JP2012180324A - Thioether-containing alkoxysilane derivative and application thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thioether-containing alkoxysilane derivative which has an excellent adhesive property enhancing effect.SOLUTION: The thioether-containing alkoxysilane derivative is a compound represented by formula 1. [Wherein, m is 1 or 2; n is 0 or 1; Ris H, a 1-18C hydrocarbon or a 1-4C hydrocarbon substituted with 1-3C alkoxy; Ris methyl or ethyl; and Ris a bivalent group represented by -CH-CH- or -CH(CH)-].

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 coating materials are applied to an inorganic base material such as a silicon substrate, a silane coupling agent has been added to the coating material for the purpose of improving adhesion (see, for example, Patent Document 1).

JP-A-7-300491

  However, many of the silane coupling agents have a low boiling point, and it is necessary to add, for example, 10 to 20 parts by weight with respect to 100 parts by weight for paints that require high temperature coating. Moreover, it cannot be said that the effect of improving adhesion is sufficient, for example, by adding simultaneously an adhesion aid 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, adhesion could be 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. In many of the silane coupling agents, the main skeleton connecting the trialkoxysilane and the reactive group is constituted by a carbon-carbon bond, and the bond angle also depends on the carbon-carbon bond angle. For this reason, the molecular structure also depends on the bond angle of carbon, and it is difficult to take a wide variety of molecular structures, so the shape of orientation is also limited.

  Therefore, the present invention has been accomplished in view of the above circumstances, and its purpose is to provide a novel thioether-containing alkoxysilane derivative excellent in adhesion improving effect on a silicon substrate and the like, and an adhesion improver using the same. It is to provide.

（式中のｍは１または２であり、nは０または１である。Ｒ^１は水素、または炭素数が１〜１８の炭化水素基、または炭素数１〜３のアルコキシ基により置換された炭素数が１〜４の炭化水素基である。Ｒ^２はメチル基またはエチル基である。Ｒ^３は−ＣＨ_２−ＣＨ_２−あるいは−ＣＨ（ＣＨ_３）−で表される２価の基である。）
〔２〕下記式２で表されるアルコキシシリル基含有化合物と下記式３で表されるチオール化合物とを反応させてなる、請求項１に記載のチオエーテル含有アルコキシシラン誘導体。

（式中のｎは０または１である。Ｒ^２はメチル基またはエチル基である。）

（式中のｍは１または２である。Ｒ^１は水素、または炭素数が１〜１８の炭化水素基、または炭素数１〜３のアルコキシ基により置換された炭素数が１〜４の炭化水素基である。）
〔３〕〔１〕または〔２〕に記載のチオエーテル含有アルコキシシラン誘導体を有効成分とする密着性向上剤。 As a result of intensive studies to solve the above problems, the present inventors have found that a thioether-containing alkoxysilane derivative having a specific structure has an excellent effect of improving adhesion to a silicon substrate, etc. The invention has been completed. That is, the present invention includes the following [1] to [3].
[1] A thioether-containing alkoxysilane derivative represented by the following formula 1.

(In the formula, m is 1 or 2, n is 0 or 1. R ¹ is substituted by hydrogen, a hydrocarbon group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. A hydrocarbon group having 1 to 4 carbon atoms, R ² is a methyl group or an ethyl group, and R ³ is a divalent group represented by —CH ₂ —CH ₂ — or —CH (CH ₃ ) —. .)
[2] The thioether-containing alkoxysilane derivative according to claim 1, wherein the alkoxysilyl group-containing compound represented by the following formula 2 is reacted with a thiol compound represented by the following formula 3.

(In the formula, n is 0 or 1. R ² is a methyl group or an ethyl group.)

(In the formula, m is 1 or 2. R ¹ is hydrogen, a hydrocarbon group having 1 to 18 carbon atoms, or a carbon atom having 1 to 4 carbon atoms substituted by an alkoxy group having 1 to 3 carbon atoms. It is a hydrogen group.)
[3] An adhesion improver comprising the thioether-containing alkoxysilane derivative according to [1] or [2] as an active ingredient.

