Composition for forming adhesive / tacky layer, method for producing the same, and adhesive / tacky polymer

Abstract

To provide a composition for forming adhesive / tacky layers capable of imparting or enhancing adhesion or tackiness, and forming adhesive layers or the like having excellent adhesion and tackiness to both similar and dissimilar materials, on various substrates.SOLUTION: A composition for forming adhesive / tacky layers is provided, comprising a first polymerizable compound represented by the following general formula (1), and a second polymerizable compound represented by the following general formula (2). (R1 to R5 each independently represent a hydrogen atom or a hydroxyl group, with at least two of R1 to R5 being hydroxyl groups. R6 represents an alkylene group having 2 to 10 carbon atoms or the like. R7 represents a straight-chain alkylene group having 2 to 4 carbon atoms or the like. R8 represents a hydrogen atom or a methyl group. R7 represents a straight-chain alkylene group having 2 to 4 carbon atoms or the like. R8 and R9 each independently represent a hydrogen atom or a methyl group. R10 represents a straight-chain or branched alkylene group having 2 to 6 carbon atoms or the like).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a composition for forming an adhesive layer, a method for producing the same, and an adhesive polymer. [Background technology]

[0002] In recent years, polymers that exhibit tackiness or adhesiveness have been proposed that use compounds having a catechol skeleton, such as dopa and dopamine, contained in marine organisms such as mussels, or their derivatives as monomers. For example, a curable resin composition containing a monomer such as dopamine acrylamide has been proposed (Patent Document 1).

[0003] It has also been proposed to use derivatives of compounds having a pyrogallol skeleton, which is similar to the catechol skeleton and is less expensive, as monomers. For example, a gallic acid derivative having a (meth)acryloyl group has been proposed as a photopolymerizable monomer used to form an adhesive layer (Patent Document 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2019 / 221135 [Patent Document 2] Patent No. 7150205 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the adhesive layer formed using the compound having a catechol skeleton proposed in Patent Document 1 was not necessarily sufficient in terms of adhesion between PET and aluminum and between PET and glass. Also, the adhesive layer formed using the compound having a pyrogallol skeleton proposed in Patent Document 2 had relatively good adhesion and tackiness between PET and glass. However, the adhesion and tackiness between PETs was not necessarily sufficient, and there was room for further improvement.

[0006] The present invention has been made in consideration of the problems associated with such conventional techniques, and an object of the present invention is to provide an adhesive / tacky layer-forming composition that imparts adhesiveness or pressure-sensitive adhesiveness or further enhances adhesiveness or pressure-sensitive adhesiveness, and that can form adhesive layers and the like having excellent adhesiveness or pressure-sensitive adhesiveness to both heterogeneous and homogeneous materials on various substrates, as well as a method for producing the same.

[0007] Another object of the present invention is to provide an adhesive and pressure-sensitive adhesive polymer that can impart adhesiveness or tackiness or further enhance adhesiveness or tackiness, and can form adhesive layers, etc., having excellent adhesiveness or tackiness to both heterogeneous and homogeneous materials on various substrates. [Means for solving the problem]

[0008] That is, according to the present invention, there is provided the following composition for forming an adhesive / pressure-sensitive adhesive layer. [1] A composition for forming an adhesive / pressure-sensitive adhesive layer, comprising a first polymerizable compound represented by the following general formula (1) and a second polymerizable compound represented by the following general formula (2):

[0009] TIFF2025045972000001.tif42170 (In the general formula (1), R1 to R5 each independently represent a hydrogen atom or a hydroxyl group, and at least two of R1 to R5 are hydroxyl groups. R6 represents an alkylene group having 2 to 10 carbon atoms which may contain an ether bond. R7 represents a linear alkylene group having 2 to 4 carbon atoms which may contain an ether bond, or a branched alkylene group having 2 to 4 carbon atoms which may have a (meth)acrylic group. R8 represents a hydrogen atom or a methyl group.)

[0010] TIFF2025045972000002.tif34170 (In the general formula (2), R7 represents a linear alkylene group having 2 to 4 carbon atoms which may contain an ether bond, or a branched alkylene group having 2 to 4 carbon atoms which may contain a (meth)acrylic group; R8 and R9 each independently represent a hydrogen atom or a methyl group; R 10 represents a linear or branched alkylene group having 2 to 6 carbon atoms which may have a (meth)acrylic group.

[0011] [2] The composition for forming an adhesive / pressure-sensitive adhesive layer according to [1] above, wherein in the general formulae (1) and (2), R7 is an ethylene group. [3] In the general formula (2), R 10 The composition for forming an adhesive / pressure-sensitive adhesive layer according to [1] or [2] above, wherein [4] The composition for forming an adhesive / pressure-sensitive adhesive layer according to any one of [1] to [3] above, further comprising a polymerization initiator. [5] A composition for forming an adhesive / pressure-sensitive adhesive layer according to any one of [1] to [4], wherein the content of the first polymerizable compound and the content of the second polymerizable compound are in a mass ratio of 20:80 to 80:20.

