JP2015098456A - Thioether-containing urea derivative and adhesion improver containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thioether-containing urea derivative which exhibits an excellent adhesion improving effect on both an inorganic substrate and an organic substrate without using an adhesion assistant.SOLUTION: The thioether-containing urea derivative is represented by formula 1 (where a is an integer of 0-3; b is 0 or 1; c is an integer of 1-4; the sum of a, b, and c is 4; Rand Rare each independently a hydrogen atom, a C1-C6 alkyl group, or a C1-C7 acyloxy group; Ris a C2-C6 alkylene group; Ris a divalent group; and Ris a methylene group, an ethylene group, or an isopropylene group).

Description

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

  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.

  Moreover, it cannot be said that the adhesion improvement effect is sufficient with the silane coupling agent, for example, by adding simultaneously an adhesion aid such as a salt such as titanium and zirconium, an amine such as imidazole, a phosphate ester, and a urethane resin. In many cases, adhesion could be achieved for the first time. However, the addition of the adhesion aid not only leads to an increase in manufacturing man-hours and costs, but also the addition of the adhesion aid reduces the storage stability of the paint at room temperature and decreases the heat resistance and hardness. There was a problem.

  Therefore, in order to improve the above-mentioned problem, Patent Document 2 discloses a resin having high adhesion particularly to an inorganic base material without using an adhesion assistant by using a thioether-containing alkoxysilane having a specific structure. A composition is disclosed. However, no attention has been paid to the effect of improving the adhesion to the organic substrate.

JP-A-7-300491 JP2011-136985A

  Therefore, the present invention has been accomplished in view of the above-mentioned actual situation, and its purpose is to contain a thioether that exhibits an excellent adhesion improving effect on both inorganic and organic substrates without an adhesion assistant. It is to provide a urea derivative.

（式中のａは０〜３の整数であり、ｂは０または１であり、ｃは１〜４の整数であり、ａとｂとｃの和は４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は炭素数２〜６のアルキレン基である。Ｒ^４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^５はメチレン基、エチレン基またはイソプロピレン基である。）

（Ｒ^６は水素原子またはメチル基である。）

（Ｒ^６は水素原子またはメチル基である。）
（２）下記式４で表されるチオエーテル含有ウレア誘導体。

（式中のｄは０〜５の整数であり、ｅは０〜２であり、ｆは１〜６の整数であり、ｄとｅとｆの和は６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は炭素数２〜６のアルキレン基である。Ｒ^４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^５はメチレン基、エチレン基またはイソプロピレン基である。Ｒ^７は下記式５で表される６価の基である。）

（Ｒ^６は水素原子またはメチル基である。）

（Ｒ^６は水素原子またはメチル基である。）

（３）下記式６で表される（メタ）アクリレートと、下記式７で表される多価チオール化合物とを反応させてなる、（１）に記載のチオエーテル含有ウレア誘導体。

（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^３は炭素数２〜６のアルキレン基である。Ｒ^６は水素原子またはメチル基である。）

（式中のｇは０または１であり、ｈは３または４であり、ｇとｈの和は４である。
Ｒ^５はメチレン基、エチレン基またはイソプロピレン基である。）
（４）下記式６で表される（メタ）アクリレートと、下記式８で表される多価チオール化合物とを反応させてなる、（２）に記載のチオエーテル含有ウレア誘導体。

（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^３は炭素数２〜６のアルキレン基である。Ｒ^６は水素原子またはメチル基である。）

（式中のｉは０〜２の整数であり、ｊは４〜６の整数であり、ｉとｊの和は６である。Ｒ^５はメチレン基、エチレン基またはイソプロピレン基である。Ｒ^７は下記式５で表される６価の基である。）

For this purpose, the present invention adopts the following means.
(1) A thioether-containing urea derivative represented by the following formula 1.

(In the formula, a is an integer of 0 to 3, b is 0 or 1, c is an integer of 1 to 4, and the sum of a, b and c is 4. 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 ³ is an alkylene group having 2 to 6 carbon atoms, R ⁴ is represented by the following formula 2 or This is a divalent group represented by Formula 3. R ⁵ is a methylene group, an ethylene group or an isopropylene group.

(R ⁶ is a hydrogen atom or a methyl group.)

