JP2013249282A - Thioether-containing urea derivative and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thioether-containing urea derivative having an excellent improvement effect on adhesion to an organic substrate and an inorganic substrate.SOLUTION: A thioether-containing urea derivative is represented by formula (1) (wherein m is 1 or 2; Rand Rare each independently a hydrogen atom, 1-6C alkyl or 1-7C acyloxy; Ris a divalent group such as a carbonyl group or the like; Ris hydrogen, a 1-18C hydrocarbon group or 2-5C hydrocarbon group substituted with 1-3C alkoxy).

Description

  The present invention relates to a novel thioether-containing urea derivative suitably used for an adhesion improver or the like.

  Conventionally, when various paints are applied to an inorganic base material such as glass, an adhesion improver such as a silane coupling agent has been added to the paint for the purpose of improving adhesion (for example, Patent Document 1). reference). However, since the silane coupling agent decomposes when heated, when used in a mass production line, silicon oxide is deposited in a heating furnace such as an oven, causing contamination. Also, the silane coupling agent cannot be said to have a sufficient effect of improving adhesion, for example, by simultaneously adding adhesion assistants such as salts such as titanium and zirconium, amines such as imidazole, phosphate esters and urethane resins. In many cases, adhesion could be achieved for the first time. The addition of the adhesion assistant not only leads to an increase in manufacturing steps and costs, but also has a problem that the heat resistance and hardness of the paint are reduced by adding the adhesion assistant.

JP-A-7-300491

  The present invention has been accomplished in view of the above circumstances, and an object of the present invention is to provide a thioether-containing urea derivative that is excellent in adhesion improving effect.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a thioether-containing urea derivative having a specific structure has an excellent adhesion improving effect, and have completed the invention.
That is, the present invention includes the following [1] to [3].

（式中のｍは１または２である。Ｒ^１およびＲ^２はそれぞれ独立して水素原子、炭素数１〜６のアルキル基、または炭素数１〜７のアシロキシ基である。Ｒ^３は下記式（２）または下記式（３）で表される２価の基である。Ｒ^４は水素、または炭素数が１〜１８の炭化水素基、または炭素数１〜３のアルコキシ基により置換された炭素数が２〜５の炭化水素基である。）

（Ｒ^５は水素原子またはメチル基であり、Ｒ^６は−ＣＯ−あるいは−ＣＯＯＲ^７−である（Ｒ^７は炭素数１〜６のアルキレン基である）。）

（Ｒ^５は水素原子またはメチル基であり、Ｒ^６は−ＣＯ−あるいは−ＣＯＯＲ^７−である（Ｒ^７は炭素数１〜６のアルキレン基である）。） [1] A thioether-containing urea derivative represented by the following formula (1)

(Respectively .R ¹ and ^{R 2} are m in the formula is 1 or 2 independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or .R ³ is an acyloxy group having 1 to 7 carbon atoms, the following A divalent group represented by the formula (2) or the following formula (3): R ⁴ is substituted by hydrogen, a hydrocarbon group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. And a hydrocarbon group having 2 to 5 carbon atoms.)

(R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is —CO— or —COOR ⁷ — (R ⁷ is an alkylene group having 1 to 6 carbon atoms).

(R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is —CO— or —COOR ⁷ — (R ⁷ is an alkylene group having 1 to 6 carbon atoms).

（式中のＲ^１およびＲ^２はそれぞれ独立して水素原子、炭素数１〜６のアルキル基、または炭素数１〜７のアシロキシ基である。Ｒ^５は水素原子またはメチル基であり、Ｒ^６は−ＣＯ−あるいは−ＣＯＯＲ^７−である（Ｒ^７は炭素数１〜６のアルキレン基である）。）

（式中のｍは１または２である。Ｒ^４は水素、または炭素数が１〜１８の炭化水素基、または炭素数１〜３のアルコキシ基により置換された炭素数が２〜５の炭化水素基である。） [2] The thioether-containing urea derivative according to claim 1, wherein a (meth) acrylate represented by the following formula (4) and a thiol compound represented by the following formula (5) are reacted. In the present specification, “(meth) acrylate” refers to acrylate and methacrylate, and “(meth) acryloyl group” refers to acryloyl group and methacryloyl group.

(In the formula, R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an acyloxy group having 1 to 7 carbon atoms. R ⁵ is a hydrogen atom or a methyl group; ⁶ is —CO— or —COOR ⁷ — (R ⁷ is an alkylene group having 1 to 6 carbon atoms).

(In the formula, m is 1 or 2. R ⁴ is hydrogen, a hydrocarbon group having 1 to 18 carbon atoms, or a carbon atom having 2 to 5 carbon atoms substituted by an alkoxy group having 1 to 3 carbon atoms. It is a hydrogen group.)

[3] An adhesion improver comprising the thioether-containing urea derivative according to [1] or [2] as an active ingredient.

