KR20130064821A - Thioether-containing alkoxysilane derivative and use thereof - Google Patents

Abstract

(식 중의 a 및 b 는 0 ∼ 2 의 정수이고, c 는 1 ∼ 3 의 정수이고, a＋b＋c = 3 이다. R¹ 은 하기 식 2 로 나타내는 3 가의 기이고, R² 는 -CH₂-CHR⁵- 또는 -CR⁵(CH₃)- 으로 나타내는 2 가의 기이고, R³ 은 -CH₂-CHR⁶- 또는 -CR⁶(CH₃)- 으로 나타내는 2 가의 기이고, R⁵ 와 R⁶ 은 각각 독립적으로 수소 원자 또는 메틸기이고, R⁴ 는 메틸기 또는 에틸기이다)
[화학식 2]

(식 중의 m 은 1 또는 2 이다)As a novel thioether containing alkoxysilane derivative excellent in the adhesive improvement effect to an inorganic base material, it is a thioether containing alkoxysilane derivative represented by following formula (1).
[Formula 1]

(A and b in the formula are integers of 0 to 2, c is an integer of 1 to 3, and a + b + c = 3. R ¹ is a trivalent group represented by the following formula (2), and R ² is —CH ₂ —CHR ^5. -Or a divalent group represented by -CR ⁵ (CH ₃ )-, R ³ is a divalent group represented by -CH ₂ -CHR ⁶ -or -CR ⁶ (CH ₃ )-, and R ⁵ and R ⁶ are each Independently a hydrogen atom or a methyl group, R ⁴ is a methyl group or an ethyl group)
(2)

Where m is 1 or 2

Description

Thioether-containing alkoxysilane derivatives and uses thereof {THIOETHER-CONTAINING ALKOXYSILANE DERIVATIVE AND USE THEREOF}

The present invention relates to novel thioether-containing alkoxysilane derivatives which are preferably used for adhesion improving agents and the like and their use.

Conventionally, when apply | coating various coating materials to inorganic base materials, such as glass, the silane coupling agent is added to the coating material for the purpose of improving adhesiveness (for example, refer patent document 1).

Japanese Patent Laid-Open No. 7-300491

However, since many of the silane coupling agents have a structure having a C1-5 alkyl group as a main skeleton, the boiling point was low, and it was necessary to add a large amount (for example, 10 to 20 wt%) to paints requiring high temperature coating. . Moreover, since it has only one trialkoxysilyl group per molecule, the adhesive improvement effect is not enough, for example, salts, such as titanium and zirconium, amines, such as imidazole, phosphate ester, a urethane resin, thiol In many cases, adhesive properties can also be achieved by adding adhesive aids such as compounds. However, the formulation of these adhesive auxiliaries required not only an increase in the number of processes but also an optimization of the adhesive auxiliaries and the amount of addition which did not impair the coating properties. Moreover, in many of the silane coupling agents which have a trialkoxy silyl group and a reactive functional group, the main skeleton which connects a trialkoxy silyl group and a reactive group is comprised by the carbon-carbon bond. Therefore, the molecule was rigid and the reaction efficiency of the alkoxysilyl group or the reactive group was low.

Then, this invention is made | formed in view of the said subject, The objective is to provide the novel thioether containing alkoxysilane derivative excellent in the adhesive improvement effect to an inorganic base material, and its use.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, it discovered that the thioether containing alkoxysilane derivative which has a specific structure had the outstanding adhesive improvement effect, and came to complete this invention. That is, the present invention is the following [1] to [4].

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

[Formula 1]

(A and b in the formula are integers of 0 to 2, c is an integer of 1 to 3, and a + b + c = 3. R ¹ is a trivalent group represented by the following formula (2), and R ² is —CH ₂ —CHR ^5. -Or a divalent group represented by -CR ⁵ (CH ₃ )-, R ³ is a divalent group represented by -CH ₂ -CHR ⁶ -or -CR ⁶ (CH ₃ )-, and R ⁵ and R ⁶ are each Independently a hydrogen atom or a methyl group, R ⁴ is a methyl group or an ethyl group)

[Formula 2]

Where m is 1 or 2

[2] The thioether-containing alkoxysilane derivative according to [1], wherein the alkoxysilyl group-containing compound represented by the following Formula 3 is reacted with the polyvalent thiol compound represented by the following Formula 4.