(R ⁶ is a hydrogen atom or a methyl group.)
(2) A thioether-containing urea derivative represented by the following formula 4.

(In the formula, d is an integer of 0 to 5, e is 0 to 2, f is an integer of 1 to 6, and the sum of d, e, and f is 6. 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 ³ is an alkylene group having 2 to 6 carbon atoms, R ⁴ is represented by the following formula 2 or This is a divalent group represented by Formula 3. R ⁵ is a methylene group, ethylene group or isopropylene group, and R ⁷ is a hexavalent group represented by Formula 5 below.

(R ⁶ is a hydrogen atom or a methyl group.)

(R ⁶ is a hydrogen atom or a methyl group.)

(3) The thioether-containing urea derivative according to (1), obtained by reacting a (meth) acrylate represented by the following formula 6 with a polyvalent thiol compound represented by the following formula 7.

(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 ³ is an alkylene group having 2 to 6 carbon atoms. R ⁶ is a hydrogen atom or a methyl group.)

(In the formula, g is 0 or 1, h is 3 or 4, and the sum of g and h is 4.
R ⁵ is a methylene group, an ethylene group or an isopropylene group. )
(4) The thioether-containing urea derivative according to (2), obtained by reacting a (meth) acrylate represented by the following formula 6 with a polyvalent thiol compound represented by the following formula 8.

(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 ³ is an alkylene group having 2 to 6 carbon atoms. R ⁶ is a hydrogen atom or a methyl group.)

(In the formula, i is an integer of 0 to 2, j is an integer of 4 to 6, and the sum of i and j is 6. R ⁵ is a methylene group, an ethylene group or an isopropylene group. R ⁷ is a hexavalent group represented by the following formula 5.

  The thioether-containing urea derivative of the present invention has an excellent adhesion improving effect on both inorganic and organic substrates. Therefore, by adding a small amount of the thioether-containing urea derivative of the present invention to the paint as an adhesion improver, it is possible to impart high adhesion to the paint without requiring the addition of an adhesion assistant.

  This 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 easy to form a chemical bond between the thioether group and the base material.

  Furthermore, it is considered that the above-described adhesion improving effect can be obtained by the amine of the pyrazole derivative that has been deprotected by subsequent heating increasing the basicity in the system and promoting the reaction of the thiol group. Therefore, although high adhesiveness improvement effect can be exhibited by heating, it is excellent in storage stability at 40 ° C. or lower. And this thioether containing urea derivative has low foamability at the time of a heating. This is presumably because the boiling point becomes high because the thiol group and the (meth) acryloyl group are bonded by a chemical bond. Therefore, it is useful as an adhesion improver.

It is IR spectrum of the compound 1 obtained in Example 1-1. It is IR spectrum of the compound 1 obtained in Example 1-2. It is IR spectrum of the compound 1 obtained in Example 1-3. It is IR spectrum of the compound 1 obtained in Example 1-4. It is IR spectrum of the compound 1 obtained in Example 1-5. It is IR spectrum of the compound 1 obtained in Example 1-6. It is IR spectrum of the compound 1 obtained in Example 1-7. 1 is a ¹ H-NMR spectrum of Compound 1 obtained in Example 1-1. It is a ¹ H-NMR spectrum of compound 1 obtained in Example 1-2. It is a ¹ H-NMR spectrum of compound 1 obtained in Example 1-3. 1 is a ¹ H-NMR spectrum of Compound 1 obtained in Example 1-4. It is a ¹ H-NMR spectrum of compound 1 obtained in Example 1-5. It is a ¹ H-NMR spectrum of compound 1 obtained in Example 1-6. It is a ¹ H-NMR spectrum of compound 1 obtained in Example 1-7.

（式中のａは０〜３の整数であり、ｂは０または１であり、ｃは１〜４の整数であり、ａとｂとｃの和は４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は炭素数２〜６のアルキレン基である。Ｒ^４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^５はメチレン基、エチレン基またはイソプロピレン基である。）

（Ｒ^６は水素原子またはメチル基である。）

（Ｒ^６は水素原子またはメチル基である。） Hereinafter, embodiments of the present invention will be described in detail.
<Thioether-containing urea derivative>
(Embodiment 1)
As Embodiment 1 of a thioether containing urea derivative, the compound represented by following formula (1) is mentioned.

