JP5158594B2 - Silicone polymer having naphthalene ring and composition thereof - Google Patents

Description

  The present invention relates to a silicone polymer having a hydrocarbon group containing a naphthalene ring, which is useful as an insulating film material for electronic parts such as liquid crystal display elements and semiconductor elements.

  In recent years, insulating films used in electronic components such as liquid crystal display elements and semiconductor elements include high transparency with high transparency to visible light, and heat resistance and chemical resistance that can withstand various processing steps when manufacturing elements. There is an increasing need for resins having characteristics such as crack resistance. Among them, a silicone resin having a silsesquioxane skeleton has excellent performance in optical characteristics and heat resistance, and has been widely used by utilizing these characteristics.

  However, the cured film has a film thickness of 1 μm or more, and the film is liable to crack. An example of an epoxy group-containing silicone resin described in Patent Document 1 is disclosed as a material having crack resistance which is an important characteristic. However, although the crack resistance is excellent, it cannot withstand a heat treatment step of 300 ° C. or higher, and the heat resistance is insufficient.

  On the other hand, flatness of the film surface is important in LSI manufacturing, and the film surface after film formation by heating is required to be flat. For example, in the multilayer wiring process of LSI manufacturing, if the film formed by heating is not flat, when a film is formed on it, the newly formed film may not be uniform and a nonuniform film may be formed. There is. When the film thus formed is exposed to light, irregular reflection or scattering of light occurs near the non-uniform film interface, and a uniform pattern cannot be formed. As described above, since the flatness of the film surface often affects film characteristics such as optical characteristics and mechanical characteristics, a flat film is required.

  Here, the flatness of the film is expressed by the surface roughness Ra (JIS-B0601). Here, Ra is the measured value of the arithmetic average of the scratch depth, and the individual deviation in the average deviation, that is, the measured length, obtained by dividing the area surrounded by the roughness curve and the center line by the measured length. The average value of In addition, Rmax is used as another parameter indicating the surface roughness, which is the maximum depth from the highest point to the lowest point in the measurement length. The larger the numerical value, the rougher the surface, and a material with a small numerical value has been demanded.

  For example, there is a flexible substrate as described in Patent Document 2 as a material that is required to be flat with a thick film. In this example, the composition of polyimide siloxane and both-end epoxy siloxane is thermally cured to form a film with a thickness of 7.5 to 35 μm, but Ra is as large as about 0.1 μm and cured. Since the temperature is as low as 80 ° C., it is not suitable for a process where the film baking temperature using a varnish containing a high boiling point solvent is 300 ° C. or higher.

In view of the above, there has been a demand for a silicone material having a thick film of 1 μm or more, further 5 μm or more, which has heat resistance and light transmission properties, small Ra and Rmax, and a flat surface.
JP 2001-040094 A JP 2004-91648 A

  The present invention was made for the purpose of providing a novel silicone polymer that has excellent smoothness and can form a film having high crack resistance, high permeability, high heat resistance, and high solvent resistance. Is.

  The present invention has the following general formula:

(In the formula, R represents a hydrocarbon group having a naphthalene ring.)
And a silicone polymer having a naphthalene ring having a weight average molecular weight of 500 to 8,000 and a dispersity of 1.1 to 1.8 .

The silicone polymer of the present invention comprises only a silsesquioxane skeleton having a hydrocarbon group containing a naphthalene ring. A composition formed by adding a silicone polymer having a hydrocarbon group containing a naphthalene ring to a silicone polymer containing a silsesquioxane unit can easily form a silicone film by heating to 200 ° C. or higher. The silicone film exhibits high flatness and excellent crack resistance. In addition, it has very excellent characteristics in heat resistance and solvent resistance.

  Since the silicone polymer of the present invention is a material having characteristics such as transparency, heat resistance, chemical resistance, and crack resistance, it can be used as an insulating film used in electronic parts such as liquid crystal display elements and semiconductor elements. . Further, the silicone polymer of the present invention can be applied not only in the field of electronic materials but also in a wide range of fields such as paints and adhesives.

  The silicone polymer having a naphthalene ring of the present invention has the following general formula:

(In the formula, R represents a hydrocarbon group having a naphthalene ring.)
It is a silicone polymer which consists only of repeating units shown by.

