Method for producing polymerizable compound

Abstract

To provide a method for efficiently producing a polymerizable compound capable of preparing an adhesive / tacky layer forming composition or an adhesive / tacky polymer that can form an adhesive layer or the like with excellent adhesiveness and tackiness on various base materials.SOLUTION: This invention relates to a method for producing a polymerizable compound for forming an adhesive / tacky layer, the method comprising a step of reacting a compound represented by the following general formula (1) with an isocyanate compound having a reactive double bond under the presence of an acid catalyst capable of generating active hydrogen, to obtain a reactant. (In the general formula (1), n represents a number from 1 to 5; R1 represents -O- or -NH-; and R2 represents a C2 or more alkylene group that may contain an ether bond).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for producing a polymerizable compound for forming an adhesive / sticky layer. [Background technology]

[0002] In recent years, polymers exhibiting various functions have been proposed, which use derivatives of compounds having a catechol skeleton such as dopa or dopamine, or derivatives of compounds having a pyrogallol skeleton such as gallic acid, as monomers. For example, a curable resin composition containing a monomer such as dopamine acrylamide has been proposed (Patent Document 1). In addition, a photocurable coating composition containing a pyrogallol derivative having a methacryloyl group as an adhesive layer-forming composition or adhesive polymer capable of forming an adhesive layer or the like with good adhesion on various substrates has been proposed (Patent Document 2). It is believed that the adhesive layer-forming composition or adhesive polymer having a catechol skeleton or pyrogallol skeleton exhibits strong adhesion by orienting the hydroxyl group directly bonded to the aromatic ring to the substrate. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2019 / 221135 [Patent Document 2] JP 2009-203408 A Summary of the Invention [Problem to be solved by the invention]

[0004] Pyrogallol derivatives having a (meth)acryloyl group can be synthesized, for example, by reacting a gallic acid derivative with methacrylic anhydride or a (meth)acrylic acid derivative having an isocyanate group. However, this synthesis method requires long-term heating to react the pyrogallol derivative with the (meth)acrylic acid derivative. Furthermore, as a result of investigation, it was found that the use of an organic metal such as dibutyltin dilaurate as a reaction accelerator (catalyst) makes it easier to produce a large amount of by-products.

[0005] 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 efficient method for producing a polymerizable compound capable of preparing an adhesive / sticky layer-forming composition or an adhesive / sticky polymer that can impart adhesiveness or pressure-sensitive adhesiveness or further enhance adhesiveness or pressure-sensitive adhesiveness and form an adhesive layer or the like having excellent adhesiveness or pressure-sensitive adhesiveness on various substrates. [Means for solving the problem]

[0006] That is, according to the present invention, there is provided a method for producing a polymerizable compound for forming an adhesive / sticky layer, as shown below. [1] A method for producing a polymerizable compound for forming an adhesive layer, comprising the step of reacting a compound represented by the following general formula (1) with an isocyanate compound having a reactive double bond in the presence of an acid catalyst capable of generating active hydrogen to obtain a reaction product.

[0007] TIFF0007634035000001.tif46170 (In the general formula (1), n ​​represents a number from 1 to 5, R1 represents -O- or -NH-, and R2 represents an alkylene group having 2 or more carbon atoms which may contain an ether bond.)

[0008] [2] The method for producing a polymerizable compound according to the above [1], wherein n is 2 to 5 in the general formula (1). [3] The method for producing a polymerizable compound according to the above [1] or [2], wherein in the general formula (1), R1 is -O-. [4] The method for producing a polymerizable compound according to any one of [1] to [3] above, wherein in general formula (1), R2 is an alkylene group having 2 to 10 carbon atoms. [5] The method for producing a polymerizable compound according to any one of [1] to [4] above, wherein the isocyanate compound is a compound represented by the following general formula (I):

[0009] TIFF0007634035000002.tif36170 (In the general formula (I), R3 represents a linear alkylene group having 2 or more carbon atoms which may contain an ether bond, or a branched alkylene group having 2 or more carbon atoms which may have a (meth)acrylic group, and R4 represents a hydrogen atom or a methyl group.)