(In the formula, a is an integer of 0 to 3, b is 0 or 1, c is an integer of 1 to 4, and the sum of a, b and c is 4. 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 ³ is an alkylene group having 2 to 6 carbon atoms, R ⁴ is represented by the following formula 2 or This is a divalent group represented by Formula 3. R ⁵ is a methylene group, an ethylene group or an isopropylene group.

(R ⁶ is a hydrogen atom or a methyl group.)

(R ⁶ is a hydrogen atom or a methyl group.)

  The thioether-containing urea derivative of Embodiment 1 represented by the above formula (1) has an excellent adhesion improving effect on both the inorganic base material and the organic base material, and in addition, an embodiment described later. Since the molecular weight is smaller than 2, the solubility is excellent. Therefore, since compatibility with many resins is higher than that of Embodiment 2, it can be used for a wide range of paints and is highly versatile.

（式中のｄは０〜５の整数であり、ｅは０〜２であり、ｆは１〜６の整数であり、ｄとｅとｆの和は６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は炭素数２〜６のアルキレン基である。Ｒ^４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^５はメチレン基、エチレン基またはイソプロピレン基である。Ｒ^７は下記式５で表される６価の基である。）

（Ｒ^６は水素原子またはメチル基である。）

（Ｒ^６は水素原子またはメチル基である。）

(Embodiment 2)
Moreover, the compound represented by following formula (4) is also mentioned as Embodiment 2 of a thioether containing urea derivative.

(In the formula, d is an integer of 0 to 5, e is 0 to 2, f is an integer of 1 to 6, and the sum of d, e, and f is 6. 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 ³ is an alkylene group having 2 to 6 carbon atoms, R ⁴ is represented by the following formula 2 or This is a divalent group represented by Formula 3. R ⁵ is a methylene group, ethylene group or isopropylene group, and R ⁷ is a hexavalent group represented by Formula 5 below.

(R ⁶ is a hydrogen atom or a methyl group.)

(R ⁶ is a hydrogen atom or a methyl group.)

  The thioether-containing urea derivative of Embodiment 2 represented by the above formula (4) is only added in a small amount as an adhesion improver to a resin composition such as a paint or an adhesive (for example, 2.5% by mass or less). High adhesion can be obtained.

<Method for producing thioether-containing urea derivative>
The thioether-containing urea derivative of Embodiments 1 and 2 represented by the above formula (1) or formula (4) is a urea group-containing compound (hereinafter referred to as A) having a (meth) acryloyl group represented by the following formula (6). Component) and a polyvalent thiol compound having a thiol group (—SH) represented by the following formula (7) or formula (8) (hereinafter referred to as “component B”). In the present specification, “(meth) acryloyl group” is a concept including both “methacryloyl group” and “acryloyl group”.

（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^３は炭素数２〜６のアルキレン基である。Ｒ^６は水素原子またはメチル基である。）

（式中のｇは０または１であり、ｈは３または４であり、ｇとｈの和は４である。
Ｒ^５はメチレン基、エチレン基またはイソプロピレン基である。）

（式中のｉは０〜２の整数であり、ｊは４〜６の整数であり、ｉとｊの和は６である。Ｒ^５はメチレン基、エチレン基またはイソプロピレン基である。Ｒ^７は上記式５で表される６価の基である。）

(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 ³ is an alkylene group having 2 to 6 carbon atoms. R ⁶ is a hydrogen atom or a methyl group.)

(In the formula, g is 0 or 1, h is 3 or 4, and the sum of g and h is 4.
R ⁵ is a methylene group, an ethylene group or an isopropylene group. )

(In the formula, i is an integer of 0 to 2, j is an integer of 4 to 6, and the sum of i and j is 6. R ⁵ is a methylene group, an ethylene group or an isopropylene group. R ⁷ is a hexavalent group represented by the above formula 5.