  The thioether-containing urea derivative of the present invention has an excellent adhesion improving effect and requires the addition of an adhesion assistant by adding a relatively small amount of, for example, 0.1 to 10% by weight to the coating material. It is possible to impart high adhesion to the paint without any problems. The above-mentioned adhesion improving effect is exhibited only when the urea structure and the thioether group coexist in one molecule. Since the urea structure attracts the base material, as a result, the distance between the thioether group and the base material becomes close, and it becomes easier to form a chemical bond between the thioether group and the base material. I believe that

It is a chart which shows IR spectrum of the compound obtained in Example 1-1. It is a chart which shows the IR spectrum of the compound obtained in Example 1-2. It is a chart which shows the IR spectrum of the compound obtained in Example 1-3. It is a chart which shows the IR spectrum of the compound obtained in Example 1-4. It is a chart which shows the IR spectrum of the compound obtained in Example 1-5. It is a chart which shows the nuclear magnetic resonance spectrum of the compound obtained in Example 1-1. It is a chart which shows the nuclear magnetic resonance spectrum of the compound obtained in Example 1-2. It is a chart which shows the nuclear magnetic resonance spectrum of the compound obtained in Example 1-3. It is a chart which shows the nuclear magnetic resonance spectrum of the compound obtained in Example 1-4. It is a chart which shows the nuclear magnetic resonance spectrum of the compound obtained in Example 1-5. It is a side view of the test piece for adhesive evaluation.

（式中のｍは１または２である。Ｒ^１およびＲ^２はそれぞれ独立して水素原子、炭素数１〜６のアルキル基、または炭素数１〜７のアシロキシ基である。Ｒ^３は下記式（２）または下記式（３）で表される２価の基である。Ｒ^４は水素、または炭素数が１〜１８の炭化水素基、または炭素数１〜３のアルコキシ基により置換された炭素数が２〜５の炭化水素基である。）

（Ｒ^５は水素原子またはメチル基であり、Ｒ^６は−ＣＯ−あるいは−ＣＯＯＲ^７−である（Ｒ^７は炭素数１〜６のアルキレン基である）。）

（Ｒ^５は水素原子またはメチル基であり、Ｒ^６は−ＣＯ−あるいは−ＣＯＯＲ^７−である（Ｒ^７は炭素数１〜６のアルキレン基である）。）
式（１）で示されるチオエーテル含有ウレア誘導体の具体例（具体的名称）を挙げてください。その中で特に好ましいものがあれば、その旨と理由を記載してください。 Embodiments that embody the present invention will be described in detail below.
<Thioether-containing urea derivative>
The thioether-containing urea derivative of this embodiment is a compound represented by the following formula (1).

(Respectively .R ¹ and ^{R 2} are m in the formula is 1 or 2 independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or .R ³ is an acyloxy group having 1 to 7 carbon atoms, the following A divalent group represented by the formula (2) or the following formula (3): R ⁴ is substituted by hydrogen, a hydrocarbon group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. And a hydrocarbon group having 2 to 5 carbon atoms.)

(R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is —CO— or —COOR ⁷ — (R ⁷ is an alkylene group having 1 to 6 carbon atoms).

(R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is —CO— or —COOR ⁷ — (R ⁷ is an alkylene group having 1 to 6 carbon atoms).
Give specific examples (specific names) of the thioether-containing urea derivatives represented by formula (1). If any of these are particularly favorable, please indicate the reason and reason.

R ¹ in the above formula (1) is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a linear alkyl group, an alkyl group having a side chain, and a cyclic alkyl group. Examples of the linear alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, and a hexyl group. Examples of the alkyl group having a side chain include an isopropyl group, an isobutyl group, and a tertiary butyl group. Examples of the cyclic alkyl group include a cyclobutyl group and a cyclohexyl group. A hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms is particularly preferable because of its good compatibility with the paint.

R ² in the above formula (1) is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a linear alkyl group, an alkyl group having a side chain, and a cyclic alkyl group. Examples of the linear alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, and a hexyl group. Examples of the alkyl group having a side chain include an isopropyl group, an isobutyl group, and a tertiary butyl group. Examples of the cyclic alkyl group include a cyclobutyl group and a cyclohexyl group. A hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms is particularly preferable because of its good compatibility with the paint.

R ⁷ in the above formulas (2) and (3) is an alkylene group having 1 to 6 carbon atoms. Examples of the alkylene group having 1 to 6 carbon atoms include a linear alkylene group, an alkylene group having a side chain, and a cyclic alkylene group. A linear alkylene group having 1 to 4 carbon atoms is particularly preferred because the effect of improving adhesion is enhanced.

