JP2023152826A - Method for producing polymerizable compound - Google Patents

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

The present invention relates to a method for producing a polymerizable compound for forming an adhesive/adhesive layer.

BACKGROUND ART In recent years, polymers exhibiting various functions have been proposed, which use derivatives of compounds having a catechol skeleton, such as dopa and dopamine, or 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, we also produce adhesive/adhesive layer-forming compositions and photocurable adhesive polymers containing pyrogallol derivatives having methacryloyl groups that can form adhesive layers with good adhesion on various substrates. A coating composition has been proposed (Patent Document 2). It is thought that adhesive/adhesive layer-forming compositions and adhesive/adhesive polymers having a catechol skeleton or pyrogallol skeleton exhibit strong adhesion due to the orientation of the hydroxyl groups directly bonded to the aromatic ring to the substrate.

International Publication No. 2019/221135 Japanese Patent Application Publication No. 2009-203408

A derivative of pyrogallol 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, in the case of this synthesis method, it was necessary to heat for a long time to react the pyrogallol derivative and the (meth)acrylic acid derivative. Further, as a result of investigation, it was found that when an organic metal such as dibutyltin dilaurate is used as a reaction promoter (catalyst), many by-products are likely to be produced.

The present invention has been made in view of the problems of the prior art, and its object is to provide adhesiveness or tackiness, or to further enhance adhesiveness or tackiness, and to improve adhesiveness. Efficient production of polymerizable compounds capable of preparing adhesive/adhesive layer-forming compositions and adhesive/adhesive polymers that can form adhesive layers with excellent properties and adhesive properties on various substrates The purpose is to provide a method.

That is, according to the present invention, the following method for producing a polymerizable compound for forming an adhesive/adhesive layer is provided.
[1] A step of obtaining a reactant by 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. A method for producing a polymerizable compound for forming an adhesive/adhesive layer.

（前記一般式（１）中、ｎは１～５の数を示し、Ｒ_１は－Ｏ－又は－ＮＨ－を示し、Ｒ_２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 (1), n represents a number from 1 to 5, R ₁ represents -O- or -NH-, and R ₂ represents an alkylene group having 2 or more carbon atoms that may contain an ether bond. )

[2] The method for producing a polymerizable compound according to the above [1], wherein in the general formula (1), n is 2 to 5.
[3] The method for producing a polymerizable compound according to the above [1] or [2], wherein in the general formula (1), R ₁ is -O-.
[4] The method for producing a polymerizable compound according to any one of [1] to [3] above, wherein R ₂ in the general formula (1) 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).

（前記一般式（Ｉ）中、Ｒ_３はエーテル結合を含んでいてもよい炭素数２以上の直鎖状アルキレン基、又は（メタ）アクリル基を有していてもよい炭素数２以上の分岐状アルキレン基を示し、Ｒ_４は水素原子又はメチル基を示す）

(In the general formula (I), R ₃ is a linear alkylene group having 2 or more carbon atoms which may contain an ether bond, or a branched chain having 2 or more carbon atoms which may have a (meth)acrylic group. ( _R4 represents a hydrogen atom or a methyl group)

[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 halide, sulfonic acid, and carboxylic acid.
[8] The polymerizable compound according to any one of [5] to [7] above, which yields the reactant in which the content of the compound represented by the following general formula (4) measured by HPLC is 20% or less. manufacturing method.

