JP2022055338A - Polymerizable compound and method for producing the same, composition for forming adhesive/sticky layers, and adhesive/sticky polymer - Google Patents

Abstract

To provide a polymerizable compound that enables preparation of a composition for forming adhesive/sticky layers or an adhesive/sticky polymer, allowing formation of an adhesive layer or the like having excellent adhesiveness or stickiness on various substrates with good adhesion.SOLUTION: A polymerizable compound is represented by general formula (1) and has a purity of 35% or more as measured by HPLC. (In the general formula (1), R1-R4 independently represent a hydrogen atom or a hydroxy group, and at least one of R1-R4 is a hydroxy group. R5 is -O- or -NH-. R6 is an alkylene group having two or more carbon atoms, optionally including ether linkage, and R7 is a hydrogen atom or a methyl group).SELECTED DRAWING: None

Description

The present invention relates to a polymerizable compound and a method for producing the same, a composition for forming an adhesive / adhesive layer, and an adhesive / adhesive polymer.

In recent years, polymers having various functions, using compounds having a catechol skeleton such as dopa and dopamine contained in marine organisms such as mussels and derivatives thereof as monomers, have been proposed. For example, a curable resin composition containing a monomer such as dopamine acrylamide has been proposed (Patent Document 1). Further, a derivative of catechols having a (meth) acryloyl group and a photocurable coating composition containing the derivative of these catechols as a deodorant have been proposed (Patent Document 2).

In addition to the catechol skeleton, it has been proposed to use a derivative of a compound having a pyrogallol skeleton as a monomer. For example, it has been proposed to use a photopolymerizable pyrogallol derivative (gallic acid derivative) as an electron-accepting compound (Patent Document 3). Further, as a monomer for a photoactive polymer used for a liquid crystal alignment layer, a gallic acid derivative having a (meth) acryloyl group has been proposed (Patent Document 4).

International Publication No. 2019/221135 Japanese Unexamined Patent Publication No. 2009-203408 Japanese Unexamined Patent Publication No. 2000-272244 Special Table 2003-505561 Gazette

However, compounds such as dopa and dopamine, which are raw materials for the monomers having a catechol skeleton proposed in Patent Documents 1 and 2, are relatively expensive and difficult to obtain. Further, even when these compounds are used, the characteristics (adhesiveness, adhesiveness) of the formed adhesive layer and the adhesive layer are not always sufficient, and there is room for further improvement.

Further, Patent Documents 3 and 4 do not disclose at all about obtaining a composition or a polymer for forming an adhesive layer or an adhesive layer by using a gallic acid derivative. Furthermore, no effective method for efficiently producing catechol derivatives and gallic acid derivatives has been known so far.

The present invention has been made in view of the problems of the prior art, and the subject thereof is good adhesion of an adhesive layer having excellent adhesiveness and adhesiveness onto various substrates. It is an object of the present invention to provide a composition for forming an adhesive / adhesive layer that can be formed by sex, and a polymerizable compound capable of preparing an adhesive / adhesive polymer. Further, an object of the present invention is to provide an efficient method for producing the above-mentioned polymerizable compound, a composition for forming an adhesive / adhesive layer using the above-mentioned polymerizable compound, and an adhesive / adhesive polymer. To do.

That is, according to the present invention, the following polymerizable compounds are provided.
[1] A polymerizable compound represented by the following general formula (1) and having a purity measured by HPLC of 35% or more.

（前記一般式（１）中、Ｒ_１～Ｒ_４は、それぞれ独立に、水素原子又は水酸基を示し、Ｒ_１～Ｒ_４のうちの１以上が水酸基である。Ｒ_５は－Ｏ－又は－ＮＨ－を示し、Ｒ_６はエーテル結合を含んでいてもよい炭素数２以上のアルキレン基を示し、Ｒ_７は水素原子又はメチル基を示す）

(In the general formula (1), R ₁ to R ₄ independently represent a hydrogen atom or a hydroxyl group, and one or more of R ₁ to R ₄ is a hydroxyl group. R ₅ is -O- or-. Indicates NH-, R ₆ indicates an alkylene group having 2 or more carbon atoms which may contain an ether bond, and R ₇ indicates a hydrogen atom or a methyl group).

[2] The polymerizable compound according to the above [1], which has a purity measured by HPLC of 60% or more.
[3] The polymerizable compound according to the above [1] or [2], wherein two or more of R ₁ to R ₄ are hydroxyl groups in the general formula (1).
[4] The polymerizable compound according to any one of the above [1] to [ ₃ ], wherein R5 is —O— in the general formula (1).
[5] The polymerizable compound according to any one of the above [1] to [4], wherein R ₆ is an alkylene group having 2 to 6 carbon atoms in the general formula (1).

Further, according to the present invention, a method for producing a polymerizable compound shown below is provided.
[6] The method for producing a polymerizable compound according to any one of the above [1] to [5], wherein the compound represented by the following general formula (2) and (meth) acrylic acid anhydride or (meth) acrylic acid anhydride or (meth). ) A method for producing a polymerizable compound, which comprises a step of reacting with an acrylic acid halide to obtain a reactant.

