JP2011136985A - Thioether-containing alkoxysilane derivative and use thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thioether-containing alkoxysilane derivative having excellent adhesiveness improving effect. <P>SOLUTION: The thioether-containing alkoxysilane derivative is a compound expressed by formula 1. In the formula: (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; (m) is 1 or 2; R<SP>1</SP>is a bivalent group expressed by -CH<SB>2</SB>-CH(CH<SB>3</SB>)- or -C(CH<SB>3</SB>)<SB>2</SB>-; and R<SP>2</SP>is methyl or ethyl. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a novel thioether-containing alkoxysilane derivative suitably used for an adhesion improver and the like and uses of the thioether-containing alkoxysilane derivative.

  Conventionally, when various paints are applied to an inorganic base material such as glass, a silane coupling agent has been added to the paint for the purpose of improving adhesion (see, for example, Patent Document 1). However, many of the silane coupling agents have a low boiling point, and it was necessary to add a large amount to a paint that requires high-temperature coating. In addition, it cannot be said that the effect of improving the adhesion is sufficient, for example, by adding simultaneously an adhesion assistant such as a salt such as titanium or zirconium, an amine such as imidazole, a phosphate ester, a urethane resin, or a thiol compound. In many cases, gender was achieved. However, the formulation of these adhesion assistants not only increases the number of steps, but also requires an optimization operation of the adhesion assistant species and addition amount that do not impair the coating properties.

JP-A-7-300491

The present invention has been accomplished in view of the above circumstances, and a first object thereof is to provide a thioether-containing alkoxysilane derivative that is excellent in the effect of improving adhesion.
Furthermore, the second object of the present invention is to provide the use of the above thioether-containing alkoxysilane derivative.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a thioether-containing alkoxysilane derivative having a specific structure has an excellent adhesion improving effect, and have completed the invention.

That is, the present invention includes the following [1] to [5].
[1] A thioether-containing alkoxysilane 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. m is 1 or 2. R ¹ is a divalent group represented by —CH ₂ —CHR ⁵ — or —CR ⁵ (CH ₃ ) — (R ⁵ is a hydrogen atom or a methyl group), and R ² is a methyl group or It is an ethyl group.)
[2] A thioether-containing alkoxysilane derivative represented by the following formula 2.

(In the formula, d is an integer of 0 to 5, e is an integer of 0 to 2, f is an integer of 1 to 6, and the sum of d, e, and f is 6. m is 1 or R ¹ is a divalent group represented by —CH ₂ —CHR ⁵ — or —CR ⁵ (CH ₃ ) — (R ⁵ is a hydrogen atom or a methyl group), and R ² is a methyl group. Or an ethyl group, and R ³ is a hexavalent group represented by the following formula 3.)

[3] The thioether-containing alkoxysilane derivative according to the above [1], obtained by reacting an alkoxysilyl group-containing compound represented by the following formula 4 with a polyvalent thiol compound represented by the following formula 5.

(In the formula, R ⁵ is a hydrogen atom or a methyl group, and R ² is a methyl group or an ethyl group.)

(In the formula, g is 0 or 1, h is 3 or 4, the sum of g and h is 4, and m is 1 or 2.)
[4] The thioether-containing alkoxysilane derivative according to the above [2], obtained by reacting an alkoxysilyl group-containing compound represented by the following formula 4 with a polyvalent thiol compound represented by the following formula 6.

(In the formula, R ⁵ is a hydrogen atom or a methyl group, and R ² is a methyl group or an ethyl group.)

(Wherein i is an integer of 0 to 2, j is an integer of 4 to 6, the sum of i and j is 6, and m is 1 or 2. R ⁴ is represented by the following formula 3. A hexavalent group.)

[5] An adhesion improver comprising the thioether-containing alkoxysilane derivative according to any one of [1] to [4] as an active ingredient.

  The thioether-containing alkoxysilane derivative of the present invention has an excellent adhesion improving effect, and it is necessary to add an adhesion aid by adding a relatively small amount of, for example, 0.1 to 10% by mass to the paint. It is possible to impart high adhesion to the paint without having to do so.

