JPH083176A - Polysiloxane oligomer and its production - Google Patents

Abstract

PURPOSE:To produce a polysiloxane oligomer reduced in impurities, having a long pot life and useful for a film-forming composition. CONSTITUTION:This polysiloxane oligomer is produced by reacting metal silicon with an alcohol to synthesize a tetraalkoxysilane and conducting a hydrolytic dehydration polycondensation of the resultant tetraalkoxysilane. In this polysiloxane oligomer, the content of chlorine is <=10ppm and the content of transition metal is <=100ppm.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polysiloxane oligomer and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, when a tetrasiloxane silane is hydrolyzed, dehydrated and polycondensed to obtain a polysiloxane oligomer, it is obtained by first reacting ferrosilicon, silica sand or the like with chlorine gas to obtain silicon chloride, and then by reacting with alcohol. It was obtained by hydrolyzing, dehydrating and condensing the tetraalkoxysilane monomer. The polysiloxane oligomer (formula 1) thus obtained is reacted with water.

[0003]

Embedded image

Since silica (SiO ₂ ) is produced, it is used as a hard coating agent for plastic materials, ceramic materials, etc., and as an electric insulating film material for semiconductors. These hard coating agents and the like are prepared by diluting a polysiloxane oligomer with a water-soluble organic solvent such as alcohol, and adding a necessary amount of water and a curing agent (mainly acids such as mineral acid and organic acid). .

[0005]

However, the conventional hard coating agent has a short pot life, and usually has a problem of gelation (solidification) in several hours, and in a maximum of about one day. It was For this reason, methods such as liquefying a hard coating agent in which a polysiloxane oligomer and water are mixed and prepared each time they are used and extending the pot life by cooling the prepared solution are used. It was inconvenient. Further, if chlorine, a transition metal, or the like remains as impurities in the electric insulating film of the semiconductor, it causes a malfunction.

[0006]

In view of these problems, the present inventors have studied the pot life of hard coating agents, electric insulation coating agents, and the reduction of impurities such as chlorine. It was found that the amount of impurities can be significantly reduced by using the tetraalkoxysilane obtained by the direct reaction, and that the pot life can be significantly extended by reducing the content of the monomer remaining in the polysiloxane oligomer, that is, tetraalkoxysilane. The present invention has been reached.

That is, the gist of the present invention is to react a polysiloxane oligomer having a tetraalkoxysilane monomer content of 1% by weight or less, a chlorine content of 10 ppm or less and a transition metal content of 100 ppm or less, and a metal silicon with an alcohol. The tetraalkoxysilane thus obtained is hydrolyzed, dehydrated and polycondensed to obtain a polysiloxane oligomer having a chlorine content of 10 ppm or less and a transition metal content of 100 ppm or less.

Hereinafter, the present invention will be described in detail. The tetraalkoxysilane used in the present invention is a compound represented by the following formula (II), and in the present invention, it is obtained by reacting metallic silicon with alcohol. The reaction is usually carried out by directly reacting at 200 ° C. or higher for 2 hours or more with a catalyst such as copper chloride, and then further adding alcohol to 40 ° C. or higher, 1
React for more than time. Then, the alcohol is separated by distillation to remove impurities such as chlorine and transition metal, and a high-purity tetraalkoxysilane monomer is obtained.

[0009]

Embedded image

(Here, R is a C1-6 alkyl group such as methyl, ethyl, propyl, butyl, etc.) Examples of the production of such a tetraalkoxysilane monomer include the following methods. First, metallic silicon is pulverized to increase the reaction area. The crushed particle size is 10-300μ
m is preferred. Then, as a catalyst, chloride or the like is added to the amount of metallic silicon in an amount of 1 to 10% by weight, preferably 3 to 6% by weight. Copper chloride is particularly preferred as the catalyst. Then, a solvent such as dodecylbenzene is added. The amount of addition is 100 to 500 parts by weight, preferably 100 to 3 with respect to the amount of metallic silicon.
It is added at 100 parts by weight, and is usually 100 ° C or higher, preferably 15
The temperature is 0 to 250 ° C. Further, alcohol is 100 to 500 parts by weight, preferably 200 to 300 parts by weight with respect to metallic silicon.
Add parts by weight and react for 1 hour or longer, preferably 6 hours or longer.

