Composition, polymer material, adhesive, and electronic device

Abstract

To provide a new composition for producing a polymer material excellent in impact absorption rate and recovery rate, a polymer material obtained through polymerization of the composition, an adhesive including the polymer material, and an electronic device including the polymer material.SOLUTION: The composition contains polyurethane (meth)acrylate (A), alkyl (meth)acrylate (B), a cyclodextrin derivative (C) having a (meth)acryloyl group, and a guest compound (D) that can be included within a ring of the cyclodextrin derivative (C) to form an inclusion compound.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composition, a polymer material, a pressure-sensitive adhesive, and an electronic device. [Background technology]

[0002] BACKGROUND ART Various polymer materials have been proposed using acrylic polymerizable compositions having high mechanical properties as raw materials (for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2023-81375 Summary of the Invention [Problem to be solved by the invention]

[0004] In recent years, the development of repeatedly foldable display panels (foldable devices) has progressed for electronic devices such as smartphones and tablet terminals. In addition to the impact absorption rate that has traditionally been required, polymer materials used in adhesives for such foldable devices are now required to have new properties such as the ability to adapt to deformation caused by repeated bending and recover to their original shape (recovery rate).

[0005] The present invention aims to provide a novel composition for producing a polymeric material having superior impact absorption rate and recovery rate; a polymeric material obtained by polymerizing the composition; an adhesive comprising the polymeric material; and an electronic device comprising the polymeric material. [Means for solving the problem]

[0006] One aspect of the present invention is a composition containing a polyurethane (meth)acrylate (A), an alkyl (meth)acrylate (B), a cyclodextrin derivative (C) having a (meth)acryloyl group, and a guest compound (D) capable of being included in the ring of the cyclodextrin derivative (C) to form an inclusion compound.

[0007] In the composition of the above embodiment, the content of the alkyl (meth)acrylate (B) is preferably more than 0 mass % and not more than 65 mass %.

[0008] The composition of the above embodiment preferably further contains a (meth)acrylate (E) having an alicyclic structure which may have a heteroatom.

[0009] Another aspect of the present invention is a polymeric material obtained by polymerizing the composition of the above aspect.

[0010] Another aspect of the present invention is a pressure-sensitive adhesive, comprising the polymer material of the above aspect.

[0011] Another aspect of the present invention is an electronic device comprising the polymer material of the above aspect. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a novel composition for producing a polymeric material having superior impact absorption rate and recovery rate; a polymeric material obtained by polymerizing the composition; an adhesive comprising the polymeric material; and an electronic device comprising the polymeric material. [Brief explanation of the drawings]

[0013] [Figure 1] FIG. 1 shows an example of a drop-type impact absorption tester used to evaluate the impact absorption rate in the examples. DETAILED DESCRIPTION OF THE INVENTION

[0014] In this specification, the expression "a to b" in the description of a range of values ​​means that the range is from a to b, unless otherwise specified.

[0015] In this specification, when multiple upper limit values ​​and multiple lower limit values ​​are separately described, all numerical ranges that can be set by freely combining these upper limit values ​​and lower limit values ​​are considered to be described in this specification.

[0016] In this specification, "(meth)acrylic" is meant to encompass both "acrylic" and "methacrylic." Also, "(meth)acrylate" is meant to encompass both "acrylate" and "methacrylate." Furthermore, "(meth)acryloyl group" is meant to encompass both "acryloyl group" and "methacryloyl group."

[0017] In this specification, the cyclodextrin derivative is at least one selected from the group consisting of α-cyclodextrin derivatives, β-cyclodextrin derivatives, and γ-cyclodextrin derivatives, and the cyclodextrin is at least one selected from the group consisting of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin.

[0018] 1. Composition The composition of this embodiment contains a polyurethane (meth)acrylate (A), an alkyl (meth)acrylate (B), a cyclodextrin derivative (C) having a (meth)acryloyl group, and a guest compound (D) capable of being included in the ring of the cyclodextrin derivative (C) to form an inclusion compound. The composition may further contain a (meth)acrylate (E) having an alicyclic structure that may contain a heteroatom. Each component and composition will be described in detail below.

[0019] 1-1.Ingredients 1-1-1. Polyurethane (meth)acrylate (A) The polyurethane (meth)acrylate (A) of this embodiment is synthesized, for example, by reacting a polyol, a polyisocyanate, and a (meth)acrylate derivative having a hydroxyl group.

[0020] The weight average molecular weight (Mw) of the polyurethane (meth)acrylate (A) of this embodiment is not particularly limited, and for example, the upper limit can be 50,000 or less, and preferably 48,000 or less, 45,000 or less, 43,000 or less, 40,000 or less, 38,000 or less, 35,000 or less, etc. The lower limit can be 5,000 or more, and preferably 6,000 or more, 7,000 or more, etc.

[0021] The weight-average molecular weight can be measured by a known method. For example, it can be measured by using gel permeation chromatography (GPC) with tetrahydrofuran (THF) as an eluent and detecting the differential refractive index. The weight-average molecular weight is calculated by creating a calibration curve based on the GPC measurement results of a standard sample, polystyrene, and calculating the measurement results of the measurement sample as a polystyrene equivalent value.

[0022] Next, suitable raw material components for the polyurethane (meth)acrylate (A) will be described in order.

[0023] (Polyol) The polyol is a compound having two or more hydroxyl groups in one molecule, and is not particularly limited as long as it does not impair the effects of the present invention. Examples of polyols used in this embodiment include polyester polyols, polycarbonate polyols, polyether polyols, and polyester ether polyols. The polyols may be used alone or in combination of two or more.

