Compound, polymer, and curable composition

Abstract

A compound having a (meth)acryloyloxy group and a linear polyoxyalkylene chain, wherein the polyoxyalkylene chain has a unit based on propylene oxide and a unit based on a monomer having one epoxy group and an ether bond other than the ether bond of the epoxy group in one molecule.

Description

Technical Field

[0001] The present invention relates to a compound, a polymer, and a curable composition. Background Art

[0002] In recent years, in addition to rigid display panels, flexible display panels having bendability or flexibility have been developed.

[0003] The flexible display panel includes, for example, a flexible laminated body in which a flexible member such as an optical film and a protective film is laminated on a flexible display panel main body such as an organic EL (Electroluminescent) display panel via an adhesive layer.

[0004] As an adhesive capable of forming the aforementioned adhesive layer, a UV-curable resin composition for laminating and integrating a display panel and a protective plate of a display device is disclosed in Patent Document 1. Specifically, the UV-curable resin composition is disclosed to include: a compound obtained by reacting a polyether monool with a (meth)acrylate having an isocyanate group, and a photopolymerization initiator.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2012-126839 Summary of the invention

[0008] Problem that the invention aims to solve

[0009] Sometimes, an article with a flexible display panel can be used in a cold place. In this case, in order for the flexible display panel to fully exert its bending properties, the adhesive layer constituting the flexible display needs to have sufficient flexibility even at low temperatures. Therefore, the glass transition temperature of the adhesive layer is required to be low.

[0010] However, the glass transition temperature of a cured product obtained by curing the ultraviolet curable resin composition described in Patent Document 1 is not sufficiently low when an article having a flexible display panel is used in a cold place.

[0011] The object of the present invention is to provide: a compound which is a raw material for forming an adhesive layer of a flexible display panel used in cold places and which becomes a cured product having a sufficient glass transition temperature; a polymer having units based on the aforementioned compound; and a curable composition comprising either or both of the aforementioned compound and the aforementioned polymer.

[0012] Solutions for solving problems

[0013] The present invention is as follows [1] to

[15] .

[0014] [1] A compound having a (meth)acryloyloxy group and a linear polyoxyalkylene chain, wherein the polyoxyalkylene chain has a unit based on propylene oxide and a unit based on a monomer having one epoxy group and an ether bond other than the ether bond of the epoxy group in one molecule.

[0015] [2] The compound according to [1], wherein the unit based on the monomer is a unit represented by the following formula 1.

[0016]

[0017] In the above formula 1, R 1 For-R 3 -OR 4 The monovalent group shown, R 2 A hydrogen atom or -R 5 -OR 6 The monovalent group shown, R 3 , R 5 Each independently represents a linear or branched alkylene group having 1 to 3 carbon atoms, R 4 , R 6 Each is independently a linear or branched alkyl group having 1 to 18 carbon atoms.

[0018] [3] The compound according to [1] or [2], wherein the number average molecular weight of the polyoxyalkylene chain is 1,000 to 35,000.

[0019] [4] The compound according to any one of [1] to [3], wherein the ratio of the units derived from the monomer to the total amount of the polyoxyalkylene chains is 10 to 90% by mass.

[0020] [5] The compound according to any one of [1] to [4], wherein the mass ratio of the units based on the monomer in the polyoxyalkylene chain to the units based on propylene oxide is 0.6 to 4.0.

[0021] [6] The compound according to any one of [1] to [5], wherein the monomer is a compound represented by the following formula 2.

[0022]

[0023] In the above formula 2, R 1 and R 2 With R in the above formula 1 1 and R 2 same.

[0024] [7] The compound according to any one of [1] to [6], wherein the monomer is methyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, lauryl glycidyl ether, or hexyl glycidyl ether.

[0025] [8] The compound according to any one of [1] to [7], wherein the compound has one or more urethane bonds per molecule.

[0026] [9] The compound according to any one of [1] to [8], wherein the glass transition temperature of a polymer comprising units derived from the compound is -90 to -35°C.

[0027]

[10] A polymer having a unit based on the compound according to any one of [1] to [9].

[0028]

[11] The polymer according to

[10] , wherein the polymer has a glass transition temperature of -90 to -35°C.

[0029]

[12] A curable composition comprising the compound according to any one of [1] to [9].

[0030]

[13] A curable composition comprising the polymer described in

[10] or

[11] .

[0031]

[14] A cured product obtained by curing the curable composition according to

[12] or

[13] .

[0032]

[15] The method for producing the compound according to any one of [1] to [9], which is the following (1), (2), or (3).

[0033] (1) A compound having one hydroxyl group and a linear polyoxyalkylene chain having a unit based on propylene oxide and a unit based on a monomer having one epoxy group and an ether bond other than the ether bond of the epoxy group in one molecule is subjected to a urethanization reaction with a compound having a (meth)acryloyloxy group and an isocyanate group.

[0034] (2) a compound having one hydroxyl group and a linear polyoxyalkylene chain is subjected to a urethanization reaction with a compound having two isocyanate groups to obtain a prepolymer having an isocyanate group at the terminal, and the isocyanate group of the prepolymer is subjected to a urethanization reaction with a compound having one hydroxyl group and a (meth)acryloyloxy group, wherein the linear polyoxyalkylene chain has: a unit based on propylene oxide and a unit based on a monomer having one epoxy group and an ether bond other than the ether bond of the epoxy group in one molecule.

[0035] (3) subjecting a compound having two hydroxyl groups and a linear polyoxyalkylene chain having a unit based on propylene oxide and a unit based on a monomer having one epoxy group and an ether bond other than the ether bond of the epoxy group in one molecule to a urethanization reaction with a compound having a (meth)acryloyloxy group and an isocyanate group.

[0036] Effects of the Invention

[0037] According to the present invention, there can be provided: a compound which is a raw material for a bonding layer constituting a flexible display panel used in cold places and which becomes a cured product having a sufficient glass transition temperature; a polymer having units based on the aforementioned compound; and a curable composition comprising either or both of the aforementioned compound and the aforementioned polymer. DETAILED DESCRIPTION

[0038] The meanings and definitions of the terms in this specification are as follows.

[0039] The numerical range indicated by "to" means a numerical range in which the numerical values ​​before and after "to" are the lower limit and the upper limit.

[0040] "Unit" refers to a group of atoms formed directly by polymerization of a monomer or compound.

[0041] The "(meth)acryloyloxy group" means either or both of an acryloyloxy group and a methacryloyloxy group.

[0042] Unless otherwise specified, the “number of functional groups” refers to the number of (meth)acryloyloxy groups in one molecule.

[0043] The “average number of functional groups” refers to the average number of (meth)acryloyloxy groups in one molecule, with the average formula weight or number average molecular weight obtained based on the chemical formula being one unit, unless otherwise specified.

[0044] A "polymer" is a substance formed by bonding monomers, including a substance formed by bonding monomers via a crosslinking agent. The mass average molecular weight of a polymer is 1,000 or more.

[0045] A polymer is liquid, gel or solid at 25±5°C and normal pressure. A polymer in a gel or solid state is particularly referred to as a "cured product".

[0046] The number average molecular weight (hereinafter also referred to as "Mn") is a polystyrene-converted molecular weight obtained by measuring by gel permeation chromatography (GPC) using a calibration curve prepared using a standard polystyrene sample with a known molecular weight. Molecular weight distribution refers to the value obtained by dividing the mass average molecular weight (hereinafter also referred to as "Mw". The polystyrene-converted molecular weight obtained by GPC in the same way as Mn) by Mn (hereinafter also referred to as "Mw / Mn"). It should be noted that, in the case where a peak of an unreacted low molecular weight component (monomer, etc.) appears in the GPC measurement, the aforementioned peak is excluded to determine Mn.

[0047] Even if Mn is used to define, when Mw / Mn does not exist, the molecular weight represented by the formula weight obtained based on the chemical formula is used instead.

[0048] The hydroxyl value of the compound having one hydroxyl group and having a linear polyoxyalkylene chain or the compound having two hydroxyl groups and having a linear polyoxyalkylene chain described below is a value measured in accordance with JIS K1557 (2007 edition).

[0049] The hydroxyl-equivalent molecular weight is a value calculated by substituting the hydroxyl value into the calculation formula of "56100 / (hydroxyl value)×(the number of hydroxyl groups of the initiator)".

[0050] The glass transition temperature of a polymer can be measured using a differential scanning calorimeter.

[0051] The glass transition temperature of a polymer in the form of a cured product can be measured as a peak temperature of the loss modulus of dynamic viscoelasticity.

[0052] The compound of the present embodiment (hereinafter referred to as "compound (a)") has a (meth)acryloyloxy group and a linear polyoxyalkylene chain. The polyoxyalkylene chain in the compound (a) has: a unit based on propylene oxide, and a unit based on a monomer having one epoxy group and an ether bond other than the ether bond of the epoxy group in one molecule (hereinafter referred to as "monomer (a)"). The compound (a) may be used alone or in combination of two or more.

[0053] <Compound (a)>

[0054] The compound (a) has a (meth)acryloyloxy group and a linear polyoxyalkylene chain.

[0055] The number of the (meth)acryloyloxy group in the compound (a) is preferably 1 or more, more preferably 1 to 4, and even more preferably 1, from the viewpoint of better flexibility and curability of the obtained cured product.

[0056] The ratio of the (meth)acryloyloxy group to the total amount of the compound (a) is preferably 0.15 to 7.0 mass %, more preferably 0.20 to 2.3 mass %, and further preferably 0.22 to 1.7 mass % from the viewpoint of better flexibility and curability of the obtained cured product.

[0057] The compound (a) preferably has a urethane bond.

[0058] The urethane bonds in the compound (a) are preferably 1 or more per molecule of the compound (a), more preferably 1 to 4, and even more preferably 1, from the viewpoint of easily reducing shrinkage during curing and easily reducing the elastic modulus after curing. The proportion of the urethane bonds relative to the total amount of the compound (a), is preferably 0.15 to 1.6% by mass, more preferably 0.18 to 2.2% by mass, and even more preferably 0.20 to 1.4% by mass, from the viewpoint of easily reducing shrinkage during curing and easily reducing the elastic modulus after curing.