  Further, since the thioether-containing alkoxysilane derivative is excellent in the adhesion imparting effect, it is useful as an adhesion improver that imparts adhesion to paints and the like.

3 is a chart showing a nuclear magnetic resonance spectrum of the compound obtained in Example 1. 3 is a chart showing a nuclear magnetic resonance spectrum of the compound obtained in Example 2. 3 is a chart showing a nuclear magnetic resonance spectrum of the compound obtained in Example 3. 6 is a chart showing a nuclear magnetic resonance spectrum of the compound obtained in Example 4. 6 is a chart showing a nuclear magnetic resonance spectrum of the compound obtained in Example 5. 10 is a chart showing a nuclear magnetic resonance spectrum of the compound obtained in Example 11. 10 is a chart showing a nuclear magnetic resonance spectrum of the compound obtained in Example 12.

Embodiments that embody the present invention will be described in detail below.
<Thioether-containing alkoxysilane derivative>
The thioether-containing alkoxysilane derivative of this embodiment is a compound 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. m is 1 or 2. R ¹ is a divalent group represented by —CH ₂ —CHR ⁵ — or —CR ⁵ (CH ₃ ) — (R ⁵ is a hydrogen atom or a methyl group), and R ² is a methyl group or An ethyl group.

  Moreover, the thioether containing alkoxysilane derivative of this embodiment is a compound represented by the following formula 2.

(In the formula, d is an integer of 0 to 5, e is an integer of 0 to 2, f is an integer of 1 to 6, and the sum of d, e, and f is 6. m is 1 or R ¹ is a divalent group represented by —CH ₂ —CHR ⁵ — or —CR ⁵ (CH ₃ ) — (R ⁵ is a hydrogen atom or a methyl group), and R ² is methyl. And R ³ is a hexavalent group represented by the following formula 3.)

The thioether-containing alkoxysilane derivative of formula 1 is compatible with many resins and can be used in a wide range of applications. The thioether-containing alkoxysilane derivative of formula 2 is suitable for a case where high adhesion is desired with a small amount of addition. Used.
<Method for producing thioether-containing alkoxysilane derivative>
The thioether-containing alkoxysilane derivative represented by Formula 1 or Formula 2 includes, for example, an alkoxysilyl group [—Si (OR ² ) ₃ ] and a compound having a double bond (hereinafter referred to as A component), a thiol group (— SH) can be obtained by reacting with a polyvalent thiol compound (hereinafter referred to as B component). In these two components, the double bond 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 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 that form the double bond of the A component bind to S of the thiol. 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 alkoxysilane derivative after production is a mixture of the products (1) and (2).

  Moreover, in producing a thioether-containing alkoxysilane derivative, since the B component has 3 to 6 thiol groups, a product in which a part of the thiol groups of the B component reacts with the A component as shown in Formula 8. Can be obtained. V represents a residue bonded to the thiol group of the B component.

The added number of the A component in Expression 8 corresponds to c in Expression 1 and f in Expression 2. In many cases, the thioether-containing alkoxysilane derivative after production is a mixture of substances having different numbers of addition-reacted substituents.

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

  In the method for producing a thioether-containing alkoxysilane derivative, the reaction can be allowed to proceed even without a solvent, but when the viscosity is to be lowered, for example, when the reaction is carried out at a low temperature, the reaction can be carried out by adding a solvent. In that case, a solvent that does not react with an alkoxysilyl group, a double bond, or a thiol group, for example, alcohols, ketones, esters, or aromatics is preferable.

  Of the thioether-containing alkoxysilane derivatives, the compound represented by Formula 1 can be obtained by reacting an alkoxysilyl group-containing compound represented by Formula 4 below with a polyvalent thiol compound represented by Formula 5 below. it can.

(In the formula, R ⁵ is a hydrogen atom or a methyl group, and R ² is a methyl group or an ethyl group.)

(In the formula, g is 0 or 1, h is 3 or 4, the sum of g and h is 4, and m is 1 or 2.)
Among the thioether-containing alkoxysilane derivatives, the compound represented by the formula 2 can be obtained by reacting the alkoxysilyl group-containing compound represented by the formula 4 with a polyvalent thiol compound represented by the following formula 6. it can.