[0010] [6] The method for producing a polymerizable compound according to any one of [1] to [5] above, wherein the acid catalyst has an acid dissociation constant of less than 5. [7] The method for producing a polymerizable compound according to any one of [1] to [6] above, wherein the acid catalyst is at least one selected from the group consisting of hydrogen halides, sulfonic acids, and carboxylic acids. [8] The method for producing a polymerizable compound according to any one of [5] to [7] above, wherein the content of the compound represented by the following general formula (4) in the reaction product as measured by HPLC is 20% or less:

[0011] TIFF0007634035000003.tif40170 (In the above general formula (4), R 11 ~R 15 each independently represents a hydrogen atom, a hydroxyl group, or a group represented by the following general formula (5), R 11 ~R 15 At least one of the above is a group represented by the following general formula (5): R1 represents -O- or -NH-, R2 represents an alkylene group having 2 or more carbon atoms which may contain an ether bond, R3 represents a linear alkylene group having 2 or more carbon atoms which may contain an ether bond, or a branched alkylene group having 2 or more carbon atoms which may have a (meth)acrylic group, and R4 represents a hydrogen atom or a methyl group.

[0012] TIFF0007634035000004.tif36170 (In the general formula (5), * indicates the bonding position to the benzene ring, R3 indicates a linear alkylene group having 2 or more carbon atoms which may contain an ether bond, or a branched alkylene group having 2 or more carbon atoms which may have a (meth)acrylic group, and R4 indicates a hydrogen atom or a methyl group.) Effect of the Invention

[0013] According to the present invention, it is possible to provide an efficient method for producing a polymerizable compound capable of preparing an adhesive / sticky layer-forming composition or an adhesive / sticky polymer that can impart adhesive properties or further enhance adhesive properties and form an adhesive layer, etc., having excellent adhesive properties and adhesive properties on various substrates. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] <Method of producing polymerizable compound> Hereinafter, the embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. The present inventors have studied the reactivity of a compound represented by general formula (1) with an isocyanate compound having a reactive double bond (hereinafter, also simply referred to as an "isocyanate compound"), and the adhesiveness and tackiness of a polymer or composition produced using the product obtained by the reaction. As a result, it has been found that when an organic metal such as dibutyltin dilaurate is used as a catalyst during the reaction of a compound represented by general formula (1) with an isocyanate compound, the urethanization reaction is promoted, but the isocyanate compound also easily reacts with a phenolic hydroxyl group, resulting in a decrease in the purity of the target polymerizable compound.

[0015] The present inventors have conducted various studies on conditions under which an isocyanate compound is preferentially reacted with an aliphatic hydroxyl group (-R2-OH) in the general formula (1) to produce a polymerizable compound with higher purity. As a result, they have found that it is effective to react a compound represented by the general formula (1) with an isocyanate compound in the presence of an acid catalyst capable of generating active hydrogen, and have arrived at the present invention. That is, one embodiment of the present invention is a method for producing a polymerizable compound for forming an adhesive layer, comprising a step (hereinafter also referred to as "step (1)") of reacting a compound represented by the following general formula (1) with an isocyanate compound having a reactive double bond in the presence of an acid catalyst capable of generating active hydrogen to obtain a reaction product.

[0016] TIFF0007634035000005.tif46170 (In the general formula (1), n ​​represents a number from 1 to 5, R1 represents -O- or -NH-, and R2 represents an alkylene group having 2 or more carbon atoms which may contain an ether bond.)

[0017] (Process (1)) In step (1), a compound represented by general formula (1) is reacted with an isocyanate compound having a reactive double bond to obtain a reaction product. The compound represented by general formula (1) is a compound (primary alcohol) having a phenolic hydroxyl group and an aliphatic hydroxyl group in one molecule. In general formula (1), n ​​is preferably 2 to 5, more preferably 3. In general formula (1), R1 is preferably -O- (ether bond). In general formula (1), R2 is preferably an alkylene group having 2 to 12 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms, particularly preferably an alkylene group having 2 to 6 carbon atoms, and most preferably an alkylene group having 2 to 4 carbon atoms, from the viewpoint of increasing the ratio of the compound represented by general formula (2) in the obtained polymerizable compound. On the other hand, in the general formula (1), from the viewpoint of production, R2 is preferably an alkylene group having 2 to 12 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms, particularly preferably an alkylene group having 3 to 6 carbon atoms, and most preferably an alkylene group having 4 to 6 carbon atoms. By using a compound having such a structure as a raw material compound, it is possible to produce a composition for forming an adhesive / sticky layer, which can form an adhesive layer having excellent adhesiveness and tackiness on various substrates, or a polymerizable compound that can provide an adhesive / tacky polymer.