(3)

(Wherein R ⁴ is a methyl group or an ethyl group, and R ⁵ is a hydrogen atom or a methyl group)

[Formula 4]

Where m is 1 or 2

[3] The thioether-containing alkoxysilane derivative according to [2], wherein the oxirane ring-containing compound represented by the following Formula 5 is simultaneously reacted.

[Chemical Formula 5]

(R ⁶ is a hydrogen atom or a methyl group)

[4] An adhesive improving agent comprising the thioether-containing alkoxysilane derivative according to any one of [1] to [3] as an active ingredient.

The thioether-containing alkoxysilane derivative of the present invention has an excellent adhesion improving effect, and by adding a relatively small amount of, for example, 0.1 to 10% by weight to the paint, it is possible to provide high adhesion to the paint without requiring the addition of an adhesive aid. It is possible.

Since the bonding angle of thiol is larger than the bonding angle of carbon, the molecule | numerator which has a thiol ether group in a molecule | numerator can take a structure more colorful than the molecule | numerator which couple | bonds only with carbon. Therefore, the thioether containing alkoxysilane derivative of this invention improves the orientation to a base material rather than the alkoxysilane derivative which couple | bonds only carbon, and can improve adhesiveness. In addition, the present invention has a wider bond angle of thioethers than conventional silane coupling agents, so that the degree of freedom in the molecular structure can be increased to achieve a dense molecular orientation, and the boiling point is high and low compared to that of the same molecular weight. It is volatile. Therefore, even if it adds a comparatively small amount of 0.1-10 weight% to paint, for example, it is possible to provide adhesiveness to a high silicon substrate, without requiring addition of an adhesive adjuvant.

Since the thioether-containing alkoxysilane derivative of the present invention has an isocyanurate ring in the main skeleton, it has excellent locality to the substrate, and an alkoxysilane group present at the terminal of the molecule forms a chemical bond between the substrate, or It exhibits excellent adhesion by physical adsorption. In addition, thioether bonds present in the molecule can flexibly change the bond angle and bond length as compared with bonds by atoms such as C, O, or N, and can take various steric positions, It is thought that orientation becomes high. Since this invention is a reaction product of a low volatile polyvalent thiol compound and an alkoxy silyl group containing compound, it becomes low volatility compared with the general alkoxy silyl group containing compound. Further, the S atom derived from the thioether bond has a larger atomic radius because the outermost shell is an M shell while the outermost shell of an atom such as C, O or N is an L shell. Therefore, having an S atom makes it possible to interact with molecules that are farther away, so that the intermolecular force is improved, leading to lower volatilization. Thereby, this invention can give high adhesiveness to paint, for example, without requiring addition of an adhesive adjuvant even in comparatively small quantity addition of 0.1-10 weight% to paint.

Furthermore, since the thioether containing alkoxysilane derivative is excellent in adhesiveness provision effect, it is useful as an adhesive improving agent which provides adhesiveness to coating materials etc.

1 is a nuclear magnetic resonance spectrum of Example 1-1.
2 is a nuclear magnetic resonance spectrum of Example 1-2.
3 is a nuclear magnetic resonance spectrum of Examples 1-3.
4 is a nuclear magnetic resonance spectrum of Examples 1-4.

<Thioether containing alkoxysilane derivative>

The thioether containing alkoxysilane derivative of this invention is a compound represented by following formula (1).

[Formula 6]

(A and b in the formula are integers of 0 to 2, c is an integer of 1 to 3, and a + b + c = 3. R ¹ is a trivalent group represented by the following formula (2), and R ² is —CH ₂ —CHR ^5. -Or a divalent group represented by -CR ⁵ (CH ₃ )-, R ³ is a divalent group represented by -CH ₂ -CHR ⁶ -or -CR ⁶ (CH ₃ )-, and R ⁵ and R ⁶ are each Independently a hydrogen atom or a methyl group, R ⁴ is a methyl group or an ethyl group)

[Formula 7]

Where m is 1 or 2

When adding the thioether containing alkoxysilane derivative of this invention to the resin composition which has a functional group which reacts with an oxirane ring, it is preferable that b is 1 or more from a viewpoint of an adhesive improvement effect.