(Wherein i is an integer of 0 to 2, j is an integer of 4 to 6, the sum of i and j is 6, and m is 1 or 2. R ⁴ is represented by the following formula 3. A hexavalent group.)

<Adhesion improver>
The thioether-containing alkoxysilane derivative can be used as an adhesion improver because it has a high adhesion improving performance particularly for inorganic substrates such as glass and metal. Adhesion improver comprising thioether-containing alkoxysilane derivative as an active ingredient should exhibit high adhesion improvement effect by blending with epoxy resin, urethane resin, acrylic resin, polyimide resin, compound having double bond, etc. Can do.

  Further, the thioether-containing alkoxysilane derivative represented by the formula 1 in which a is not 0 or the thioether-containing alkoxysilane derivative in which d is not 0 has a thiol group, Reacts with groups, double bonds and isocyanate groups. For this reason, by adding a thioether-containing alkoxysilane derivative to an epoxy resin, an acrylic resin, a urethane resin, or a compound having a double bond, an even higher adhesion effect can be exhibited.

  The adhesion improver comprising a thioether-containing alkoxysilane derivative as an active ingredient preferably exhibits 0.1 to 30% by mass, more preferably 0.1 to 10% by mass of the resin as an active ingredient, and exhibits high adhesion. be able to.

Hereinafter, the embodiment will be described more specifically with reference to synthesis examples, examples, and comparative examples. The measurement methods and evaluation methods used in each example and comparative example are shown below.
<Infrared absorption spectrum analysis (IR)>
Model: JASCO Corporation FT / IR-600
Cell: Expanded on KBr, decomposed; 4 cm ⁻¹ , integration number: 16 times <Nuclear magnetic resonance spectrum analysis (NMR)>
Model: Nippon Bruker Co., Ltd., 400 MHz-Advanced 400, conditions: 16 times of accumulation, solvent: heavy chloroform <viscosity>
Model: Toki Sangyo Co., Ltd. (R type viscometer), temperature: 25 ° C
<Adhesion evaluation>
A sample with a cured film formed thereon was treated at a temperature of 121 ° C. and a relative humidity (RH) of 100% for 8 hours, and then the mechanical properties-adhesiveness (cross-cut method) test of the coating film defined in JIS K5600-5-6 Evaluation was performed by the law. And what did not peel at all was set as the pass.

The reagents used in the examples and comparative examples are shown below.
<Compound having alkoxysilyl group: Component A>
3-methacryloxypropyltrimethoxysilane (hereinafter referred to as A-1). The structure is shown in the following formula 9.

3-acryloxypropyltrimethoxysilane (hereinafter referred to as A-2). The structure is shown in the following formula 10.

3-methacryloxypropyltriethoxysilane (hereinafter referred to as A-3). The structure is shown in the following formula 11.

<Multivalent thiol compound: Component B>
Trimethylolpropane tris (3-mercaptopropionate) (hereinafter referred to as B-1). The structure is shown in the following formula 12 (viscosity 0.1 Pa · s).

Pentaerythritol tetrakis (3-mercaptopropionate) (hereinafter referred to as B-2). The structure is shown in the following formula 13 (viscosity 0.4 Pa · s).

Dipentaerythritol hexakis (3-mercaptopropionate) (hereinafter referred to as B-3). The structure is shown in the following formula 14 (viscosity 2.5 Pa · s).

Methyl-3-mercaptopropionate (hereinafter referred to as β-1). The structure is shown in the following formula 15.

Tetraethylene glycol bis (3-mercaptopropionate) (hereinafter referred to as β-2). The structure is shown in the following formula 16.

(Examples 1-5 and 11, 12)
A separable four-necked flask was equipped with a thermometer and a reflux tube, and the inside was made a nitrogen atmosphere. Into this four-necked flask, A component and B component were charged according to the following Table 1, and reacted at 90 ° C. for 6 hours. Table 1 shows the viscosity after the reaction for 6 hours. In addition, IR and NMR results are shown below according to Table 1 and shown in FIGS.
(Synthesis Examples 1 and 2)
A separable four-necked flask was equipped with a thermometer and a reflux tube, and the inside was made a nitrogen atmosphere. In accordance with the following Table 1, A and B components were charged into this four-necked flask and reacted at 90 ° C. for 6 hours.