（前記一般式（４）中、Ｒ_１１～Ｒ_１５は、それぞれ独立に、水素原子、水酸基、又は下記一般式（５）で表される基を示し、Ｒ_１１～Ｒ_１５のうちの１以上が下記一般式（５）で表される基である。Ｒ_１は－Ｏ－又は－ＮＨ－を示し、Ｒ_２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_３は、エーテル結合を含んでいてもよい炭素数２以上の直鎖状アルキレン基、又は（メタ）アクリル基を有していてもよい炭素数２以上の分岐状アルキレン基を示し、Ｒ_４は水素原子又はメチル基を示す）

(In the general formula (4), R ₁₁ to R ₁₅ each independently represent a hydrogen atom, a hydroxyl group, or a group represented by the following general formula (5), and one or more of R ₁₁ to R ₁₅ is a group represented by the following general formula (5). R ₁ represents -O- or -NH-, R ₂ represents an alkylene group having 2 or more carbon atoms that may contain an ether bond, R ₃ represents a linear alkylene group having 2 or more carbon atoms which may include an ether bond, or a branched alkylene group having 2 or more carbon atoms which may have a (meth)acrylic group, and R ₄ indicates a hydrogen atom or a methyl group)

（前記一般式（５）中、＊はベンゼン環との結合位置を示し、Ｒ_３はエーテル結合を含んでいてもよい炭素数２以上の直鎖状アルキレン基、又は（メタ）アクリル基を有していてもよい炭素数２以上の分岐状アルキレン基を示し、Ｒ_４は水素原子又はメチル基を示す）

(In the above general formula (5), * indicates the bonding position with the benzene ring, and R ₃ has a linear alkylene group having 2 or more carbon atoms that may contain an ether bond, or a (meth)acrylic group. ( _R4 represents a hydrogen atom or a methyl group)

According to the present invention, adhesives and adhesives that can impart adhesiveness and tackiness, or further enhance adhesiveness and tackiness, and form an adhesive layer, etc. with excellent adhesiveness and tackiness, on various base materials. It is possible to provide an efficient method for producing a polymerizable compound that can prepare a layer-forming composition and an adhesive/adhesive polymer.

<Method for producing polymerizable compound>
Embodiments of the present invention will be described below, but the present invention is not limited to the following embodiments. The present inventors investigated the reactivity of the compound represented by the general formula (1) with an isocyanate compound having a reactive double bond (hereinafter also simply referred to as "isocyanate compound"), and the product obtained by the reaction. We investigated the adhesion and tackiness of polymers and compositions produced using these materials. As a result, when an organic metal such as dibutyltin dilaurate is used as a catalyst during the reaction between the compound represented by the general formula (1) and an isocyanate compound, the urethanization reaction is accelerated, but the isocyanate compound also reacts with phenolic hydroxyl groups. It has been found that the purity of the desired polymerizable compound decreases.

The present inventors have investigated various conditions under which a polymerizable compound with higher purity can be produced by preferentially reacting an isocyanate compound with the aliphatic hydroxyl group (-R ₂ --OH) in general formula (1). As a result, it was discovered that it is effective to react the compound represented by the general formula (1) with an isocyanate compound in the presence of an acid catalyst capable of generating active hydrogen, leading to the present invention. That is, one embodiment of the present invention involves 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. This is a method for producing a polymerizable compound for forming an adhesive/adhesive layer, which includes a step of obtaining a reactant (hereinafter also referred to as "step (1)").

（前記一般式（１）中、ｎは１～５の数を示し、Ｒ_１は－Ｏ－又は－ＮＨ－を示し、Ｒ_２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 (1), n represents a number from 1 to 5, R ₁ represents -O- or -NH-, and R ₂ represents an alkylene group having 2 or more carbon atoms that may contain an ether bond. )

(Step (1))
In step (1), a reactant is obtained by reacting a compound represented by general formula (1) with an isocyanate compound having a reactive double bond. The compound represented by the 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), R ₁ is preferably -O- (ether bond). In general formula (1), R ₂ is preferably an alkylene group having 2 to 12 carbon atoms from the viewpoint of increasing the proportion of the compound represented by general formula (2) in the resulting polymerizable compound. , 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. On the other hand, in general formula (1), R ₂ is preferably an alkylene group having 2 to 12 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms, from the viewpoint of production. The number of carbon atoms is particularly preferably 3 to 6, and the number of carbon atoms is most preferably 4 to 6. By using a compound with such a structure as a raw material compound, adhesive/adhesive layer forming compositions and adhesive/adhesive polymers that can form adhesive layers with superior adhesiveness and adhesive properties on various substrates can be created. It is possible to produce a polymerizable compound that can provide

