TW201605783A - Thioether-containing (meth)acrylate derivative and adhesion improving agent containing the derivative - Google Patents

Abstract

This thioether-containing alkoxysilane derivative has a structure represented by formula (1). (In formula (1), a represents an integer of 1-3; b represents 0 or 1; c represents an integer of 1-3; the sum of a, b and c is 4; R1 represents a methylene group, an ethylene group or an isopropylene group; R2 represents a divalent functional group represented by formula (2) or formula (3); R3 represents a methyl group or an ethyl group; and R4 represents a hydrocarbon group having 1-12 carbon atoms.) (In formula (2), R5 represents a hydrogen atom or a methyl group.) (In formula (3), R5 represents a hydrogen atom or a methyl group.)

Description

Thioether-containing (meth) acrylate derivative and adhesion improving agent containing the same

The present invention relates to a novel thioether-containing (meth) acrylate derivative which is suitable for use as an adhesion improving agent and the like.

In the past, when a coating material is applied to an inorganic substrate such as glass, an adhesion improving agent such as a decane coupling agent is added to the coating material in order to improve the adhesion (for example, see Patent Document 1). However, there is a problem in that if the decane coupling agent is heated, it is decomposed, and if it is used in a production line, cerium oxide is precipitated in a heating furnace such as an oven to cause contamination. In addition, in the case of the decane coupling agent alone, it cannot be said that the effect of improving the adhesion is sufficient. For example, in many cases, a salt such as titanium or zirconium or an amine such as imidazole or a phosphate resin or a urethane resin is added. Adhesive additives can achieve practical level of adhesion. Further, the addition of the adhesion aid not only involves an increase in the production process and cost, but also causes deterioration in storage stability of the coating at room temperature due to the addition of the adhesion aid, and the heat resistance and hardness of the coating film are lowered. .

Patent Document 2 discloses that in order to solve the above problem, by using a sulfur-containing urea derivative having a specific structure as a patch improving agent, the adhesion can be improved even without an attaching aid.

Further, Patent Document 3 discloses a photocurable resin composition containing an addition reaction product and a photopolymerization initiator in which a polythiol compound or a polyene compound is added to a decane coupling agent, and exhibits excellent adhesion. . CITATION LIST Patent Literature Patent Document 1: JP 7-300491 A Patent Document 2: Laid-Open Publication No. 2013-249282 Patent Document 3: Laid-Open Patent Publication No. 2001-89568

Technical problem to be solved by the present invention

However, in the cold region, the adhesion of the coating material to the flexible film substrate has been studied, and as a result, it has been found that there is a problem in that the sulfur-containing urea derivative or the polythiol compound is used. When the addition reactant of the polyene compound and the decane coupling agent is used as an adhesion improving agent for a coating material, the obtained coating film lacks flexibility, and cracks are likely to occur when the coating film is bent.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a material which can exhibit a high relative to a substrate even when it is applied to a paint or the like without an attaching aid in a cold region. The adhesion improving effect is obtained, and the obtained coating film has flexibility. Technical means to solve technical problems

In order to achieve the above object, the thioether-containing (meth) acrylate derivative of the present invention has a structure represented by the following formula 1. (in the formula 1, a is an integer of 1 to 3, b is 0 or 1, c is an integer of 1 to 3, and the sum of a and b and c is 4. R ¹ is a methylene group, an ethylene group or a hetero-Asia. R. R ² is a divalent functional group represented by the following formula 2 or the following formula 3. R ³ is a methyl group or an ethyl group. R ⁴ is a hydrocarbon group having 1 to 12 carbon atoms. (R ⁵ is a hydrogen atom or a methyl group.) (R ⁵ is a hydrogen atom or a methyl group.)

The thioether-containing (meth) acrylate derivative having the structure represented by the above formula 1 is preferably formed by reacting an acryl compound represented by the following formula 4 with a polythiol compound represented by the following formula 5. . (R ^{4 in} Formula 4 is a hydrocarbon group having 1 to 12 carbon atoms. R ⁷ is a hydrogen atom or a methyl group.) (g in the formula 5 is 0 or 1, h is 3 or 4, and the sum of g and h is 4. R ¹ is a methylene group, an ethylene group or an isopropylidene group. R ³ is a methyl group or an ethyl group. )

Further, the thioether-containing (meth) acrylate derivative of the present invention may contain a structure represented by the following formula 6. (d in the formula 6 is an integer of 1 to 5, e is an integer of 0 to 2, f is an integer of 1 to 5, and the sum of d and e and f is 6. R ¹ is a methylene group, an ethylene group or isopropylidene .R ² by the following formula or the following formula 2 a divalent functional group represented by ³ .R 3 .R ⁴ is methyl or ethyl is a hydrocarbon group having ⁶ .R 1 ~ 12 by the following a hexavalent functional group represented by Formula 7.) (R ⁵ is a hydrogen atom or a methyl group.) (R ⁵ is a hydrogen atom or a methyl group.)