  The following skeleton of the silicone polymer having a naphthalene ring of the present invention

Represents a silsesquioxane skeleton, wherein each silicon atom is bonded to three oxygen atoms, and each oxygen atom is bonded to two silicon atoms. The silsesquioxane skeleton has, for example, the following general formula

It can be shown by the structural formula shown in

Further, silicone down the polymer having a naphthalene ring of the present invention, for example, the following formula

In a ladder-type silicone emissions may be a polymer that is shown.
As the hydrocarbon group having a naphthalene ring represented by R, a hydrocarbon group may be bonded to the naphthalene ring.

(In the formula, D represents a hydrogen atom or an organic group and is bonded to the naphthalene ring. E represents a hydrocarbon group.)
And a hydrocarbon group having a naphthalene ring.

  Preferred examples of the substituent D bonded to the naphthalene ring include a hydrogen atom, a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms, an organic group having an ether bond, or an ester bond. An organic group having Among them, from the ease of raw material acquisition and monomer purification, hydrogen atom or methyl group, ethyl group, n-propyl group, iso-propyl group, methoxy group, ethoxy group, acetoxy group, ethylcarbonyloxy group, carboxylic acid, A methoxycarbonyl group and an ethoxycarbonyl group are more preferable, and a hydrogen atom, a methyl group, and a methoxy group are more preferable.

  Preferred examples of the substituent E bonded to silicon of silsesquioxane are preferably a linear, branched, or cyclic hydrocarbon group having 1 to 10 carbon atoms or a hydrocarbon group containing an ester group. From the viewpoint of availability of raw materials and monomer purification, a methylene group, an ethylene group, an n-propylene group, an iso-propylene group, and a carbonyloxypropyl group are more preferable, and a methylene group, an ethylene group, and a carbonyloxypropyl group are more preferable.

  The hydrocarbon group having a particularly preferred naphthalene ring is represented by the following general formula:

And a hydrocarbon group containing a naphthalene ring.

Silicone down the polymer having a naphthalene ring of the present invention has a weight average molecular weight (polystyrene equivalent), area by near 5 00～8,000. The silicone copolymer of the present invention preferably has a dispersity in the range of 1.1 to 2.5, and more preferably in the range of 1.1 to 1.8.

  The weight average molecular weight was measured using a gel permeation chromatography (hereinafter abbreviated as GPC) apparatus. In this product, the measurement was performed using a GPC measuring apparatus HLC-8220 manufactured by Tosoh Corporation. In the measurement, a Tosoh GPC column (two TSKgel GMHXLs in parallel) was used, a calibration curve was prepared using polystyrene as a standard substance, and then the measurement was performed. The degree of dispersion is represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained from the measurement. In general, when the weight average molecular weight is 20,000 or more, the degree of dispersion is 1.8 or more, which may be insoluble in an organic solvent.

  The silicone polymer having a naphthalene skeleton of the present invention is preferably soluble in an organic solvent, and is a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl cyclohexanone, methanol, ethanol, isopropanol, n-butanol, Alcohol solvents such as cyclohexanol, aromatic hydrocarbon solvents such as benzene, toluene and xylene, ester solvents such as methyl acetate, ethyl acetate, butyl acetate and ethyl lactate, ether solvents such as diethyl ether, dibutyl ether and tetrahydrofuran, acetonitrile , Nitrile solvents such as benzonitrile, glycols such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol monomethyl ether acetate Solvent is soluble.

  The present invention represented by the following general formula

(In the formula, R represents a hydrocarbon group having a naphthalene ring.)
In the case of producing a silicone polymer having a naphthalene ring represented by, for example, it can be synthesized by a hydrolysis reaction or polycondensation reaction using water shown below.

(In the formula, R represents a hydrocarbon group having a naphthalene ring. X represents a hydrolyzable group.)

  Here, X represents a hydrolyzable group, preferably a halogen atom of chlorine, bromine or iodine, or an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group or a butoxy group, particularly a chlorine atom, a methoxy group or an ethoxy group. Is particularly preferred because of the availability of raw materials and high reactivity.