As the compound represented by general formula (1), a commercially available product or a synthetic product may be used. The compound represented by the general formula (1) is, for example, a compound represented by the following general formula (3) (hydroxybenzoic acids) and a compound represented by the following general formula (II), as shown in the reaction formula below. It can be prepared by reacting with. Note that R ₁ and R ₂ in the following general formula (II) have the same meanings as R ₁ and R ₂ in the general formula (1). Further, as the catalyst, acid catalysts such as para-toluenesulfonic acid, para-toluenesulfonic anhydride, sulfuric acid, hydrochloric acid, and phosphoric acid can be used.

An isocyanate compound is a compound having a reactive (polymerizable) double bond and an isocyanate group (-NCO group) in one molecule. Higher purity polymerizability is achieved by preferentially reacting the isocyanate group (-NCO group) of the isocyanate compound with the aliphatic hydroxyl group (-R ² -OH) in general formula (1) to form a urethane bond. compound can be obtained.

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

（前記一般式（Ｉ）中、Ｒ_３はエーテル結合を含んでいてもよい炭素数２以上の直鎖状アルキレン基、又は（メタ）アクリル基を有していてもよい炭素数２以上の分岐状アルキレン基を示し、Ｒ_４は水素原子又はメチル基を示す）

(In the general formula (I), R ₃ is a linear alkylene group having 2 or more carbon atoms which may contain an ether bond, or a branched chain having 2 or more carbon atoms which may have a (meth)acrylic group. ( _R4 represents a hydrogen atom or a methyl group)

In general formula (I), R ₃ is preferably an alkylene group having 2 to 12 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an alkylene group having 2 to 6 carbon atoms. is particularly preferred, and most preferably an alkylene group having 2 carbon atoms.

In step (1), the compound represented by general formula (1) and an isocyanate compound are reacted in the presence of an acid catalyst (hereinafter also simply referred to as "acid catalyst") capable of generating active hydrogen. By using the above acid catalyst instead of conventional organometallic catalysts (organotin compounds, organobismuth compounds, etc.) used when forming urethane bonds by reacting hydroxyl groups and isocyanate groups, isocyanate compounds and phenolic The reaction between the isocyanate compound and the aliphatic hydroxyl group can proceed preferentially (selectively) rather than the reaction with the hydroxyl group. Thereby, the production of by-products represented by the following general formula (4) can be suppressed, and a higher purity polymerizable compound can be efficiently produced. Specifically, a reactant can be obtained in which the content of the compound represented by the following general formula (4) measured by HPLC is 20% or less.

（前記一般式（４）中、Ｒ_１１～Ｒ_１５は、それぞれ独立に、水素原子、水酸基、又は下記一般式（５）で表される基を示し、Ｒ_１１～Ｒ_１５のうちの１以上が下記一般式（５）で表される基である。Ｒ_１は－Ｏ－又は－ＮＨ－を示し、Ｒ_２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_３は、エーテル結合を含んでいてもよい炭素数２以上の直鎖状アルキレン基、又は（メタ）アクリル基を有していてもよい炭素数２以上の分岐状アルキレン基を示し、Ｒ_４は水素原子又はメチル基を示す）

(In the general formula (4), R ₁₁ to R ₁₅ each independently represent a hydrogen atom, a hydroxyl group, or a group represented by the following general formula (5), and one or more of R ₁₁ to R ₁₅ is a group represented by the following general formula (5). R ₁ represents -O- or -NH-, R ₂ represents an alkylene group having 2 or more carbon atoms that may contain an ether bond, R ₃ represents a linear alkylene group having 2 or more carbon atoms which may include an ether bond, or a branched alkylene group having 2 or more carbon atoms which may have a (meth)acrylic group, and R ₄ indicates a hydrogen atom or a methyl group)

