TW201226414A - Thioether-containing alkoxysilane derivative and use thereof - Google Patents

Abstract

A novel thioether-containing alkoxysilane derivative that excels in an effect for improving adhesion to an inorganic base material and that is represented by formula (1). [Compound 1] (In the formula, a and b are each an integer between 0 and 2, c is an integer between 1 and 3, and a+b+c=3. R1 denotes a trivalent group represented by formula 2, R2 denotes a divalent group represented by -CH2-CHR5- or -CR5(CH3)-, R3 denotes a divalent group represented by -CH2-CHR6- or CR6(CH3)-, R5 and R6 each independently denote a hydrogen atom or a methyl group, and R4 denotes a methyl group or an ethyl group.) [Compound 2](In the formula, m is 1 or 2.)

Description

201226414 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a novel inclusion-containing oxy-acene derivative suitable for an adhesion promoter (adhesi〇n impr〇ver) and the like and use thereof . [Prior Art] When the various coating materials are applied to an inorganic substrate such as glass, a scouring coupling agent is added to the coating material for the purpose of improving adhesion (for example, see Patent Document 1). CITATION LIST PATENT DOCUMENT Patent Document 1: Japanese Patent Application Laid-Open No. Hei No. Heisei No. Hei. The structure of the rack is therefore low, and it is necessary to add a large amount (for example, 10 to 2% by weight) to the coating which requires high-temperature coating. In addition, since each molecule contains only one of the three courtyards, it can not be said that it has sufficient effect of improving the attachment. For example, K, and s. J., by adding titanium, wrong salt, etc. The taste of the amine, or the linonic acid g, the cover of the ''V虱Ss tree 曰, thiol and other adhesion aids to achieve improved adhesion 4 right month. However, the addition of these auxiliaries not only increases the number of working chambers, but also requires an appropriate selection of adhesion aids that do not impair the properties of the coating and the addition of I. Further, a decane coupling agent having 4 201226414 tris-oxyalkylene group and a reactive functional group is mostly a main frame which is bonded to a reactive group by a carbon-carbon bond. Therefore, the molecule is rigid, and the reaction efficiency of the alkoxyalkyl group or the reactive group is lowered. Accordingly, the present invention has been made in view of the above problems, and an object thereof is to provide a novel thioether-containing alkoxydecane derivative which is excellent in an effect of improving adhesion to an inorganic substrate and an application thereof. Means for Solving the Problems In order to solve the above problems, the present inventors have conducted intensive studies to find that a sulfide-containing alkoxydecane derivative having a specific structure has an excellent adhesion effect, and thus the present invention has been made. That is, the present invention is a thioether-containing alkoxydecane derivative represented by the following formula (1) to (4) 〇(1).

Wherein 'a and b are integers of 〇~2, c is an integer of 卜3, a+b + c = 3; R1 is a ternary group represented by the following formula 2, and R2 is _CH2_chrS_ or gas r5 (ch3)-the binary group shown, the ruler 3 is a binary group represented by _CH2_CHR6_ or _cr6(ch3)_, and R5 and V are each independently a hydrogen atom or a fluorenyl group, and R4 is a methyl group. Or ethyl. 5 201226414

(2) The thioether-containing alkoxydecane derivative according to (1), which is an alkoxyalkyl group-containing compound represented by the following formula 3, and the following formula 4 The illustrated polythiol compound is reacted. R5, OR4. * Ji-OR^ (Formula 3) wherein R4 is a methyl group or an ethyl group, and R is a mouse atom or a fluorenyl group.