[0024] Examples of polyester polyols include polyester polyols such as polypropylene glycol obtained by a dehydration condensation reaction of an aliphatic dicarboxylic acid such as succinic acid, adipic acid, sebacic acid, or azelaic acid; an aromatic dicarboxylic acid such as phthalic acid, terephthalic acid, isophthalic acid, or naphthalenedicarboxylic acid; an alicyclic dicarboxylic acid such as hexahydrophthalic acid, hexahydroterephthalic acid, or hexahydroisophthalic acid; or an acid ester or anhydride thereof with ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, or a mixture thereof; and polylactone diols obtained by ring-opening polymerization of lactone monomers such as ε-caprolactone or methylvalerolactone.

[0025] Examples of polycarbonate polyols include those obtained by reacting at least one polyhydric alcohol such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, or diethylene glycol with diethylene carbonate, dimethyl carbonate, diethyl carbonate, or the like.

[0026] Examples of polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc., which are obtained by polymerizing cyclic ethers such as ethylene oxide, propylene oxide, tetrahydrofuran, etc., and copolyethers thereof. Polyether polyols can also be obtained by polymerizing the above-mentioned cyclic ethers using polyhydric alcohols such as glycerin and trimethylolethane.

[0027] Examples of polyester ether polyols include those obtained by a dehydration condensation reaction of aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as hexahydrophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid; or acid esters or acid anhydrides of these with glycols such as diethylene glycol or propylene oxide adducts, or mixtures thereof.

[0028] (Polyisocyanate) Polyisocyanates are compounds having two or more isocyanate groups in one molecule. For example, bifunctional polyisocyanates include 2,4-toluene diisocyanate (2,4-TDI), 2,6-toluene diisocyanate (2,6-TDI), m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 2,2'-diphenylmethane diisocyanate (2,2'-MDI), hydrogenated diphenylmethane diisocyanate (hydrogenated MDI), xylylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, and polymethyl ether. Examples of the isocyanate include aromatic isocyanates such as phenyl polyphenyl polyisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate (XDI), hydrogenated xylene diisocyanate (hydrogenated XDI), and tetramethyl xylene diisocyanate (TMXDI); alicyclic isocyanates such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (HMDI), and methylcyclohexane diisocyanate; and alkylene isocyanates such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, and lysine diisocyanate.

[0029] Examples of tri- or higher functional polyisocyanates include 1-methylbenzene-2,4,6-triisocyanate, 1,3,5-trimethylbenzene-2,4,6-triisocyanate, biphenyl-2,4,4'-triisocyanate, diphenylmethane-2,4,4'-triisocyanate, methyldiphenylmethane-4,6,4'-triisocyanate, 4,4'-dimethyldiphenylmethane-2,2',5,5'tetraisocyanate, triphenylmethane-4,4',4''-triisocyanate, polymeric MDI, lysine ester triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,6,11-undecane triisocyanate, bicycloheptane triisocyanate, 1,8-diisocyanatomethyloctane, and the like, as well as modified products and derivatives thereof.

[0030] ((Meth)acrylate derivatives having a hydroxyl group) The (meth)acrylate derivative having a hydroxyl group has a (meth)acryloyl group and a hydroxyl group, and is preferably a (meth)acrylate derivative having one hydroxyl group, such as hydroxyalkyl (meth)acrylate (wherein the alkyl preferably has 2 to 12 carbon atoms), hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, and 2-hydroxypropyl methacrylate.

[0031] The polyurethane acrylate (A) preferably has the following structure: In the following formula, n is not particularly limited as long as it is an integer, and is preferably 5 to 100, and more preferably 15 to 30. Furthermore, a suitable polyurethane methacrylate has a structure in which the terminal acryloyl group in the following structural formula has been substituted with a methacryloyl group. [ka] [ka]

[0032] 1-1-2. Alkyl (meth)acrylate (B) The alkyl(meth)acrylate (B) of this embodiment is a polymerizable monomer (e.g., a monomer having an unsaturated carbon-carbon double bond), and the number of carbon atoms in the main chain of the alkyl group is not particularly limited, with the lower limit being, for example, 1 or more, 3 or more, 5 or more, or 6 or more. The upper limit being, for example, 20 or less, 15 or less, or 12 or less. The alkyl(meth)acrylate (B) may have either a branched or linear structure. The alkyl(meth)acrylate (B) serves as a solvent (diluent) for dissolving the powdery cyclodextrin derivative (C), and can also be incorporated as the main chain. The inclusion of the alkyl(meth)acrylate (B) can improve the recovery rate and transparency of the polymer material described below.

[0033] Specific examples include (meth)acrylate compounds that do not have a hydroxyl group, such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, and lauryl (meth)acrylate.

[0034] Among these, the compound represented by the following formula (1) {2-ethylhexyl acrylate (2EHA)}, the compound represented by the following formula (2) (hexyl acrylate), etc. are preferred, and the compound represented by the following formula (1) {2-ethylhexyl acrylate (2EHA)} is more preferred. [ka] [ka]

[0035] 1-1-3.Cyclodextrin derivatives (C) The cyclodextrin derivative (C) of this embodiment is not particularly limited as long as it is a cyclodextrin derivative having a (meth)acryloyl group. The cyclodextrin derivative refers to a molecule having a structure in which a cyclodextrin molecule is substituted with another organic group.

[0036] A suitable cyclodextrin derivative (C) has a structure in which the hydrogen atom of at least one hydroxyl group of the cyclodextrin is substituted with at least one group selected from the group consisting of a hydrocarbon group, an acyl group, and -CONHR (wherein R is a methyl group or an ethyl group).

[0037] Hereinafter, in this specification, "at least one group selected from the group consisting of a hydrocarbon group, an acyl group, and -CONHR (R is a methyl group or an ethyl group)" may be referred to as "a hydrocarbon group, etc." for convenience.