R ⁴ in the above formula (1) is hydrogen, a hydrocarbon group having 1 to 18 carbon atoms, or a hydrocarbon group having 2 to 5 carbon atoms substituted by an alkoxy group having 1 to 3 carbon atoms. . Examples of the hydrocarbon group having 1 to 18 carbon atoms include a linear hydrocarbon group, a hydrocarbon group having a side chain, and a cyclic hydrocarbon group. Linear hydrocarbon groups include hydrocarbon groups consisting only of saturated carbon bonds (straight chain alkyl groups) and hydrocarbon groups having unsaturated carbon bonds. Examples of the hydrocarbon group include a methyl group, a butyl group, an octyl group, and an octadecyl group. Examples of the hydrocarbon group having a linear unsaturated carbon bond include a vinyl group, an allyl group, and a palmitoleyl group. . A hydrocarbon group having a side chain includes a hydrocarbon group having only a saturated carbon bond (an alkyl group having a side chain) and a hydrocarbon group having an unsaturated carbon bond, and a saturated carbon having a side chain. Examples of the hydrocarbon consisting of only a bond include a 2-ethylhexyl group, and examples of the hydrocarbon group having an unsaturated carbon bond having a side chain include an isopropenyl group. Cyclic hydrocarbon groups include hydrocarbon groups consisting only of saturated bonds (cyclic alkyl groups) and hydrocarbon groups having unsaturated bonds. Cyclohexyl groups and cyclopropyl are the hydrocarbon groups consisting only of cyclic saturated bonds. A methyl group etc. are mentioned. Examples of the hydrocarbon group having a cyclic unsaturated bond include a phenyl group and a benzyl group.

  Moreover, as a C1-C4 hydrocarbon group substituted by a C1-C3 alkoxy group, what substituted the hydrocarbon group which consists only of a saturated carbon bond by the alkoxy group, and unsaturated carbon Some of the bonds are substituted with alkoxy groups. As what substituted the hydrocarbon group which consists only of a saturated carbon bond by the alkoxy group, a methoxymethyl group, a propoxymethyl group, a methoxybutyl group, a propoxypentyl group etc. are mentioned. Examples of those in which a hydrocarbon group having an unsaturated carbon bond is substituted with an alkoxy group include a methoxyallyl group and a vinyloxyallyl group. Since the storage stability of the paint containing the thioether-containing urea derivative is improved, the alkyl group having 1 to 18 carbon atoms or the alkyl group having 2 to 5 carbon atoms substituted by an alkoxy group having 1 to 3 carbon atoms Is preferred.

  As the thioether-containing urea derivative represented by the above formula (1), 3- [3- [2- (3,5-dimethylpyrazole-1-carbonyl) amino] ethoxy] -2-methyl-3-oxo-propyl] sulfur Nylpropanoic acid, 2-[(3,5-dimethylpyrazole-1-carbonyl) amino] ethyl 3- (3-methoxy-3-oxy-propylsulfanyl-2-methylpropanoate, 2-[(3 , 5-Dimethylpyrazole-1-carbonyl) amino] ethyl 3- (3- (2-ethylhexoxy) -3-oxy-propylsulfanyl-2-methylpropanoate, 2-[(3,5-dimethylpyrazole-1 -Carbonyl) amino] ethyl 3- (3-octadecoxy-3-oxy-propylsulfanyl-2-methylpropanoate and the like are preferred examples. That.

（式中のＲ^１およびＲ^２はそれぞれ独立して水素原子、炭素数１〜６のアルキル基、または炭素数１〜７のアシロキシ基である。Ｒ^５は水素原子またはメチル基であり、Ｒ^６は−ＣＯ−あるいは−ＣＯＯＲ^７−である（Ｒ^７は炭素数１〜６のアルキレン基である）。）

（式中のｍは１または２である。Ｒ^４は水素、または炭素数が１〜１８の炭化水素基、または炭素数１〜３のアルコキシ基により置換された炭素数が２〜５の炭化水素基である。） <Method for producing thioether-containing urea derivative>
The thioether-containing urea derivative represented by the formula (1) includes, for example, a compound having a (meth) acryloyl group (hereinafter referred to as component A) as represented by the following formula (4), and the following formula (5): It can be obtained by reacting with a thiol compound having a thiol group (—SH) represented (hereinafter referred to as B component).

(In the formula, R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an acyloxy group having 1 to 7 carbon atoms. R ⁵ is a hydrogen atom or a methyl group; ⁶ is —CO— or —COOR ⁷ — (R ⁷ is an alkylene group having 1 to 6 carbon atoms).

(In the formula, m is 1 or 2. R ⁴ is hydrogen, a hydrocarbon group having 1 to 18 carbon atoms, or a carbon atom having 2 to 5 carbon atoms substituted by an alkoxy group having 1 to 3 carbon atoms. It is a hydrogen group.)

R ¹ in the above formula (4) is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a linear alkyl group, an alkyl group having a side chain, and a cyclic alkyl group. Examples of the linear alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, and a hexyl group. Examples of the alkyl group having a side chain include an isopropyl group, an isobutyl group, and a tertiary butyl group. Examples of the cyclic alkyl group include a cyclobutyl group and a cyclohexyl group. A hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms is particularly preferable because the compatibility between the thioether-containing urea derivative obtained after the reaction and the paint is improved.