  Since the bond angle of thiol is larger than the bond angle of carbon, a molecule having a thiol ether group in the molecule can have a variety of structures than a molecule bonded only with carbon. Therefore, the thioether-containing alkoxysilane derivative of the present invention can improve the orientation of the reaction site on the base material and improve the adhesion as compared with the alkoxysilane derivative bonded only with carbon. In addition, according to the present invention, the bond angle of thioether is wider than that of conventional silane coupling agents, so the degree of freedom in the molecular structure is increased and a dense molecular orientation can be achieved. Therefore, it has a higher boiling point and lower volatility than those of the same molecular weight. Therefore, for example, even if a relatively small amount of 0.1 to 10% by weight is added to the paint, it is possible to impart high adhesion to the silicon substrate to the paint without requiring the addition of an adhesion aid. .

  Moreover, if the manufacturing method of the thioether containing alkoxysilane derivative of this invention is used, it is possible to obtain a thioether containing alkoxysilane derivative simply with a sufficient yield. In addition, since the thioether-containing alkoxysilane derivative is excellent in adhesion imparting effect, it is useful as an adhesion improver that imparts adhesion to paints and the like.

2 is a chart showing an IR spectrum of the compound obtained in Example 1. 3 is a chart showing an IR spectrum of the compound obtained in Example 2. 6 is a chart showing an IR spectrum of the compound obtained in Example 3. 6 is a chart showing an IR spectrum of the compound obtained in Example 4. 6 is a chart showing an IR spectrum of the compound obtained in Example 5. 6 is a chart showing an IR spectrum of the compound obtained in Example 6. 6 is a chart showing an IR spectrum of the compound obtained in Example 7. 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. 6 is a chart showing a nuclear magnetic resonance spectrum of the compound obtained in Example 6. 10 is a chart showing a nuclear magnetic resonance spectrum of the compound obtained in Example 7.

（式中のｍは１または２であり、nは０または１である。Ｒ^１は水素、または炭素数が１〜１８の炭化水素基、または炭素数１〜３のアルコキシ基により置換された炭素数が１〜４の炭化水素基である。Ｒ^２はメチル基またはエチル基である。Ｒ^３は−ＣＨ_２−ＣＨ_２−あるいは−ＣＨ（ＣＨ_３）−で表される２価の基である。） The present invention is described in detail below. The thioether-containing alkoxysilane derivative of the present invention is a compound represented by the following formula 1.

(In the formula, m is 1 or 2, n is 0 or 1. R ¹ is substituted by hydrogen, a hydrocarbon group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. A hydrocarbon group having 1 to 4 carbon atoms, R ² is a methyl group or an ethyl group, and R ³ is a divalent group represented by —CH ₂ —CH ₂ — or —CH (CH ₃ ) —. .)

  Since the thioether-containing alkoxysilane derivative of Formula 1 is compatible with many resins, it can be used for a wide range of applications. For example, since the adhesion between the resin and the inorganic material can be improved by using this thioether-containing alkoxysilane derivative, FRP (fiber reinforced plastic), FRTP (fiber reinforced thermoplastic), resin concrete, artificial marble, plastic magnet, It is useful as an adhesion improver for composite materials combining inorganic materials and resins, such as rubber magnets and magnetic tapes. In particular, it is suitable as an adhesion improver when various paints are applied to an inorganic base material such as a silicon substrate.