<Results of IR>
(Result I1)
2945 cm ⁻¹ : 57% T, 2841 cm ⁻¹ : 64% T, 1736 cm ⁻¹ : 41% T, 1464 cm ⁻¹ : 72% T, 1414 cm ⁻¹ : 70% T, 1388 cm ⁻¹ : 78% T, 1352 cm ^{− 1} : 76% T, 1192 cm ⁻¹ : 49% T, 1086 cm ⁻¹ : 41% T, 820 cm ⁻¹ : 57% T
(Result I2)
2945 cm ⁻¹ : 44% T, 2841 cm ⁻¹ : 50% T, 1736 cm ⁻¹ : 26% T, 1466 cm ⁻¹ : 61% T, 1414 cm ⁻¹ : 70% T, 1388 cm ⁻¹ : 66% T, 1352 cm ^{− 1} : 63% T, 1192 cm ⁻¹ : 31% T, 1086 cm ⁻¹ : 25% T, 982 cm ⁻¹ : 70% T, 820 cm ⁻¹ : 57% T
(Result I3)
2945 cm ⁻¹ : 47% T, 2841 cm ⁻¹ : 52% T, 1736 cm ⁻¹ : 30% T, 1464 cm ⁻¹ : 62% T, 1414 cm ⁻¹ : 71% T, 1388 cm ⁻¹ : 67% T, 1352 cm ^{− 1} : 64% T, 1192 cm ⁻¹ : 35% T, 1086 cm ⁻¹ : 30% T, 982 cm ⁻¹ : 70% T, 820 cm ⁻¹ : 45% T
(Result I4)
^{2945cm -1: 46% T, 2841cm} -1: 54% T, 2569cm -1: 94% T, 1736cm -1: 22% T, 1464cm -1: 60% T, 1414cm -1: 63% T, 1388cm - ¹ : 60% T, 1354 cm ⁻¹ : 54% T, 1192 cm ⁻¹ : 30% T, 1086 cm ⁻¹ : 27% T, 822 cm ⁻¹ : 45% T
(Result I5)
^{2945cm -1: 57% T, 2841cm} -1: 68% T, 2569cm -1: 92% T, 1738cm -1: 24% T, 1464cm -1: 67% T, 1390cm -1: 62% T, 1356cm - ¹ : 56% T, 1153 cm ⁻¹ : 33% T, 1084 cm ⁻¹ : 36% T, 822 cm ⁻¹ : 59% T
(Result I6)
2945 cm ⁻¹ : 60% T, 2841 cm ⁻¹ : 67% T, 1737 cm ⁻¹ : 29% T, 1465 cm ⁻¹ : 79% T, 1414 cm ⁻¹ : 78% T, 1389 cm ⁻¹ : 77% T, 1355 cm ^{− 1} : 73% T, 1193 cm ⁻¹ : 39% T, 1086 cm ⁻¹ : 30% T, 821 cm ⁻¹ : 53% T
(Result I7)
^{2974cm -1: 52% T, 2927cm} -1: 63% T, 1738cm -1: 36% T, 1460cm -1: 76% T, 1389cm -1: 67% T, 1353cm -1: 74% T, 1166cm - ¹ : 42% T, 1079 cm ⁻¹ : 39% T, 958 cm ⁻¹ : 59% T, 791 cm ⁻¹ : 66% T
As a result, the peak at 2569 cm ⁻¹ in I4 and I5 is attributed to the thiol group. In the results I1 to I7, since a peak of 1600 to 1700 cm ⁻¹ derived from C═C is not observed, it is understood that A-1, A-2, and A-3 are reacted.
<Results of NMR>
1 shows the NMR spectrum of the result N1 shown in Table 1, FIG. 2 shows the NMR spectrum of the result N2, FIG. 3 shows the NMR spectrum of the result N3, FIG. 4 shows the NMR spectrum of the result N4, and FIG. The NMR spectrum of the result N6 is shown in FIG. 6 and the NMR spectrum of the result N7 is shown in FIG.

