less. When n is within the above range, adhesion is excellent and handling tends to improve.

[0049] Furthermore, the reaction molar ratio between the compound (X) containing both terminal isocyanate groups and the hydroxyl group-containing (meth)acrylate (a3) ​​is typically around 1:1 when the compound (X) containing both terminal isocyanate groups has two isocyanate groups and the hydroxyl group-containing (meth)acrylate (a3) ​​has one hydroxyl group, and around 1:1.5 when the compound (X) containing both terminal isocyanate groups has three isocyanate groups and the hydroxyl group-containing (meth)acrylate (a3) ​​has one hydroxyl group.

[0050] The reaction molar ratio between the compound (X) containing isocyanate groups at both ends and the monool (a4) is typically about 1:1 when the compound (X) contains two isocyanate groups, and about 1:1.5 when the compound (X) contains three isocyanate groups.

[0051] Furthermore, when reacting a compound (X) containing isocyanate groups at both ends with a hydroxyl group-containing (meth)acrylate (a3) ​​and a monool (a4), the molar ratio of the hydroxyl group-containing (meth)acrylate (a3) ​​to the monool (a4) is typically about 1:1, for example, if the hydroxyl group-containing (meth)acrylate (a3) ​​has one hydroxyl group.

[0052] In the addition reaction between this compound (X) containing isocyanate groups at both ends and a hydroxyl group-containing (meth)acrylate (a3) ​​and a monool (a4), the reaction is terminated when the remaining isocyanate group content in the reaction system becomes 0.5% by mass or less, thereby obtaining a urethane (meth)acrylate compound (A1).

[0053] In the reaction between the polyol (a1) and the polyvalent isocyanate (a2), and further in the reaction between the compound (X) containing both terminal isocyanate groups and the hydroxyl group-containing (meth)acrylate (a3) ​​and monool (a4), it is also preferable to use a catalyst to accelerate the reaction.

[0054] Examples of catalysts include organometallic compounds such as dibutyltin dilaurate, dibutyltin diacetate, trimethyltin hydroxide, tetra-n-butyltin, zinc bisacetylacetonate, zirconium tris(acetylacetonate)ethylacetoacetate, and zirconium tetraacetylacetonate; metal salts such as tin octenoate, zinc hexanoate, zinc octenoate, zinc stearate, zirconium 2-ethylhexanoate, cobalt naphthenate, stannous chloride, stannous chloride, and potassium acetate; triethylamine, triethylenediamine, benzyldiethylamine, 1,4-diazabicyclo[2,2,2]octane, 1,8-diazabicyclo[5,4,0]undecene, N,N,N', Examples of bismuth catalysts include amine-based catalysts such as N'-tetramethyl-1,3-butanediamine, N-methylmorpholine, and N-ethylmorpholine; organic bismuth compounds such as bismuth nitrate, bismuth bromide, bismuth iodide, bismuth sulfide, dibutylbismuth dilaurate, and dioctylbismuth dilaurate; and organic acid bismuth catalysts such as bismuth 2-ethylhexanoate, bismuth naphthenate, bismuth isodecanate, bismuth neodecanoate, bismuth laurate, bismuth maleate, bismuth stearate, bismuth oleate, bismuth linoleate, bismuth acetate, bismuth lybisneodecanoate, bismuth disalicylate, and bismuth digallate. These may be used individually or in combination of two or more. Among these, dibutyltin dilaurate and 1,8-diazabicyclo[5,4,0]undecene are preferred.

[0055] Furthermore, in the production of urethane (meth)acrylate compounds (A1), organic solvents that do not have functional groups that react with isocyanate groups may be used as needed, such as esters like ethyl acetate and butyl acetate, ketones like methyl ethyl ketone and methyl isobutyl ketone, and aromatics like toluene and xylene.

[0056] The reaction temperature in the production of the urethane (meth)acrylate compound (A1) is usually 30 to 90°C, preferably 40 to 80°C, and the reaction time is usually 2 to 10 hours, preferably 3 to 8 hours.

[0057] The content of the urethane (meth)acrylate compound (A) in this composition is usually 1 to 90% by mass, preferably 10 to 80% by mass, and more preferably 20 to 70% by mass.

