JP2688507B2 - Adhesion imparting agent and curable resin composition containing the adhesion imparting agent - Google Patents

Description

TECHNICAL FIELD OF THE INVENTION The present invention relates to a tackifier containing an organosilicon compound having a plurality of organic functional groups as an active ingredient, and a curable resin composition containing the organosilicon compound.

[Technical background of the invention and its problems]

Various kinds of silanes are known as organosilicon compounds having an organic functional group, and are used as powder surface treatment agents, adhesion imparting agents, and the like.

For example, curable resin compositions such as silicone-based, polyepoxy-based, phenol-based, polyester-based, epoxy-based, and polysulfide-based resins are widely used as sealing materials and encapsulating materials for devices. In some cases, adhesion to the substrate surface such as glass is insufficient, and in such a case, it becomes necessary to subject the substrate surface to a primer treatment. In some cases, it becomes necessary to impart adhesiveness to these curable compositions themselves. As a primer or an additive in such a case, γ-as a silane having an organic functional group for the purpose of imparting and improving adhesiveness
Aminopropyltrialkoxysilane, γ-glycidoxypropyltrialkoxysilane, etc. are used,
These silanes have a problem that they are inferior in moisture resistance and are susceptible to peeling due to the presence of water.

Taking an epoxy resin as an example, it is cured by an epoxy curing agent such as acid anhydride, amine, phenol, isocyanate and polyaminobismaleimide, and has excellent mechanical and electrical properties, and has relatively high thermal or chemical stability. It is used in various fields such as casting, impregnation, lamination and transfer molding, painting and adhesion in order to give high epoxy resin cured products.

However, the above-mentioned epoxy resin cured product does not have sufficient adhesiveness to inorganic substances such as inorganic fillers and metals, and the epoxy resin cured product deteriorates especially in an environment with high humidity, and the epoxy resin cured product and the inorganic substance In addition, there is a defect that moisture penetrates from the interface of the metal or the like to cause peeling of the cured epoxy resin product or accompanying corrosion of the metal.

[Object of the invention]

An object of the present invention is to provide an organosilicon compound as a tackifier useful as a primer or an additive, and to provide a curable resin composition having excellent adhesiveness.

[Configuration of the invention]

The present inventors have conducted extensive studies to obtain such an adhesion-imparting agent and a curable resin composition, and as a result, an organosilicon compound containing a plurality of organic functional groups was used as an active ingredient of the adhesion-imparting agent, or cured. By blending with a resin
The inventors have found that a composition having excellent adhesiveness can be obtained, and completed the present invention.

The present invention has the following general formula (I) (However, X is H ₂ NCH ₂ CH ₂ −, H ₂ NCH ₂ CH ₂ CH ₂ −, One functional group selected from, Y ¹ is CH ₂ = CHCH ₂ - or the formula ^{_{-CH 2 CH 2 CH 2 SiR 1}} n Z 1 3-n the same group, R ¹ is a substituted or unsubstituted 1 A valent hydrocarbon group, Z ¹ represents an alkoxy group having 1 to 6 carbon atoms, and n represents an integer of 0 to 2. ) Or general formula (II) (However, Y ² is Or the same group as -CH ₂ CH ₂ CH ₂ SiR ² _m Z ² _{3-m in the} above formula,
Alternatively, a substituted or unsubstituted monovalent hydrocarbon group, R ² is a substituted or unsubstituted monovalent hydrocarbon group, Z ² is an alkoxy group having 1 to 6 carbon atoms, and m is an integer of 0 to 2. . And an adhesion promoter containing an organosilicon compound represented by the formula (1) as an active ingredient, and a curable resin comprising the organosilicon compound represented by the general formula (I) or (II). It is a composition.

The organosilicon compound having a plurality of organic functional groups, which is an active ingredient of the adhesion-imparting agent of the present invention, is represented by the above general formula (I) or (II), and is N, N-bis {3- ( Methyldimethoxysilyl) propyl} ethylenediamine, N, N-bis {3- (trimethoxysilyl)
Propyl} propylenediamine, N-allyl-N- {3
-(Trimethoxysilyl) propyl} ethylenediamine, N-allyl-N- {3- (methyldimethoxysilyl) propyl} propylenediamine, N, N-bis {3-
(Methyldiethoxysilyl) propyl} methacrylamide, N, N-bis {3- (dimethylethoxysilyl) propyl} acrylamide, N, N-bis {3- (trimethoxysilyl) propyl} methacrylamide, N-allyl-
N- (3-methyldiethoxysilyl) propylmethacrylamide, N-allyl-N- (3-trimethoxysilyl) propylacrylamide, N-glycidyl-N, N-
Bis {3- (methyldimethoxysilyl) propyl} amine, N-glycidyl-N, N-bis {3- (trimethoxysilyl) propyl} amine, N-glycidyl-N-allyl-N- {3- (dimethylethoxy) Silyl) propyl}
Amine, N-glycidyl-N-allyl-N- {3- (trimethoxysilyl) propyl} amine, N, N-diglycidyl-N- {3- (trimethoxysilyl) propyl} amine, N-glycidyl-N- Ethyl-N- {3- (trimethoxysilyl) propyl} amine, N-glycidyl-
Examples thereof include N-phenyl-N- {3- (trimethoxysilyl) propyl} ami. Further, two or more kinds of these compounds may be mixed and used.

These compounds are disclosed, for example, in Japanese Patent Application Nos. Sho 63-170475 and 63.
-170476, 63-170477, 63-170478 or Dok
l.Akad.Navk.Azerd., 20 [6], 25 (1964).

When the organosilicon compound having a plurality of organic functional groups is used as an adhesion-imparting agent, it may be used as a treating agent such as a primer or may be mixed with a curable resin.
In the former case, various substrate surfaces (metal, glass, stone, enamel, wood, paper, plastics) in contact with the curable composition may be used as they are or adjusted to a concentration of about 40% by weight or less with an organic solvent. Etc.) in advance. The type of this solvent is not particularly limited,
This includes water or toluene, xylene, cyclohexane,
Hydrocarbon solvents such as n-hexane, n-heptane, naphtha, mineral spirits, petroleum benzine; halogenated hydrocarbon solvents such as chloroform, carbon tetrachloride, trichlorethylene, perchloroethylene, 1,1,1-trichloroethane Solvents; ether solvents such as ethyl ether, tetrahydrofuran, ethylene glycol diethyl ether; ester solvents such as ethyl acetate, butyl acetate, amyl acetate; acetone, methyl ethyl ketone,
Ketone solvents such as methyl isobutyl ketone; methanol, ethanol, isopropanol, butanol, 2
-Methoxyethanol, 2-ethoxyethanol, 2-
Alcoholic solvents such as butoxyethanol, ethylene glycol, propylene glycol; aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide; hexamethyldisiloxane, 1,1,3,3,5,5,7, Examples thereof include one or a mixture of two or more organopolysiloxane solvents such as 7,9,9-decamethylcyclopentasiloxane.

On the other hand, when it is added to the curable resin composition as an adhesion-imparting agent, it is desirable that it is not dissolved in a component such as a solvent, unlike the case of a primer or the like. As the resin in this case,
Epoxy resin, silicone resin, urethane resin,
Polysulfide resin, phenol resin, polyester resin and the like are listed. The blending amount is not particularly limited, but is in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the resin.

For example, the epoxy resin has at least two epoxy groups in one molecule, and specific examples of such an epoxy resin include bisphenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, Examples thereof include cycloaliphatic epoxy resins, heterocyclic epoxy resins and halogenated epoxy resins. The epoxy resins may be used alone or in combination of two or more.

The organosilicon compound used in the present invention has a compound itself, an amino group and an amide group, and thus acts as a curing agent for an epoxy resin by itself, but phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride. It can be used as a mixture with acid anhydrides such as acid, benzophenonetetracarboxylic acid anhydride, dodecanedioic acid anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride and methylnadic acid anhydride. Also, diethylenetriamine,
Epoxy resin curing agents such as amines such as triethylenetetramine, metaphenylenediamine and diaminodiphenylmethane can also be used.

In this case, known curing accelerators can be used, and examples thereof include tertiary amines, triazoles and imidazoles. Specific examples thereof include benzyldimethylamine, triethanolamine, dimethylaminomethylphenol, tris (dimethylaminomethyl) phenol, triethyltetramine, 3,9-bis (3-aminopropyl) -2,4,8,10. -Teroxaspiro [5.5] undecane and other tertiary amines; 1,2,3-benzotriazole, 5-methyltriazole and other triazoles; 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-methyl Imidazole, 2-ethylimidazole, 2,4-dimethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole,
1-vinyl-2-methylimidazole, 2-phenyl-
4,5-dihydroxymethylimidazole, 2-phenyl-4-methylimidazole, 2-isopropylimidazole, 1-cyanomethyl-2-methylimidazole, 2
-[Β- (2'-methylimidazole- (1) ')]-
Ethyl-4,6-diamino-s-polyazine-isocyanurate, 1-aminoethyl-2-methylimidazole,
Imidazoles such as 4,4'-methylene-bis (2-ethyl-5-methylimidazole) and 2-phenyl-4-benzyl-5-hydroxymethylimidazole; reaction formation of 2-methylimidazole and phenol novolac resin And a reaction product of a bisphenol A type epoxy resin with tris (dimethylaminomethyl) phenol. An inorganic filler may be added to the epoxy resin composition.

As the inorganic filler, spherical silica, glass fiber, glass powder, crystalline silica, zirconium oxide, alpha quartz, fused silica, clay, alumina, aluminum hydroxide, calcium carbonate, glass powder, asbestos, gypsum, magnesite, mica , Kaolin, talc, graphite, cement, ferrite, molybdenum disulfide, zinc white, titanium white, carbon black, silver powder, nickel powder, copper powder and the like. Also, two or more of these may be blended.

Further, various additives such as pigments, dyes, flow control agents, leveling agents, defoaming agents and solvents can be added.

As the silicone resin, for example, a polyorganosiloxane containing a hydrolyzable group such as a silanol group and an organosilicon compound containing an average of more than two hydrolyzable groups bonded to a silicon atom in one molecule are used. Of a polyorganosiloxane containing an alkenyl group and an organosilicon compound containing an average of more than 2 hydrogen atoms bonded to a silicon atom in one molecule in the presence of the above moisture, Examples thereof include a curing method in the presence of a peroxide, a curing method of a polyorganosiloxane containing an alkenyl group in the presence of an organic peroxide, a curing method by UV, and a curing method by EB. Applied to curable silicone compositions.

Incidentally, the composition comprising the adhesion promoter and the curable polyorganosiloxane of the present invention may optionally contain other components which may be contained in the composition of the prior art of this kind, as long as the object of the present invention is not impaired. It can be blended. For example, such ingredients include reinforcing fillers such as fumed silica, precipitated silica, silica airgel; diatomaceous earth, ground quartz,
Titanium oxide, aluminum oxide, iron oxide, zinc oxide, calcium carbonate, magnesium carbonate, magnesium silicate,
Non-reinforcing fillers such as glass powder, surface hydrophobized products thereof, stabilizers for preventing or delaying deterioration of the polyorganosiloxane cured product upon receiving heat or ultraviolet rays, catalyst inhibition for delaying the curing reaction Examples are agents, pigments, flame retardants, and thermally and / or electrically conductive substances.

〔The invention's effect〕

The adhesion-imparting agent of the present invention is extremely excellent in the effect of improving water-resistant adhesion to various substrate surfaces of curable resin compositions such as silicone-based, polyurethane-based, phenol-based, polyester-based, epoxy-based, and polysulfide-based, It is useful in applications where a high degree of water resistant adhesion is required.

Further, the curable resin composition containing the adhesion-imparting agent of the present invention has excellent adhesiveness, particularly an epoxy resin composition,
Silicone resin compositions and the like are extremely useful for applications where the adhesive function requires water resistance.

〔Example〕

The present invention will be described in more detail by way of examples. However, the examples do not limit the present invention in any way. All "parts" shown below are "parts by weight". Further, in the chemical formula, Me represents a methyl group.

Example 1 A polyurethane-based sealant (Hamatite UH-30; Yokohama Rubber Co., Ltd.) was used with the adhesion promoter shown in Table 1 (concentration: 100%).
1% by weight), cured on a glass plate and an aluminum plate, left for 7 days, then left for 7 days at 60 ° C
After leaving it for 7 days in warm water, peel it off with a finger and evaluate the degree of adhesion on a scale of 5 (1: 100% adhesion, 2; 70% or more of the adhered surface, 3; 50% or more of the surface is bonded, 4; 20% or more of the adhered surface is bonded, 5;
%Less than). The results are summarized in Table 1.

Comparative Example 1 In the same manner as in Example 1, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane and silane compound were not added. Four types of tests were conducted. The results are summarized in Table 1.

Example 2, Comparative Example 2 In Example 1 and Comparative Example 1, the polyurethane-based sealant was replaced with a polysulfide-based sealant (Hamatite SC-50).
Instead of 0, manufactured by Yokohama Rubber Co., Ltd., other tests were conducted in the same manner. The results are summarized in Table 2.

Example 3, Comparative Example 3 (1) Preparation of primer: A 10 wt% solution of the organosilicon compound shown in Table 3 in toluene: isopropanol = 1: 1 (v / v) was prepared.

(2) Adhesion test: The primer shown in Table 3 was applied on a glass plate and an aluminum plate, and then a polyurethane sealant (Hamatite UH-30) was applied on the primer.

Next, the same test as in Example 1 was performed. The results are summarized in Table 3.

Example 4, Comparative Example 4 In the same manner as in Example 3 and Comparative Example 3, a silicone sealant (Tosseal 381, manufactured by Toshiba Silicone Co., Ltd.) was applied and tested. The results are summarized in Table 4.

Example 5 After coating the above-mentioned primer Nos. 1 to 8 on each metal surface of a phenol resin plate, an epoxy resin laminated plate, an ABS resin plate, a polycarbonate plate, a polyphenylene oxide plate, a nickel plate, a stainless plate, a mild steel plate, a steel plate , And a polysulfide sealant (Hamatite SC500) was applied and cured. Next, when these test bodies were peeled off with a finger, the adhesive surface was not peeled off and the cured sealant itself was broken.

Example 6 Epoxy resin (Epicoat # 1001, Yuka Shell Co., Ltd.)
Made, epoxy equivalent 450) 100 parts methyl anhydric acid 38
Part, tris-2,4,6-dimethylaminomethylphenol
0.5 parts and 50 parts of n-butanol / butyl cellosolve = 1/1 mixed solvent were added and mixed with stirring.

N, N-bis {3-
(Trimethoxysilyl) propyl} ethylenediamine 0.
5 parts were added and further mixed with stirring to prepare an epoxy resin composition. The resulting epoxy resin composition was applied on a degreased stainless steel plate and cured by heating at 160 ° C for 60 minutes to give a film thickness of 3
A 0 μm transparent coating film was obtained.

The stainless steel plate on which the epoxy resin cured coating film was formed was boiled in boiling water for 8 hours.

Before and after boiling, a scotch tape peeling test was performed, and the state after boiling was visually observed.

As shown in Table 5, the coating film was almost unchanged from that before boiling.
The water resistance and adhesion were excellent.

Examples 7 to 13 0.5 g of the compound shown in Table 5 as the organosilicon compound
Using the same method as in Example 6, an epoxy resin composition was obtained. A boiling test was conducted using this, and the results are summarized in Table 5.

Comparative Example 5 An epoxy resin was obtained and a boiling test was performed in the same manner as in Example 6 without using any organosilicon compound. The results are summarized in Table 5.

Comparative Examples 6 and 7 An epoxy resin was obtained and a boiling test was performed in the same manner as in Example 6 except that γ-aminopropyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane were used as the organosilicon compound. The results are summarized in Table 5.