[0018] The compound represented by the general formula (1) may be a commercially available product or a synthetic product. The compound represented by the general formula (1) may be prepared by reacting a compound represented by the following general formula (3) (hydroxybenzoic acids) with a compound represented by the following general formula (II), as shown in the following reaction formula. R1 and R2 in the following general formula (II) are the same as R1 and R2 in the general formula (1). As the catalyst, an acid catalyst such as paratoluenesulfonic acid, paratoluenesulfonic anhydride, sulfuric acid, hydrochloric acid, or phosphoric acid may be used.

[0019] TIFF0007634035000006.tif46170

[0020] An isocyanate compound is a compound having a reactive (polymerizable) double bond and an isocyanate group (-NCO group) in one molecule. The isocyanate group (-NCO group) of an isocyanate compound is converted into an aliphatic hydroxyl group (-R 2 By preferentially reacting with aryl groups (—OH) to form a urethane bond, a polymerizable compound with higher purity can be obtained.

[0021] As the isocyanate compound, a compound represented by the following general formula (I) can be used.

[0022] TIFF0007634035000007.tif36170 (In the general formula (I), R3 represents a linear alkylene group having 2 or more carbon atoms which may contain an ether bond, or a branched alkylene group having 2 or more carbon atoms which may have a (meth)acrylic group, and R4 represents a hydrogen atom or a methyl group.)

[0023] In general formula (I), R3 is preferably an alkylene group having 2 to 12 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms, particularly preferably an alkylene group having 2 to 6 carbon atoms, and most preferably an alkylene group having 2 carbon atoms.

[0024] In step (1), the compound represented by the general formula (1) is reacted with an isocyanate compound in the presence of an acid catalyst capable of generating active hydrogen (hereinafter, also simply referred to as "acid catalyst"). By using the above-mentioned acid catalyst instead of the conventional organometallic catalyst (organotin compound, organobismuth compound, etc.) used when reacting a hydroxyl group with an isocyanate group to form a urethane bond, the reaction between the isocyanate compound and an aliphatic hydroxyl group can be preferentially (selectively) proceeded over the reaction between the isocyanate compound and a phenolic hydroxyl group. This suppresses the generation of the by-product represented by the following general formula (4), and allows efficient production of a polymerizable compound with a higher purity. Specifically, a reaction product having a content of the compound represented by the following general formula (4) of 20% or less as measured by HPLC can be obtained.

[0025] TIFF0007634035000008.tif40170 (In the above general formula (4), R 11 ~R 15 each independently represents a hydrogen atom, a hydroxyl group, or a group represented by the following general formula (5), R 11 ~R 15 At least one of the above is a group represented by the following general formula (5): R1 represents -O- or -NH-, R2 represents an alkylene group having 2 or more carbon atoms which may contain an ether bond, R3 represents a linear alkylene group having 2 or more carbon atoms which may contain an ether bond, or a branched alkylene group having 2 or more carbon atoms which may have a (meth)acrylic group, and R4 represents a hydrogen atom or a methyl group.

[0026] TIFF0007634035000009.tif36170 (In the general formula (5), * indicates the bonding position to the benzene ring, R3 indicates a linear alkylene group having 2 or more carbon atoms which may contain an ether bond, or a branched alkylene group having 2 or more carbon atoms which may have a (meth)acrylic group, and R4 indicates a hydrogen atom or a methyl group.)

[0027] In the reaction product, the content of the compound represented by general formula (4) (by-product) measured by HPLC is preferably 20% or less, more preferably 10% or less, and particularly preferably 8% or less. When an organometallic catalyst is used, the reaction between the isocyanate compound and the phenolic hydroxyl group proceeds, and the isocyanate compound is likely to be consumed in excess. Therefore, when the compound represented by general formula (1) and the isocyanate compound are reacted in the presence of an organometallic catalyst, a large amount of unreacted raw material (the compound represented by general formula (1)) tends to remain.