（前記一般式（２）中、Ｒ_１～Ｒ_４は、それぞれ独立に、水素原子又は水酸基を示し、Ｒ_１～Ｒ_４のうちの１以上が水酸基である。Ｒ_５は－Ｏ－又は－ＮＨ－を示し、Ｒ_６はエーテル結合を含んでいてもよい炭素数２以上のアルキレン基を示す）

(In the general formula (2), R ₁ to R ₄ independently represent a hydrogen atom or a hydroxyl group, and one or more of R ₁ to R ₄ is a hydroxyl group. R ₅ is -O- or-. Indicates NH-, where R6 indicates an alkylene group having ₂ or more carbon atoms which may contain an ether bond).

[7] The method for producing a polymerizable compound according to the above [6], further comprising a step of treating the reactant under basic conditions.

Further, according to the present invention, the following composition for forming an adhesive / adhesive layer is provided.
[8] A composition for forming an adhesive / adhesive layer containing the polymerizable compound according to any one of the above [1] to [5].
[9] The composition for forming an adhesive / adhesive layer according to the above [8], which further contains a polymerization initiator.

Further, according to the present invention, the following adhesive / adhesive polymers are provided.
[10] An adhesive / adhesive polymer having a structural unit derived from the polymerizable compound according to any one of the above [1] to [5].

According to the present invention, a composition for forming an adhesive / adhesive layer and an adhesive / adhesive polymer capable of forming an adhesive layer having excellent adhesiveness and adhesiveness on various substrates with good adhesiveness are prepared. It is possible to provide a polymerizable compound which can be used. Further, according to the present invention, it is possible to provide an efficient method for producing the above-mentioned polymerizable compound, a composition for forming an adhesive / adhesive layer using the above-mentioned polymerizable compound, and an adhesive / adhesive polymer. can.

<Polymerizable compound>
Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. One embodiment of the polymerizable compound of the present invention is a compound having a polymerizable property represented by the following general formula (1), and the purity measured by HPLC is 35% or more. Hereinafter, the polymerizable compound of the present embodiment will be described in detail.

（前記一般式（１）中、Ｒ_１～Ｒ_４は、それぞれ独立に、水素原子又は水酸基を示し、Ｒ_１～Ｒ_４のうちの１以上が水酸基である。Ｒ_５は－Ｏ－又は－ＮＨ－を示し、Ｒ_６はエーテル結合を含んでいてもよい炭素数２以上のアルキレン基を示し、Ｒ_７は水素原子又はメチル基を示す）

(In the general formula (1), R ₁ to R ₄ independently represent a hydrogen atom or a hydroxyl group, and one or more of R ₁ to R ₄ is a hydroxyl group. R ₅ is -O- or-. Indicates NH-, R ₆ indicates an alkylene group having 2 or more carbon atoms which may contain an ether bond, and R ₇ indicates a hydrogen atom or a methyl group).

In the general formula (1), it is preferable that two or more of R ₁ to R ₄ are hydroxyl groups, and it is more preferable that three or more of R ₁ to R ₄ are hydroxyl groups. Further, in the general formula ( ₁ ), R5 is preferably —O— (ether bond). In the general formula (1), R ₆ is preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an alkylene group having 2 to 6 carbon atoms. With such a structure, a composition for forming an adhesive / adhesive layer and an adhesive / adhesive weight capable of forming an adhesive layer having better adhesiveness and adhesiveness on various base materials with even better adhesion. It can be a polymerizable compound that can provide a coalescence. In the general formula (1), when the alkylene group represented by R ₆ has 2 carbon atoms, the alcohol compound used as a raw material has high water solubility, and it becomes somewhat difficult to purify the obtained polymerizable compound. , Purity and yield may decrease. Therefore, from the viewpoint of ease of synthesis, purity, yield, etc. of the polymerizable compound, R ₆ in the general formula (1) is preferably an alkylene group having 3 to 6 carbon atoms, and is preferably carbon. It is more preferably an alkylene group having 4 to 6 carbon atoms, and particularly preferably an alkylene group having 4 carbon atoms.

The polymerizable compound of the present embodiment has a purity measured by HPLC (High Performance Liquid Chromatography) of 35% or more, preferably 50% or more, more preferably 60% or more, still more preferably 70% or more, and particularly preferably 80. % Or more, most preferably 90% or more. By using such a high-purity polymerizable compound, it is possible to prepare an adhesive / adhesive layer forming composition or the like capable of forming an adhesive layer or the like having better adhesiveness and adhesiveness.

The purity of the polymerizable compound of this embodiment is measured by HPLC. The purity of the polymerizable compound is the polymerization represented by the general formula (1), which occupies the total peak area of the chromatogram in which the change in the absorption intensity of light (ultraviolet rays (UV)) having a wavelength of 294 nm, which is measured by HPLC, is recorded. It is expressed as a percentage of the area of the absorption peak corresponding to the sex compound. The total peak area of the chromatogram means the total area of absorption peaks derived from each component separated by HPLC. However, the absorption peak derived from the diluting solvent and bubbles of the polymerizable compound; the absorption peak derived from the impurities contained in the diluting solvent and the eluent; the absorption peak due to the background change due to the gradient of the composition of the eluent; the area ratio is 0. Absorption peaks of 1% or less; and background peaks obtained when only the diluted solvent is measured; are not included in the total peak area of the chromatogram. The HPLC conditions can be as follows.
Analytical equipment: LCMS system consisting of LC-30AD, SPD-M20A, and LCMS-8050 (manufactured by Shimadzu Corporation)
Eluent: Acetonitrile-3% aqueous acetic acid solution (1:19 → 17: 3 (v / v), gradient over 40 minutes)
Flow velocity: 0.2 mL / min
Column: L-column2 ODS. 2 μm (3.0 × 100 mm) (manufactured by Chemicals Evaluation and Research Institute)
Column temperature: 40 ° C
Sample: Approximately 100 ppm THF solution 2.0 μL
Detection wavelength: 294 nm

