JP2012197233A - Thioether-containing alkoxysilane derivative, and application thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thioether-containing alkoxysilane derivative excellent in adhesivity-improving effect.SOLUTION: The thioether-containing alkoxysilane derivative represented by formula 1 (wherein, (a) is an integer of 1-4, b is an integer of 0-3, and c is 0 or 1, wherein (a+b+c) =4; m is 1 or 2; n is 0 or 1; Ris a group of -CH-CH- or -CH(CH)-; and Ris methyl, ethyl or acetyl) is provided.

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).

JP-A-7-300491

  However, since most of the silane coupling agents have a structure having an alkyl group having 1 to 5 carbon atoms as the main skeleton, the boiling point is low, and for paints that require high-temperature coating, 100% by mass of the paint. It was necessary to add a large amount of 10 to 20% by mass. Moreover, since it has only one trialkoxysilyl group per molecule, it cannot be said that the effect of improving adhesion is sufficient. For example, salts such as titanium and zirconium, amines such as imidazole, phosphate esters, urethane resins, thiols In many cases, the necessary adhesion can be achieved for the first time by simultaneously adding an adhesion aid such as a compound. 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.

  Therefore, the present invention has been achieved in view of the above-mentioned actual situation, and the purpose thereof is a novel thioether-containing alkoxysilane derivative excellent in adhesion improving effect to an inorganic base material such as glass, and adhesion using the same. It is to provide an improver.

（式中のａは１〜４の整数であり、ｂは０〜３の整数であり、ｃは０または１であり、ａ＋ｂ＋ｃ＝４である。ｍは１または２であり、ｎは０または１である。Ｒ^１は−ＣＨ_２−ＣＨ_２−あるいは−ＣＨ（ＣＨ_３）−で表される基である。Ｒ^２はメチル基、エチル基またはアセチル基である。）
〔２〕下記式２で表されるチオエーテル含有アルコキシシラン誘導体。

（式中のａ´は１〜３の整数であり、ｂ´は０〜２の整数であり、ｃ´は０または１であり、ａ´＋ｂ´＋ｃ´＝３である。ａ´´は０〜３の整数であり、ｂ´´は０〜２の整数であり、ｃ´´は０または１であり、ａ´´＋ｂ´´＋ｃ´´＝３である。ｍは１または２であり、ｎは０または１である。Ｒ^１は−ＣＨ_２−ＣＨ_２−あるいは−ＣＨ（ＣＨ_３）−で表される基である。Ｒ^２はメチル基、エチル基またはアセチル基
〔３〕下記式３で表されるアルコキシシリル基含有化合物と下記式４で表される多価チオール化合物とを反応させてなる、〔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Ｒ^３はビニル基またはアリル基である。Ｒ^２はメチル基、エチル基、またはアセチル基である。）

（式中のｄは０または１であり、ｅは３または４であり、ｄ＋ｅ＝４である。ｍは１または２である。）
〔４〕下記式３で表されるアルコキシシリル基含有化合物と下記式５で表される多価チオール化合物とを反応させてなる、〔２〕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Ｒ^３はビニル基またはアリル基である。Ｒ^２はメチル基、エチル基、またはアセチル基である。）

（式中のｆは２または３であり、ｇは０または１であり、ｆ＋ｇ＝３である。ｆ´は２または３であり、ｇ´は０または１であり、ｆ´＋ｇ´＝３である。ｍは１または２である。）
〔５〕〔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 adhesion improving effect on an inorganic base material such as glass. The headline and the present invention were completed. 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 1 to 4, b is an integer of 0 to 3, c is 0 or 1, and a + b + c = 4. M is 1 or 2, and n is 0 or R ¹ is a group represented by —CH ₂ —CH ₂ — or —CH (CH ₃ ) —, and R ² is a methyl group, an ethyl group or an acetyl group.
[2] A thioether-containing alkoxysilane derivative represented by the following formula 2.

(Wherein a ′ is an integer of 1 to 3, b ′ is an integer of 0 to 2, c ′ is 0 or 1, and a ′ + b ′ + c ′ = 3. A ″ is An integer of 0 to 3, b ″ is an integer of 0 to 2, c ″ is 0 or 1, and a ″ + b ″ + c ″ = 3. M is 1 or 2. And n is 0 or 1. R ¹ is a group represented by —CH ₂ —CH ₂ — or —CH (CH ₃ ) —, where R ² is a methyl group, an ethyl group or an acetyl group [3]. The thioether-containing alkoxysilane derivative according to [1], obtained by reacting an alkoxysilyl group-containing compound represented by the following formula 3 with a polyvalent thiol compound represented by the following formula 4.

(In the formula, R ³ is a vinyl group or an allyl group. R ² is a methyl group, an ethyl group, or an acetyl group.)

(In the formula, d is 0 or 1, e is 3 or 4, and d + e = 4. M is 1 or 2.)
[4] The thioether-containing alkoxysilane derivative according to [2], obtained by reacting an alkoxysilyl group-containing compound represented by the following formula 3 with a polyvalent thiol compound represented by the following formula 5.