[0028] The acid catalyst is not particularly limited as long as it is a compound capable of generating active hydrogen in the reaction system. However, the acid dissociation constant (pKa) of the acid catalyst at 25°C is preferably less than 5, more preferably 4.8 or less. By using an acid catalyst with a pKa of less than 5, a polymerizable compound with a higher purity can be produced more efficiently.

[0029] Examples of the acid catalyst include inorganic acids such as hydrogen halides, phosphoric acid, sulfuric acid, and nitric acid, and organic acids such as sulfonic acids and carboxylic acids. Among these, it is preferable to use at least one selected from the group consisting of hydrogen halides, sulfonic acids, and carboxylic acids. The hydrogen halide may be hydrogen halide itself such as hydrogen chloride (pKa=-4.0) or hydrogen bromide, or a compound capable of generating hydrogen halide in the reaction system. Examples of the compound capable of generating hydrogen halide in the reaction system include acetyl chloride, acetyl bromide, acetyl iodide, dimethylcarbamoyl chloride, acrylic acid chloride, and methacrylic acid chloride. It is known that hydrogen chloride is generated from dimethylcarbamoyl chloride. Examples of the sulfonic acid include methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid (pKa=-2.8), and trifluoromethanesulfonic acid. Examples of the carboxylic acid include benzoic acid (pKa=4.2), gallic acid (pKa=4.5), formic acid, acetic acid (pKa=4.8), butyric acid, lauric acid, palmitic acid, stearic acid, etc. These acid catalysts may be used alone or in combination of two or more.

[0030] The amount of the acid catalyst used may be appropriately determined depending on the amounts of the compound represented by formula (1) and the isocyanate compound used as raw materials. Specifically, the amount of the acid catalyst used is preferably 0.5 to 10 mol %, more preferably 1 to 5 mol %, based on the amount of the compound represented by formula (1).

[0031] An example of the reaction scheme in which the compound represented by the general formula (1) is reacted with an isocyanate compound in the presence of an acid catalyst to obtain a reaction product is shown below.

[0032] TIFF0007634035000010.tif54170

[0033] In the above reaction formula, the compound represented by the general formula (2) is an example of a polymerizable compound for forming a desired adhesive layer. n, R1, and R2 in the general formula (2) are the same as n, R1, and R2 in the general formula (1). That is, in the general formula (2), n is preferably 2 to 5, and more preferably 3. In the general formula (2), R1 is preferably -O- (ether bond). In the general formula (2), R2 is preferably an alkylene group having 2 to 12 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms, particularly preferably 2 to 6 carbon atoms, and most preferably 2 to 4 carbon atoms, from the viewpoint of increasing the ratio of the compound represented by the general formula (2) in the obtained polymerizable compound. On the other hand, in the general formula (2), R2 is preferably an alkylene group having 2 to 12 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms, particularly preferably 3 to 6 carbon atoms, and most preferably 4 to 6 carbon atoms, from the viewpoint of production.

[0034] Furthermore, R3 and R4 in general formula (2) have the same meaning as R3 and R4 in general formula (I). That is, in general formula (2), R3 is a linear alkylene group having 2 or more carbon atoms which may contain an ether bond, or a branched alkylene group having 2 or more carbon atoms which may have a (meth)acrylic group, preferably an alkylene group having 2 to 12 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms, particularly preferably an alkylene group having 2 to 6 carbon atoms, and most preferably an alkylene group having 2 carbon atoms.

[0035] (Process (2)) The method for producing a polymerizable compound according to the present embodiment preferably further includes a step of treating the reaction product obtained in the above step (1) with an alcohol (hereinafter, also referred to as "step (2)"). By treating the reaction product obtained in the step (1) with an alcohol, the amount of the compound represented by general formula (I) remaining in the reaction product can be reduced, and the purity of the obtained polymerizable compound can be further increased.

[0036] In step (2), for example, the reaction product obtained in step (1) is treated by adding and mixing an alcohol such as ethanol or propanol. The treatment temperature is preferably room temperature (25° C.) to 100° C., more preferably 50 to 90° C. After step (1) or step (2), the target polymerizable compound can be obtained by separation and purification according to a conventional method.