[0058] [Monofunctional ethylenically unsaturated monomer (B)] The monofunctional ethylenically unsaturated monomer (B) includes a monofunctional ethylenically unsaturated monomer (B1) having a glass transition temperature of 0 to 130°C [hereinafter referred to as "ethylenically unsaturated monomer (B1)"] and a monofunctional ethylenically unsaturated monomer (B2) having an aryl group [hereinafter referred to as "ethylenically unsaturated monomer (B2)"]. In other words, in this composition, by using in combination an ethylenically unsaturated monomer (B1) with a high glass transition temperature and an ethylenically unsaturated monomer (B2) having an aryl group, it is possible to achieve excellent adhesion to the adherend.

[0059] The content of the monofunctional ethylenically unsaturated monomer (B) is preferably 20 to 300 parts by mass, more preferably 30 to 280 parts by mass, and particularly preferably 60 to 260 parts by mass, per 100 parts by mass of the urethane (meth)acrylate compound (A). When the content of the monofunctional ethylenically unsaturated monomer (B) is within the above range, the viscosity is low and the adhesion to various materials tends to be excellent.

[0060] [Ethylene-unsaturated monomer (B1)] The above-mentioned ethylenically unsaturated monomer (B1) has a glass transition temperature of 0 to 130°C, preferably 10 to 120°C, and more preferably 20 to 100°C. When the glass transition temperature of the ethylenically unsaturated monomer (B1) is within the above range, it tends to have low viscosity and excellent adhesion to various materials.

[0061] The glass transition temperature of the ethylenically unsaturated monomer (B1) is the glass transition temperature when the ethylenically unsaturated monomer (B1) is used as a homopolymer. For example, values ​​found in the Polymer Handbook, Fourth Edition, John Wiley & Sons, Inc. (1999) or the Polymer Data Handbook, edited by the Society of Polymer Science, Japan (1986) can be used. For homopolymers not listed in these sources, values ​​found in other literature or product catalogs, or values ​​measured by manufacturing homopolymers, can be used.

[0062] Examples of monofunctional ethylenically unsaturated monomers (B1) having a glass transition temperature of 0 to 130°C include alkyl (meth)acrylates such as methyl (meth)acrylate (Tga 8°C, Tgm 105°C), ethyl methacrylate (Tgm 65°C), n-butyl methacrylate (Tgm 20°C), isobutyl methacrylate (Tgm 48°C), t-butyl (meth)acrylate (Tga 41°C, Tgm 107°C), and n-stearyl (meth)acrylate (Tga 30°C, Tgm 38°C), hydroxyl-containing (meth)acrylates such as 2-hydroxyethyl methacrylate (Tgm 55°C) and 2-hydroxypropyl methacrylate (Tgm 26°C), and dimethylaminoethyl methacrylate (Tgm 18°C) and diethylaminoethyl methacrylate (Tgm 16 to 24°C). Examples include (meth)acrylate monomers such as amino group-containing (meth)acrylates, isobornyl acrylate (Tga 97°C), cyclohexyl (meth)acrylate (Tga 15°C, Tgm 66°C), 3,3,5-trimethylcyclohexyl acrylate (Tga 52°C), heterocyclic (meth)acrylates such as tetrahydrofurfuryl methacrylate (Tgm 60°C), glycidyl (meth)acrylate (Tga 60°C, Tgm 46°C), (3-ethyloxetan-3-yl)methyl methacrylate (Tgm 2°C), and cyclic trimethylolpropane formal acrylate (Tga 27°C); vinyl acetate (29°C); amide monomers such as hydroxyethylacrylamide (98°C) and diethylacrylamide (81°C). These may be used individually or in combination of two or more. Among these, alicyclic (meth)acrylates are preferred as the ethylenically unsaturated monomer (B1), more preferably heterocyclic (meth)acrylates, even more preferably isobonyl acrylates, cyclic trimethylolpropane formal acrylates, and particularly preferably isobonyl acrylates. The numbers in parentheses indicate the glass transition temperature. Also, "Tga" indicates acrylate and "Tgm" indicates methacrylate.