As the alcohol, methanol, ethanol, butanol, isopropanol or the like or a mixture thereof can be used. When an alkaline earth metal oxide such as calcium oxide is added to the reaction mixture containing the trialkoxysilane thus obtained in an amount of 0.1 to 5%, preferably 1 to 2%, based on the amount of metal silicon, the reaction is completed. Desirable for progress. Further alcohol can be added to the reaction mixture. The amount added is 50 to 500 parts by weight, preferably 50 to 100 parts by weight, based on the reaction mixture. It is preferable to carry out the reaction again for 1 hour or more, preferably 3 hours or more. Then, distillation is carried out, dealcoholation is performed,
Remove impurities. In this way, a tetraalkoxysilane monomer having a purity of 99% or more can be obtained.

The polysiloxane oligomer obtained by hydrolytic dehydration polycondensation of tetraalkoxysilane is a compound represented by the formula (I).

[0013]

Embedded image

(Where R _{1 is} an alkyl group of C1-6,
n: 2 to 10) The polysiloxane oligomer is a mixture of oligomers having different degrees of polymerization n. The polysiloxane oligomer of the present invention is characterized in that the tetraalkoxysilane remaining unreacted in the oligomer is 1% by weight or less, the chlorine content is 10 ppm or less, and the transition metal content is 100 ppm or less. The chlorine content and the transition metal content can be remarkably suppressed by using metallic silicon and alcohol as raw materials, but can be further suppressed by using high-purity materials as these raw materials. When used as a semiconductor insulation material, the chlorine content is 1 ppm or less and the transition metal content is 1
It is desirable to set it to 0 ppm or less.

The polysiloxane oligomer is produced by adding the required amount of water and a catalyst to the tetraalkoxysilane monomer, and removing the alcohol (two moles of the added water) generated by the reaction.
The amount of water required here is determined from the desired hydrolysis rate. The hydrolysis rate is a value calculated according to the formulas (III) and (IV).

[0016]

[Chemical 4]

That is, when all the alkoxy groups of tetraalkoxysilane are decomposed, the hydrolysis rate is 100%, 2
Decomposition of two alkoxy groups is expressed as a hydrolysis rate of 50%. Hydrolysis is possible up to 100%, but 10
A 0% hydrolyzed product is a completely solid SiO ₂ , a gel with a hydrolysis rate of more than 70% is a gelatinous gel or a solid, and a hydrolyzate with a hydrolysis rate of 65 to 70% has a high viscosity. Furthermore, it reacts with a small amount of water in the air to form a gel, which has poor storage stability and is very difficult to handle. Therefore, the hydrolysis rate is suitably 0 to 65%, preferably 10 to 65%, more preferably 3
It is 0 to 60%.

A solvent may be used when reacting the tetraalkoxysilane with water. As the solvent, a water-soluble organic solvent such as alcohol, ether or ketone is used, but it is most preferable to use the same alcohol as the alcohol generated by hydrolysis as the solvent. The amount of solvent used is 0.1 to 10 relative to tetraalkoxysilane.
It is a weight times, preferably 0.1 to 0.5 times by weight. In the hydrolysis dehydration polycondensation, a catalyst may be used to promote the reaction smoothly, but this is not always essential.

As the catalyst, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, organic acids such as carboxylic acid and sulfonic acid, and basic physical properties such as ammonia, caustic soda and amine are used. Hydrochloric acid is preferred because it can be removed from the polysiloxane oligomer by distillation.