[0038] The type of hydrocarbon group is not particularly limited, and examples thereof include alkyl groups, alkenyl groups, and alkynyl groups. The number of carbon atoms in the hydrocarbon group is not particularly limited, and is preferably 1 to 4, for example. Specific examples of hydrocarbon groups having 1 to 4 carbon atoms include methyl groups, ethyl groups, propyl groups, and butyl groups. When the hydrocarbon group is a propyl group or a butyl group, it may be either linear or branched.

[0039] The hydrocarbon group may have a substituent, which is one or more selected from the group consisting of halogen atoms such as fluorine, chlorine, boron, and iodine, alkoxy groups such as methoxy and ethoxy, carboxy groups, nitro groups, and benzoyl groups.

[0040] Examples of the acyl group include an acetyl group, a propionyl group, and a formyl group, and an acetyl group is preferred. The acyl group may further have a substituent. Here, the substituent is one or more selected from the group consisting of halogen atoms such as fluorine, chlorine, boron, and iodine; alkoxy groups such as methoxy and ethoxy; a carboxy group; a nitro group; and a benzoyl group. The acyl group is preferably an acetyl group.

[0041] -CONHR (R is a methyl group or an ethyl group) is a methyl carbamate group or an ethyl carbamate group. -CONHR is preferably an ethyl carbamate group.

[0042] Here, if the total number of hydroxyl groups in one cyclodextrin molecule is N, then N=18 for α-cyclodextrin, N=21 for β-cyclodextrin, and N=24 for γ-cyclodextrin.

[0043] The cyclodextrin derivative (C) preferably has a structure in which the hydrogen atoms of 70% or more of the hydroxyl groups, out of the total number of hydroxyl groups present in one molecule, are substituted with the hydrocarbon group or the like, more preferably the hydrogen atoms of 80% or more of the hydroxyl groups, out of the total number of hydroxyl groups present in one molecule of the cyclodextrin derivative, are substituted with the hydrocarbon group or the like, and particularly preferably the hydrogen atoms of 90% or more of the hydroxyl groups, out of the total number of hydroxyl groups, are substituted with the hydrocarbon group or the like.

[0044] From another perspective, when the cyclodextrin derivative (C) is an α-cyclodextrin derivative, it preferably has a structure in which the hydrogen atoms of 13 or more of the total hydroxyl groups present in one molecule are substituted with the hydrocarbon group or the like, more preferably the hydrogen atoms of 15 or more of the total hydroxyl groups present in one molecule are substituted with the hydrocarbon group or the like, and particularly preferably the hydrogen atoms of 17 of the total hydroxyl groups are substituted with the hydrocarbon group or the like.

[0045] When the cyclodextrin derivative (C) is a β-cyclodextrin derivative, it preferably has a structure in which the hydrogen atoms of 15 or more of the total hydroxyl groups present in one molecule are substituted with the hydrocarbon group or the like, more preferably the hydrogen atoms of 17 or more of the total hydroxyl groups present in one molecule are substituted with the hydrocarbon group or the like, and particularly preferably the hydrogen atoms of 19 or more of the total hydroxyl groups are substituted with the hydrocarbon group or the like.

[0046] When the cyclodextrin derivative (C) is a γ-cyclodextrin derivative, it preferably has a structure in which the hydrogen atoms of 17 or more of the total hydroxyl groups present in one molecule are substituted with the hydrocarbon group or the like, more preferably the hydrogen atoms of 19 or more of the total hydroxyl groups present in one molecule are substituted with the hydrocarbon group or the like, and particularly preferably the hydrogen atoms of 21 or more of the total hydroxyl groups are substituted with the hydrocarbon group or the like.

[0047] As described above, the cyclodextrin derivative (C) has a (meth)acryloyl group. A suitable cyclodextrin derivative (C) having a (meth)acryloyl group is one in which at least one hydroxyl group of cyclodextrin is substituted with the following formula: That is, the cyclodextrin derivative (C) preferably has one or two (meth)acryloyl groups, and more preferably has one (meth)acryloyl group. [ka] (wherein R1 is a hydrogen atom or a methyl group, and R2 is NH, O, or NHCHO).

[0048] 1-1-4. Guest compound (D) The guest compound (D) of this embodiment is a compound that can be included within the ring of the cyclodextrin derivative (C) (host compound) to form an inclusion compound. That is, in this embodiment, the cyclodextrin derivative (C) (host compound) and the guest compound (D) are contained in a composition to form an inclusion compound. The inclusion compound is a compound in which the guest compound (D) is included within the ring of the cyclodextrin derivative (C) having a (meth)acryloyl group, which serves as a host compound. The inclusion compound can be produced, for example, according to the method described in WO2019 / 168128.

[0049] That is, the composition of this embodiment contains an inclusion compound in which a guest compound (D) is enclosed within the ring of a cyclodextrin derivative (C) having a (meth)acryloyl group as a host compound. Therefore, in a polymer material described below, the toughness and strength of the polymer material can be improved by utilizing reversible host-guest interactions within or between molecules, and the impact absorption rate can be improved.

[0050] As described above, the guest compound (D) is not particularly limited as long as it is a compound that can be included within the ring of the cyclodextrin derivative (C) (host compound) to form an inclusion compound. Examples of the guest compound (D) include compounds having one or two (meth)acryloyl groups, compounds having one or two amino groups, compounds having one or two hydroxyl groups, compounds having one or two carboxyl groups, compounds having one or two epoxy groups, compounds having one or two isocyanate groups, compounds having one or two thiol groups, and compounds having one or two carboxylic acid chlorides.