[0059] The ratio of the urethane bond to the total amount of the compound (a) was calculated by the following calculation formula, assuming that all the isocyanate groups in the compound used for the production of the compound (a) formed urethane bonds (molecular weight 59).

[0060] Urethane bond content (unit: %) = Mi × 59 / Wb × 100

[0061] Wb: total mass of compound (a)

[0062] Mi: the total number of moles of isocyanate groups present in the isocyanate compound used in the production of compound (a) having a mass Wa

[0063] The Mn of the polyoxyalkylene chain in the compound (a) is preferably 1,000 to 35,000, more preferably 2,000 to 30,000, and even more preferably 3,000 to 28,000, since the obtained cured product has better flexibility and the curable composition containing the compound (a) tends to have a low viscosity.

[0064] The Mw / Mn of the polyoxyalkylene chain in the compound (a) is preferably 1.01 to 2.5, more preferably 1.02 to 2.3, and even more preferably 1.02 to 2.0, from the viewpoint of lower viscosity.

[0065] The Mn and Mw / Mn of the polyoxyalkylene chain in the compound (a) are obtained by measuring the Mn and Mw of a compound having one hydroxyl group and a linear polyoxyalkylene chain or a compound having two hydroxyl groups and a linear polyoxyalkylene chain used in the three production methods described below.

[0066] Specifically, the urethane bond of the compound (a) is hydrolyzed under alkaline conditions, and the Mn and Mw of the obtained compound having one hydroxyl group and a linear polyoxyalkylene chain or the compound having two hydroxyl groups and a linear polyoxyalkylene chain are measured.

[0067] The Mn of the compound (a) is preferably 1,000 to 35,000, more preferably 2,000 to 30,500, and further preferably 3,000 to 28,000. When the Mn of the compound (a) is within the above range, it is easy to adjust the viscosity of the curable composition described later. In addition, when it is above the lower limit of the above range, the curing shrinkage of the curable composition described later is easy to be reduced.

[0068] When two or more compounds (a) are used in the polymer or curable composition described below, it is preferred that the Mn of each of them is within the above range.

[0069] The Mw / Mn of the compound (a) is preferably 1.01 to 2.5, more preferably 1.02 to 2.3, and even more preferably 1.02 to 2.0.

[0070] When two or more compounds (a) are used in the polymer or curable composition described below, it is preferred that the Mw / Mn of each of them is within the above range.

[0071] The polyoxyalkylene chain in the compound (a) has a unit based on propylene oxide and a unit based on a monomer (a) having one epoxy group and an ether bond other than the ether bond of the epoxy group in one molecule.

[0072] The ratio of the units based on monomer (a) to the total amount of polyoxyalkylene chains in compound (a) is preferably 10 to 90% by mass, more preferably 15 to 85% by mass, and further preferably 20 to 80% by mass. When the ratio of the units based on monomer (a) is above the aforementioned lower limit, the glass transition temperature of the obtained polymer is easily reduced. When it is below the upper limit, the viscosity is low and it is easy to handle, which is preferred.

[0073] The ratio of the units based on propylene oxide to the total amount of the polyoxyalkylene chains in the compound (a) is preferably 10 to 90% by mass, more preferably 15 to 85% by mass, and further preferably 20 to 80% by mass. When the ratio of the units based on propylene oxide is above the lower limit, the elastic modulus after curing is easily reduced. When it is below the upper limit, the shrinkage during curing is easily reduced.

[0074] The ratio of the total of the units based on propylene oxide and the units based on monomer (a) to the total amount of the polyoxyalkylene chains in compound (a) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 100% by mass. The above ratio is preferably 98% by mass or less, and more preferably 95% by mass or less.

[0075] When the ratio of the total of the units derived from propylene oxide and the units derived from the monomer (a) is at least the lower limit of the above range, the glass transition temperature of the obtained polymer tends to decrease.

[0076] The mass ratio of the units derived from the monomer (a) to the units derived from propylene oxide in the polyoxyalkylene chain in the compound (a) is preferably 0.6 to 4.0, more preferably 0.8 to 3.5, and even more preferably 1.0 to 3.0.

[0077] The unit based on the monomer (a) is preferably a unit represented by the following formula 1.

[0078]

[0079] In the above formula 1, R 1 For-R 3 -OR 4 The monovalent group shown, R 2 A hydrogen atom or -R 5 -OR 6 The monovalent group shown, R 3 , R 5 Each independently represents a linear or branched alkylene group having 1 to 3 carbon atoms, R 4 , R 6 Each is independently a linear or branched alkyl group having 1 to 18 carbon atoms.

[0080] As R 3 , R 5 The alkylene groups are each independently preferably methylene, ethylene, n-propylene, or isopropylene, more preferably methylene or ethylene, and further preferably methylene.

[0081] R 4 , R 6 The carbon number of each of the above groups is independently preferably 1-14, more preferably 1-12, and further preferably 2-10.

[0082] As R 4 , R 6 The straight-chain alkyl group may be exemplified by methyl, ethyl, n-propyl, n-butyl, n-octyl, n-decyl, lauryl, cetyl, and stearyl, and preferably methyl, ethyl, and n-butyl. The branched alkyl group has a structure in which the hydrogen atoms in the straight-chain alkyl group (except the hydrogen atoms bonded to the terminal carbon) are substituted by an alkyl group. As the alkyl group as the substituent group, methyl and ethyl groups may be exemplified. As the branched alkyl group, 2-ethylhexyl is preferred.

[0083] The ratio of the unit represented by the above formula 1 to the total amount of units based on the monomer (a) is preferably 10 to 100% by mass, more preferably 15 to 100% by mass, and even more preferably 20 to 90% by mass.

[0084] The monomer (a) is a monomer having one epoxy group and an ether bond other than the ether bond of the epoxy group in one molecule. Two or more monomers (a) may be used to constitute the polyoxyalkylene chain in the compound (a).

[0085] The number of ether bonds other than the ether bonds of the epoxy group in the monomer (a) is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1, from the viewpoint that the glass transition point of the obtained polymer is likely to be sufficiently low.

[0086] As the monomer (a), a monomer represented by the following formula 2 is preferred.

[0087]

[0088] R in the above formula 2 1 and R 2 With R in the above formula 1 1 and R 2 The monomer (a) may be used alone or in combination of two or more.

[0089] The monomer represented by the above formula 2 is preferably methyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, lauryl glycidyl ether or hexyl glycidyl ether, and is more preferably butyl glycidyl ether or 2-ethylhexyl glycidyl ether in terms of better flexibility and compatibility.

[0090] Compound (a) can be obtained, for example, by the following three production methods (1) to (3).

[0091] (1) Compound (a) is obtained by urethanization reaction of a compound having one hydroxyl group and a linear polyoxyalkylene chain with a compound having a (meth)acryloyloxy group and an isocyanate group. The polyoxyalkylene chain has a unit based on propylene oxide and a unit based on the monomer (a).

[0092] (2) Compound (a) is obtained by subjecting a compound having one hydroxyl group and a linear polyoxyalkylene chain to a urethanization reaction with a compound having two isocyanate groups to obtain a prepolymer having an isocyanate group at the end, and the prepolymer is obtained by subjecting the isocyanate group of the prepolymer to a urethanization reaction with a compound having one hydroxyl group and a (meth)acryloyloxy group. The polyoxyalkylene chain has units based on propylene oxide and units based on the monomer (a).

[0093] (3) Compound (a) is obtained by urethanization reaction of one hydroxyl group of a compound having two hydroxyl groups and a linear polyoxyalkylene chain with a compound having a (meth)acryloyloxy group and an isocyanate group. The polyoxyalkylene chain has a unit based on propylene oxide and a unit based on the monomer (a).

[0094] The conditions for the urethanization reaction in the above-mentioned production methods (1) to (3) are not particularly limited, but the reaction is preferably carried out at a temperature of 50 to 120°C for 0.5 to 6 hours, and more preferably at 60 to 100°C for 1 to 5 hours.

[0095] In the production process of compound (a), by-products other than compound (a) such as the reaction product of the above-mentioned water and the isocyanate group-containing compound may be generated in the product (hereinafter referred to as "product (a)").

[0096] The ratio of the total amount of by-products to the total amount of product (a) is preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 0% by mass. When the ratio of the total amount of by-products to the total amount of product (a) is below the above upper limit, the function as compound (a) can be fully exerted, so product (a) can be regarded as compound (a).

[0097] Examples of the compound (a) include a compound (a-1) represented by the following formula 3, a compound (a-2) represented by the following formula 4, and a compound (a-3) described later.

[0098] Compound (a-1) is obtained by a urethanization reaction of a compound having one hydroxyl group and a linear polyoxyalkylene chain represented by the following formula 3a (hereinafter referred to as "compound (3a)") and a compound having a (meth)acryloyloxy group and an isocyanate group represented by the following formula 3b (hereinafter referred to as "compound (3b)") The polyoxyalkylene chain has a unit based on propylene oxide and a unit based on the above monomer (a).

[0099] Since the number of groups capable of undergoing urethanization reaction in one molecule of compound (3a) and compound (3b) is one each, it is easy to control the number of urethanate bonds in one molecule of compound (a-1) to one. If the number of urethanate bonds in one molecule of compound (a-1) is small, the viscosity tends to be low. Therefore, in terms of the low viscosity of the curable composition and the easy acquisition of a cured product with excellent flexibility, it is more preferred that compound (a) contains compound (a-1).

