JPS6165891A - Novel silane and its production - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (R<1> is H, lower alkyl; R<2> is H, formula II; R<3> is trimethylene chain, ethylpropylamino chain; X is methoxy, ethoxy, acetoxy). EXAMPLE:The compound of formula III. USE:A silane coupling agent that gives a printed circuit base with high heat resistance. PREPARATION:At first, the reaction of nitrobenzyl halide with allylamine, preferably in an amount 10 times or more the molar amount of the benzyl halide is effected to give an aromatic nitro intermediate of formula IV or V. The nitro group only in the intermediate is reduced, preferably using tin and hydrochloric acid to form an amino group, then in the presence of a platinum catalyst preferably chloroplatinic acid, a compound of HSiX3 such as trimethoxysilane is added to give a compound of formula I where R<1> is H and R<3> is trimethylene chain.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a novel silane compound and its manufacturability, and more particularly to a silane coupling agent having an aromatic amine gold functional group and its It is related to manufacturability.

(Prior Art) In recent years, along with the rapid technological progress in the electronics industry, the demand for related materials has increased. For example, increased heat generation due to higher integration of ICs has led to demands for even higher heat resistance of printed wiring boards. Among the materials used as printed wiring boards, the heat resistance of laminates made by impregnating and curing glass fabric with epoxy resin as a core material depends on the performance of the silane coupling agent used for surface treatment of the glass fibers. Much depends on.

(Problems to be Solved by the Invention) The following laminated plates with poor heat resistance exhibit various defects during their processing steps, including etching, washing with water, drilling, cleaning with organic solvents, and soldering. It's coming. For example, if a laminate with poor heat resistance is placed in a high-temperature environment during the soldering process, the shape may be distorted, many blisters may appear on the surface, and the laminate, glass fibers, and resin may peel off. etc., which may cause problems in practical use.

(Means for Solving the Problems) In order to obtain a heat-resistant printed wiring board that does not exhibit the following defects, both in the manufacturing process and in the finished product, the present inventors developed a method using a large number of silanes having a new structure. As a result of synthesizing and evaluating compounds, we were able to find a silane compound with excellent psychological performance.

The silane compound of the present invention is represented by general formula (I). In the above general formula, R1 is hydrogen, next is methyl group,
Lower alkyl R1 with or without a substituent such as an ethyl group or a cyanoethyl group is a trimethylene chain -C 几C) I, CH, -1 or an ethylpropylamino chain -C
H, CH, NHCH, 0H1C1 (, -, and X represents any one of methoxy group, ethoxy group, acetoxy group. One NHRI group bonded to the aromatic ring and -CH
1NR"SiX, ortho, meta, para 3 with respect to the group
Isomers of the species are possible.

The above compounds of the present invention are prepared by the following three-way method.

In method io, an aromatic nitro compound intermediate having the structure of the following formula oi is synthesized from nitrobenzyl halide and allylamine, and only the nitro group is selectively reduced with the following compound. This is a method in which KH81X and t-addition are performed in the presence of a platinum catalyst after the amino group is removed. The structure of the silane compound obtained by this method is
It is represented by the following formula (IID or (m)').

(wherein, This is a method in which an intermediate having the structure (V) is synthesized, and then the nitro group and the azomethine chain are reduced simultaneously or stepwise in the presence of a dehydrating agent.Structure of the silane compound obtained by this method is represented by the following formula (I[D or (to)).

(wherein, ■)' (wherein, The formula is represented by (IID'. Even when the silane compound represented by the formula (IID, (IID') is mixed in the reaction product,
When there is no significant difference in performance pressure as a silane coupling agent, these components can be used without being separated.

The nitrobenzyl halide used in the first and third methods is preferably nitrobenzyl bromide or para-, meta-, ortho-isomers of nitrobenzyl bromide. In some cases, nitrobenzyl iodide can also be used, but this is disadvantageous in terms of cost.

The reaction between nitrobenzyl halide and allylamine usually proceeds easily in an organic solvent at a temperature ranging from room temperature to 100C and is completed in 1 to 10 hours.

By using allylamine in large excess (at least 5 times the mole, preferably at least 10 times the mole) relative to the nitrobenzyl halide, the conversion rate of nitrobenzyl halide is 1100.
%, and at such a raw material charging ratio, the amount of secondary amine (II) in the reaction product is overwhelmingly larger ((951 or more) than the tertiary amine (■)'). ), even if no particular separation operation is performed, the silane compound finally obtained has substantially the structure of formula (I[D).