（式中のｎは０または１である。Ｒ^２はメチル基またはエチル基である。）

（式中のｍは１または２である。Ｒ^１は水素、または炭素数が１〜１８の炭化水素基、また炭素数１〜３のアルコキシ基により置換された炭素数が１〜４の炭化水素基である。） <Method for producing thioether-containing alkoxysilane derivative>
The thioether-containing alkoxysilane derivative represented by the formula 1 includes an alkoxysilyl group-containing compound represented by the following formula 2 (hereinafter sometimes referred to as A component) and a thiol compound represented by the following formula 3 (hereinafter referred to as B). It may be obtained by reacting with a component). The reaction at that time is an addition reaction in which the functional group ratio of the double bond of the A component and the thiol group of the B component is 1: 1.

(In the formula, n is 0 or 1. R ² is a methyl group or an ethyl group.)

(In the formula, m is 1 or 2. R ¹ is hydrogen, a hydrocarbon group having 1 to 18 carbon atoms, or a carbon atom having 1 to 4 carbon atoms substituted by an alkoxy group having 1 to 3 carbon atoms. It is a hydrogen group.)

  As the alkoxysilyl group-containing compound represented by Formula 2, for example, vinyltrimethoxysilane, vinyltriethoxysilane where n = 0, allyltrimethoxysilane, allyltriethoxysilane where n = 1 are used. Can do.

Examples of the hydrocarbon group having 1 to 18 carbon atoms which is R ¹ in Formulas 1 and 3 include a methyl group, a butyl group, an octyl group, an octadecyl group, and a 2-ethylhexyl group.

Examples of the hydrocarbon group having 1 to 4 carbon atoms substituted by an alkoxy group having 1 to 3 carbon atoms, which is R ¹ in Formulas 1 and 3, include a methoxymethyl group, a propoxymethyl group, a methoxybutyl group, and propoxypentyl. Group.

As such a thiol compound represented by Formula 3 having R ¹ , for example, as m = 1, thioglycolic acid, methylthioglycolic acid, butylthioglycolic acid, octylglycolic acid, octadecylthioglycolic acid, 2-ethylhexylthioglycolic acid, methoxymethylthioglycolic acid, propoxymethylthioglycolic acid, methoxybutylthioglycolic acid, propoxybutylglycolic acid and the like. Examples of m = 2 include mercaptopropionic acid, methyl-3-mercaptopropionate, butyl-3-mercaptopropionate, octyl-3-mercaptopropionate, octadecyl-3-mercaptopropionate, 2- In ethylhexyl-3-mercaptopropionate, methoxymethyl-3-mercaptopropionate, propoxymethyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, propoxybutyl-3-mercaptopropionate, etc. is there.

In the thiol compound represented by Formula 3, a hydrocarbon group having 1 or more carbon atoms of R ¹ , a hydrocarbon group having 6 or more carbon atoms substituted by an alkoxy group having 1 to 3 carbon atoms, or carbon In the hydrocarbon group having 2 to 5 carbon atoms substituted by an alkoxy group having 4 or more, the steric hindrance increases, and thus the effect of improving the adhesion of the present invention is reduced.

  The A component and the B component are preferably reacted in the presence of a catalyst or a radical generator. This is because if a catalyst or a radical generator is added, the reaction can be performed in a shorter time and with a higher yield.

  The catalyst is preferably an amine-based basic 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] undeca-aminomethyl) phenol, and the like. Examples of imidazole compounds include 1-methylimidazole, 1,2-dimethylimidazole, 1,4-dimethyl-2-ethylimidazole, imidazole analogues such as 1-phenylimidazole, 1-methyl-2-oxymethylimidazole, Alkyl derivatives such as 1-methyl-2-oxyethylimidazole, nitro and amino derivatives such as 1-methyl-4 (5) -nitroimidazole, 1,2-dimethyl-5 (4) -aminoimidazole, benzimidazole, Examples thereof include methylbenzimidazole and 1-methyl-benzylbenzimidazole.

  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).

  When A component and B component are made to react, the double bond of A component and the thiol group of B component react by the reaction formula represented by following formula 4. In Formula 4, X represents a hydrogen atom or a methyl group, and Z represents a residue bonded to the thiol group of the B component.