[0012] Further, according to the present invention, there is provided a method for producing a composition for forming an adhesive / pressure-sensitive adhesive layer, as described below. [6] A method for producing a composition for forming an adhesive / pressure-sensitive adhesive layer according to any one of [1] to [5] above, comprising the steps of reacting a compound represented by the following general formula (3) with a compound represented by the following general formula (4) in an amount exceeding a molar equivalent of the compound represented by the following general formula (3), and then further reacting with a compound represented by the following general formula (5).

[0013] TIFF2025045972000003.tif46170 (In the general formula (3), R1 to R5 each independently represent a hydrogen atom or a hydroxyl group, and at least two of R1 to R5 are hydroxyl groups. R6 represents an alkylene group having 2 to 10 carbon atoms which may contain an ether bond. In the general formula (4), R7 represents a linear alkylene group having 2 to 4 carbon atoms which may contain an ether bond, or a branched alkylene group having 2 to 4 carbon atoms which may have a (meth)acrylic group, and R8 represents a hydrogen atom or a methyl group. In the general formula (5), R9 represents a hydrogen atom or a methyl group, and R 10 represents a linear or branched alkylene group having 2 to 6 carbon atoms which may have a (meth)acrylic group.

[0014] Furthermore, according to the present invention, there is provided the following adhesive and pressure-sensitive adhesive polymer. [7] An adhesive polymer having a structural unit (i) derived from a first polymerizable compound represented by the following general formula (1) and a structural unit (ii) derived from a second polymerizable compound represented by the following general formula (2):

[0015] TIFF2025045972000004.tif42170 (In the general formula (1), R1 to R5 each independently represent a hydrogen atom or a hydroxyl group, and at least two of R1 to R5 are hydroxyl groups. R6 represents an alkylene group having 2 to 10 carbon atoms which may contain an ether bond. R7 represents a linear alkylene group having 2 to 4 carbon atoms which may contain an ether bond, or a branched alkylene group having 2 to 4 carbon atoms which may have a (meth)acrylic group. R8 represents a hydrogen atom or a methyl group.)

[0016] TIFF2025045972000005.tif34170 (In the general formula (2), R7 represents a linear alkylene group having 2 to 4 carbon atoms which may contain an ether bond, or a branched alkylene group having 2 to 4 carbon atoms which may contain a (meth)acrylic group; R8 and R9 each independently represent a hydrogen atom or a methyl group; R 10 represents a linear or branched alkylene group having 2 to 6 carbon atoms which may have a (meth)acrylic group.

[0017] [8] The adhesive polymer according to the above [7], wherein in the above general formulae (1) and (2), R7 is an ethylene group. [9] In the general formula (2), R 10 The adhesive polymer according to [7] or [8] above, wherein R is a linear alkylene group having 2 to 4 carbon atoms.

[10] The adhesive and pressure-sensitive adhesive polymer according to any one of [7] to [9], wherein the content of the structural unit (i) and the content of the structural unit (ii) are in a mass ratio of 20:80 to 80:20. Effect of the Invention

[0018] According to the present invention, it is possible to provide an adhesive / tacky layer-forming composition that imparts adhesiveness or pressure-sensitive adhesiveness or further enhances adhesiveness or pressure-sensitive adhesiveness and is capable of forming adhesive layers, etc., having excellent adhesiveness or pressure-sensitive adhesiveness to both heterogeneous and homogeneous materials on various substrates, as well as a method for producing the same.

[0019] Furthermore, according to the present invention, it is possible to provide an adhesive and pressure-sensitive adhesive polymer that can impart adhesive properties or further enhance adhesive properties and adhesive properties, and can form adhesive layers and the like that have excellent adhesive properties and adhesive properties for both heterogeneous and homogeneous materials on various substrates. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0020] <Composition for forming adhesive / adhesive layer> Hereinafter, an embodiment of the present invention will be described, but the present invention is not limited to the following embodiment. One embodiment of the composition for forming an adhesive / tacky layer of the present invention is a composition used as a material for forming an adhesive layer or a tacky layer, containing a first polymerizable compound represented by the following general formula (1) and a second polymerizable compound represented by the following general formula (2). Hereinafter, the composition for forming an adhesive / tacky layer of this embodiment will be described in detail.