The thioether-containing (meth) acrylate derivative having the structure represented by Formula 6 is preferably reacted with an acryl compound represented by Formula 4 below and a polythiol compound represented by Formula 8 below. to make. (R ^{4 in} Formula 4 is a hydrocarbon group having 1 to 12 carbon atoms. R ⁷ is a hydrogen atom or a methyl group.) (i in the formula 8 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 ¹ is a methylene group, an ethylene group or an isopropylidene group. R ³ is a methyl group. Or ethyl. R ⁶ is a hexavalent functional group represented by the following formula 7.)

Further, the present invention provides an adhesion improving agent which comprises any one of the thioether-containing (meth) acrylate derivatives as an active ingredient.

In addition, in the present specification, "(meth) acrylate" means a concept including both "methacrylate" and "acrylate". In addition, the description of "○○~××" in the present specification means "○○ or more and XX or less" unless otherwise stated. Effect of the invention

In the case where the thioether-containing (meth) acrylate derivative of the present invention is added to a paint or the like, for example, even in a cold environment of -10 ° C, it has a relative non-adhesive auxiliary agent. The substrate exhibits a high adhesion improving effect, and the obtained coating film has a softening effect. The above effect is considered to be because the ester group having a specific carbon chain imparts flexibility to the coating in a cold environment, and the ester group does not hinder the proximity of the thioether group to the substrate, so that the attachment of the thioether group is reliably exerted. Sexual improvement effect.

Hereinafter, embodiments of the present invention will be described in detail. <Sulfur ether-containing (meth) acrylate derivative> (Embodiment 1)

The thioether-containing (meth) acrylate derivative of the present embodiment is a compound represented by the following formula 1. (in the formula 1, a is an integer of 1 to 3, b is 0 or 1, c is an integer of 1 to 3, and the sum of a and b and c is 4. R ¹ is a methylene group, an ethylene group or a hetero-Asia. R. R ² is a divalent functional group represented by the following formula 2 or the following formula 3. R ³ is a methyl group or an ethyl group. R ⁴ is a hydrocarbon group having 1 to 12 carbon atoms. (R ⁵ is a hydrogen atom or a methyl group.) (R ⁵ is a hydrogen atom or a methyl group.)

The hydrocarbon group having 1 to 12 carbon atoms of R ⁴ in the above formula 1 may, for example, be a linear alkyl group, a branched alkyl group or a cyclic alkyl group. In the above formula 1, R ¹ is a methylene group, an ethylene group or an isopropylidene group, and an ethylene group or an isopropylidene group is particularly preferable from the viewpoint of improving the adhesion improving effect.

When the thioether-containing (meth) acrylate derivative represented by Formula 1 is added to a paint or the like, for example, even in an environment of -10 ° C, the following excellent effects are obtained: In the case of an auxiliary auxiliary agent, the effect of improving the adhesion with respect to the substrate is exhibited, and the obtained coating film is imparted with flexibility. Further, the thioether-containing (meth) acrylate derivative represented by Formula 1 has a smaller molecular weight than the thioether-containing (meth) acrylate derivative of Embodiment 2 to be described later, and thus is excellent in solubility. Therefore, for most resins, the thioether-containing (meth) acrylate derivative represented by Formula 1 has higher compatibility with the thioether-containing (meth) acrylate derivative of Embodiment 2, and thus It is highly versatile for use in a wide range of coatings. [01] (Embodiment 2)

In the second embodiment of the thioether-containing (meth) acrylate derivative, a compound represented by the following formula 6 can be mentioned. (d in the formula 6 is an integer of 1 to 5, e is an integer of 0 to 2, f is an integer of 1 to 5, and the sum of d and e and f is 6. R ¹ is a methylene group, an ethylene group or isopropylidene .R ² by the following formula or the following formula 2 a divalent functional group represented by ³ .R 3 .R ⁴ is methyl or ethyl is a hydrocarbon group having ⁶ .R 1 ~ 12 by the following a hexavalent functional group represented by Formula 7.) (R ⁵ is a hydrogen atom or a methyl group.) (R ⁵ is a hydrogen atom or a methyl group.)