  As shown in Formula 4, either of the two carbons forming the double bond of the A component can be bonded to the thiol S. The ratio of the two products varies depending on the reaction conditions. For example, when a base catalyst such as an amine is added to the reaction system, a large amount of product (1) is generated, and when a radical generator is added to the reaction system. There is a tendency to produce a large amount of product (2). In many cases, the thioether-containing alkoxysilane derivative after production is a mixture of the products (1) and (2).

  In the method for producing a thioether-containing alkoxysilane derivative, the reaction can be carried out at a temperature of 5 ° C. or higher, but in order to react in a short time such as within 6 hours, a base catalyst such as amine or a radical generator is used in the reaction system. More preferably, it is made to react at 60-80 degreeC.

  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.

Alcohols that do not react with alkoxysilyl groups, double bonds, and thiol groups are preferably those having 3 or less carbon atoms and primary, and those having a boiling point higher than the reaction temperature. Within the temperature range, those having a high reaction temperature are even better. Further, there is a possibility that alcohol and alkoxysilyl groups undergo transesterification during the reaction, because it may yield reduction of the desired product occurs, those having a structure of R ² OH in order to suppress the reduction yield Good. Examples of the reaction solvent that satisfies these include methanol and ethanol.

  As ketones that do not react with an alkoxysilyl group, double bond, or thiol group, those having a boiling point higher than the reaction temperature are preferred, and those having 6 or less carbon atoms are preferred from the viewpoint of solubility. Examples of those satisfying these include methyl ethyl ketone and methyl isobutyl ketone.

  As the esters that do not react with the alkoxysilyl group, double bond, or thiol group, those having a boiling point higher than the reaction temperature are preferred, and those having a straight chain carbon number of 6 or less are preferred from the viewpoint of solubility. Examples of those satisfying these include butyl acetate and ethyl acetate.

<Adhesion improver>
Since the thioether-containing alkoxysilane derivative has a high adhesion improving performance particularly with respect to a silicon substrate, it can be used as an adhesion improving agent for the silicon substrate. Adhesion improver comprising thioether-containing alkoxysilane derivative as an active ingredient has high adhesion improvement effect by compounding with compound having double bond such as epoxy resin, urethane resin, acrylic resin, polyimide resin, polyacetylene, etc. It can be demonstrated. The adhesion improver comprising a thioether-containing alkoxysilane derivative as an active ingredient preferably exhibits high adhesion when added as an active ingredient in an amount of preferably 0.1 to 30% by mass, more preferably 0.1 to 10% by mass. be able to.

  Examples of the present invention will be specifically described below. The reagents used in the examples and comparative examples are as follows. The viscosity at 25 ° C. of each thiol was measured using an R-type viscometer manufactured by Toki Sangyo Co., Ltd.

<Compound having alkoxysilyl group: Component A>
(A-1)
Vinyltrimethoxysilane. The structure is shown in the following formula.

(A-2)
Vinyltriethoxysilane. The structure is shown in the following formula.

(A-3)
Allyltrimethoxysilane. The structure is shown in the following formula.

<Thiol compound: Component B>
(B-1)
β-mercaptopropionic acid (viscosity 8.4 mPa · s). The structure is shown in the following formula.

(B-2)
Methyl-3-mercaptopropionate (viscosity 1.5 mPa · s). The structure is shown in the following formula.

(B-3)
2-ethylhexyl-3 mercaptopropionate (viscosity 3.7 mPa · s). The structure is shown in the following formula.

(B-4)
Methoxybutyl-3-mercaptopropionate (viscosity 3.6 mPa · s). The structure is shown in the following formula.

(B-5)
Stearyl-3-mercaptopropionate (room temperature solid). The structure is shown in the following formula.