<Manufacturing method of polymerizable compound>
Next, a method for producing the polymerizable compound of the present invention will be described. One embodiment of the method for producing a polymerizable compound of the present invention is the above-mentioned method for producing a polymerizable compound, wherein the compound represented by the following general formula (2) and (meth) acrylic acid anhydride or (meth) acrylic acid anhydride or (meth). ) It has a step of reacting with an acrylic acid halide to obtain a reactant (hereinafter, also referred to as "step (1)").

（前記一般式（２）中、Ｒ_１～Ｒ_４は、それぞれ独立に、水素原子又は水酸基を示し、Ｒ_１～Ｒ_４のうちの１以上が水酸基である。Ｒ_５は－Ｏ－又は－ＮＨ－を示し、Ｒ_６はエーテル結合を含んでいてもよい炭素数２以上のアルキレン基を示す）

(In the general formula (2), R ₁ to R ₄ independently represent a hydrogen atom or a hydroxyl group, and one or more of R ₁ to R ₄ is a hydroxyl group. R ₅ is -O- or-. Indicates NH-, where R6 indicates an alkylene group having ₂ or more carbon atoms which may contain an ether bond).

R ₁ to R ₆ in the general formula (2) are synonymous with R ₁ to R ₆ in the general formula (1). That is, in the general formula (1), it is preferable that two or more of R ₁ to R ₄ are hydroxyl groups, and it is more preferable that three or more of R ₁ to R ₄ are hydroxyl groups. Further, in the general formula ( ₁ ), R5 is preferably —O— (ether bond). In the general formula (1), R ₆ is preferably an alkylene group having 2 to 8 carbon atoms, more preferably an alkylene group having 2 to 6 carbon atoms, and further preferably an alkylene group having 3 to 6 carbon atoms. Particularly preferably, it is 4 to 6 alkylene groups, and most preferably 4 alkylene groups.

In step (1), as shown in the reaction formula below, the compound represented by the general formula (2) is reacted with (meth) acrylic acid anhydride or (meth) acrylic acid halide. Thereby, the polymerizable compound represented by the general formula (1) can be obtained. A catalyst may be used in the reaction. As the catalyst, acid catalysts such as paratoluenesulfonic acid, paratoluenesulfonic acid anhydride, sulfuric acid, hydrochloric acid, and phosphoric acid can be used. When (meth) (meth) acrylic acid anhydride is used, it is preferable to react the (meth) (meth) acrylic acid anhydride in the presence of a catalyst. R ₇ in the following reaction formula has the same meaning as R ₇ in the general formula (1) and indicates a hydrogen atom or a methyl group. Further, X in the following reaction formula indicates a halogen atom.

As the (meth) acrylic acid halide, chlorides, bromides, iodides and the like of (meth) acrylic acid can be used. Further, it is preferable to react the substrate (material compound) in a state of being dissolved or dispersed in an appropriate organic solvent. Examples of the organic solvent include 1,4-dioxane, 1,2-dimethoxyethane, diglyme, N-methylpyrrolidone, N, N-dimethylacetamide and the like. The reaction may be carried out under low temperature to heating conditions, preferably 0 to 120 ° C. The temperature at which the (meth) acrylic acid halide is reacted is preferably 0 to 60 ° C. The temperature at which the (meth) acrylic acid anhydride is reacted is preferably 80 to 120 ° C.

As the compound represented by the general formula (2), a commercially available product may be used, or a synthetic product may be used. The compound represented by the general formula (2) can be prepared by reacting hydroxybenzoic acids with glycols, for example, as shown in the following reaction formula. In addition, R ₁ to R ₆ in the following reaction formula has the same meaning as R ₁ to R ₆ in the general formula (1). Further, as the catalyst, the same catalyst as the catalyst that can be used in the above step (1) can be used.

In step (1), the (meth) acrylic anhydride or (meth) acrylic acid halide preferentially prefers the aliphatic hydroxyl group over the aromatic hydroxyl groups (R ₁ to R ₄ ) in the general formula (2). react. However, the (meth) acrylic acid anhydride or the (meth) acrylic acid halide also reacts with some aromatic hydroxyl groups to form a side reaction product, which is mixed as an impurity in the obtained polymerizable compound. Examples of the side reaction product include compounds represented by the following general formula (3). The content of the compound represented by the following general formula (3) measured by HPLC in the polymerizable compound of the present embodiment is preferably 20% or less, more preferably 10% or less.