[0051] Examples of compounds having one or two (meth)acryloyl groups include 2-methyladamantan-2-yl-acrylate (CAS 249562-06-9), 2-methacryloyloxy-2-methyladamantane (CAS 177080-67-0), 2-ethyl-2-adamantyl acrylate (CAS 303186-14-3), 2-ethyl-2-methacryloyloxyadamantane (CAS 209982-56-9), phenyl acrylate, phenyl methacrylate, 4-hydroxyphenyl methacrylate, 2-(o-phenylphenoxy)ethyl acrylate, p-methoxyphenyl methacrylate, p-tert-butylphenyl methacrylate, benzyl methacrylate, and phenylethyl methacrylate.

[0052] Examples of the compound having one or two amino groups include 1-adamantanamine, benzylamine, tert-butylamine, n-butylamine, 1-aminopyrene, aminoferrocene, 4-aminoazobenzene, 4-aminostilbene, cyclohexylamine, hexylamine, 4,4'-diaminodiphenylmethane, p-xylylenediamine, diaminoferrocene, 4,4'-diaminoazobenzene, 4,4'-diaminostilbene, 1,4-diaminocyclohexane, 1,6-diaminocyclohexane, α,ω-diaminopolyethylene glycol, α,ω-diaminopolypropylene glycol, 2,2-bis(4-aminophenyl)propane, 1,1-bis(4-aminophenyl)-1-phenylethane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2 , 2-bis(4-aminophenyl)butane, bis(4-aminophenyl)diphenylmethane, 2,2-bis(3-methyl-4-aminophenyl)propane, bis(4-aminophenyl)-2,2-dichloroethylene, 1,1-bis(4-aminophenyl)ethane, 2,2-bis(4-amino-3-isopropylphenyl)propane, 1,3-bis(2-(4-aminophenyl)-2-propyl)benzene, bis(4-aminophenyl)sulfone, 1,4-bis(2-(4-aminophenyl)-2-propyl)benzene, 5,5'-(1-methylethylidene)-bis[1,1'-(bisphenyl)-2-amine]propane, 1,1-bis(4-aminophenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-aminophenyl)cyclohexane, and the like.

[0053] Examples of compounds having one or two hydroxyl groups include 1-hydroxyadamantane, benzyl alcohol, tert-butyl alcohol, n-butyl alcohol, 1-hydroxypyrene, 1-hydroxymethylferrocene, 4-hydroxyazobenzene, 4-hydroxystilbene, cyclohexanol, hexanol, 4,4'-dihydroxydiphenylmethane, 2,2-bis(4-hydroxyphenyl)propane, 1,4-benzenedimethanol, 1,1'-dihydroxymethylferrocene, 4,4'-dihydroxyazobenzene, 4,4'-dihydroxystilbene, 1,4-cyclohexynol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 2,2-bis( 4-hydroxyphenyl)butane, bis(4-hydroxyphenyl)diphenylmethane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)-2,2-dichloroethylene, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxy-3-isopropylphenyl)propane, 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene, bis(4-hydroxyphenyl)sulfone, 1,4-bis(2-(4-hydroxyphenyl)-2-propyl)benzene, 5,5'-(1-methylethylidene)-bis[1,1'-(bisphenyl)-2-hydroxy]propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bisphenol A, and the like can be mentioned.

[0054] Examples of compounds having one or two carboxy groups include 1-carboxyadamantane, benzoic acid, pivalic acid, butanoic acid, 1-carboxypyrene, 1-carboxyferrocene, 4-carboxyazobenzene, 4-carboxystilbene, cyclohexanoic acid, hexanoic acid, 4,4'-dicarboxydiphenylmethane, 1,4-benzenedicarboxylic acid, 1,4-phenylenediacetic acid, 1,1'-dicarboxyferrocene, 4,4'-dicarboxyazobenzene, 4,4'-dicarboxystilbene, 1,4-cyclohexanedicarboxylic acid, 1,6-hexanedicarboxylic acid, α,ω-dicarboxypolyethylene glycol, α,ω-dicarboxypolypropylene glycol, 2,2-bis(4-carboxyphenyl)propane, 1,1-bis(4-carboxyphenyl)-1-phenylethane, 2,2-bis(4-carboxyphenyl)hexafluoro bis(4-carboxyphenyl)-2,2-dichloroethylene, 1,1-bis(4-carboxyphenyl)ethane, 2,2-bis(4-carboxy-3-isopropylphenyl)propane, 1,3-bis(2-(4-carboxyphenyl)-2-propyl)benzene, bis(4-carboxyphenyl)sulfone, 1,4-bis(2-(4-carboxyphenyl)-2-propyl)benzene, 5,5'-(1-methylethylidene)-bis[1,1'-(bisphenyl)-2-carboxy]propane, 1,1-bis(4-carboxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-carboxyphenyl)cyclohexane, and the like.

[0055] Examples of the compound having one or two epoxy groups include adamantane oxide, styrene oxide, 1,2-epoxybutane, 1-epoxypyrene, epoxyferrocene, 4-epoxyazobenzene, 4-epoxystilbene, cyclohexyl oxide, 1, 2-Epoxyhexane, 2,2'-bis(4-glycidyloxyphenyl)propane, p-diglycidyloxybenzene, diglycidyloxyferrocene, 4,4'-diglycidyloxyazobenzene, 4,4'-diglycidyloxyferrocene, 1,4-diglycidyloxycyclohexane, 1,6-diglycidyloxycyclohexane, α,ω-diglycidyloxypolyethylene glycol, α,ω-diglycidyloxypolypropylene glycol, 1,1-bis(4-glycidyloxyphenyl)-1-phenylethane, 2,2-bis(4-glycidyloxyphenyl)hexafluoropropane, 2,2-bis(4-glycidyloxyphenyl)butane, bis(4-glycidyloxyphenyl)diphenylmethane, 2,2-bis(3-methyl-4-glycidyloxyphenyl) bis(4-glycidyloxyphenyl)propane, bis(4-glycidyloxyphenyl)-2,2-dichloroethylene, 1,1-bis(4-glycidyloxyphenyl)ethane, 2,2-bis(4-glycidyloxy-3-isopropylphenyl)propane, 1,3-bis(2-(4-glycidyloxyphenyl)-2-propyl)benzene, bis(4-glycidyloxyphenyl)sulfone, 1,4-bis(2-(4-glycidyloxyphenyl)-2-propyl)benzene, 5,5'-(1-methylethylidene)-bis[1,1'-(bisphenyl)-2-glycidyloxy]propane, 1,1-bis(4-glycidyloxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-glycidyloxyphenyl)cyclohexane, and the like can be mentioned.