  The assignment of peaks in each NMR spectrum is shown in the following formula 15.

a: 3.4-3.6 ppm, b: 0.6-0.7 ppm, c: 1.7-1.8 ppm, d: 4.0-4.2 ppm, e, g, h, i: 2. 6-2.8 ppm, f: 1.1-1.3 ppm, j: 3.9-4.2 ppm, k: 1.5-1.6 ppm, l: 0.6-0.7 ppm, m: 1. 6-1.7ppm
Peaks derived from thiol were confirmed in results N4 and N5, but no peaks derived from thiol groups were observed in results N1 to N3, results N6, and results N7. Further, from the results N1~ result N7, since the peak derived from _CH 2 = C is not observed, A-1, A-2 and A-3 were found to react.
(Examples 6 to 10 and 13, 14)
As an epoxy resin, 98% by mass of YDPN638 [phenol novolac type epoxy resin: manufactured by Toto Kasei Co., Ltd., product name] and 2% by mass of EH-4344S [imidazole type catalyst: manufactured by Adeka Co., Ltd., product name] A mixture was selected (hereinafter referred to as E-1). This E-1 and the adhesion improvers obtained in Examples 1 to 5 and Examples 11 and 12 were blended according to the blending amounts in Table 2. The blended sample is applied to OA-10 [non-alkali glass: product name, manufactured by Nippon Denki Glass Co., Ltd.] with a bar coater, and cured at 150 ° C. for 1 hour to obtain a cured film as a resin molded product. It was. The adhesion of the obtained cured film was evaluated, and the results are shown in Table 2.
(Comparative Examples 1-3)
E-1 and the sample obtained in Synthesis Example 1 or 2 or A-1 were blended according to the blending amounts in Table 2. The blended sample is applied to OA-10 [non-alkali glass: product name, manufactured by Nippon Denki Glass Co., Ltd.] with a bar coater, and cured at 150 ° C. for 1 hour to obtain a cured film as a resin molded product. It was. The adhesion of the obtained cured film was evaluated, and the results are shown in Table 2.

From the results shown in Table 2, in Examples 6 to 10 and Examples 13 and 14, no peeling was observed, and the adhesion was good. On the other hand, in Comparative Examples 1 to 3, since compounds other than the thioether-containing alkoxysilane derivative of the present invention were used, peeling occurred and the adhesion was poor.

Claims (5)

A thioether-containing alkoxysilane 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. m is 1 or 2. R ¹ is a divalent group represented by —CH ₂ —CHR ⁵ — or —CR ⁵ (CH ₃ ) — (R ⁵ is a hydrogen atom or a methyl group), and R ² is a methyl group or It is an ethyl group.) A thioether-containing alkoxysilane derivative represented by the following formula 2.
(In the formula, d is an integer of 0 to 5, e is an integer of 0 to 2, f is an integer of 1 to 6, and the sum of d, e, and f is 6. m is 1 or R ¹ is a divalent group represented by —CH ₂ —CHR ⁵ — or —CR ⁵ (CH ₃ ) — (R ⁵ is a hydrogen atom or a methyl group), and R ² is methyl. And R ³ is a hexavalent group represented by the following formula 3.)
The thioether-containing alkoxysilane derivative according to claim 1, wherein the alkoxysilyl group-containing compound represented by the following formula 4 is reacted with a polyvalent thiol compound represented by the following formula 5.
(In the formula, R ⁵ is a hydrogen atom or a methyl group, and R ² is a methyl group or an ethyl group.)
(In the formula, g is 0 or 1, h is 3 or 4, the sum of g and h is 4, and m is 1 or 2.) The thioether-containing alkoxysilane derivative according to claim 2, wherein the alkoxysilyl group-containing compound represented by the following formula 4 is reacted with a polyvalent thiol compound represented by the following formula 6.
(In the formula, R ⁵ is a hydrogen atom or a methyl group, and R ² is a methyl group or an ethyl group.)
(Wherein i is an integer of 0 to 2, j is an integer of 4 to 6, the sum of i and j is 6, and m is 1 or 2. R ⁴ is represented by the following formula 3. A hexavalent group.)
An adhesion improver comprising the thioether-containing alkoxysilane derivative according to any one of claims 1 to 4 as an active ingredient.