（前記一般式（３）中、Ｒ_１１～Ｒ_１４は、それぞれ独立に、水素原子、水酸基、又は下記一般式（４）で表される基を示し、Ｒ_１１～Ｒ_１４のうちの１以上が下記一般式（４）で表される基である。Ｒ_５は－Ｏ－又は－ＮＨ－を示し、Ｒ_６はエーテル結合を含んでいてもよい炭素数２以上のアルキレン基を示し、Ｒ_７は水素原子又はメチル基を示す）

(In the general formula (3), R ₁₁ to R ₁₄ each independently represent a hydrogen atom, a hydroxyl group, or a group represented by the following general formula (4), and one or more of R ₁₁ to R ₁₄ . Is a group represented by the following general formula (4). R ₅ represents -O- or -NH-, R ₆ represents an alkylene group having 2 or more carbon atoms which may contain an ether bond, and R ₇ indicates a hydrogen atom or a methyl group)

（前記一般式（４）中、＊はベンゼン環との結合位置を示し、Ｒ_７は水素原子又はメチル基を示す）

(In the general formula (4), * indicates a bond position with a benzene ring, and R ₇ indicates a hydrogen atom or a methyl group).

In the polymerizable compound obtained by the step (1), a compound represented by the general formula (2), which is an unreacted raw material compound, may be mixed as an impurity. The content of the compound represented by the general formula (2) measured by HPLC in the polymerizable compound of the present embodiment is preferably 20% or less, more preferably 10% or less.

The method for producing the polymerizable compound of the present embodiment further preferably includes a step of treating the reaction product obtained in the above step (1) under basic conditions (hereinafter, also referred to as "step (2)"). .. By treating the reaction product obtained in the step (1) under basic conditions, a side reaction product such as a compound represented by the general formula (3) is decomposed, preferably hydrolyzed, to obtain a polymerizable compound. The purity can be increased.

In the step (2), for example, the reaction product obtained in the step (1) is treated in an aqueous solution of an alkali metal hydroxide such as sodium hydroxide and potassium hydroxide. The treatment temperature is preferably room temperature (25 ° C.) to 100 ° C., more preferably 40 to 80 ° C. After the step (1) or the step (2), the desired polymerizable compound can be obtained by separating and purifying according to a conventional method.

<Composition for forming an adhesive / adhesive layer>
One embodiment of the composition for forming an adhesive / adhesive layer of the present invention contains the above-mentioned polymerizable compound. Since the composition for forming an adhesive / adhesive layer of the present embodiment contains the above-mentioned polymerizable compound, an adhesive layer / adhesive layer having excellent adhesiveness and adhesiveness can be formed on various substrates. Further, by using the composition for forming an adhesive / adhesive layer of the present embodiment, it is possible to form an adhesive layer or an adhesive layer having excellent adhesion on various substrates.

The content of the polymerizable compound represented by the general formula (1) in the composition for forming an adhesive / adhesive layer may be appropriately set according to the purpose and is not particularly limited. Specifically, the content of the polymerizable compound is usually 0.1 to 90% by mass, preferably 0.3 to 50% by mass, and further, based on the solid content in the composition for forming an adhesive / adhesive layer. It is preferably 0.5 to 20% by mass, and particularly preferably 0.5 to 10% by mass.

The composition for forming an adhesive / adhesive layer of the present embodiment may contain a polymerizable monomer, a resin, or the like other than the polymerizable compound represented by the above general formula (1). As the polymerizable monomer and resin, various conventionally known polymerizable monomers and resins can be used.

The composition for forming an adhesive / adhesive layer of the present embodiment preferably further contains a polymerization initiator. As the polymerization initiator, a photopolymerization initiator or a thermal polymerization initiator can be used. Acylphosphin oxides such as diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide; 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy as photopolymerization initiators. -2-Phenylacetophenone and acetophenones such as diethoxyacetophenone; ketals such as benzyldimethylketal; benzoins and benzoins such as benzoinmethyl ether; benzophenones such as benzophenone, benzoylbenzoic acid, and hydroxybenzophenone; other Examples thereof include a halogenated ketone and an acylphosphanate.

As the thermal polymerization initiator, an azo compound, an organic peroxide or the like can be used. Examples of the azo compound include azobisisobutyronitrile, 1,1'-azobis (cyclohexanecarbonitrile), 2,2'-azobis (2-methylpropanoic acid) dimethyl and the like. Examples of the organic peroxide include hydroperoxide-based compounds, dialkyl peroxide-based compounds, peroxyester-based compounds, diacyl peroxide-based compounds, ketone peroxide-based compounds, peroxyketal-based compounds, and peroxydicarbonate-based compounds. And so on.

The composition for forming an adhesive / adhesive layer of the present embodiment can be made into a paint having appropriate coatability (coatability) by further containing a solvent. As the solvent, water or various organic solvents can be used.

The composition for forming an adhesive / adhesive layer of the present embodiment may contain other additives. Other additives include, for example, silane coupling agents, thixo-imparting agents, anti-blocking agents, leveling agents, antifoaming agents, antioxidants, thermoplastic resins, antistatic agents, waxes, heat stabilizers, flame retardants, etc. Examples thereof include an ultraviolet absorber, an antibacterial agent, and a deodorant.

An adhesive layer or an adhesive layer can be formed by applying the adhesive / adhesive layer forming composition of the present embodiment on a substrate and curing the coated layer. Examples of the method of applying the adhesive / adhesive layer forming composition on the substrate include roll coating, gravure coating, comma coating, knife coating, and die coating.