Since the thioether containing alkoxysilane derivative of this invention represented by Formula 1 is compatible with many resins, it can be used for a wide range of uses, and high adhesiveness can be obtained by addition of a small amount (for example, 0.1-10 weight%). For example, since the adhesiveness of resin and an inorganic material can be improved by using the thioether containing alkoxysilane derivative of this invention, FRP (fiber-reinforced plastics), FRTP (fiber-reinforced thermoplastics), resin concrete, artificial marble, It is useful as an adhesive agent for composite materials which combined an inorganic material and resin, such as a plastic magnet, a rubber magnet, and a magnetic tape. Moreover, in an adhesive, an adhesive agent, a sealing agent, a sealant, etc., it mix | blends the thioether containing alkoxysilane derivative of this invention in a resin component, and is effective in improving adhesive force with an inorganic base material. It is especially suitable as an adhesive improving agent at the time of apply | coating various coating materials to inorganic base materials, such as a glass substrate.

<Manufacturing method of a thioether containing alkoxysilane derivative>

The thioether-containing alkoxysilane derivative represented by the formula (1) includes at least an alkoxysilyl group [—Si (OR ⁴ ) 3] and a compound having a double bond (hereinafter may be referred to as A component), and a thiol group (-SH) It can obtain by making the polyhydric thiol compound (Hereinafter, it may be called B component) which has. Specifically, it can obtain by making at least the alkoxy silyl group containing compound represented by following formula 3 and the polyhydric thiol compound represented by following formula 4 react.

[Formula 8]

(Wherein R ⁴ is a methyl group or an ethyl group, and R ⁵ is a hydrogen atom or a methyl group)

[Chemical Formula 9]

(M in the formula is an integer of 1 or 2)

As an alkoxy silyl group containing compound represented by Formula 3, 3-methacryloxypropyl trimethoxysilane, 3-acryloxypropyl trimethoxysilane, 3-methacryloxypropyl triethoxysilane, 3- Acryloxypropyl trimethoxysilane etc. can be used.

As a polyvalent thiol compound represented by Formula 4, m = 2 tris [(3-mercaptopropionyloxy) -ethyl] isocyanurate is mentioned. As a polyhydric thiol compound of m = 1 in Formula 4, the compound of isocyanuric tris (2-hydroxyethyl) and thioglycolic acid is mentioned. When m≥3 compound is used in Formula 4, hydrophobic and nonpolar hydrocarbon number increases, the orientation of a thioether group to a base material becomes weak, and the adhesiveness which is an effect of this invention is not acquired easily.

In addition, when adding the thioether containing alkoxysilane derivative of this invention to the resin composition which has a functional group which reacts with an oxirane ring, In addition to the alkoxy silyl group containing compound represented by Formula 3, and the polyhydric thiol compound represented by Formula 4, It is preferable to also react the oxirane ring containing compound represented by following formula 5 simultaneously. Thereby, higher adhesiveness can be provided.

[Formula 10]

(R ⁶ is a hydrogen atom or a methyl group)

A glycidyl (meth) acrylate is mentioned as an oxirane ring containing compound represented by Formula 5.

Component A and component B are preferably reacted in the presence of a catalyst or a radical generator. This is because the addition of a catalyst and a radical generator can cause the reaction to be performed in a shorter time and in a higher yield.