[0100]

[0101]

[0102]

[0103] In the above formulae 3, 3a and 3b, R 11 R is a hydrogen atom or a methyl group, preferably a hydrogen atom. 12 is a linear or branched alkylene group having 2 or 4 carbon atoms, and a plurality of R 12 They may be the same or different from each other. 12 In the case of -OR 12 - can be connected in blocks or randomly. 12 Ethylene is preferred. 13 represents an alkyl group having 1 to 20 carbon atoms, or R 13 Together with the oxygen atom to which it is bonded, it represents a carboxylic acid residue having 1 to 20 carbon atoms. The carboxylic acid residue is a monovalent group obtained by removing one hydrogen atom from the carboxyl group of a monocarboxylic acid having 1 to 20 carbon atoms including the carbon atom in the carboxyl group. 13 In view of the ease of reaction, an alkyl group having 1 to 20 carbon atoms is preferred, and an alkyl group having 2 to 8 carbon atoms is more preferred. 15 For-R 17 -OR 18 The monovalent group shown, R 16 A hydrogen atom or -R 19 -OR 20 The monovalent group shown, R 17 , R 19 Each independently represents a linear or branched alkylene group having 1 to 3 carbon atoms, R 18 , R 20 Each R is independently a linear or branched alkyl group having 1 to 18 carbon atoms. 15 , R 16 Each is optionally the same or different.

[0104] b is an integer of 1 to 8, preferably an integer of 1 to 4. c is an integer of 0 to 77, preferably an integer of 0 to 70, more preferably an integer of 0 to 65. x1 is an integer of 1 to 484, preferably an integer of 1 to 415, more preferably an integer of 1 to 387. y1 is an integer of 1 to 242, preferably an integer of 2 to 207, more preferably an integer of 3 to 194.

[0105] R 17 , R 19 With R in the above formula 1 3 , R 5 Likewise, the preferred aspects are also the same.

[0106] R 18 , R 20 With R in the above formula 1 4 , R 6 Likewise, the preferred aspects are also the same.

[0107] The ratio of x1 to the total of c, x1, and y1 is preferably 0.10 to 0.98, more preferably 0.15 to 0.97, and further preferably 0.20 to 0.95.

[0108] The ratio of y1 to the total of c, x1, and y1 is preferably 0.02 to 0.90, more preferably 0.03 to 0.85, and further preferably 0.05 to 0.80.

[0109] The ratio of the total of x1 and y1 to the total of c, x1, and y1 is preferably 0.80 to 1.00, more preferably 0.85 to 1.00.

[0110] Compound (3a) is obtained by a known method of ring-opening addition polymerization of alkylene oxide using a monohydric alcohol or a compound obtained by adding alkylene oxide to a monohydric alcohol as an initiator; or by a known method of ring-opening addition polymerization of alkylene oxide and the hydroxyl group of a monocarboxylic acid. As the alkylene oxide, propylene oxide and monomer (a) are used as essential components. Specific examples of other alkylene oxides include ethylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, etc.

[0111] The Mn of the compound (3a) is preferably 1,000 to 35,000, more preferably 2,000 to 30,000, and even more preferably 3,000 to 28,000, since the flexibility of the obtained cured product is further improved and the curable composition containing the compound (a-1) tends to have a low viscosity.

[0112] The hydroxyl value of compound (3a) is preferably 2.0 to 56.1 mgKOH / g, more preferably 2.0 to 15.0 mgKOH / g. The hydroxyl-equivalent molecular weight of compound (3a) is preferably 1,000 to 35,000, more preferably 3,000 to 28,000. When the hydroxyl-equivalent molecular weight of compound (3a) is within the above range, the Mn of compound (a-1) can be adjusted to the range of 1,000 to 35,000. When the hydroxyl-equivalent molecular weight of compound (3a) is within the above range, it is easy to adjust the average number of functional groups of the generated compound (a-1) to 0.8 to 1.3. When the hydroxyl-equivalent molecular weight is small, it is easy to adjust the upper limit of the above average number of functional groups to 1.3 or less.

[0113] In the manufacture of compound (3a), it is not particularly necessary to remove water by degassing under reduced pressure, etc., and the amount of water usually contained in the raw materials etc. put into the reaction system is allowed. For example, the less the amount of water in the initiator, the better, more preferably 500 mass ppm or less, and further preferably 300 mass ppm or less. When the amount of water is within this range, the amount of diol generated by water can be suppressed, so the amount of by-products formed by adding (meth)acryloyloxy groups to the aforementioned diols can be suppressed, and it is easy to adjust the upper limit of the average number of functional groups of the product (a-1) containing the aforementioned by-products and compound (a-1) to 1.2 or less.

[0114] Compound (3b) can be a commercially available product, for example, Karenz-AOI (R in Formula 3b) 11 =H, b = 2), Karenz-MOI (R in Formula 3b 11 =CH3, b=2) (all are product names of Showa Denko K.K.).

[0115] The reaction between compound (3a) and compound (3b) is a carbamate reaction, which can be carried out using a known method. When reacting them, the mixing ratio of compound (3b) to compound (3a) is preferably 80 to 100, more preferably 90 to 100, and particularly preferably 100 in terms of index (NCO / OH ratio). By setting the index in the above range, it is easy to adjust the average number of functional groups of the product (a-1) to the range of 0.8 to 1.3.

[0116] The compound (3a) may be a mixture of two or more kinds thereof. In this case, each compound (3a) is preferably a compound within the above range.

[0117] The ratio of compound (a-1) to the total amount of product (a-1) is preferably 80% by mass or more, more preferably 85 to 100% by mass, in order to fully exert the function as compound (a). When product (a-1) contains compound (a-1) in the above ratio, the function of compound (a) can be fully exerted, so product (a-1) can be regarded as compound (a-1).

[0118] When the product (a-1) can be regarded as the compound (a-1), the average number of functional groups obtained from the Mn and the number of functional groups of the product (a-1) can be regarded as the average number of functional groups of the compound (a-1). In this case, the average number of functional groups in the product (a-1) is preferably 0.8 to 1.3, more preferably 0.9 to 1.2. The product (a-1) within the above range is easy to reduce the shrinkage during curing and the elastic modulus of the obtained cured product.

[0119] Compound (a-2) is obtained as follows: a compound having one hydroxyl group and a linear polyoxyalkylene chain as shown in the following formula 4a (hereinafter referred to as "compound (4a)") is subjected to a carbamate reaction with a compound having two isocyanate groups as shown in the following formula 4b (hereinafter referred to as "compound (4b)") to obtain a prepolymer having an isocyanate group at the end (isocyanate-terminated carbamate prepolymer), and then a compound having one hydroxyl group and a (meth)acryloyloxy group as shown in the following formula 4c (hereinafter referred to as "compound (4c)") is reacted with the isocyanate group of the aforementioned prepolymer.

[0120] The polyoxyalkylene chain has a unit based on propylene oxide and a unit based on the monomer (a).

[0121]

[0122]

[0123] O=C=NR 24 -N=C=O (Formula 4b)

[0124]

[0125] In the above formulae 4, 4a, 4b, and 4c, R 21 R is a hydrogen atom or a methyl group, preferably a hydrogen atom. 22 is an alkylene group having 2 or 4 carbon atoms, and a plurality of R 22 They may be the same or different from each other. 22 In the case of -OR 22 - can be connected in blocks or randomly. 22 Ethylene is preferred. 23 represents an alkyl group having 1 to 20 carbon atoms, or R 23 Together with the oxygen atom to which it is bonded, it represents a carboxylic acid residue having 1 to 20 carbon atoms. The carboxylic acid residue is a monovalent group obtained by removing one hydrogen atom from the carboxyl group of a monocarboxylic acid having 1 to 20 carbon atoms including the carbon atom in the carboxyl group. 23 In view of the ease of reaction, an alkyl group having 1 to 20 carbon atoms is preferred, and an alkyl group having 2 to 8 carbon atoms is more preferred.

[0126] R 24 It is a divalent group obtained by removing an isocyanate group from compound (4b). As compound (4b), for example, a compound having two isocyanate groups can be cited, and non-yellowing aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and various modified forms of these diisocyanates (modified forms having two isocyanate groups) can be cited. Two or more diisocyanates can also be used in combination.

[0127] As the diisocyanate, aliphatic diisocyanate and alicyclic diisocyanate are preferred from the viewpoints of excellent light resistance, weather resistance, and heat resistance and ability to maintain transparency.

[0128] Examples of the non-yellowing aromatic diisocyanate include xylylene diisocyanate and tetramethylxylene diisocyanate. Examples of the aliphatic diisocyanate include 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate and lysine diisocyanate. Examples of the alicyclic diisocyanate include isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,5-norbornane diisocyanate and 2,6-norbornane diisocyanate.

[0129] As the compound (4b), isophorone diisocyanate and 1,6-hexamethylene diisocyanate are preferred.

[0130] R 25 For-R 27 -OR 28 The monovalent group shown, R 26 A hydrogen atom or -R 29 -OR 30 The monovalent group shown, R 27 , R 29 Each independently represents a linear or branched alkylene group having 1 to 3 carbon atoms, R 28 , R 30 Each R is independently a linear or branched alkyl group having 1 to 18 carbon atoms. 25 , R 26 Each is optionally the same or different.

[0131] d is an integer of 1 to 8, preferably an integer of 1 to 4. e is an integer of 0 to 77, preferably an integer of 0 to 70, more preferably an integer of 0 to 65. x2 is an integer of 1 to 484, preferably an integer of 1 to 415, more preferably an integer of 1 to 387. y2 is an integer of 1 to 242, preferably an integer of 2 to 207, more preferably an integer of 3 to 194.

[0132] The ratio of x2 to the total of e, x2, and y2 is preferably 0.10 to 0.98, more preferably 0.15 to 0.97, and further preferably 0.20 to 0.95.

[0133] The ratio of y2 to the total of e, x2, and y2 is preferably 0.02 to 0.90, more preferably 0.03 to 0.85, and further preferably 0.05 to 0.80.

[0134] The ratio of the total of x2 and y2 to the total of e, x2, and y2 is preferably 0.8 to 1.00, more preferably 0.85 to 1.00.

[0135] R 27 , R 29 With R in the above formula 1 3 , R 5 Likewise, the preferred aspects are also the same.

[0136] R 28 , R 30 With R in the above formula 1 4 , R 6 Likewise, the preferred aspects are also the same.

[0137] Compound (4a) is obtained by a known method of ring-opening addition polymerization of alkylene oxide using a monohydric alcohol or a compound obtained by adding alkylene oxide to a monohydric alcohol as an initiator; or by a known method of ring-opening addition polymerization of alkylene oxide and the hydroxyl group of a monocarboxylic acid. As the alkylene oxide, propylene oxide and monomer (a) are used as essential components. Specific examples of other alkylene oxides include ethylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, etc.