The hydrocarbon group having 1 to 12 carbon atoms of R ⁴ in the formula 6 may, for example, be a linear alkyl group, a branched alkyl group or a cyclic alkyl group. R ¹ in the above formula 6 is a methylene group, an ethylene group or an isopropylidene group, and an ethylene group and an isopropylidene group are particularly preferable from the viewpoint of improving the adhesion improving effect.

The thioether-containing (meth) acrylate derivative represented by the above formula 6 is, for example, a resin which is added in a small amount to a coating material or an adhesive as an adhesion improving agent even in a cold environment of -10 ° C. In the composition, it is possible to impart high adhesion to the composition and impart softness to the obtained coating film. <Method for Producing Thioether-Containing (Meth)acrylate Derivative>

The thioether-containing (meth) acrylate derivative of the first embodiment shown in the above formula 1 can be, for example, an acrylic compound having a (meth) acrylate group represented by the following formula 4 (hereinafter referred to as It is obtained by reacting a component A with a polythiol compound having a thiol group (-SH) (hereinafter referred to as a component B) represented by the following formula 5. (R ^{4 in} Formula 4 is a hydrocarbon group having 1 to 12 carbon atoms. R ⁷ is a hydrogen atom or a methyl group.) (g in the formula 5 is 0 or 1, h is 3 or 4, and the sum of g and h is 4. R ¹ is a methylene group, an ethylene group or an isopropylidene group. R ³ is a methyl group or an ethyl group. )

On the other hand, the thioether-containing (meth) acrylate derivative of Embodiment 2 shown in Formula 6 can be, for example, an acrylic acid having a (meth) acrylate group represented by Formula 4 The compound (component A) is obtained by a reaction with a polythiol compound (component B) having a thiol group (-SH) represented by the following formula 8. (i in the formula 8 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 ¹ is a methylene group, an ethylene group or an isopropylidene group. R ³ is a methyl group. Or ethyl. R ⁶ is a hexavalent functional group represented by the following formula 7.)

Examples of the acrylic compound (component A) represented by the above formula 4 include methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, and dodecyl acrylate. .

Examples of the polyvalent thiol compound (component B) represented by the above formula 5 or the above formula 8 include trimethylolpropane tris(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptopropionate). , trimethylolpropane tris(3-mercaptobutyrate), trimethylolethane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), dipentaerythritol hexa(3-indenyl) Propionate) and the like.

For the two components of the component A and the component B, the (meth) acrylate group of the component A and the thiol group of the component B are reacted by a reaction formula represented by the following formula 9. Further, X represents a hydrogen atom or a methyl group, Y represents a residue other than X bonded to a (meth)acryloyl group of the component A, and Z represents a residue bonded to a thiol group of the component B.

As shown in Formula 9, both carbons forming a double bond of the (meth) acrylate group of the component A can be bonded to S of a thiol group, and the ratio of formation of the two products varies depending on the reaction conditions, for example, In the catalyst of the present reaction, when a basic catalyst such as an amine is added to the reaction system, the product 1 tends to be formed, and when the radical initiator is added to the reaction system, it is often produced. The tendency of product 2 is produced. In most cases, the thioether-containing acrylic acid derivative after the production is a mixture of the products 1 and 2.

In order to produce a sulfide-containing (meth) acrylate derivative, it is only necessary to react the component A and the component B at a temperature of 5 ° C or higher, preferably at 60 to 100 ° C. When the reaction is carried out at 60 ° C or higher, the reaction can be carried out in a short time. On the other hand, in the case of the reaction at a temperature exceeding 100 ° C, since the A component is polymerized with each other, it is not possible to obtain only the sulfide-containing (meth) acrylate derivative as the intended product, and thus it is not preferable. of. Further, when a basic catalyst or a radical initiator is added to the reaction system, the reaction can be carried out not only in a shorter period of time but also in the yield of the sulfide-containing (meth) acrylate derivative.