[0021] TIFF2025045972000006.tif42170 (In the general formula (1), R1 to R5 each independently represent a hydrogen atom or a hydroxyl group, and at least two of R1 to R5 are hydroxyl groups. R6 represents an alkylene group having 2 to 10 carbon atoms which may contain an ether bond. R7 represents a linear alkylene group having 2 to 4 carbon atoms which may contain an ether bond, or a branched alkylene group having 2 to 4 carbon atoms which may have a (meth)acrylic group. R8 represents a hydrogen atom or a methyl group.)

[0022] TIFF2025045972000007.tif34170 (In the general formula (2), R7 represents a linear alkylene group having 2 to 4 carbon atoms which may contain an ether bond, or a branched alkylene group having 2 to 4 carbon atoms which may contain a (meth)acrylic group; R8 and R9 each independently represent a hydrogen atom or a methyl group; R 10 represents a linear or branched alkylene group having 2 to 6 carbon atoms which may have a (meth)acrylic group.

[0023] In the general formula (1), it is preferable that two or more of R1 to R5 are hydroxyl groups, and it is more preferable that three or more of R1 to R5 are hydroxyl groups. In the general formula (1), R6 is preferably an alkylene group having 2 to 8 carbon atoms, more preferably an alkylene group having 2 to 6 carbon atoms, and particularly preferably an alkylene group having 2 to 4 carbon atoms. On the other hand, in the general formula (1), from the viewpoint of production, R6 is preferably an alkylene group having 2 to 8 carbon atoms, more preferably an alkylene group having 3 to 6 carbon atoms, and particularly preferably an alkylene group having 4 to 6 carbon atoms. In addition, in the general formula (1), it is preferable that R7 is an alkylene group having 2 carbon atoms, that is, an ethylene group. By making it into such a structure, it is possible to obtain a composition for forming an adhesive layer that can form an adhesive layer, etc., having excellent adhesiveness and adhesion on various substrates.

[0024] In the general formula (2), R7 is preferably an alkylene group having 2 carbon atoms, i.e., an ethylene group. 10 is preferably a linear alkylene group having 2 to 4 carbon atoms.

[0025] The content of each of the first polymerizable compound and the second polymerizable compound in the composition for forming an adhesive layer is not particularly limited and may be appropriately set according to the purpose. Specifically, the content of the first polymerizable compound is usually 0.1 to 90 mass%, preferably 0.3 to 50 mass%, more preferably 0.5 to 20 mass%, and particularly preferably 0.5 to 10 mass%, based on the solid content in the composition for forming an adhesive layer. The content of the second polymerizable compound is usually 0.1 to 90 mass%, preferably 0.3 to 50 mass%, more preferably 0.5 to 20 mass%, and particularly preferably 0.5 to 10 mass%, based on the solid content in the composition for forming an adhesive layer.

[0026] In the composition for forming an adhesive / tacky layer, the mass ratio of the content of the first polymerizable compound to the content of the second polymerizable compound is preferably 20:80 to 80:20, and more preferably 25:75 to 75:25. By setting the mass ratio of the content of the first compound to the content of the second compound within the above range, an adhesive layer or the like having even better adhesiveness and tackiness to different and the same materials can be formed.

[0027] The adhesive layer forming composition of the present embodiment may contain polymerizable monomers, resins, etc. other than the first polymerizable compound and the second polymerizable compound. As the polymerizable monomer and resin, various conventionally known polymerizable monomers and resins can be used. As the polymerizable monomer and resin, urethane (meth)acrylate, dipentaerythritol hexa(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, diethylene glycol monophenyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate can be mentioned. These polymerizable monomers and resins may be used alone or in combination of two or more kinds.

[0028] The adhesive layer forming composition of this embodiment preferably further contains a polymerization initiator. As the polymerization initiator, a photopolymerization initiator or a thermal polymerization initiator can be used. As the photopolymerization initiator, acylphosphine oxides such as diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide; acetophenones such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-2-phenylacetophenone, and diethoxyacetophenone; ketals such as benzyl dimethyl ketal; benzoins such as benzoin and benzoin methyl ether; benzophenones such as benzophenone, benzoylbenzoic acid, and hydroxybenzophenone; other halogenated ketones, and acylphosphanates can be mentioned.

[0029] As the thermal polymerization initiator, an azo compound, an organic peroxide, etc. can be used. As the azo compound, azobisisobutyronitrile, 1,1'-azobis(cyclohexanecarbonitrile), 2,2'-azobis(2-methylpropanoic acid)dimethyl, etc. can be mentioned. As the organic peroxide, hydroperoxide compounds, dialkyl peroxide compounds, peroxyester compounds, diacyl peroxide compounds, ketone peroxide compounds, peroxyketal compounds, peroxydicarbonate compounds, etc. can be mentioned.