Examples of the alkyl group having 1 to 6 carbon atoms, which is R ¹ and R ² in the above formulas (1), (4), and (6), include a linear alkyl group, an alkyl group having a side chain, and a cyclic alkyl group. Groups. Examples of the linear alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl 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. Examples of the acyloxy group having 1 to 7 carbon atoms include methanoyloxy group, ethanoyloxy group, propanoyloxy group, butanoyloxy group, pentanoyloxy group, hexanoyloxy group, and heptanoyloxy group. R ¹ and R ² are preferably a hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms, and a methyl group is particularly preferred because of good compatibility with the paint.

Examples of the alkylene group having 2 to 6 carbon atoms as R ³ in the above formulas (1), (4), and (6) include a linear alkylene group, an alkylene group having a side chain, and a cyclic alkylene group. It is done. Examples of the linear alkylene group include an ethylene group, a propylene group, and a butylene group. Examples of the alkylene group having a side chain include an isopropylene group and an isobutylene group. Examples of the cyclic alkylene group include cyclobutylene. Group and the like. R ³ is particularly preferably a straight-chain alkylene group having 2 to 4 carbon atoms because the effect of improving adhesion is enhanced, but an ethylene group is particularly preferable.

R ⁵ in the above formulas (1), (4), (7), and (8) is preferably an ethylene group or an isopropylene group in terms of a high effect of improving adhesion. In addition, R ⁶ in the above formulas (2), (3), and (6) is preferably a methyl group in that the effect of improving adhesion is high.

  Specific examples of the component A (urea group-containing compound having a (meth) acryloyl group) represented by the above formula (6) include 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate, 2- [ Preferable examples include (3,5-dimethylpyrazolyl) carbonylamino] ethyl acrylate, 2-[(3,5-dimethylpyrazolyl) carbonylamino] propyl methacrylate, 2- (pyrazolylcarbonylamino) ethyl methacrylate and the like.

  Specific examples of the B component (polyvalent thiol compound) represented by the above formula (7) or formula (8) include trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropio). Nate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexakis (3-mercaptopropionate), and the like.

  In order to produce the thioether-containing urea derivative of Embodiment 1 or Embodiment 2, the component A and the component B can be reacted at a temperature of 5 ° C. or higher, but it is preferable to react at 60 to 100 ° C. When the reaction is performed at 60 ° C. or higher, the reaction can be performed in a short time such as within 5 hours. Moreover, elimination of amine can be prevented by reacting at 100 ° C. or lower. From the viewpoint of elimination of the amine, the reaction is more preferably carried out at 80 to 90 ° C. If a basic catalyst and a radical generator are added, it can be made to react with 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, 1 -Methylbenzimidazole, 1-methyl-benzylbenzimidazole and the like.

  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 this method for producing a thioether-containing urea derivative, the reaction can be allowed to proceed even without a solvent. However, when the reaction is to be carried out at a low temperature, for example, when it is desired to reduce the viscosity, the reaction can be carried out 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, and function 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 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 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 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 (9). 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 (9), 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. The ratio of the two products varies depending on the reaction conditions. For example, when a base catalyst such as an amine is added to the reaction system, a large amount of product 1 is generated and a radical generator is added to the reaction system. In this case, a large amount of product 2 tends to be generated. In many cases, the thioether-containing urea derivative after production is a mixture of products 1 and 2.

  The number of added A components in equation (9) corresponds to c in equation (1) and f in equation (4). In many cases, the thioether-containing urea derivative after production is a mixture of substances having different numbers of addition-reacted substituents.

<Adhesion improver>
By blending the thioether-containing urea derivatives of Embodiments 1 and 2 into a resin composition such as a paint or an adhesive, adhesion to both inorganic and organic materials can be improved. Therefore, it can be used as an adhesion improver as it is or after blending with a solvent or the like. In particular, by blending with a compound having a double bond such as an epoxy resin, a urethane resin, an acrylic resin, a polyimide resin, or polyacetylene, a high effect of improving adhesion can be exhibited. The adhesion improving effect of the adhesion improving agent is attributed to the thioether group of the thioether-containing urea derivative. Therefore, substrates that form chemical bonds with thioether groups (high chemical affinity), for example, inorganic substrates such as transition metals or their alloys, silicon compounds, phosphorus compounds, sulfur compounds, or boron compounds, It is excellent in the effect of improving adhesion to an organic substance having a saturated bond (including an aromatic ring), an organic substance having a hydroxyl group or a carboxyl group, or an organic substance treated with plasma or UV ozone. Specifically, 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.

