WO2015137264A1

WO2015137264A1 - Thioether-containing (meth)acrylate derivative and adhesion improver containing same

Info

Publication number: WO2015137264A1
Application number: PCT/JP2015/056773
Authority: WO
Inventors: 寛田代; 一洋幸田; 俊伸藤村
Original assignee: 日油株式会社
Priority date: 2014-03-11
Filing date: 2015-03-09
Publication date: 2015-09-17
Also published as: TWI527802B; KR101748067B1; CN105473561B; TW201534592A; CN105473561A; KR20160006759A; JP2015168679A; JP6326875B2

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 improver containing the same

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

Conventionally, when various paints are applied to an inorganic substrate 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, JP-A-7-300491). Issue no.). However, since the silane coupling agent decomposes when heated, when used in a mass production line, silicon oxide is deposited in a heating furnace such as an oven, causing contamination. Also, the silane coupling agent cannot be said to have a sufficient effect of improving adhesion, for example, by simultaneously adding adhesion assistants such as salts such as titanium and zirconium, amines such as imidazole, phosphate esters and urethane resins. In many cases, adhesion could be achieved for the first time. In addition, the addition of the adhesion aid not only leads to an increase in manufacturing man-hours and costs, but 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 problem, Japanese Patent Application Laid-Open No. 2013-249282 discloses that a thioether-containing urea derivative having a specific structure is used as an adhesion improver, thereby improving adhesion without using an adhesion aid. Is disclosed.

However, as a result of examination on a film base material having flexibility in a cold region, when the thioether-containing urea derivative is used as an adhesion improver for a paint, the coating film is poor in flexibility and cracks are not generated when bent. It has been found that there is a problem that is likely to occur.

The present invention has been accomplished in view of the above circumstances, and the object thereof is to add to paints and the like, exhibit an effect of improving adhesion without an adhesion aid even in cold regions, and the obtained coating film It is to provide a material having flexibility.

The present invention includes the following [1] to [3].

[1] A thioether-containing (meth) acrylate derivative represented by the following formula 1.

(A in the formula is an integer from 1 to 2, b is an integer from 1 to 2, .R ¹ is a + b = 3 is a trivalent group represented by the following formula 2, ^{R 2} is A divalent group represented by the following

formula

3 or 4. The R ³ is a hydrocarbon group having 1 to 12 carbon atoms.

_(-CH 2 ^{R 4} in the formula _{_{-, - CH 2 CH 2 -}} , or _-CH 2 CH (CH ₃₎ - and is.)

(R ₅ is a hydrogen atom or a methyl group.)

(R ₅ is a hydrogen atom or a methyl group.)

[2] The thioether-containing (meth) acrylate derivative according to [1] above, wherein an acrylic compound represented by the following formula 5 and a polyvalent thiol compound represented by the following formula 6 are reacted.

(In the formula, R ³ is a hydrocarbon group having 1 to 12 carbon atoms. R ⁵ is a hydrogen atom or a methyl group.)

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

In the present invention, “(meth) acrylate” is a concept including both “methacrylate” and “acrylate”.

The thioether-containing (meth) acrylate derivative of the present invention exhibits an effect of improving adhesion without an adhesion assistant even in a cold environment such as −10 ° C., and the resulting coating film has flexibility. Have. Therefore, for example, by adding a small amount to the paint, it is possible to impart high adhesion to the paint without requiring the addition of an adhesion assistant. The above effect is that, in a cold environment, the ester group having a specific carbon chain imparts flexibility to the paint, and this ester group does not prevent the thioether group and the base material from approaching each other. It is considered that the effect of improving the performance is accurately demonstrated.

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

Embodiments that embody the present invention will be described in detail below.
<Thioether-containing (meth) acrylate derivative>
The thioether-containing (meth) acrylate derivative of this embodiment is a compound represented by the following formula 1.

formula

3 or 4. The R ³ 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.)

Examples of the hydrocarbon group having 1 to 12 carbon atoms, which is R ³ in the above formula 1, include a linear alkyl group, an alkyl group having a side chain, and a cyclic alkyl group.

R ⁴ in the above formula 2 is a methylene group, an ethylene group, or an isopropylene group, and an ethylene group or an isopropylene group is particularly preferable because the effect of improving adhesion is enhanced.

<Method for producing thioether-containing (meth) acrylate derivative>
The thioether-containing (meth) acrylate derivative represented by the above formula 1 is represented by, for example, an acrylic compound having a (meth) acrylate group (hereinafter referred to as A component) as represented by the following formula 5 and the following formula 6. It can be obtained by reacting with a polyvalent thiol compound having a thiol group (—SH) (hereinafter referred to as B component).

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

As the component B represented by the above formula 6, tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, tris-[(3-mercaptobutyryloxy) -ethyl]]-isocyanurate, tris- [ (3-mercaptobutyryloxy) -ethyl]]-isocyanurate.