（前記一般式（５）中、＊はベンゼン環との結合位置を示し、Ｒ_３はエーテル結合を含んでいてもよい炭素数２以上の直鎖状アルキレン基、又は（メタ）アクリル基を有していてもよい炭素数２以上の分岐状アルキレン基を示し、Ｒ_４は水素原子又はメチル基を示す）

(In the above general formula (5), * indicates the bonding position with the benzene ring, and R ₃ has a linear alkylene group having 2 or more carbon atoms that may contain an ether bond, or a (meth)acrylic group. ( _R4 represents a hydrogen atom or a methyl group)

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

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

Examples of the acid catalyst include hydrogen halides, inorganic acids such as phosphoric acid, sulfuric acid, and nitric acid, sulfonic acids, and organic acids such as 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 a 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 compounds that can generate hydrogen halide in the reaction system include acetyl chloride, acetyl bromide, acetyl iodide, dimethylcarbamoyl chloride, acrylic chloride, and methacrylic chloride. Note that 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 carboxylic acids include benzoic acid (pKa = 4.2), gallic acid (pKa = 4.5), formic acid, acetic acid (pKa = 4.8), butyric acid, lauric acid, palmitic acid, and stearic acid. I can do it. These acid catalysts may be used alone or in combination of two or more.

The amount of the acid catalyst to be used may be appropriately set depending on the amount of the compound represented by the general 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%, preferably 1 to 5 mol%, based on the amount of the compound represented by general formula (1). More preferred.

An example of a reaction formula for obtaining a reactant by reacting a compound represented by general formula (1) with an isocyanate compound in the presence of an acid catalyst is shown below.

In the above reaction formula, the compound represented by general formula (2) is an example of a polymerizable compound for forming an adhesive/adhesive layer. n, R ₁ and R ₂ in general formula (2) have the same meanings as n, R ₁ and R ₂ in general formula (1). That is, in general formula (2), n is preferably 2 to 5, more preferably 3. In general formula (2), R ₁ is preferably -O- (ether bond). In general formula (2), R ₂ is preferably an alkylene group having 2 to 12 carbon atoms from the viewpoint of increasing the proportion of the compound represented by general formula (2) in the resulting polymerizable compound. , 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. On the other hand, in general formula (2), R ₂ is preferably an alkylene group having 2 to 12 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms, from the viewpoint of production. The number of carbon atoms is particularly preferably 3 to 6, and the number of carbon atoms is most preferably 4 to 6.

Further, R ₃ and R ₄ in general formula (2) have the same meanings as R ₃ and R ₄ in general formula (I). That is, in the general formula (2), R ₃ is a linear alkylene group having 2 or more carbon atoms which may contain an ether bond, or a branched chain having 2 or more carbon atoms which may have a (meth)acrylic group. is an alkylene 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, Most preferably, it is an alkylene group having 2 carbon atoms.

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

In step (2), for example, an alcohol such as ethanol or propanol is added to and mixed with the reaction product obtained in step (1). 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 desired polymerizable compound can be obtained by separation, purification, etc. according to conventional methods.

<Polymerizable compound>
The polymerizable compound produced by the above production method is, for example, a compound represented by the following general formula (2). Adhesive/adhesive layer-forming compositions and adhesive/adhesive layer-forming compositions that can form adhesive layers with superior adhesion and tackiness on various substrates by having a structure represented by the following general formula (2). Polymers can be produced.