  The adhesion improver comprising the thioether-containing urea derivative as an active ingredient is preferably added in an amount of 0.1 to 30% by mass, more preferably 0.1 to 10% by mass as an active ingredient, relative to the resin component in the resin composition. Then, high adhesiveness can be exhibited.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples.
(Examples 1-1 to 1-4)
First, thioether-containing urea derivatives (composites 1 to 7) of Examples 1-1 to 1-7 were synthesized using the following A component and B component. The A component and B component used are as follows. The viscosity at 25 ° C. of each component was measured using an R-type viscometer manufactured by Toki Sangyo Co., Ltd.

<Urea group-containing compound: Component A>
(A-1)
2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate. The structure is shown below (viscosity 0.13 Pa · s, temperature: 25 ° C.).

<Multivalent thiol compound: Component B>
(B-1)
Pentaerythritol tetrakis (3-mercaptopropionate). The structure is shown below (viscosity 0.4 Pa · s, temperature: 25 ° C.).

(B-2)
Trimethylolpropane tris (3-mercaptopropionate). The structure is shown below (viscosity 0.1 Pa · s, temperature: 25 ° C.).

(B-3)
Dipentaerythritol hexakis (3-mercaptopropionate). The structure is shown below (viscosity 2.5 Pa · s, temperature: 25 ° C.).

[Synthesis of thioether-containing urea derivatives]
In a three-necked flask equipped with a thermometer, a stirrer, and a dropping pump, the component B was charged according to the following Table 1, and after raising the temperature to 90 ° C., the component A was added dropwise over 1 hour. After completion of dropping, the mixture was further stirred at 90 ° C. for 4 hours for reaction.

[Infrared absorption spectrum analysis (IR)]
The obtained composites 1 to 7 were subjected to infrared absorption spectrum analysis (IR) under the following conditions. The IR spectra are shown in FIGS. 1 to 7 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 times

Example 1-1 (Compound 1): FIG.
^{1725cm -1: 85% T, 1516cm} -1: 87% T, 1416cm -1: 95% T, 1346cm -1: 89% T, 1153cm -1: 89% T, 1030cm -1: 94% T, 968cm - ¹ : 95% T, 802 cm ⁻¹ : 94% T

Example 1-2 (Compound 2): FIG.
^{1732cm -1: 82% T, 1516cm} -1: 88% T, 1346cm -1: 89% T, 1153cm -1: 86% T, 1030cm -1: 94% T, 968cm -1: 95% T, 810cm - ¹ : 95% T

Example 1-3 (Compound 3): FIG.
1732 cm ⁻¹ : 81% T, 1516 cm ⁻¹ : 91% T, 1346 cm ⁻¹ : 91% T, 1150 cm ⁻¹ : 84% T, 1030 cm ⁻¹ : 94% T, 972 cm ⁻¹ : 95% T, 806 cm ^{− 1} : 95% T

Example 1-4 (Compound 4): FIG.
1728 cm ⁻¹ : 83% T, 1516 cm ⁻¹ : 86% T, 1416 cm ⁻¹ : 95% T, 1346 cm ⁻¹ : 88% T, 1161 cm ⁻¹ : 88% T, 1030 cm ⁻¹ : 94% T, 968 cm ^{− 1} : 95% T, 802 cm ⁻¹ : 95% T

Example 1-5 (Compound 5): FIG.
1728 cm ⁻¹ : 84% T, 1512 cm ⁻¹ : 86% T, 1377 cm ⁻¹ : 94% T, 1346 cm ⁻¹ : 89% T, 1161 cm ⁻¹ : 89% T, 1030 cm ⁻¹ : 94% T, 968 cm ^{− 1} : 95% T, 849 cm ⁻¹ : 96% T, 791 cm ⁻¹ : 95% T

Example 1-6 (Compound 6): FIG.
^{1732cm -1: 82% T, 1516cm} -1: 88% T, 1346cm -1: 89% T, 1153cm -1: 87% T, 1030cm -1: 93% T, 968cm -1: 95% T, 802cm - ¹ : 95% T

Example 1-7 (Compound 7): FIG.
^{1732cm -1: 81% T, 1516cm} -1: 94% T, 1346cm -1: 92% T, 1153cm -1: 84% T, 1026cm -1: 94% T, 972cm -1: 95% T, 798cm - ¹ : 96% T, 756 cm ⁻¹ : 97% T

As apparent from the result of the infrared absorption spectrum analysis, since a peak of 1600 to 1680 cm ⁻¹ derived from C═C is not observed, A-1 is B-1, B-2, B-3, and It turns out that it is reacting.