In the formula, m is a 1 or Z ° - + thioether-containing oxime derivative, and (3) as in (2), 6 201226414 is also obtained by the following formula. Reaction of an oxirane ring-containing compound represented by R6 (Formula 5) R6 is a hydrogen atom or a methyl group. (4) The adhesion promoter of the thioether-containing alkoxydecane derivative according to any one of (1) to (7) as an active ingredient. [Advantageous Effects] The sulfur-containing light amphoteric oxide derivative of the present invention has an excellent adhesion improving effect, and by adding a small amount to the coating, for example, 〇. It is possible to impart high adhesion to the coating. Since the bond angle of the thiol is larger than the bond angle of the carbon atom, the molecule 'having a thiol ether group in the molecule can obtain a more diverse structure than a molecule bonded only with a carbon atom. Therefore, the thioether-containing alkoxy decane of the present invention can improve the orientation to the substrate and improve the adhesion as compared with the alkoxydecane derivative which is bonded only by a carbon atom. In addition, in the present month, the existing decane coupling agent phase &amp; thioether has a larger bond angle, hence the molecular weight. The degree of freedom in the structure is improved by the fact that a close molecular orientation can be obtained, and the material having the same molecular weight has a higher boiling point and a lower volatility. Therefore, even if only a small amount is added to the material, for example, 〇. Η 〇% by weight, it is not necessary to add a tribute to the customer, which is sufficient to impart high adhesion to the substrate. f &amp; March sulfur-containing alkoxydecane derivative, due to the presence of isocyanuric acid in the main frame for 5 mornings, so the localization of the substrate is excellent 201226414, through the alkane present at the molecular end The oxyalkylene group forms a chemical bond or physical adsorption with the substrate to exhibit excellent adhesion. In addition, the thioether bond present in the molecule can flexibly change the bond angle and the bond length as compared with the bond formed by the c, 0 or N atom, and various stereo structures can be obtained, so that (10) orientation to the substrate can be obtained. improve. The present invention produces a product of a reaction of a low volatility polythiol compound and an alkoxyalkylalkyl group-containing compound, and thus is less volatile than a general alkoxyalkyl group-containing compound. Further, the outermost layer relative to the c, 〇 or N atom is the L layer, and the outermost layer of the s atom derived from the sulfur screaming bond is the M layer, and thus has a larger atomic radius. Therefore, it is related to low volatility because it has the S original and can be considered to affect and interact with molecules existing further away, thereby increasing the intermolecular force. According to the present invention, even if a small amount, for example, 01 to w% by weight, is added to the coating material, it is possible to impart high coating properties without adding an adhesion aid. No. 3, the sulphur-supplemented oxysulphate derivative is excellent in adhesion to the monument, and therefore can be used as an adhesion promoter for imparting adhesion to paints and the like. [Embodiment] <Alkoxydecane derivative containing a sulfide" The sulfide-containing alkoxydecane derivative of the present invention. The creature is shown below. 8 201226414

, s, iR4 Λ • (Formula 1) wherein a and R are a diradical group represented by the following formula 2 _CR5(CH3)-, and R is a mercapto group or an ethyl group. An integer of 0 to 2, c is an integer of Bu 3, a+b+c = 3; a ternary group of no, R2 is _CH2_CHR5_ or

Wherein R3 is -Cih-CHR6- or -CR6(CH3)- and R6 are each independently a hydrogen atom or a fluorenyl group, V

(Formula 2) where m is 1 or 2. When alkoxydecane derivative of the oxime thiol of the present invention is added to a resin composition having a functional group reactive with a ruthenium/ether oxide ring,

It is preferable that the effect of the improvement of the human condition is "1" or more. ☆ The thioether-containing alkoxydecane derivative of the present invention can be used in a variety of resins, so that it can be widely used in various applications, and can be used in a small amount (for example, 0.1% by weight). Get high adhesion. Example: 'By using the sulfur-containing material of the present invention to burn oxygen (4) (4) organisms, it is possible to 'good adhesion between the resin and the inorganic material, so it can be used as a composite material 9 201226414 adhesion: accelerator 'the composite material is an inorganic material Combined with resin, various types of &gt;FRP (fiber reinforced plastic), FRTp (fiber reinforced thermoplastic plastic) resin concrete, artificial marble, plastic magnet, rubber magnet, tape and the like. Further, in the case of an adhesive, a binder, a sealer, a sealant, etc., the addition of the sulfide-containing alkoxydecane derivative of the present invention to the resin component can be improved between the inorganic substrate and the inorganic substrate. The effect of the adhesion is particularly suitable as an adhesion promoter when coating various coating materials on an inorganic substrate such as a glass substrate. <Preparation method of a thioether-containing oxonium derivative> The thioether-containing alkoxydecane derivative is a compound having at least an alkoxyalkyl group (-SK0R4) 3) and a double bond (hereinafter, often referred to as component A) and a thiol group (_SH). A thiol compound (hereinafter referred to as 'component B') is reacted. Specifically, at least an alkoxyalkyl group-containing compound represented by the following formula 3 and a polythiol represented by the following formula 4 may be used. The compound is prepared by reaction. OR4