R ² in the above formula (4) is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a linear alkyl group, an alkyl group having a side chain, and a cyclic alkyl group. Examples of the linear alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, and a hexyl group. Examples of the alkyl group having a side chain include an isopropyl group, an isobutyl group, and a tertiary butyl group. Examples of the cyclic alkyl group include a cyclobutyl group and a cyclohexyl group. A hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms is particularly preferable because the compatibility between the thioether-containing urea derivative obtained after the reaction and the paint is improved.

R ^{7 in the} above formula (4) is an alkylene group having 1 to 6 carbon atoms. Examples of the alkylene group having 1 to 6 carbon atoms include a linear alkylene group, an alkylene group having a side chain, and a cyclic alkylene group. A linear alkylene group having 1 to 4 carbon atoms is particularly preferred since the storage stability of the paint containing the thioether-containing urea derivative obtained after the reaction is improved.

  As the A component represented by the above formula (4), 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate, 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl acrylate, 2- [ Preferable examples include (3,5-dimethylpyrazolyl) carbonylamino] methyl methacrylate, 2- (pyrazolylcarbonylamino) ethyl methacrylate and the like.

R ⁴ in the above formula (5) is hydrogen, a hydrocarbon group having 1 to 18 carbon atoms, or a hydrocarbon group having 2 to 5 carbon atoms substituted by an alkoxy group having 1 to 3 carbon atoms. . Examples of the hydrocarbon group having 1 to 18 carbon atoms include a linear hydrocarbon group, a hydrocarbon group having a side chain, and a cyclic hydrocarbon group. Linear hydrocarbon groups include hydrocarbon groups consisting only of saturated carbon bonds (straight chain alkyl groups) and hydrocarbon groups having unsaturated carbon bonds. Examples of the hydrocarbon group include a methyl group, a butyl group, an octyl group, and an octadecyl group. Examples of the hydrocarbon group having a linear unsaturated carbon bond include a vinyl group, an allyl group, and a palmitoleyl group. . A hydrocarbon group having a side chain includes a hydrocarbon group having only a saturated carbon bond (an alkyl group having a side chain) and a hydrocarbon group having an unsaturated carbon bond, and a saturated carbon having a side chain. Examples of the hydrocarbon consisting of only a bond include a 2-ethylhexyl group, and examples of the hydrocarbon group having an unsaturated carbon bond having a side chain include an isopropenyl group. Cyclic hydrocarbon groups include hydrocarbon groups consisting only of saturated bonds (cyclic alkyl groups) and hydrocarbon groups having unsaturated bonds. Cyclohexyl groups and cyclopropyl are the hydrocarbon groups consisting only of cyclic saturated bonds. A methyl group etc. are mentioned. Examples of the hydrocarbon group having a cyclic unsaturated bond include a phenyl group and a benzyl group.
Moreover, as a C1-C4 hydrocarbon group substituted by a C1-C3 alkoxy group, what substituted the hydrocarbon group which consists only of a saturated carbon bond by the alkoxy group, and unsaturated carbon Some of the bonds are substituted with alkoxy groups. As what substituted the hydrocarbon group which consists only of a saturated carbon bond by the alkoxy group, a methoxymethyl group, a propoxymethyl group, a methoxybutyl group, a propoxypentyl group etc. are mentioned. Examples of those in which a hydrocarbon group having an unsaturated carbon bond is substituted with an alkoxy group include a methoxyallyl group and a vinyloxyallyl group. Since the storage stability of the paint containing the thioether-containing urea derivative obtained after the reaction is improved, the number of carbon atoms substituted by an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 3 carbon atoms is 2 to 2. An alkyl group of 5 is preferred.

  As the thiol compound represented by the above formula (5), for example, those with m = 1 include thioglycolic acid, methylthioglycolic acid, butylthioglycolic acid, octylglycolic acid, octadecylthioglycolic acid, 2-ethylhexylthioglycol Acid, methoxymethylthioglycolic acid, propoxymethylthioglycolic acid, methoxybutylthioglycolic acid, propoxybutylglycolic acid and the like. Examples of m = 2 include mercaptopropionic acid, methyl-3-mercaptopropionate, butyl-3-mercaptopropionate, octyl-3-mercaptopropionate, octadecyl-3-mercaptopropionate, 2- In ethylhexyl-3-mercaptopropionate, methoxymethyl-3-mercaptopropionate, propoxymethyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, propoxybutyl-3-mercaptopropionate, etc. is there. Of the compounds represented by the above formula (5), a thiol compound of m = 2 is preferable because it can easily control the reactivity with a double bond.

  In the method for producing a thioether-containing urea derivative, the reaction can be performed at a temperature of 5 ° C. or higher, but it is more preferable to perform the reaction at 60 to 80 ° C. in order to react in a short time such as within 5 hours. If a base catalyst and a radical generator are added, it can be made to react in a high yield in a shorter time.