[0138] The Mn of the compound (4a) is preferably 1,000 to 35,000, more preferably 2,000 to 30,000, and even more preferably 3,000 to 28,000, since the resulting cured product has better flexibility and the curable composition containing the compound (a-2) tends to have a low viscosity.

[0139] The hydroxyl value of compound (4a) is preferably 2.0 to 56.1 mgKOH / g, more preferably 2.0 to 15.0 mgKOH / g. The hydroxyl-equivalent molecular weight of compound (4a) is preferably 1,000 to 35,000, more preferably 3,000 to 28,000. When the hydroxyl-equivalent molecular weight of compound (4a) is within the above range, the Mn of compound (a-2) can be adjusted to the range of 1,000 to 35,000. When the hydroxyl-equivalent molecular weight of compound (4a) is within the above range, it is easy to adjust the average number of functional groups of the generated compound (a-2) to 0.8 to 1.3. When the hydroxyl-equivalent molecular weight is small, it is easy to adjust the upper limit of the above average number of functional groups to 1.3 or less.

[0140] The water content and molecular weight when producing compound (4a) are the same as those of the aforementioned compound (3a). In the production of compound (4a), as in the aforementioned compound (3a), a product containing a by-product obtained by adding a (meth)acryloyloxy group to a diol generated from water contained in the raw material and compound (a-2) (hereinafter referred to as "product (a-2)") may be obtained.

[0141] The reaction of reacting compound (4a) with compound (4b) to obtain a prepolymer having an isocyanate group at the terminal (isocyanate group-terminated urethane prepolymer) is a urethanization reaction, which can be carried out by a known method. When reacting these, the mixing ratio of compound (4b) to compound (4a) is preferably 100 to 200, more preferably 180 to 200, and particularly preferably 200 in terms of index (NCO / OH ratio).

[0142] The reaction between the obtained isocyanate group-terminated urethane prepolymer and the compound (4c) is a urethanization reaction, and can be carried out by a known method.

[0143] The mixing ratio of the prepolymer and the compound (4c) when reacting them is preferably 1:1.0 to 1:1.1, more preferably 1:1.00 to 1:1.05. When it is within the above range, it is easy to adjust the average number of functional groups of the product (a-2) to the range of 0.8 to 1.3.

[0144] The ratio of compound (a-2) to the total mass of product (a-2) is preferably 80% by mass or more, more preferably 85 to 100% by mass, in order to fully exert the function as compound (a). When product (a-2) contains compound (a-2) in the above ratio, the function of compound (a) can be fully exerted, so product (a-2) can be regarded as compound (a-2).

[0145] When the product (a-2) can be regarded as the compound (a-2), the average number of functional groups calculated based on the Mn and the number of functional groups of the product (a-2) can be regarded as the average number of functional groups of the compound (a-2). In this case, the average number of functional groups in the product (a-2) is preferably 0.8 to 1.3, more preferably 0.9 to 1.2. The product (a-2) within the above range is easy to reduce the shrinkage during curing and the elastic modulus of the obtained cured product.

[0146] Compound (a-3) is a monomer having a functional group of 1 obtained by a urethanization reaction of a compound having two hydroxyl groups and a linear polyoxyalkylene chain (hereinafter referred to as "compound (5a)") with the aforementioned compound (3b). The aforementioned polyoxyalkylene chain has a unit based on propylene oxide and a unit based on the aforementioned monomer (a).

[0147] Compound (5a) is a polyoxyalkylene glycol obtained by ring-opening addition polymerization of alkylene oxide using a diol or a compound obtained by adding alkylene oxide to a diol as an initiator. Compound (5a) has an initiator residue, a polyoxyalkylene chain, and a hydroxyl group corresponding to the number of alcoholic hydroxyl groups of the initiator. For the ring-opening addition polymerization of diol and alkylene oxide, and the ring-opening addition polymerization of initiator and alkylene oxide, a conventionally known method can be used in the presence of a catalyst such as a basic catalyst such as KOH and a composite metal cyanide complex catalyst.

[0148] The carbon number of the diol is preferably 1 to 12, more preferably 2 to 8. Specific examples of the diol include polyethylene glycols such as ethylene glycol and diethylene glycol; polypropylene glycols such as propylene glycol and dipropylene glycol; and diols such as 1,4-butanediol and 1,6-hexanediol.

[0149] Compound (5a) may have a unit based on propylene oxide and an alkylene oxide unit other than the unit based on the monomer (a), and the carbon number of the unit based on the alkylene oxide is preferably 2 or 4. Specifically, ethylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, etc. are mentioned. The unit based on monomer (a) is the same as the unit represented by the above formula 1, and the preferred embodiment is also the same.

[0150] The number of repetitions of the unit based on alkylene oxide having 2 or 4 carbon atoms contained in the compound (5a) per molecule is f, the number of repetitions of the unit based on propylene oxide is x3, and the number of repetitions of the unit based on the above-mentioned monomer (a) is y3. f is an integer of 0 to 77, preferably an integer of 0 to 70, and more preferably an integer of 0 to 65. x3 is an integer of 1 to 484, preferably an integer of 1 to 415, and more preferably an integer of 1 to 387. y3 is an integer of 1 to 242, preferably an integer of 2 to 207, and more preferably an integer of 3 to 194.

[0151] The ratio of x3 to the total of f, x3, and y3 is preferably 0.10 to 0.98, more preferably 0.15 to 0.97, and further preferably 0.20 to 0.95.

[0152] The ratio of y3 to the total of f, x3, and y3 is preferably 0.02 to 0.90, more preferably 0.03 to 0.85, and further preferably 0.05 to 0.80.

[0153] The ratio of the total of x3 and y3 to the total of f, x3, and y3 is preferably 0.80 to 1.00, more preferably 0.85 to 1.00.

[0154] The Mn of the compound (5a) is preferably 1,000 to 35,000, more preferably 2,000 to 30,000, and even more preferably 3,000 to 28,000, since the resulting cured product has better flexibility and the curable composition containing the compound (a-3) tends to have a low viscosity.

[0155] The hydroxyl value of the compound (5a) is preferably 2.0 to 56.1 mgKOH / g, more preferably 2.0 to 15.0 mgKOH / g. The hydroxyl-equivalent molecular weight of the compound (5a) is preferably 1,000 to 35,000, more preferably 3,000 to 28,000.

[0156] When the hydroxyl-equivalent molecular weight of compound (5a) is within the above range, the Mn of compound (a-3) can be adjusted to the range of 1,000 to 35,000. When the hydroxyl-equivalent molecular weight of compound (5a) is within the above range, it is easy to adjust the average number of functional groups of the generated compound (a-3) to 0.8 to 1.3. When the hydroxyl-equivalent molecular weight is small, it is easy to adjust the upper limit of the above average number of functional groups to 1.3 or less.

[0157] The compound (5a) may be a mixture of two or more polyoxyalkylene glycols. In this case, it is preferred that each polyoxyalkylene glycol is a compound within the above range.

[0158] The reaction between the compound (5a) and the compound (3b) is a urethanization reaction and can be carried out using a known method.

[0159] In the above reaction, the hydroxyl groups at both terminals of compound (5a) react with compound (3b), thereby generating a product containing a monomer having a functional group number of 2 as a by-product in addition to a monomer having a functional group number of 1 (hereinafter referred to as "product (a-3)").

[0160] The average number of functional groups of the product (a-3) is preferably 0.8 to 1.3, more preferably 0.9 to 1.2.

[0161] In the above reaction, the mixing ratio of compound (3b) to compound (5a) is preferably 30 to 50, more preferably 40 to 50, and particularly preferably 50 in terms of index (NCO / OH ratio). When the index is within the above range, it is easy to obtain a compound formed by the reaction of one molecule of compound (5a) and one molecule of compound (3b), and it is easy to adjust the average number of functional groups of the above product (a-3) to the range of 0.8 to 1.3.

[0162] The ratio of compound (a-3) to the total amount of product (a-3) is preferably 80% by mass or more, more preferably 85 to 100% by mass, in order to fully exert the function as compound (a). When product (a-3) contains compound (a-3) at a ratio within the above range, the function of compound (a) can be fully exerted, so product (a-3) can be regarded as compound (a-3).

[0163] When the product (a-3) can be regarded as a compound (a-3), the average number of functional groups calculated from the Mn and the number of functional groups of the product (a-3) can be set as the average number of functional groups of the compound (a-3). In this case, the average number of functional groups in the product (a-3) is preferably 0.8 to 1.3, more preferably 0.9 to 1.2. The product (a-3) within the above range is easy to reduce shrinkage during curing and the elastic modulus of the obtained cured product.

[0164] The proportion of the compound (a-1) is preferably 50 to 100% by mass, more preferably 75 to 100% by mass, and even more preferably 80 to 100% by mass, based on the total amount of the compound (a).

[0165] The proportion of the compound (a-2) is preferably 0 to 50% by mass, more preferably 0 to 25% by mass, and even more preferably 0 to 20% by mass, based on the total amount of the compound (a).

[0166] The proportion of the compound (a-3) is preferably 0 to 50% by mass, more preferably 0 to 25% by mass, and even more preferably 0 to 20% by mass, based on the total amount of the compound (a).

[0167] It is particularly preferred that the compound (a) contains one or more selected from the group consisting of the compound (a-1) and the compound (a-2).

[0168] The total amount of compound (a-1) and compound (a-2) relative to the total amount of compound (a) is preferably 50% by mass or more, more preferably 80% by mass or more, particularly preferably 100% by mass.

[0169] When the total ratio of compound (a-1) to compound (a-2) is greater than the lower limit of the above range, the low temperature adhesion is easily improved and the storage modulus of the obtained cured product at low temperature is easily improved. The mass ratio of compound (a-1) to compound (a-2) (a-1): (a-2) is preferably 1:0 to 1:1.