[0037] <Polymerizable compound> The polymerizable compound produced by the above-mentioned production method is, for example, a compound represented by the following general formula (2): By forming a structure represented by the following general formula (2), it is possible to produce an adhesive layer-forming composition or an adhesive polymer capable of forming an adhesive layer, etc., having excellent adhesiveness and tackiness on various substrates.

[0038] TIFF0007634035000011.tif38170 (In the general formula (2), n represents a number from 1 to 5, R1 represents -O- or -NH-, R2 represents an alkylene group having 2 or more carbon atoms which may contain an ether bond, R3 represents a linear alkylene group having 2 or more carbon atoms which may contain an ether bond, or a branched alkylene group having 2 or more carbon atoms which may have a (meth)acrylic group, and R4 represents a hydrogen atom or a methyl group.)

[0039] The polymerizable compound preferably has a purity of 25% or more, more preferably 50% or more, even more preferably 70% or more, particularly preferably 80% or more, and most preferably 90% or more, as measured by HPLC (high performance liquid chromatography). By using such a high-purity polymerizable compound, it is possible to prepare a composition for forming an adhesive / tacky layer that can form an adhesive layer having excellent adhesiveness and adhesion.

[0040] The purity of the polymerizable compound is measured by HPLC. The purity of the polymerizable compound is expressed as the ratio (percentage) of the area of ​​the absorption peak corresponding to the polymerizable compound to the total peak area of ​​the chromatogram recording the change in the absorption intensity of light (ultraviolet light (UV)) at a wavelength of 294 nm measured by HPLC. The total peak area of ​​the chromatogram means the sum of the areas of the absorption peaks originating from each component separated by HPLC. However, the total peak area of ​​the chromatogram does not include the following: absorption peaks originating from the dilution solvent and bubbles of the polymerizable compound; absorption peaks originating from impurities contained in the dilution solvent and eluent; absorption peaks associated with background changes due to the gradient of the composition of the eluent; absorption peaks with an area ratio of 0.1% or less; and background peaks obtained when only the dilution solvent is measured. The HPLC conditions can be as follows. 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

[0041] <Composition for forming adhesive / adhesive layer> By using the above-mentioned polymerizable compound, a composition for forming an adhesive / tacky layer can be produced. That is, the composition for forming an adhesive / tacky layer contains the above-mentioned polymerizable compound, and an adhesive / tacky layer having excellent adhesiveness and tackiness can be formed on various substrates.

[0042] The content of the 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 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.

[0043] The composition for forming an adhesive layer may contain polymerizable monomers, resins, etc. other than the 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.

[0044] The composition for forming an adhesive layer 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.

[0045] 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.

[0046] The adhesive layer-forming composition 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.

[0047] The adhesive layer-forming composition 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.

[0048] An adhesive layer or a pressure-sensitive adhesive layer can be formed by applying the composition for forming an adhesive layer on a substrate and curing the coating layer formed. Methods for applying the composition for forming an adhesive layer on a substrate include roll coating, gravure coating, comma coating, knife coating, and die coating.

[0049] 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.

[0050] <Adhesive / adhesive polymer> By using the above-mentioned polymerizable compound, an adhesive / tacky polymer can be produced. That is, the adhesive / tacky polymer has a structural unit derived from the above-mentioned polymerizable compound, and can form an adhesive / tacky layer with excellent adhesiveness and tackiness on various substrates.

[0051] The content of the structural unit derived from the polymerizable compound in the adhesive polymer is not particularly limited and may be appropriately set according to the purpose.Specifically, the content of the structural unit derived from the 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 total amount of the adhesive polymer.

[0052] The adhesive polymer may have a structural unit (other structural unit) other than the structural unit derived from the polymerizable compound represented by the above-mentioned general formula (1). The other structural unit can be formed using a conventionally known polymerizable monomer or resin that constitutes a normal adhesive polymer.

[0053] <Various products> By using the composition for forming an adhesive layer or the adhesive polymer, 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 composition for forming an adhesive layer or the 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.

[0054] 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.

[0055] 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), polycarbonate (PC), Examples of suitable 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

[0056] 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.