  This hydrolysis and polycondensation reaction is carried out using water, but it is usually preferred to carry out by adding a catalyst. In this case, the reaction is preferably performed under acidic conditions from the viewpoint of molecular weight control, and it is particularly preferable to use a catalyst such as hydrochloric acid, acetic acid, citric acid, or oxalic acid. The amount of the catalyst used is preferably 0.01 to 1.0 equivalent, more preferably 0.05 to 0.5 equivalent, relative to the number of moles of the raw material monomer.

  As the hydrolysis and polycondensation conditions, a reaction temperature of 0 to 100 ° C. is preferable, and the reaction proceeds easily by using a catalyst, and therefore 10 to 40 ° C. is more preferable.

  Although water is required for this hydrolysis and polycondensation reaction, it is preferable to use 3 to 100 equivalents, particularly preferably 5 to 50 equivalents, based on the number of moles of the raw material monomer.

  In this reaction, an organic solvent is preferably used. Examples of the organic solvent include aprotic solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and alcohol solvents such as methanol, ethanol and 2-propanol. , Ether solvents such as diethyl ether and tetrahydrofuran, and the like can be used.

  After completion of the reaction, a non-polar solvent is added to separate the reaction product and water, and the reaction product dissolved in an organic solvent is recovered. After washing with water, the solvent is distilled off to obtain the desired product. Can be obtained.

  For example, the silicone polymer of the present invention can be synthesized in this manner.

  Silicone polymer having naphthalene ring of the present invention, and the following general formula

(In the formula, A represents a hydrocarbon group having an aromatic hydrocarbon group, B represents an aliphatic hydrocarbon group, m and n represent mol%, and 0 ≦ m and n ≦ 100. However, m + n = 100.)
The composition with the silicone polymer having a silsesquioxane unit represented by the above formula forms a silicone film after heating at 200 ° C. or higher, and the formed silicone film becomes a material excellent in crack resistance and flatness.

  The following general formula

(In the formula, A represents a hydrocarbon group having an aromatic hydrocarbon group, B represents an aliphatic hydrocarbon group, m and n represent mol%, and 0 ≦ m and n ≦ 100, where m + n. = 100.)
The aromatic hydrocarbon group shown as A of the silicone polymer containing a silsesquioxane unit shown by the following is preferable examples of phenyl group, benzyl group, phenethyl group, phenylpropyl group, diphenylmethyl group, cinnamyl group, styryl. And a substituent having a benzene ring and a hydrocarbon group such as a group and a trityl group, an aromatic hydrocarbon group having a substituent bonded to a benzene ring such as a toluyl group, a cumenyl group, a mesyl group, and a xylyl group. A substituent may be bonded to the benzene ring such as a 4-methylphenylethyl group, a 4-methylphenylpropyl group, or a 2,4-dimethylphenylethyl group.

  The aromatic hydrocarbon group has an effect of improving the heat resistance of the resin during film formation by heating, and can improve the heat resistance of the resin. The aromatic hydrocarbon group is particularly preferably an aromatic hydrocarbon group such as a phenyl group, a toluyl group, a cumenyl group, a mesyl group, or a xylyl group, and more preferably a phenyl group that is generally readily available. If there is a substituent between the aromatic ring and the silicon atom, the glass transition temperature generally improves and the heat resistance tends to improve as compared with the case where there is no substituent.

  Preferred aliphatic hydrocarbon groups as B of the silicone polymer containing silsesquioxane units are linear hydrocarbon groups having 1 to 20 carbon atoms, branched hydrocarbon groups, cyclic hydrocarbon groups, and bridged cyclic carbon groups. A hydrogen group, a hydrocarbon group having a double bond, and a linear hydrocarbon group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, etc. These hydrocarbon groups are mentioned. As the branched hydrocarbon group, a hydrocarbon group such as isopropyl group and isobutyl group is preferable. As the cyclic hydrocarbon group, a cyclic hydrocarbon group such as a cyclopentyl group, a cyclohexyl group, or a cycloheptyl group is preferable, and a bridged cyclic hydrocarbon group having a norbornane skeleton is also preferable. A vinyl group having a double bond and a hydrocarbon group having an allyl group are also preferred. Among these hydrocarbon groups, straight-chain hydrocarbon groups having 1 to 5 carbon atoms such as a methyl group, an ethyl group, and a propyl group are more preferable, and a methyl group is more preferable from the viewpoint of obtaining raw materials.

m and n represent mol% of the silicone copolymer. m is a portion for improving the heat resistance of the silicone film is 4 0 mol% or more. n represents the chemical resistance to an organic solvent or an alkaline developing solution after the silicone film formed is 6 0 mol% or less.