（前記一般式（２）中、ｎは１～５の数を示し、Ｒ_１は－Ｏ－又は－ＮＨ－を示し、Ｒ_２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_３は、エーテル結合を含んでいてもよい炭素数２以上の直鎖状アルキレン基、又は（メタ）アクリル基を有していてもよい炭素数２以上の分岐状アルキレン基を示し、Ｒ_４は水素原子又はメチル基を示す）

(In the general formula (2), n represents a number from 1 to 5, R ₁ represents -O- or -NH-, and R ₂ represents an alkylene group having 2 or more carbon atoms that 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 have a (meth)acrylic group. , R ₄ represents a hydrogen atom or a methyl group)

The polymerizable compound preferably has a purity measured by HPLC (high performance liquid chromatography) of 25% or more, more preferably 50% or more, more preferably 70% or more, and 80% or more. It is especially preferable that it is, and it is most preferable that it is 90% or more. By using such a highly purified polymerizable compound, it is possible to prepare a composition for forming an adhesive/adhesive layer, etc., which can form an adhesive layer, etc. with excellent adhesiveness and tackiness.

The purity of the polymerizable compound is measured by HPLC. The purity of a polymerizable compound is determined by the area of the absorption peak corresponding to the polymerizable compound in the total peak area of a chromatogram that records changes in the absorption intensity of light with a wavelength of 294 nm (ultraviolet (UV)), measured by HPLC. It is expressed as a percentage. The total peak area of a chromatogram means the sum of the areas of absorption peaks derived from each component separated by HPLC. However, absorption peaks derived from the dilution solvent of the polymerizable compound and air bubbles; absorption peaks derived 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; area ratio 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. 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% acetic acid aqueous solution (1:19→17:3 (v/v), gradient over 40 minutes)
Flow rate: 0.2mL/min
Column: L-column2 ODS. 2 μm (3.0 x 100 mm) (manufactured by Chemical Evaluation Research Institute)
Column temperature: 40℃
Sample: 2.0 μL of approximately 100 ppm THF solution
Detection wavelength: 294nm

<Composition for forming adhesive/adhesive layer>
By using the above-mentioned polymerizable compound, a composition for forming an adhesive/adhesive layer can be manufactured. That is, the composition for forming an adhesive/adhesive layer contains the above-mentioned polymerizable compound, and can form an adhesive layer/adhesive layer with excellent adhesiveness and tackiness on various substrates.

The content of the polymerizable compound in the composition for forming an adhesive/adhesive layer may be appropriately set depending on 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, based on the solid content in the composition for forming an adhesive/adhesive layer. It is preferably 0.5 to 20% by weight, particularly preferably 0.5 to 10% by weight.

The adhesive/adhesive layer forming composition 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. Polymerizable monomers and resins include urethane (meth)acrylate, dipentaerythritol hexa(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, diethylene glycol monophenyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2- Examples include hydroxybutyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. These polymerizable monomers and resins may be used alone or in combination of two or more.

It is preferable that the composition for forming an adhesive/adhesive layer further contains a polymerization initiator. As the polymerization initiator, a photopolymerization initiator or a thermal polymerization initiator can be used. As a photopolymerization initiator, acylphosphine oxides such as diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide; 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy Acetophenones such as -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; Others Examples include halogenated ketones and acylphosphanates.

As the thermal polymerization initiator, an azo compound, an organic peroxide, etc. can be used. Examples of the azo compound include azobisisobutyronitrile, 1,1'-azobis(cyclohexanecarbonitrile), and dimethyl 2,2'-azobis(2-methylpropanoate). Examples of organic peroxides include hydroperoxide compounds, dialkyl peroxide compounds, peroxyester compounds, diacyl peroxide compounds, ketone peroxide compounds, peroxyketal compounds, and peroxydicarbonate compounds. etc. can be mentioned.

By further containing a solvent, the composition for forming an adhesive/adhesive layer can be made into a paint having appropriate coating properties. As the solvent, water and various organic solvents can be used.

The adhesive/adhesive layer forming composition may contain other additives. Other additives include, for example, silane coupling agents, thixotropic agents, antiblocking agents, leveling agents, antifoaming agents, antioxidants, thermoplastic resins, antistatic agents, waxes, thermal stabilizers, flame retardants, Examples include ultraviolet absorbers, antibacterial agents, and deodorants.