As a method of curing the coating layer (composition for forming an adhesive / adhesive layer), when a photopolymerization initiator is used, an irradiation device of active energy rays such as visible light, ultraviolet rays, and electron beams is used for coating. A method of irradiating the work layer with active energy rays with a predetermined amount of light can be adopted. 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, for example, a method of using a high-temperature furnace or the like and preferably heating to 50 to 250 ° C. can be adopted.

<Adhesive / adhesive polymer>
One embodiment of the adhesive / adhesive polymer of the present invention has a structural unit derived from the polymerizable compound represented by the above-mentioned general formula (1). Since the adhesive / adhesive polymer of the present embodiment has a structural unit derived from the polymerizable compound represented by the above-mentioned general formula (1), various adhesive layers / adhesive layers having excellent adhesiveness and adhesiveness can be obtained. Can be formed on the substrate of. Further, by using the adhesive / adhesive polymer of the present embodiment, it is possible to form an adhesive layer or an adhesive layer having excellent adhesion on various substrates.

The content of the structural unit derived from the polymerizable compound represented by the general formula (1) in the adhesive / adhesive polymer may be appropriately set according to the purpose and is not particularly limited. Specifically, the content of the structural unit derived from the polymerizable compound represented by the general formula (1) is usually 0.1 to 90% by mass, preferably 0.1 to 90% by mass, based on the whole of the adhesive / adhesive polymer. Is 0.3 to 50% by mass, more preferably 0.5 to 20% by mass, and particularly preferably 0.5 to 10% by mass.

The adhesive / adhesive polymer of the present embodiment 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). Other structural units can be formed by using conventionally known polymerizable monomers or resins constituting ordinary adhesive / adhesive polymers.

<Various products>
By using the adhesive / adhesive layer forming composition or the adhesive / adhesive polymer of the present embodiment, a product such as an adhesive sheet can be formed. The pressure-sensitive adhesive sheet includes a sheet-shaped support and a pressure-sensitive adhesive layer formed of an adhesive / adhesive layer-forming composition or an adhesive / adhesive polymer provided on one or both sides of the support. Examples of the support include a resin film, a laminated film containing a resin film, paper, a woven fabric, a non-woven fabric, and the like. Examples of the material of the resin film include polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), polyethylene, polypropylene, and polycarbonate. A release film may be laminated on the surface of the pressure-sensitive adhesive layer in order to protect the pressure-sensitive adhesive layer.

Further, by using a composition for forming an adhesive / adhesive layer or an adhesive / adhesive polymer, various laminates useful as an optical film or the like can be formed. In the laminated body, the first base material and the second base material were laminated via the adhesive layer or the adhesive layer formed by the above-mentioned adhesive / adhesive layer forming composition or the adhesive / adhesive polymer. It is a thing. The first base material and the second base material may be made of the same material or may be made of different materials.

As the material of the base material (first base material and second base material), inorganic materials such as glass, hydroxyapatite, titanium oxide, zinc oxide, iron oxide, indium tin oxide (ITO); aluminum (Al), Metallic materials such as copper (Cu), iron (Fe), gold (Au), platinum (Pt), silver (Ag), zinc (Zn), tin (Sn), titanium (Ti), and alloys thereof; polyproprene. (PP), polyethylene (PE), polytetrafluoroethylene (PTFE), polyimide (PI), polycarbonate (PC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polymethylmethacrylate (PMMA), polyphenylene sulfide. (PPS), polyphenylene ether (modified PPE), triacetyl cellulose (TAC), cycloolefin polymer (COP), acrylonitrile-butadiene-styrene copolymer (ABS), fiber reinforced plastic (FRP), molybdenum-aluminum-molybdenum laminate Organic materials such as structure (MAM); can be mentioned.

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. In addition, "part" and "%" in Examples and Comparative Examples are based on mass unless otherwise specified.

<Manufacturing of polymerizable compounds>
(Example 1)
After suspending 73 parts of the compound represented by the following formula (2-1) in 300 parts of 1,4-dioxane, 56 parts of methacrylic anhydride and 3 parts of p-toluenesulfonic acid hydrate were added, and 100 parts were added. It was heated at ° C. for 4 hours. After cooling, the mixture was separated, filtered, and dried under reduced pressure to obtain 185 parts (yield: 91%) of a polymerizable compound containing the compound represented by the following formula (1-1) as a main component. The purity (HPLC purity) of the polymerizable compound 1 measured by HPLC was 79%. The measurement result (chemical shift) of ¹ H-NMR of the obtained polymerizable compound 1 (compound represented by the formula (1-1)) is shown below. The conditions for measuring purity by HPLC are shown below.
^{1 1} H-NMR (DMSO-d6,400MHz): δ = 1.75 (4H, m), 1.88 (3H, s), 4.16 (2H, t, J = 5.6Hz), 4.20 (2H, t, J = 5.4Hz), 5.67 (1H, m), 6.03 (1H, m), 6.95 (2H, s), 9.17 (3H, s, br)

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

(Example 2)
Twelve parts of the compound represented by the formula (2-1) were dissolved in 36 parts of N-methylpyrrolidone, 8 parts of methacrylic acid chloride was added, and the mixture was reacted at room temperature (25 ° C.) for 2.5 hours. The mixture was separated, filtered, and dried under reduced pressure to obtain 215 parts (yield: 99%) of a polymerizable compound containing the compound represented by the formula (1-1) as a main component. The HPLC purity of the obtained polymerizable compound 2 was 82%.