[0063] The content of the ethylenically unsaturated monomer (B1) is usually 15 to 130 parts by mass, preferably 20 to 120 parts by mass, and particularly preferably 25 to 80 parts by mass, per 100 parts by mass of the urethane (meth)acrylate compound (A). When the content of the ethylenically unsaturated monomer (B1) is within the above range, it tends to result in a low viscosity.

[0064] [Ethylene-unsaturated monomer (B2)] The ethylenically unsaturated monomer (B2) is not particularly limited as long as it has an aryl group, but examples include benzene-based monomers such as styrene, vinyltoluene, chlorostyrene, and α-methylstyrene; phenoxyalkyl (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and phenoxypropyl (meth)acrylate; phenoxydialkylene glycol (meth)acrylates such as phenoxydiethylene glycol (meth)acrylate and phenoxydipropylene glycol (meth)acrylate; phenoxypolyethylene glycol (meth)acrylate; phenoxypolyethylene glycol-polypropylene glycol (meth)acrylate; (meth)acrylate of p-cumylphenol alkylene oxide adducts; (meth)acrylate of o-phenylphenol alkylene oxide adducts; (meth)acrylate of phenol alkylene oxide adducts; and (meth)acrylate of nonylphenol alkylene oxide adducts. These may be used individually or in combination of two or more. In particular, monofunctional (meth)acrylate monomers having an aryl group are preferred due to their excellent adhesion to the adherend, more preferably phenoxydialkylene glycol (meth)acrylate, and especially preferably phenoxydiethylene glycol (meth)acrylate.

[0065] The content of the ethylenically unsaturated monomer (B2) is usually 15 to 130 parts by mass, preferably 20 to 120 parts by mass, and particularly preferably 25 to 80 parts by mass, per 100 parts by mass of the urethane (meth)acrylate compound (A). When the content of the ethylenically unsaturated monomer (B2) is within the above range, it tends to result in a low viscosity.

[0066] Furthermore, the mass content ratio (B1 / B2) of the ethylenically unsaturated monomer (B1) and ethylenically unsaturated monomer (B2) is preferably 70 / 30 to 30 / 70, more preferably 65 / 35 to 35 / 65, and even more preferably 60 / 40 to 40 / 60. When the mass content ratio of ethylenically unsaturated monomer (B1) and ethylenically unsaturated monomer (B2) is within the above range, the viscosity is low and the adhesion to various materials tends to be excellent.

[0067] The monofunctional ethylenically unsaturated monomer (B) may contain other monofunctional ethylenically unsaturated monomers (B3) other than the ethylenically unsaturated monomer (B1) and ethylenically unsaturated monomer (B2) in an amount that does not hinder the effects of the present invention [for example, 10% by weight or less of the monofunctional ethylenically unsaturated monomer (B)]. However, in this embodiment, it is preferable that the monofunctional ethylenically unsaturated monomer (B) consists only of ethylenically unsaturated monomer (B1) and ethylenically unsaturated monomer (B2).

[0068] [Hydrolysis inhibitor (C)] The composition is preferably further enriched with a hydrolysis inhibitor (C) in terms of hydrolysis resistance. The hydrolysis inhibitor (C) is not particularly limited, and conventionally known compounds can be used, such as carbodiimide group-containing compounds.

[0069] [Carbodiimide group-containing compounds] As the carbodiimide group-containing compound, a known carbodiimide having one or more carbodiimide groups (-N=C=N-) in its molecule can usually be used. However, to improve durability under high temperature and high humidity conditions, it is preferable to use a compound containing two or more carbodiimide groups in its molecule, i.e., a polyvalent carbodiimide compound. In particular, it is preferable to use a compound containing three or more carbodiimide groups in its molecule, even more so five or more, and especially seven or more. Furthermore, the number of carbodiimide groups in the molecule is usually 50 or less, in order to ensure compatibility with urethane (meth)acrylate compounds (A).

[0070] As the carbodiimide group-containing compound, it is preferable to use one with a high weight-average molecular weight from the viewpoint of hydrolysis resistance. The weight-average molecular weight of a carbodiimide group-containing compound is usually 1,000 or more, preferably 2,000 or more, and more preferably 3,000 or more. The upper limit of the weight-average molecular weight is usually 50,000 or less.

