JPH09295988A - New organic silicon compound and its production and surface-treating agent and resin additive using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound useful as a surface-treating agent for improving the adhesivity of inorganic substances to resins, a curing accelerator for epoxy resins, a resin additive for improving the strengths of the resins, etc., by reacting a dialkylaminoalkanethiol with an epoxy silane. SOLUTION: A new organic silicon compound of formula I [R<1> -R<4> are each 1 a 1-5Calkyl; (1) is 1-5; (m) is 1-10; (n) is 1-3]. The compound of formula I is useful as a surface-treating agent for improving the adhesivity of metals such as copper, steel and aluminum or inorganic substances such as glass fibers, silica and aluminum oxide to resins, a curing accelerator for epoxy resins, a resin additive for improving the mechanical strength of the resin, etc. The compound of formula I is obtained by reacting a dialkylaminoalkanethiol of formula II (e.g. dinethylaminoethane thiol) with an epoxsilane of formula III (e.g. 3-glycidoixypropyltrimethyxysilane) at 60-200 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 resin such as a metal such as copper, steel and aluminum or glass fiber, an inorganic substance such as silica, aluminum oxide and aluminum hydroxide and a resin. , Or a resin additive for promoting curing of a resin such as an epoxy resin and improving mechanical strength, and an organosilicon compound useful for them.

[0002]

2. Description of the Related Art Boards for electrical equipment are copper foil and paper-phenolic resin-impregnated base material, glass-epoxy resin-impregnated base material, etc. are heated and pressed to form a copper-clad laminate, which is then etched to form a network. And a device such as a semiconductor device is mounted thereon.

In these processes, adhesion between the copper foil and the base material,
Since heating, immersion in an acid or alkaline solution, application of resist ink, soldering, etc. are performed, various performances are required. In order to meet these requirements, copper foil is treated with a brass layer forming treatment (Japanese Patent Publication No. 51-35711, 54-6).
No. 701), chromate treatment, zinc-chromium group mixture coating treatment of zinc or zinc oxide and chromium oxide (Japanese Patent Publication No. 58-7077), silane coupling agent treatment, and the like. Further, the resin satisfies the above-mentioned required characteristics by changing the types of the resin and the curing agent and the compounding amounts thereof, and by adding additives and the like. In addition, surface treatment of silane coupling agent or the like has been studied for glass fiber. However, recently, since the printed circuit has become more and more dense, the characteristics required for the board for the electronic equipment used have become more and more severe.

In order to cope with the improvement in etching accuracy accompanying this, a further lower surface roughness (low profile) is also required for the roughened surface (M surface) bonded to the prepreg of the copper foil. On the other hand, the surface roughness of the M surface, on the other hand, brings about an anchor effect in bonding with the prepreg. Therefore, there is a trade-off relationship between the requirement of the low profile and the improvement of the adhesive force for the M surface, and the low profile is required. The reduction of the anchor effect needs to be compensated by improving the adhesive force by another means.

In addition, as a casting material for electrical insulation used for encapsulation of high-voltage and high-capacity equipment such as power plants and semiconductors, a matrix of epoxy resin is filled with an inorganic substance such as silica or alumina. It is a composite material. These materials are required to have various electrical and mechanical properties, and in order to satisfy those properties, it is necessary to improve the adhesiveness between the inorganic substance and the resin. As measures against this, it has been proposed to add a silane coupling agent to the resin or to perform a surface treatment of an inorganic substance with the silane coupling agent, but further improvement of the resin / inorganic substance interface is required.

[0006]

DISCLOSURE OF THE INVENTION The present invention can meet such a requirement, that is, improve the adhesiveness between a resin such as metal such as copper, steel and aluminum or an inorganic substance such as glass fiber, silica, alumina and the like. It is an object of the present invention to provide a novel organosilicon compound, a method for producing the same, and a surface treating agent or a resin additive using the same.

[0007]

As a result of intensive studies, the present inventor has found that when a novel organic silicon compound represented by the general formula (1) is surface-treated with a metal or an inorganic substance, the adhesion with a resin is improved. It has been found that it can be improved, and that the curing reaction is promoted and the mechanical strength is improved even when it is added to a resin such as an epoxy resin.

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

[0009]

Embedded image

[However, in the general formula (1), R ¹ ,
R ² , R ³ and R ⁴ are each an alkyl group having 1 to 5 carbon atoms, 1 is 1 to 5, m is 1 to 10 and n is 1 to 3] (2) In the following general formula (2) The method for producing an organosilicon compound according to claim 1, wherein the represented dialkylaminoalkanethiol and the epoxysilane represented by the following general formula (3) are reacted at 60 to 200 ° C.