[0057] <Production of polymerizable compound> Example 1 29 parts of the compound represented by the following formula (1-1) was suspended in 60 parts of 1,2-dimethoxyethane and then heated to 92°C. 23 parts of 2-methacryloyloxyethyl isocyanate, 0.6 parts of dimethylcarbamoyl chloride (4.6 mol% relative to the compound represented by the following formula (1-1)), and 4 parts of 1,2-dimethoxyethane were added and heated at 95°C for 270 minutes. Then, 14 parts of ethanol were added and heated at 85°C for 90 minutes. After cooling, the mixture was dried under reduced pressure to obtain 64 parts of polymerizable compound 1 mainly composed of a compound represented by the following formula (2-1). The purity (HPLC purity) of polymerizable compound 1 measured by HPLC was 84%. The content of by-products was 5.8%. The obtained polymerizable compound 1 (compound represented by formula (2-1)) 1 The results of H-NMR (chemical shift) are shown below. The conditions for measuring the purity by HPLC are also shown below. 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)

[0058] [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

[0059] TIFF0007634035000012.tif86170

[0060] Example 2 29 parts of the compound represented by the formula (1-1) was suspended in 60 parts of 1,2-dimethoxyethane and then heated to 85°C. 23 parts of 2-methacryloyloxyethyl isocyanate, 0.6 parts of p-toluenesulfonic acid monohydrate (2.8 mol% relative to the compound represented by the formula (1-1)), and 4 parts of 1,2-dimethoxyethane were added and heated at 95°C for 140 minutes. Then, 14 parts of ethanol were added and heated at 85°C for 120 minutes. After cooling, the mixture was dried under reduced pressure to obtain 65 parts of polymerizable compound 2 mainly composed of the compound represented by the formula (2-1). The purity of polymerizable compound 2 measured by HPLC (HPLC purity) was 84%. The content of by-products was 4.7%.

[0061] Example 3 29 parts of the compound represented by the formula (1-1) was suspended in 60 parts of 1,2-dimethoxyethane and then heated to 85°C. 23 parts of 2-methacryloyloxyethyl isocyanate, 0.2 parts of acetic acid (2.8 mol% relative to the compound represented by the formula (1-1)), and 4 parts of 1,2-dimethoxyethane were added and heated at 95°C for 420 minutes. Then, 14 parts of ethanol were added and heated at 85°C for 120 minutes. After cooling, the mixture was dried under reduced pressure to obtain 60 parts of polymerizable compound 3 mainly composed of the compound represented by the formula (2-1). The purity of polymerizable compound 3 measured by HPLC (HPLC purity) was 79%. The content of by-products was 8.0%.

[0062] Example 4 29 parts of the compound represented by the formula (1-1) was suspended in 60 parts of 1,2-dimethoxyethane and then heated to 85°C. 23 parts of 2-methacryloyloxyethyl isocyanate, 0.6 parts of gallic acid monohydrate (2.8 mol% relative to the compound represented by the formula (1-1)), and 4 parts of 1,2-dimethoxyethane were added and heated at 95°C for 300 minutes. Then, 14 parts of ethanol were added and heated at 85°C for 90 minutes. After cooling, the mixture was dried under reduced pressure to obtain 60 parts of polymerizable compound 4 mainly composed of the compound represented by the formula (2-1). The purity of polymerizable compound 4 measured by HPLC (HPLC purity) was 79%. The content of by-products was 6.0%.

[0063] Example 5 29 parts of the compound represented by the formula (1-1) was suspended in 60 parts of 1,2-dimethoxyethane and then heated to 92°C. 23 parts of 2-methacryloyloxyethyl isocyanate, 0.4 parts of dimethylcarbamoyl chloride (2.8 mol% relative to the compound represented by the following formula (1-1)), and 4 parts of 1,2-dimethoxyethane were added and heated at 95°C for 270 minutes. Then, 14 parts of ethanol were added and heated at 85°C for 90 minutes. After cooling, the mixture was dried under reduced pressure to obtain 64 parts of polymerizable compound 5 mainly composed of the compound represented by the formula (2-1). The purity of polymerizable compound 5 measured by HPLC (HPLC purity) was 83%. The content of by-products was 6.2%.

[0064] Comparative Example 1 29 parts of the compound represented by the formula (1-1) was suspended in 48 parts of tetrahydrofuran, and then 1.8 parts of dibutyltin dilaurate (product name "KS-1260", manufactured by Sakai Chemical Industry Co., Ltd., 1% toluene solution) and 18 parts of 2-methacryloyloxyethyl isocyanate were added. The mixture was heated at 60°C for 1,110 minutes while appropriately adding 80 parts of tetrahydrofuran. After cooling, the mixture was dried under reduced pressure to obtain 65 parts of polymerizable compound 6, the main component of which was the compound represented by the formula (2-1). The purity of polymerizable compound 6 measured by HPLC (HPLC purity) was 39%. The content of by-products was 32%.

[0065] Comparative Example 2 29 parts of the compound represented by the formula (1-1) was suspended in 42 parts of tetrahydrofuran, and then 0.8 parts of bismuth tris(2-ethylhexanoate) (trade name "Neostan U-600", manufactured by Nitto Kasei Co., Ltd., 1% toluene solution), 18 parts of 2-methacryloyloxyethyl isocyanate, and 6 parts of tetrahydrofuran were added, followed by heating at 60°C for 1,380 minutes. After cooling, the mixture was dried under reduced pressure to obtain 55 parts of polymerizable compound 7, the main component of which was the compound represented by the formula (2-1). The purity of polymerizable compound 7 measured by HPLC (HPLC purity) was 41%. The content of by-products was 27%.

[0066] The resulting polymerizable compounds are shown in Table 1.

[0067] TIFF0007634035000013.tif117170

[0068] <Production of composition for forming adhesive layer> (Production Example 1) 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 compound.

[0069] (Production example 2, reference example 1) Except for using the formulation shown in Table 2, the same procedure as in Production Example 1 described above was carried out to obtain a composition (paint) for forming an adhesive / tacky layer.

[0070] TIFF0007634035000014.tif60170

[0071] <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. ◎: 200% or more ○: 100% or more but less than 200% ×: Less than 100%

[0072] (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. ◎: 200% or more ○: 100% or more but less than 200% ×: Less than 100%

[0073] TIFF0007634035000015.tif50170

Claims

1. A method for producing a polymerizable compound for forming an adhesive layer, comprising the step of reacting a compound represented by the following general formula (1) with an isocyanate compound having a reactive double bond in the presence of an acid catalyst capable of generating active hydrogen to obtain a reaction product: (In the general formula (1), n ​​represents a number from 3 to 5, and R １ represents -O- or -NH-; R ２ represents an alkylene group having 2 or more carbon atoms which may contain an ether bond.

2. In the general formula (1), R １ The method for producing a polymerizable compound according to claim 1, wherein is -O-.

3. In the general formula (1), R ２ The method for producing a polymerizable compound according to claim 1, wherein is an alkylene group having 2 to 10 carbon atoms.

4. The method for producing a polymerizable compound according to claim 1 , wherein the isocyanate compound is a compound represented by the following general formula (I): (In the above general formula (I), R ３ represents a linear alkylene group having 2 or more carbon atoms which may contain an ether bond, or a branched alkylene group having 2 or more carbon atoms which may contain a (meth)acrylic group; R ４ represents a hydrogen atom or a methyl group)

5. 2. The method for producing a polymerizable compound according to claim 1, wherein the acid catalyst has an acid dissociation constant of less than 5.

6. 2. The method for producing a polymerizable compound according to claim 1, wherein the acid catalyst is at least one selected from the group consisting of hydrogen halide, sulfonic acid, and carboxylic acid.

7. The method for producing a polymerizable compound according to any one of claims 4 to 6, wherein the content of the compound represented by the following general formula (4) in the reaction product measured by HPLC is 20% or less: (In the general formula (4), R １１ ~R １５ each independently represents a hydrogen atom, a hydroxyl group, or a group represented by the following general formula (5), R １１ ~R １５ At least one of R is a group represented by the following general formula (5). １ represents -O- or -NH-; R ２ represents an alkylene group having 2 or more carbon atoms which may contain an ether bond, R ３ represents a linear alkylene group having 2 or more carbon atoms which may contain an ether bond, or a branched alkylene group having 2 or more carbon atoms which may contain a (meth)acrylic group; R ４ represents a hydrogen atom or a methyl group) (In the general formula (5), * indicates the bonding position to the benzene ring, and R ３ represents a linear alkylene group having 2 or more carbon atoms which may contain an ether bond, or a branched alkylene group having 2 or more carbon atoms which may contain a (meth)acrylic group; R ４ represents a hydrogen atom or a methyl group)

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