  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, the A component and the B component were charged according to the composition shown in Table 1, and when the A component and the B component were 100 parts by weight, 1 part by weight of the catalyst (1.8-diazabicyclo [5,4,0 ] Undec-7-ene, manufactured by Wako Pure Chemical Industries, Ltd.) was added, followed by reaction at 90 ° C for 12 hours to obtain Examples 1 to 7. Table 1 shows the viscosity at 25 ° C. after the reaction in Examples 1 to 4, 6 and 7, and the viscosity at 40 ° C. after the reaction in Example 5. The viscosity was measured using an R-type viscometer manufactured by Toki Sangyo Co., Ltd. It turns out that the viscosity of the obtained Examples 1-7 is reacting with A component from having increased viscosity compared with B component before reaction.

<Infrared absorption spectrum analysis (IR)>
The obtained Examples 1 to 7 were subjected to infrared absorption spectrum analysis under the following conditions. The results are shown in FIGS. 1 to 7 and typical IR peaks are shown below.
Model: JASCO Corporation FT / IR-600
Cell: Expanded on KBr, decomposed; 4 cm ⁻¹ , number of integrations: 32 times

Example 1
2947 cm ⁻¹ : 57% T, 2843 cm ⁻¹ : 52% T, 1739 cm ⁻¹ : 72% T, 1712 cm ⁻¹ : 67% T, 1437 cm ⁻¹ : 37% T, 1360 cm ⁻¹ : 76% T, 1192 cm ^{− 1} : 68% T, 1086 cm ⁻¹ : 79% T, 877 cm ⁻¹ : 22% T, 822 cm ⁻¹ : 57% T

(Example 2)
2947 cm ⁻¹ : 23% T, 2841 cm ⁻¹ : 22% T, 1739 cm ⁻¹ : 32% T, 1437 cm ⁻¹ : 16% T, 1360 cm ⁻¹ : 14% T, 1194 cm ⁻¹ : 28% T, 1086 cm ^{− 1} : 36% T, 822 cm ⁻¹ : 24% T

(Example 3)
2958 cm ⁻¹ : 41% T, 2841 cm ⁻¹ : 29% T, 1738 cm ⁻¹ : 46% T, 1464 cm ⁻¹ : 20% T, 1348 cm ⁻¹ : 16% T, 1192 cm ⁻¹ : 39% T, 1090 cm ^{− 1} : 51% T, 1009 cm ⁻¹ : 17% T, 806 cm ⁻¹ : 30% T

Example 4
2943 cm ⁻¹ : 45% T, 2841 cm ⁻¹ : 40% T, 1736 cm ⁻¹ : 63% T, 1464 cm ⁻¹ : 23% T, 1354 cm ⁻¹ : 27% T, 1279 cm ⁻¹ : 32% T, 1244 cm ^{− 1} : 40% T, 1192 cm ⁻¹ : 57% T, 1086 cm ⁻¹ : 71% T, 879 cm ⁻¹ : 19% T, 825 cm ⁻¹ : 43% T

(Example 5)
2924 cm ⁻¹ : 69% T, 2852 cm ⁻¹ : 58% T, 1738 cm ⁻¹ : 52% T, 1468 cm ⁻¹ : 26% T, 1350 cm ⁻¹ : 17% T, 1242 cm ⁻¹ : 29% T, 1192 cm ^{− 1} : 41% T, 1090 cm ⁻¹ : 58% T, 825 cm ⁻¹ : 29% T

(Example 6)
^{2976cm -1: 31% T, 2927cm} -1: 23% T, 1741cm -1: 44% T, 1437cm -1: 21% T, 1390cm -1: 76% T, 1360cm -1: 17% T, 1279cm - ^{1: 18% T, 1246cm -1} : 24% T, 1169cm -1: 35% T, 1080cm -1: 49% T, 960cm -1: 30% T, 777cm -1: 26% T

(Example 7)
2946 cm ⁻¹ : 25% T, 2841 cm ⁻¹ : 22% T, 1740 cm ⁻¹ : 41% T, 1438 cm ⁻¹ : 18% T, 1359 cm ⁻¹ : 14% T, 1193 cm ⁻¹ : 31% T, 1085 cm ^{− 1} : 46% T, 816 cm ⁻¹ : 28% T

As is clear from the results of the infrared absorption spectrum analysis, since a peak of 1600 to 1700 cm ⁻¹ derived from C═C is not observed, A-1, A-2 and A-3 are respectively B-1 to It turns out that it reacts with B-5.