[0030] The adhesive layer-forming composition of the present embodiment can be made into a coating material having appropriate coatability by further containing a solvent. As the solvent, water or various organic solvents can be used.

[0031] The adhesive layer-forming composition of the present embodiment may contain other additives, such as silane coupling agents, thixotropic agents, antiblocking agents, leveling agents, defoamers, antioxidants, thermoplastic resins, antistatic agents, waxes, heat stabilizers, flame retardants, UV absorbers, antibacterial agents, and deodorants.

[0032] The adhesive layer or pressure-sensitive adhesive layer can be formed by applying the adhesive layer-forming composition of the present embodiment to a substrate and curing the resulting coating layer. Methods for applying the adhesive layer-forming composition to a substrate include roll coating, gravure coating, comma coating, knife coating, and die coating.

[0033] As a method for curing the coating layer (composition for forming an adhesive layer), when a photopolymerization initiator is used, a method can be adopted in which an irradiation device for active energy rays such as visible light, ultraviolet light, and electron beams is used to irradiate the coating layer with active energy rays at a predetermined light amount. Examples of the irradiation device include a xenon lamp, a xenon-mercury lamp, a metal halide lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, and a fusion lamp. On the other hand, when a thermal polymerization initiator is used, a method can be adopted in which, for example, a high-temperature furnace or the like is used and heating is preferably performed to 50 to 250°C.

[0034] <Method of manufacturing the composition for forming the adhesive / tacky layer> The composition for forming an adhesive layer can be produced, for example, by mixing a first polymerizable compound and a second polymerizable compound that have been synthesized separately. The first polymerizable compound can be synthesized by reacting a compound represented by the following general formula (3) with a compound represented by the following general formula (4).

[0035] TIFF2025045972000008.tif45170 (In the general formula (3), R1 to R5 each independently represent a hydrogen atom or a hydroxyl group, and at least two of R1 to R5 are hydroxyl groups. R6 represents an alkylene group having 2 to 10 carbon atoms which may contain an ether bond. In the general formula (4), R7 represents a linear alkylene group having 2 to 4 carbon atoms which may contain an ether bond, or a branched alkylene group having 2 to 4 carbon atoms which may have a (meth)acrylic group, and R8 represents a hydrogen atom or a methyl group.)

[0036] Examples of the compound represented by general formula (3) include 2-hydroxyethyl protocatechuate, 2-hydroxyethyl gallate, 4-hydroxybutyl protocatechuate, 4-hydroxybutyl gallate, 10-hydroxydecyl protocatechuate, 10-hydroxydecyl gallate, etc. Examples of the compound represented by general formula (4) include 2-isocyanatoethyl (meth)acrylate, 4-isocyanatobutyl (meth)acrylate, 2-(2-(meth)acryloyloxyethyloxy)ethyl isocyanate, etc.

[0037] The second polymerizable compound can be synthesized by reacting a compound represented by the above general formula (4) with a compound represented by the following general formula (5).

[0038] TIFF2025045972000009.tif33170 (In the general formula (5), R9 represents a hydrogen atom or a methyl group, and R 10 represents a linear or branched alkylene group having 2 to 6 carbon atoms which may have a (meth)acrylic group.

[0039] Examples of the compound represented by general formula (5) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, polyethylene glycol monoacrylate, and polypropylene glycol monoacrylate.

[0040] The composition for forming an adhesive / tacky layer is also preferably produced by the method described below. That is, one embodiment of the method for producing a composition for forming an adhesive / tacky layer of the present invention is the above-mentioned method for producing a composition for forming an adhesive / tacky layer, which includes a step of reacting a compound represented by the following general formula (3) with a compound represented by the following general formula (4) in an amount exceeding the molar equivalent of the compound represented by the following general formula (3), and then further reacting with a compound represented by the following general formula (5) (hereinafter also referred to as "step (1)").

[0041] TIFF2025045972000010.tif46170 (In the general formula (3), R1 to R5 each independently represent a hydrogen atom or a hydroxyl group, and at least two of R1 to R5 are hydroxyl groups. R6 represents an alkylene group having 2 to 10 carbon atoms which may contain an ether bond. In the general formula (4), R7 represents a linear alkylene group having 2 to 4 carbon atoms which may contain an ether bond, or a branched alkylene group having 2 to 4 carbon atoms which may have a (meth)acrylic group, and R8 represents a hydrogen atom or a methyl group. In the general formula (5), R9 represents a hydrogen atom or a methyl group, and R 10 represents a linear or branched alkylene group having 2 to 6 carbon atoms which may have a (meth)acrylic group.