An adhesive layer or an adhesive layer can be formed by applying a composition for forming an adhesive/adhesive layer onto a base material and curing the formed coating layer. Examples of methods for applying the composition for forming an adhesive/adhesive layer onto a base material include roll coating, gravure coating, comma coating, knife coating, and die coating.

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

<Adhesive/adhesive polymer>
By using the above-mentioned polymerizable compound, an adhesive/adhesive polymer can be produced. In other words, adhesive/adhesive polymers have structural units derived from the above-mentioned polymerizable compounds, and can be used to form adhesive layers/adhesive layers with excellent adhesiveness and tackiness on various substrates. can.

The content of the structural unit derived from the polymerizable compound in the adhesive/adhesive polymer may be appropriately set depending on the purpose and is not particularly limited. Specifically, the content of the structural unit derived from the polymerizable compound is usually 0.1 to 90% by mass, preferably 0.3 to 50% by mass, based on the entire adhesive/adhesive polymer. More preferably 0.5 to 20% by weight, particularly preferably 0.5 to 10% by weight.

The adhesive/adhesive polymer may have structural units (other structural units) other than the structural unit derived from the polymerizable compound represented by the above-mentioned general formula (1). Other structural units can be formed using conventionally known polymerizable monomers and resins that constitute ordinary adhesive/adhesive polymers.

<Various products>
Products such as adhesive sheets can be formed by using adhesive/adhesive layer forming compositions and adhesive/adhesive polymers. The adhesive sheet includes a sheet-like support and an adhesive layer formed from 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 resin films, laminate films containing resin films, paper, woven fabrics, and nonwoven fabrics. 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 adhesive layer to protect the adhesive layer.

Further, by using the composition for forming an adhesive/adhesive layer or the adhesive/adhesive polymer, various laminates useful as optical films and the like can be formed. In the laminate, a first base material and a second base material are laminated via an adhesive layer or an adhesive layer formed from the aforementioned adhesive/adhesive layer forming composition or adhesive/adhesive polymer. It is something. The first base material and the second base material may be made of the same material or may be made of different materials.

Materials for the base materials (first base material and second base material) include inorganic materials such as glass, hydroxyapatite, titanium oxide, zinc oxide, iron oxide, and indium tin oxide (ITO); aluminum (Al); Metal materials such as 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), 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), molybdenum-aluminum-molybdenum laminate organic materials such as structure (MAM);

Hereinafter, the present invention will be specifically explained based on Examples, but the present invention is not limited to these Examples. Note that "parts" and "%" in Examples and Comparative Examples are based on mass unless otherwise specified.

<Manufacture of polymerizable compound>
(Example 1)
29 parts of a compound represented by the following formula (1-1) was suspended in 60 parts of 1,2-dimethoxyethane, and then heated to 92°C. Add 23 parts of 2-methacryloyloxyethyl isocyanate, 0.6 part of dimethylcarbamoyl chloride (4.6 mol% based on the compound represented by the following formula (1-1)), and 4 parts of 1,2-dimethoxyethane. and heated at 95°C for 270 minutes. Then, 14 parts of ethanol was 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 containing a compound represented by the following formula (2-1) as a main component. The purity of Polymerizable Compound 1 measured by HPLC (HPLC purity) was 84%. Moreover, the content of by-products was 5.8%. The ¹ H-NMR measurement results (chemical shift) of the obtained polymerizable compound 1 (compound represented by formula (2-1)) are shown below. Further, the conditions for measuring purity by HPLC are 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)

[Measurement conditions for purity by HPLC]
Analytical equipment: LCMS system consisting of LC-30AD, SPD-M20A, and LCMS-8050 (manufactured by 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. 2 μm (3.0 x 100 mm) (manufactured by Chemical Evaluation Research Institute)
Column temperature: 40℃
Sample: 2.0 μL of approximately 100 ppm THF solution
Detection wavelength: 294nm

(Example 2)
29 parts of the compound represented by the above formula (1-1) were 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% based on the compound represented by formula (1-1)), and 1,2- 4 parts of dimethoxyethane were added and heated at 95°C for 140 minutes. Then, 14 parts of ethanol was 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 containing the compound represented by formula (2-1) as a main component. The purity of polymerizable compound 2 measured by HPLC (HPLC purity) was 84%. Moreover, the content of by-products was 4.7%.