<Nuclear magnetic resonance spectrum analysis (NMR)>
Moreover, about Examples 1-7, the nuclear magnetic resonance spectrum analysis was performed on the following conditions. The results are shown in FIGS. 8 to 14 and the peak assignments in each NMR spectrum are shown below. Since Comparative Example 1 was not dissolved in the heavy solvent for NMR, it could not be measured.
Model: Nippon Bruker Co., Ltd., 400 MHz-Advanced 400,
Condition: Integration 16 times Solvent: Deuterated chloroform

ａ：３．４〜３．６ｐｐｍ、ｂ：０．９〜１．０ｐｐｍ、ｃ、ｄ：２．６〜２．８ｐｐｍ、e：２．７〜２．８ｐｐｍ、ｆ：３．５〜３．６ｐｐｍ Example 1

a: 3.4 to 3.6 ppm, b: 0.9 to 1.0 ppm, c, d: 2.6 to 2.8 ppm, e: 2.7 to 2.8 ppm, f: 3.5 to 3. 6ppm

ａ：３．６〜３．７ｐｐｍ、ｂ：０．９〜１．１ｐｐｍ、ｃ、ｄ：２．６〜２．７ｐｐｍ、e：２．７〜２．８ｐｐｍ、ｆ：３．５〜３．６ｐｐｍ (Example 2)

a: 3.6-3.7 ppm, b: 0.9-1.1 ppm, c, d: 2.6-2.7 ppm, e: 2.7-2.8 ppm, f: 3.5-3. 6ppm

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

a, e: 0.8 to 1.0 pm, b, c, d, f, g: 1.1 to 1.4 ppm, h: 4.0 to 4.1 ppm, h: 0.9 to 1.0 ppm, i, j: 2.5 to 2.7 ppm, k: 2.7 to 2.8 ppm, l: 3.5 to 3.6 ppm

ａ：１．０〜１．１ｐｐｍ、ｂ：３．４〜３．５ｐｐｍ、ｃ：３．３〜３．４ｐｐｍ、ｄ：１．７〜１．８ｐｐｍ、ｅ：４．１〜４．２ｐｐｍ、ｆ：０．９〜１．０ｐｐｍ、ｇ、ｈ：２．５〜２．７ｐｐｍ、i：２．７〜２．８ｐｐｍ、i：３．５〜３．６ｐｐｍ Example 4

a: 1.0-1.1 ppm, b: 3.4-3.5 ppm, c: 3.3-3.4 ppm, d: 1.7-1.8 ppm, e: 4.1-4.2 ppm, f: 0.9-1.0 ppm, g, h: 2.5-2.7 ppm, i: 2.7-2.8 ppm, i: 3.5-3.6 ppm

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

a: 0.8 to 1.0 ppm, b: 1.2 to 1.4 ppm, c: 1.6 to 1.7 ppm, d: 4.0 to 4.2 ppm, e: 0.9 to 1.0 ppm, f, g: 2.5-2.7 ppm, h: 2.6-2.8 ppm, i: 3.5-3.6 ppm

ａ：３．６〜３．７ｐｐｍ、ｂ：０．９〜１．０ｐｐｍ、ｃ、ｄ：２．５〜２．７ｐｐｍ、e：２．７〜２．８ｐｐｍ、ｆ：３．６〜３．８ｐｐｍ、ｇ：１．２〜１．３ｐｐｍ (Example 6)

a: 3.6 to 3.7 ppm, b: 0.9 to 1.0 ppm, c, d: 2.5 to 2.7 ppm, e: 2.7 to 2.8 ppm, f: 3.6 to 3. 8 ppm, g: 1.2-1.3 ppm