(In the formula, R ³ is a vinyl group or an allyl group. R ² is a methyl group, an ethyl group, or an acetyl group.)

(In the formula, f is 2 or 3, g is 0 or 1, and f + g = 3. F ′ is 2 or 3, g ′ is 0 or 1, and f ′ + g ′ = 3. M is 1 or 2.)
[5] An adhesion improver comprising the thioether-containing alkoxysilane derivative according to [1] or [2] as an active ingredient.

  A general alkoxysilyl group-containing compound has an alkyl group as a main skeleton, whereas the thioether-containing alkoxysilane derivative of the present invention contains a thioether bond in the molecule. Since the bond length and bond angle of the thioether bond are more flexible than those of atoms such as C, O, and N, molecules having a thioether bond can take various conformations. Therefore, it is considered that the molecule having a thioether bond has an increased degree of molecular structure, and the alkoxysilyl group is selectively adsorbed and bonded to the substrate (orientation of the adhesion improving agent). Therefore, it is considered that the thioether-containing alkoxysilane derivative of the present invention exhibits a higher adhesion improving effect than the alkoxysilyl group-containing compound having an alkyl group as the main skeleton. Moreover, while a general alkoxysilane derivative has only one trialkoxysilyl group per molecule, the thioether-containing alkoxysilane derivative of the present invention has a plurality of alkoxysilane groups in one molecule. Is possible. Therefore, since the alkoxysilane group present at the molecular end easily forms a chemical bond with the substrate or easily adsorbs physically, excellent adhesion is exhibited. Since the thioether-containing alkoxysilane derivative of the present invention has a thioether bond, the degree of freedom of the molecular structure is increased, so that dense molecular orientation can be achieved. It has become sex. The S atom derived from the thioether bond has a larger atomic radius and atomic weight because the outermost shell of atoms such as C, O, and N is the L shell while the outermost shell is the M shell. Therefore, it is considered that the presence of S atoms improves intermolecular force and leads to low volatility. In addition, since the present invention is a reaction product of a low-volatility polyvalent thiol compound and an alkoxysilyl group-containing compound, it is less volatile than a general alkoxysilyl group-containing compound. As a result, the present invention can impart high adhesion to the paint without requiring the addition of an adhesion aid even when added in a relatively small amount of 0.1 to 10% by weight, for example.

The chart which shows IR spectrum of the compound obtained in Example 1-1. The chart which shows IR spectrum of the compound obtained in Example 1-2. The chart which shows IR spectrum of the compound obtained in Example 1-3. The chart which shows IR spectrum of the compound obtained in Example 1-4. The chart which shows IR spectrum of the compound obtained in Example 1-5. The chart which shows IR spectrum of the compound obtained in Example 1-6. The chart which shows IR spectrum of the compound obtained in Example 2-1. The chart which shows IR spectrum of the compound obtained in Example 2-2. 6 is a chart showing an IR spectrum of the compound obtained in Comparative Example 1. The chart which shows the nuclear magnetic resonance spectrum of the compound obtained in Example 1-1. The chart which shows the nuclear magnetic resonance spectrum of the compound obtained in Example 1-2. The chart which shows the nuclear magnetic resonance spectrum of the compound obtained in Example 1-3. The chart which shows the nuclear magnetic resonance spectrum of the compound obtained in Example 1-4. The chart which shows the nuclear magnetic resonance spectrum of the compound obtained in Example 1-5. The chart which shows the nuclear magnetic resonance spectrum of the compound obtained in Example 1-6. The chart which shows the nuclear magnetic resonance spectrum of the compound obtained in Example 2-1. The chart which shows the nuclear magnetic resonance spectrum of the compound obtained in Example 2-2. 3 is a chart showing a nuclear magnetic resonance spectrum of the compound obtained in Comparative Example 1.

（式中のａは１〜４の整数であり、ｂは０〜３の整数であり、ｃは０または１であり、ａ＋ｂ＋ｃ＝４である。ｍは１または２であり、ｎは０または１である。Ｒ^１は−ＣＨ_２−ＣＨ_２−あるいは−ＣＨ（ＣＨ_３）−で表される基である。Ｒ^２はメチル基、エチル基またはアセチル基である。）

（式中のａ´は１〜３の整数であり、ｂ´は０〜２の整数であり、ｃ´は０または１であり、ａ´＋ｂ´＋ｃ´＝３である。ａ´´は０〜３の整数であり、ｂ´´は０〜２の整数であり、ｃ´´は０または１であり、ａ´´＋ｂ´´＋ｃ´´＝３である。ｍは１または２であり、ｎは０または１である。Ｒ^１は−ＣＨ_２−ＣＨ_２−あるいは−ＣＨ（ＣＨ_３）−で表される基である。Ｒ^２はメチル基、エチル基またはアセチル基である。） 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 or the following formula 2.

(In the formula, a is an integer of 1 to 4, b is an integer of 0 to 3, c is 0 or 1, and a + b + c = 4. M is 1 or 2, and n is 0 or R ¹ is a group represented by —CH ₂ —CH ₂ — or —CH (CH ₃ ) —, and R ² is a methyl group, an ethyl group or an acetyl group.