(In the formula, R represents a hydrocarbon group containing a naphthalene ring.)
A silicone polymer having a repeating unit represented by the following general formula:

(In the formula, A represents a hydrocarbon group having an aromatic hydrocarbon group, B represents an aliphatic hydrocarbon group, m and n represent mol%, and 0 ≦ m and n ≦ 100, where m + n. = 100.)
In the case of forming a silicone film by heating a composition with a silicone copolymer containing a repeating unit represented by formula (2) to 200 ° C. or more, the composition ratio of the silicone polymer having a hydrocarbon group containing a naphthalene ring is 30% by weight. Is preferred.

  Hereinafter, the present invention will be specifically described with reference to examples.

  In the following examples, the following apparatus was used for the measurement, and general reagents purchased from reagent manufacturers (Tokyo Chemicals, Wako Pure Chemicals, Nacalai Tesque, Azmax, Shin-Etsu Chemical) were used as raw materials.

<Measurement device>
NMR measurement: JEOL 400 MHz NMR measuring instrument IR measurement: Shimadzu IR Prestige-21. A small amount of a synthetic product was applied to a KBr plate, and the measurement was performed by passing infrared light through another KBr plate.
GPC measurement: Tosoh HLC-8220
GC measurement: Shimadzu GC-2010 series

<Evaluation of coating>
For the coating films formed by the film forming methods described in Examples 5 to 9 and Comparative Example 2, film evaluation was performed by the following method.

[Measurement of surface roughness]
(Center line average value Ra)
At the central part of the final cured film formed on the silicon wafer, three points were measured using a Tokyo Seimitsu stylus type surface roughness measuring device Surfcom 1500A under the conditions of a cutoff value of 0.25 mm and a measurement length of 1 mm. The average value was calculated.

(Maximum height Rmax)
At the central portion of the final cured film formed on the silicon wafer, three points were measured at a measurement length of 1 mm using a stylus type surface roughness measuring device Surfcom 1500A manufactured by Tokyo Seimitsu, and the average value was calculated.

(Roughness evaluation)
When Ra measured above is 0.005 or less and Rmax is 0.05 or less, ◎, when Ra is 0.005 to 0.010 and Rmax is 0.050 to 0.500, ○, Ra is 0.010. When 0.050 and Rmax were 0.500 to 1.000, Δ, and when Ra was 0.050 or more and Rmax was 1.000 or more, ×.

[Evaluation of crack resistance]
With respect to the final cured film formed on the silicon wafer, the presence or absence of in-plane cracks at a magnification of 10 to 100 times was confirmed with a metal microscope. The case where no crack was generated was judged as ◯, and the case where a crack was seen was judged as ×.

[Evaluation of solvent resistance]
The final cured film formed on the silicon wafer was immersed in a dimethyl sulfoxide solvent heated to a temperature of 90 ° C. for 120 minutes to test whether the film surface was rough, the film peeled, or dissolved. The case where there was no film surface roughness, film peeling, or dissolution was judged as ◯, and the film surface roughness, film peeling, or dissolution was confirmed as x.

(Measurement of transmittance)
The transmittance at a deep ultraviolet exposure wavelength of 365 nm (i-line) was measured using a UV3310 manufactured by Hitachi on a film coated on a glass substrate having no absorption in the visible light region.

Synthesis example 1
Example of synthesis of 2-methyl-1-naphthyltrimethoxysilane To a 500 mL four-necked flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 11.5 g (0.475 mol) of magnesium and 300 mL of tetrahydrofuran were added. The temperature was raised to 40 ° C. Next, a small amount of 1,2-dibromoethane was added as an initiator, and 100 g (0.452 mol) of 1-bromo-2-methylnaphthalene was added dropwise over 6 hours so as not to exceed 45 ° C. After completion of dropping, the mixture was aged at 40 to 45 ° C. for 2 hours to prepare a Grignard reagent.