[0056] Examples of compounds having one or two isocyanate groups include 1-adamantane isocyanate, benzyl isocyanate, phenyl isocyanate, tert-butyl isocyanate, butyl isocyanate, 1-pyrene isocyanate, ferrocene isocyanate, azobenzene-4-isocyanate, stilbene-4-isocyanate, cyclohexane isocyanate, hexane isocyanate, 4,4'-diisocyanate phenylmethane, p-benzenediisocyanate, and the like. Anate, ferrocene-1,1'-diisocyanate, azobenzene-4,4'-diisocyanate, stilbene-4,4'-diisocyanate, cyclohexane-1,4-diisocyanate, cyclohexane-1,6-diisocyanate, polyethylene glycol diisocyanate, polypropylene glycol diisocyanate, 2,2-bis(4-phenylisocyanate)propane, 1,1-bis(4-phenylisocyanate)-1-phenylethane, 2,2-bis(4 -phenylisocyanate)hexafluoropropane, 2,2-bis(4-phenylisocyanate)butane, bis(4-phenylisocyanate)diphenylmethane, 2,2-bis(3-methyl-4-phenylisocyanate)propane, bis(4-phenylisocyanate)-2,2-dichloroethylene, 1,1-bis(4-phenylisocyanate)ethane, 2,2-bis(3-isopropyl-4-phenylisocyanate)propane, 1,3-bis(2-(4-phenyl Examples of the isocyanate-containing methyl methyl ether include 1,4-bis(2-(4-phenylisocyanate-)-2-propyl)benzene, bis(4-phenylisocyanate-)sulfone, 1,4-bis(2-(4-phenylisocyanate-)-2-propyl)benzene, 5,5'-(1-methylethylidene)-bis[1,1'-(bisphenyl)-2-isocyanate]propane, 1,1-bis(4-phenylisocyanate-)-3,3,5-trimethylcyclohexane, and 1,1-bis(4-phenylisocyanate-)cyclohexane.

[0057] Examples of the compound having one or two thiol groups include 1-adamantanethiol, benzylthiol, tert-mercaptan, butanethiol, 1-thiolpyrene, ferrocene thiol, 4-thioazobenzene, 4-thiostilbene, cyclohexylthiol, hexanethiol, 4,4'-dithiophenylmethane, p-benzenedithiol, 1,1'-dithioferrocene, 4,4'-dithioazobenzene, 4,4'-dithiostilbene, 1,4-dithiocyclohexane, 1,6-dithiocyclohexane, α,ω-dithiopolyethylene glycol, α,ω-dithiopolypropylene glycol, 1,1-bis(4-thiophenyl)-1-phenylethane, 2,2-bis(4-thiophenyl)hexafluoropropane, 2,2-bis( 4-thiophenyl)butane, bis(4-thiophenyl)diphenylmethane, 2,2-bis(3-methyl-4-thiophenyl)propane, bis(4-thiophenyl)-2,2-dichloroethylene, 1,1-bis(4-thiophenyl)ethane, 2,2-bis(4-thio-3-isopropylphenyl)propane, 1,3-bis(2-(4-thiophenyl)-2-propyl)benzene, bis(4-thiophenyl)sulfone, 1,4-bis(2-(4-thiophenyl)-2-propyl)benzene, 5,5'-(1-methylethylidene)-bis[1,1'-(bisphenyl)-2-thiol]propane, 1,1-bis(4-thiophenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-thiophenyl)cyclohexane, and the like can be mentioned.

[0058] Examples of the compound having one or two carboxylic acid chlorides include 1-adamantanecarbonyl chloride, terephthaloyl chloride, trimethylacetyl chloride, butyryl chloride, 1-pyrenecarbonyl chloride, 1-ferrocenecarbonyl chloride, 4-azobenzenecarbonyl chloride, 4-stilbenecarbonyl chloride, cyclohexanecarbonyl chloride, hexyl chloride, 4,4'-diphenylmethanedicarbonyl chloride, 1,4-benzenedicarbonyl chloride, and 1,4-phenylene. dicarbonyl chloride, 1,1'-ferrocenedicarbonyl chloride, 4,4'-azobenzenedicarbonyl chloride, 4,4'-stilbenecarbonyl chloride, 1,4-cyclohexanedicarbonyl chloride, 1,6-hexanedicarbonyl chloride, α,ω-polyethylene glycol dicarbonyl chloride, α,ω-polypropylene glycol dicarbonyl chloride, 2,2-bis(4-phenylcarbonyl chloride)propane, 1,1-bis(4-phenylcarbonyl chloride)-1-phenylethane, 2,2-bis(4-phenylcarbonyl chloride)hexafluoropropane, 2,2-bis(4-phenylcarbonyl chloride)butane, bis(4-phenylcarbonyl chloride)diphenylmethane, 2,2-bis(3-methyl-4-phenylcarbonyl chloride)propane, bis(4-phenylcarbonyl chloride)-2,2-dichloroethylene, 1,1-bis(4-phenylcarbonyl chloride)ethane, 2,2-bis(3-isopropylphenyl-4-carbonyl chloride)propane, 1,3-bis(2- Examples of such bis(4-phenylcarbonyl chloride)-2-propyl)benzene, bis(4-phenylcarbonyl chloride)sulfone, 1,4-bis(2-(4-phenylcarbonyl chloride)-2-propyl)benzene, 5,5'-(1-methylethylidene)-bis[1,1'-(bisphenyl)-2-carbonyl chloride]propane, 1,1-bis(4-phenylcarbonyl chloride)-3,3,5-trimethylcyclohexane, 1,1-bis(4-phenylcarbonyl chloride)cyclohexane, and the like.