The amount of hydrochloric acid used is 1 × 10 ⁻⁶ to 1 × 10 ⁻¹ mole times that of tetraalkoxysilane, which is HCl.
It is preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻² molar amount.
When tetramethoxysilane is used as the tetraalkoxysilane, 1 × 10 ⁻⁶ of tetramethoxysilane is used.
1 × 10 ⁻² molar amount, preferably 1 × 10 ⁻⁵ to 1 × 1
0 ^-3 mol times the amount.

Next, a method for producing a polysiloxane oligomer having a low monomer content will be described. A tetraalkoxysilane monomer and a solvent alcohol (the same alcohol as the monomer alkoxy) are added to a reactor equipped with a stirrer, and a predetermined amount of a mixture of water and a catalyst is added with sufficient stirring.
Then, the solution is heated to raise the temperature, and the hydrolysis dehydration polycondensation reaction is allowed to proceed in the reflux state. The reflux temperature is a temperature close to the boiling point of the solvent. The reaction time in the reflux state depends on the type of catalyst, but is usually 0.5 to 10 hours, preferably 1 to
5 hours.

Next, the alcohol produced by the reaction is distilled out of the reactor at a temperature higher than that during the hydrolysis dehydration polycondensation. As this method, various distillation and evaporation operations can be applied. That is, a method of heating and distilling the solution above the boiling point of the alcohol generated by the reaction with the solvent under normal pressure or reduced pressure, or nitrogen, carbon dioxide gas, argon, helium and the like inert gas even if it is less than the boiling point. There is a method of introducing and distilling. Industrially, a method in which the solution is heated to normal temperature at 80 to 200 ° C., preferably 120 to 180 ° C. and distilled off is suitable. When tetramethoxysilane is used as the tetraalkoxysilane and polymethoxypolysiloxane is used, the temperature at this time is 80 to 130 ° C, preferably 100 to 120 ° C. In addition, the time for this removal is
Although not particularly limited, it is usually 1 to 5 hours. In the case of industrial implementation, the temperature is raised to this range, and then the temperature is kept as it is for 0.5 to 10 hours, preferably 1 to 5 hours to complete the reaction. Since the temperature can be made uniform, the composition of the product can be made uniform, which is preferable. At this time, the residual amount of the monomer is 5 to 10% when the hydrolysis rate is 10 to 50%.

Next, by distilling off this monomer,
Lower the monomer concentration in the polysiloxane oligomer.
As the method, since the monomer has the lowest boiling point in the reaction solution, various distillation and evaporation operations can be applied as in the solvent distillation. That is, a method of heating and distilling the solution above the boiling point of the monomer under atmospheric pressure or reduced pressure, or nitrogen, carbon dioxide gas, argon, even if heated below the boiling point, an inert gas such as helium is introduced and distilled off. There is a way to do it.
However, industrially, in order to reduce the concentration of the monomer to 1% by weight or less, the concentration of the monomer is not less than the boiling point of the monomer and the inert gas is S
The method of blowing at V1 to 100 (1 / Hr) is most suitable. If the temperature at this time is 200 ° C. or higher, the polysiloxane oligomer undergoes a depolymerization reaction to produce a monomer, so 100 to 250 ° C., preferably 120 to 2 ° C.
It is 00 ° C. When tetramethoxysilane is used as the tetraalkoxysilane and polymethoxypolysiloxane oligomer is used as the polysiloxane oligomer,
The temperature at this time is 130 to 200 ° C., preferably 140 to
It is 170 ° C.

In this manner, a polysiloxane oligomer having a tetraalkoxysilane content of 1% by weight or less is obtained. Incidentally, the above-mentioned production method shows a typical method, and it goes without saying that the low-monomer polysiloxane oligomer may be obtained by another method. The tetraalkoxysilane content of the tetraalkoxysilane of the polysiloxane oligomer in the present invention is preferably 0.
It is 001-0.2 weight% or less. When the above value is 0.2% by weight or less, the effect of the present invention is good as shown in the following examples, and when it is 0.001 or less,
Not only is the effect not improved, but it is industrially complicated and inconvenient.