As the basic catalyst, an amine-based basic catalyst is preferable, and a primary amine, a secondary amine or a tertiary amine, or an imidazole compound can be used. For example, examples of the primary amine include methylamine, ethylamine, propylamine, butylamine, ethylenediamine, and the like. Examples of the secondary amine include dimethylamine, diethylamine, dipropylamine, methylethylamine, and diphenylamine. The tertiary amine may, for example, be trimethylamine, triethylamine, tripropylamine, triphenylamine or 1,8-diazabicyclo [5.4.0]undecylamino)phenol. Examples of the imidazole compound include imidazole homologues such as 1-methylimidazole, 1,2-dimethylimidazole, 1,4-dimethyl-2-ethylimidazole, and 1-phenylimidazole, and 1- An alkyl derivative such as methyl-2-oxomethylimidazole or 1-methyl-2-oxoethylimidazole, 1-methyl-4(5)-nitroimidazole, 1,2-dimethyl-5 (4) Nitro and amino derivatives such as aminoimidazole, benzimidazole, 1-methylbenzimidazole, 1-methyl-benzylbenzimidazole, and the like.

As the radical initiator, a peroxide or an azo compound is preferably selected, and examples of the peroxide include, for example, benzammonium peroxide, t-butylperoxy-2-ethylhexanoate, and peroxidation. February Guiyan and so on. Examples of the azo compound include azobis(iso-butyronitrile) or 2,2'-azobis(2-methylbutyronitrile).

In the method for producing a thioether-containing (meth) acrylate derivative, the reaction can be carried out in the absence of a solvent. However, when it is desired to lower the viscosity in the case of a reaction at a low temperature, a solvent may be added. reaction. In this case, a solvent which does not preferably react with a carbon-carbon double bond or a thiol group of a (meth) acrylate group, for example, an alcohol, a ketone or an ester is preferably selected.

The alcohol used as the solvent does not contain a functional group such as a carbon-carbon double bond, a thiol group, an epoxy group, an isocyanate group, a carboxyl group, a sulfonyl group, a nitrile group or a halogen atom which reacts with a carbon-carbon double bond or a thiol group. Examples of the alcohol not containing the above functional group include alkyl ethers or esters of methanol, ethanol, isopropanol, tert-butanol, hexanol, propylene glycol, glycerin, and ethylene glycol. Among them, an alcohol having a boiling point of 80 ° C or higher can maintain a high reaction temperature, and thus is a preferred choice.

The ketone used as the solvent does not contain a functional group such as a carbon-carbon double bond, a thiol group, an epoxy group, an isocyanate group, a carboxyl group, a sulfonyl group, a nitrile group or a halogen atom which reacts with a carbon-carbon double bond or a thiol group. Examples of the ketone which does not contain the above functional group include acetone, methyl ethyl ketone, methyl isobutyl ketone, and methyl isopropyl ketone. Among them, ketones having a boiling point of 80 ° C or higher can maintain a high reaction temperature, and thus are preferred.

The ester used as the solvent does not contain a functional group such as a carbon-carbon double bond, a thiol group, an epoxy group, an isocyanate group, a carboxyl group, a sulfonyl group, a nitrile group or a halogen atom which reacts with a carbon-carbon double bond or a thiol group. Examples of the ester not containing the above functional group include ethyl acetate, butyl acetate, ethyl benzoate, and propylene glycol acetate. Among them, esters having a boiling point of 80 ° C or higher are preferable because they can maintain a high reaction temperature. <Adhesion improver>

By adding the thioether-containing (meth) acrylate derivative of the present embodiment to a resin composition such as a coating material or an adhesive, the adhesion to both the inorganic material and the organic material can be improved. Therefore, it can be used as a patch improver directly or in combination with a solvent or the like. In particular, it can be added to a compound having a double bond such as an epoxy resin, a urethane resin, an acrylic resin, a polyimide resin, or a polyacetylene to exhibit a high adhesion improving effect. The adhesion improving effect of the adhesion improving agent is caused by a thioether group of a thioether-containing (meth) acrylate derivative. Therefore, it is excellent in the effect of improving the adhesion of a substrate which forms a chemical bond (high chemical affinity) with a thioether group such as a transition metal or an alloy thereof, a telluride, a phosphide, a sulfide, or a boride. An inorganic substrate, an organic substance having an unsaturated bond (including an aromatic ring), an organic substance having a hydroxyl group or a carboxyl group, or an organic substance treated by plasma or ultraviolet ozone. Specifically, examples of the inorganic substrate include glass, enamel, various metals, and the like. As the organic substrate, polyethylene terephthalate, polybutylene terephthalate, polyethylene, polypropylene, polycarbonate, polyimine, ABS resin, and poly are preferably exemplified. Vinyl alcohol, vinyl chloride, polyacetal, and the like.

