JP2001354853A - Material composition having high refractive index - Google Patents

Abstract

PROBLEM TO BE SOLVED: To develop a high refractive index-having material composition having a >=1.70 refractive index and a >=150 deg.C glass transition temperature. SOLUTION: This high refractive index-having material composition having a >=1.70 refractive index and a >=150 deg.C glass transition temperature comprises a polyimide expressed by general formula (I) and inorganic fine particles having 1-100 nm average particle size.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has a high refractive index,
Specifically, the present invention relates to a high refractive index material composition that can be suitably used for an optical lens, an antireflection film, and the like.

[0002]

2. Description of the Related Art In recent years, plastic optical materials are lighter, harder to crack, and easier to process than inorganic materials.
It is rapidly spreading as an optical element such as a spectacle lens and a camera lens.

A resin widely used for these purposes at present is, for example, a resin obtained by radical polymerization of diethylene glycol bisallyl carbonate, as disclosed in JP-A-61-28513. This resin is
It is said to be excellent in heat resistance, high refraction, low shrinkage, and releasability. However, the refractive index of this resin is 1.51
The resin has a low glass transition temperature of 87 ° C., which is as low as 1.53, and cannot be used in applications exposed to high temperatures (150 ° C. or more), such as lenses for laser printers, due to insufficient heat resistance. There was also a drawback.

On the other hand, for use as an optical multilayer film (selective reflection film, selective transmission film, etc.), a higher refractive index (for example,
(A refractive index of 1.70 or more) is required, but there are few plastic materials having such a high refractive index, and high refractive index materials generally have problems of transparency and adhesion. There was a problem that it was not suitable.

[0005] For this reason, the optical multi-layer film currently used is formed by vapor deposition of an inorganic material, and it is difficult to vapor-deposit a large area and the cost is high. It has not yet been used. Therefore, there has been an increasing demand for a plastic high-refractive-index material capable of forming a coating film by a simple coating method.

[0006]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned conventional problems.
It has a high refractive index of 1.70 or more, and has excellent heat resistance,
It is to provide a high refractive index material composition having a glass transition temperature of 150 ° C. or higher.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. As a result, 100 parts by weight of a polyimide having a specific structure and an inorganic particle having an average particle diameter of 1 to 100 nm were obtained. The resin composition comprising 10 to 400 parts by weight of fine particles is transparent and has a refractive index of 1.70 or more.2.
The present inventors have found that they have a high refractive index of 50 or less and have a glass transition temperature of 150 ° C. or more, and have completed the present invention.

That is, the present invention relates to a compound represented by the general formula (I):
High molecular weight compound 1 having a repeating unit structure represented by
1.70 parts by weight and 10 to 400 parts by weight of inorganic fine particles having an average particle diameter of 1 to 100 nm.
The present invention provides a high refractive index material composition having a glass transition temperature of 150 ° C. or higher at 50 or lower. That is, the invention according to the present application is specified by the following items [1] to [7].

[0009]

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[1] 100 parts by weight of a high molecular weight compound having a repeating unit structure represented by the general formula (I) [formula 2] and inorganic fine particles 10 to 4 having an average particle diameter of 1 to 100 nm
A high-refractive-index material composition having a refractive index of 1.70 or more and 2.50 or less and a glass transition temperature of 150 ° C. or more, comprising 00 parts by weight.

[2] The high refractive index material composition according to [1], wherein the inorganic fine particles are oxide fine particles.

[3] The high refractive index material composition according to [1], wherein the inorganic fine particles are sulfide fine particles.

[4] The high refractive index material composition according to [1], wherein the inorganic fine particles are selenide fine particles.

[5] The high refractive index material composition according to [1], wherein the inorganic fine particles are telluride fine particles.

[6] The high refractive index material composition according to [2], wherein the oxide fine particles are titanium oxide.

[7] The high refractive index material composition according to [3], wherein the sulfide fine particles are zinc sulfide.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Polyimide which is a high molecular weight compound having a repeating unit structure represented by the general formula (I) [Chemical Formula 3], which constitutes the high refractive material composition of the present invention, has, for example, the following general formula (I) II) It can be obtained by reacting a diphenyl ether tetracarboxylic dianhydride represented by [Chemical Formula 4] with an aromatic diamine compound represented by General Formula (III) [Chemical Formula 5].