[Nuclear magnetic resonance spectroscopy ⁽¹ H-NMR)]
Moreover, about the composites 1-7 obtained in Examples 1-1 to 1-7, the nuclear magnetic resonance spectrum analysis was performed on the following conditions. The results are shown in FIGS. 8 to 14, and the assignment of peaks in each spectrum and the structure of each synthesized product analyzed thereby are shown below.
Model: Nippon Bruker Co., Ltd., 400MHz-Advanced400
Accumulation count: 32 times Solvent; Deuterated chloroform Standard; TMS

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

a, c: 2.5 to 2.6 ppm, b: 5.9 to 6.0 ppm, d: 7.4 to 7.6 ppm, e, f, l: 4.1 to 4.4 ppm, g, i, j, k: 2.6 to 2.8 ppm, h: 1.3 to 1.4 ppm

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

a, c, m, n: 2.5 to 2.6 ppm, b: 5.9 to 6.0 ppm, d: 7.4 to 7.6 ppm, e, f, l: 4.1 to 4.4 ppm, g, i, j, k: 2.6 to 2.8 ppm, h: 1.3 to 1.4 ppm, o: 1.6 to 1.8 ppm

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

a, c, m, n: 2.5 to 2.6 ppm, b: 5.9 to 6.0 ppm, d: 7.4 to 7.6 ppm, e, f, l: 4.1 to 4.4 ppm, g, i, j, k: 2.6 to 2.8 ppm, h: 1.3 to 1.4 ppm, o: 1.6 to 1.8 ppm

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

a, c: 2.5 to 2.6 ppm, b: 5.9 to 6.0 ppm, d: 7.4 to 7.6 ppm, e, f, l: 4.1 to 4.4 ppm, g, i, j, k: 2.6-2.8 ppm, h: 1.3-1.4 ppm, m: 0.8-1.0 ppm

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

a, c: 2.5-2.6 ppm, b: 5.9-6.0 ppm, d: 7.4-7.6 ppm, e, f, l, m: 4.1-4.4 ppm, g, i, j, k: 2.6 to 2.8 ppm, h: 1.3 to 1.4 ppm

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

a, c: 2.5-2.6 ppm, b: 5.9-6.0 ppm, d: 7.4-7.6 ppm, e, f, l, m: 4.1-4.4 ppm, g, i, j, k, n, o: 2.6 to 2.8 ppm, h: 1.3 to 1.4 ppm, p: 1.6 to 1.8 ppm

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

a, c: 2.5-2.6 ppm, b: 5.9-6.0 ppm, d: 7.4-7.6 ppm, e, f, l, m: 4.1-4.4 ppm, g, i, j, k, n, o: 2.6 to 2.8 ppm, h: 1.3 to 1.4 ppm, p: 1.6 to 1.8 ppm

From FIGS. 8 to 14 and the above-mentioned assignment, since a peak derived from CH ₂ ═C (CH ₃ ) — in the vicinity of 5.0 to 5.8 ppm is not observed, A-1 is B-1, B-2 It was found to react with B-3.

(Examples 2-1 to 2-4, Comparative Examples 1-1 to 1-6)
Next, in Examples 2-1 to 2-7, the composites 1 to 7 were used as adhesion improvers, and their performance was evaluated. In the formulation shown in Table 2, an adhesion improver was added to the resin composition to prepare a sample. As the resin composition, tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate (C-1, the following formula) and YDPN638 [phenol novolac type epoxy resin: trade name, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.] A mixture of D-1) was used. In addition, in Comparative Examples 1-1 to 1-5, the following materials were used as adhesion improvers, and in Comparative Example 1-6, the performance was similarly evaluated without using the adhesion improver.