(Example 3)
After suspending 73 parts of the compound represented by the formula (2-1) in 300 parts of 1,4-dioxane, 56 parts of methacrylic anhydride and 3 parts of p-toluenesulfonic acid hydrate were added, and 100 parts were added. It was heated at ° C. for 4 hours. Then, 19 parts of sodium hydroxide and 300 parts of water were added, and the mixture was heated at 60 ° C. for 8 hours. After cooling, the mixture was separated, filtered, and dried under reduced pressure to obtain 382 parts (yield: 88%) of a polymerizable compound containing the compound represented by the above formula (1-1) as a main component. The HPLC purity of the obtained polymerizable compound 3 was 98%.

(Example 4)
After suspending 81 parts of the compound represented by the following formula (2-2) in 300 parts of 1,4-dioxane, 56 parts of methacrylic anhydride and 3 parts of p-toluenesulfonic acid hydrate were added, and 100 parts were added. It was heated at ° C. for 4 hours. Then, 19 parts of sodium hydroxide and 300 parts of water were added, and the mixture was heated at 60 ° C. for 8 hours. After cooling, the mixture was separated, filtered, and dried under reduced pressure to obtain 489 parts (yield: 88%) of a polymerizable compound containing the compound represented by the following formula (1-2) as a main component. The HPLC purity of the obtained polymerizable compound 4 was 83%. The measurement result (chemical shift) of ¹ H-NMR of the obtained polymerizable compound 4 (compound represented by the formula (1-2)) is shown below.
^{1 1} H-NMR (DMSO-d6,400 MHz): δ = 1.35-1.44 (4H, m), 1.60-1.71 (4H, m), 1.88 (3H, s), 4 .10 (2H, t, J = 6.6Hz), 4.16 (2H, t, J = 6.3Hz), 5.66 (1H, m), 6.01 (1H, m), 6.95 (2H, s), 8.94 (3H, s, br)

(Example 5)
After suspending 68 parts of the compound represented by the following formula (2-3) in 300 parts of 1,4-dioxane, 56 parts of methacrylic anhydride and 3 parts of p-toluenesulfonic acid hydrate are added, and 100 parts are added. It was heated at ° C. for 4 hours. Then, 19 parts of sodium hydroxide and 300 parts of water were added, and the mixture was heated at 60 ° C. for 8 hours. After cooling, the mixture was separated, filtered, and dried under reduced pressure to obtain 584 parts (yield: 95%) of a polymerizable compound containing the compound represented by the following formula (1-3) as a main component. The HPLC purity of the obtained polymerizable compound 5 was 83%. The measurement result (chemical shift) of ¹ H-NMR of the obtained polymerizable compound 5 (compound represented by the formula (1-3)) is shown below.
^{1 1} H-NMR (DMSO-d 6,400 MHz): δ = 1.75 (4H, m), 1.88 (3H, s), 4.16 (2H, t, J = 5.9Hz), 4.22 (2H, t, J = 5.9Hz), 5.67 (1H, m), 6.03 (1H, m), 6.81 (1H, d, J = 8.3Hz), 7.31 (1H) , Dd, J = 2.0, 8.3Hz), 7.36 (1H, d, J = 2.0Hz), 9.58 (3H, s, br)

(Example 6)
Similar to Example 2 described above, the main component is the compound represented by the following formula (1-4), except that 7 parts of the acrylate product is used instead of 8 parts of the methacrylic acid chloride. 14 parts (yield: 92%) of the polymerizable compound was obtained. The HPLC purity of the obtained polymerizable compound 6 was 97%. The measurement result (chemical shift) of ¹ H-NMR of the obtained polymerizable compound 6 (compound represented by the formula (1-4)) is shown below.
^{1 1} H-NMR (DMSO-d 6,400 MHz): δ = 1.75 (4H, m), 4.19 (4H, m), 5.55 (3H, s, br), 5.94 (1H, dd) , J = 10.2, 1.8Hz), 6.18 (1H, dd, J = 17.4, 10.2Hz), 6.34 (1H, dd, J = 17.4, 1.8Hz), 6.96 (2H, s)

(Comparative Examples 1 and 2)
Commercially available compounds represented by the following formulas (A) and (B) were designated as polymerizable compounds 13 and 14 (Comparative Examples 1 and 2), respectively.

(Examples 7 and 8, Comparative Example 3)
An appropriate amount of the intermediate compound represented by the formula (2-1) was added to the polymerizable compound 3 (HPLC purity: 98%) obtained in Example 3 to dilute the polymerizable compound 3, and the HPLC purity was 60%, 40. % And 30% of polymerizable compounds 7, 8 and 15 were obtained.

(Example 9)
After suspending 21 parts of the compound represented by the following formula (2-4) in 500 parts of 1,4-dioxane, 40 parts of methacrylic anhydride and 1 part of p-toluenesulfonic acid hydrate are added, and 100 parts are added. It was heated at ° C. for 16 hours. Then, 18 parts of sodium hydroxide and 334 parts of water were added, and the mixture was heated at 60 ° C. for 3 hours. After drying under reduced pressure, liquid separation, and filtration, the mixture was dried under reduced pressure again to obtain 917 parts (yield: 62%) of a polymerizable compound containing the compound represented by the following formula (1-5) as a main component. .. The HPLC purity of the obtained polymerizable compound 9 was 64%.