ａ：３．７〜３．８ｐｐｍ、ｂ：０．７〜０．８ｐｐｍ、ｃ、ｄ：２．５〜２．７ｐｐｍ、e：２．７〜２．８ｐｐｍ、ｆ：１．６〜１．７ｐｐｍ、ｇ：３．５〜３．６ｐｐｍ (Example 7)

a: 3.7 to 3.8 ppm, b: 0.7 to 0.8 ppm, c, d: 2.5 to 2.7 ppm, e: 2.7 to 2.8 ppm, f: 1.6 to 1. 7 ppm, g: 3.5 to 3.6 ppm

Figure 8-14 and from the above results, since the peak of 5.5~6.5ppm derived from _CH 2 = C is not observed, A-1, A-2 and A-3 are respectively B-1 to B It turns out that it is reacting with -5.

<Adhesion evaluation>
Next, the adhesion was evaluated using Examples 1 to 7 described above. Furthermore, when only A-1 before reaction is used, when only B-1 before reaction is used, when decyltrimethoxysilane (made by Shin-Etsu Silicone Co., Ltd., C-1) is used The adhesion was also evaluated when the adhesion improver was not used. A phenol novolac type epoxy resin [manufactured by Toto Kasei Co., Ltd., YDPN638] was used as an evaluation target for adhesion. Examples 1 to 7, A-1, and B were prepared by mixing 98% by mass of the epoxy resin with 2% by mass of a catalyst [imidazole type catalyst: manufactured by Adeka Co., Ltd., EH-4344S] (referred to as E-1). -1 and C-1 were blended according to the blending amounts in Table 2 as adhesion improvers. The composition is applied to a single crystal silicon substrate [6 inch bare silicon wafer N type manufactured by Silicon Technology Co., Ltd.] with a bar coater and cured at 150 ° C. for 1 hour to obtain a cured film as a resin molded product. (Samples 1-11). After the samples 1 to 11 thus obtained were treated at a temperature of 121 ° C. and a relative humidity (RH) of 100% for 8 hours, the mechanical properties of the coating film as defined in JIS K5600-5-6—adhesiveness ( The cross-cut method was evaluated by the test method. These results are shown in Table 2. The evaluation criteria are as follows.
○: No peeling at all ×: Peeling occurs even a little

From the results shown in Table 2, in Samples 1 to 7 using the adhesion improvers of Examples 1 to 7, no peeling was observed, and the adhesion was good. Samples 8 and 9 used the compound before thioether formation, and both had peeling and poor adhesion. Since sample 10 did not have a thioether group in the molecular structure of the adhesion improver, peeling occurred and the adhesion was poor. In Sample 11, the adhesion improving material was not added, so peeling occurred and the adhesion was poor.

Claims (3)

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

(In the formula, m is 1 or 2, n is 0 or 1. R ¹ is substituted by hydrogen, a hydrocarbon group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. A hydrocarbon group having 1 to 4 carbon atoms, R ² is a methyl group or an ethyl group, and R ³ is a divalent group represented by —CH ₂ —CH ₂ — or —CH (CH ₃ ) —. .) The thioether-containing alkoxysilane derivative according to claim 1, wherein the alkoxysilyl group-containing compound represented by the following formula 2 is reacted with a thiol compound represented by the following formula 3.

(In the formula, n is 0 or 1. R ² is a methyl group or an ethyl group.)

(In the formula, m is 1 or 2. R ¹ is hydrogen, a hydrocarbon group having 1 to 18 carbon atoms, or a carbon atom having 1 to 4 carbon atoms substituted by an alkoxy group having 1 to 3 carbon atoms. It is a hydrogen group.) The adhesion improver which uses the thioether containing alkoxysilane derivative of Claim 1 or Claim 2 as an active ingredient.

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