Example 14, Comparative Example 8 100 parts of polydimethylsiloxane having a viscosity of 3,200 cSt at both ends blocked with dimethylvinylsilyl groups at both ends, 100 parts of polydimethylsiloxane having a viscosity of 15 cSt at 25 ° C. blocked at both ends with trimethylsilyl groups, and chloride Platinic acid in isopropyl alcohol, platinum as 20ppm (Compound with primary amino group is difficult to cure, so
0 ppm) was uniformly mixed and dispersed to prepare a base composition. To 100 parts of this base composition, 2 parts of the adhesion promoter used in Example 1 and Comparative Example 1 was added and uniformly mixed to obtain compositions A1 to A11 of the present invention. These compositions were applied to an aluminum plate and heated at 70 ° C. for 8 hours to cure. The adhesion and water resistance after curing were tested as in Example 1.

 The results are summarized in Table 6.

Example 15, Comparative Example 9 100 parts of silanol-terminated polydimethylsiloxane having a viscosity of 100,000 cSt at 25 ° C., 13 parts of fumed silica having polysiloxane consisting of dimethylsiloxane units on the surface by surface treatment, dibutyltin dioctoate 0.2
Parts and methyltris (methylethylketoxime) silane 5.
0 part was added and stirred uniformly to prepare a base composition. To 100 parts of this base composition, 2 parts of the adhesion promoter used in Example 1 and Comparative Example 1 was added and uniformly mixed to obtain compositions B1 to B11 of the present invention. These compositions were applied to an aluminum plate and cured at 25 ° C for 7 days. The adhesion and water resistance after curing were tested as in Example 1.

 The results are summarized in Table 6.

Example 16, Comparative Example 10 Methyl vinyl vinyl group polysiloxane 100 containing about 0.1 mol of a methyl vinyl group siloxane unit having an average degree of polymerization of about 6,000.
Part and end blocked with silanol groups have a viscosity at 25 ° C of 2
2 parts of 0.0cSt polydimethylsiloxane, 10 parts of fumed silica with polysiloxane consisting of dimethylsiloxane units on the surface by surface treatment, 2,5-dimethyl-2,5-
0.5 part of di-tert-butyl peroxyhexane was kneaded with a roll. For 100 parts of this kneaded material, Example 1,
2 parts of the adhesion promoter used in Comparative Example 1 was added and uniformly mixed to obtain compositions C1 to C11. These compositions were applied to an aluminum plate and heated at 170 ° C. for 10 minutes to cure. The adhesion and water resistance after curing were tested as in Example 1.

 The results are summarized in Table 6.

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Claims (4)

(57) [Claims] 1. The compound of the general formula (I) (However, X is H ₂ NCH ₂ CH ₂ −, H ₂ NCH ₂ CH ₂ CH ₂ −, One functional group selected from, Y ¹ is CH ₂ = CHCH ₂ - or the formula ^{_{-CH 2 CH 2 CH 2 SiR 1}} n Z 1 3-n the same group, R ¹ is a substituted or unsubstituted 1 A valent hydrocarbon group, Z ¹ represents an alkoxy group having 1 to 6 carbon atoms, and n represents an integer of 0 to 2. ) Or general formula (II) (However, Y ² is Or the same group as -CH ₂ CH ₂ CH ₂ SiR ¹ _m Z ² _{3-m in the} above formula,
Alternatively, a substituted or unsubstituted monovalent hydrocarbon group, R ² is a substituted or unsubstituted monovalent hydrocarbon group, Z ² is an alkoxy group having 1 to 6 carbon atoms, and m is an integer of 0 to 2. . ) An adhesion-imparting agent comprising an organosilicon compound represented by the formula (4) as an active ingredient. 2. The general formula (I) or (I according to claim 1.
A curable resin composition comprising an organosilicon compound represented by I). 3. The curable resin is an epoxy resin.
A composition as described. 4. The composition according to claim 2, wherein the curable resin is a silicone resin.