[0011]

Embedded image

[In the general formulas (2) and (3), R ¹ , R ² , R ³ and R ⁴ are each an alkyl group having 1 to 5 carbon atoms, 1 is 1 to 5 and m is 1 to 1] 10, n is 1 to 3] (3) A surface treatment agent containing the organosilicon compound according to (1) above as an active ingredient.

(4) A resin additive containing the organosilicon compound described in (1) above as an active ingredient.

The present invention will be described in more detail below.

If R ¹ and R ² in the above general formula (1) are alkyl groups having 1 to 5 carbon atoms, the effect of the present invention is sufficiently exhibited, but amine is effective as a curing agent or curing accelerator for resins. In order to work effectively, it is preferable that the number of carbon atoms is small, and a methyl group is preferable. R ³ and R ⁴ have 1 to 5 carbon atoms
In particular, a methyl group or an ethyl group is preferable from the viewpoints of easiness of synthesis and hydrolysis and condensation of silane. Further, n is 1 to 3, but n or 2 or 3 is preferable because the higher the reactivity with the metal, the inorganic substance or the resin and the higher the crosslinkability, the better the adhesive property. Also, l
Is 1 to 5, m is 1 to 10, and preferably 1 to 5.

The above novel organosilicon compound of the present invention (1)
Is synthesized by the reaction represented by the following reaction formula (4).
That is, it can be produced by dropping epoxysilane into the dialkylaminoalkanethiol heated to 60 to 200 ° C. and reacting it.

[0017]

Embedded image

[However, each symbol in the reaction formula (4) has the same meaning as above.] The dialkylaminoalkanethiol used in the above reaction formula (4) is preferably 2-dimethylaminoethanethiol or 2-diethylaminoethanethiol. Two
-Diisopropylaminoethanethiol and the like.

The epoxysilane used in the above reaction is glycidoxyalkyltrialkoxysilane, glycidoxyalkyldialkoxyalkylsilane, glycidoxyalkylalkoxydialkylsilane, and glycidoxyalkyltrialkoxysilane. As, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3
-Glycidoxypropyltripropoxysilane and the like are preferred. Examples of the glycidoxypropyl dialkoxyalkylsilane include 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropyldimethoxyethylsilane, 3-glycidoxypropyldiethoxymethylsilane, and 3-glycidoxypropyldiethoxy. Ethylsilane and the like are preferred. Examples of the glycidoxypropylalkoxydialkylsilane include 3-glycidoxypropylmethoxydimethylsilane, 3-glycidoxypropylethoxydimethylsilane, 3-glycidoxypropylmethoxydiethylsilane, and 3-glycidoxypropylethoxydiethylsilane. Is preferred.

The reaction between the dialkylaminoalkanethiol and the epoxysilane is prepared by dropping 0.1 to 1 mole of epoxysilane into the dialkylaminoalkanethiol heated to 60 to 200 ° C. and reacting it. be able to. After the dropping, the reaction time is enough to stir for about 5 minutes to 2 hours. This reaction does not particularly require a solvent, but an organic solvent such as chloroform, dioxane, methanol, and ethanol may be used as a reaction solvent. Note that this reaction is preferably carried out in an atmosphere of a gas containing no water, such as dry nitrogen or argon, so that water is not mixed in because this reaction is disliked.

In this reaction, the organosilicon compound of the above-mentioned general formula (1) obtained as a product has an OH group and a SiOR group in the molecule and as shown in the following reaction formulas (5) and (6). The molecules react with each other and some cyclic compounds and oligomers are formed.

[0022]

[Chemical 6]

These substances can be isolated by a known means such as column chromatography. However, when they are used as surface treatment agents or additives for resins, these compounds do not necessarily have to be isolated, and they are mixed. It is preferable to use it as it is because it is simple.

When the organosilicon compound is used as a surface treatment agent for a metal or an inorganic substance, the metal or the inorganic substance is not particularly limited. For example, in metal, copper,
Iron, aluminum, zinc and the like or alloys thereof, and inorganic materials include glass fiber, silica, aluminum oxide, aluminum hydroxide, magnesium oxide, barium carbonate, talc and the like. The surface treatment may be applied as it is,
Water, methanol, ethanol, acetone, ethyl acetate,
It is convenient and preferable to dilute with a solvent such as toluene so as to have a concentration of 0.001 to 20% by weight and spray, or to apply a method of immersing a metal or inorganic substance in this liquid.