The materials used as adhesion improvers in Comparative Examples 1-1 to 1-5 are as follows.
Comparative Example 1-1: A-1 above
Comparative Example 1-2: B-1 above
Comparative Example 1-3: 3,5-dimethylpyrazole (E-1)
Comparative Example 1-4: 2-Methacryloyloxyethyl isocyanate (E-2)
Comparative Example 1-5: Reaction product of 3-methacryloxypropyltrimethoxysilane and methyl-3-mercaptopropionate (E-3)

(C-1) (Curing agent)
Tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate. The structure is shown in the following formula (viscosity 5.4 Pa · s, temperature: 25 ° C.).

[Adhesion evaluation 1]
JIS K5600-5-6: Adhesiveness was evaluated by a mechanical property-adhesiveness (cross-cut method) test method of the coating film. Using a non-alkali glass (OA-10, manufactured by Nippon Electric Glass Co., Ltd., thickness 0.7 mm) as a base material, each sample was coated on the base material with a bar coater to a thickness of 100 μm, and 150 ° C. And heated for 1 hour to form a cured film on each substrate to prepare a test piece. The evaluation criteria were ○ where no peeling occurred and × otherwise. The results are shown in Table 2.

[Adhesion evaluation 2]
JIS K6854-1: Adhesive-Peeling adhesion strength test method-Part 1: Adhesion was evaluated by 90-degree peeling. The test piece was made of alkali-free glass (OA-10, manufactured by Nippon Electric Glass Co., Ltd., thickness 0.7 mm) as a base material, and each sample was coated on the base material with a bar coater to a thickness of 100 μm. Then, a 25 mm wide PET film (A4300, manufactured by Toyobo Co., Ltd., thickness 50 μm) was bonded, and the sample was cured by heating at 150 ° C. for 1 hour to prepare a test piece. The evaluation criteria were ○ when the PET film was broken and × when it was peeled off. The results are shown in Table 2.

[Foaming]
The test piece obtained in the adhesion evaluation 2 was visually checked to determine whether there was a float due to foaming. The ones that did not float were marked with ○, and the others were marked with ×. The results are shown in Table 2.

[Storage stability]
Immediately after mixing the resin composition and the adhesion improver, the viscosity at 25 ° C. (viscosity after mixing) was measured, and after heating at 40 ° C. for 12 hours, the viscosity (viscosity after heating) was measured again. In Comparative Example 1-6 in which no adhesion improver was used, the viscosity of the resin composition at 25 ° C. was measured instead of the viscosity after mixing. The viscosity after heating was divided by the viscosity after mixing to calculate the thickening rate. The results are shown in Table 2. The viscosity was measured under the following conditions using an R-type viscometer manufactured by Toki Sangyo Co., Ltd.
Rotor used: 1 ° 34 '× R24
Measurement range: 0.5183 to 103.7 Pa · s

  From the results shown in Table 2, peeling occurred in the adhesion evaluation 1 and the adhesion evaluation 2 in Comparative Example 1-6 in which no adhesion improver was added, but in Examples 2-1 to 2-7, adhesion occurred. In any of the property evaluations 1 and 2, peeling did not occur, and it was revealed that the adhesion of the resin composition was effectively improved by adding the compounds 1 to 7. On the other hand, in Comparative Examples 1-1 to 1-5, none of the adhesion evaluations 1 and 2 did not cause peeling.

  As a result of the adhesion evaluation 1, there was no peeling between Comparative Example 1-5 using E-3 containing silane as an adhesion improver and Examples 2-1 to 2-7 using Compounds 1-7. High adhesion to the inorganic substrate was observed. However, referring to the result of the adhesion evaluation 2, there was peeling in Comparative Example 1-5. In Comparative Example 1-5, peeling occurred at the interface between the PET film and the sample, and E-3 showed no improvement in adhesion to organic materials. On the other hand, in Examples 2-1 to 2-7, there is no peeling, and by adding the composites 1 to 7, not only can a high adhesion improving effect be exerted on the inorganic base material, but also organic It became clear that the adhesiveness-improving effect was exerted on the substrate. Moreover, in Examples 2-1 to 2-7, it was confirmed by foaming evaluation that there was no foaming due to heating and no floating occurred, and that storage stability was excellent.