Unreacted allylamine can be recovered from the reaction product by distillation and used again in the next reaction. The residual liquid after distillation contains the product and allylamine hydrochloride, and after neutralization with alkali, operations such as extraction and distillation are performed.
Through this process, an intermediate containing 95% or more of 0 and 5- or less (IID ffi) is obtained.

Next, the above intermediate is treated with tin, or a mixed reagent of tin chloride and hydrochloric acid, and the first is iron, a mixed reagent of iron chloride and hydrochloric acid, etc., to reduce only the nitro group without reducing the unsaturated bonds, and then to form an amino group. An aromatic amine intermediate is prepared using a reducing agent that can be used as an aromatic amine intermediate.

The reaction of adding silane to the unsaturated bond of the aromatic amine intermediate in the presence of a platinum-based catalyst is carried out by heating the reaction solution in the presence or absence of an organic solvent. As the platinum-based catalyst, chloroplatinic acid is most preferred, but platinum or oxidized platinum wood can also be used.

The reduction of intermediate QV), (V) in the second method can be carried out using molecular sieves, zeolites, anhydrous calcium sulfate,
It is carried out in the presence of a dehydrating agent such as anhydrous magnesium sulfate. This is because the water produced by the reduction of the nitro group hydrolyzes the alkoxysilane i or acetoxysilane to produce a condensate that is insoluble in the solvent. In the method in which the nitro group is easily reduced compared to the azomethine chain, the first step is to reduce only the nitro group under mild conditions in the presence of a dehydrating agent, then completely remove water and reduce the , the second at a higher temperature
It is advantageous to reduce the diazomethy/chain in six turns.

When a severe reaction is carried out in the presence of moisture, acetoxysilane is easily hydrolyzed and a condensate is formed. It is preferably carried out in a lower alcohol such as methanol or ethanol. In the second method, a hydrogenation reaction using a noble metal catalyst is preferable, and in the reduction using a reducing agent, alkoxysilane' = primary is acetoxysilane. The disadvantage is that it is easily decomposed.

The dehydrating agent used in the third method is the same type as the dehydrating agent used in the second method.

Furthermore, in the fifth method, unless a strong base such as triethylamine is used as a scavenger for hydrogen chloride produced by the reaction, the reaction will stop midway. If the silane having an amino group used as a raw material does not have extremely poor performance as a silane coupling agent, the reaction can be completed by using at least twice the mole of the raw material silane as the nitrobenzyl halide. Although the resulting product contains unreacted silane in the same mole as the product, the reduction reaction can be carried out as it is, and the mixed composition can be used as a silane coupling agent.

The novel silane compound of the present invention can be used as a silane coupling agent using inorganic materials such as glass, silica, alumina, talc, kaolin clay, mica, calcium carbonate, barium titanate, shirasu, aluminum hydroxide, zeolite, titanium oxide, It is applied to the surface of naturally occurring minerals such as asbestos and silicon nitride, as well as artificially synthesized single compositions.

(Effects of the Invention) A composite material made of an inorganic material and an organic polymer surface-treated with the silane compound of the present invention is generally strong and has excellent heat resistance.

In particular, a printed wiring board made of glass fabric whose surface is treated with the silane compound of the present invention has excellent solder heat resistance and chemical resistance, and can meet the high demands of the electronics industry.

(Example) Hereinafter, the present invention will be explained in more detail with reference to examples.

Example 1 Allylamine 148.5SF and ) ethylamine 52.6S' were mixed in a 1t flask, and the mixed solution Kp-nitrobenzyl chloride was 82.5SF. ? f fTetrahydroneran 2613 PK was dissolved and the solution was added dropwise little by little while stirring. After dropping, in a nitrogen stream and in a water bath for 20 to 30 minutes.
9. The reaction was continued at a temperature of C for 15.5 hours with stirring. After the reaction, put the reaction solution into a rotary evaporator and heat at 30C.
Unreacted allylamine was evaporated to give a residual liquid of about 220%. This was dissolved in 220 d of water, subjected to batch extraction four times with 340 d of ethyl acetate, and the ethyl acetate was evaporated using a rotary evaporator again.
97. A reaction product of St was obtained. The product was replaced with deuterium and tetramethylsilane (TMS) was added. Dissolve in chloroform and analyze with nuclear magnetic resonance (NMR)
The entire chart in Figure 1 was obtained.