(Wherein a ′ is an integer of 1 to 3, b ′ is an integer of 0 to 2, c ′ is 0 or 1, and a ′ + b ′ + c ′ = 3. A ″ is An integer of 0 to 3, b ″ is an integer of 0 to 2, c ″ is 0 or 1, and a ″ + b ″ + c ″ = 3. M is 1 or 2. And n is 0 or 1. R ¹ is a group represented by —CH ₂ —CH ₂ — or —CH (CH ₃ ) —, and R ² is a methyl group, an ethyl group or an acetyl group. )

  The thioether-containing alkoxysilane derivative of the present invention includes a structure represented by a, a ′, and a ″ in Formula 1 and Formula 2, and has a chemical structure in which a or a ′ is 1 or more. Have.

Since the thioether-containing alkoxysilane derivative represented by Formula 1 and Formula 2 is compatible with many resins, it can be used for a wide range of applications. For example, in a pressure-sensitive adhesive, adhesive, sealant, sealant, etc., by blending a thioether-containing alkoxysilane derivative represented by Formula 1 or Formula 2 into the resin component, Effective in improving adhesion. Moreover, it is used suitably when it is desired to obtain a high adhesion with a small amount of addition.
<Method for producing thioether-containing alkoxysilane derivative>

（式中のＲ^３はビニル基またはアリル基である。Ｒ^２はメチル基、エチル基、またはアセチル基である。）

（式中のｄは０または１であり、ｅは３または４であり、ｄ＋ｅ＝４である。ｍは１または２である。）

（式中のｆは２または３であり、ｇは０または１であり、ｆ＋ｇ＝３である。ｆ´は２または３であり、ｇ´は０または１であり、ｆ´＋ｇ´＝３である。ｍは１または２である。） The thioether-containing alkoxysilane derivative represented by Formula 1 can be obtained by reacting an alkoxysilyl group-containing compound represented by Formula 3 below with a polyvalent thiol compound represented by Formula 4 below. On the other hand, the thioether-containing alkoxysilane derivative represented by Formula 2 can be obtained by reacting an alkoxysilyl group-containing compound represented by Formula 3 below with a polyvalent thiol compound represented by Formula 5 below. .

(In the formula, R ³ is a vinyl group or an allyl group. R ² is a methyl group, an ethyl group, or an acetyl group.)

(In the formula, d is 0 or 1, e is 3 or 4, and d + e = 4. M is 1 or 2.)

(In the formula, f is 2 or 3, g is 0 or 1, and f + g = 3. F ′ is 2 or 3, g ′ is 0 or 1, and f ′ + g ′ = 3. M is 1 or 2.)

Examples of the alkoxysilyl group-containing compound represented by Formula 3 include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, allyltrimethoxysilane, allyltriethoxysilane, and allyltriacetoxysilane. When R ² is a compound other than methyl group, ethyl group, and acetyl group in Formula 3, the reactivity between the alkoxysilyl group and the base material of the resulting thioether-containing alkoxysilane derivative, or between alkoxylsilyl groups is reduced. It becomes difficult to obtain the adhesion improving effect which is the effect of the present invention.

  Among the polyvalent thiol compounds represented by Formula 4, d = 1, e = 3, m = 2 trimethylolpropane tris (3-mercaptopropionate), d = 0 , E = 4, m = 2 pentaerythritol tetrakis (3-mercaptopropionate. Examples of polyvalent thiol compounds with d = 1, e = 3, and m = 1 include trimethylolpropane and thioglycolic acid. Examples of the polyvalent thiol compound having a reaction product of d = 0, e = 4, and m = 1 include a reaction product of pentaerythritol and 3-mercaptopropionic acid, wherein m ≧ 3 in formula 4. When the number of hydrocarbons that are hydrophobic and non-polar in the resulting thioether-containing alkoxysilane derivative is increased, the orientation of the thioether group on the substrate Is weakened, and it becomes difficult to obtain the effect of improving the adhesion which is the effect of the present invention.

  Among the polyvalent thiol compounds represented by Formula 5, dipentaerythritol hexakis (f = 3, f ′ = 3, g = 0, g ′ = 0, m = 2 as industrially easily available substances) 3-mercaptopropionate). In addition, as a polyvalent thiol compound of f = 3, f ′ = 3, g = 0, g ′ = 0, m = 1, a reaction product of dipentaerythritol and thioglycolic acid is represented by f = 2, f ′. = 2, g = 1, g ′ = 1, m = 2, the reaction product of ditrimethylolpropane and 3-mercaptopropionic acid is f = 2, f ′ = 2, g = 1 As a polyvalent thiol compound with g ′ = 1 and m = 1, the reaction product of ditrimethylolpropane and thioglycolic acid is f = 3, f ′ = 2, g = 1, g ′ = 1, m = 2 or f = 2, f ′ = 3, g = 1, g ′ = 1, m = 2 as a polyvalent thiol compound, a reaction product of a condensation reaction product of pentaerythritol and trimethylolpropane and 3-mercaptopropionic acid If the product is f = 3, f ′ = 2, g = 1, g ′ = 1, m = 1 Is a polyhydric thiol compound of f = 2, f ′ = 3, g = 1, g ′ = 1, m = 1, a reaction product of a condensation reaction product of pentaerythritol and trimethylolpropane and thioglycolic acid. Can be mentioned. When a compound with m ≧ 3 in Formula 5 is used, the number of hydrocarbons that are hydrophobic and nonpolar in the resulting thioether-containing alkoxysilane derivative increases, so that the orientation of the thioether group on the substrate is weakened. It becomes difficult to obtain the effect of improving the adhesion which is the effect of.

  The alkoxysilyl group-containing compound and the polyvalent thiol compound 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 base catalyst, and primary, secondary or tertiary amines, or imidazole compounds can be used. For example, methylamine, ethylamine, propylamine, butylamine, ethylenediamine etc. as primary amine, dimethylamine, diethylamine, dipropylamine, methylethylamine, diphenylamine etc. as secondary amine, trimethylamine, triethylamine, tripropylamine, triamine as tertiary amine, etc. Examples include phenylamine, 1,8-diazabicyclo (5,4,0) -undecene-7, 2,4,6-tris (dimethylaminomethyl) phenol. 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, Oxyalkyl 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 1-methylbenzimidazole and 1-methyl-2-benzylbenzimidazole.

  As the radical generator, a peroxide or an azo compound is preferable. Examples of the peroxide include dibenzoyl peroxide, tert-butylperoxy-2-ethylhexanoate, dilauroyl peroxide, tert-butyl hydroperoxide, and the like. Examples of the azo compound include azobis (iso-butyronitrile) and 2,2'-azobis (2-methylbutanenitrile).

When the alkoxysilyl group-containing compound and the polyvalent thiol compound are reacted, the double bond of the alkoxysilyl group-containing compound reacts with the thiol group of the polyvalent thiol compound according to the reaction formula represented by the following formula 6. In Formula 6, X represents a hydrogen atom, Y represents a residue other than X bonded to the double bond of the alkoxysilyl group-containing compound, and Z represents a residue bonded to the thiol group of the polyvalent thiol compound.

  As shown in Formula 6, both of the two carbons forming the double bond of the alkoxysilyl group-containing compound are bonded 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 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. Tends 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).

Moreover, in producing a thioether-containing alkoxysilane derivative, since the polyvalent thiol compound has a plurality of thiol groups, a part of the thiol groups of the polyvalent thiol compound is an alkoxysilyl group-containing compound as shown in the following formula 7. A product reacted with can be obtained. V represents a residue that binds to the thiol group of the polyvalent thiol compound.

  The added number of the alkoxysilyl group-containing compound in Formula 7 corresponds to A, A ′, and A ″ represented by Formula 1 and Formula 2. In many cases, the thioether-containing alkoxysilane derivative after production is a mixture of substances having different numbers of addition-reacted substituents.

  As a 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 (for example, within 5 hours), a base catalyst such as amine or a radical generator is reacted. More preferably, it is added to the system and reacted at 60-80 ° C.

  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.

As alcohols that do not react with alkoxysilyl groups, double bonds, and thiol groups, those having an appropriate boiling point with respect to the reaction temperature are preferred, and those having a boiling point of 50 to 180 ° C. are particularly preferred. The reason is that when the boiling point is lower than the above range, it is difficult to produce when industrialized. When the boiling point is higher than the above range, it is difficult to remove the solvent when the solvent needs to be removed. Because it becomes. More preferred as alcohols are methanol and ethanol. This is because the alcohol as the reaction solvent and the alkoxysilyl group-containing compound represented by the above formula 3 may cause a transesterification reaction during the reaction, which may reduce the yield of the target product. . Therefore, in the above formula 3, it is preferable to use methanol as a reaction solvent when a compound having R ² is a methyl group and to use ethanol as a reaction solvent when a compound having R ² is an ethyl group. In addition, when a compound in which R ² is an acetyl group is used, it is preferable to use a solvent other than alcohol because the yield of the target product is reduced by using an alcohol solvent.

  As the ketones that do not react with the alkoxysilyl group, double bond, and thiol group, those having an appropriate boiling point with respect to the reaction temperature are preferable, and those having a boiling point of 50 to 180 ° C. are particularly preferable. The reason is that when the boiling point is lower than the above range, it is difficult to produce when industrialized. When the boiling point is higher than the above range, it is difficult to remove the solvent when the solvent needs to be removed. Because it becomes. Examples include methyl ethyl ketone and methyl isobutyl ketone.

  As the esters that do not react with the alkoxysilyl group, double bond, and thiol group, those having an appropriate boiling point with respect to the reaction temperature are preferable, and those having a boiling point of 50 to 180 ° C. are particularly preferable. The reason is that when the boiling point is lower than the above range, it is difficult to produce when industrialized. When the boiling point is higher than the above range, it is difficult to remove the solvent when the solvent needs to be removed. Because it becomes. Examples thereof include ethyl acetate, methyl acetate, butyl acetate, methoxybutyl acetate, cellosolve acetate, amyl acetate, normal propyl acetate, and isopropyl acetate.

<Adhesion improver>
The thioether-containing alkoxysilane derivative has a high adhesion improving performance especially for inorganic substrates such as glass and metals, and therefore can be used as an adhesion improver for inorganic substrates such as glass and metals. it can. Adhesion improver containing 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, monomer, etc. It can be demonstrated. Furthermore, the thioether-containing alkoxysilane derivative, which is a compound represented by Formula 1 and Formula 2 and b, b ′, or b ″ is not 0, has a thiol group, and thus reacts with an epoxy group, a double bond, or an isocyanate group. . 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.

（Ａ−２）
ビニルトリエトキシシラン。その構造を下記式９に示す。

（Ａ−３）
ビニルトリアセトキシシラン。その構造を下記式１０に示す。

（Ａ−４）
アリルトリメトキシシラン。その構造を下記式１１に示す。

Examples of the present invention will be specifically described below. The reagents used in the examples and comparative examples are as follows.
<Compound having alkoxysilyl group: Component A>
(A-1)
Vinyltrimethoxysilane. The structure is shown in the following formula 8.

(A-2)
Vinyltriethoxysilane. The structure is shown in the following formula 9.

(A-3)
Vinyl triacetoxysilane. The structure is shown in the following formula 10.

(A-4)
Allyltrimethoxysilane. The structure is shown in the following formula 11.

（Ｂ−２）
ペンタエリスリトールテトラキス（3-メルカプトプロピオネート）
その構造を下記式１３に示す。（粘度０．４Ｐａ・ｓ）

（Ｂ−３）
ジペンタエリスリトールヘキサキス（3-メルカプトプロピオネート）
その構造を下記式１４に示す。（粘度２．５Ｐａ・ｓ）

（β−１）
比較例用として、メチル−３−メルカプトプロピオネート（粘度１．５ｍＰａ・ｓ）。その構造を下記式１５に示す。

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

(B-2)
Pentaerythritol tetrakis (3-mercaptopropionate)
The structure is shown in the following formula 13. (Viscosity 0.4 Pa · s)

(B-3)
Dipentaerythritol hexakis (3-mercaptopropionate)
The structure is shown in the following formula 14. (Viscosity 2.5 Pa · s)

(Β-1)
As a comparative example, methyl-3-mercaptopropionate (viscosity 1.5 mPa · s). The structure is shown in the following formula 15.

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, components A and B were charged according to the composition shown in Table 1 below, and reacted at 90 ° C. for 8 hours without using a catalyst to obtain a thioether-containing alkoxysilane derivative. Table 1 also shows the viscosities at 25 ° C. of the thioether-containing alkoxysilane derivatives of Examples 1-1 to 1-6, 2-1, 2-2, and Comparative Example 1. The viscosity was measured using an R-type viscometer manufactured by Toki Sangyo Co., Ltd.

<Infrared absorption spectrum analysis (IR)>
For the thioether-containing alkoxysilane derivatives of Examples 1-1 to 1-6, 2-1, 2-2 and Comparative Example 1, infrared absorption spectrum analysis was performed under the following conditions. The results are shown in FIGS. 1 to 8 and typical peaks are shown below.
Model: JASCO Corporation FT / IR-600
Cell: Expanded on KBr, decomposed; 4 cm ⁻¹ , accumulated number: 16 times

<Nuclear magnetic resonance spectrum analysis (NMR)>
For the thioether-containing alkoxysilane derivatives of Examples 1-1 to 1-6, 2-1, 2-2 and Comparative Example 1, nuclear magnetic resonance spectrum analysis was performed under the following conditions. The results are shown in FIGS. 9 to 16, and the assignment of peaks in each NMR spectrum is shown below.
Model: Nippon Bruker Co., Ltd., 400 MHz-Advanced 400,
Condition: Integration 16 times Solvent: Deuterated chloroform

ａ：３．５〜３．７ｐｐｍ、ｂ：０．９〜１．０ｐｐｍ、ｃ、ｄ、ｅ：２．５〜２．９ｐｐｍ、ｆ：３．９〜４．１ｐｐｍ、ｇ：１．４〜１．６ｐｐｍ、ｈ：０．９〜１．０ｐｐｍ、ｉ：１．６〜１．７ｐｐｍ (Example 1-1)
<IR>
2943 cm ⁻¹ : 53% T, 2841 cm ⁻¹ : 62% T, 1738 cm ⁻¹ : 15% T, 1466 cm ⁻¹ : 66% T, 1415 cm ⁻¹ : 66% T, 1388 cm ⁻¹ : 63% T, 1356 cm ^{− 1} : 55% T, 1192 cm ⁻¹ : 28% T, 1086 cm ⁻¹ : 25% T, 825 cm ⁻¹ : 56% T
<NMR>

a: 3.5 to 3.7 ppm, b: 0.9 to 1.0 ppm, c, d, e: 2.5 to 2.9 ppm, f: 3.9 to 4.1 ppm, g: 1.4 to 1.6 ppm, h: 0.9 to 1.0 ppm, i: 1.6 to 1.7 ppm

ａ：１．１〜１．４ｐｐｍ、ｂ：４．０〜４．２ｐｐｍ、ｃ：０．８〜１．０ｐｐｍ、ｄ、ｅ、ｆ：２．５〜２．９ｐｐｍ、ｇ：４．０〜４．２ｐｐｍ、ｈ：１．４〜１．６ｐｐｍ、ｉ：０．８〜１．０ｐｐｍ、ｊ：１．６〜１．７ｐｐｍ (Example 1-2)
<IR>
2974 cm ⁻¹ : 53% T, 2889 cm ⁻¹ : 70% T, 1739 cm ⁻¹ : 30% T, 1466 cm ⁻¹ : 80% T, 1415 cm ⁻¹ : 76% T, 1388 cm ⁻¹ : 66% T, 1356 cm ^{− 1} : 67% T, 1165 cm ⁻¹ : 44% T, 1080 cm ⁻¹ : 41% T, 781 cm ⁻¹ : 67% T
<NMR>

a: 1.1-1.4 ppm, b: 4.0-4.2 ppm, c: 0.8-1.0 ppm, d, e, f: 2.5-2.9 ppm, g: 4.0 4.2 ppm, h: 1.4-1.6 ppm, i: 0.8-1.0 ppm, j: 1.6-1.7 ppm

ａ：２．０〜２．３ｐｐｍ、ｂ：０．８〜１．０ｐｐｍ、ｃ、ｄ、ｅ：２．５〜２．９ｐｐｍ、ｆ：４．０〜４．２ｐｐｍ、ｇ：１．４〜１．６ｐｐｍ、ｈ：０．８〜１．０ｐｐｍ、ｈ：４．１〜４．３ｐｐｍ、ｉ：１．６〜１．７ｐｐｍ (Example 1-3)
<IR>
2970 cm ⁻¹ : 76% T, 2889 cm ⁻¹ : 78% T, 1732 cm ⁻¹ : 58% T, 1466 cm ⁻¹ : 84% T, 1415 cm ⁻¹ : 76% T, 1387 cm ⁻¹ : 75% T, 1360 cm ^{− 1: 74% T, 1151cm -1} : 68% T, 1016cm -1: 70% T, 775cm -1: 81% T
<NMR>

a: 2.0 to 2.3 ppm, b: 0.8 to 1.0 ppm, c, d, e: 2.5 to 2.9 ppm, f: 4.0 to 4.2 ppm, g: 1.4 to 1.6 ppm, h: 0.8 to 1.0 ppm, h: 4.1 to 4.3 ppm, i: 1.6 to 1.7 ppm

ａ：３．５〜３．７ｐｐｍ、ｂ：１．６〜１．８ｐｐｍ、ｃ：０．６〜０．７ｐｐｍ、ｄ、ｅ、ｆ：２．５〜２．９ｐｐｍ、ｇ：４．０〜４．２ｐｐｍ、ｈ：１．４〜１．６ｐｐｍ、ｉ：０．８〜０．９ｐｐｍ、ｉ：１．６〜１．８ｐｐｍ (Example 1-4)
<IR>
2945 cm ⁻¹ : 63% T, 2841 cm ⁻¹ : 65% T, 1739 cm ⁻¹ : 41% T, 1466 cm ⁻¹ : 80% T, 1417 cm ⁻¹ : 82% T, 1387 cm ⁻¹ : 83% T, 1352 cm ^{− 1} : 78% T, 1192 cm ⁻¹ : 47% T, 1086 cm ⁻¹ : 35% T, 816 cm ⁻¹ : 75% T
<NMR>

a: 3.5 to 3.7 ppm, b: 1.6 to 1.8 ppm, c: 0.6 to 0.7 ppm, d, e, f: 2.5 to 2.9 ppm, g: 4.0 to 4.2 ppm, h: 1.4-1.6 ppm, i: 0.8-0.9 ppm, i: 1.6-1.8 ppm

ａ：３．５〜３．７ｐｐｍ、ｂ：０．８〜１．１ｐｐｍ、ｃ、ｄ、ｅ：２．５〜２．９ｐｐｍ、ｆ：４．０〜４．２ｐｐｍ、ｇ：１．４〜１．６ｐｐｍ、ｈ：０．８〜１．１ｐｐｍ
（実施例１−６）
＜ＩＲ＞
２９４５ｃｍ^−１：７６％Ｔ、２８４１ｃｍ^−１：８２％Ｔ、１７３９ｃｍ^−１：４２％Ｔ、１７１ｃｍ^−１：８３％Ｔ、１４１４ｃｍ^−１：７９％Ｔ、１３９０ｃｍ^−１：７８％Ｔ、１３５６ｃｍ^−１：７１％Ｔ、１１９２ｃｍ^−１：５４％Ｔ、１０８４ｃｍ^−１：５７％Ｔ、８０６ｃｍ^−１：７７％Ｔ
＜ＮＭＲ＞