As the catalyst, an amine base catalyst is preferable, and primary, secondary or tertiary amines or imidazole compounds can be used. For example, tertiary amine, such as methylamine, ethylamine, propylamine, butylamine, ethylenediamine, etc. as secondary amine, dimethylamine, diethylamine, dipropylamine, methylethylamine, diphenylamine, etc. As amine, trimethylamine, triethylamine, tripropylamine, triphenylamine, 1,8-diazabicyclo (5,4,0) -undecene-7,2,4,6-tris (dimethylaminomethyl) phenol Etc. can be mentioned. Examples of the imidazole compound include imidazole homologues such as 1-methylimidazole, 1,2-dimethylimidazole, 1,4-dimethyl-2-ethylimidazole, 1-phenylimidazole, Oxyalkyl derivatives such as 1-methyl-2-oxymethylimidazole, 1-methyl-2-oxyethylimidazole, 1-methyl-4 (5) -nitroimidazole, 1,2-dimethyl-5 ( Nitro and amino derivatives such as 4) -aminoimidazole, benzoimidazole, 1-methylbenzoimidazole, 1-methyl-2-benzylbenzoimidazole and the like.

As a 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. As an azo compound, azobis (isobutyronitrile), 2,2'- azobis (2-methylbutanenitrile), etc. are mentioned, for example.

This A * B2 component reacts by the reaction formula in which the double bond of component A and the thiol group of component B are represented by following formula (6). In addition, X represents a hydrogen atom or a methyl group, Y represents residues other than X couple | bonded with the double bond of A component, Z represents the residue couple | bonded with the thiol group of B component.

[Formula 11]

As shown in Formula 6, either of the two carbons forming the double bond of the A component is bonded to S of the thiol. The production rate of the two products differs 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 a radical generator is added to the reaction system. In the case of addition, there is a tendency for a large amount of product (2) to be produced. In most cases, the thioether containing alkoxysilane derivative after manufacture becomes a mixture of product (1) and (2).

Moreover, when manufacturing a thioether containing alkoxysilane derivative, since B component has three thiol groups, the product which some of the thiol groups of B component reacted with A component can be obtained like Formula (7). In addition, V represents the residue (isocyanurate ring containing residue) couple | bonded with the thiol group of B component.

[Chemical Formula 12]

The addition number of the A component in Formula 7 corresponds to c of Formula 1. In most cases, the thioether containing alkoxysilane derivative after manufacture is a mixture of the substance from which the number of substituents reacted addition was different.

In the manufacturing method of a thioether containing alkoxysilane derivative, although it can make it react at the temperature of 5 degreeC or more, in order to make it react in a short time like 5 hours or less, it is preferable to add a base catalyst and a radical generator in 60-80 degreeC. Do.

In the manufacturing method of a thioether containing alkoxysilane derivative, even if it is a solvent-free, reaction can advance, but when it wants to lower a viscosity, for example, when making it react at low temperature, you may add a solvent and make it react. In that case, the solvent which does not react with an alkoxysilyl group, a double bond, a thiol group, for example, alcohols, ketones, esters, or aromatics is preferable.

As alcohols which do not react with an alkoxysilyl group, a double bond, or a thiol group, it is preferable that carbon number is primary at 3 or less, and it is preferable that boiling point is higher than reaction temperature (for example, boiling point 50-190 degreeC). . This is because, when the boiling point is lower than the above range, it is difficult to manufacture in the case of industrialization. When the boiling point is higher than the above range, the solvent distillation becomes difficult when the removal of the solvent is necessary. Therefore, the boiling point should be as high as possible. Moreover, methanol and ethanol are more preferable as alcohols. This is because alcohols, which are reaction solvents, and the alkoxysilyl group-containing compound represented by Formula 3 may cause transesterification during the reaction, and the yield of the target product may be lowered. Therefore, it is preferable to use methanol as a reaction solvent when R <^4> uses the compound of methyl group in said Formula 3, and ethanol as a reaction solvent when R <^4> uses the compound of ethyl group.

As ketones which do not react with an alkoxysilyl group, a double bond, or a thiol group, those having a boiling point higher than the reaction temperature are preferable, and those having 6 or less carbon atoms are preferable from the viewpoint of solubility. As what satisfy | fills these, methyl ethyl ketone, methyl isobutyl ketone, etc. are mentioned, for example.

As esters which do not react with an alkoxysilyl group, a double bond, or a thiol group, it is preferable that boiling point is higher than reaction temperature, and it is preferable that it is C6 or less of linear carbon from a viewpoint of solubility. As satisfying these, ethyl acetate, methyl acetate, butyl acetate, methoxy butyl acetate, cellosolve, amyl acetate, methyl lactate, ethyl lactate, butyl lactate etc. are mentioned, for example.