[0018]

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[0019]

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[0020]

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Examples of the above diphenyl ether tetracarboxylic dianhydride include 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride and 2,3,3', 4-diphenyl ether tetracarboxylic dianhydride. Can be These diphenyl ether tetracarboxylic dianhydrides may be used alone or in combination as appropriate. Examples of the aromatic diamine compound include 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 1,3-bis (3-aminophenoxy) benzene, and 1,3-bis (4-aminophenoxy) benzene , 2,6-bis (3-aminophenoxy) benzonitrile, 1,3-bis (3-aminophenoxy) -5-chlorobenzene, 4,4'-bis (3-aminophenoxy) diphenyl sulfide, 4,4 ' -Bis (4-aminophenoxy) diphenyl sulfide, 4,4'-bis (3-
Aminophenoxy) biphenyl and 4,4'-bis (4-aminophenoxy) biphenyl. These aromatic diamine compounds may be used alone or in combination as appropriate.

By combining the above diphenyl ether tetracarboxylic dianhydride with an aromatic diamine compound, a polyimide having a repeating unit structure represented by the general formula (I) [formula 3] can be obtained for the first time. When the proportion of the repeating unit structure represented by the general formula (I) [formula 3] is at least 80 mol%, the performance as a polymer compound that can be used in the high refractive index material composition of the present invention will be improved. Since it is ensured, within the range, it is also possible to use other aromatic tetracarboxylic dianhydrides other than the above diphenyl ether tetracarboxylic dianhydride and other aromatic tediamine compounds other than the above-described aromatic diamines in combination. it can. However, the general formula (I)
The preferred content of the repeating unit structure represented by Chemical Formula 3 is at least 80 mol%, and the most preferable range is at least 95 mol%.

The other aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3'4,4 '
-Benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'
-Biphenyltetracarboxylic dianhydride, 2,3,3 ', 4-biphenyltetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride,
2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride Anhydrides can be used, and these can be used alone or in combination.

Further, as other diamine compounds,
4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone , 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylpropane, p-phenylenediamine, 4,4'-diaminodiphenyl sulfide, 3,3'-dimethoxy-4,4'-diaminodiphenylmethane, 3,3 '-Dimethyl-4,4'-diaminodiphenylmethane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 4-bis (3-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl]
-1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (3
-Aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane and the like, and can be used alone or in combination.

The high refractive material composition of the present invention is substantially composed of a high molecular weight compound having a repeating unit structure of the general formula (I) [formula 3] and inorganic fine particles having an average particle diameter of 1 to 100 nm. However, the composition ratio is 10 to 400 parts by weight, preferably 10 to 100 parts by weight of inorganic fine particles with respect to 100 parts by weight of the polymer compound having a repeating unit structure represented by the general formula. Content of inorganic fine particles is 1
If it is less than 0 parts by weight, a high refractive index material having a refractive index of 1.70 or more cannot be obtained, and if it exceeds 400 parts by weight, the moldability of the resin composition and the transparency of the obtained molded article are impaired. Cause When the average particle diameter of the inorganic fine particles used is less than 1 nm, aggregation of the inorganic fine particles or the like causes
It is difficult to uniformly disperse the inorganic fine particles in the composition, causing non-uniformity of the refractive index, and cannot be used as an optical material. Further, when the average particle diameter of the inorganic fine particles used exceeds 100 nm, the light transmittance is reduced and the inorganic fine particles cannot be used as an optical material.

According to the present invention, the refractive index is 1.70 or more and 2.50.
The following melt-moldable high-refractive-index material composition can be obtained. However, in consideration of the melt fluidity and the transparency of the molded product, the refractive index is preferably from 1.70 to 2.20.

The high molecular weight compound used in the high refractive index material composition of the present invention may be a polyimide in the form of the general formula (I) [formula 3] or a polyimide of the general formula (IV) [formula 6]. It can be used in the form of a precursor polyamic acid.