(Example 10)
Twelve parts of the polymerizable compound 9 (HPLC purity: 64%) obtained in Example 9 was purified by column chromatography, dried under reduced pressure, and containing the compound represented by the above formula (1-5) as a main component. 10 5 parts of the polymerizable compound to be used was obtained. The HPLC purity of the obtained polymerizable compound 10 was 92%. The measurement result (chemical shift) of ¹ H-NMR of the obtained polymerizable compound 10 (compound represented by the formula (1-5)) is shown below.
^{1 1} H-NMR (DMSO-d 6,400 MHz): δ = 1.88 (3H, s), 4.38-4.44 (2H, m), 5.70 (1H, m), 6.04 (1H) , M), 6.95 (2H, s), 9.24 (3H, s, br)

(Example 11)
After suspending 74 parts of the compound represented by the following formula (2-5) in 90 parts of 1,4-dioxane, 48 parts of methacrylic anhydride and 2 parts of p-toluenesulfonic acid hydrate were added, and 95 parts were added. It was heated at ° C. for 5 hours. Then, 15 parts of sodium hydroxide and 135 parts of water were added, and the mixture was heated at 75 ° C. for 2 hours. The mixture was separated, filtered, and dried under reduced pressure to obtain 33 parts (yield: 40%) of a polymerizable compound containing the compound represented by the following formula (1-6) as a main component. The HPLC purity of the obtained polymerizable compound 11 was 83%. The measurement result (chemical shift) of ¹ H-NMR of the obtained polymerizable compound 11 (compound represented by the formula (1-6)) is shown below.
^{1 1} H-NMR (DMSO-d6,400 MHz): δ = 1.28 (12H, m), 1.62 (4H, m), 1.88 (3H, m), 4.08 (2H, t, J) = 6.8Hz), 4.15 (2H, t, J = 6.8Hz), 5.66 (1H, m), 6.01 (1H, m), 6.95 (2H, s)

(Example 12)
After suspending 73 parts of the compound represented by the following formula (2-6) in 120 parts of 1,4-dioxane, 69 parts of methacrylic anhydride and 3 parts of p-toluenesulfonic acid hydrate were added, and 95 parts were added. It was heated at ° C. for 4 hours. Then, 15 parts of sodium hydroxide and 135 parts of water were added, and the mixture was heated at 75 ° C. for 2 hours. After drying under reduced pressure, the mixture was purified by liquid phase chromatography and dried again under reduced pressure to obtain 1250 parts (yield: 53%) of a polymerizable compound containing the compound represented by the following formula (1-7) as a main component. Obtained. The HPLC purity of the obtained polymerizable compound 12 was 95%. The measurement result (chemical shift) of ¹ H-NMR of the obtained polymerizable compound 12 (compound represented by the formula (1-7)) is shown below.
^{1 1} H-NMR (DMSO-d6,400MHz): δ = 1.78 (4H, m), 1.88 (3H, s), 4.16 (2H, t, J = 6.0Hz), 4.31 (2H, t, J = 6.0Hz), 5.67 (1H, m), 6.03 (1H, m), 6.35 (1H, d, J = 8.8Hz), 7.14 (1H) , D, J = 8.8Hz), 10.05 (3H, m, br)

The obtained polymerizable compounds are collectively shown in Tables 1-1 and 1-2.

<Manufacturing of composition for forming adhesive / adhesive layer (1)>
(Example 13)
UV curable urethane acrylate (UV-3700B) (trade name "Shikou UV-3700B", manufactured by Mitsubishi Chemical Co., Ltd.) 50 parts, polymerization initiator (diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (TPO)) 5 A composition (paint) for forming an adhesive / adhesive layer was obtained by mixing 49 parts of an acrylic monomer (tetrahydrofurfuryl acrylate (THFA)) and 1 part of a polymerizable compound.

(Examples 14 to 24, Comparative Examples 4 to 6, Reference Example 1)
A composition (paint) for forming an adhesive / adhesive layer was obtained in the same manner as in Example 13 described above, except that the formulations shown in Table 2 were used.

<Evaluation of composition for forming adhesive / adhesive layer (1)>
(OCR evaluation (evaluation of adhesive strength))
The produced paint was applied to the easily adhesive surface of the polyethylene terephthalate (PET) film to form a coating layer. It was placed and laminated on a PET film, an aluminum plate, and a coating layer on which glass was formed, respectively. After UV irradiation was applied to cure the coating layer, a strip-shaped test piece was obtained by cutting to obtain a strip-shaped test piece, and the peel strength was measured after being left for 3 days. The peel strength of the test pieces obtained by using the paint of Reference Example 1 was set to "100 (%)", and the adhesive strength of each test piece was relatively evaluated. The evaluation criteria are shown below. The evaluation results are shown in Table 3.
⊚: 150% or more ○: 100% or more and less than 150% Δ: 50% or more and less than 100% ×: less than 50%