[0042] In the general formula (3), R1 to R6 are the same as R1 to R6 in the general formula (1). That is, in the general formula (3), it is preferable that two or more of R1 to R5 are hydroxyl groups, and it is more preferable that three or more of R1 to R5 are hydroxyl groups. In addition, in the general formula (3), R6 is preferably an alkylene group having 2 to 8 carbon atoms, more preferably an alkylene group having 2 to 6 carbon atoms, and particularly preferably an alkylene group having 2 to 4 carbon atoms. On the other hand, in the general formula (1), from the viewpoint of production, R6 is preferably an alkylene group having 2 to 8 carbon atoms, more preferably an alkylene group having 3 to 6 carbon atoms, and particularly preferably an alkylene group having 4 to 6 carbon atoms.

[0043] R7 and R8 in the general formula (4) are the same as R7 and R8 in the general formula (1). That is, in the general formula (4), R7 is preferably an alkylene group having 2 carbon atoms, i.e., an ethylene group. In addition, R9 and R 10 R and R in general formula (2) 10 That is, in the general formula (5), R 10 is preferably a linear alkylene group having 2 to 4 carbon atoms.

[0044] In step (1), a compound represented by general formula (3) is reacted with a compound represented by general formula (4) in an amount exceeding the molar equivalent of the compound represented by general formula (3). As a result, a first polymerizable compound represented by general formula (1) is formed, and an excess of the compound represented by general formula (4) remains in the reaction system. A catalyst may be used during the reaction. Examples of catalysts that can be used include Lewis acid catalysts such as dibutyltin laurate, tetra n-butyl titanate, tetrakis acetylacetonate zirconium, zinc 2-ethylhexanoate, and bismuth 2-ethylhexanoate, Bronsted acid catalysts such as hydrogen halide, phosphoric acid, sulfuric acid, nitric acid, sulfonic acid, and carboxylic acid, and compounds capable of generating Bronsted acids such as acetyl chloride, acetyl bromide, acetyl iodide, dimethylcarbamoyl chloride, acrylic acid chloride, and methacrylic acid chloride.

[0045] In step (1), the compound represented by general formula (3) is reacted with the compound represented by general formula (4), and then the compound represented by general formula (5) is added, and the compound represented by general formula (4) remaining in the reaction system is reacted with the compound represented by general formula (5). As a result, the second polymerizable compound represented by general formula (2) is formed, and a composition for forming an adhesive layer containing the first polymerizable compound generated earlier and the second polymerizable compound generated later can be obtained. After step (1), separation and purification may be performed according to a conventional method.

[0046] <Adhesive / adhesive polymer> One embodiment of the adhesive / tacky polymer of the present invention has a constitutional unit (i) derived from a first polymerizable compound represented by the above-mentioned general formula (1), and a constitutional unit (ii) derived from a second polymerizable compound represented by the above-mentioned general formula (2). Since the adhesive / tacky polymer of this embodiment has these constitutional units (i) and (ii), an adhesive layer / tacky layer having excellent adhesiveness and tackiness can be formed on various substrates. In addition, by using the adhesive / tacky polymer of this embodiment, an adhesive layer / tacky layer having excellent adhesion can be formed on various substrates.

[0047] The content of each of the structural units (i) and (ii) in the adhesive / tacky polymer may be appropriately set according to the purpose, and is not particularly limited. Specifically, the content of the structural unit (i) is usually 0.1 to 90% by mass, preferably 0.3 to 50% by mass, more preferably 0.5 to 20% by mass, and particularly preferably 0.5 to 10% by mass, based on the entire adhesive / tacky polymer. The content of the structural unit (ii) is usually 0.1 to 90% by mass, preferably 0.3 to 50% by mass, more preferably 0.5 to 20% by mass, and particularly preferably 0.5 to 10% by mass, based on the entire adhesive / tacky polymer.

[0048] In the adhesive / tacky polymer, the mass ratio of the content of the structural unit (i) to the content of the structural unit (ii) is preferably 20:80 to 80:20, and more preferably 25:75 to 75:25. By setting the mass ratio of the content of the structural unit (i) to the content of the structural unit (ii) within the above range, an adhesive layer or the like having even better adhesiveness and tackiness to both different and the same materials can be formed.

[0049] The adhesive polymer of the present embodiment may have a structural unit (other structural unit) other than the structural units (i) and (ii). The other structural unit can be formed using a conventionally known polymerizable monomer or resin that constitutes a normal adhesive polymer.

[0050] <Various products> By using the adhesive layer forming composition or adhesive polymer of this embodiment, a product such as an adhesive sheet can be formed. The adhesive sheet comprises a sheet-like support and an adhesive layer formed by the adhesive layer forming composition or adhesive polymer provided on one or both sides of the support. Examples of the support include a resin film, a laminate film containing a resin film, paper, woven fabric, and nonwoven fabric. Examples of the material of the resin film include polyester such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), polyethylene, polypropylene, and polycarbonate. A release film may be laminated on the surface of the adhesive layer to protect the adhesive layer.