  As the basic catalyst, amine-based basic catalysts are preferable, and primary, secondary or tertiary amines, or imidazole compounds can be used. For example, examples of the primary amine include methylamine, ethylamine, propylamine, butylamine, and ethylenediamine. Secondary amines include dimethylamine, diethylamine, dipropylamine, methylethylamine, diphenylamine and the like. Tertiary amines include trimethylamine, triethylamine, tripropylamine, triphenylamine, 1,8-diazabicyclo [5.4.0] undeca-aminomethyl) phenol, and the like. Examples of imidazole compounds include 1-methylimidazole, 1,2-dimethylimidazole, 1,4-dimethyl-2-ethylimidazole, imidazole analogues such as 1-phenylimidazole, 1-methyl-2-oxymethylimidazole, Alkyl derivatives such as 1-methyl-2-oxyethylimidazole, nitro and amino derivatives such as 1-methyl-4 (5) -nitroimidazole, 1,2-dimethyl-5 (4) -aminoimidazole, benzimidazole, Examples thereof include methylbenzimidazole and 1-methyl-benzylbenzimidazole.

  As the radical generator, a peroxide or an azo compound is preferable. Examples of the peroxide include dibenzoyl peroxide, tert-butylperoxy-2-ethylhexanoate, and dilauroyl peroxide. Examples of the azo compound include azobis (iso-butyronitrile) and 2,2′-azobis (2-methylbutanenitrile).

  In the method for producing a thioether-containing urea derivative, the reaction can be allowed to proceed even without a solvent, but when the viscosity is to be lowered, for example, when the reaction is performed at a low temperature, the reaction can be performed by adding a solvent. In that case, the solvent which does not react with the carbon-carbon double bond of a (meth) acryloxy group or a thiol group, for example, alcohols, ketones, and esters is preferable.

  Alcohols used as solvents react with carbon-carbon double bonds and thiol groups, such as carbon-carbon double bonds, thiol groups, epoxy groups, isocyanate groups, carboxyl groups, sulfonyl groups, nitrile groups, and halogen atoms. Must not contain groups. Examples of alcohols that do not contain the above functional group include methanol, ethanol, isopropyl alcohol, tertiary butanol, hexanol, propylene glycol, glycerin, and alkyl ethers and esters of ethylene glycol. Among these, alcohols having a boiling point of 80 ° C. or higher are preferable because the reaction temperature can be kept high.

  Ketones used as solvents react with carbon-carbon double bonds and thiol groups, and function with carbon-carbon double bonds, thiol groups, epoxy groups, isocyanate groups, carboxyl groups, sulfonyl groups, nitrile groups, halogen atoms, etc. Must not contain groups. Examples of the ketones that do not contain the functional group include acetone, methyl ethyl ketone, methyl isobutyl ketone, and methyl isopropyl ketone. Of these, ketones having a boiling point of 80 ° C. or higher are preferable because the reaction temperature can be kept high.

  Esters used as solvents react with carbon-carbon double bonds and thiol groups, such as carbon-carbon double bonds, thiol groups, epoxy groups, isocyanate groups, carboxyl groups, sulfonyl groups, nitrile groups, and halogen atoms. Must not contain groups. Examples of ketones that do not contain the above functional group include ethyl acetate, butyl acetate, ethyl benzoate, and propylene glycol acetate. Of these, esters having a boiling point of 80 ° C. or higher are preferable because the reaction temperature can be kept high.

In the two components, the A component and the B component, the (meth) acryloyl group of the A component and the thiol group of the B component react by the reaction formula represented by the following formula (6). X represents a hydrogen atom or a methyl group, Y represents a residue other than X bonded to the double bond of the (meth) acryloyl group of the A component, and Z represents a residue bonded to the thiol group of the B component.

  As shown in Formula (6), both of the two carbons forming the double bond of the (meth) acryloyl group of the A component are bonded to S of the thiol group. The production ratio of the two products varies depending on the reaction conditions. For example, when a base catalyst such as amine is added to the reaction system as a catalyst for this reaction, a large amount of product (1) is produced, and the radical generator is produced in the reaction system. When added to, a large amount of product (2) tends to be formed. In many cases, the thioether-containing urea derivative after production is a mixture of the products (1) and (2).

<Adhesion improver>
The paint containing the thioether-containing urea derivative of the present invention has high adhesion to both the inorganic base material and the organic material. This adhesion improving effect is attributed to the thioether group of the thioether-containing urea derivative of the present invention. Therefore, substrates that form chemical bonds with thioether groups (high chemical affinity) such as transition metals or their alloys, silicon compounds, phosphorus compounds, sulfur compounds, boron compounds, unsaturated bonds (aromatic rings) Excellent in the effect of improving adhesion to organic substances having a hydroxyl group or a carboxyl group, organic substances having a plasma or UV ozone treatment, and the like. Examples of the inorganic base material include glass, silicon, and various metals. Preferred examples of the organic substrate include polyethylene terephthalate, polybutylene terephthalate, polyethylene, polypropylene, polycarbonate, polyimide, ABS resin, polyvinyl alcohol, vinyl chloride, and polyacetal.