[0170] The glass transition temperature of the polymer containing units based on compound (a) is preferably -90 to -35°C, more preferably -85 to -40°C, and further preferably -80 to -45°C. When the glass transition temperature of the polymer is within the above range, the adhesion at low temperatures is easily improved and the storage modulus at low temperatures is easily improved when the polymer is a cured product. The polymer containing units based on compound (a) is obtained by adding a photopolymerization initiator to compound (a) and polymerizing.

[0171] <Polymer>

[0172] The polymer of the present embodiment (hereinafter referred to as "polymer (A)") is a polymer having units based on compound (a). In addition to units based on compound (a), polymer (A) may also have units based on other compounds. Other compounds may be copolymerizable with compound (a).

[0173] As the unit based on other compounds, there can be exemplified a unit based on a (meth)acrylic acid ester which does not belong to the compound (a).

[0174] Examples of the other compounds include (meth)acrylic acid alkyl esters, carboxyl-containing compounds, hydroxyl-containing compounds, amino-containing compounds, epoxy-containing compounds, amide-containing compounds, vinyl compounds, and macromolecular compounds described in

[0095] to

[0110] of International Publication No. 2018 / 173896.

[0175] Examples of other compounds include the following compounds (d1), (d2), (d3), and (d4).

[0176] Compound (d1): an alkyl (meth)acrylate in which an alkyl group having 4 to 18 carbon atoms is bonded to a (meth)acryloyloxy group.

[0177] Compound (d2): a compound having a carboxyl group and being copolymerizable with compound (d1).

[0178] Compound (d3): a compound having an organic functional group other than a carboxyl group and being copolymerizable with compound (d1).

[0179] Compound (d4): (meth)acrylate of a polyoxyalkylene monool other than the compound (a).

[0180] The alkyl group having 4 to 18 carbon atoms bonded to the (meth)acryloyloxy group of the compound (d1) is preferably a straight chain or a branched chain. Examples of the compound (d1) include n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, isopentyl (meth)acrylate, neopentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, isobutyl (meth)acrylate, isostearyl (meth)acrylate, cetyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, and the like.

[0181] When a compound (d1) having a linear or branched alkyl group having 4 to 12 carbon atoms bonded to a (meth)acryloyloxy group is used, the resulting cured product tends to become soft. The compound (d1) having a linear or branched alkyl group having 4 to 12 carbon atoms bonded to it is preferred, and n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, or lauryl (meth)acrylate is more preferred.

[0182] Examples of compound (d2) include (meth)acrylic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxypropylhexahydrophthalic acid, 2-(meth)acryloyloxyethylphthalic acid, 2-(meth)acryloyloxypropylphthalic acid, 2-(meth)acryloyloxyethylmaleic acid, 2-(meth)acryloyloxypropylmaleic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxypropylsuccinic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, and the like.

[0183] When the compound (d2) is used, the obtained cured product is less likely to become cloudy under high temperature and high humidity conditions (moisture heat resistance), and the adhesive strength is likely to be improved. (Meth)acrylic acid is particularly preferred.

[0184] The organic functional group of compound (d3) is preferably a hydroxyl group or an amide group, and more preferably a hydroxyl group. Examples of compound (d3) include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-butyl (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-methylol propane (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, diacetone (meth)acrylamide, maleic acid amide, and maleimide.

[0185] When the compound (d3) is used, the moist heat resistance is likely to be improved. Hydroxyalkyl (meth)acrylates are particularly preferred, and 4-hydroxybutyl (meth)acrylate is more preferred.

[0186] Examples of compound (d4) include polyoxyethylene monoalcohol (meth)acrylates such as methoxypolyethylene glycol (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, 2-ethylhexylpolyethylene glycol (meth)acrylate, octyloxypolyethylene glycol (meth)acrylate, laurylpolyethylene glycol (meth)acrylate, stearyloxypolyethylene glycol (meth)acrylate, and phenoxypolyethylene glycol (meth)acrylate; methoxypolypropylene glycol (meth)acrylate, ethoxypolypropylene glycol (meth)acrylate, 2-ethylhexylpolypropylene glycol (meth)acrylate, octyloxypolypropylene glycol (meth)acrylate, laurylpolyethylene glycol (meth)acrylate, stearyloxypolyethylene glycol (meth)acrylate, and phenoxypolyethylene glycol (meth)acrylate; and Polyoxypropylene monohydric alcohol (meth)acrylates such as lauryloxypolypropylene glycol (meth)acrylate, stearyloxypolypropylene glycol (meth)acrylate, and phenoxypolypropylene glycol (meth)acrylate; methoxypolyethylene glycol-polypropylene glycol (meth)acrylate, ethoxypolyethylene glycol-polypropylene glycol (meth)acrylate, 2-ethylhexylpolyethylene glycol-polypropylene glycol (meth)acrylate, octyloxypolyethylene glycol-polypropylene glycol (meth)acrylate, laurylpolyethylene glycol-polypropylene glycol (meth)acrylate, stearyloxypolyethylene glycol-polypropylene glycol (meth)acrylate, and phenoxypolyethylene glycol-polypropylene glycol (meth)acrylate.

[0187] The polyoxyalkylene monool constituting the compound (d4) is the compound (3a) wherein y1 is 0 and preferably has an Mn of less than 1,000.

[0188] As the compound (d4), polyoxyethylene monool (meth)acrylate or polyoxypropylene monool (meth)acrylate having a molecular weight of 1,000 or less as calculated from the number average molecular weight or the structural formula is preferred.

[0189] Preferably, the ratio of the units based on the aforementioned compound (d1) to the total amount of the units based on the (meth)acrylate that do not belong to the compound (a) in the polymer (A) is 50 to 99.9% by mass, the ratio of the units based on the compound (d2) is 0.1 to 5.0% by mass, and the total ratio of these is 50.1 to 100% by mass.

[0190] Alternatively, the following embodiment is preferred: with respect to the total amount of units based on (meth)acrylates not belonging to compound (a) in polymer (A), the proportion of units based on compound (d1) is 50 to 99.9% by mass, the proportion of units based on compound (d3) is 1.0 to 20.0% by mass, and the total proportion of these is 51.0 to 100% by mass.

[0191] The Mn of the (meth)acrylate not belonging to the compound (a) used in the production of the polymer (A) is preferably 1,000 or less, more preferably 70 to 1,000, further preferably 70 to 700, and particularly preferably 80 to 400. When the Mn of the (meth)acrylate not belonging to the compound (a) is below the upper limit, the obtained cured product tends to be soft.

[0192] When two or more (meth)acrylates are used, it is preferred that the Mn of each of them be within the above range.

[0193] The ratio of the unit based on compound (a) to the total units of polymer (A) is preferably 70% by mass or more, more preferably 80% by mass or more. As the upper limit, it can be 100% by mass. When the ratio of the unit based on compound (a) is above the lower limit of the aforementioned range, the glass transition temperature of polymer (A) is further reduced. When it is below the upper limit, the adhesion of the cured product at low temperature is more excellent.

[0194] The total ratio of the units derived from the compound (a) and the units derived from the (meth)acrylate ester not belonging to the compound (a) to the total units of the polymer (A) is preferably 70% by mass or more, more preferably 80% by mass or more, and may be 100% by mass.

[0195] The polymer (A) is obtained by copolymerizing a mixture containing the compound (a). The copolymerization method can be a known method of polymerizing a compound having a (meth)acryloyloxy group using a photopolymerization initiator. As the polymerization method, for example, a known polymerization method such as a solution polymerization method, a suspension polymerization method, a bulk polymerization method, an emulsion polymerization method, etc. can be applied.

[0196] The Mw of the polymer (A) is more than 200,000 and less than 2,000,000, preferably 240,000 to 1,600,000, more preferably 280,000 to 1,200,000, and further preferably 280,000 to 960,000. When the Mw of the polymer (A) is greater than the lower limit of the above range (exceeds the lower limit), the creep recovery rate and curling residual rate of the obtained cured product are likely to be good, and when it is less than the upper limit, the viscosity is low, so it is easy to obtain good coating properties.

[0197] The Mn of the polymer (A) is preferably 25,000 to 1,000,000, more preferably 30,000 to 500,000, further preferably 35,000 to 200,000, and particularly preferably 35,000 to 120,000. When the Mn of the polymer (A) is at least the lower limit of the above range, the creep recovery rate and curling residual rate of the obtained cured product are likely to be good, and the storage modulus at low temperature is likely to be good. When it is at most the upper limit, the viscosity is low, so it is easy to obtain good coating properties.

[0198] The Mw / Mn of the polymer (A) is preferably 2.0 to 8.0, more preferably 2.1 to 7.8, and further preferably 2.2 to 7.5. When the Mw / Mn of the polymer (A) is above the lower limit of the aforementioned range, the adhesive force of the obtained cured product is likely to be good, and when it is below the upper limit of the aforementioned range, the creep recovery rate of the obtained cured product is more excellent.

[0199] When the pressure-sensitive adhesive layer described below contains two or more polymers (A), it is preferred that Mw, Mn, and Mw / Mn of each polymer be within the above ranges.

[0200] The glass transition temperature of the polymer (A) is preferably -90 to -35°C, more preferably -85 to -40°C, further preferably -80 to -45°C.

[0201] When two or more polymers are contained in the curable composition described below, it is preferred that the glass transition temperature of each polymer is within the above range.

[0202] <Curable Composition>

[0203] The curable composition of the present embodiment includes compound (a). The curable composition may include polymer (A), and may also include any one or both of the following polymers (hereinafter referred to as "polymer (B)" and compounds (hereinafter referred to as "compound (b)", wherein the polymer (B) is a homopolymer or copolymer having a unit based on a (meth)acrylate that does not belong to compound (a), and does not have a unit based on compound (a), and the compound (b) has two (meth)acryloyloxy groups, a carbamate bond, and a linear polyoxyalkylene chain in one molecule, and the polyoxyalkylene chain does not have a unit based on the monomer (a). Furthermore, a crosslinking agent, a photopolymerization initiator, and other components are contained as needed.

[0204] The ratio of compound (a) to the total amount of the curable composition is preferably 100% by mass or less, more preferably 1 to 80% by mass, and further preferably 5 to 50% by mass. When the compound (a) is within the above range, it is preferred in that the low-temperature repeated durability and low-temperature adhesiveness of the obtained cured product become better.