(Example 3)
29 parts of the compound represented by the above formula (1-1) were suspended in 60 parts of 1,2-dimethoxyethane, and then heated to 85°C. Adding 23 parts of 2-methacryloyloxyethyl isocyanate, 0.2 part of acetic acid (2.8 mol% relative to the compound represented by the above formula (1-1)), and 4 parts of 1,2-dimethoxyethane, Heated at 95°C for 420 minutes. Then, 14 parts of ethanol was 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 containing the compound represented by formula (2-1) as a main component. The purity of polymerizable compound 3 measured by HPLC (HPLC purity) was 79%. Moreover, the content of by-products was 8.0%.

(Example 4)
29 parts of the compound represented by the above formula (1-1) were 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% based on the compound represented by the above formula (1-1)), and 4 parts of 1,2-dimethoxyethane. of the mixture was added and heated at 95° C. for 300 minutes. Then, 14 parts of ethanol was 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 containing the compound represented by formula (2-1) as a main component. The purity of polymerizable compound 4 measured by HPLC (HPLC purity) was 79%. Moreover, the content of by-products was 6.0%.

(Example 5)
29 parts of the compound represented by formula (1-1) above were suspended in 60 parts of 1,2-dimethoxyethane, and then heated to 92°C. Add 23 parts of 2-methacryloyloxyethyl isocyanate, 0.4 part of dimethylcarbamoyl chloride (2.8 mol% based on the compound represented by the following formula (1-1)), and 4 parts of 1,2-dimethoxyethane. and heated at 95°C for 270 minutes. Then, 14 parts of ethanol was added and heated at 85° C. for 90 minutes. After cooling, the mixture was dried under reduced pressure to obtain 564 parts of a polymerizable compound containing the compound represented by formula (2-1) as a main component. The purity of polymerizable compound 5 measured by HPLC (HPLC purity) was 83%. Moreover, the content of by-products was 6.2%.

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

(Comparative example 2)
After suspending 29 parts of the compound represented by the above formula (1-1) in 42 parts of tetrahydrofuran, bismuth tris (2-ethylhexanoate) (trade name "Neostane U-600", manufactured by Nitto Kasei Co., Ltd.) was added. 0.8 parts of 1% toluene solution), 18 parts of 2-methacryloyloxyethyl isocyanate, and 6 parts of tetrahydrofuran were added, and the mixture was heated at 60° C. for 1,380 minutes. After cooling, the mixture was dried under reduced pressure to obtain 55 parts of polymerizable compound 7 containing the compound represented by formula (2-1) as a main component. The purity of polymerizable compound 7 measured by HPLC (HPLC purity) was 41%. Moreover, the content of by-products was 27%.

The obtained polymerizable compounds are summarized in Table 1.

<Production of adhesive/adhesive layer forming composition>
(Manufacturing example 1)
50 parts of UV-curable urethane acrylate (UV-3700B) (trade name "Shikou UV-3700B", manufactured by Mitsubishi Chemical Corporation), 5 parts of polymerization initiator (diphenyl (2,4,6-trimethylbenzoyl)phosphine oxide (TPO)) 1 part, 49 parts of an acrylic monomer (tetrahydrofurfuryl acrylate (THFA)), and 1 part of Polymerizable Compound 1 were mixed to obtain a composition for forming an adhesive/adhesive layer (paint).