[0051] In addition, by using the composition for forming an adhesive / sticky layer or the adhesive / sticky polymer, various laminates useful as optical films and the like can be formed. The laminate is formed by laminating a first substrate and a second substrate via an adhesive layer or a sticking layer formed by the composition for forming an adhesive / sticky layer or the adhesive / sticky polymer described above. The first substrate and the second substrate may be made of the same material or different materials.

[0052] Materials for the substrates (first substrate and second substrate) include inorganic materials such as glass, hydroxyapatite, titanium oxide, zinc oxide, iron oxide, and indium tin oxide (ITO); metal materials such as aluminum (Al), copper (Cu), iron (Fe), gold (Au), platinum (Pt), silver (Ag), zinc (Zn), tin (Sn), titanium (Ti), and alloys thereof; polypropylene (PP), polyethylene (PE), polytetrafluoroethylene (PTFE), polyimide (PI), and polycarbonate (PC). Examples of such materials include organic materials such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polymethyl methacrylate (PMMA), polyphenylene sulfide (PPS), polyphenylene ether (modified PPE), triacetyl cellulose (TAC), cycloolefin polymer (COP), acrylonitrile-butadiene-styrene copolymer (ABS), fiber reinforced plastic (FRP), and molybdenum-aluminum-molybdenum laminate (MAM). EXAMPLES

[0053] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the examples and comparative examples, "parts" and "%" are by mass unless otherwise specified.

[0054] <Production of polymerizable composition (polymerizable compound)> Example 1 15 parts of a compound represented by the following formula (3-1) and 0.3 parts of paratoluenesulfonic acid were suspended in 30 parts of 1,2-dimethoxyethane, and then heated to 85°C. 15 parts of 2-methacryloyloxyethyl isocyanate and 2 parts of 1,2-dimethoxyethane were added, and the mixture was heated at 90°C for 210 minutes. Next, 24 parts of 4-hydroxybutyl acrylate was added, and the mixture was heated at 90°C for 120 minutes and then cooled to obtain 150 parts of a polymerizable composition containing a compound represented by the following formula (1-1) and a compound represented by the following formula (2-1). The structures of the compounds in the obtained polymerizable composition are as follows: 1 The compound was identified by H-NMR. The chemical shifts are shown below. Compound represented by formula (1-1): 1.68 (4H,m), 1.86 (3H,s), 3.27 (2H,q), 4.00 (2H,t), 4.08 (2H,t), 4.18 (2H,t), 5.65 (1H,m), 6.05 (1H,m), 6.95 (2H,s), 7.25 (1H,t), 9.18 (3H,br) Compounds represented by formula (2-1): 1.68(4H,m),3.27(2H,m),3.41(2H,m),4.00(2H,t),4.12(2H,t),4.18(2H, m),5.68(1H,m),5.92(1H,m),6.05(1H,m),6.17(1H,m),6.20(1H,m),6.34(1H,m),6.96(1H,m)

[0055] TIFF2025045972000011.tif114170

[0056] Example 2 15 parts of the compound represented by the formula (3-1) and 0.3 parts of paratoluenesulfonic acid were suspended in 30 parts of 1,2-dimethoxyethane and then heated to 85°C. 15 parts of 2-methacryloyloxyethyl isocyanate and 2 parts of 1,2-dimethoxyethane were added and heated at 90°C for 210 minutes. Next, 24 parts of 2-hydroxyethyl methacrylate were added, heated at 90°C for 120 minutes, and then cooled to obtain 250 parts of a polymerizable composition containing the compound represented by the formula (1-1) and the compound represented by the following formula (2-2). The structures of the compounds in the obtained polymerizable composition are as follows: 1 The compound was identified by H-NMR. The chemical shifts are shown below. Compound represented by formula (2-2): 1.88 (6H,m), 3.27 (2H,m), 4.11 (2H,t), 4.22 (2H,m), 4.26 (2H,m), 5.63 (2H,m), 6.05 (2H,m), 6.96 (1H,m)

[0057] TIFF2025045972000012.tif35170

[0058] Example 3 15 parts of the compound represented by the formula (3-1) and 0.3 parts of paratoluenesulfonic acid were suspended in 30 parts of 1,2-dimethoxyethane, and then heated to 85°C. 15 parts of 2-methacryloyloxyethyl isocyanate and 2 parts of 1,2-dimethoxyethane were added, and the mixture was heated at 90°C for 210 minutes. The solvent was then distilled off and the mixture was aged to obtain the compound represented by the formula (1-1). In addition, 13 parts of 2-hydroxyethyl methacrylate, 15 parts of 2-methacryloyloxyethyl isocyanate, and 20 parts of 1,2-dimethoxyethane were mixed. 2 parts of 0.5% zirconium tetraacetylacetonate-toluene solution were added, and the mixture was heated at 65°C for 390 minutes. The solvent was then distilled off to obtain the compound represented by the formula (2-2). A polymerizable composition 3 was obtained by mixing the compound represented by the formula (1-1), the compound represented by the formula (2-2), and 2-hydroxyethyl methacrylate in a mass ratio of 1:1:3.