[0059] Among the above, the guest compound (D) is preferably a compound having a (meth)acryloyl group, and more preferably an adamantyl derivative or a phenyl derivative, such as the compound shown in the following formula {methyl adamantyl methacrylate (MADMA)}. [ka]

[0060] 1-1-5. (Meth)acrylate (E) The (meth)acrylate (E) of this embodiment is a polymerizable monomer (e.g., a monomer having an unsaturated carbon-carbon double bond) and is a compound having an alicyclic structure which may have a heteroatom. The (meth)acrylate (E) serves as a solvent (diluent) for dissolving the powdery cyclodextrin derivative (C), and can also be introduced as the main chain. The (meth)acrylate (E) can also serve as the guest compound (D) described above. An example of the (meth)acrylate (E) is the compound represented by the following formula {tetrahydrofurfuryl acrylate (THF-A)}. [ka]

[0061] 1-1-6. Other ingredients The composition according to the present embodiment may contain other components in addition to the components described above. Examples of such components include photopolymerization initiators, defoamers, fillers, plasticizers, pigments, dyes, antioxidants, antioxidants, antistatic agents, flame retardants, antibacterial agents, light stabilizers, stabilizers, dispersants, tackifiers, and catalysts. For example, a suitable photopolymerization initiator is the compound represented by the following formula (1-hydroxycyclohexyl-phenyl ketone): [ka]

[0062] 1-2.Composition Next, the composition of the present embodiment will be described. Based on the total mass of the composition, it is preferable that the content of polyurethane (meth)acrylate (A) is 5% by mass or more and 82.5% by mass or less, or 5% by mass or more and 50% by mass or less, the content of alkyl (meth)acrylate (B) is more than 0% by mass and 65% by mass or less, or 10% by mass or more and 65% by mass or less, the content of cyclodextrin derivative (C) is 5% by mass or more and 20% by mass or less, the content of guest compound (D) is 0.5% by mass or more and 2% by mass or less, and the content of (meth)acrylate (E) is 15% by mass or more and 65% by mass or less.

[0063] The molar ratio of cyclodextrin derivative (C) to polyurethane (meth)acrylate (A) is preferably 1:20 to 0.1, more preferably 1:10 to 0.5, and particularly preferably 1:10 to 1. The molar ratio of cyclodextrin derivative (C) to guest compound (D) is preferably 1:20 to 0.1, more preferably 1:10 to 0.5, and particularly preferably 1:10 to 1.

[0064] 2. Manufacturing methods for polymer materials The method for producing a polymeric material according to this embodiment includes a step of polymerizing the composition described above. Specifically, this step involves radically polymerizing the unsaturated double bonds present in the composition. This step is preferably a step of irradiating the composition with light. The light irradiation can be carried out by irradiating the composition with light of a specific wavelength at which photoreactive functional groups or the like react, or with which the added photopolymerization initiator acts. The amount of light irradiation can be set depending on the blending and thickness of the raw material composition, the type and amount of the photopolymerization initiator, and the like, and is, for example, 600 to 1,800 mJ / cm. 2 It can be said that:

[0065] 3.Polymer materials The polymer material of this embodiment is a polymer material obtained by polymerizing the above-described composition. The chemical structure, physical properties, etc. of the polymer material will be described in detail below.

[0066] 3-1.Chemical structure As described above, the polymer material of this embodiment is obtained by polymerizing a composition containing an inclusion compound. The inclusion compound is a compound in which a cyclodextrin derivative (C) having a (meth)acryloyl group is used as a host compound, and a guest compound (D) having a (meth)acryloyl group is included within the ring of the cyclodextrin derivative (C). The polymer material preferably has a structure in which the (meth)acryloyl group of the cyclodextrin derivative (C) and the (meth)acryloyl group of the guest compound (D) are chemically bonded to the polymer chain by addition polymerization.

[0067] 3-2.Physical properties The polymer material of this embodiment is preferably an elastomer. Here, in this specification, "elastomer" is a general term for all polymeric substances that exhibit rubber elasticity at or near room temperature. Suitable polymeric materials include all polymeric materials that exhibit rubber elasticity at or near room temperature, have mechanical strength, low-temperature properties, abrasion resistance, bending resistance, flex resistance, oil resistance, chemical resistance, and weather resistance, and can be processed into various shapes.

[0068] 3-2-1. Peel strength The peel strength of the polymeric material of this embodiment measured by the following measurement method can have a lower limit of, for example, 0.1 N / cm or more, 0.3 N / cm or more, 0.5 N / cm or more, 1.0 N / cm or more, 1.5 N / cm or more, 2.0 N / cm or more, and an upper limit of 50 N / cm or less, 30 N / cm or less, 15 N / cm or less, etc. When the peel strength is within this range, a polymeric material can be obtained that has flexibility and better mechanical properties.

[0069] The peel strength is a value measured in accordance with JIS Z 0237;2022. (The details of the measurement method will be explained in the examples below.)