  Next, in a 1000 mL four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 206.5 g (1.357 mol) of normal methyl silicate was charged, and the internal temperature of the can was raised to 80 ° C., Grignard reagent Was added dropwise at a temperature of 80 to 85 ° C. over 2 hours. After completion of dropping, the mixture was aged at 80 to 85 ° C. for 2 hours and then cooled, the magnesium salt was filtered, the solvent was distilled off, and 46.4 g (0.177 mol) of a fraction at 110 to 115 ° C. was obtained at a reduced pressure of 1 Torr. It was. As a result of GC analysis of the obtained fraction, GC purity was 98.6%. As a result of NMR and IR analysis, it was 2-methyl-1-naphthyltrimethoxysilane.

  The spectrum data of the obtained compound is shown below.

Infrared absorption spectrum (IR) data ^{2839,2941cm -1 (-CH3, Ar),} 1080cm -1 (Si-O)
Nuclear magnetic resonance spectrum (NMR) data ( ¹ H-NMR solvent: CDCl 3)
2.73 ppm (s, 3 H, Ar—CH 3), 3.64 ppm (s, 9 H, —OCH 3), 7.24-7.50 ppm (m, 3 H, Ar—H), 7.78 ppm (dd, J = 11.6, 8.8 Hz, 2H, Ar—H), 8.61 ppm (d, J = 8.8 Hz, 1H, Ar—H).

Synthesis example 2
Example of synthesis of 6-methoxy-2-naphthyltrimethoxysilane To a 500 mL four-necked flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 10.8 g (0.443 mol) of magnesium and 300 mL of tetrahydrofuran were added. The temperature was raised to 40 ° C. Next, a small amount of 1,2-dibromoethane was added as an initiator, and then 100.0 g (0.422 mol) of 2-bromo-6-methoxynaphthalene was added dropwise over 6 hours so as not to exceed 45 ° C. After completion of dropping, the mixture was aged at 40 to 45 ° C. for 2 hours to prepare a Grignard reagent.

  Next, in a 1000 mL four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 192.8 g (1.267 mol) of normal methyl silicate was charged, and the internal temperature of the can was raised to 80 ° C., Grignard reagent Was added dropwise at a temperature of 80 to 85 ° C. over 2 hours. After completion of dropping, the mixture was aged at 80 to 85 ° C. for 2 hours and then cooled, the magnesium salt was filtered, the solvent was distilled off, and 37.6 g (0.135 mol) of a fraction at 135 to 138 ° C. was obtained at a reduced pressure of 1 mmHg. . As a result of GC analysis of the obtained fraction, GC purity was 98.7%, and NMR and IR analysis showed that it was 6-methoxy-2-naphthyltrimethoxysilane.

  The spectrum data of the obtained compound is shown below.

Infrared absorption spectrum (IR) data ^{2838,2943cm -1 (-CH3, Ar),} 1080cm -1 (Si-O)
Nuclear magnetic resonance spectrum (NMR) data ( ¹ H-NMR solvent: CDCl 3)
3.63 ppm (s, 9H, Si-OCH3), 3.87 ppm (s, 3H, Ar-OCH3), 7.04-7.30 ppm (m, 3H, Ar-H), 7.77 ppm (dd, J = 11.6, 8.8 Hz, 2H, Ar-H), 8.60 ppm (d, J = 8.8 Hz, 1H, Ar-H).

Synthesis example 3
Example of synthesis of 1-acenaphthenyltriethoxysilane In a 200 mL four-necked flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 55.1 g (0.329 mol) of acenaphthylene and 0.1 mol / L were added. 0.83 mL of an isopropanol solution of chloroplatinic acid hexahydrate was added and heated to 80 ° C. When the yellow crystals of acenaphthylene were dissolved, 56.7 g (0.345 mol) of triethoxysilane was added dropwise at 80 to 85 ° C. Thereafter, aging was performed at 75 to 80 ° C. for 2 hours. Subsequently, distillation under reduced pressure was performed as it was, and a fraction of 130 to 140 ° C./0.5 mmHg was collected to obtain 63.4 g (0.200 mol) of a yellow transparent solution. As a result of GC analysis of the obtained fraction, GC purity was 96.9%. As a result of NMR and IR analysis, it was 1-acenaphthenyltriethoxysilane.