Wherein 'R4 is a fluorenyl group or an ethyl group, and R5 is a hydrogen atom or a fluorenyl group. 10 201226414

Wherein 'm is an integer of 1 or 2. As the alkoxyalkylalkyl group-containing compound represented by Formula 3, for example, 3-mercaptoacryloxypropyltrimethoxydecane, 3-acryloxypropyldimethoxydecane, 3- Methacryloxypropyltriethoxydecane, 3-acryloyloxypropyltrimethoxydecane, and the like. The polythiol compound represented by Formula 4 may, for example, be tri[(3-mercaptopropionyl)-ethyl]isocyanurate having m=2. As the polythiol compound of m = 1 in the formula 4, a synthesis product of tris(2-hydroxyethyl)isocyanurate and mercaptoacetic acid is exemplified. In the formula 4, when the compound of m23 is used, the number of hydrophobic and non-polar hydrocarbons increases, so that the orientation of the thioether group to the substrate is weakened, and it is difficult to obtain the adhesion of the effect of the present invention. Further, when the thioether-containing alkoxydecane derivative of the present invention is added to a resin composition having a functional group reactive with an oxirane ring, the alkoxyalkyl group-containing compound represented by Formula 3 is removed. In addition to the polythiol compound represented by Formula 4, it is also preferred to simultaneously react with the oxirane ring-containing compound represented by the following Formula 5. In this way, it is possible to impart higher adhesion. 201226414

(Formula s) R6 is a hydrogen atom or a fluorenyl group. The oxirane ring-containing compound represented by Formula 5 is exemplified by glycidyl (meth) acrylate. The component A and the component B preferably react in the presence of a catalyst or a radical generator. This is because if a catalyst or a radical generator is added, it is possible to react in a shorter time and at a high yield. The catalyst ' is preferably an amine-based basic catalyst, and a primary amine, a secondary amine or a tertiary amine may be used, or an imidazole compound may be used. For example, as the primary amine, methylamine, ethylamine, propylamine, butylamine, ethylenediamine or the like can be exemplified; as the secondary compound, diamine, diethylamine, dipropylamine, methylethylamine, diphenylamine can be exemplified. And, as the tertiary amine, trimethylamine, triethylamine, tripropylamine, triphenylmamine 1,8-diazabicyclo(5,4,fluorene)-undecyl-7-ene, 2 4 6_ may be exemplified. Tribasin thiol). Examples of the imidazole compound include imidazole homologues such as methylimidazole, 1'2-dimethylimidazole, l 4 dimethyl-2-ethylimidazole, and bumamine = azole; and methyl 2-oxo Methylimidazole, methyl methyl ethyl ester. Oxygen-based derivatives; nitro- 4 (5) - succinyl sulphate, sulfonyl 5 (4) aminoimidazole and other nitro and amino derivatives; stupid imidazole, methyl benzimidazole, 1-methyl-2 - Benzyl benzimidazole and the like. &quot; As a radical generator, a peroxide or an azo compound is preferred. The peroxide may, for example, be benzoyl peroxide, t-butylperoxy-ethylhexanoic acid, oxidized 12 ugly, or tertiary T-based hydrogen peroxide. Examples of the compound of 12 201226414 include azobisisobutyronitrile and 2,2'-azobis(2-methylbutyronitrile).

The two components of A and D B, the double bond of component A and the thiol group of component B are as follows:

The reaction is shown in the reaction formula shown in Fig. 6. Further, X is a hydrogen atom or a fluorenyl group, and V - Y represents a residue other than X which may be bonded to the double bond of the component A, and Z is a residue which cannot be bonded to a thiol group of the β component.