Next, the reaction product 96,5 f f ethanol 200
? Dissolve stannous chloride (2
Water salt) 576ft Ethanol 5 a OfK The dissolved liquid was cooled with ice water and added dropwise over about 1 hour.

Next, 35% hydrochloric acid (43 Qrdf) was added dropwise over about 45 minutes, and after the addition was completed, the reaction was carried out at room temperature for 13 hours. After the reaction was completed, the reaction solution (approximately 1.4 t) was diluted with 3.6 t of water,
It was neutralized with a 5N aqueous solution of caustic soda (pH→11).

This neutralized solution was extracted in several portions with ethyl acetate, and the entire extract was placed in a rotary evaporator to evaporate the ethyl acetate, yielding a total of 6 El and 5 f of the product. The NMR chart of the product is shown in Figure 2.

Then the product, 64.8p,)rimethoxysilane 58
．． 77f mix, add about 0.05p chloroplatinic acid, reflux trimethoxysilane at 120C, 3.
Let it react for 5 hours. The obtained novel sila/compound 'iN
Measurement was carried out by MR, and the chart shown in FIG. 3 was obtained. The large peak of δ÷5.5 tpts in the chart is based on 6 hydrogen atoms of the methyl group of methanol used as a solvent.

Example 2 p-Nitrobenzaldehyde 15.12'f! : Dehydrated methanol 1o01RtK was dissolved, and 5-aminopropyltriethoxysilane 22,17'i was added dropwise little by little to the solution, and after completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour to react. The reaction proceeds quantitatively, producing equimolar amounts of water and Schiff salt. In order to remove all the produced water in the reaction solution, calcined at 600C and added about 502 grams of Molecular Sheep, followed by stirring at night. A portion of the reaction solution was taken out, the solvent was evaporated using a rotary evaporator, and the yellow residue was analyzed by NMR, and the chart shown in Figure 4 was obtained. The absorption based on one hydrogen of the azomethine bond appears on the leftmost side (δ
- knee 7.8 ppm). Next, remove by molecular sieve filtration and use new molecular seeds 5a2.
Added an earpick of platinum oxide and reacted in an autoclave under hydrogen pressure of 10 kg/dG for 8 hours.9. The reaction temperature temporarily rose to 30C due to heat generation, but was generally kept at 20-25C.

After the reaction, remove the molecular sieve by filtration, replace it with new molecular sieve, and set aside overnight. The molecular sheep was removed again, an earpickful of platinum oxide was added, and the mixture was heated under a hydrogen pressure of 10 kg/adG.
The reaction was carried out at 5C for 9 hours. After cooling the reaction solution, the catalyst and a small amount of solid matter were removed by filtration. The reaction solution was a dark brown, slightly viscous liquid. A portion of the reaction solution was taken out, ethanol gold was evaporated, and the product was analyzed by t-NMR. The results (Figure 5) showed that the product was as follows. The following is found to be a compound with the structure:

Analysis of the product was performed by NMR. Since the raw material ethoxysilane is used as a solvent during the reaction process and is replaced by diluted methanol, only the absorption of methoxy groups is δ + 3.5.
(psm).

Example 3 15.1 pi of m-nitrobenzaldehyde was dissolved in too much dehydrated methanol, and 1 c of the solution was dissolved in 22.2 ft of m-nitrobenzaldehyde.
- It was added dropwise little by little, and after the dropwise addition, it was allowed to react at room temperature for 1 hour to generate Schiff salt. The Schiff salt was subjected to the same reaction and separation procedure as in Example 2 to obtain the following compound.

Shu! Example 4 33.2 ft of 5-aminopropyltriethoxysilane was dissolved in 501 dehydrated ethanol, refluxed the ethanol at about 78 G, and reacted for 5 hours. . When the liberated bromine was titrated with silver nitrate, the yield was about 90%.

Next, an earpick of platinum oxide and Molecular Sheep SA (dehydrating agent) (I-1Of) were added to the reaction solution, and the mixture was reacted in an autoclave at 60C under a hydrogen pressure of 10k1iI/c++tG for 9 hours.

The reaction solution was a dark brown viscous liquid), which was applied to a partially embedded potash crystal plate and dried, and the absorption of nitro groups was examined by infrared spectroscopy, and the presence of nitro groups was confirmed. I couldn't. The composition contained in the reaction solution is unreacted 5-aminopropyltriethoxysilane and the following compound in an equimolar amount thereto.