  The spectrum data of the obtained compound is shown below.

Infrared absorption spectrum (IR) data 2887-3043 cm ⁻¹ (—CH—, —CH 2 —, —CH 3, Ar), 1080-1101 cm ⁻¹ (Si—O)
Nuclear magnetic resonance spectrum (NMR) data ( ¹ H-NMR solvent: CDCl 3)
1.10 ppm (t, 9H, CH3), 3.19 ppm (t, 1H, Si-CH-), 3.57 ppm (s, 2H, Ar-CH2-), 3.71 ppm (q, 6H, Si-OCH3) ), 7.25-7.56 ppm (m, 6H, Ar-H).

Example 1
Synthesis of 1-naphthylsilsesquioxane (the following general formula)

  A 500 mL four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was charged with 75.1 g of toluene and 36.7 g of water, and 3.13 g (0.03 mol) of 35% hydrochloric acid was added. . Next, a solution of 75.1 g (0.302 mol) of 1-naphthyltrimethoxysilane in 37.5 g of toluene was added dropwise at 20 to 30 ° C. After completion of dropping, the mixture was aged at the same temperature for 2 hours. As a result of analyzing the reaction solution at this time by GC, it was found that no raw material remained. Next, toluene and water were added for extraction, and after washing with an aqueous sodium hydrogen carbonate solution, the solution was washed with water until the solution became neutral. The toluene oil layer was recovered and toluene was removed to obtain 57.6 g of the target white solid compound.

  The spectrum data of the obtained copolymer is shown below.

Infrared absorption spectrum (IR) data 1026-1151 cm ⁻¹ (Si—O), 2980-3080 cm ⁻¹ (C—H), 3080-3700 cm ⁻¹ (Si—OH)
Nuclear magnetic resonance spectrum (NMR) data ( ¹ H-NMR δ (ppm), solvent: CDCl ₃ )
7.19-8.43 (m, Ar)
GPC analysis data: Mw = 660, Mw / Mn = 1.14 (polystyrene conversion).

Example 2
Synthesis of 2-methyl-1-naphthylsilsesquioxane (the following general formula)

  A 500 mL four-necked flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer was charged with 79.3 g of toluene and 36.7 g of water, and 3.13 g (0.03 mol) of 35% hydrochloric acid was added. . Next, a solution of 79.3 g (0.302 mol) of 2-methyl-1-naphthyltrimethoxysilane in 39.3 g of toluene was added dropwise at 20 to 30 ° C. After completion of dropping, the mixture was aged at the same temperature for 2 hours. As a result of analyzing the reaction solution at this time by GC, it was found that no raw material remained. Next, toluene and water were added for extraction, and after washing with an aqueous sodium hydrogen carbonate solution, the solution was washed with water until the solution became neutral. The toluene oil layer was collected and toluene was removed to obtain 60.8 g of the target white solid compound.

  The spectrum data of the obtained copolymer is shown below.

Infrared absorption spectrum (IR) data 1025-1151 cm ⁻¹ (Si—O), 2979-3081 cm ⁻¹ (C—H), 3081-3700 cm ⁻¹ (Si—OH)
Nuclear magnetic resonance spectrum (NMR) data ( ¹ H-NMR δ (ppm), solvent: CDCl ₃ )
2.73 (s, 3H, -CH3), 7.19-8.43 (m, Ar)
GPC analysis data: Mw = 682, Mw / Mn = 1.14 (polystyrene conversion).