<Adhesive improver>

The thioether-containing alkoxysilane derivative of the present invention can be used as an adhesion improving agent, in particular, in view of having high adhesion improving performance with respect to inorganic substrates such as glass and metal. The adhesive improving agent which uses a thioether containing alkoxysilane derivative as an active component can exhibit a high adhesive improvement effect by mix | blending with an epoxy resin, a urethane resin, an acrylic resin, a polyimide resin, the compound etc. which have a double bond.

Moreover, the thioether containing alkoxysilane derivative which is a compound represented by Formula 1 and whose a is not 0 has a thiol group, and reacts with an epoxy group, a double bond, and an isocyanate group. For this reason, a higher adhesive effect can be exhibited by adding the thioether containing alkoxysilane derivative whose a is not 0 in Formula 1 to an epoxy resin, an acrylic resin, a urethane resin, and the compound which has a double bond.

Moreover, the thioether containing alkoxysilane derivative which is a compound represented by Formula 1, and b is not 0 has an oxirane ring, and reacts with an epoxy group, a carboxyl group, a phenolic hydroxyl group, an acid anhydride group, an amino group, and an amide group. For this reason, a higher adhesive effect can be exhibited by adding the thioether containing alkoxysilane derivative whose b is not 0 in Formula 1 to the resin composition which has a functional group which reacts with an oxirane ring.

The adhesive improving agent which uses a thioether containing alkoxysilane derivative as an active ingredient can exhibit high adhesiveness when it adds 0.1-30 mass% with respect to resin as an active ingredient, More preferably, 0.1-15 mass%.

Example

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples. The measuring method and evaluation method which were used by each Example and the comparative example are shown below.

<Infrared Absorption Spectrum Analysis (IR)>

Type; Nippon Spectroscopy Co., Ltd. manufacture FT / IR-600

Cell; Development and decomposition on KBr; 4 cm ^-1 , integration count; 16 times

<Nuclear Magnetic Resonance Spectrum Analysis (NMR)>

Type; Nippon Burker Co., Ltd. product, 400 MHz-Advance 400, conditions; 16 times of integration times, solvent; Heavy chloroform

<Viscosity>

Type; Toki Sangyo Co., Ltd. product (R type viscometer), temperature; 25 ℃

<Adhesive evaluation>

After the sample which formed the cured film was processed for 30 hours at the temperature of 121 degreeC, and 100% of a relative humidity (RH), evaluation was evaluated by the mechanical property-adhesive (crosscut method) test method of the coating film prescribed | regulated to JISK5600-5-6. Was carried out. In this test, the thing without peeling at all was made into "(circle)". Furthermore, as a result of performing the same test about the sample after processing for 40 hours at the temperature of 121 degreeC and 100% of a relative humidity (RH), it was set as "(◎)" that there was no peeling at all. Peeling was observed as "x".

Below, the reagent used by the present Example and the comparative example is shown.

<Compound Having Alkoxysilyl Group: Component A>

A-1: 3-methacryloxypropyl trimethoxysilane. The structure is shown in following formula 12.

[Chemical Formula 13]

A-2: 3-acryloxypropyl trimethoxysilane. The structure is shown in following formula (13).

[Formula 14]

A-3: 3-methacryloxypropyl triethoxysilane. The structure is shown in following formula 14.

[Formula 15]

<Polyvalent thiol compound: B component>

B-1: Tris [(3-mercaptopropionyloxy) -ethyl] isocyanurate. The structure is shown in following formula (viscosity 5.4 Pa.s).

[Chemical Formula 16]

β-1: methyl-3-mercaptopropionate. The structure is shown in following formula 16.

[Chemical Formula 17]

<Oxirane ring containing compound: C component>

C-1: glycidyl methacrylate. The structure is shown in following formula 17.

[Chemical Formula 18]

<Amine: Catalyst>

Diazabicycloundecene (DBU).