  In Comparative Example 1-1 in which the component A as the raw material of the composites 1 to 7 was used alone as an adhesion improver, although it was peeled off in the adhesion evaluation 1, there was no peeling in the adhesion evaluation 2, and it was exceptional for inorganic materials. Although no high adhesion improvement effect was observed, an adhesion improvement effect was observed for both inorganic and organic materials. Since the same result was obtained in Comparative Example 1-3, it is considered that the bonding strength of isocyanate to the base material was exhibited. However, from the evaluation results of storage stability and foamability, it was found that when component A alone was added to the resin composition, the storage stability decreased and foamed. Moreover, in Comparative Example 1-2 in which the component B, which is the other raw material of the composites 1 to 3, was used alone as an adhesion improver, peeling occurred in both the adhesion evaluations 1 and 2, and the adhesion improvement effect Was not recognized. From these facts, the A component and the B component cannot be used alone as an adhesion improver, and an effective material as an adhesion improver can be obtained by synthesizing the A component and the B component. Became clear.

  The reason why foaming occurred in Comparative Example 1-1 is that component A is desorbed into an isocyanate component and a pyrazole component by heating, but it is thought that foaming occurred due to volatilization of the highly volatile isocyanate component. In this case, the coating film may have a poor appearance due to foaming, or may float in the field of adhesion. On the other hand, foaming was not recognized in Examples 2-1 to 2-4 using the composites 1-4. This is because the thioether-containing urea derivatives of Compounds 1 to 4 have a high molecular weight by synthesizing the A component and the B component, and are difficult to thermally decompose because the isocyanate component contains a thiol group or a thioether group. It is considered that no foaming occurs.

Moreover, the evaluation result of the storage stability in Comparative Example 1-1 was poor because when A-1 was used alone as an adhesion improver and heated at 40 ° C. for 12 hours, it reacted with C-1 as a thiol component. This is because the viscosity of the resin composition increases. On the other hand, since the compounds 1-4 synthesized with the component B are not deprotected at 40 ° C., they are excellent in storage stability.

Claims (4)

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

(In the formula, a is an integer of 0 to 3, b is 0 or 1, c is an integer of 1 to 4, and the sum of a, b and c is 4. 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 ³ is an alkylene group having 2 to 6 carbon atoms, R ⁴ is represented by the following formula 2 or This is a divalent group represented by Formula 3. R ⁵ is a methylene group, an ethylene group or an isopropylene group.

(R ⁶ is a hydrogen atom or a methyl group.)

(R ⁶ is a hydrogen atom or a methyl group.) A thioether-containing urea derivative represented by the following formula 4.

(In the formula, d is an integer of 0 to 5, e is 0 to 2, f is an integer of 1 to 6, and the sum of d, e, and f is 6. 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 ³ is an alkylene group having 2 to 6 carbon atoms, R ⁴ is represented by the following formula 2 or This is a divalent group represented by Formula 3. R ⁵ is a methylene group, ethylene group or isopropylene group, and R ⁷ is a hexavalent group represented by Formula 5 below.

(R ⁶ is a hydrogen atom or a methyl group.)

(R ⁶ is a hydrogen atom or a methyl group.)

The thioether-containing urea derivative according to claim 1, wherein a (meth) acrylate represented by the following formula 6 is reacted with a polyvalent thiol compound represented by the following formula 7.

(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 ³ is an alkylene group having 2 to 6 carbon atoms. R ⁶ is a hydrogen atom or a methyl group.)

(In the formula, g is 0 or 1, h is 3 or 4, and the sum of g and h is 4.
R ⁵ is a methylene group, an ethylene group or an isopropylene group. ) The thioether-containing urea derivative according to claim 2, wherein a (meth) acrylate represented by the following formula 6 is reacted with a polyvalent thiol compound represented by the following formula 8.

6

(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 ³ is an alkylene group having 2 to 6 carbon atoms. R ⁶ is a hydrogen atom or a methyl group.)

(In the formula, i is an integer of 0 to 2, j is an integer of 4 to 6, and the sum of i and j is 6. R ⁵ is a methylene group, an ethylene group or an isopropylene group. R ⁷ is a hexavalent group represented by the following formula 5.

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