[0059] Example 4 A polymerizable composition 4 was obtained in the same manner as in Example 3, except that the compound represented by the formula (1-1), the compound represented by the formula (2-2), and 2-hydroxyethyl methacrylate were mixed in a mass ratio of 2:8:15.

[0060] Comparative Example 1 A commercially available compound represented by the following formula (A) was used as polymerizable composition 5.

[0061] TIFF2025045972000013.tif32170

[0062] Comparative Example 2 29 parts of the compound represented by the formula (3-1) was suspended in 64 parts of 1,2-dimethoxyethane and then heated to 85°C. 33 parts of 2-methacryloyloxyethyl isocyanate and 4 parts of 1,2-dimethoxyethane were added and heated at 85°C for 18 hours. Then, 64 parts of ethanol were added and heated at 77°C for 6 hours. After cooling, the mixture was filtered, separated, and dried under reduced pressure to obtain 64 parts of a polymerizable composition 6 mainly composed of the compound represented by the formula (1-1). The content (HPLC purity) of the compound represented by the formula (1-1) measured by HPLC was 83.0%. The conditions for measuring the purity by HPLC are shown below. The details of the obtained polymerizable composition are summarized in Table 1.

[0063] [HPLC Purity Measurement Conditions] Analytical equipment: LC-30AD, SPD-M20A, and LCMS-8050 LCMS system (Shimadzu Corporation) Eluent: Acetonitrile-3% acetic acid aqueous solution (1:19 → 17:3 (v / v), gradient over 40 minutes) Flow rate: 0.2mL / min Column: L-column2 ODS.2μm (3.0×100mm) (Chemicals Evaluation and Research Institute, Inc.) Column temperature: 40℃ Sample: 2.0 μL of approximately 100 ppm THF solution Detection wavelength: 294 nm

[0064] TIFF2025045972000014.tif240170

[0065] <Production of composition for forming adhesive layer> Example 5 A composition for forming an adhesive / tacky layer (coating material) was obtained by mixing 50 parts of a UV-curable urethane acrylate (UV-3700B) (product name "Shikoh UV-3700B", manufactured by Mitsubishi Chemical Corporation), 5 parts of a polymerization initiator (diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO)), 49 parts of an acrylic monomer (tetrahydrofurfuryl acrylate (THFA)), and 11 parts of a polymerizable composition.

[0066] (Examples 6 to 8, Comparative Examples 3 and 4, Reference Example 1) Except for using the formulation shown in Table 2, the same procedure as in Example 5 above was carried out to obtain a composition (paint) for forming an adhesive / tacky layer.

[0067] TIFF2025045972000015.tif89170

[0068] <Evaluation of compositions for forming adhesive / tacky layers> (OCR evaluation (evaluation of adhesive strength)) The prepared coating material was applied to the adhesive surface of a polyethylene terephthalate (PET) film to form a coating layer. The PET film, aluminum plate, and glass were placed on the formed coating layer and laminated. The coating layer was cured by UV irradiation, then cut to obtain rectangular test pieces, which were left for one day and then their peel strengths were measured. The peel strength of the test piece obtained using the coating material of Reference Example 1 was set to "100(%)", and the adhesive strength of each test piece was evaluated relatively. The evaluation criteria are shown below. The evaluation results are shown in Table 3. ◎: 150% or more ○: 100% or more but less than 150% △: 50% or more but less than 100% ×: Less than 50%

[0069] (OCA evaluation (evaluation of adhesive strength)) The prepared coating material was applied to the adhesive surface of a polyethylene terephthalate (PET) film to form a coating layer. A silicone-treated PET film was placed on the formed coating layer and laminated, and then the coating layer was cured by UV irradiation. After one day, the silicone-treated PET film was peeled off and removed, and a PET film, an aluminum plate, and a glass were placed on the exposed cured layer (adhesive layer) and pressed. Strip-shaped test pieces were obtained by cutting and processing, and the peel strength was measured after leaving it for one day. The peel strength of the test piece obtained using the coating material of Reference Example 1 was set to "100 (%)", and the adhesive strength of each test piece was evaluated relatively. The evaluation criteria are shown below. The evaluation results are also shown in Table 3. ◎: 150% or more ○: 100% or more but less than 150% △: 50% or more but less than 100% ×: Less than 50%

[0070] TIFF2025045972000016.tif77170 [Industrial Applicability]

[0071] The composition for forming an adhesive / tacky layer of the present invention is useful as a material for forming adhesive layers and the like having excellent adhesiveness and tackiness to both dissimilar and homogeneous materials on various substrates.

