TW201534592A - Thioether-containing (meth)acrylate derivative and adhesion improving agent containing the derivative - Google Patents

Abstract

A thioether-containing (meth)acrylate derivative represented by formula (1). (In formula (1), a represents an integer of 1 or 2, b represents an integer of 1 or 2, and a + b = 3; R1 represents a trivalent group represented by formula (2); R2 represents a divalent group represented by formula (3) or formula (4); and R3 represents a hydrocarbon group having 1-12 carbon atoms.) (In formula (2), R4 represents -CH2-, -CH2CH2- or -CH2CH(CH3)-.) (In formula (3), R5 represents a hydrogen atom or a methyl group.) (In formula (4), 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 in an adhesion improving agent or 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, since the decane coupling agent is thermally decomposed, if it is used in a production line, there is a problem that cerium oxide is precipitated in a heating furnace such as an oven to cause contamination. Further, the effect of improving the adhesion of the decane coupling agent is not sufficient. For example, initial adhesion may be achieved by simultaneously adding a salt such as titanium or zirconium or an adhesion aid such as an amine such as an imidazole or a phosphate resin. . Further, the addition of the adhesion aid not only increases the man-hour and the cost of preparation, but also causes the problem that the storage stability of the coating at room temperature is deteriorated, the heat resistance and the hardness are lowered due to the addition of the adhesion aid.

Therefore, in order to improve the above-mentioned problem, Patent Document 2 discloses that a sulfur-containing urea derivative having a specific structure is used as a patch improving agent, and the adhesion can be improved even without an attaching aid.

CITATION LIST Patent Literature Patent Literature 1: JP-A-2013-249282

Technical problem to be solved by the present invention

However, it has been found that, in the case of applying a flexible film substrate in a cold zone, in the case where the above-mentioned sulfur-containing urea derivative is used as an adhesion improving agent for a coating material, there is a lack of flexibility of the coating film. Cracking is easy to occur when bending.

The present invention has been made in view of the above-described actual circumstances, and an object thereof is to provide a material which is added to a paint or the like, and which does not require an attaching aid to exhibit an effect of improving adhesion even in a cold zone, and the obtained The coating film is soft. Technical means to solve technical problems

The present invention is as follows [1] to [3].

Thioether-containing (meth) acrylate derivative [1] represented by the following formula 1, wherein, a is an integer of 1 to 2, b is an integer of 1 to 2, a + b = 3; R 1 is the following The trivalent group represented by Formula 2, R ² is a divalent group represented by the following Formula 3 or the following Formula 4; and R ³ is a hydrocarbon group having 1 to 12 carbon atoms, wherein R ⁴ is -CH ₂ -, -CH ₂ CH ₂ - or -CH ₂ CH(CH ₃ )-, wherein R ⁵ is a hydrogen atom or a methyl group, wherein R ⁵ is a hydrogen atom or a methyl group.

[2] The thioether-containing (meth) acrylate derivative according to the above [1], wherein the derivative is an acryl compound represented by the following formula 5 and a polythiol compound represented by the following formula 6 The reaction is carried out, wherein R ³ is a hydrocarbon group having 1 to 12 carbon atoms; R ⁵ is a hydrogen atom or a methyl group, wherein R ⁴ is -CH ₂ -, -CH ₂ CH ₂ - or -CH ₂ CH (CH) ₃ )-.

[3] The adhesion improving agent containing the thioether-containing (meth) acrylate derivative described in the above [1] or [2] as an active ingredient.

Further, in the present invention, "(meth) acrylate" includes two concepts of "methacrylate" and "acrylate". Effect of the invention

The thioether-containing (meth) acrylate derivative of the present invention has a patch-improving effect, for example, even in a cold environment of -10 ° C, and does not require an attaching aid, and the obtained coating film Has a soft effect. Therefore, for example, by adding a small amount to the coating material, it is possible to impart high adhesion to the coating without adding an adhesion aid. The effect is considered to be that in a cold environment, an ester group having a specific carbon chain imparts flexibility to the coating, and the ester group does not hinder the proximity of the thioether group to the substrate, thereby reliably exhibiting a thioether-based group. The adhesion improvement effect.

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

The thioether-containing (meth) acrylate derivative of the present embodiment is a compound represented by the following formula 1.

Wherein, a is an integer of 1 to 2, b is an integer of 1 to 2, a + b = 3; R 1 represented by the following formula 2 a trivalent group represented by, R ² is represented by the following formula 3 or formula 4 a divalent group represented; R ³ is a hydrocarbon group having 1 to 12 carbon atoms, wherein R ⁴ is -CH ₂ -, -CH ₂ CH ₂ - or -CH ₂ CH(CH ₃ )-, wherein R ⁵ It is a hydrogen atom or a methyl group, wherein R ⁵ is a hydrogen atom or a methyl group.

The hydrocarbon group having 1 to 12 carbon atoms of R ³ in the above formula 1 may, for example, be a linear alkyl group, a side chain-containing alkyl group or a cyclic alkyl group.

R ⁴ in the above formula 2 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.

<Preparation method of the thioether-containing (meth) acrylate derivative> The thioether-containing (meth) acrylate derivative represented by the above formula 1 can be represented, for example, by the following formula 5 ( The methyl acrylate-based acrylate compound (hereinafter referred to as component A) is obtained by reacting a polythiol compound having a thiol group (-SH) represented by the following formula 6 (hereinafter referred to as component B).

Wherein R ³ is a hydrocarbon group having 1 to 12 carbon atoms; R ⁵ is a hydrogen atom or a methyl group; wherein R ⁴ is -CH ₂ -, -CH ₂ CH ₂ - or -CH ₂ CH(CH ₃ )-.

Examples of the component A represented by the above formula 5 include methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, and dodecyl acrylate.

The component B represented by the above formula 6 is tris-[(3-mercaptopropyloxy)-ethyl]-isocyanurate or tris-[(3-mercaptobutyloxy)-ethyl] ]-Isocyanurate, tris-[(3-mercaptobutyloxy)-ethyl]]-isocyanurate.

In order to prepare the thioether-containing (meth) acrylate derivative of the present embodiment, the component A and the component B may be reacted 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 within 5 hours. Further, when a basic catalyst or a radical initiator is added, the reaction can be carried out in a high yield in a shorter period of time.

As the basic catalyst, an amine-based basic catalyst is preferable, and an amine of a primary, secondary or 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. Examples of the tertiary amine include trimethylamine, triethylamine, tripropylamine, triphenylamine, 1,8-diazabicyclo[5.4.0]undecylaminomethylphenol, and the like. Examples of the imidazole compound include imidazole homologues such as 1-methylimidazole, 1,2-dimethylimidazole, 1,4-dimethyl-2-ethylimidazole, and 1-phenylimidazole. An alkyl derivative such as benzyl-2-oxomethylimidazole or 1-methyl-2-oxoethylimidazole, 1-methyl-4(5)-nitroimidazole, 1,2-dimethyl- Nitro and amino derivatives such as 5(4)-aminoimidazole, benzimidazole, 1-methylbenzimidazole, 1-methyl-benzylbenzimidazole, and the like.

As the radical initiator, a peroxide or an azo compound is preferred. Examples of the peroxide include dibenzoyl peroxide, tert-Butylperoxy 2-ethyl hexanoate, and dilaurin peroxide. 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 even in the absence of a solvent. However, when the reaction is carried out at a low temperature or the viscosity is desired, a solvent may be added. Carry out the reaction. In this case, a solvent which does not react with a carbon-carbon double bond or a thiol group of a (meth) acrylate group, for example, an alcohol, a ketone, an ester or the like is preferable.

The alcohol used as the solvent does not contain 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. Functional groups such as. 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 be preferably maintained at a high reaction temperature.

The ketone used as a solvent does not contain 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. Functional groups such as. Examples of the ketone which does not contain the above functional group include acetone, methyl ethyl ketone, methyl isobutyl ketone, and methyl isopropanone. Among them, ketones having a boiling point of 80 ° C or higher are preferred because they can maintain a high reaction temperature.

The ester used as a solvent does not contain 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. Functional groups such as. 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 preferred because they can maintain a high reaction temperature.

The A component and the B component are two components, and 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 7. Further, X is a hydrogen atom or a methyl group, Y represents a residue other than X in which the A component is bonded to the (meth)acryl fluorenyl group, and Z represents a residue bonded to the thiol group in the B component.

As shown in Formula 7, both carbons of the double bond forming the (meth) acrylate group of the component A are bonded to S of the thiol group. The ratio of the formation of the two kinds of products varies depending on the reaction conditions. For example, when a basic catalyst such as an amine is added to the reaction system in the catalyst of the present reaction, the product (1) tends to be formed in the reaction system. When a radical initiator is added, it tends to produce a product (2). In most cases, the prepared thioether-containing acrylic acid derivative is a mixture of the products (1) and (2).

<Adhesion improving agent> The thioether-containing (meth) acrylate derivative of the present embodiment can be improved in adhesion to both inorganic materials and organic materials by being added to a resin composition such as a coating material or a binder. Attached. Therefore, it can be used as an adhesion improving agent either 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 derived from the thioether group of the thioether-containing (meth) acrylate derivative. Therefore, it has an unsaturated bond (including an aromatic ring) with respect to a substrate (chemical affinity) which forms a chemical bond with a thioether group, such as a transition metal or an alloy thereof, a ruthenium compound, a phosphorus compound, a sulfur compound or a boron compound. The organic substance, the organic substance having a hydroxyl group or a carboxyl group, or the organic substance treated by plasma or UV ozone is excellent in adhesion improving effect. Specifically, examples of the inorganic substrate include glass, enamel, various metals, and the like. Preferred examples of the organic substrate include polyethylene terephthalate, polybutylene terephthalate, polyethylene, polypropylene, polycarbonate, polyimine, ABS resin, and polyvinyl alcohol. , vinyl chloride, polyacetal, etc.

The adhesion improving agent containing the thioether-containing (meth) acrylate derivative as an active ingredient is 0.1 to 80% by mass based on the resin component in the resin composition such as a coating material or a binder, based on the active ingredient. When added, it is possible to exhibit high adhesion. The adhesion improving agent also has an effect of improving the flexibility of the resin by the ester group, and the obtained coating film has excellent flexibility. Example

Hereinafter, the present invention will be specifically described by way of examples and comparative examples.

(Examples 1-1 to 1-5) First, the thioether-containing (meth) acrylate derivative (composition 1~) was synthesized by using the following A component and B component by the following Examples 1-1 to 1-5. 5). The A component and the B component used are as follows. <Acrylic compound: component A> A-1: butyl acrylate A-2: isobutyl acrylate A-3: dodecyl acrylate A-4: 2-ethylhexyl acrylate <multivalent thiol compound: Component B> B-1: Tris-[(3-mercaptopropyloxy)-ethyl]-isocyanurate (Formula 8 below).

[Synthesis of a thioether-containing (meth) acrylate derivative] In a three-necked flask equipped with a thermometer, a stirrer, and a titration pump, component B was added according to the following Table 1, and the temperature was raised to 60 ° C, and then the component A was titrated for 1 hour. . After completion of the titration, the mixture was stirred at 60 ° C for 2 hours to cause a reaction.

[Infrared Absorption Spectrum Analysis (IR)] For the obtained compositions 1 to 5, infrared absorption spectrum analysis (IR) was performed under the following conditions. The IR spectrum is shown in Figs. 1 to 5, and representative IR peaks are shown below. Model: Travel Japan's Travel IR decomposition: 8cm ^-1 , cumulative (integrated) times: 32 times

Example 1-1 (composition 1): the first FIG. ^{1 2960cm -1: 99% T,} 1733cm -1: 84% T, 1690cm -1: 73% T, 1459cm -1: 81% T, 1351cm -1: 95% T, 1243 cm ^-1 : 91% T, 1158 cm ^-1 : 87% T, 1007 cm ^-1 : 96% T, 764 cm ^-1 : 91% T

Example 1-2 (Synthesis 2): Fig. 2 Fig. 2960 cm ^-1 : 98% T, 1732 cm ^-1 : 84% T, 1690 cm ^-1 : 78% T, 1459 cm ^-1 : 84% T, 1351 cm ^-1 : 95% T, 1243 cm ^-1 : 91% T, 1158 cm ^-1 : 88% T, 764 cm ^-1 : 93% T

Example 1-3 (composition 3): Fig. 3 ^{2964cm -1: 99% T, 1733cm} -1: 84% T, 1690cm -1: 73% T, 1459cm -1: 81% T, 1351cm -1: 95% T, 1243 cm ^-1 : 91% T, 1158 cm ^-1 : 87% T, 1003 cm ^-1 : 96% T, 818 cm ^-1 : 97% T, 764 cm ^-1 : 91% T

Examples 1-4 (composition 4): Fig. 4 ^{2925cm -1: 97% T, 1737cm} -1: 87% T, 1690cm -1: 78% T, 1459cm -1: 84% T, 1351cm -1: 96% T, 1243 cm ^-1 : 93% T, 1158 cm ^-1 : 90% T, 1003 cm ^-1 : 97% T, 837 cm ^-1 : 96% T, 764 cm ^-1 : 92% T

Example 1-5 (composition 5): the first FIG. ^{5 2956cm -1: 99% T,} 1733cm -1: 86% T, 1690cm -1: 76% T, 1459cm -1: 83% T, 1351cm -1: 95% T, 1243 cm ^-1 : 92% T, 1158 cm ^-1 : 88% T, 1007 cm ^-1 : 97% T, 764 cm ^-1 : 92% T

As is clear from the results of the above analysis of the infrared absorption spectrum, it was found that a peak of 1600 to 1680 cm ^-1 from C=C was not observed, and therefore the component A reacted with the component B.

[NMR spectrum analysis ⁽¹ H-NMR)] In addition, 1 to 5, nuclear magnetic resonance spectrum analysis under the following conditions for the compositions obtained in Examples 1-1 to 1-5. The results are shown in Figs. 6 to 10, and the assignment of the peaks in each spectrum and the structure of each composition analyzed by the same are as follows. Model: Japan Bruker Co., Ltd., 400MHz-Advance400 Cumulative: 32 times Solvent: Deuterated chloroform Reference: TMS

Example 1-1 (Synthesis 1): Figure 6 a: 0.9 to 1.0 ppm, b: 1.3 to 1.5 ppm, c, o: 1.5 to 1.7 ppm, e, f, g, h, m, n: 2.5 ~2.9ppm, d, i, j, k, l: 4.0~4. 5ppm Example 1-2 (Synthesis 2): Figure 7 a: 0.9~1.0ppm, b: 1.3~1.6ppm, c, o : 1.5~1.7ppm, e, f, g, h, m, n: 2.5~2.9ppm, d, i, j, k, l: 4.0~4. 5ppm

Example 1-3 (Synthesis 3): Fig. 8 a, b: 0.8 to 1.1 ppm, c, o: 1.6 to 2.1 ppm, e, f, g, h, m, n: 2.5 to 3.0 ppm, d , i, j, k, l: 3.8~4. 6ppm

Example 1-4 (Synthesis 4): Figure 9 a: 0.8 to 0.9 ppm, b, c, d, e, f, g, h, i, j: 1.1 to 1.4 ppm, k, w: 1.5~ 1.7ppm, n, m, p, o, u, v: 2.5~2.9ppm, l, q, r, s, t: 4.0~4.5ppm

Example 1-5 (Synthesis 5): Figure 10 a, e: 0.7 to 1.0 ppm, b, c, d, f: 1.1 to 1.4 ppm, q, s: 1. 5 to 1.8 ppm, i, j , k, l, q, r: 2.5~2.9ppm, h, m, n, o, p: 3.8~4.4ppm

From Fig. 6 to Fig. 10 and the attribution, it is known that since the peak from CH=C(CH ₃ )- is not observed near 5.0 to 5.8 ppm, A-1 to A-4 and B-1 occur. The reaction.

(Examples 2-1 to 2-5, Comparative Examples 2-1 to 2-5) Next, in the examples 2-1 to 2-5, the above-mentioned composites 1 to 5 were added as adhesion improving agents. In the resin composition, the properties were evaluated. Further, in the comparative example, the case where only the component A before the reaction is used as the adhesion improving agent, the case where only the component B before the reaction is used, the case where the component A and the component B before the reaction are used, and the unused In the case of the adhesion improving agent, the performance evaluation was performed.

As the resin composition, a phenol novolac type epoxy resin (manufactured by Tohto Kasei Co., Ltd., YDPN638) was used. In a mixture (as C-1) prepared by mixing 2% by mass of a catalyst (imidazole-type catalyst: manufactured by ADEKA Co., Ltd., EH-4344S) in 98% by mass of the epoxy resin, according to the ratio table of Table 2 Add to. This composition was applied to a 25 mm wide PET film [manufactured by TORAY Co., Ltd., lumirror U46-100] at a thickness of 100 μm using a bar coater. The PET film was placed on the opposite substrate, and then cured at 150 ° C for 1 hour to obtain a test piece for evaluation.

[Adhesiveness 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 following evaluation was performed. ○: Tensile strength is 5 N/mm or more (including PET fracture) ×: Tensile strength is less than 5 N/mm

[Adhesiveness 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 the following evaluation was performed. ○: Tensile strength is 5 N/mm or more (including PET fracture) ×: Tensile strength is less than 5 N/mm

[Softness] The test piece for evaluation described above was allowed to stand at -10 ° C for 24 hours, and then wound on a rod having a diameter of 8 mm for 1 minute in 5 minutes, and the following evaluation was carried out. ○: 0 cracks ×: 1 or more cracks

[Storage Stability] C-1 was mixed with an adhesion improving agent, and then its viscosity at 25 ° C (viscosity after mixing) was measured, and the viscosity was measured again after heating at 40 ° C for 12 hours (after heating) Viscosity), the viscosity increase after heating was calculated by dividing the viscosity after heating by the viscosity after mixing, and the following evaluation was performed. In addition, the viscosity was measured by the following conditions using the R-type viscometer manufactured by Toki Sangyo Co., Ltd. Use rotor: 1°34'×R24 Measurement range: 0.5183~103.7 PA・s ○: Thickening ratio 1.0~5.0 ×: Thickening ratio other than 1.0~5.0

According to the results of Examples 2-1 to 2-5, 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 not only at normal temperature conditions (adhesiveness 1), even Under cold conditions (adhesiveness 2), it is excellent in adhesion and flexibility, and further, excellent storage stability of the resin composition in which the adhesion improving agent is mixed can be achieved.

On the other hand, in Comparative Examples 2-2, 2-3, and 2-5, although the softness was improved by using the component A, the effect of improving the adhesion was not observed. Further, from the results of Comparative Examples 2-4 and 2-5, the use of the component B alone or the reaction with the component A did not provide an effect of improving the adhesion under cold conditions. Further, in Comparative Example 2-5, in which the component B was not reacted with the component A, the storage stability was lowered. As apparent from the above results, only by reacting the component A with the component B, a material which is effectively used as an adhesion improving agent in cold conditions can be obtained.

no.

Fig. 1 is an IR chart of the composition 1 obtained in Example 1-1.

Fig. 2 is an IR spectrum of the composition 2 obtained in Example 1-2.

Fig. 3 is an IR spectrum of the composition 3 obtained in Example 1-3.

Fig. 4 is an IR spectrum of the composition 4 obtained in Example 1-4.

Fig. 5 is an IR spectrum of the composition 5 obtained in Example 1-5.

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

Fig. 7 is a ¹ H-NMR chart of the composition 2 obtained in Example 1-2.

Fig. 8 is a ¹ H-NMR chart of the composition 3 obtained in Example 1-3.

Fig. 9 is a ¹ H-NMR chart of the composition 4 obtained in Example 1-4.

Fig. 10 is a ¹ H-NMR chart of the composition 5 obtained in Example 1-5.

Claims (3)

A thioether-containing (meth) acrylate derivative represented by the following formula 1, wherein a is an integer of 1-2, b is an integer of 1-2, a+b=3; and R ¹ is Formula 2 below The trivalent group represented, R ² is a divalent group represented by the following formula 3 or the following formula 4; and R ³ is a hydrocarbon group having 1 to 12 carbon atoms, wherein R ⁴ is -CH ₂ -, -CH ₂ CH ₂ - or -CH ₂ CH(CH ₃ )- , wherein R ⁵ is a hydrogen atom or a methyl group, wherein R ⁵ is a hydrogen atom or a methyl group. The thioether-containing (meth) acrylate derivative according to the first aspect of the invention, wherein the derivative is an acryl compound represented by the following formula 5 and a polythiol compound represented by the following formula 6 The reaction is carried out, wherein R ³ is a hydrocarbon group having 1 to 12 carbon atoms; R ⁵ is a hydrogen atom or a methyl group, wherein R ⁴ is -CH ₂ -, -CH ₂ CH ₂ - or -CH ₂ CH (CH) ₃ )-. An adhesion improving agent comprising, as an active ingredient, a thioether-containing (meth) acrylate derivative as described in claim 1 or 2.