[0071] Furthermore, it is preferable to use a carbodiimide group-containing compound that has low volatility, and therefore it is preferable to use one with a high number-average molecular weight. The number-average molecular weight of carbodiimide group-containing compounds is typically 300 to 10,000, preferably 1,000 to 5,000.

[0072] When the molecular weight of the carbodiimide group-containing compound is within the aforementioned range, hydrolysis resistance tends to improve, and compatibility with urethane (meth)acrylate compound (A) tends to be excellent.

[0073] The carbodiimide equivalent of the carbodiimide group-containing compound is preferably 50 to 10,000, particularly preferably 100 to 1,000, and even more preferably 150 to 500. Note that the carbodiimide equivalent refers to the chemical formula weight per carbodiimide group.

[0074] Furthermore, as the carbodiimide group-containing compound, it is also preferable to use a polycarbodiimide compound produced by decarboxylating and condensing diisocyanate in the presence of a carbodiimide catalyst.

[0075] (Polycarbodiimide compounds) Polycarbodiimide compounds can be obtained by condensation reactions of organic diisocyanate compounds. Examples of the aforementioned organic diisocyanate compounds include 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tole diisocyanate, 2,6-tole diisocyanate, a mixture of 2,4-tole diisocyanate and 2,6-tole diisocyanate, xylylene diisocyanate, tetramethyl Examples include aromatic diisocyanate compounds such as tylxylylene diisocyanate; acyclic aliphatic diisocyanates such as hexamethylene diisocyanate; aliphatic diisocyanates such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, methylcyclohexane diisocyanate, and cyclic aliphatic diisocyanates such as 2,5(2,6)-bis(isocyanatomethyl)bicyclo[2.2.1]heptane. These may be used individually or in combination of two or more. Among these, aromatic diisocyanate compounds are preferred due to their excellent resistance to moisture and heat, and tetramethylxylylene diisocyanate is more preferred. In other words, the polycarbodiimide compound is preferably an aromatic polycarbodiimide compound because it exhibits minimal haze change even under high temperature and high humidity conditions, and can be used as an adhesive with excellent heat and humidity resistance.

[0076] The aforementioned polycarbodiimide compounds can be obtained by decarboxylating and condensing an organic diisocyanate compound using a known carbodiimide catalyst in a conventional manner.

[0077] Examples of commercially available polycarbodiimide compounds include Carbodilite® V-09GB, V-02B, V-04K, V-04PF, and V-07 manufactured by Nisshinbo Chemical Corporation, and Elastostab H01 manufactured by BASF.

[0078] If the composition contains a hydrolysis inhibitor (C), its content is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.2 to 3 parts by mass, relative to the composition. When the content of the hydrolysis inhibitor (C) is within the above range, the composition tends to exhibit excellent hydrolysis resistance.

[0079] [Photopolymerization initiator (D)] Preferably, this composition further contains a photopolymerization initiator (D) to enable more efficient curing by active energy rays.

[0080] Examples of the above photopolymerization initiator (D) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 4-(2-hydroxyethoxy)-phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2-hydroxy Acetophenones such as -2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]-phenyl}-2-methyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, and phenylglyoxylic acid methyl ester; Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, o-benzoyl methyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, and 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo Benzophenones such as [2-propenyloxy)ethyl]benzenemethanaminonium bromide and (4-benzoylbenzyl)trimethylammonium chloride; thioxanthones such as 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and 2-(3-dimethylamino-2-hydroxy)-3,4-dimethyl-9H-thioxanthone-9-one mesochloride;Examples include acyl phosphine oxides such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; these may be used individually or in combination of two or more.

[0081] Among these, acetophenones and benzoins are preferred, more preferably benzyldimethyl ketal, 1-hydroxycyclohexylphenyl ketone, benzoin isopropyl ether, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl) ketone, and 2-hydroxy-2-methyl-1-phenylpropan-1-one, with 1-hydroxycyclohexylphenyl ketone being particularly preferred.