The organosilicon compound may be used alone, or may be used as a mixture with other silane or titanate coupling agent and rust preventive agent.

When the above 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, but when added to an epoxy resin, a curing agent is particularly preferable. Alternatively, it can effectively act as a curing accelerator and can sufficiently exert the effects of the present invention. As for the addition, alcohol type,
It may be added after being dissolved in an aromatic or aliphatic organic solvent. If the addition amount is 0.001 to 50 relative to the resin 100, the effect of the present invention can be sufficiently exhibited. The novel organosilicon compound of the present invention may be used in combination with a curing agent, a silane coupling agent, an additive such as a plasticizer, and the like.

[0027]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in more detail with reference to the following examples.

Example 1 Synthesis of silane compound having dimethylamino group (reaction of dimethylaminoethanethiol with 3-glycidoxypropyltrimethoxysilane)

[0029]

Embedded image

5.26 g of dimethylaminoethanethiol
(0.05 mol) was heated to 95 ° C., and 11.82 g (0.05 mol) of 3-glycidoxypropyltrimethoxysilane was slowly added dropwise while stirring under an argon atmosphere. After the dropping is completed, the reaction is further performed at 95 ° C. for 1 hour,
An organosilicon compound having a dimethylamino group was obtained. The obtained compound was ¹ H-NMR, ¹³ C-NMR, and FT-I.
It was identified by R. The results are shown in FIGS.

Example 2 Application as metal surface treatment agent Aluminum alloy plate (A202 specified in JIS H4000)
4P, made by Japan Test Panel, thickness 1.6mm, 25x1
00 mm) was immersed in a 0.4% methanol solution of the above-mentioned silane compound having a dimethylamino group, and then dried by a dryer for surface treatment. Epoxy resin composition (Epicoat 828 (epoxy resin, oil-based shell epoxy): 100 parts, HN-2200 (methyl tetrahydrophthalic anhydride, manufactured by Hitachi Chemical): 80 parts as a curing agent 2-Ethyl-4-methylimidazole as a promoter (manufactured by Shikoku Kasei): 1 part,
The curing conditions were 100 ° C. for 1 hour and then 150 ° C. for 1 hour for adhesion, and a tensile shear adhesion test was performed according to JIS K6850. Table 1 shows the results. For comparison, an untreated aluminum alloy plate, 0.4% 3-glycidoxypropyltrimethoxysilane or 0.4% 3-
The aluminum alloy plate treated with a methanol solution of aminopropyltrimethoxysilane was also evaluated in the same manner. The results are shown in Table 1.

[0032]

[Table 1]

Example 3 Application of Inorganic Substance as Surface Treatment Agent 0.3 g of the silane compound having a dimethylamino group was dissolved in 30 g of methanol, 3 drops of 0.1N HCl was added and mixed, and the mixture was stirred for 1 hour to prepare silane. After hydrolyzing the compound, aluminum hydroxide powder (Higilite H-43
M, manufactured by Showa Denko) 30 g and methanol 70 g,
The mixture was further stirred for 1 hour. After removing methanol with an evaporator, it was dried in a vacuum dryer at 100 ° C. for 1 hour to prepare an aluminum hydroxide powder treated with an organosilicon compound having a 1% dimethylamino group.

0.5 g of this 1% surface-treated aluminum hydroxide powder and an epoxy resin composition (Epicoat 82
8: 100 parts, HN-2200: 80 parts) (1.0 g) were mixed and the curing reactivity was analyzed by DSC (differential scanning calorimetry) (see FIG. 4). As a result, an exothermic peak appeared at around 170 ° C. As a comparison, 0.5 g of untreated aluminum hydroxide powder and an epoxy resin composition (Epicoat 82
8: 100 parts, HN-2200: 80 parts) (1.0 g) were mixed and similarly subjected to DSC analysis (see FIG. 5). As a result, 2
An exothermic peak appeared at around 10 ° C., and it was confirmed that the aluminum hydroxide powder surface-treated with the organic silicon compound having a dimethylamino group has a curing promoting action.

The surface treatment of the aluminum hydroxide powder was carried out under the same conditions as above except that the amount of the organosilicon compound having a dimethylamino group was 0.03 g.
Aluminum hydroxide powder treated with an organosilicon compound having a 0.1% dimethylamino group was prepared.