The solution obtained by removing the monomer by the above-mentioned method has a small amount of impurities such as chlorine and transition metal, and is used as it is as a polysiloxane oligomer as a raw material for a hard coating agent, an electric insulating coating material for a semiconductor or the like. I can do things.

The polysiloxane oligomer of the present invention has an OH group content in terms of alcohol OH of 0.5% by weight.
Below, preferably 0.1% by weight or less, the content of the alkyl group is 0.01 to 0.2% by weight, preferably 0.012
It is preferably 0.17% by weight. Here, the "alcohol" in the OH group converted into alcohol OH is an alcohol corresponding to the alkoxy group of the polysiloxane oligomer, that is, an alcohol represented by R-OH having the same R as R in the formula (I). By setting the OH group in terms of alcohol OH within this range, the storage stability of the polysiloxane oligomer becomes particularly excellent. Further, if the content of the alkyl group exceeds 0.2% by weight, problems may occur in properties such as adhesion to a substrate, hardness and heat resistance when the polysiloxane oligomer is used as a hard coat. On the other hand, when the content of the alkyl group is less than 0.01% by weight, the storage stability tends to be slightly inferior. The content of the alkyl group in the polysiloxane obtained by using tetraalkoxysilane obtained by the reaction of silicon and alcohol and having an alkyl group content of 0.1 to 1% by weight. By setting the above range, it is possible to obtain a particularly excellent effect of improving storage stability. Here, the content of OH group in terms of alcohol OH can be measured as follows. When measuring the content of OH groups, in order to ensure accuracy, a highly sensitive Fourier transform infrared absorption spectrometer (FT-IR) is used to determine the absorption spectrum of the contained alcohol from the absorption spectrum of the polysiloxane oligomer. Can be calculated by using the absorption spectrum of the alcohol hydroxyl group as the absorption coefficient of the silanol group using the difference spectrum method. Also,
The content of the alkyl group may be measured by a known method such as NMR, or when the tetraalkoxysilane is hydrolyzed, dehydrated and polycondensed to form a polysiloxane oligomer, the content of the alkyl group in the tetraalkoxysilane may be determined. It can be easily calculated by conversion.

The polysiloxane oligomer of the present invention also has a viscosity at 20 ° C. of 60 cp (centipoise) or less,
It is desirable to set it to 40 cp or less. 60c
This is because those exceeding p tend to thicken and gel easily. Such a polysiloxane oligomer of the present invention is very excellent in storage stability, and when the gas in the container is replaced with an inert gas such as dry nitrogen gas at −5 ° C. to 60 ° C. and kept for 6 months under sealing. , The increase in viscosity is 100 cp or less,
Further, it can be 50 cp or less. It is also possible that the viscosity does not substantially change even after one year or more under the sealed room temperature.

[0028]

EXAMPLES Next, the present invention will be described in more detail by way of examples, but the scope of the present invention is not limited by the following examples unless it exceeds the gist. [Example 1] "Production of tetraalkoxysilane" An extraction tube having a metal (JIS SUS304) cooler, an alcohol introduction tube, a metal (JIS SUS30)
4) 1 liter metal (J) with stirrer and thermometer
IS SUS304) reactor with metallic silicon powder (particle size 20
˜100 μm, purity 99%) 210 g, cuprous chloride 3.7 g as catalyst and dodecylbenzene 410 ml were charged. Next, when the reactor was heated and the internal liquid temperature reached 220 ° C, methyl alcohol was introduced at a rate of 300 ml / hour, the reaction was performed at a reaction temperature of 220 ° C for 6 hours, and the extract was collected in a glass container. 1720 g of extract (reaction mixture) was obtained.