(OCA evaluation (evaluation of adhesive strength))
The produced paint was applied to the easily adhesive surface of the polyethylene terephthalate (PET) film to form a coating layer. After placing and laminating on the coating layer on which the silicone-treated PET film was formed, UV irradiation was performed to cure the coating layer. After one day, the silicone-treated PET film was peeled off and removed, and then the PET film, the aluminum plate, and the glass were placed on the exposed cured layer (adhesive layer) and pressure-bonded. A strip-shaped test piece was obtained by cutting, and the peel strength was measured after being left for 1 day. The peel strength of the test pieces obtained by using the paint of Reference Example 1 was set to "100 (%)", and the adhesive strength of each test piece was relatively evaluated. The evaluation criteria are shown below. The evaluation results are shown in Table 3.
⊚: 150% or more ○: 100% or more and less than 150% Δ: 50% or more and less than 100% ×: less than 50%

<Manufacturing of composition for forming adhesive / adhesive layer (2)>
(Example 25)
UV curable urethane acrylate (UT-5181) (trade name "Shikou UT-5181", manufactured by Mitsubishi Chemical Co., Ltd.) 125 parts, dipentaerythritol hexaacrylate (DPHA) 50 parts, polymerizable compound 35 parts, polymerization initiator ( 5 parts of TPO) and 35 parts of propylene glycol monoethyl ether (PGME) were mixed to obtain a composition (paint) for forming an adhesive / adhesive layer.

(Examples 26 and 27, Comparative Example 7)
A composition (paint) for forming an adhesive / adhesive layer was obtained in the same manner as in Example 25 described above, except that the formulations shown in Table 4 were used.

<Evaluation of composition for forming adhesive / adhesive layer (2)>
(Evaluation of adhesion)
The produced paint was applied onto a substrate (aluminum plate and glass) using a bar coater # 7, and then dried at 105 ° C. for 1 minute to form a coating film. Then, using an 80 W high-pressure mercury lamp, UV irradiation was performed under the condition of 5 m / min × 3 pass to cure the coating film, and a test piece was obtained. After allowing the obtained test piece to stand at room temperature for 24 hours, JIS K5600-5-6: 1999 "General paint test method-Part 5: Mechanical properties of the coating film-Section 6: Adhesion (cross-cut method) ) ”Was conducted an adhesion test. Specifically, the coating film cured using a cutter knife is cross-cut (25 squares) in a 2 x 2 mm grid pattern, and then a 24 mm wide cellophane tape (manufactured by Nichiban Co., Ltd.) is attached for 2 minutes. Pressed and crimped. Next, a peeling test in which the cellophane tape was peeled off from the substrate at an angle of 45 ° was tried five times, and the adhesion was evaluated according to the evaluation criteria shown below. The results are shown in Table 5. In Table 5, for example, in the case of "number of trials" 5 "" and "classification" 0 "", the classification was "0" when the peeling test was tried "5" times at the same location. means. Further, for example, in the case of "number of trials" 1 "" and "classification" 5 "", it means that the classification was "5" in the "1" th peeling test.
"Category 0": No grid can be peeled off.
"Category 1": There is a small peeling of the coating film at the intersection of the cuts, but it is less than 5%.
"Category 2": The coating film is peeled off at an intersection along the line of the cut, and is 5% or more and less than 15%.
"Category 3": The coating film is partially and completely peeled off along the cut line, and is 15% or more and less than 35%.
"Category 4": The coating film is partially and completely peeled off along the cut line, and is 35% or more and less than 65%.
"Category 5": "Category 4" or higher.

The polymerizable compound of the present invention is useful as a material for preparing an adhesive / adhesive layer forming composition capable of forming an adhesive layer having excellent adhesiveness and adhesiveness on various substrates with good adhesiveness. Is.

Claims (10)

A polymerizable compound represented by the following general formula (1) and having a purity measured by HPLC of 35% or more.

(In the general formula (1), R ₁ to R ₄ independently represent a hydrogen atom or a hydroxyl group, and one or more of R ₁ to R ₄ is a hydroxyl group. R ₅ is -O- or-. Indicates NH-, R ₆ indicates an alkylene group having 2 or more carbon atoms which may contain an ether bond, and R ₇ indicates a hydrogen atom or a methyl group). The polymerizable compound according to claim 1, wherein the purity measured by HPLC is 60% or more. The polymerizable compound according to claim 1 or 2, wherein in the general formula (1), two or more of _R1 to _R4 are hydroxyl groups. The polymerizable compound according to any one of claims 1 to ₃ , wherein R5 is —O— in the general formula (1). The polymerizable compound according to any one of claims 1 to 4, wherein R ₆ is an alkylene group having 2 to 6 carbon atoms in the general formula (1). The method for producing a polymerizable compound according to any one of claims 1 to 5.
A method for producing a polymerizable compound, which comprises a step of reacting a compound represented by the following general formula (2) with a (meth) acrylic acid anhydride or a (meth) acrylic acid halide to obtain a reactant.

(In the general formula (2), R ₁ to R ₄ independently represent a hydrogen atom or a hydroxyl group, and one or more of R ₁ to R ₄ is a hydroxyl group. R ₅ is -O- or-. Indicates NH-, where R6 indicates an alkylene group having ₂ or more carbon atoms which may contain an ether bond). The method for producing a polymerizable compound according to claim 6, further comprising a step of treating the reaction product under basic conditions. A composition for forming an adhesive / adhesive layer containing the polymerizable compound according to any one of claims 1 to 5. The composition for forming an adhesive / adhesive layer according to claim 8, further comprising a polymerization initiator. An adhesive / adhesive polymer having a structural unit derived from the polymerizable compound according to any one of claims 1 to 5.