• • Product 1 I—ζ • * (Expression 6) S—Ζ·Product 2 Υ As shown in Formula 6, the two carbons forming the double bond of the a component can be bonded to the S of the thiol. The ratio of formation of the two kinds of products differs depending on the reaction conditions. For example, there is a tendency that when a test catalyst such as an amine is added to the reaction system, the product (1) is formed mostly; when freely added to the reaction system In the case of a base generating agent, most of the product (2) is produced. In most cases, the thioether-containing alkoxydecane derivative obtained after the preparation is a mixture of the products (丨) and (2). Further, in the preparation of the thioether-containing alkoxydecane derivative, since the B component has three thiol groups, a product obtained by reacting a partial thiol group of the component b with the component A can be obtained as shown in the formula 7. Further, v represents a residue (residue containing an isocyanurate ring) which can be bonded to a thiol group of the £ component. 13 201226414 IA-S, v-A 1 HS\V/SH 1 1 SH 1 SH Monofunctional difunctional group 1 + A -SH B component Λ component As, ν/-Α ... s-A trifunctional group 7 The number of additions of the A component in the above corresponds to the case of the formula 1, and the thioether-containing alkoxydecane derivative obtained after the preparation is a compound of a substance having a different number of substituents in the addition reaction. In the method for producing a sulfide-containing alkoxydecane derivative, it can be reacted at a temperature of 5 t or more, but in order to cause a reaction within a short period of 5 hours or less, it is preferably added at 60 to 8 Torr. A basic catalyst or a free radical generator. In the method for producing a sulfide-containing alkoxydecane derivative, the reaction can be carried out without a solvent, but it is also possible to carry out a reaction at a low temperature, and if a viscosity is lowered, a solvent is added to carry out the reaction. In this case, a solvent which does not react with an alkoxy group, a double bond or a thiol group, such as an alcohol, a ketone, an ester or an aromatic is preferable. The alcohol which does not react with an alkoxyalkyl group, a double bond or a thiol group is preferably a primary alcohol having 3 or less carbon atoms, and further preferably has a boiling point more than a reaction temperature (for example, a boiling point of 5 〇 to 19 0 0) Alcohols. The reason for this is that when the boiling point is lower than the above range, it is difficult to carry out the preparation in the case of industrialization; when the boiling point is higher than the above range, it is difficult to carry out the evaporation of the solvent in the case where the solvent needs to be removed. Therefore, the boiling point is preferably as high as possible. Further, as the alcohol of the 2012 20121414, methanol and ethanol are more preferable. The reason for this is that the alcohol as the reaction solvent may undergo a transesterification reaction with the alkoxyalkyl group-containing compound represented by the above formula 3, which may cause a decrease in the yield of the target product. Therefore, in the above formula 3, in the case of using a compound in which R4 is a mercapto group, it is preferred to use decyl alcohol as a reaction solvent; and in the case of using a compound in which R4 is an ethyl group, ethanol is preferably used as a reaction solvent. The ketone which does not react with an alkoxyalkyl group, a double bond, or a thiol group is preferably a ketone having a higher melting point than the reaction temperature, and further preferably has a carbon number of Θ or less from the viewpoint of solubility. Ketones. Examples of the _ class which satisfy the above conditions include methyl ethyl ketone, decyl isobutyl ketone and the like. The ester which does not react with an alkoxyalkyl group, a double bond, or a thiol group is preferably an ester having a boiling point higher than the reaction temperature, and further preferably has a linear carbon number of 6 or less from the viewpoint of solubility. Esters. The esters satisfying the above conditions are, for example, ethyl acetate, acetic acid, butyl acetate, methoxybutyl acetate, ethylene glycol ethyl acetate (cell 〇s〇lveacetate), amyl acetate, lactic acid. Methyl ester, ethyl lactate, butyl lactate, and the like. <Adhesion promoter> The thioether-containing alkoxydecane derivative of the present invention has excellent adhesion improving properties to an inorganic substrate such as glass or metal, and thus can be used as an adhesion promoter. An adhesion promoter containing a sulfide-containing alkoxydecane derivative as an active ingredient, which has been added to an epoxy resin, a polyacryl resin, an acrylic resin, a polyimide resin, and a compound having a double bond. In this case, a good adhesion improving effect can be exhibited. The thioether-containing alkoxy group and the compound represented by the formula 1, a is not 15 201226414 The basestone derivative has a thiol group which can be bonded to an epoxy group, a double bond or a mer. Sit-in response. Therefore, by adding a gamma-containing oxyxanthene derivative having a formula of not more than 0 to an epoxy resin, an acrylic resin, or a compound having a double bond, 16 can further exhibit good adhesion improvement. effect. Further, the compound represented by Formula 1 wherein b is not a sulfonated thioether-containing oxime derivative has an epoxidized ring, which may be bonded to an epoxy group, a thiol group, a thiol group, an acid needle, or an amino group. Amido group reaction. Therefore, by adding a thioether-containing alkoxydecane derivative which is not a hydrazine to a resin composition having a functional group reactive with an oxirane ring, "the adhesion improvement effect can be further exerted. The sulfur-containing (four) oxy-xanthene derivative is used as an active ingredient (4) to promote the right-handed agent as the active ingredient, preferably in an amount of 0. The mass is preferably 0.H5 mass%. The present invention will be further described below by way of Synthesis Examples, Examples and Comparative Examples. The measurement methods and evaluation methods used in the respective Examples and Comparative Examples are as follows. <Infrared Absorption Spectrum Analysis (IR)> Model. Manufactured by JASCO Corporation, FT/IR-600 Sample Cell: Expanded and decomposed on KBr; 4cnfl, Times: 16 times <NMR Spectroscopy (Nmr) 〉 16 201226414 Manufactured by, Ltd., Solvent: Deuterated model: Bruker Japan 4_HZ-AdVance 400, condition: cumulative number of times produced by gas viscosity <viscosity> (R type viscometer), temperature Model: Toki Sangyo (strain