[0082] If the composition contains a photopolymerization initiator (D), its content is usually 0.1 to 20 parts by mass, preferably 1 to 10 parts by mass, and more preferably 2 to 5 parts by mass, based on 100 parts by mass of the total of the urethane (meth)acrylate compound (A) and the monofunctional ethylenically unsaturated monomer (B) [including the polyfunctional ethylenically unsaturated monomer described later, if present]. When the content of the photopolymerization initiator is within the above range, the composition tends to exhibit excellent adhesiveness and suppress discoloration such as yellowing.

[0083] Furthermore, triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michler ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4-dimethylaminobenzoate ethyl, 4-dimethylaminobenzoate (n-butoxy)ethyl, 4-dimethylaminobenzoate isoamyl, 4-dimethylaminobenzoate 2-ethylhexyl, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, etc. can also be used in combination as auxiliary agents for the photopolymerization initiator (D).

[0084] This composition may optionally contain additional additives such as polyfunctional ethylenically unsaturated monomers, surface modifiers, leveling agents, and polymerization inhibitors. These may be used individually or in combination of two or more. If this composition contains additives, the additive content is usually 20% by mass or less, preferably 10% by mass or less, and more preferably 5% by mass or less.

[0085] Examples of the polyfunctional ethylenically unsaturated monomers include difunctional ethylenically unsaturated monomers and trifunctional or more ethylenically unsaturated monomers. These may be used individually or in combination of two or more.

[0086] The aforementioned bifunctional ethylenically unsaturated monomer can be any monomer containing two ethylenically unsaturated groups, for example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide-modified bisphenol A type di(meth)acrylate, propylene oxide-modified bisphenol A type di(meth)acrylate Examples include rilate, 1,6-hexanediol di(meth)acrylate, 1,6-hexanediol ethylene oxide-modified di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, diglycidyl phthalate diglycidyl ester di(meth)acrylate, hydroxypivalic acid-modified neopentyl glycol di(meth)acrylate, isocyanurate ethylene oxide-modified diacrylate, and 2-(meth)acryloyloxyethyl acid phosphate diester.

[0087] The aforementioned trifunctional or more ethylenically unsaturated monomers can be any monomer containing three or more ethylenically unsaturated groups, such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri(meth)acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly(meth)acrylate, isocyanurate ethylene oxide-modified triacrylate, and ethylene oxide-modified dipentaerythritol. Examples include penta(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified pentaerythritol tri(meth)acrylate, ethylene oxide-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, succinic acid-modified pentaerythritol tri(meth)acrylate, and others.

[0088] The surface modifier is not particularly limited, and examples include alkyd resins. The aforementioned alkyd resin has the effect of providing film-forming properties during coating and improving adhesion to metal thin film surfaces.

[0089] As the leveling agent, any known leveling agent can be used, as long as it has the effect of imparting wettability to the substrate of the coating liquid and reducing surface tension. Examples include silicone-modified resins, fluorine-modified resins, alkyl-modified resins, etc. One or more of these may be used in combination.

[0090] Examples of polymerization inhibitors include p-benzoquinone, naphthoquinone, tolquinone, 2,5-diphenyl-p-benzoquinone, hydroquinone, 2,5-di-t-butylhydroquinone, methylhydroquinone, methoxyphenol, 2,6-di-t-butyl-p-cresol, mono-t-butylhydroquinone, and pt-butylcatechol. These may be used individually or in combination of two or more. Methoxyphenol and 2,6-di-t-butyl-p-cresol are particularly preferred.

[0091] This composition can be obtained by mixing the urethane (meth)acrylate compound (A), a monofunctional ethylenically unsaturated monomer (B), preferably a hydrolysis inhibitor (C), a photopolymerization initiator (D), and additives as needed. The mixing method is not particularly limited, and various methods can be used for mixing. For example, each component can be mixed all at once, or some components can be mixed first and then the remaining components can be mixed, or other methods can be selected as appropriate. Thus, the present composition can be obtained.

[0092] This composition can be suitably used as an adhesive composition. Furthermore, the adhesive composition is cured by irradiation with active energy rays and exhibits its function as an adhesive. Typically, the adhesive composition is coated onto various substrates, dried, and then cured by irradiation with active energy rays.

[0093] The method for applying the adhesive composition is not particularly limited and includes, for example, wet coating methods such as spraying, showering, dipping, rolling, spinning, curtaining, flowing, slitting, die printing, gravure printing, comma printing, dispenser printing, screen printing, and inkjet printing.