ａ：３．５〜３．７ｐｐｍ、ｂ：０．９〜１．１ｐｐｍ、ｃ、ｄ、ｅ：２．５〜２．９ｐｐｍ、ｆ：４．１〜４．３ｐｐｍ、ｇ：１．６〜１．８ｐｐｍ (Example 1-5)
<IR>
2943 cm ⁻¹ : 53% T, 2841 cm ⁻¹ : 62% T, 1738 cm ⁻¹ : 15% T, 1466 cm ⁻¹ : 66% T, 1415 cm ⁻¹ : 66% T, 1388 cm ⁻¹ : 63% T, 1356 cm ^{− 1} : 55% T, 1192 cm ⁻¹ : 28% T, 1086 cm ⁻¹ : 25% T, 825 cm ⁻¹ : 59% T
<NMR>

a: 3.5 to 3.7 ppm, b: 0.8 to 1.1 ppm, c, d, e: 2.5 to 2.9 ppm, f: 4.0 to 4.2 ppm, g: 1.4 to 1.6 ppm, h: 0.8 to 1.1 ppm
(Example 1-6)
<IR>
^{2945cm -1: 76% T, 2841cm} -1: 82% T, 1739cm -1: 42% T, 171cm -1: 83% T, 1414cm -1: 79% T, 1390cm -1: 78% T, 1356cm - ¹ : 71% T, 1192 cm ⁻¹ : 54% T, 1084 cm ⁻¹ : 57% T, 806 cm ⁻¹ : 77% T
<NMR>

a: 3.5 to 3.7 ppm, b: 0.9 to 1.1 ppm, c, d, e: 2.5 to 2.9 ppm, f: 4.1 to 4.3 ppm, g: 1.6 to 1.8ppm

ａ：３．５〜３．７ｐｐｍ、ｂ：０．９〜１．０ｐｐｍ、ｃ、ｄ、ｅ：２．５〜３．０ｐｐｍ、ｆ：４．１〜４．３ｐｐｍ、ｇ：１．６〜１．８ｐｐｍ、ｈ：４．１〜４．３ｐｐｍ (Example 2-1)
<IR>
2945 cm ⁻¹ : 72% T, 2841 cm ⁻¹ : 80% T, 1738 cm ⁻¹ : 31% T, 1469 cm ⁻¹ : 77% T, 1415 cm ⁻¹ : 73% T, 1388 cm ⁻¹ : 70% T, 1353 cm ^{− 1} : 43% T, 1192 cm ⁻¹ : 46% T, 1084 cm ⁻¹ : 54% T, 825 cm ⁻¹ : 78% T
<NMR>

a: 3.5 to 3.7 ppm, b: 0.9 to 1.0 ppm, c, d, e: 2.5 to 3.0 ppm, f: 4.1 to 4.3 ppm, g: 1.6 to 1.8 ppm, h: 4.1 to 4.3 ppm

（式中のＲ^５はそれぞれ独立して下記式２４、２５で表される１価の基である。）

ａ、ｂ：２．５〜２．９ｐｐｍ、ｃ、ｄ：４．０〜４．１ｐｐｍ、ｅ：３．５〜３．７ｐｐｍ、ｆ：０．８〜１．０ｐｐｍ、ｇ：２．５〜２．９ｐｐｍ、ｈ：１．４〜１．６ｐｐｍ、ｉ：０．８〜１．０ｐｐｍ (Example 2-2)
<IR>
2945 cm ⁻¹ : 67% T, 2841 cm ⁻¹ : 69% T, 1739 cm ⁻¹ : 50% T, 1466 cm ⁻¹ : 83% T, 1415 cm ⁻¹ : 83% T, 1387 cm ⁻¹ : 85% T, 1352 cm ^{− 1} : 80% T, 1192 cm ⁻¹ : 55% T, 1086 cm ⁻¹ : 46% T, 825 cm ⁻¹ : 64% T
<NMR>

(R ⁵ in the formula is independently a monovalent group represented by the following formulas 24 and 25.)

a, b: 2.5-2.9 ppm, c, d: 4.0-4.1 ppm, e: 3.5-3.7 ppm, f: 0.8-1.0 ppm, g: 2.5- 2.9 ppm, h: 1.4-1.6 ppm, i: 0.8-1.0 ppm

ａ：３．４〜３．６ｐｐｍ、ｂ：０．６〜０．７ｐｐｍ、ｃ：１．７〜１．８ｐｐｍ、ｄ：４．０〜４．２ｐｐｍ、ｅ、ｇ、ｈ、ｉ：２．５〜２．８ｐｐｍ、ｆ：１．１〜１．３ｐｐｍ、ｊ：３．６〜３．７ｐｐｍ (Comparative Example 1)
<IR>
3460 cm ⁻¹ : 91% T, 2947 cm ⁻¹ : 25% T, 2481 cm ⁻¹ : 31% T, 2360 cm ⁻¹ : 95% T, 1738 cm ⁻¹ : 11% T, 1439 cm ⁻¹ : 39% T, 1360 cm ^{− 1} : 45% T, 1194 cm ⁻¹ : 15% T, 1086 cm ⁻¹ : 10% T, 980 cm ⁻¹ : 57% T, 822 cm ⁻¹ : 23% T, 677 cm ⁻¹ : 88% T
<NMR>