Claims

1. A composition for forming an adhesive / sticky layer, comprising a first polymerizable compound represented by the following general formula (1) and a second polymerizable compound represented by the following general formula (2). (In the general formula (1), R １ ~R ５ each independently represents a hydrogen atom or a hydroxyl group; R １ ~R ５ At least two of R are hydroxyl groups. ６ represents an alkylene group having 2 to 10 carbon atoms which may contain an ether bond; R ７ represents a linear alkylene group having from 2 to 4 carbon atoms which may contain an ether bond, or a branched alkylene group having from 2 to 4 carbon atoms which may contain a (meth)acrylic group; R ８ represents a hydrogen atom or a methyl group) (In the above general formula (2), R ７ represents a linear alkylene group having from 2 to 4 carbon atoms which may contain an ether bond, or a branched alkylene group having from 2 to 4 carbon atoms which may contain a (meth)acrylic group; R ８ and R ９ each independently represents a hydrogen atom or a methyl group; R １０ represents a linear or branched alkylene group having from 2 to 6 carbon atoms which may have a (meth)acrylic group.

2. In the general formulas (1) and (2), R ７ The composition for forming an adhesive / tacky layer according to claim 1, wherein is an ethylene group.

3. In the general formula (2), R １０ The composition for forming an adhesive / tacky layer according to claim 1 , wherein is a linear alkylene group having from 2 to 4 carbon atoms.

4. The composition for forming an adhesive / tacky layer according to claim 1 , further comprising a polymerization initiator.

5. The composition for forming an adhesive / tacky layer according to claim 1, wherein the content of the first polymerizable compound and the content of the second polymerizable compound are in a mass ratio of 20:80 to 80:

20.

6. A method for producing the composition for forming an adhesive layer according to any one of claims 1 to 5, A method for producing a composition for forming an adhesive / tacky layer, comprising the steps of reacting a compound represented by the following general formula (3) with a compound represented by the following general formula (4) in an amount exceeding a molar equivalent of the compound represented by the following general formula (3), and then further reacting the compound with a compound represented by the following general formula (5). (In the general formula (3), R １ ~R ５ each independently represents a hydrogen atom or a hydroxyl group; R １ ~R ５ At least two of R are hydroxyl groups. ６ represents an alkylene group having 2 to 10 carbon atoms which may contain an ether bond. ７ represents a linear alkylene group having from 2 to 4 carbon atoms which may contain an ether bond, or a branched alkylene group having from 2 to 4 carbon atoms which may contain a (meth)acrylic group; R ８ represents a hydrogen atom or a methyl group. ９ represents a hydrogen atom or a methyl group, R １０ represents a linear or branched alkylene group having from 2 to 6 carbon atoms which may have a (meth)acrylic group.

7. An adhesive polymer having a structural unit (i) derived from a first polymerizable compound represented by the following general formula (1) and a structural unit (ii) derived from a second polymerizable compound represented by the following general formula (2): (In the general formula (1), R １ ~R ５ each independently represents a hydrogen atom or a hydroxyl group; R １ ~R ５ At least two of R are hydroxyl groups. ６ represents an alkylene group having 2 to 10 carbon atoms which may contain an ether bond; R ７ represents a linear alkylene group having from 2 to 4 carbon atoms which may contain an ether bond, or a branched alkylene group having from 2 to 4 carbon atoms which may contain a (meth)acrylic group; R ８ represents a hydrogen atom or a methyl group) (In the above general formula (2), R ７ represents a linear alkylene group having from 2 to 4 carbon atoms which may contain an ether bond, or a branched alkylene group having from 2 to 4 carbon atoms which may contain a (meth)acrylic group; R ８ and R ９ each independently represents a hydrogen atom or a methyl group; R １０ represents a linear or branched alkylene group having from 2 to 6 carbon atoms which may have a (meth)acrylic group.

8. In the general formulas (1) and (2), R ７ The adhesive and pressure-sensitive adhesive polymer according to claim 7, wherein is an ethylene group.

9. In the general formula (2), R １０ The adhesive and pressure-sensitive adhesive polymer according to claim 7, wherein is a linear alkylene group having from 2 to 4 carbon atoms.

10. The adhesive polymer according to any one of claims 7 to 9, wherein the content of the structural unit (i) and the content of the structural unit (ii) are in a mass ratio of 20:80 to 80:20.

Images