The thioether-containing (meth) acrylate derivative of the present embodiment is produced by reacting the A component and the B component at a temperature of 5 ° C. or higher, and is preferably reacted 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. Furthermore, if a base catalyst and a radical generator are added, it can be made to react in a high yield in a shorter time.

The base catalyst is preferably an amine base catalyst, 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) undec-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 (meth) acrylate derivative, the reaction can be allowed to proceed even without a solvent. However, when the reaction is performed at a low temperature, for example, when it is desired to lower the viscosity, the reaction can be performed by adding a solvent. In that case, a solvent that does not react with the carbon-carbon double bond of the (meth) acrylate group or the thiol group, for example, alcohols, ketones, and esters is preferable.

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

In the two components, the A component and the B component, the (meth) acrylate group of the A component and the thiol group of the B component react by the reaction formula represented by the following formula 7. 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 7, both of the two carbons forming the double bond of the (meth) acrylate group of the A component are bonded to S of the thiol group. The production ratio of the two products varies depending on the reaction conditions. For example, when a base catalyst such as amine is added to the reaction system as a catalyst for this reaction, a large amount of product (1) is produced, and the radical generator is produced in the reaction system. When added to, a large amount of product (2) tends to be formed. In many cases, the thioether-containing acrylic derivative after production is a mixture of products (1) and (2).

<Adhesion improver>
By blending the thioether-containing (meth) acrylate derivative of this embodiment into a resin composition such as a paint or an adhesive, adhesion to both inorganic materials 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 (meth) acrylate derivative. Therefore, a substrate that forms a chemical bond with a thioether group (high chemical affinity), for example, an inorganic substrate such as a transition metal or an alloy thereof, a silicon compound, a phosphorus compound, a sulfur compound, or a boron compound, 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 (meth) acrylate derivative as an active ingredient is highly adhesive when added in an amount of 0.1 to 80% by mass as the active ingredient relative to the resin component in the resin composition such as paint or adhesive. Can demonstrate its sexuality. This adhesion improver also has the effect of increasing the flexibility of the resin by the ester group, and the resulting coating film has excellent flexibility.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples.

(Examples 1-1 to 1-5)
First, in Examples 1-1 to 1-5, thioether-containing (meth) acrylate derivatives (composites 1 to 5) were synthesized using the following components A and B. The A component and 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 <Polyvalent thiol compound: Component B>
B-1: Tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate (Formula 8 below).

[Synthesis of thioether-containing (meth) acrylate 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 60 ° C., the component A was added dropwise over 1 hour. After completion of dropping, the mixture was further stirred at 60 ° C. for 2 hours for reaction.

[Infrared absorption spectrum analysis (IR)]
The obtained composites 1 to 5 were subjected to infrared absorption spectrum analysis (IR) under the following conditions. The IR spectra are shown in FIGS. 1 to 5 and typical IR peaks are shown below.
Model: Travel IR, manufactured by ST Japan
Decomposition: 8 cm ⁻¹ , Integration count: 32 times

Example 1-1 (Compound 1): FIG.
2960 cm ⁻¹ : 99% T, 1733 cm ⁻¹ : 84% T, 1690 cm ⁻¹ : 73% T, 1459 cm ⁻¹ : 81% T, 1351 cm ⁻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 (Compound 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 (Compound 3): FIG.
2964 cm ⁻¹ : 99% T, 1733 cm ⁻¹ : 84% T, 1690 cm ⁻¹ : 73% T, 1459 cm ⁻¹ : 81% T, 1351 cm ⁻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

Example 1-4 (Compound 4): FIG.
2925 cm ⁻¹ : 97% T, 1737 cm ⁻¹ : 87% T, 1690 cm ⁻¹ : 78% T, 1459 cm ⁻¹ : 84% T, 1351 cm ⁻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 (Compound 5): FIG.
2956 cm ⁻¹ : 99% T, 1733 cm ⁻¹ : 86% T, 1690 cm ⁻¹ : 76% T, 1459 cm ⁻¹ : 83% T, 1351 cm ⁻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 infrared absorption spectrum analysis, since the peak of 1600 to 1680 cm ⁻¹ derived from C═C was not observed, it was found that the A component reacted with the B component.

[Nuclear magnetic resonance spectrum analysis ( ¹ H-NMR)]
Further, the synthesized products 1 to 5 obtained in Examples 1-1 to 1-5 were subjected to nuclear magnetic resonance spectrum analysis under the following conditions. The results are shown in FIGS. 6 to 10, and the assignment of peaks in each spectrum and the structure of each synthesized product analyzed thereby are shown below.
Model: Nippon Bruker Co., Ltd., 400MHz-Advanced400
Integration count: 32 times Solvent: Deuterated chloroform standard: TMS

Example 1-1 (Compound 1): FIG.

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 to 2. 9 ppm, d, i, j, k, l: 4.0 to 4.5 ppm

Example 1-2 (Compound 2): FIG.

a: 0.9 to 1.0 ppm, b: 1.3 to 1.6 ppm, c, o: 1.5 to 1.7 ppm, e, f, g, h, m, n: 2.5 to 2. 9 ppm, d, i, j, k, l: 4.0 to 4.5 ppm

Example 1-3 (Compound 3): FIG.