The reaction mixture 172 thus obtained
Charge 0 g into a 3 liter glass Kolben equipped with a Dimroth condenser and stirrer, and add 2 g of calcium oxide.
g was added. Then 1000 ml of methyl alcohol
It was added and reacted with the reaction mixture. The reaction time is 3 hours,
It was carried out under reflux (60 ° C).

Next, a 10-stage Oldershaw type distillation column having an inner diameter of 3 cm was attached to the Kolben, and distillation was carried out under the conditions of normal pressure and a reflux ratio of 2, and 1008 g of a component having a boiling point of 120 to 121 ° C.
I got When this was analyzed by gas chromatography, it was a tetramethoxysilane monomer having a purity of 99% and contained 0.5% of methyltrimethoxysilane. This corresponds to 0.055% by weight when converted to a methyl group. The analysis conditions of gas chromatography are as follows.

Equipment: Shimadzu GC-7A Column: J & W Fused Silica Megapore Column DB-5 (inner diameter 0.53 mm x length 30 mm) Carrier gas: Helium 8 ml / min (mass flow control) Temperature: Column tank 50 8 ℃ / min from ℃ to 250 ℃
Temperature rise Injection port 250 ° C. detector 270 ° C. detector: FID detector Helium gas was introduced as a make-up gas at 60 ml / min at the column outlet in order to suppress the spread of the peak. Internal standard: m-xylene (sample / internal standard = 10/1 weight ratio) Injection volume: 0.5 μl (direct injection method)

"Production of Polysiloxane Oligomer" Tetramethoxysilane (1520 g) and methanol (480 g) were charged into a 3-liter, 5-necked Korben equipped with a stirrer, Dimroth condenser, thermometer and nitrogen blowing tube, and the mixture was stirred for 5 minutes, and then 144 g of water ( Hydrolysis rate 40%), 20
% Hydrochloric acid 0.36 g was added. Then, the return state (65
(° C), and reacted at 65 ° C for 4 hours. Next, the Dimroth condenser was replaced with a L-shaped tube equipped with a Liebig condenser and a receiver, and methanol was distilled off while heating until the internal temperature reached 130 ° C to obtain polymethoxypolysiloxane. The methanol was distilled off over 2 hours. At this stage, a part of the content liquid was sampled and the monomer concentration was analyzed by gas chromatography to find that it was 5.7%. Then, this content liquid
The mixture was placed in a flask heated to ℃, heated up to 150 ℃, while maintaining the internal temperature at 150 ℃, nitrogen gas was introduced under the condition of SV50 from the blowing tube to distill off the monomer.

After bubbling nitrogen gas for 3 hours, a part of the content liquid was sampled and the monomer concentration was analyzed and found to be 0.1% or less. The polymethoxypolysiloxane thus obtained has a density of 1.2 g / cm ³ and a viscosity of 5
The cp and SiO ₂ contents were 52.0%. An oligomer having a degree of polymerization of 2 to 8 was confirmed by gas chromatography, and the weight average molecular weight by standard polystyrene conversion GPC was 550.

The chlorine content was below the detection limit of 1 ppm, the chromium content was 0.02 ppm, the nickel content was 0.01 ppm or less, and the iron content was 0.1 ppm or less. Furthermore, the OH group content of this polymethoxypolysiloxane converted to methanol OH was measured by Fourier transform infrared absorption spectrum measuring apparatus (FT
-IR) was used and the measurement was performed under the following measurement conditions.

FT-IR device: Analect AQS-20M Measurement conditions: Number of sample scans 64 Number of blank scans 64 Detector TGS (triglycerine sulf)
ate) Sample preparation method: A sample is diluted 10-fold (weight / volume) with carbon tetrachloride. Calculation formula: OH group content (wt%) in terms of methanol OH =
(Absorbance x dilution rate (ml / g)) / (cell length (cm) x
2.8 (L / g · cm) × 10)

As a result, the OH group content in terms of methanol OH in the polymethoxypolysiloxane was 0.02% by weight.
Met. 15 kg of polymethoxypolysiloxane was produced by the same method. 18 of this in a polyethylene bag
It was put in a liter petroleum can, and the air inside was replaced with dry nitrogen gas, and then sealed. This was stored in the warehouse for 1 year.
The temperature in the warehouse changed over −5 to 35 ° C. in one year, but the polymethoxypolysiloxane taken out one year later showed no change in viscosity and was 5 cp.