[0070] 3-2-2.Tensile strength / elongation The polymeric material of this embodiment has a tensile strength of preferably 0.05 to 5.0 MPa, more preferably 0.1 to 5.0 MPa, and even more preferably 0.2 to 5.0 MPa, and an elongation of preferably 10 to 2000%, more preferably 100 to 2000%, and even more preferably 200 to 2000%.

[0071] The tensile strength and elongation were measured in accordance with JIS K 6400-5 (No. 3 dumbbell, tensile speed 100 mm / min).

[0072] 3-2-3.Impact absorption rate The impact absorption rate of the polymer material of this embodiment can be, for example, 18% or more, 20% or more, 25% or more, 30% or more, or the like. The upper limit is not particularly limited. By setting the impact absorption rate within this range, a polymer material that can adapt to deformation due to repeated bending can be obtained.

[0073] The impact absorption rate is a value measured in a surface impact absorption test using a drop impact absorption tester (see FIG. 1). (The details of the measurement method will be explained in the examples below.)

[0074] 3-2-4.Total light transmittance The total light transmittance of the polymer material of this embodiment can be, for example, 95% or more, 98% or more, or more than 99%, for example. The upper limit is not particularly limited. When the total light transmittance is within this range, a transparent polymer material can be obtained. The total light transmittance is a value measured in accordance with JIS K-7361 for a polymer material with a thickness of 50 μm.

[0075] 3-2-5. Recovery rate The recovery rate of the polymer material of this embodiment can be, for example, 50% or more, 60% or more, 70% or more, 80% or more, etc. The upper limit is not particularly limited. By setting the recovery rate within this range, it is possible to obtain a polymer material that can recover to its original shape even if it is deformed by repeated bending.

[0076] The recovery rate is calculated from the strain measured after applying a load to the polymer material for 10 minutes using a parallel plate oscillatory rheometer (MCR-302, manufactured by Anton-Paar). (The details of the measurement method will be explained in the Examples below.)

[0077] 3-2-6.Storage modulus / loss modulus / loss tangent The storage modulus of the polymer material of this embodiment is preferably 2 kPa or more, 5 kPa or more, 10 kPa or more, 20 kPa or more, and is preferably 500 kPa or less, 250 kPa or less, 100 kPa or less, 50 kPa or less.

[0078] The loss modulus of the polymer material of this embodiment is preferably 1 kPa or more, 2 kPa or more, 5 kPa or more, 10 kPa or more, 15 kPa or more, etc., and is preferably 200 kPa or less, 100 kPa or less, 50 kPa or less, 30 kPa or less, etc.

[0079] The loss tangent tanδ (loss modulus / storage modulus) of the polymer material of this embodiment is preferably 0.1 or more, 0.2 or more, 0.3 or more, 0.35 or more, 0.4 or more, etc., and is preferably 1.0 or less, 0.9 or less, 0.8 or less, 0.75 or less, 0.7 or less, etc. More specifically, the loss tangent tanδ is preferably 0.3 to 0.7, and more preferably 0.4 to 0.7.

[0080] The storage modulus and loss modulus are measured by molding a polymer material to a predetermined size, sandwiching it between parallel plates, and using a parallel plate oscillatory rheometer (Anton-Paar, MCR-302) at a measurement temperature of 23°C, a frequency of 1 Hz, and a strain of 0.1%.

[0081] 3-2-7. Glass transition temperature The polymer material of this embodiment preferably has a glass transition temperature (Tg) of −50 to 60° C. The glass transition temperature is set to the temperature corresponding to the peak value of the loss tangent tanδ described above.

[0082] 4.Applications The polymer material of this embodiment can be used as an adhesive, a sealing material, a vibration damping material, a shock absorbing material, a buffer material, a surface protection material, etc., which are used in electronic devices such as smartphones and tablet terminals.

[0083] The adhesive of the present embodiment includes the polymer material described above, and therefore has excellent impact absorption and recovery rates, making it suitable for use as an adhesive for foldable devices.

[0084] The electronic device of this embodiment includes the polymer material described above, and can therefore be suitably used as an electronic device equipped with a foldable device. [Example]

[0085] <Host-guest elastomer> <Production of Prepolymer A> Prepolymer A was produced using the raw materials shown in Table 1 below. Specifically, 88.0 g of isophorone diisocyanate (IPDI), 2.0 g of catalyst, and 0.5 g of antioxidant (dibutylhydroxytoluene (BHI)) were added to 889.0 g of polyol (polypropylene glycol (PPG)) placed in a vessel, and the mixture was allowed to react overnight at 80°C under a nitrogen atmosphere. 22.9 g of hydroxyethyl acrylate (HEA) was then added and reacted to obtain prepolymer A. The molar ratio of IPDI:PPG:HEA was 4:3:2.

[0086] <Production of Prepolymer B> Prepolymer B was produced using the raw materials shown in Table 1 below. Specifically, 14.0 g of dicyclohexylmethane 4,4'-diisocyanate (HMDI), 2.0 g of catalyst, and 0.5 g of antioxidant (dibutylhydroxytoluene (BHT)) were added to 800.0 g of polyol (polypropylene glycol (PPG)) placed in a vessel, and the mixture was allowed to react overnight at 80°C under a nitrogen atmosphere. 60.0 g of hydroxyethyl acrylate (HEA) was then added and reacted to obtain Prepolymer B. The molar ratio of HMDI:PPG:HEA was 2:1:2.