Example 5 The various silane coupling agents and comparative agents obtained in Examples 1 to 4 were treated on glass fabric in the following manner, and the 90 silane coupling agents were dissolved in water to form a 0.5% by weight aqueous solution. Then, add acetic acid to the aqueous solution to adjust the pH to 5 (treatment liquid).

A glass fabric with a thickness of 0.18111 [7628 manufactured by Asahi Schniebel Co., Ltd.] was immersed in the above treatment liquid, and then the liquid was removed so that the retention rate of the treatment liquid was about 50%, and then 120C hot air was immersed. dried by.

In addition, brominated bisphenol A type epoxy resin AER7
11-EK130 (manufactured by Asahi Kasei Industries, Ltd.) 100 parts, N
, N'-dimethylformamide 9.3 parts, methyl cellosolve 9.3 parts, dicyandiamide 2.0 parts, N,N
Epoxy varnish containing 0.17 parts i of '-dimethylbenzylamine? :'HAM.

A glass fabric treated with the silane coupling agent was impregnated with the varnish, dried, and a prepreg having a resin content of 45 inches was cut out. Next, all 8 sheets of the prepreg were stacked, a 35 μm thick copper foil was pasted on the surface layer of the image, and 4 sheets were heated at 175C for 60 minutes.
Pressurized at 50 kg/dQ and molded into one piece, 1.6 inch thick.
We made steel-clad steel plates.

Furthermore, a portion of the copper foil was etched out using an etching solution, washed with water, and air-dried to form a test laminate.

For the above test laminates made from glass fabrics treated with various silane coupling agents, the impregnability of the resin,
The solder heat resistance, chemical resistance, and electrical properties were measured, and the performance of the silane coupling agents was evaluated, and the results are shown in Table 1. In Table 1, the silane coupling agents of comparative examples are as follows.

Comparative Example 1 (r-glycidoxyclovir)trimethoxysilane Comparative Example 2 3-aminoprobyltriethoxysilane x 1 The impregnability of the resin was visually determined. be.

Good (○), Fairly good (Δ), Poor (×) *2 JI
According to the heat resistance of S-C-6481, heat treatment was performed at 120C for 2.5 hours, 3.0 hours, and 5.5 hours using a pressure cooker (PC), and then floated on the solder surface at 260C for 1 minute. The presence (×) and absence (○) of the occurrence of cracks was investigated.

*3 According to the trichlene resistance test of JIS-C-6481, the surface condition of the throw that was immersed in 20C trichlene for 20 minutes t? Examined.

Remaining 4 In accordance with the trichlene resistance test of JIS-C-6481, the surface condition was examined after immersion in 20C methylene chloride for 20 minutes.

*5 Conforms to JIS-C-6481K.

[Brief explanation of the drawing]

Claims (4)

[Claims] (1) The following general formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 may or may not have hydrogen, or a substituent such as a methyl group, ethyl group, or cyanoethyl group. Lower alkyl group, R^2 is hydrogen, or ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ group, R^3 is trimethylene chain -C
H_2CH_2CH_2-, or ethylpropylamino chain -CH_2CH_2NHCH_2CH_2CH_2
- and X represent any one of a methoxy group, an ethoxy group, and an acetoxy group. ) A novel silane compound represented by (2) From nitrobenzyl halide and allylamine, the structure of the following formula (II) or (II)′ ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II)′ The following formula (III) or (III)'▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III)' (In the formula, X is a group of methoxy, ethoxy, or acetoxy. ). (3) Nitrobenzaldehyde and 3-aminopropyltrialkoxysilane or N-2-aminoethyl-3-
From aminopropyltrimethoxysilane, a silane salt having the structure of the following formula (IV) or (V) ▲Mathematical formula, chemical formula, table, etc. available▼(IV) ▲Mathematical formula, chemical formula, table, etc. available▼(V) is formed. and then reduce the nitro group and the azomethine chain simultaneously or stepwise in the presence of a dehydrating agent.
VI) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(VI) (In the formula, X represents any of the methoxy group, ethoxy group, or acetoxy group. ) A method for producing a silane compound shown in (4) From nitrobenzyl halide and 3-aminopropyltrialkoxysilane, the following formula (VII) or (VII)'
▲There are mathematical formulas, chemical formulas, tables, etc.▼(VII) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(VII) Synthesize a compound with the structure ′, and then reduce the nitro group in the presence of a dehydrating agent Characteristics of the following formula (III) or (III)′ ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III)′ (In the formula, X is a methoxy group, an ethoxy or acetoxy group).