(Examples 1-1 to 1-4, Comparative Example 1)

The separable four-necked flask was equipped with a thermometer and a reflux tube, and the inside was made into nitrogen atmosphere. A, B and C components were injected into this four-necked flask according to the following Table 1, and reacted at 90 ° C for 8 hours under the conditions of Table 1. The viscosity after reaction is shown in Table 1.

The result of IR of each Example is shown next.

<Result of IR>

(Example 1-1)

(Example 1-2)

(Example 1-3)

(Examples 1-4)

<Result of NMR>

The NMR spectrum of Example 1-1 is shown in FIG. 1, the NMR spectrum of Example 1-2 is shown in FIG. 2, the NMR spectrum of Examples 1-3 is shown in FIG. 3, and the NMR spectrum of Example 1-4 is shown in FIG. 4. Respectively.

The attribution of the peak in the NMR spectrum of FIG. 1 is shown in Equation 18 below.

[Chemical Formula 19]

The attribution of the peak in the NMR spectrum of FIG. 2 is shown in Equation 19 below.

[Chemical Formula 20]

The attribution of the peak in the NMR spectrum of FIG. 3 is shown in Equation 20 below.

[Chemical Formula 21]

The attribution of the peak in the NMR spectrum of FIG. 4 is shown in Equation 21 below.

[Formula 22]

1-4 and the said peak, Example 1-2 and Example 1-3 confirmed the peak derived from a thiol, but in Example 1-1 and Example 1-4, the peak derived from a thiol group was observed. It wasn't. In addition, in that the peak is not observed, which comes from the _{CH 2 = CH, A-1} , A-2, A-3 has been found that the reaction.

(Examples 2-1 to 2-4, Comparative Examples 2-1 to 2-2)

As an epoxy resin, 95 mass% of YDPN638 [phenolic novolak-type epoxy resin: Toto Kasei Co., Ltd. brand name] and 5 mass% of EH-4344S [imidazole type catalyst: Adeka Corporation make, brand name] A mixture of was selected (E-1). The said Example 1-1-1-4, the comparative example 1, and B-1 alone were mix | blended with this E-1 according to the compounding quantity of Table 2 as an adhesive improving agent. The blended sample was applied to OA-10 [alkali glass: Nippon Electric Glass Co., Ltd., product name] with a bar coater, and cured under conditions of 150 ° C. for 1 hour to obtain a cured film as a resin molded product. The adhesiveness of the obtained cured film is evaluated, and their results are shown in Table 2. In addition, the numerical value of Table 2 is g.

From the result shown in Table 2, peeling was not observed at all in Examples 2-1 to 2-4, and adhesiveness was favorable. On the other hand, in Comparative Examples 2-1 to 2-2, since a compound other than the thioether containing alkoxysilane derivative of this invention was used, peeling generate | occur | produced all and adhesiveness was inferior.

Claims (4)

Thioether containing alkoxysilane derivative represented by following formula (1).
[Formula 1]

(A and b in the formula are integers of 0 to 2, c is an integer of 1 to 3, and a + b + c = 3. R ¹ is a trivalent group represented by the following formula (2), and R ² is —CH ₂ —CHR ^5. -Or a divalent group represented by -CR ⁵ (CH ₃ )-, R ³ is a divalent group represented by -CH ₂ -CHR ⁶ -or -CR ⁶ (CH ₃ )-, and R ⁵ and R ⁶ are each Independently a hydrogen atom or a methyl group, R ⁴ is a methyl group or an ethyl group)
(2)

Where m is 1 or 2 The method of claim 1,
The thioether containing alkoxysilane derivative formed by making the alkoxy silyl group containing compound represented by following formula 3 and the polyhydric thiol compound represented by following formula 4 react.
(3)

(Wherein R ⁴ is a methyl group or an ethyl group, and R ⁵ is a hydrogen atom or a methyl group)
[Chemical Formula 4]

Where m is 1 or 2 3. The method of claim 2,
Furthermore, the thioether containing alkoxysilane derivative which makes the oxirane ring containing compound represented by following formula 5 react simultaneously.
[Chemical Formula 5]

(R ⁶ is a hydrogen atom or a methyl group) An adhesive improving agent comprising the thioether-containing alkoxysilane derivative according to any one of claims 1 to 3 as an active ingredient.

Images