Example 3
Synthesis of 6-methoxy-2-naphthylsilsesquioxane (the following general formula)

  A 500 mL four-necked flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer was charged with 84.1 g of toluene and 36.7 g of water, and 3.13 g (0.03 mol) of 35% hydrochloric acid was added. . Next, a solution of 82.1 g (0.302 mol) of 2-methyl-1-naphthyltrimethoxysilane in 42.1 g of toluene was added dropwise at 20 to 30 ° C. After completion of dropping, the mixture was aged at the same temperature for 2 hours. As a result of analyzing the reaction solution at this time by GC, it was found that no raw material remained. Next, toluene and water were added for extraction, and after washing with an aqueous sodium hydrogen carbonate solution, the solution was washed with water until the solution became neutral. The toluene oil layer was recovered, and toluene was removed to obtain 64.6 g of the target white solid compound.

  The spectrum data of the obtained copolymer is shown below.

Infrared absorption spectrum (IR) data 1026-1151 cm ⁻¹ (Si—O), 1150-1170 cm ⁻¹ (Ar—O—CH 3), 2980-3080 cm ⁻¹ (C—H), 3080-3700 cm ⁻¹ (Si— OH)
Nuclear magnetic resonance spectrum (NMR) data ( ¹ H-NMR δ (ppm), solvent: CDCl ₃ )
3.86 (s, 3H, -OCH3), 7.10-8.23 (m, Ar)
GPC analysis data: Mw = 690, Mw / Mn = 1.15 (polystyrene conversion).

Example 4
Synthesis of 1-acenaphthenylsilsesquioxane (the following general formula)

  A 500 mL four-necked flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer was charged with 95.6 g of toluene and 36.7 g of water, and 3.13 g (0.03 mol) of 35% hydrochloric acid was added. . Next, a solution of 95.6 g (0.302 mol) of 1-acenaphthenyltriethoxysilane in 47.8 g of toluene was added dropwise at 20 to 30 ° C. After completion of dropping, the mixture was aged at the same temperature for 2 hours. As a result of analyzing the reaction solution at this time by GC, it was found that no raw material remained. Next, toluene and water were added for extraction, and after washing with an aqueous sodium hydrogen carbonate solution, the solution was washed with water until the solution became neutral. The toluene oil layer was recovered, and toluene was removed to obtain 73.4 g of the target white solid compound.

  The spectrum data of the obtained copolymer is shown below.

Infrared absorption spectrum (IR) data 1022-1150 cm ⁻¹ (Si—O), 2975-3085 cm ⁻¹ (C—H), 3085-3700 cm ⁻¹ (Si—OH)
Nuclear magnetic resonance spectrum (NMR) data ( ¹ H-NMR δ (ppm), solvent: CDCl ₃ )
3.00-3.20 ppm (m, Si-CH-), 3.20-3.50 ppm (m, Ar-CH2-), 7.19-8.20 (m, Ar)
GPC analysis data: Mw = 698, Mw / Mn = 1.14 (polystyrene conversion).

Comparative Example 1
Synthesis of phenylsilsesquioxane / methylsilsesquioxane copolymer (general formula below)

(50:50 in the structural formula is the molar ratio of the raw materials used)
A 500 mL four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer was charged with 50.6 g of toluene and 33.4 g of water, and 3.13 g (0.03 mol) of 35% hydrochloric acid was added. . Next, a solution of phenyltrimethoxysilane 30.0 g (0.151 mol) and methyltrimethoxysilane 20.6 g (0.151 mol) in toluene 25.3 g was added dropwise at 20 to 30 ° C. After completion of dropping, the mixture was aged at the same temperature for 2 hours. As a result of analyzing the reaction solution at this time by GC, it was found that no raw material remained. Next, toluene and water were added for extraction, and after washing with an aqueous sodium hydrogen carbonate solution, the solution was washed with water until the solution became neutral. The toluene oil layer was recovered, and toluene was removed to obtain 27.2 g of the target white solid compound.

  The spectrum data of the obtained copolymer is shown below.

Infrared absorption spectrum (IR) data ^{1028-1132cm -1 (Si-O),} 2970-3070 cm -1 (C-H), 3070-3700 cm -1 (Si-OH)
Nuclear magnetic resonance spectrum (NMR) data ( ¹ H-NMR δ (ppm), solvent: CDCl ₃ )
0.16 (bs), 7.00-7.57 (m), 7.57-7.90 (m)
GPC analysis data: Mw = 960, Mw / Mn = 1.25 (polystyrene conversion).