[0205] The ratio of polymer (A) to the total amount of the curable composition is preferably 80% by mass or less, more preferably 0 to 60% by mass, and further preferably 1 to 50% by mass. When the polymer (A) is within the above range, it is preferred in that the low-temperature repeated durability and low-temperature adhesiveness of the obtained cured product become better.

[0206] The ratio of the polymer (B) to the total amount of the curable composition is preferably 99% by mass or less, more preferably 30 to 80% by mass, and still more preferably 40 to 70% by mass. When the polymer (B) is within the above range, it is preferred in that the repeated durability of the obtained cured product becomes better.

[0207] The ratio of compound (b) to the total amount of the curable composition is preferably 50% by mass or less, more preferably 0 to 40% by mass, and still more preferably 10 to 30% by mass. When the compound (b) is within the above range, the heat resistance of the obtained cured product is further improved.

[0208] (Polymer (B))

[0209] The polymer (B) is a homopolymer or copolymer having a unit based on a (meth)acrylate ester. The polymer (B) does not contain a unit based on the compound (a).

[0210] Preferred compounds used for the production of the polymer (B) include the above-mentioned compounds (d1), (d2), (d3) and (d4).

[0211] For example, it is preferred that the units derived from the compound (d1) account for 50 to 99.9% by mass, the units derived from the compound (d2) account for 0.1 to 5.0% by mass, and the total of these accounts for 50.1 to 100% by mass, based on all units of the polymer (B).

[0212] Alternatively, preferably, the unit based on the compound (d1) accounts for 50 to 99.0 mass%, the unit based on the compound (d3) accounts for 1.0 to 20.0 mass%, and the total of these accounts for 51.0 to 100 mass% based on all units of the polymer (B).

[0213] The Mw of the polymer (B) is preferably 300,000 to 1,500,000, more preferably 400,000 to 1,400,000, further preferably 450,000 to 1,300,000, and particularly preferably 500,000 to 1,200,000. When the Mw of the polymer (B) is above the lower limit of the above range, the creep recovery rate and curling residual rate of the obtained cured product become better, and when it is below the upper limit, the viscosity is low, so it is easy to obtain good coating properties.

[0214] The Mn of the polymer (B) is preferably 40,000 to 750,000, more preferably 70,000 to 700,000, further preferably 100,000 to 500,000, and particularly preferably 140,000 to 300,000. When the Mn of the polymer (B) is above the lower limit of the above range, the creep recovery rate and curling residual rate of the obtained cured product are likely to be good, and when it is below the upper limit, the viscosity is low, so it is easy to obtain good coating properties.

[0215] When two or more polymers (B) are contained in the curable composition, it is preferred that the Mn of each polymer is within the above range.

[0216] The Mw / Mn of the polymer (B) is preferably 2.0 to 8.0, more preferably 2.1 to 7.5, and further preferably 2.2 to 7.0. When the Mw / Mn of the polymer (B) is at least the lower limit of the above range, the adhesive force of the obtained cured product is likely to be good, and when it is at most the upper limit, the creep recovery rate of the obtained cured product is more excellent.

[0217] When two or more polymers (B) are contained in the curable composition, it is preferred that Mw / Mn of each polymer is within the above range.

[0218] The glass transition temperature of the polymer (B) is preferably -75 to -40°C, more preferably -70 to -45°C, and further preferably -68 to -50°C. When the glass transition temperature of the polymer (B) is within the above range, the obtained cured product is less likely to peel in a bending test at low temperature.

[0219] When two or more polymers (B) are contained in the curable composition, it is preferred that the glass transition temperature of each of the polymers (B) is within the above range.

[0220] (Compound (b))

[0221] The compound (b) has two (meth)acryloyloxy groups, a urethane bond, and a linear polyoxyalkylene chain in one molecule, wherein the polyoxyalkylene chain does not have a unit based on the monomer (a).

[0222] From the viewpoint of faster curing speed, it is preferred that the compound (b) has an acryloyloxy group.

[0223] The compound (b) may be used alone or in combination of two or more.

[0224] Compound (b) can be obtained, for example, by the following two production methods (1) and (2).

[0225] (1) The compound (b) is obtained by a urethanization reaction of two hydroxyl groups of a compound having two hydroxyl groups and a linear polyoxyalkylene chain with a compound having a (meth)acryloyloxy group and an isocyanate group.

[0226] (2) Compound (b) is obtained by subjecting a compound having two hydroxyl groups and a linear polyoxyalkylene chain to a carbamate reaction with a compound having two isocyanate groups to obtain a prepolymer having isocyanate groups at both ends, and the compound is obtained by subjecting the isocyanate group of the prepolymer to a carbamate reaction with a compound having one hydroxyl group and a (meth)acryloyloxy group.

[0227] In the production methods (1) and (2), as the compound having two hydroxyl groups and having a linear polyoxyalkylene chain, the compound (5a) having no unit based on the monomer (a) can be used.

[0228] In the production method (1), the compound (3b) can be used as the compound having a (meth)acryloyloxy group and an isocyanate group.

[0229] In the production method (2), the compound (4b) can be used as the compound having two isocyanate groups.

[0230] In the production method (2), the compound (4c) can be used as the compound having one hydroxyl group and a (meth)acryloyloxy group.

[0231] The number of urethane bonds in one molecule of the compound (b) is preferably one or more.

[0232] The Mn of the polyoxyalkylene chain in the compound (b) is preferably 1,000 to 35,000, more preferably 5,000 to 30,000, and even more preferably 8,000 to 25,000, from the viewpoint of lower viscosity of the curable composition and better flexibility of the obtained cured product.

[0233] The Mw / Mn of the polyoxyalkylene chain in the compound (b) is preferably 1.01 to 2.5, more preferably 1.03 to 2.3, and even more preferably 1.02 to 2.0, from the viewpoint of lowering the viscosity of the curable composition.

[0234] The Mn and Mw / Mn of the polyoxyalkylene chain in the compound (b) are obtained by measuring the Mn and Mw of the compound having two hydroxyl groups and a linear polyoxyalkylene chain used in the above two production methods.

[0235] Specifically, it can be measured by the same method as Mn and Mw / Mn of the polyoxyalkylene chain in the above-mentioned compound (a).

[0236] The Mn of the compound (b) is preferably 1,000 to 35,000, more preferably 6,000 to 30,000, and still more preferably 9,000 to 25,000. When the Mn of the compound (b) is within the above range, the viscosity of the curable composition can be easily adjusted, and the adhesiveness of the obtained cured product can be easily improved.

[0237] When two or more compounds (b) are contained in the curable composition, it is preferred that the Mn of each compound (b) is within the above range.

[0238] The Mw / Mn of the compound (b) is preferably 1.01 to 2.5, more preferably 1.03 to 2.3.

[0239] When two or more compounds (b) are contained in the curable composition, it is preferred that Mw / Mn of each of them be within the above range.

[0240] The glass transition temperature of the polymer containing units based on the compound (b) is preferably -90 to -35°C, more preferably -85 to -40°C, and further preferably -80 to -45°C. The polymer containing units based on the compound (b) is obtained by adding a photopolymerization initiator to the compound (b) alone and curing the resulting compound (b).

[0241] When two or more compounds (b) are contained in the curable composition, it is preferred that the glass transition temperature of each of them is within the above range.

[0242] In the production process of compound (b), by-products other than compound (b) may be generated in the product (hereinafter referred to as "product (b)".

[0243] The content of by-products in the product (b) is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, and particularly preferably 0% by mass. When it is 20% by mass or less, the function as the compound (b) can be fully exerted, so the product (b) can be regarded as the compound (b).

[0244] When the product (b) can be regarded as the compound (b), the average number of functional groups obtained from the Mn and the number of functional groups of the product (b) can be regarded as the average number of functional groups of the compound (b). In this case, the average number of functional groups in the product (b) is preferably 1.6 to 2.0, more preferably 1.7 to 2.0, and further preferably 1.8 to 1.96. For the product (b) having an average number of functional groups within the above range, the adhesiveness of the obtained cured product tends to be good.

[0245] The compound (b) preferably includes a compound (b-PO) in which the content of oxypropylene groups is 50 to 100% by mass and the content of oxyethylene groups is 0 to 50% by mass based on all oxyalkylene groups.

[0246] When compound (b-PO) is used, the content of compound (b-PO) relative to compound (b) is preferably 50 to 100% by mass, more preferably 80 to 100% by mass. When the content of compound (b-PO) is within the above range, flexibility of the obtained cured product is easily obtained.

[0247] The compound (b-PO) is particularly preferably a reaction product of a polyoxyalkylene glycol, a non-yellowing diisocyanate and a hydroxyalkyl acrylate, wherein the polyoxyalkylene glycol has a content of 80 to 100% by mass of oxypropylene groups, a content of 0 to 20% by mass of oxyethylene groups, an average number of hydroxyl groups of 2 to 3, and a number average molecular weight of 1,000 to 3,000 relative to all oxyalkylene groups.

[0248] As the non-yellowing diisocyanate, a diisocyanate selected from the group consisting of aliphatic diisocyanates, alicyclic diisocyanates and non-yellowing aromatic diisocyanates is preferred, and specific examples thereof include hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate and xylylene diisocyanate.

[0249] As the hydroxyalkyl acrylate, compound 7 represented by the following formula 7 is preferred.

[0250] CH2=CH-C(=O)O-R' (Formula 7)

[0251] R' represents a group in which one hydrogen atom of an alkyl group having 1 to 6 carbon atoms is substituted with a hydroxyl group.

[0252] Specific examples of the compound 7 include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

[0253] <Crosslinking agent>

[0254] The curable composition of the present embodiment may contain a crosslinking agent. A crosslinking agent is a compound having two or more crosslinkable functional groups. When a crosslinking agent is added, heat resistance is likely to be improved.

[0255] The crosslinkable functional group is preferably at least one selected from a (meth)acryloyl group, an epoxy group, an isocyanate group, a carboxyl group, a hydroxyl group, a carbodiimide group, an oxazoline group, an aziridine group, a vinyl group, an amino group, an imino group and an amide group.