1.0 g of this 0.1% surface-treated aluminum hydroxide powder and an epoxy resin composition (Epicoat 8
28: 100 parts, HN-2200: 80 parts, 2-ethyl 4-methylimidazole: 1 part) (1.8 g) are mixed, and two untreated aluminum alloy plates are adhered (curing condition: 100 ° C.
After 1 hour at 150 ° C for 1 hour), JIS K6850
The tensile shear adhesion test was carried out in accordance with. The results are shown in Table 2. For comparison, the untreated aluminum hydroxide powder and the aluminum hydroxide powder treated with 0.1% 3-glycidoxypropyltrimethoxysilane were also evaluated in the same manner. The results are shown in Table 2.

[0037]

[Table 2]

Example 4 Application as Additive to Resin Epoxy resin composition (Epicoat 828: 100 parts, H
N-2200: 80 parts) (0.01 part) was added with 0.01 g of the above-mentioned organosilicon compound having a dimethylamino group, and DSC analysis was performed (see FIG. 6). As a result, 150
An exothermic peak was confirmed in the vicinity of ° C. As a comparison, the same DSC analysis was performed on the epoxy resin composition to which the organosilicon compound having a dimethylamino group was not added (see FIG. 7), and no clear exothermic peak was obtained. From the above results, it was confirmed that the organosilicon compound having a dimethylamino group had a curing-accelerating action when added to the resin.

Epoxy resin (Epicoat 828) 100
10 g of the above-mentioned silane compound having a dimethylamino group was added to g, and DSC analysis was performed (see FIG. 8). As a result, an exothermic peak was confirmed at around 110 ° C. Further, as a comparison, when an epoxy resin (Epicoat 828) to which an organic silicon compound having a dimethylamino group was not added was also subjected to the same DSC analysis, an exothermic peak was not confirmed. From the above results, it was confirmed that the organosilicon compound having a dimethylamino group acts as a curing agent when added to the resin.

Two untreated aluminum alloy plates were mixed with an epoxy resin composition (Epicoat 828: 100 parts, HN-220).
0:80 parts, the above-mentioned dimethylamino group-containing organosilicon compound: 1 part, curing conditions are 100 ° C. and after 1 hour, 150
Bonding was performed at 1 ° C. for 1 hour), and a tensile shear adhesion test was performed according to JIS K6850. Table 3 shows the results. In addition, as a comparison, the same evaluation was conducted by changing the organosilicon compound having a dimethylamino group in the epoxy resin composition: 1 part to 2-ethyl-4-methylimidazole: 1 part. The results are also shown in Table 3.

[0041]

[Table 3]

[0042]

As described above, the organosilicon compound of the present invention serves as a surface treatment agent for metals and inorganic substances to improve the adhesion between these and resins, and also serves as a resin additive to accelerate the curing reaction. It has a function and can improve the adhesiveness between the metal and the resin.

[Brief description of drawings]

¹ H-NMR of the organosilicon compound of the present invention obtained in Example 1,

FIG. 2 Same as above, ¹³ C-NMR,

FIG. 3 same as above FT-IR,

FIG. 4 is a diagram showing the results of DSC analysis of a mixture of aluminum hydroxide treated with the organosilicon compound of the present invention obtained in Example 1 and an epoxy resin composition (containing a curing agent),

FIG. 5 is a view showing a DSC analysis result when untreated aluminum hydroxide is used.

FIG. 6 D of a mixture with an epoxy resin (containing a curing agent) added with the organosilicon compound of the present invention obtained in Example 1
Figure showing the results of SC analysis,

FIG. 7 is a view showing a result of DSC analysis in the case where the organosilicon compound is not added.

FIG. 8 is a diagram showing the results of DSC analysis of the epoxy resin (without a curing agent) added with the organosilicon compound of the present invention obtained in Example 1,

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 , R ² , R ³ , R ⁴
Are each an alkyl group having 1 to 5 carbon atoms, 1 is 1 to 5,
m represents 1 to 10 and n represents 1 to 3] 2. The organosilicon according to claim 1, wherein a dialkylaminoalkanethiol represented by the following general formula (2) is reacted with an epoxysilane represented by the following general formula (3) at 60 to 200 ° C. Method for producing compound. Embedded image [However, in the general formulas (2) and (3), R ¹ ,
R ² , R ³ and R ⁴ are each an alkyl group having 1 to 5 carbon atoms, 1 is 1 to 5, m is 1 to 10 and n is 1 to 3] 3. A surface treatment agent containing the organosilicon compound according to claim 1 as an active ingredient. 4. A resin additive containing the organosilicon compound according to claim 1 as an active ingredient.