  Adhesion improver with thioether-containing urea derivative as an active ingredient demonstrates high adhesion improvement effect by compounding with compound having double bond such as epoxy resin, urethane resin, acrylic resin, polyimide resin, polyacetylene, etc. can do. The adhesion improver comprising a thioether-containing urea derivative as an active ingredient exhibits high adhesion when added as an active ingredient, preferably 0.1 to 30% by mass, more preferably 0.1 to 10% by mass. Can do.

Examples of the present invention will be specifically described below. The reagents used in this example are as follows. The viscosity at 25 ° C. of each thiol was measured using an R-type viscometer manufactured by Toki Sangyo Co., Ltd.

<Blocked isocyanate: Component A>
(A-1)
2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate. The structure is shown below.

<Thiol compound: Component B>
(B-1)
β-mercaptopropionic acid (viscosity 8.4 mPa · s). The structure is shown in the following formula.

(B-2)
Methyl-3-mercaptopropionate (viscosity 1.5 mPa · s). The structure is shown in the following formula.

(B-3)
2-ethylhexyl-3 mercaptopropionate (viscosity 3.7 mPa · s). The structure is shown in the following formula.

(B-4)
Methoxybutyl-3-mercaptopropionate (viscosity 3.6 mPa · s). The structure is shown in the following formula.

(B-5)
Stearyl-3-mercaptopropionate (room temperature solid). The structure is shown in the following formula.

  A separable four-necked flask was equipped with a stirring blade, a thermometer, and a reflux tube, and the inside was made a nitrogen atmosphere. Into this four-necked flask, the amount of B component shown in Table 1 was squeezed, and the amount of A component shown in Table 1 was dropped at a rate of 0.14 g / min under the condition of 90 ° C. After dripping, it was further reacted at 90 ° C. for 4 hours to obtain Examples 1-1 to 1-5. Table 1 shows the viscosity at 25 ° C. of Examples 1-1 to 1-4 and the viscosity at 40 ° C. of Example 1-5. The viscosity was measured using an R-type viscometer manufactured by Toki Sangyo Co., Ltd.

<Infrared absorption spectrum analysis (IR)>
The obtained Examples 1-1 to 1-5 were subjected to infrared absorption spectrum analysis under the following conditions. The results are shown in FIGS. 1 to 5 and typical IR peaks are shown below.
Model: JASCO Corporation FT / IR-600
Cell: Expanded on KBr, decomposed; 4 cm ⁻¹ , number of integrations: 32

Example 1-1 (Result I1)
^{3352cm -1: 25% T, 2931cm} -1: 26% T, 1730cm -1: 51% T, 1520cm -1: 47% T, 1415cm -1: 29% T, 1377cm -1: 31% T, 1346cm - ¹ : 58% T, 1167 cm ⁻¹ : 36% T, 1030 cm ⁻¹ : 19% T, 970 cm ⁻¹ : 15% T, 800 cm ⁻¹ : 12% T, 756 cm ⁻¹ : 19% T

Example 1-2 (Result I2)
3392 cm ⁻¹ : 17% T, 2952 cm ⁻¹ : 19% T, 1732 cm ⁻¹ : 63% T, 1574 cm ⁻¹ : 16% T, 1518 cm ⁻¹ : 56% T, 1493 cm ⁻¹ : 29% T, 1375 cm ^{− 1} : 28% T, 1346 cm ⁻¹ : 48% T, 1167 cm ⁻¹ : 39% T, 1030 cm ⁻¹ : 20% T, 970 cm ⁻¹ : 19% T, 756 cm ⁻¹ : 14% T

Example 1-3 (Result I3)
3394 cm ⁻¹ : 10% T, 2958 cm ⁻¹ : 27% T, 2931 cm ⁻¹ : 28% T, 1732 cm ⁻¹ : 53% T, 1574 cm ⁻¹ : 10% T, 1518 cm ⁻¹ : 43% T, 1462 cm ^{− 1: 21% T, 1377cm -1} : 21% T, 1346cm -1: 36% T, 1169cm -1: 29% T, 1028cm -1: 15% T, 970cm -1: 14% T, 756cm -1: 8% T

Example 1-4 (Result I4)
3394 cm ⁻¹ : 15% T, 2972 cm ⁻¹ : 36% T, 2931 cm ⁻¹ : 31% T, 2823 cm ⁻¹ : 15% T, 1732 cm ⁻¹ : 76% T, 1574 cm ⁻¹ : 16% T, 1518 cm ^{− 1} : 62% T, 1462 cm ⁻¹ : 32% T, 1375 cm ⁻¹ : 41% T, 1346 cm ⁻¹ : 56% T, 1250 cm ⁻¹ : 42% T, 1159 cm ⁻¹ : 52% T, 1084 cm ⁻¹ : 38% T, 1030 cm ⁻¹ : 27% T, 970 cm ⁻¹ : 23% T, 758 cm ⁻¹ : 11% T