[0256] The number of crosslinkable functional groups in one molecule is preferably 2 to 4, more preferably 2 or 3, and even more preferably 2.

[0257] The cross-linkable functional group may be protected by a removable protecting group.

[0258] As a crosslinking agent, a polyfunctional (meth) acrylate is preferred. For example, the polyfunctional (meth) acrylate described in

[0136] of International Publication No. 2018 / 173896 can be cited.

[0259] 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, and ethoxylated isocyanuric acid triacrylate are preferred because the creep recovery rate of the obtained cured product is easily improved.

[0260] The cross-linking agent may be used alone or in combination of two or more.

[0261] The amount of the crosslinking agent used is preferably 0.2 to 5 parts by mass, and more preferably 0.5 to 3 parts by mass, relative to 100 parts by mass of the total of the polymer (A), the compound (a), the polymer (B) and the compound (b). When the amount of the crosslinking agent used is above the lower limit of the above range, the heat resistance of the obtained cured product tends to be good, and when it is below the upper limit, the strength of the obtained cured product tends to be improved.

[0262] <Photopolymerization Initiator>

[0263] The curable composition of the present embodiment may be a photocurable resin composition or a thermosetting resin composition. A photocurable resin composition is preferred because it can be cured at a lower temperature and has a higher curing speed.

[0264] When the curable composition is a photocurable resin composition, it preferably contains a photopolymerization initiator. When the photocurable resin composition is used, for example, in the manufacture of a display device, a high temperature is not required, so there is little concern about damage to the display device due to high temperature.

[0265] The photopolymerization initiator functions as a reaction initiation aid in the crosslinking reaction of the crosslinking agent. A photopolymerization initiator that is sensitive to ultraviolet light having a wavelength of 380 nm or less is preferred from the viewpoint of ease of control of the crosslinking reaction.

[0266] Examples of the photopolymerization initiator include the photopolymerization initiators described in

[0147] to

[0151] of International Publication No. 2018 / 173896.

[0267] As the photopolymerization initiator, it is preferred that the photoexcited initiator forms an excited complex with the hydrogen donor in the system to transfer the hydrogen of the hydrogen donor. Specific examples of the hydrogen abstraction type photopolymerization initiator include benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 3,3-dimethyl-4-methoxybenzophenone, 4-(meth)acryloyloxybenzophenone, 4-[2-((meth)acryloyloxy)ethoxy]benzophenone, 4-(meth)acryloyloxy-4'-methoxybenzophenone, methyl 2-benzoylbenzoate, and methyl benzoylformate.

[0268] Two or more photopolymerization initiators may be used in combination.

[0269] The amount of the photopolymerization initiator used is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the total of the polymer (A), the compound (a), the polymer (B) and the compound (b). When the amount of the photopolymerization initiator used is above the lower limit of the above range, the heat resistance of the obtained cured product tends to be good, and when it is below the upper limit, the strength of the obtained cured product tends to be improved.

[0270] <Other ingredients>

[0271] The curable composition of the present embodiment may contain known components as other components other than the above components as necessary.

[0272] Examples of other components include silane coupling agents, tackifier resins, antioxidants, light stabilizers, metal deactivators, rust inhibitors, antioxidants, moisture absorbents, hydrolysis inhibitors, antistatic agents, defoaming agents, and inorganic particles.

[0273] If necessary, a reaction catalyst (such as a tertiary amine compound, a quaternary ammonium compound, and a tin laurate compound) may be contained.

[0274] If necessary, a polyfunctional isocyanate compound may be contained. Specific examples of the polyfunctional isocyanate compound include components described in paragraph 0062 of Japanese Patent No. 6375467.

[0275] The curable composition of this embodiment can also be used in a solvent-free state. A solvent may be contained as needed. The solvent is preferably removed during or after curing.

[0276] <Cured product>

[0277] The cured product of the present embodiment is a gel or solid polymer obtained by curing the curable composition of the present embodiment. For example, the curable composition is formed into a desired shape and irradiated with ultraviolet rays to be cured.

[0278] Examples of the method for molding the curable composition include a method of applying the composition onto a substrate, a method of performing extrusion molding, and a method of injecting the composition into a mold.

[0279] The amount of ultraviolet radiation is preferably 0.1 to 5 J / cm 2 , more preferably 0.3 to 4 J / cm 2 , more preferably 0.5 to 3 J / cm 2 When the irradiation amount is at least the lower limit of the above range, the heat resistance and creep recovery rate become better, and when it is at most the upper limit, coloration is less likely to occur.

[0280] The glass transition temperature of the cured product of the present embodiment is preferably -35°C or lower, more preferably -40°C or lower, and further preferably -45°C or lower.

[0281] When the glass transition temperature is not more than the upper limit value of the above range, the bending durability at low temperature is more excellent.

[0282] The lower limit of the glass transition temperature is preferably -90°C or higher, more preferably -85°C or higher, and further preferably -80°C or higher, from the viewpoint that the residual curl rate tends to be good.

[0283] The storage modulus of the cured product of the present embodiment at -20°C is preferably 0.01 to 0.24 MPa, more preferably 0.015 to 0.22 MPa, and still more preferably 0.02 to 0.20 MPa.

[0284] The storage modulus of the cured product of the present embodiment at -40°C is preferably 0.01 to 1.18 MPa, more preferably 0.05 to 1.14 MPa, and still more preferably 0.1 to 1.0 MPa.

[0285] <Adhesive Sheet>

[0286] The cured product of the present embodiment can be used as an adhesive layer. The adhesive sheet of the present embodiment has a sheet-shaped adhesive layer containing the cured product of the present embodiment. A release film is preferably provided in a manner in contact with both sides of the adhesive layer. As the release film, a known release film can be used.

[0287] The pressure-sensitive adhesive sheet can be produced, for example, by applying a curable composition on a first release film, curing the composition, and then laminating a second release film thereon.

[0288] Alternatively, the film may be produced by applying the curable composition on a first release film, laminating a second release film thereon, and then curing the film.

[0289] In the adhesive sheet of the present embodiment, the thickness of the adhesive layer is preferably 10 to 150 μm, more preferably 20 to 120 μm, and further preferably 25 to 100 μm. When the thickness of the adhesive layer is at least the lower limit of the above range, the adhesive layer tends to be smooth, and when it is at most the upper limit, the repeated bending durability is more excellent.

[0290] <Laminate>

[0291] The laminated body of the present embodiment includes an adhesive layer formed of the cured product of the present embodiment and a flexible member laminated via the adhesive layer.

[0292] As the flexible member, a member constituting a flexible display panel can be exemplified. As the flexible member, for example, a surface protection panel, an optical film, a touch panel, a display panel main body, etc. can be cited.

[0293] Examples of the surface protection panel include thin plate-shaped cover glass and cover film.

[0294] An optical film is a member having an optical function and examples of the optical film include polarizing films, phase difference films, optical filters, antireflection films, near infrared blocking films, and electromagnetic wave shielding films.

[0295] The touch panel has a structure in which a contact sensor is mounted on a thin plate-shaped glass substrate or a plastic substrate, for example.

[0296] As a display panel main body, an organic EL display panel is mentioned, for example.

[0297] The laminate of this embodiment is flexible, and preferably has a property that it will not break even if fixed in a bent shape in a static state (Bendable), a property that it can restore its shape even if it is bent or curled with a bending radius of more than 3 mm (Rollable), or a property that it can restore its shape even if it is folded with a bending radius of less than 3 mm (Foldable).

[0298] In the laminate of this embodiment, the thickness of the adhesive layer is preferably 10 to 150 μm, more preferably 20 to 120 μm, and further preferably 25 to 100 μm. When it is at least the lower limit of the above range, the adhesive layer tends to be smooth, and when it is at most the upper limit, the repeated bending durability is more excellent.

[0299] <Flexible Display>

[0300] The flexible display of this embodiment includes the laminated body of this embodiment.

[0301] The curable composition of this embodiment can reduce the elastic modulus of the cured product, reduce the change in elastic modulus due to temperature, and reduce the glass transition temperature. Therefore, even when used in an adhesive layer between components constituting a flexible display, for example, it is possible to achieve both bending durability and shape recovery.

[0302] As the flexible display, a foldable display having a structure in which a display screen can be folded is particularly suitable.

[0303] Example

[0304] Hereinafter, the present invention will be specifically described using Examples, but the present invention is not limited to the following description.

[0305] [Determination of hydroxyl value]

[0306] The hydroxyl value is measured by a titration method in accordance with JIS K0070:1992 "Test methods for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponifiable matter of chemicals".

[0307] [Determination of molecular weight]

[0308] The number average molecular weight (Mn) is measured by gel permeation chromatography (GPC) under the following conditions.

[0309] ·Analysis device: HLC-8120GPC Tosoh Corporation product name

[0310] ·Column: G7000HXL+GMHXL+GMHXL Tosoh Corporation product name

[0311] Column size: each Total 90cm

[0312] Column temperature: 40°C

[0313] Flow rate: 0.8mL / min

[0314] Injection volume: 100μL

[0315] ·Eluent: Tetrahydrofuran

[0316] Detector: Differential Refractometer (RI)

[0317] Standard sample: polystyrene

[0318] [Adhesion to glass]

[0319] According to the test method described in "10 Adhesion" of the adhesive tape and adhesive sheet test method of JIS Z 0237:2009, a 25 mm wide test piece was attached to a float glass in an atmosphere of 25°C, and pressed with a 2 kg rubber roller at a speed of 300 mm / min for one reciprocating motion. After leaving it for 20 minutes, the peeling force at room temperature (23°C) was measured under the conditions of a peeling angle of 180 degrees and a peeling speed of 300 mm / min.

[0320] Furthermore, the sample after being left standing for 20 minutes was further left in a thermostatic chamber at 0°C for 20 minutes, and the peeling force at 0°C was measured under the conditions of a peeling angle of 180 degrees and a peeling speed of 300 mm / min.

[0321] The adhesive force is good when it is 0.1 to 1.0 N / 15 mm at both room temperature (23°C) and 0°C.