[0087] [Table 1]

[0088] <Production of elastomers> Compositions were synthesized using the raw materials and formulations shown in Tables 2 and 3 below to produce the elastomers of each Example and Comparative Example. More specifically, prepolymer A or B was mixed with polymerizable monomer (THF-A), the host compound β-cyclodextrin (PAcβCDAAmMe) (β-CD), and the guest compound (MADMA) at room temperature for 2 hours, and the resulting solution was added to the polymerizable monomer (2EHA) and photopolymerization initiator, followed by stirring and degassing. The mixture was poured into a silicone mold (size: 3 cm x 4 cm x 1 mm thick), sandwiched between a peelable PET sheet and a glass plate, and irradiated with UV light under the conditions described below to obtain the elastomers of Examples 1 to 3 and Comparative Examples 1 to 3. (UV irradiation conditions) Wavelength: 395nm Illuminance: 56mW / cm 2 Accumulated light output: 500mJ / cm 2

[0089] The evaluations for each of the Examples and Comparative Examples were carried out as follows, and the evaluation results are shown in Table 3 below. (gel fraction) The sample was immersed in THF in an amount 20 times the sample weight, and after stirring for 24 hours, the insoluble matter that remained in the THF without dissolving was removed, dried in vacuum, and its weight was measured and divided by the weight of the sample before immersion to calculate the weight.

[0090] (peel strength) The peel strength of the sample was measured in accordance with JIS Z 0237;2022. Polyimide (PI) tape (5 cm wide x 10 cm long x 0.06 mm thick) (product name: DanYun) was attached to a SUS plate. A sample (25 mm wide x 100 mm long x 1 mm thick) was attached to the surface of the polyimide tape. A PET film (25 mm wide x 150 mm long x 50 μm thick) was attached to the surface of the sample. The sample was then aged for 24 hours in a thermostatic chamber at 23°C and 50% RH. The PET film was then gripped using an autograph, and the sample was peeled off under the following conditions. (Test conditions) Test speed: 300 mm / min

[0091] (tensile strength) The tensile strength of the sample was measured in accordance with JIS K 6400-5 (No. 3 dumbbell, tensile speed 100 mm / min).

[0092] (stretch) The elongation of the sample was measured in accordance with JIS K 6400-5 (No. 3 dumbbell, tensile speed 100 mm / min).

[0093] (shock absorption rate) The impact absorption rate was calculated using a drop-type impact absorption tester (see Figure 1) according to the following formula. Measurements were carried out under the following conditions, with samples cut to a size of 50 mm x 50 mm x 0.1 mm thick placed on a sample stage. (Measurement conditions) Temperature: 23℃ Impactor weight: 13.96g Impactor drop height: 300mm (formula) Surface impact absorption rate (%) = {(fa0-fa1) / fa0} x 100

[0094] In the above formula, fa0 is the impact load when an impact absorption test is performed without placing a sample on the sample stage and only a 5 mm thick acrylic plate is placed on the sample stage, and fa1 is the impact load when an impact absorption test is performed with a sample placed on the sample stage and a 5 mm thick acrylic plate placed at the position where the sample comes into contact with the impactor. Measurements were taken from a drop height of 100 mm. The impact load was measured using a sensor installed on the sample stage. The impact absorption rate was evaluated according to the following evaluation criteria. (Evaluation criteria) A: Impact absorption rate is 20% or more C: Impact absorption rate is less than 20%

[0095] (Total light transmittance) Measurement was carried out in accordance with JIS K-7361 using a sample with a thickness of 50 μm.

[0096] (recovery rate) The recovery rate was measured using a parallel plate oscillatory rheometer (MCR-302, manufactured by Anton-Paar) in which a sample cut to a size of φ8 mm x t0.5 mm was placed and a load of 200% strain was applied for 10 minutes. After 10 minutes, the load was removed and the strain of the sample (strain after 10 minutes) (%) was measured. The residual strain (%) and recovery rate (%) were calculated using the following formula. The recovery rate was evaluated according to the following evaluation criteria. (formula) Residual strain (%) = {(strain after 10 minutes) / 200} x 100 Recovery rate (%) = 100 - (residual strain) (Evaluation criteria) A: Recovery rate is 75% or more B: Recovery rate is between 50% and 75% C: Recovery rate is less than 50% or measurement is impossible

[0097] (storage modulus / loss modulus) The storage modulus and loss modulus were measured by processing the sample into a size of φ20 mm × t0.5 mm, sandwiching it between parallel plates, and using a parallel plate oscillatory rheometer (Anton-Paar, MCR-302) at a measurement temperature of 23°C, a frequency of 1 Hz, and a strain of 0.1%.

[0098] (loss tangent) The loss tangent (tan δ) was determined by dividing the loss modulus measured by the above-mentioned method by the storage modulus.

[0099] (glass transition temperature (Tg)) The glass transition temperature was determined as the peak value of the loss tangent (tan δ) measured by the method described above.

[0100] [Table 2] [Table 3] [Industrial Applicability]

[0101] The composition and polymer material of the present invention have excellent impact absorption rate and recovery rate, and therefore can be used as adhesives, sealing materials, vibration damping materials, impact absorbing materials, cushioning materials, surface protective materials, etc., used in electronic devices such as smartphones and tablet terminals.

Claims

1. A polyurethane (meth)acrylate (A), an alkyl (meth)acrylate (B); a cyclodextrin derivative (C) having a (meth)acryloyl group; and a guest compound (D) capable of being included in the ring of the cyclodextrin derivative (C) to form an inclusion compound.

2. The composition according to claim 1, wherein the content of the alkyl (meth)acrylate (B) is more than 0% by mass and not more than 65% by mass.

3. The composition according to claim 1 , further comprising a (meth)acrylate (E) having an alicyclic structure which may have a heteroatom.

4. A polymeric material obtained by polymerizing the composition according to any one of claims 1 to 3.

5. A pressure-sensitive adhesive comprising the polymer material according to claim 4.

6. An electronic device comprising the polymer material according to claim 4.

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