With respect to 100% by mass of the resin composition such as a coating material or a binder containing a resin component, 0.1 to 80% by mass of the thioether-containing (meth) acrylate derivative as an active ingredient is added as an active ingredient. An additive improver can exhibit high adhesion. This adhesion improving agent has an effect of improving the flexibility of the resin by the ester group, and the obtained coating film also has excellent flexibility. Example

Hereinafter, the present invention will be specifically described by way of examples and comparative examples. (Example 1-1) [Synthesis of a thioether-containing (meth) acrylate derivative]

In a three-necked flask equipped with a thermometer, a stirrer, and a drip pump, 85.9 g of dipentaerythritol hexa(3-mercaptopropionate) (component B) was added, and after heating to 60 ° C, 14.1 g of butyl acrylate was added dropwise over 1 hour. A component). After completion of the dropwise addition, the mixture was further stirred at 60 ° C for 2 hours to cause a reaction, thereby obtaining a sulfide-containing (meth) acrylate derivative (Synthesis 1). [03] (Examples 1-2 to 1-6)

Next, in Examples 1-2 to 1-6, a sulfide-containing (meth) acrylate derivative was synthesized in the same manner as in Example 1-1, except that the components A and B described in Table 1 below were used. (composition 2~6). Further, the components A and B used were as follows: <component A: acrylic compound> A-1: butyl acrylate A-2: isobutyl acrylate A-3: dodecyl acrylate A-4: acrylic acid-2- Ethylhexyl ester <B component: polythiol compound> B-1: dipentaerythritol hexa(3-mercaptopropionate) B-2: trimethylolpropane tris(3-mercaptopropionate) B-3: Pentaerythritol tetrakis(3-mercaptopropionate) [04] [Table 1] [05] [Infrared Absorption Spectroscopy (IR)]

With respect to the obtained compositions 1 to 6, infrared absorption spectrum analysis (IR) was carried out under the following conditions. The IR spectrum is shown in Figures 1 to 6, and the representative IR peaks are shown below. Type of machine: TRavel IR manufactured by ST Japan Co., Ltd. Decomposition: 8cm ^-1 , cumulative number: 32 times

Example 1-1 (Synthesis 1): Fig. ¹ 2960 cm ^-1 : 99% T, 2898 cm ^-1 : 99% T, 1733 cm ^-1 : 80% T, 1466 cm ^-1 : 98% T, 1389 cm ^-1 : ^{96% T, 1355cm -1: 94} % T, 1289cm -1: 96% T, 1243cm -1: 90% T, 1150cm -1: 84% T, 1054cm -1: 95% T, 1015cm -1: 95% T, 938 cm ^-1 : 96% T, 895 cm ^-1 : 97% T, 868 cm ^-1 : 97% T, 837 cm ^-1 : 97% T, 803 cm ^-1 : 97% T, 777 cm ^-1 : 98% T

Example 1-2 (Synthesis 2): Fig. 2 Fig. 2960 cm ^-1 : 99% T, 1732 cm ^-1 : 80% T, 1470 cm ^-1 : 97% T, 1385 cm ^-1 : 96% T, 1354 cm ^-1 : 95% T, 1289 cm ^-1 : 96% T, 1243 cm ^-1 : 90% T, 1153 cm ^-1 : 84% T, 1054 cm ^-1 : 95% T, 1011 cm ^-1 : 94% T, 938 cm ^-1 : 96% T, 907 cm ^-1 : 97% T, 864 cm ^-1 : 97% T, 837 cm ^-1 : 98% T, 822 cm ^-1 : 97% T, 791 cm ^-1 : 98% T, 760 cm ^-1 : 98% T

Example 1-3 (Synthesis 3): Fig. 3 Fig. 2925 cm ^-1 : 97% T, 2856 cm ^-1 : 99% T, 1737 cm ^-1 : 83% T, 1466 cm ^-1 : 98% T, 1412 cm ^-1 : 97% T, 1389 cm ^-1 : 97% T, 1354 cm ^-1 : 95% T, 1289 cm ^-1 : 96% T, 1243 cm ^-1 : 91% T, 1189 cm ^-1 : 90% T, 1153 cm ^-1 : 87% ^{T, 1050cm -1: 96% T} , 1007cm -1: 96% T, 934cm -1: 97% T, 891cm -1: 97% T, 864cm -1: 97% T, 826cm -1: 98% T, 760cm ^-1 :98%T

Example 1-4 (Synthesis 4): Fig. 4 Fig. 2956 cm ^-1 : 98% T, 2933 cm ^-1 : 98% T, 2871 cm ^-1 : 99% T, 1737 cm ^-1 : 82% T, 1632 cm ^-1 : 99% T, 1466 cm ^-1 : 97% T, 1389 cm ^-1 : 96% T, 1355 cm ^-1 : 95% T, 1289 cm ^-1 : 96% T, 1243 cm ^-1 : 90% T, 1154 cm ^-1 : 95% T, 1011 cm ^-1 : 95% T, 934 cm ^-1 : 97% T, 868 cm ^-1 : 97% T, 826 cm ^-1 : 97% T, 795 cm ^-1 : 97% T, 776 cm ^-1 : 97% T

Example 1-5 (Synthesis 5): Fig. 5 Fig. 2960 cm ^-1 : 98% T, 1733 cm ^-1 : 81% T, 1463 cm ^-1 : 97% T, 1416 cm ^-1 : 97% T, 1389 cm ^-1 : ^{96% T, 1355cm -1: 95} % T, 1243cm -1: 90% T, 1150cm -1: 86% T, 1057cm -1: 96% T, 1019cm -1: 96% T, 938cm -1: 97% T, 880 cm ^-1 : 97% T, 860 cm ^-1 : 97% T, 837 cm ^-1 : 97% T, 783 cm ^-1 : 97% T

Example 1-6 (Synthesis 6): Fig. 6 Fig. 2964 cm ^-1 : 99% T, 1733 cm ^-1 : 80% T, 1470 cm ^-1 : 98% T, 1412 cm ^-1 : 96% T, 1389 cm ^-1 : 96% T, 1355 cm ^-1 : 94% T, 1289 cm ^-1 : 96% T, 1243 cm ^-1 : 89% T, 1150 cm ^-1 : 83% T, 1053 cm ^-1 : 95% T, 1019 cm ^-1 : 95% T, 934 cm ^-1 : 96% T, 876 cm ^-1 : 97% T, 852 cm ^-1 : 97% T, 818 cm ^-1 : 98% T, 799 cm ^-1 : 98% T, 783 cm ^-1 : 98% T

As is clear from the results of the infrared absorption spectrum analysis, since the peak of 1600 to 1680 cm ^-1 from C=C was not observed, it was found that the component A reacted with the component B in each composition. [06] [NMR Spectroscopy ( ¹ H-NMR)]

With respect to the compositions 1 to 6 obtained in Examples 1-1 to 1-6, nuclear magnetic resonance spectrum analysis was carried out under the following conditions. The results are shown in Figs. 7 to 12, and the assignment of the peaks in the respective spectra and the structures of the respective compositions obtained by the analysis are as follows. Machine type: Japan Bruker Co., Ltd., 400MHz-Advance400 Accumulated number: 32 times Solvent: Heavy chloroform Standard: TMS

Example 1-1 (Composition 1): Figure 7 [Formula 25] o: 0.7~0.9ppm, n: 1.2~1.5ppm, a, m: 1.5~1.7ppm, b, c, h, i, j, k: 2.4~3.0ppm, e, f: 3.2~3.5ppm, d , g, l: 3.9~4.2ppm

Example 1-2 (Composition 2): Fig. 8 [Formula 26] n, o: 0.7~1.0ppm, a: 1.5~1.7ppm, m: 1.8~2.0ppm, b, c, h, i, j, k: 2.4~3.0ppm, e, f: 3.2~3.5ppm, l : 3.7~3.9ppm, d, g: 3.9~4.3ppm

Example 1-3 (Composition 3): Figure 9 [Formula 27] w: 0.7~0.9ppm, n, o, p, q, r, s, t, u, v: 1.0~1.4ppm, a, m: 1.4~1.7ppm, b, c, h, i, j, k : 2.4~3.0ppm, e, f: 3.2~3.5ppm, d, g, l: 3.8~4.2ppm

Example 1-4 (Synthesis 4): Fig. 10 [Formula 28] q, s: 0.7~1.0ppm, n, o, p, r: 1.1~1.4ppm, a, m: 1.4~1.8ppm, b, c, h, i, j, k: 2.3~3.0ppm, e, f: 3.0~3.7ppm, d, g, l: 3.8~4.2ppm

Example 1-5 (Synthesis 5): Figure 11 [Formula 29] o, f: 0.7~1.0ppm, a, e, m, n: 1.2~1.7ppm, b, c, h, i, j, k: 2.4~3.0ppm, d, g, l: 3.8~4.2ppm

Example 1-6 (composition 6): Fig. 12 [Formula 30] m: 0.7~1.0ppm, a, k, l: 1.1~1.7ppm, b, c, f, g, h, i: 2.4~2.9ppm, d, e, j: 3.8~4.3ppm

From the 7th to the 12th and the attribution, it is not observed that a peak derived from -CH=C(CH ₃ )- is in the vicinity of 5.0 to 5.8 ppm. Therefore, it is understood that the A component and the B component in each composition. The reaction was carried out. [07] (Example 2-1)

A resin composition of 2% by mass of a catalyst [imidazole-type catalyst: manufactured by ADEKA Co., Ltd., EH-4344S] was mixed with a 98% by mass of a phenol novolak-type epoxy resin (YDPN638, manufactured by Tohto Kasei Co., Ltd.) In the compound C-1), 80% by mass of the composition 1 as an adhesion improving agent was evaluated for its performance by the following test method. The evaluation results are shown in Table 2 below. [08] (Examples 2-2 to 2-6, Comparative Examples 2-1 to 2-7)

Then, in the examples 2-2 to 2-6, the resin was used in the same manner as in Example 2-1 except that the compositions 2 to 6 described in Table 2 below were used as the adhesion improving agent. The composition (C-1) was mixed with the compositions 2 to 6, and the properties were evaluated. Further, in Comparative Examples 2-1 to 2-7, the adhesion improving agent was used in addition to the A component or the B component described in Table 2 or the unreacted A component and B component, and Example 2-1. Similarly, the resin composition (C-1) was mixed with at least one of the A component and the B component, and the performance was evaluated. The results are shown in Table 2 below. In addition, the unit of the numerical value in Table 2 is mass %. [09] <Test method> [Production of test piece for evaluation]

The mixture obtained in each of the examples and the comparative examples was applied to a thickness of 100 μm by a bar coater on a 25 mm wide PET film [manufactured by Toray Industries, Inc., Lumirror U46-100], and the PET film was overlapped. After the film was placed on the opposite substrate, it was cured at 150 ° C for 1 hour to obtain a test piece for evaluation. [10] [Attachment 1]

The test piece for evaluation was allowed to stand at 25 ° C for 24 hours, and then measured by a T-peel method defined in JIS K6854-3 within 5 minutes, and the evaluation was as follows. ○: Tensile strength is 5 N/mm or more (including PET fracture) ×: Tensile strength is less than 5 N/mm [11] [Attachment 2]

The test piece for evaluation was allowed to stand at -10 ° C for 24 hours, and then measured by a T-peel method prescribed in JIS K6854-3 within 5 minutes, and evaluated as follows. ○: Tensile strength is 5 N/mm or more (including PET fracture) ×: Tensile strength is less than 5 N/mm [12] [Softness]

The test piece for evaluation was allowed to stand at -10 ° C for 24 hours, and then wound with a rod having a diameter of 8 mm for 1 minute within 5 minutes, and visually observed, and evaluated as follows. ○: 0 cracks ×: 1 or more cracks [13] [Storage stability]

Immediately after the resin composition (C-1) and the adhesion improving agent were mixed, the viscosity at 25 ° C (viscosity after mixing) was measured, and after heating at 40 ° C for 12 hours, the viscosity was measured again (after heating) The viscosity was measured by dividing the viscosity after heating by the viscosity after mixing, and the evaluation was as follows. In addition, the viscosity was measured under the following conditions by using an R-type viscometer manufactured by Toki Sangyo Co., Ltd. Use rotor: 1°34′×R24 Measurement range: 0.5183~103.7Pa×S ○: Viscosity increase rate 1.0~5.0×: Viscosity increase rate is less than 1.0 or exceeds 5.0 [14] [Table 2]

According to the results of the examples 2-1 to 2-6, it is clear that when the composition obtained by reacting the component A and the component B is used as a patch improving agent, the coating film is attached not only under normal temperature conditions. It is excellent in the adhesiveness (adhesiveness 2) and the softness, and the outstanding storage stability of the resin composition is excellent. On the other hand, since the adhesion improving agent was not contained in the comparative example 2-1, the improvement of the adhesiveness and the softness was not seen. It is apparent that in Comparative Examples 2-2, 2-3, and 2-7, when the component A was used alone or in combination with the component B in the case of no reaction, although the flexibility was improved, the sticker was not confirmed. Attachment to improve the effect. Further, from the results of Comparative Examples 2-4, 2-5, 2-6, and 2-7, it is clear that when the component B is used alone or in combination with the component A in the case of no reaction, it is not obtained under cold conditions. Attachment improvement effect. Further, in Comparative Example 2-7, which was used without reacting the component B and the component A, the storage stability was lowered. As is clear from the above results, it is possible to obtain a material which effectively exhibits the performance of the adhesion improving agent under cold conditions only by reacting the component A with the component B.

no

Figure 1 is an IR spectrum of the composition 1 obtained in Example 1-1;

Figure 2 is an IR spectrum of the composition 2 obtained in Example 1-2;

Figure 3 is an IR spectrum of the composition 3 obtained in Example 1-3;

Figure 4 is an IR spectrum of the composition 4 obtained in Example 1-4;

Figure 5 is an IR spectrum of the composition 5 obtained in Example 1-5;

Figure 6 is an IR spectrum of the composition 6 obtained in Example 1-6;

Figure 7 is a ¹ H-NMR spectrum of the composition 1 obtained in Example 1-1;

Figure 8 is a ¹ H-NMR spectrum of the composition 2 obtained in Example 1-2;

Figure 9 is a ¹ H-NMR spectrum of the composition 3 obtained in Example 1-3;

Figure 10 is a ¹ H-NMR spectrum of the composition 4 obtained in Example 1-4;

Figure 11 is a ¹ H-NMR spectrum of the composition 5 obtained in Example 1-5;

Fig. 12 is a ¹ H-NMR spectrum of the composition 6 obtained in Example 1-6.

Claims (5)

A thioether-containing (meth) acrylate derivative represented by the following formula 1, wherein: In the formula 1, a is an integer of 1 to 3, b is 0 or 1, c is an integer of 1 to 3, a sum of b and c is 4; and R ¹ is a methylene group, an ethylene group or an isopropylene group. R ² is a divalent functional group represented by the following formula 2 or the following formula 3; R ³ is a methyl group or an ethyl group; and R ⁴ is a hydrocarbon group having 1 to 12 carbon atoms; R ^{5 in} Formula 2 is a hydrogen atom or a methyl group. R ^{5 in} Formula 3 is a hydrogen atom or a methyl group. The thioether-containing (meth) acrylate derivative according to claim 1, wherein the derivative is reacted with an acryl compound represented by the following formula 4 and a polythiol compound represented by the following formula 5; Made out, Formula 4 R ⁴ is a hydrocarbon group having 1 to 12; R ⁷ is a hydrogen atom or a methyl group, g in Formula 5 is 0 or 1, h is 3 or 4, and the sum of g and h is 4; R ¹ is a methylene group, an ethylene group or an isopropylidene group; and R ³ is a methyl group or an ethyl group. a thioether-containing (meth) acrylate derivative represented by the following formula 6, wherein In the formula 6, d is an integer of 1 to 5, e is an integer of 0 to 2, f is an integer of 1 to 5, and the sum of d and e and f is 6; and R ¹ is a methylene group, an ethylene group or a different a propylene group; R ² is a divalent functional group represented by the following formula 2 or the following formula 3; R ³ is a methyl group or an ethyl group; R ⁴ is a hydrocarbon group having 1 to 12 carbon atoms; and R ⁶ is a formula: a hexavalent functional group as shown in 7, R ^{5 in} Formula 2 is a hydrogen atom or a methyl group. R ^{5 in} Formula 3 is a hydrogen atom or a methyl group. . The thioether-containing (meth) acrylate derivative according to claim 3, wherein the derivative is reacted with an acryl compound represented by the following formula 4 and a polythiol compound represented by the following formula 8 Made out, Formula 4 R ⁴ is a hydrocarbon group having 1 to 12; R ⁷ is a hydrogen atom or a methyl group, i in the formula 8 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 ¹ is a methylene group, an ethylene group or an isopropylidene group; and R ³ is a methyl group or Ethyl; R ⁶ is a hexavalent functional group represented by the following formula 7, . A sulphur-containing (meth) acrylate derivative according to any one of claims 1 to 4, which is an active ingredient.