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. 5 to 2.8 ppm, f: 1.1 to 1.3 ppm, j: 3.6 to 3.7 ppm

As is clear from the results of FIGS. 1 to 8, since a peak at 1600 to 1700 cm ⁻¹ derived from the C═C bond is not observed, A-1, A-2, A-3, and A-4 are B -1, B-2, B-3 and β-1.
As is clear from the results of FIGS. 9 to 16, since a peak of 5.5 to 6.5 ppm derived from the C═C bond is not observed, A-1, A-2, A-3, A-4 Is reacted with B-1, B-2, B-3 and β-1.

<Adhesion evaluation>
Next, adhesion was evaluated when the thioether-containing alkoxysilane derivatives of Examples 1-1 to 1-6, 2-1, 2-2 and Comparative Example 1 were used as adhesion improvers. Thereafter, the thioether-containing alkoxysilane derivatives obtained from Examples 1-1 to 1-6, 2-1, 2-2 and Comparative Example 1 were synthesized as synthetic products 1-1 to 1-6, 2-1, 2-2. And referred to as comparative product 1. Furthermore, the adhesion was also evaluated when no adhesion improver was used.
A phenol novolac type epoxy resin [manufactured by Toto Kasei Co., Ltd., YDPN638] was used as an evaluation target for adhesion. Synthetic products 1-1 to 1-6, 2 to a mixture (referred to as E-1) in which 98% by mass of the epoxy resin and 2% by mass of a catalyst [imidazole type catalyst: manufactured by Adeka Co., Ltd., EH-4344S] were mixed. −1, 2-2 and Comparative Product 1 were blended according to the blending amounts shown in Table 2 below as adhesion improvers. The composition was applied to alkali-free glass [manufactured by Nippon Electric Glass Co., Ltd., OA-10] with a bar coater and cured at 150 ° C. for 1 hour to obtain a cured film as a resin molded product. The cured films of Examples 3-1 to 3-16, Comparative Examples 3-1 and 3-2 thus obtained were treated at a temperature of 121 ° C. and a relative humidity (RH) of 100% for 24 hours, and then JIS. Evaluation was performed by the mechanical property-adhesion (cross-cut method) test method of the coating film specified in K5600-5-6. 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 Examples 3-1 to 3-8 in which the synthetic products 1-1 to 1-6 and 2-1, 2-2 were used as adhesion improvers, no peeling was observed, Adhesion was good. Moreover, also in Examples 3-9 to 3-16 in which the addition amount of the adhesion improver was reduced, no peeling was observed and the adhesion was good. On the other hand, in Comparative Example 3-1, since a compound other than the thioether-containing alkoxysilane derivative of the present invention was used, peeling occurred and the adhesion was poor. Moreover, in Comparative Example 3-2, since no adhesion improver was used, peeling occurred and adhesion was poor.

Claims (5)

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

(In the formula, a is an integer of 1 to 4, b is an integer of 0 to 3, c is 0 or 1, and a + b + c = 4. M is 1 or 2, and n is 0 or R ¹ is a group represented by —CH ₂ —CH ₂ — or —CH (CH ₃ ) —, and R ² is a methyl group, an ethyl group or an acetyl group. A thioether-containing alkoxysilane derivative represented by the following formula 2.

(Wherein a ′ is an integer of 1 to 3, b ′ is an integer of 0 to 2, c ′ is 0 or 1, and a ′ + b ′ + c ′ = 3. A ″ is An integer of 0 to 3, b ″ is an integer of 0 to 2, c ″ is 0 or 1, and a ″ + b ″ + c ″ = 3. M is 1 or 2. And n is 0 or 1. R ¹ is a group represented by —CH ₂ —CH ₂ — or —CH (CH ₃ ) —, and R ² is a methyl group, an ethyl group or an acetyl group. ) The thioether-containing alkoxysilane derivative according to claim 1, wherein the alkoxysilyl group-containing compound represented by the following formula 3 is reacted with a polyvalent thiol compound represented by the following formula 4.

(In the formula, R ³ is a vinyl group or an allyl group. R ² is a methyl group, an ethyl group, or an acetyl group.)

(In the formula, d is 0 or 1, e is 3 or 4, and d + e = 4. 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 3 is reacted with a polyvalent thiol compound represented by the following formula 5.

(In the formula, R ³ is a vinyl group or an allyl group. R ² is a methyl group, an ethyl group, or an acetyl group.)

(In the formula, f is 2 or 3, g is 0 or 1, and f + g = 3. F ′ is 2 or 3, g ′ is 0 or 1, and f ′ + g ′ = 3. M is 1 or 2.) An adhesion improver comprising the thioether-containing alkoxysilane derivative according to claim 1 or 2 as an active ingredient.

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