<Manufacture of insulation coating>
Example 5
The silicone compounds produced according to Example 1 and Comparative Example 1 were each dissolved in propylene glycol monomethyl ether acetate to prepare a solution so that the solid concentration was 40% by weight. Next, each solution was mixed so that the weight ratio of each silicone compound manufactured according to Example 1 and Comparative Example 1 was 30:70. The mixed solution was filtered with a PTFE filter, and applied on a silicon wafer or glass substrate by spin-coating for 30 seconds at a rotational speed such that the film thickness after removal of the solvent was 5.0 μm. Thereafter, the solvent was removed over 150 ° C./2 minutes, and then the film was finally cured over 350 ° C./30 minutes in a quartz tube furnace in which the O 2 concentration was controlled to less than 1000 ppm to obtain an insulating coating.

Example 6
The silicone compounds produced according to Example 1 and Comparative Example 1 were each dissolved in propylene glycol monomethyl ether acetate to prepare a solution so that the solid concentration was 40% by weight. Next, each solution was mixed so that the weight ratio of each silicone compound produced according to Example 1 and Comparative Example 1 was 10:90. The mixed solution was filtered with a PTFE filter, and applied on a silicon wafer or glass substrate by spin-coating for 30 seconds at a rotational speed such that the film thickness after removal of the solvent was 5.0 μm. Thereafter, the solvent was removed over 150 ° C./2 minutes, and then the film was finally cured over 350 ° C./30 minutes in a quartz tube furnace in which the O 2 concentration was controlled to less than 1000 ppm to obtain an insulating coating.

Example 7
A final cured insulating coating was obtained in the same manner as in Example 5 except that “silicone compound produced according to Example 1” described in Example 5 was changed to “silicone compound produced according to Example 2”. It was.

Example 8
A final cured insulating coating was obtained in the same manner as in Example 5 except that “silicone compound produced according to Example 1” described in Example 5 was changed to “silicone compound produced according to Example 3”. It was.

Example 9
A final cured insulating coating was obtained in the same manner as in Example 5 except that “silicone compound produced according to Example 1” described in Example 5 was changed to “silicone compound produced according to Example 4”. It was.

Comparative Example 2
The silicone compound produced according to Comparative Example 1 was dissolved in propylene glycol monomethyl ether acetate to prepare a solution so that the solid concentration was 40% by weight. The prepared solution was filtered through a PTFE filter and applied on a silicon wafer or glass substrate by spin-coating for 30 seconds at a rotational speed such that the film thickness after removal of the solvent was 5.0 μm. Thereafter, the solvent was removed over 150 ° C./2 minutes, and then the film was finally cured over 350 ° C./30 minutes in a quartz tube furnace in which the O 2 concentration was controlled to less than 1000 ppm to obtain an insulating coating.

<Evaluation results>
Table 1 below shows each evaluation result of the insulating film and a comprehensive evaluation based thereon.

  Thus, the film surface is greatly improved by adding a silicone polymer having a naphthalene ring. The silicone polymer having a naphthalene ring in the present invention is further improved in crack resistance and is a material that can be used for other applications.

Claims (3)

The following general formula

(In the formula, R represents a hydrocarbon group having a naphthalene ring.)
A silicone polymer having a naphthalene ring having a weight average molecular weight of 500 to 8,000 and a dispersity of 1.1 to 1.8. The following general formula

(In the formula, R represents a hydrocarbon group having a naphthalene ring, and X represents a hydrolyzable group.)
The manufacturing method of the silicone polymer which has a naphthalene ring which hydrolyzes the monomer shown by above on acidic conditions, and manufactures the silicone polymer which has a naphthalene ring of Claim 1. The silicone polymer having a naphthalene ring according to claim 1 , 30% by weight, and the following general formula

(In the formula, A represents a hydrocarbon group having an aromatic hydrocarbon group, B represents an aliphatic hydrocarbon group, m and n represent mol%, and 40 ≦ m and n ≦ 60. However, m + n = 100.)
A silicone polymer comprising 70% by weight of a silicone polymer comprising a repeating unit represented by the formula: