JPH1192481A - New organic silicon compound, its production and surface-treating agent produced by using the compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the subject new compound composed of a specific organic silicon compound having epoxy group, effective for improving the adhesivity to inorganic substances such as metal and glass and useful e.g. as a surface- treating agent for glass fiber, a coupling agent for various primers, etc. SOLUTION: This new organic silicon compound is expressed by the formula I [R<1> is the structure of the formula II ((l) is 2-10) or the formula III (R<4> is H or methyl); R<2> and R<3> are each a 1-5C alkyl or an alkoxyalkyl; (m) is 1-10; (n) is 1-3]. It can be used e.g. as a surface-treating agent for improving the adhesivity of a resin to inorganic substances such as metal and glass and an epoxy-based silane coupling agent useful e.g. as a resin additive for improving the mechanical strength of epoxy resin, etc. The compound can be produced by reacting an epoxy compound having double bond and expressed by the formula IV with a mercaptosilane expressed by the formula V at 40-150 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface treatment agent for improving the adhesion between a metal such as copper, steel and aluminum or an inorganic substance such as glass fiber, silica, aluminum oxide and aluminum hydroxide and a resin. And a novel organosilicon compound used as a resin additive or the like for improving the mechanical strength of a resin such as an epoxy resin.

[0002]

2. Description of the Related Art Coupling agents include glass fiber surface treatment agents for fiber reinforced plastic (FRP), primers for bonding and painting, surface treatment agents for various fillers, primers for promoting adhesion between silicon wafer and photoresist, copper foil. Are widely used in various fields such as metal surface treatment agents and additives such as various resins. Among them, epoxy-based silane coupling agents are particularly effective for epoxy resins, phenolic resins, melamine resins, etc., and are used as additives for resins, and surface treatment agents for fillers, glass fibers, metals, etc., which are combined with resins. It is used in various fields. However, recently, in the fields of FRP, resist, printed wiring board, etc., there is a strong demand for their environmental resistance, and it is desired to further improve the adhesiveness between the inorganic substance such as filler, glass fiber, metal and the resin interface. ing.

[0003]

SUMMARY OF THE INVENTION The present invention can meet such a demand, that is, to improve the adhesiveness between a resin such as a metal such as copper, steel and aluminum, or an inorganic substance such as glass fiber, silica and alumina. It is an object of the present invention to provide a novel epoxy-based silane coupling agent, a method for producing the same, and a surface treating agent using the same.

[0004]

Means for Solving the Problems As a result of diligent research, the present inventor has found that the novel organosilicon compound represented by the general formula (1) can be used as a surface treating agent for the above-mentioned metals and inorganic substances, especially copper foil. As a result, it has been found that the adhesiveness at the interface between the copper foil and the resin is improved, and the present invention has been achieved.

The present invention has been made based on such findings, and the gist of the present invention is to provide (1) a novel organosilicon compound represented by the following general formula (1):

[0006]

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(In the general formula (1), R ¹ has ^one of the following structures:

[0008]

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R ² and R ³ each represent an alkyl or alkoxyalkyl group having 1 to 5 carbon atoms, R ⁴ represents a hydrogen or methyl group, m is 1 to 10, n is 1 to 3, and 1 is 2 to 10)
(2) The epoxy compound having a double bond represented by the following general formula (2) and a mercaptosilane represented by the following general formula (3) are reacted at 40 to 150 ° C. (1). A method for producing an organosilicon compound according to the description,

[0010]

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(However, in the general formulas (2) and (3), R ² , R ³ , m and n are as defined above, and R ⁵ has one of the following structures:

[0012]

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R ³ is hydrogen or a methyl group. (3) A surface treating agent containing the compound of (1) as an active ingredient; (4) A surface treating agent of copper foil containing the compound of (1) as an active ingredient; It is in.

Hereinafter, the present invention will be described in more detail.

R ¹ in the general formula (1) is

[0016]

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Any structure having any of the above structures can sufficiently exhibit the effects of the present invention. R ² and R ^{3 each} have 1 to 5 carbon atoms.
In particular, a methyl group or an ethyl group is preferable from the viewpoint of easiness of synthesis and hydrolysis and condensation of silane. Also, n
Is 1 to 3. However, n is preferably 2 or 3, since the higher the reactivity with a metal, an inorganic substance or a resin improves the adhesive property. Further, if m is 1 to 10, l is 2 to 10, and R ⁴ is hydrogen or a methyl group, the effects of the present invention are sufficiently exhibited.

The novel organosilicon compound of the present invention (1)
Is synthesized by a reaction represented by the following reaction formula (4).
That is, it can be produced by heating a container containing an epoxy compound having a double bond and mercaptosilane at 40 to 150 ° C. to react. This reaction proceeds without a catalyst, but as a catalyst, oxygen, peroxide,
The reaction proceeds smoothly by using azoisobutyronitrile, ultraviolet irradiation or the like.

[0019]

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(In the general formula (4), each symbol is as defined above.) The epoxy compound having a double bond represented by the above reaction formula (4) has a double bond and an epoxy group in one molecule. Any of the compounds having the above formula can be reacted with mercaptosilane to synthesize the novel organosilicon compound of the present invention, but preferably, allyl glycidyl ether, glycidyl methacrylate and the like.

Preferred examples of the above mercaptosilane include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropyltriethoxysilane.
Mercaptopropylmethyldimethoxysilane, (mercaptomethyl) dimethylethoxysilane, (mercaptomethyl) diethylethoxysilane, mercaptomethyltrimethoxysilane and the like.

The reaction molar ratio between the epoxy compound having a double bond and the mercaptosilane is prepared by reacting 0.1 to 10 mol of mercaptosilane with respect to 1 mol of the epoxy compound having a double bond. be able to. The peroxide, azoisobutyronitrile, and the like used as a catalyst for the reaction are added in an amount of 0.001 to 1 mol based on 1 mol of the epoxy compound having a double bond. A reaction time of about several hours is sufficient. This reaction does not particularly require a solvent, but an organic solvent such as toluene, chloroform, dioxane, methanol, or ethanol may be used as a reaction solvent. Note that since this reaction dislikes water, it is preferable to perform the reaction under an atmosphere of a gas containing no water such as nitrogen or argon so that water is not mixed.

These novel organosilicon compounds are prepared by distillation,
It can be isolated by known means such as column chromatography, but when it is used as a surface treatment agent or an additive for a resin, these compounds do not necessarily need to be isolated and may be used as a reaction mixture.

When the novel organosilicon compound is used as a surface treating agent for a metal or inorganic substance, the metal or inorganic substance is not particularly limited. For example, in metal,
Copper, iron, aluminum, zinc or the like or alloys thereof, and inorganic materials include glass fiber, silica, alumina, magnesium oxide, barium carbonate, and talc. Surface treatment is
Although it may be applied as it is, it may be applied to a solvent such as water, methanol, ethanol, acetone, ethyl acetate, and toluene.
It is convenient and preferable to dilute the solution so as to have a concentration of 01 to 20% by weight or to spray the solution or to immerse a metal or inorganic substance in the solution.

The novel organosilicon compound may be used alone, or may be used in combination with another silane or titanate coupling agent or rust inhibitor.

When the novel organosilicon compound of the present invention is used as a resin additive, the resin is not particularly limited, and may be a thermoplastic resin or a thermosetting resin. Fully demonstrates the effect of The organosilicon compound of the present invention may be added to the resin as it is, or may be added after being dissolved in an alcohol-based, aromatic-based, aliphatic-based organic solvent, or the like. The effect of the present invention can be sufficiently exhibited by adding 0.001 to 50 to the resin 100. The novel organosilicon compound of the present invention may be used in combination with additives such as a curing agent, a silane coupling agent, and a plasticizer which are generally added to a resin.

[0027]

【Example】

 Synthesis example 1 of new organosilicon compound

[0028]

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22.8 g of allyl glycidyl ether
(0.2 mol), 39.3 g (0.2 mol) of 3-mercaptopropyltrimethoxysilane and AIBN 1.0
g, heated at 60 ° C. for 2 hours, and then distilled under reduced pressure to obtain a novel organosilicon compound 1 represented by the above formula (yield: 54.5 g (yield; 88%), boiling point: 130 to
134 ° C / 0.1 mmHg). The obtained compound was FT-
It was identified by IR and NMR. ¹ H-NM of the compound
The R, ¹³ C-NMR, ²⁹ Si-NMR, and FT-IR spectra are shown in FIGS.

Synthesis Example 2 of New Organosilicon Compound

[0031]

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28.4 g of glycidyl methacrylate (0.
2 mol), 39.3 g (0.2 mol) of 3-mercaptopropyltrimethoxysilane and 1.0 g of AIBN, heated at 60 ° C. for 2 hours, and then distilled under reduced pressure to obtain a novel organosilicon compound 2 represented by the above formula. (Yield;
9.5 g (yield; 14%), boiling point: 147 to 154 ° C /
0.1 mmHg). The obtained compound was FT-IR, NM
Identified by R. ¹ H-NMR, ¹³ C-N of this compound
The MR, ²⁹ Si-NMR and FT-IR spectra are shown in FIG.
FIG.

Preparation of Adhesion Evaluation Sample Electrolytic copper foil (manufactured by Nikko Gould foil, JTC foil, 25
The novel organosilicon compounds 1 and 2 were diluted to 0.4% with methanol and applied to a roughened surface (cm × 25 cm, thickness: 17 μm) by dipping. After application, 5 at 100 ° C
Dried for minutes.

Evaluation of Adhesion The adhesive evaluation sample was heated and pressed with a prepreg in which a glass substrate was impregnated with an epoxy resin to prepare a copper-clad laminate. The normal peel strength of this copper clad laminate was measured by the method specified in JIS C6481. After heat-treating this copper-clad laminate at 177 ° C. for 10 days, the heat resistance was evaluated by measuring the peel strength. In addition, 1m
A circuit having a width of m was formed, and after immersion in boiling water for 5 hours, the peel strength was measured to evaluate the boiling resistance. The results are shown in Table 1. For comparison, untreated copper foil was similarly evaluated.

[0035]

[Table 1]

As is clear from Table 1, it was confirmed that the heat resistance and the boiling resistance of the examples were improved as compared with the untreated ones.

[0037]

As described above, the novel organosilicon compound of the present invention can improve the adhesion between an inorganic substance such as metal or glass and a resin as a surface treating agent.

[Brief description of the drawings]

FIG. 1 is a ¹ H-NMR chart of the novel organosilicon compound of the present invention obtained in Synthesis Example 1.

FIG. 2 is a ¹³ C-NMR chart, same as above.

FIG. 3 is a ²⁹ Si-NMR chart of the above.

FIG. 4 is an FT-IR chart of the above.

FIG. 5 shows the results of the novel organosilicon of the present invention obtained in Synthesis Example 2.
¹ H-NMR chart.

FIG. 6 is a ¹³ C-NMR chart.

FIG. 7 is the same as the above, a ²⁹ Si-NMR chart.

FIG. 8 is an FT-IR chart.

Claims (4)

[Claims] 1. A novel organosilicon compound represented by the following general formula (1). Embedded image (However, in the general formula (1), R ¹ has any ^one of the following structures; R ² and R ³ each represent an alkyl or alkoxyalkyl group having 1 to 5 carbon atoms; R ⁴ represents a hydrogen or methyl group;
Is 1 to 10, n is 1 to 3, l is 2 to 10) 2. The method according to claim 1, wherein the epoxy compound having a double bond represented by the following general formula (2) is reacted with a mercaptosilane represented by the following general formula (3) at 40 to 150 ° C. 2. The method for producing an organosilicon compound according to 1. Embedded image (However, in the general formulas (2) and (3), R ² , R ³ ,
m and n are as defined above, and R ⁵ has one of the following structures: R ⁶ is hydrogen or methyl group) 3. A surface treating agent comprising the compound of claim 1 as an active ingredient. 4. A surface treating agent for copper foil comprising the compound of claim 1 as an active ingredient.