[0094] During the aforementioned coating process, organic solvents may be added as needed to adjust the viscosity. Examples of the aforementioned organic solvents include alcohols such as methanol, ethanol, propanol, n-butanol, and isobutanol; ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone, and cyclohexanone; cellosolves such as ethyl cellosolve; aromatics such as toluene and xylene; glycol ethers such as propylene glycol monomethyl ether; acetic acid esters such as methyl acetate, ethyl acetate, and butyl acetate; and diacetone alcohol. These may be used individually or in combination of two or more.

[0095] Furthermore, if the adhesive composition is a solid or a high-viscosity liquid, the adhesive composition may be heated to reduce its viscosity before being coated using the coating method described above (hot melt method).

[0096] Examples of the aforementioned substrates include thermoplastic resins such as polyolefin resins, polyester resins, polycarbonate resins, acrylonitrile butadiene styrene copolymers (ABS), polystyrene resins, and polyamide resins; metal vapor-deposited layers and metals such as copper, stainless steel (SUS304, SUSBA, etc.), aluminum, zinc, and magnesium; glass; and composite substrates thereof.

[0097] The shape of the substrate is not particularly limited, and examples include sheets, plates, and molded products made from the substrate. Furthermore, if the substrate is a thermoplastic resin and is in the shape of a sheet, an adhesive sheet can be made by coating it with an adhesive composition, drying it, and then irradiating it with active energy rays.

[0098] Examples of the active energy rays include far-ultraviolet rays, ultraviolet rays, near-ultraviolet rays, infrared rays, and other light rays, as well as electromagnetic waves such as X-rays and gamma rays, and electron beams, proton beams, and neutron beams. Ultraviolet rays are preferred due to their curing speed, availability of irradiation equipment, and cost. When curing is performed using electron beams, curing can be achieved without using a photopolymerization initiator (D).

[0099] When curing with ultraviolet light, use high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, LEDs, etc., that emit light in the 150-450 nm wavelength range, at a pressure of 30-3000 mJ / cm². 2 A certain amount of ultraviolet light should be applied. After UV irradiation, heating can be performed as needed to ensure complete curing.

[0100] The thickness of the cured coating film (adhesive layer) is typically 1 to 300 μm, preferably 2 to 250 μm, and more preferably 5 to 200 μm, considering light transmission to ensure uniform reaction of the photopolymerization initiator (D).

[0101] The adhesive strength of the adhesive layer to stainless steel is typically 5 N / 25 mm or more, preferably 10 N / 25 mm or more, more preferably 20 N / 25 mm or more, and even more preferably 30 N / 25 mm or more. The upper limit of the adhesive strength is typically 80 N / 25 mm or less.

[0102] The adhesive strength of the adhesive layer to the polycarbonate resin is typically 5 N / 25 mm or more, preferably 7 N / 25 mm or more, and more preferably 10 N / 25 mm or more. The upper limit of the adhesive strength is typically 60 N / 25 mm or less.

[0103] The adhesive strength of the adhesive layer to the acrylonitrile butadiene styrene copolymer is typically 5 N / 25 mm or more, preferably 10 N / 25 mm or more, and more preferably 15 N / 25 mm or more. The upper limit of the adhesive strength is typically 60 N / 25 mm or less.

[0104] The adhesive strength of the adhesive layer to the polyester resin is typically 5 N / 25 mm or more, preferably 10 N / 25 mm or more, and more preferably 15 N / 25 mm or more. The upper limit of the adhesive strength is typically 60 N / 25 mm or less.

[0105] The adhesive strength of the adhesive layer can be measured according to the measurement method of the embodiment described later.

[0106] This composition exhibits good adhesion to various materials, particularly when used as an adhesive. Therefore, it can be applied to various uses such as coatings, paints, inks, and adhesives, and is especially useful as an adhesive due to its excellent tackiness. [Examples]

[0107] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist of the invention. In the examples, "parts" and "%" refer to mass.

[0108] Prior to the examples, the following components were prepared.