Example 1-5 (Result I5)
3396 cm ⁻¹ : 10% T, 2925 cm ⁻¹ : 44% T, 2854 cm ⁻¹ : 30% T, 1730 cm ⁻¹ : 49% T, 1518 cm ⁻¹ : 43% T, 1464 cm ⁻¹ : 20% T, 1375 cm ^{− 1} : 19% T, 1346 cm ⁻¹ : 35% T, 1167 cm ⁻¹ : 26% T, 1028 cm ⁻¹ : 22% T, 968 cm ⁻¹ : 12% T, 771 cm ⁻¹ : 7% T

As apparent from the results of the infrared absorption spectrum analysis, since a peak of 1600 to 1700 cm ⁻¹ derived from C═C is not observed, A-1 reacts with B-1 to B-5, respectively. I understand that.

<Nuclear magnetic resonance spectrum analysis (NMR)>
Further, Examples 1-1 to 1-5 were subjected to nuclear magnetic resonance spectrum analysis under the following conditions. The results are shown in FIGS. 6 to 10, and the assignment of peaks in each NMR spectrum is shown below.
Model: Nippon Bruker Co., Ltd., 400 MHz-Advanced 400,
Condition: Number of integrations 16 times Solvent: Deuterated chloroform Standard peak: TMS

a：２．１〜２．２ｐｐｍ、ｂ、ｃ、ｄ、e：２．６〜２．９ｐｐｍ、ｆ：１．２〜１．３ｐｐｍ、ｇ：４．１〜４．３ｐｐｍ、ｈ：３．６〜３．８ｐｐｍ、i：８．０〜８．１ｐｐｍ、ｊ、ｌ：２．５〜２．６ｐｐｍ、ｋ：５．９〜６．０ｐｐｍ Example 1-1 (Result N1)

a: 2.1-2.2 ppm, b, c, d, e: 2.6-2.9 ppm, f: 1.2-1.3 ppm, g: 4.1-4.3 ppm, h: 3. 6-3.8 ppm, i: 8.0-8.1 ppm, j, l: 2.5-2.6 ppm, k: 5.9-6.0 ppm

a：３．６〜３．７ｐｐｍ、ｂ、ｃ、ｄ、e：２．６〜２．９ｐｐｍ、ｆ：１．２〜１．３ｐｐｍ、ｇ：４．２〜４．３ｐｐｍ、ｈ：３．５〜３．５ｐｐｍ、i：８．０〜８．１ｐｐｍ、ｊ、ｌ：２．５〜２．６ｐｐｍ、ｋ：５．９〜６．０ｐｐｍ Example 1-2 (Result N2)

a: 3.6-3.7 ppm, b, c, d, e: 2.6-2.9 ppm, f: 1.2-1.3 ppm, g: 4.2-4.3 ppm, h: 3. 5-3.5 ppm, i: 8.0-8.1 ppm, j, l: 2.5-2.6 ppm, k: 5.9-6.0 ppm

a、e：０．９〜１．０ｐｐｍ、ｂ、ｃ、ｄ、ｆ、ｇ：１．０〜１．６ｐｐｍ、ｈ：４．２〜４．３ｐｐｍ、i、j、ｋ、ｌ：２．６〜３．０ｐｐｍ、ｍ：１．０〜１．２ｐｐｍ、n：４．２〜４．３ｐｐｍ、o：３．６〜３．８ｐｐｍ、ｐ：８．０〜８．１ｐｐｍ、q、ｓ：２．５〜２．６ｐｐｍ、ｒ：５．９〜６．０ｐｐｍ Example 3 (Result N3)

a, e: 0.9 to 1.0 ppm, b, c, d, f, g: 1.0 to 1.6 ppm, h: 4.2 to 4.3 ppm, i, j, k, l: 2. 6-3.0 ppm, m: 1.0-1.2 ppm, n: 4.2-4.3 ppm, o: 3.6-3.8 ppm, p: 8.0-8.1 ppm, q, s: 2.5-2.6 ppm, r: 5.9-6.0 ppm

a：３．２〜３．３ｐｐｍ、b：１．２〜１．３ｐｐｍ、ｃ：３．３〜３．４ｐｐｍ、ｄ：１．６〜１．８ｐｐｍ、e：４．１〜４．２ｐｐｍ、ｆ、ｊ：１．１〜１．２ｐｐｍ、ｇ、ｈ、i：２．６〜２．９ｐｐｍ、ｋ：４．２〜４．３ｐｐｍ、ｌ：３．６〜３．７ｐｐｍ、ｍ：８．０〜８．１ｐｐｍ、n、ｐ：２．５〜２．６ｐｐｍ、o：５．８〜５．９ｐｐｍ、 Example 1-4 (Result N4)

a: 3.2-3.3 ppm, b: 1.2-1.3 ppm, c: 3.3-3.4 ppm, d: 1.6-1.8 ppm, e: 4.1-4.2 ppm, f, j: 1.1 to 1.2 ppm, g, h, i: 2.6 to 2.9 ppm, k: 4.2 to 4.3 ppm, l: 3.6 to 3.7 ppm, m: 8. 0 to 8.1 ppm, n, p: 2.5 to 2.6 ppm, o: 5.8 to 5.9 ppm,

a：０．８〜０．９ｐｐｍ、b、ｆ、i：１．２〜１．４ ｐｐｍ、ｃ：１．５〜１．７ ｐｐｍ、ｄ、ｊ：４．０〜４．３、ｆ、ｇ、ｈ：３．６〜４．０ ｐｐｍ、ｋ：３．６〜３．７ｐｐｍ、 ｌ：８．０〜８．１ｐｐｍ、 ｍ、o：３．５〜３．６ｐｐｍ、n：５．９〜６．０ｐｐｍ Example 1-5 (Result N5)

a: 0.8-0.9 ppm, b, f, i: 1.2-1.4 ppm, c: 1.5-1.7 ppm, d, j: 4.0-4.3, f, g, h: 3.6-4.0 ppm, k: 3.6-3.7 ppm, l: 8.0-8.1 ppm, m, o: 3.5-3.6 ppm, n: 5.9 ~ 6.0ppm

6-10 and from the above results, since the peak of 5.5~6.5ppm derived from _CH 2 = C is not observed, the A-1 is reacted with B-1 to B-5, respectively I understand.

<Adhesion evaluation>
Next, the adhesion was evaluated using Examples 1-1 to 1-5. Furthermore, when only A-1 before the reaction was used as a comparative example, when only B-1 before the reaction was used, it was obtained by reacting 3-methacryloxypropyltrimethoxysilane with B-2. Adhesion was evaluated for the case where the product (C-1) and the adhesion improver were not used. The structural formula of C-1 is shown in the following formula.

(C-1)

A phenol novolac type epoxy resin [manufactured by Toto Kasei Co., Ltd., YDPN638] was used as an evaluation target for adhesion. Examples 1-1 to 1-5, A to a mixture (referred to as D-1) in which 98% by mass of the epoxy resin was mixed with 2% by mass of a catalyst [imidazole type catalyst: manufactured by Adeka Co., Ltd., EH-4344S] -1, B-1 and C-1 were blended according to the blending amounts in Table 2 as adhesion improvers. The composition (adhesion improver) 2 is applied to a PET film 3 having a width of 25 mm (Lumirror 100-U46, manufactured by Toray Industries, Inc.) with a bar coater to a thickness of 100 microns, and the PET film 4 is applied to the opposing substrate. Then, the test pieces for evaluation were obtained by curing at 110 ° C. for 1 hour (Examples 2-1 to 2-5, Comparative Examples 2-1 to 2-4: FIG. Put a side view). The adhesion of the test piece thus obtained was evaluated by a T-type peeling method defined in JIS K6854-3 under the condition of 90 ° C. These results are shown in Table 2. The evaluation criteria are as follows. ○: Tensile strength is 5 N / mm or more (including PET fracture) ×: Tensile strength is less than 5 N / mm

  From the results shown in Table 2, in the test pieces (Examples 2-1 to 2-5) using the adhesion improvers of Examples 1-1 to 1-5, the adhesion was good. Comparative Example 2-1 and Comparative Example 2-2 used raw materials for thioether-containing urea derivatives, and both showed low adhesion. In Comparative Example 2-3, a compound having no urea structure was used, and the adhesion was low. In Comparative Example 2-4, since the adhesion improver was not added, the adhesion was low.

Claims (3)

A thioether-containing urea derivative represented by the following formula (1).

(Respectively .R ¹ and ^{R 2} are m in the formula is 1 or 2 independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or .R ³ is an acyloxy group having 1 to 7 carbon atoms, the following A divalent group represented by the formula (2) or the following formula (3): R ⁴ is substituted by hydrogen, a hydrocarbon group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. And a hydrocarbon group having 2 to 5 carbon atoms.)

(R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is —CO— or —COOR ⁷ — (R ⁷ is an alkylene group having 1 to 6 carbon atoms).

(R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is —CO— or —COOR ⁷ — (R ⁷ is an alkylene group having 1 to 6 carbon atoms). The thioether containing urea derivative of Claim 1 formed by making the (meth) acrylate represented by following formula (4) react with the thiol compound represented by following formula (5).

(In the formula, R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an acyloxy group having 1 to 7 carbon atoms. R ⁵ is a hydrogen atom or a methyl group; ⁶ is —CO— or —COOR ⁷ — (R ⁷ is an alkylene group having 1 to 6 carbon atoms).

(In the formula, m is 1 or 2. R ⁴ is hydrogen, a hydrocarbon group having 1 to 18 carbon atoms, or a carbon atom having 2 to 5 carbon atoms substituted by an alkoxy group having 1 to 3 carbon atoms. It is a hydrogen group.) An adhesion improver comprising the thioether-containing urea derivative according to claim 1 as an active ingredient.

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