25〇C <Adhesion evaluation> The sample formed with the cured film was adhered to the mechanical properties of the coating film specified in JIS K5_|6 after being treated at a temperature of 121 ° C and relative humidity (for example, at a temperature of 1% by weight for 30 hours). The evaluation was carried out by the test method of the cross-cutting method. In this test, the sample with and without peeling was "〇," and, for conditions of temperature 121 ° C and relative humidity (RH) 1〇〇% The sample after the next treatment for 4 hours was subjected to the same test, and the sample which was not peeled at all was "?". The sample which was observed to be peeled off was "X". The reagents used in the examples and the comparative examples are shown below. A compound of a oxyalkylene group: a component: - mercaptopropionyl oxaoxypropyltrimethoxy zeoxime. Its structure is as shown in the following formula 12. /y0v\/si+OCH3)3~e12) 0 A- 2: 3-acryloyloxypropyltrimethoxydecane having a structure as shown in the following formula 13. 17 201226414

(Formula 1 3) A-3: 3-methacryloxypropyltriethoxydecane. The structure is as shown in the following Equation 14.

0 <Multivalent thiol compound: Component B> B-1: Tris[(3-mercaptopropionyl)-ethyl]isocyanurate. The structure is as shown in the following formula 15 (viscosity 5. 4Pa.s)

β - I '· 3 - thioglycolic acid methyl vinegar. The structure is as shown in the following formula: <Ethylene oxide ring-containing compound: c component> C-1: methacrylic acid glycidol vinegar. Its structure is not described in Equation 17. 7 201226414 shows 0

<Amine: Catalyst> Azabicycloundecene (DBU). (Examples 1-1 to 1-4, Comparative Example A thermometer and a reflux tube were placed in a split four-necked flask, and the inside was filled with nitrogen gas. Into the four-necked bottle, the A component, the B component, and the C were added according to the following Table 1. 'According to the conditions of Table 1, the reaction was carried out for 8 hours at 9 ° C. The viscosity after the reaction is shown in Table 1. Table 1 Example Comparative Example 1-1 1-2 1-3 1-4 1 Α component (g Al 586 235 445 A-2 308 A-3 525 B component (g) Bl 414 692 475 497 β-\ 120 c component (g) Cl 268 Catalyst Cg) DBU 10 Functional group ratio U/B/C:) 3/ 1/0 2/1/0 1/1/0 1/1/2 Viscosity (Pa.s) 6.0 8.3 &gt; 1000 &gt; 1000 - The IR results of the respective examples are shown below. &lt;IR result〉 (Example 1-1) 3629 cnT1 : 92%T, 2945cm -1 : 51%T, 2841 cm -1 : 590/〇T, 19 201226414

1736 cm'1 : 21%T Ί 697 cm'1 : 18%T '1462cm'1 : 26%T '1371cm'1 : 70%T, 1192cm.1 : 32%T, 1 086 cm.1 : 21%T 820cm-1 : 45%T, 764cm'1 : 52%T (Example 1-2) 3627cm&quot; : 91%T ' 2947cm'1 : 65%Τ ' 2841cm'1 : 76%Τ ' 2571 CHT1 : 97 %Τ ' 2360cm·1 : 98% Τ, 1 736cm-1 : 14% Τ, 1 693cm-1 : 90/〇Τ, 1462CHT1 : 15% Τ, 1 352CHT1 : 57% Τ, 1 284cm.1 : 62% Τ, 1244cm'1 : 42°/〇Τ ' 1159cm'1 : 3 2% Τ &gt; 1 084cm'1 : 33°/〇Τ ' 82 2cm_1 : 59%Τ ' 764cm'1 : 46°/〇Τ ( Example 1-3) 2925 cm'1 : 63% Τ, 1 734 cm.1 : 74% Τ, 1 697 cm.1 : 73% Τ, 1462 cm'1 : 6 9% Τ&gt; 1 3 73 cm'1 : 84°/ 〇Τ' 1080cm'1 : 76%Τ' 958cm'1 : 83%Τ &gt; 764cm'1 : 80%Τ (Example 1-4) 3527cm'1 : 77%Τ ' 2949cm'1 : 49%Τ ' 2841cm'1 : 66%Τ ' 2571cm'1 : 92%Τ&gt; 23 60cm'1 : 93%Τ' 1734cm&quot; : 16%Τ' 1 6 95cm'1 : 13%Τ ' 1462cm'1 : 17%Τ ' 1371cm'1 : 44%Τ ' 1352cm'1 : 46%Τ ' 1161cm'1 : 23%Τ &gt; 1084cm·1 : 25%Τ ' 820cm·1 : 49%Τ ' 764cm'1 : 34%Τ ' 671 cm'1 : 89°/〇Τ <Ν Μ R results> The NMR spectrum of Example 1-1 is shown in Fig. 1. The NMR spectrum of Example 2 is shown in Fig. 2, and the NMR spectrum of Example 3 is as follows. As shown in Fig. 3, the NMR spectrum of Example 1-4 is shown in Fig. 4. The peak assignment in the NMR spectrum of Fig. 1 is as shown in the following formula 18. 20 201226414

• (Expression 18) afa: 3. 5~3. 6ppm, b: 0. 6~0· 7ppm, c: 1·7~1. 8, d: 4.3~4.4ppm, e: 2.5~2.7ppm , f:ll~1.3ppm, g: 2.6~2.8ppm, h: 2. 6~2_ 8ppm, i: 2.6~2.7ppm, j: 4.2~4.4ppm, k: 3.4~3·5ppm NMR spectrum of Fig. 2 The peak in the group is as shown in the following formula 19.

• (Equation 1 9) a: 3.5 to 3.6 ppm, b: 0.6 to 0.7 ppm, c: 1.7 to 1.8, d: 4·3 to 4_4 ppm, e: 2. 5 to 2·7 ppm, g: 2.6~ 2.8 ppm, h: 2.6~2·8ρριη, i: 2.6 to 2.7 ppm, j: 4.1 to 4.2 ppm, k: 3·5 to 3.6 ppm, 1 : 3.4 to 3·5 ppm, m: 4.0 to 4.2 ppm, n 6~2. 6 ppm ' o : 2. 7 to 2. 9 ppm ' p · 1.6 to 1.7 ppm The peak assignment in the NMR spectrum of Fig. 3 is as shown in the following formula 20. 21 201226414 〇&gt;ρ〇^Ρ a°5a. f 1 k ° • · · (Formula 2 0) a : 1. 2~1. 3ppm, a' : 3· 7~3. 9ppm, b : 0. 6~0· 7ppm, c: 1. 7~1. 8, d: 4· 3~4· 4ppm, e: 2. 5~2· 7ppm, f: 1. 1~1. 3ppm, g: 2. 6~2.8ppm, h: 2. 6~2.8ppm, i: 2. 6~2.7ppm, j: 4.1~4.2ppm, k: 3.7~3.8ppm, 1: 3.7~3.8ppm, m: 4. 0~ 4. 2 ppm, n: 2. 5 to 2·6 ppm, o: 2. 7 to 2. 9 ppm, p: 1. 7 to 1.8 ppm The peak in the NMR spectrum of Fig. 4 is represented by the following formula 21.

• · (Expression 2 1 ) aa: 1.2~1.3ppm, b: 0.6~0.7ppm, c: 1.7~1.8, d: 4.3~4.4ppm, e · 2·5~2.7ppm, f : 1·0~ 1.2ppm, g: 2.6~2.8ppm, h: 2. 6~2.8ppm, i: 2. 5~2_ 7ppm, j: 4. Bu 4. 2ppm, k: 3· 7~3. 8ppm, 1: 3.7 ~3.8ppm, m: 4·0~4. 2ppm, η: 2.5~2.6ppm, o: 2.7~2.9ppm, p: 2.6~2.8ppm, q: 2. 6~2.8ppm, r: 1. 1~ 1.3ppm, s: 4.0~4·2ppm, t: 2. 8~2. 9ppm, u: 2.5~2.7ppm From Figure 4 and the above attribution, Example 2 and Example 1-3 can be confirmed 22 201226414 Bees from thiol, but in Examples 实施 and Example 4, no peaks derived from thiol groups were observed. Further, since no peak derived from CH2 = CH was observed, @ , μ · · 5Γ Λ · A 1 Λ „ 哗 Therefore, it was found that A-1, η, and Α-3 reacted. (Examples 2-1 to 2) -4, Comparative Examples 2-1 to 2-2) As the epoxy resin, 95% by mass of side 638 (phenol phenolic disk type epoxy resin: manufactured by Tohto Kasei Co., Ltd., trade name) and 5% by mass were selected. EH-4344S (flavored catalyst: a mixture (E-1) produced by Edico Co., Ltd.. For the above-mentioned Example H+4 of the addition amount of the adhesion promoter according to the amount of Table 2, Example i and the separate β 1 The prepared sample was applied to a glass 'Sakamoto Electric Co., Ltd.' by the bar coater, and it was solidified under the hunger hour: The cured film of the molded product was evaluated for the adhesion of the cured film, and the results are shown in Table 2. Further, the resin in the crucible 2 was g.

23 201226414 From the results shown in Table 2, it was found that Example 2 - 2 - 4 did not show peeling at all, and the adhesion was good. On the other hand, in Comparative Example 2-b-2-2, a compound other than the thioether-containing alkoxydecane derivative of the present invention was used, and thus peeling occurred and the adhesion was not good. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a nuclear magnetic resonance spectrum of Example 1-1. Figure 2 is a nuclear magnetic resonance spectrum of Example 1-2. Figure 3 is a nuclear magnetic resonance spectrum of Example 1-3. Fig. 4 is a nuclear magnetic resonance spectrum of Example 4. [Main component symbol description] None 24

Claims (1)

201226414 VII. Patent application scope: 1 · A thioether-containing alkoxydecane derivative, represented by the following formula: In the formula, a and b are integers of 〇~2, c is an integer of 1 to 3, a + b + c = 3; R1 is a ternary group represented by the following formula 2, and R2 is -CH2-CHR5- Or a binary group represented by ~CR5(CH3)-, R3 is a binary group represented by -CH2-CHR6- or -CR6(CH3), and R5 and R6 are each independently a hydrogen atom or a fluorenyl group. R4 is methyl or ethyl; Where m is 1 or 2. 2. The thioether-containing alkoxydecane derivative according to claim 1, wherein the alkoxyalkylalkyl group-containing compound represented by the following formula 3 and the polysulfide compound represented by the following formula 4 Alcohol compound reaction prepared: 25 201226414 Where m is 1 or 2. 3. The thioether-containing alkoxydecane derivative according to claim 2, which is also obtained by reacting with an oxirane ring-containing compound represented by the following formula 5: 4. The adhesion promoter according to any one of the invention, wherein the thioether-containing alkane is an active ingredient as in the oxydecane derivative of the first to third aspects of the patent application. 26