[0109] [Urethane (meth)acrylate compound (A)] [Urethane (meth)acrylate compound (A1-1)] In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet, 119.4 g (0.54 mol) of isophorone diisocyanate (a2), 861.3 g (0.43 mol) of bifunctional polyester polyol (a1) [hydroxyl value 56 mg KOH / g, number average molecular weight calculated from hydroxyl value 2,000], 0.12 g of dibutylhydroxytoluene as a polymerization inhibitor, and 0.03 g of dibutyltin dilaurate as a reaction catalyst were charged, and the mixture was reacted at 60°C for 2 hours. Next, 12.9 g (0.11 mol) of 2-hydroxyethyl acrylate (a3) ​​and 6.5 g (0.11 mol) of 2-propanol (a4) were added to this system, and the reaction was carried out at 60°C for 3 hours. The reaction was terminated when the remaining isocyanate group was 0.3%, thereby obtaining a monofunctional urethane acrylate compound (A1-1) having a polyester structure [weight-average molecular weight 30,000].

[0110] [Urethane (meth)acrylate compounds (A1-2)] In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet, 135.7 parts (0.61 mol) of isophorone diisocyanate (a2), 801.3 g (0.41 mol) of bifunctional polyester polyol (a1) [hydroxyl value: 57 mg KOH / g, number average molecular weight calculated from hydroxyl value: 22,000], 0.06 parts of 2,6-di-tert-butylcresol as a polymerization inhibitor, and 0.01 parts of dibutyltin dilaurate as a reaction catalyst were charged, and the mixture was reacted at 60°C. Next, 29.4 parts (0.2 moles) of 4-hydroxybutyl acrylate (a3) ​​and 33.6 parts (0.21 moles) of isohexadecanol (a4) were added to this system, and the reaction was terminated when the remaining isocyanate group content was 0.3% or less, thereby obtaining monofunctional urethane acrylate compounds (A1-2) having a polyester structure [weight-average molecular weight 24,000].

[0111] [Urethane (meth)acrylate compound (A-3)] In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet, 135.8 g (0.61 mol) of isophorone diisocyanate (a2), 817.6 g (0.42 mol) of a bifunctional polyester polyol (a1) [hydroxyl value 56 mg KOH / g, number average molecular weight calculated from hydroxyl value 2,000], 0.12 g of dibutylhydroxytoluene as a polymerization inhibitor, and 0.03 g of dibutyltin dilaurate as a reaction catalyst were charged, and the mixture was reacted at 60°C for 2 hours. Next, 46.6 g (0.40 mol) of 2-hydroxyethyl acrylate (a3) ​​was charged into this system, and the mixture was reacted at 60°C for 3 hours. The reaction was terminated when the remaining isocyanate group was 0.3%, thereby obtaining a monofunctional urethane acrylate compound (A-3) having a polyester structure [weight average molecular weight 10,000].

[0112] [Monofunctional ethylenically unsaturated monomer (B)] [Monofunctional ethylenically unsaturated monomer (B1) with a glass transition temperature of 0-130°C] • B1-1: Isovonyl acrylate (glass transition temperature 97°C) [Monofunctional ethylenically unsaturated monomer having an aryl group (B2)] • B2-1: Phenoxydiethylene glycol acrylate (glass transition temperature -13°C) [Other monofunctional ethylenically unsaturated monomers (B3)] • B3-1: Tetrahydrofurfuryl acrylate (glass transition temperature -15°C)

[0113] <Examples 1-7, Comparative Examples 1 and 2> A urethane (meth)acrylate compound (A) and a monofunctional ethylenically unsaturated monomer (B) were blended to the composition shown in Table 1 below. Furthermore, 4 parts of Omnirad 184 (manufactured by IGM RESIN) were added as a photopolymerization initiator (D) to 100 parts of the total of the urethane (meth)acrylate compound (A) and monofunctional ethylenically unsaturated monomer (B), and the mixture was uniformly mixed to obtain the composition. The following evaluations were performed using each of the obtained compositions.