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 to 4.6 ppm

Example 1-4 (Compound 4): FIG.

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 to 1.7 ppm, n, m, p, o, u, v: 2.5 to 2.9 ppm, l, q, r, s, t: 4.0 to 4.5 ppm

Example 1-5 (Compound 5): FIG.

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 to 2.9 ppm, h, m, n, o, p: 3.8 to 4.4 ppm

From FIGS. 6 to 10 and the above assignments, since no peak derived from CH═C (CH ₃ ) — in the vicinity of 5.0 to 5.8 ppm is observed, A-1 to A-4 react with B-1. I found out.

(Examples 2-1 to 2-5, Comparative Examples 2-1 to 2-5)
Next, in Examples 2-1 to 2-5, the above composites 1 to 5 were added to the resin composition as an adhesion improver, and the performance was evaluated. Furthermore, in the comparative example, when only the A component before the reaction is used as the adhesion improver, only the B component before the reaction is used, the A component and the B component before the reaction are used, and the adhesion is improved. The performance was evaluated when the agent was not used.

As the resin composition, a phenol novolac type epoxy resin [manufactured by Toto Kasei Co., Ltd., YDPN638] was used. A mixture (referred to as C-1) in which 98% by mass of the epoxy resin was mixed with 2% by mass of a catalyst [imidazole type catalyst: manufactured by Adeka Co., Ltd., EH-4344S] was blended according to the formulation table of Table 2. The composition was applied on a PET film having a width of 25 mm [manufactured by Toray Industries, Inc., Lumirror U46-100] with a bar coater to a thickness of 100 microns, and the PET film was laminated on the opposing substrate, and then the coating was applied at 150 ° C., 1 The test piece for evaluation was obtained by curing under time conditions.

[Adhesion 1]
The test piece for evaluation was allowed to stand at 25 ° C. for 24 hours, and was measured by the T-type peeling method defined in JIS K6854-3 within 5 minutes, and evaluated as follows.
○: Tensile strength of 5 N / mm or more (including PET fracture)
X: Tensile strength is less than 5 N / mm [Adhesion 2]
The test piece for evaluation was allowed to stand at −10 ° C. for 24 hours, and was measured within 5 minutes by the T-peeling method defined in JIS K6854-3, and evaluated as follows.
○: Tensile strength of 5 N / mm or more (including PET fracture)
X: Tensile strength is less than 5 N / mm

[Flexibility]
The test specimen for evaluation was allowed to stand at −10 ° C. for 24 hours, and then wound for 1 minute on a rod having a diameter of 8 mm within 5 minutes, and evaluated as follows.
○: 0 cracks ×: 1 or more cracks

[Storage stability]
Immediately after mixing C-1 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, The viscosity increase was calculated by dividing the viscosity by the viscosity after mixing and evaluated as follows.
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
○: Thickening rate 1.0 to 5.0
X: Viscosity increase rate other than 1.0 to 5.0

From the results of Examples 2-1 to 2-5, when a composite obtained by reacting the A component and the B component is used as an adhesion improver, the coating film can be used only at normal temperature conditions (adhesion 1). In particular, it was revealed that the resin composition was excellent in adhesion and flexibility under cold conditions (adhesion 2), and further excellent storage stability of the resin composition mixed with the adhesion improver could be realized. On the other hand, in Comparative Examples 2-2, 3, and 5, when the component A was used, the flexibility was improved, but the effect of improving the adhesion was not recognized. Further, from the results of Comparative Examples 2-4 and 5, it became clear that even if the B component was used alone or not reacted with the A component, the effect of improving the adhesion could not be obtained under cold conditions. Moreover, in Comparative Example 2-5 used without reacting the B component and the A component, the storage stability was lowered. From these results, it was clarified that an effective material as an adhesion improver can be obtained even under cold conditions by reacting the A component and the B component.

Claims

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

(A in the formula is an integer from 1 to 2, b is an integer from 1 to 2, .R 1 is a + b = 3 is a trivalent group represented by the following formula 2, R 2 is A divalent group represented by the following formula 3 or 4. The R 3 is a hydrocarbon group having 1 to 12 carbon atoms.

(-CH 2 R 4 in the formula -, - CH 2 CH 2 - , or -CH 2 CH (CH 3) - and is.)

(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 | guide_body of Claim 1 formed by making the polyhydric thiol compound represented by the acrylic compound represented by following formula 5 and the following formula 6 react.

(In the formula, R 3 is a hydrocarbon group having 1 to 12 carbon atoms. R 5 is a hydrogen atom or a methyl group.)

(-CH 2 R 4 in the formula -, - CH 2 CH 2 - , or -CH 2 CH (CH 3) - and is.)
An adhesion improver comprising the thioether-containing (meth) acrylate derivative according to claim 1 or 2 as an active ingredient.