[Example 2] Polymethoxypolysiloxane was obtained by the same method as in "Example 1""Production of polysiloxane oligomer" except that the amount of water was 151 g (hydrolysis rate 50%). . The obtained polymethoxypolysiloxane has a density of 1.3 g / cm ³ , a viscosity of 36 cp, and an S
The iO ₂ content was 57.1%. An oligomer having a degree of polymerization of 2 to 8 was confirmed by gas chromatography, and the weight average molecular weight by standard polystyrene conversion GPC was 1060.
Met.

The amount of chlorine is 2 ppm and the amount of chromium is 0.02.
ppm, nickel content 0.01ppm or less, iron 0.1pp
It was m or less. Methanol OH equivalent OH group content is
It was 0.09% by weight.

[0039]

EFFECTS OF THE INVENTION According to the present invention, a polysiloxane oligomer containing few impurities and suitable for use as an electric insulating film of a semiconductor can be obtained.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Nobuyuki Matsuzoe 2-5-2 Marunouchi, Chiyoda-ku, Tokyo Sanryo Chemical Co., Ltd. New Business Development Office

Claims (13)

[Claims] 1. A polysiloxane oligomer having a tetraalkoxysilane monomer content of 1% by weight or less, a chlorine content of 10 ppm or less, and a transition metal content of 100 ppm or less. 2. The polysiloxane oligomer according to claim 1, wherein the tetraalkoxysilane is tetramethoxysilane. 3. The OH group content in terms of alcohol OH is 0.
The polysiloxane oligomer according to claim 1, which is 5% by weight or less. 4. The content of alkyl group is 0.01 to 0.2.
The polysiloxane oligomer according to any one of claims 1 to 3, wherein the polysiloxane oligomer is in a weight percentage. 5. The polysiloxane oligomer according to claim 1, wherein the viscosity at 20 ° C. is 60 cp or less. 6. The polysiloxane oligomer according to claim 1, which has an increase in viscosity of 100 cp or less when kept at −5 to 60 ° C. for 6 months in a sealed condition. 7. A polysiloxane oligomer having a chlorine content of 10 ppm or less and a transition metal content of 100 ppm or less, characterized by hydrolyzing, dehydrating, and polycondensing tetraalkoxysilane obtained by reacting metallic silicon with an alcohol. Manufacturing method. 8. The method for producing a polysiloxane oligomer according to claim 7, wherein after the tetraalkoxysilane is hydrolyzed and dehydrated and polycondensed, the tetraalkoxysilane monomer is removed by heating to a temperature higher than that during the hydrolyzed and dehydrated polycondensation. Law. 9. The method for producing a polysiloxane oligomer according to claim 7, wherein the heating is performed at a temperature not lower than the boiling point of tetraalkoxysilane. 10. The method for producing a polysiloxane oligomer according to claim 7, wherein the heating temperature at the time of heating to a temperature higher than that at the time of hydrolysis dehydration condensation is 140 to 170 ° C. 11. The method for producing a polysiloxane oligomer according to claim 7, wherein the heating is performed under reduced pressure. 12. The method for producing a polysiloxane oligomer according to claim 7, wherein the heating is performed while blowing an inert gas into the solution. 13. The tetraalkoxysilane obtained by reacting metallic silicon with alcohol has an alkyl group content of 0.1 to 1% by weight, according to any one of claims 7 to 12. The method for producing a polysiloxane oligomer according to item 1.