[0114] [Adhesive strength] The obtained composition was applied to an easily adhesive treated polyethylene terephthalate (PET) film (thickness 125 μm) using an applicator so that the cured film thickness would be 100 μm. With the UV irradiation surface exposed to air, it was subjected to UV irradiation at 80 W / cm (high-pressure mercury lamp) × 18 cmH × 1.9 m / min × 3 Passes (cumulative irradiation dose 2400 mJ / cm²) using a tabletop UV irradiation device (iGraphics Co., Ltd., "Conveyor-type tabletop irradiation device"). 2 An adhesive sheet for measuring adhesive strength was obtained by curing it with ultraviolet light under the following conditions.

[0115] After cutting the obtained adhesive sheet for adhesion strength measurement into 25 mm x 100 mm pieces, test specimens were prepared by pressing the sheet onto stainless steel plates (SUSBA plates), polycarbonate (PC) plates, acrylonitrile butadiene styrene copolymer (ABS) plates, and polyethylene terephthalate (PET) films using a 2 kg rubber roller, moving it back and forth twice in an atmosphere of 23°C and 50% relative humidity. After the test specimen was left to stand in the same atmosphere for 30 minutes, a 180-degree peel test was performed at a peeling speed of 0.3 m / min, and the adhesive strength (N / 25 mm) was measured and evaluated according to the following evaluation criteria. (Evaluation criteria) ○...Adhesion strength of 10N / 25mm or more to all substrates △···Adhesion to at least one substrate is 5N / 25mm or more and less than 10N / 25mm ×...Adhesion to at least one substrate is less than 5N / 25mm

[0116] [Table 1]

[0117] As shown in Table 1 above, the compositions of Examples 1 to 7, which contain a urethane (meth)acrylate compound (A), a monofunctional ethylenically unsaturated monomer (B1) with a glass transition temperature of 0 to 130°C, and a monofunctional ethylenically unsaturated monomer (B2) having an aryl group, exhibited excellent adhesive strength to various materials when used as an adhesive. On the other hand, the compositions of Comparative Example 1, which did not contain a monofunctional ethylenically unsaturated monomer (B1) having a glass transition temperature of 0 to 130°C, and Comparative Example 2, which did not contain a monofunctional ethylenically unsaturated monomer (B2) having an aryl group, exhibited inferior adhesive strength when used as a stuffing. [Industrial applicability]

[0118] This composition exhibits good adhesion to various materials, particularly when used as an adhesive, and can be applied to a variety of uses such as coatings, paints, inks, and adhesives.

Claims

1. A composition comprising a urethane (meth)acrylate compound (A) and a monofunctional ethylenically unsaturated monomer (B), A composition in which the monofunctional ethylenically unsaturated monomer (B) contains a monofunctional ethylenically unsaturated monomer (B1) having a glass transition temperature of 0 to 130°C and a monofunctional ethylenically unsaturated monomer (B2) having an aryl group.

2. The composition according to claim 1, wherein the urethane (meth)acrylate compound (A) is a reaction product of a polyol (a1), a polyvalent isocyanate (a2), a hydroxyl group-containing (meth)acrylate (a3), and a monool (a4).

3. The composition according to claim 2, wherein the monool (a4) is a monool having 2 or more carbon atoms.

4. The composition according to claim 1 or 2, wherein the urethane (meth)acrylate compound (A) is a monofunctional urethane (meth)acrylate compound.

5. The composition according to claim 1 or 2, wherein the weight-average molecular weight of the urethane (meth)acrylate compound (A) is 20,000 to 100,000.

6. The composition according to claim 1 or 2, wherein the content of the monofunctional ethylenically unsaturated monomer (B) is 20 to 300 parts by mass per 100 parts by mass of the urethane (meth)acrylate compound (A).

7. The composition according to claim 1 or 2, wherein the mass content ratio (B1 / B2) of a monofunctional ethylenically unsaturated monomer (B1) having a glass transition temperature of 0 to 130°C and a monofunctional ethylenically unsaturated monomer (B2) having an aryl group is 70 / 30 to 30 / 70.

8. Furthermore, the composition according to claim 1 or 2, wherein it contains a hydrolysis inhibitor (C), and the content of the hydrolysis inhibitor (C) is 0.01 to 10% by mass relative to the composition.

9. Furthermore, the composition according to claim 1 or 2, further containing a photopolymerization initiator (D).

10. An adhesive composition comprising the composition according to claim 1 or 2.

11. An adhesive obtained by curing the adhesive composition according to claim 10.

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