(Production example 2, reference example 1)
An adhesive/adhesive layer forming composition (paint) was obtained in the same manner as in Production Example 1 above, except that the formulations shown in Table 2 were used.

<Evaluation of composition for forming adhesive/adhesive layer>
(OCR evaluation (adhesive strength evaluation))
The produced paint was applied to the easily adhesive surface of a polyethylene terephthalate (PET) film to form a coating layer. The PET film, aluminum plate, and glass were placed on the coating layers and laminated. After the coating layer was cured by UV irradiation, it was cut to obtain a strip-shaped test piece, and after being left for one day, the peel strength was measured. The peel strength of the test piece obtained using the paint of Reference Example 1 was set as "100 (%)", and the adhesive strength of each test piece was relatively evaluated. The evaluation criteria are shown below. Furthermore, the evaluation results are shown in Table 3.
◎: 200% or more ○: 100% or more and less than 200% ×: less than 100%

(OCA evaluation (adhesive force evaluation))
The produced paint was applied to the easily adhesive surface of a polyethylene terephthalate (PET) film to form a coating layer. After the silicone-treated PET film was placed on the formed coating layer and laminated, the coating layer was cured by UV irradiation. After one day, the silicone-treated PET film was peeled off and removed, and then the PET film, aluminum plate, and glass were each placed and pressure-bonded on the exposed cured layer (adhesive layer). A strip-shaped test piece was obtained by cutting, and after being left for one day, the peel strength was measured. The peel strength of the test piece obtained using the paint of Reference Example 1 was set as "100 (%)", and the adhesive strength of each test piece was evaluated relatively. The evaluation criteria are shown below. Furthermore, the evaluation results are shown in Table 3.
◎: 200% or more ○: 100% or more and less than 200% ×: Less than 100%

Claims (8)

An adhesion method 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 reactant. A method for producing a polymerizable compound for forming an adhesive layer.

(In the general formula (1), n represents a number from 1 to 5, R ₁ represents -O- or -NH-, and R ₂ represents an alkylene group having 2 or more carbon atoms that may contain an ether bond. ) The method for producing a polymerizable compound according to claim 1, wherein n in the general formula (1) is 2 to 5. The method for producing a polymerizable compound according to claim 1, wherein in the general formula (1), R ₁ is -O-. The method for producing a polymerizable compound according to claim 1, wherein in the general formula (1), R ₂ is an alkylene group having 2 to 10 carbon atoms. 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 general formula (I), R ₃ is a linear alkylene group having 2 or more carbon atoms which may contain an ether bond, or a branched chain having 2 or more carbon atoms which may have a (meth)acrylic group. ( _R4 represents a hydrogen atom or a methyl group) The method for producing a polymerizable compound according to claim 1, wherein the acid catalyst has an acid dissociation constant of less than 5. 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 halides, sulfonic acids, and carboxylic acids. The method for producing a polymerizable compound according to any one of claims 5 to 7, wherein the reactant has a content of the compound represented by the following general formula (4) measured by HPLC of 20% or less.

(In the general formula (4), R ₁₁ to R ₁₅ each independently represent a hydrogen atom, a hydroxyl group, or a group represented by the following general formula (5), and one or more of R ₁₁ to R ₁₅ is a group represented by the following general formula (5). R ₁ represents -O- or -NH-, R ₂ represents an alkylene group having 2 or more carbon atoms that may contain an ether bond, R ₃ represents a linear alkylene group having 2 or more carbon atoms which may include an ether bond, or a branched alkylene group having 2 or more carbon atoms which may have a (meth)acrylic group, and R ₄ indicates a hydrogen atom or a methyl group)

(In the above general formula (5), * indicates the bonding position with the benzene ring, and R ₃ has a linear alkylene group having 2 or more carbon atoms that may contain an ether bond, or a (meth)acrylic group. ( _R4 represents a hydrogen atom or a methyl group)