[0322] [Measurement of storage modulus and glass transition temperature of cured product]

[0323] 100 parts by weight of the compounds 1 to 3 described later and 0.3 parts by weight of a photopolymerization initiator (Irgacure-819, manufactured by BASF) were poured into a silicone mold of 5 mm in width, 15 mm in length, and 2 mm in thickness. The mold was then irradiated with a conveyor-type UV irradiator (manufactured by ORC) under a nitrogen atmosphere under the illumination of a HgXe lamp at an illumination of 100 mW / cm 2 , cumulative light intensity 1J / cm 2 The obtained cured product was used as a test sample.

[0324] For the test sample, the storage modulus E' (kPa) was measured using a dynamic viscoelasticity measuring device (EXSTAR DMS6100, Seiko Instruments Inc. product name) in the tensile mode, in the temperature range of -100°C to 130°C, a heating rate of 3°C / min, a measurement frequency of 1 Hz, and a strain of 1%. In addition, the peak temperature of the loss elastic modulus obtained by the measurement was taken as the glass transition temperature.

[0325] (Production Example 1-1: Production of Monohydric Alcohol 1)

[0326] In a pressure-resistant reactor equipped with a stirrer and a nitrogen inlet pipe, 12.5 g of zinc hexacyanocobaltate-tert-butyl alcohol complex catalyst (hereinafter referred to as "TBA-DMC catalyst") and 93 g of n-butanol were added, and a nitrogen atmosphere was set at 130°C. A mixed solution of 3270 g of propylene oxide (hereinafter referred to as "PO") and 9137 g of 2-ethylhexyl glycidyl ether was added at a constant rate over 6 hours. Next, after confirming that the internal pressure of the pressure-resistant reactor had stopped decreasing, the product was taken out to obtain a polyoxyalkylene monool (monool 1). The hydroxyl value, hydroxyl-equivalent molecular weight, the ratio of units based on a monomer having one epoxy group and an ether bond other than the ether bond of the epoxy group in one molecule (referred to as "unit (a)" in Table 1), and the mass ratio of units based on the monomer to units based on propylene oxide in the polyoxyalkylene chain (referred to as "unit (a) / PO" in Table 1) of the monool 1 are shown in Table 1 (hereinafter, the same is shown).

[0327] (Production Example 1-2: Production of Monohydric Alcohol 2)

[0328] In a pressure-resistant reactor equipped with a stirrer and a nitrogen inlet pipe, 5.5 g of a TBA-DMC catalyst and 93 g of n-butanol were added, a nitrogen atmosphere was set at 130° C., and a mixed solution of 1925 g of PO and 3483 g of butyl glycidyl ether was added at a constant rate over 6 hours. Then, after confirming that the internal pressure of the pressure-resistant reactor had stopped decreasing, the product was taken out to obtain a polyoxyalkylene monool (monool 2).

[0329] (Production Example 1-3: Production of Monohydric Alcohol 3)

[0330] In a pressure-resistant reactor equipped with a stirrer and a nitrogen inlet pipe, 0.2 g of a TBA-DMC catalyst and 30 g of n-butanol were added, and a nitrogen atmosphere at 130° C. was set, and 3970 g of PO was added at a constant rate over 7 hours. Then, after confirming that the internal pressure of the pressure-resistant reactor had stopped decreasing, the product was taken out to obtain a polyoxyalkylene monool (monool 3).

[0331] [Table 1]

[0332] Table 1

[0333]

[0334] (Production Example 2-1: Production of Compound 1)

[0335] In a reaction vessel equipped with a stirrer and a nitrogen inlet pipe, 100 parts by mass of the monool 1 obtained in Preparation Example 1-1, 2-acryloyloxyethyl isocyanate (KarenzAOI, manufactured by Showa Denko K.K., hereinafter also referred to as "AOI") 2.23 parts by mass, and 0.008 parts by mass of bismuth 2-ethylhexanoate were added, and the reaction was carried out at 70°C for 3 hours to obtain Compound 1. The number of isocyanate bonds per molecule of Compound 1 is 1. The amount of each component blended and the ratio of the NCO group of 2-acryloyloxyethyl isocyanate to the OH group of the monool 1 (index (number of NCO groups / number of OH groups)), Mn, and Mw / Mn are shown in Table 2 (hereinafter, the same is shown).

[0336] (Production Example 2-2: Production of Compound 2)

[0337] In Production Example 2-1, 100 parts by mass of Monool 2 was used instead of 100 parts by mass of Monool 1, and the compounding amount of AOI was changed to 3.65 parts by mass, thereby obtaining Compound 2. The number of isocyanate bonds per molecule of Compound 2 was 1.

[0338] (Production Example 2-3: Production of Compound 3)

[0339] In Production Example 2-1, 100 parts by mass of Monool 3 was used instead of 100 parts by mass of Monool 1, and the compounding amount of AOI was changed to 1.39 parts by mass, thereby obtaining Compound 3. The number of isocyanate bonds per molecule of Compound 3 was 1.

[0340] [Table 2]

[0341] Table 2

[0342]

[0343] [Example 1]

[0344] As shown in Table 3, 100 parts by mass of compound 1 and 0.3 parts by mass of a photopolymerization initiator (Irgacure 819, manufactured by BASF) were mixed and degassed to obtain a curable composition. The obtained curable composition was applied to a polyester film having a thickness of 38 μm using a knife coater under nitrogen flow so that the dry film thickness was 25 μm. Then, the film was heated to 40°C with an HgXe lamp at an illumination of 100 mW / cm 2 .Irradiation cumulative light quantity 3000mJ / m 2 The obtained product was cured by applying light of 100° to obtain a cured product as a test piece for measuring adhesive strength.

[0345] The adhesive force of the obtained cured product to glass, the glass transition temperature of the cured product containing units based on Compound 1 measured by the above-mentioned method, and the evaluation results of the storage modulus are shown in Table 3 (the same applies hereinafter).

[0346] [Example 2]

[0347] In Example 1, a cured product was obtained in the same manner as in Example 1 except that 100 parts by mass of Compound 2 was used instead of 100 parts by mass of Compound 1.

[0348] [Example 3]

[0349] In Example 1, a cured product was obtained in the same manner as in Example 1 except that 100 parts by mass of Compound 3 was used instead of 100 parts by mass of Compound 1.

[0350] Examples 1 and 2 are embodiments, and Example 3 is a comparative example.

[0351] [Table 3]

[0352] Table 3

[0353]

[0354] The glass transition temperatures of the cured products of Examples 1 and 2 are -79°C and -77°C, respectively, and the glass transition temperature of the cured product of Example 3 is lower. Furthermore, the storage modulus of the cured product containing the unit based on compound 1 of Example 1 and the cured product containing the unit based on compound 2 of Example 2 at -20°C and -40°C is lower than the storage modulus of the cured product containing the unit based on compound 3 of Example 3 at -20°C and -40°C.

Claims

1. A compound having a (meth)acryloyloxy group and a linear polyoxyalkylene chain, The polyoxyalkylene chain has a unit based on propylene oxide and a unit based on a monomer having one epoxy group and an ether bond other than the ether bond of the epoxy group in one molecule. The unit based on the monomer is a unit represented by the following formula 1, In Formula 1, R 1 For-R 3 -OR 4 The monovalent group shown, R 2 A hydrogen atom or -R 5 -OR 6 The monovalent group shown, R 3 , R 5 Each independently represents a linear or branched alkylene group having 1 to 3 carbon atoms, R 4 , R 6 are each independently a linear or branched alkyl group having 1 to 18 carbon atoms, The compound has one or more urethane bonds per molecule.

2. The compound according to claim 1, wherein The number average molecular weight of the polyoxyalkylene chain is 1,000 to 35,000.

3. The compound according to claim 1 or 2, wherein The ratio of the units based on the monomer to the total amount of the polyoxyalkylene chains is 10 to 90% by mass.

4. The compound according to claim 1 or 2, wherein The mass ratio of the units based on the monomer to the units based on propylene oxide in the polyoxyalkylene chain is 0.6 to 4.

0.

5. The compound according to claim 1 or 2, wherein The monomer is a compound represented by the following formula 2: In Formula 2, R 1 and R 2 With R in Formula 1 1 and R 2 same.

6. The compound according to claim 1 or 2, wherein The monomer is methyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, lauryl glycidyl ether, or hexyl glycidyl ether.

7. The compound according to claim 1 or 2, wherein The glass transition temperature of the polymer including units based on the compound is -90 to -35°C. 8 . A polymer comprising a unit based on the compound according to claim 1 .

9. The polymer according to claim 8, wherein The glass transition temperature of the polymer is -90 to -35°C. 10 . A curable composition comprising the compound according to claim 1 .

11. A curable composition comprising the polymer according to claim 8 or 9.

12. A cured product obtained by curing the curable composition according to claim 10 or 11.

13. The method for producing a compound according to any one of claims 1 to 7, which is the following (1), (2), or (3): (1) subjecting a compound having one hydroxyl group and a linear polyoxyalkylene chain having a unit based on propylene oxide and a unit based on a monomer having one epoxy group and an ether bond other than the ether bond of the epoxy group in one molecule to a urethanization reaction with a compound having a (meth)acryloyloxy group and an isocyanate group, (2) subjecting a compound having one hydroxyl group and a linear polyoxyalkylene chain to a urethanization reaction with a compound having two isocyanate groups to obtain a prepolymer having an isocyanate group at a terminal, and subjecting the isocyanate group of the prepolymer to a urethanization reaction with a compound having one hydroxyl group and a (meth)acryloyloxy group, wherein the linear polyoxyalkylene chain has a unit based on propylene oxide and a unit based on a monomer having one epoxy group and an ether bond other than the ether bond of the epoxy group in one molecule, (3) subjecting a compound having two hydroxyl groups and a linear polyoxyalkylene chain having a unit based on propylene oxide and a unit based on a monomer having one epoxy group and an ether bond other than the ether bond of the epoxy group in one molecule to a urethanization reaction with a compound having a (meth)acryloyloxy group and an isocyanate group.

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