[0028]

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Polyamic acid, which is a precursor of polyimide, can be obtained by polymerizing the above aromatic tetracarboxylic dianhydride and an aromatic diamine compound. This polyamic acid formation reaction is usually carried out in an organic solvent. Organic solvents that can be used in this reaction include, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-
Diethylacetamide, N, N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, 1,2-dimethoxyethane, bis (2-methoxyethyl) Ether, 1,2-bis (2-methoxyethoxy) ethane, bis {2- (2-methoxyethoxy) ethyl} ether, tetrahydrofuran, 1,3
-Dioxane, 1,4-dioxane, pyridine, picoline,
Dimethyl sulfoxide, dimethyl sulfone, tetramethyl urea, hexamethyl phosphoramide, m-cresol,
p-cresol, cresylic acid, p-chlorophenol, o-
Chlorophenol, phenol, anisole and the like can be mentioned.

These organic solvents may be used alone or in combination of two or more. The reaction temperature is usually at most 200 ° C, preferably at most 50 ° C. The reaction pressure is not particularly limited, and the reaction can be sufficiently performed at normal pressure (for example, 0.8 to 1.2 atm). The reaction time varies depending on the type of the solvent and the reaction temperature, and the reaction is usually performed for a time sufficient to complete the formation of the polyamic acid represented by the general formula (IV) [Formula 6]. Usually 4 to 24 hours is sufficient. By such a reaction, a polyamic acid having a repeating structural unit represented by the general formula (IV) [Formula 7] is obtained.

[0031]

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The logarithmic viscosity of polyamic acid which is a precursor of polyimide which is a high molecular weight compound which can be used in the high refractive index material composition of the present invention is 0.1 to 4.0 dl / g.
And preferably 0.3 to 1.0 dl / g. When the logarithmic viscosity is less than 0.3 dl / g, the mechanical strength of the optical material obtained using the high refractive index material composition is not sufficient. It is not preferable because the coatability as a multilayer film is reduced.

Further, the obtained polyamic acid is mixed with 100 to 4
A polyimide having a repeating unit structure represented by the general formula (I) [formula 8] can be obtained by heating to 00 ° C. for imidization or by chemically imidizing using an imidizing agent such as acetic anhydride.

[0034]

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The above-mentioned aromatic tetracarboxylic dianhydride and an aromatic diamine compound are suspended or dissolved in an organic solvent and then heated to produce polyamic acid, a precursor of polyimide, and imidize by dehydration. Can be obtained at the same time to obtain a polyimide having a repeating unit of the general formula (I) [formula 8]. In this polymerization reaction involving imidization, the polymerization temperature is usually in the range of 80 to 400 ° C, preferably in the range of 100 to 350 ° C.
When the reaction temperature is lower than the above temperature range, the intended polymerization reaction does not proceed at a speed that can withstand practical use, and it is difficult to obtain a high molecular weight compound having a required molecular weight. On the other hand, if the reaction temperature is higher than the above range, side reactions other than the intended polymerization reaction cannot be ignored, and the resulting high molecular weight compound will be significantly colored or the melt moldability will be greatly impaired. The time required for the polymerization reaction varies depending on the type of the reaction raw material components and the like, but is usually in the range of 10 minutes to 100 hours, preferably in the range of 1 hour to 24 hours. In the production of the high molecular weight compound, it is preferable that oxygen is not present as an atmosphere in which the reaction is performed, and good results can be obtained when the reaction is performed in an inert gas such as nitrogen. This is because the amino group of the aromatic diamine is easily oxidized when heated in the presence of oxygen, which hinders the intended polymerization reaction and makes it difficult to increase the molecular weight, or causes coloring of the resulting high molecular weight compound. This is because Therefore, a reducing agent or the like can be used in combination for the purpose of suppressing coloring when producing a high molecular weight compound. That is, a polyimide having a film-like or powder-like repeating unit structure can be obtained by a conventionally known technique.

The types of the inorganic fine particles used in the present invention include TiO ₂ , ZnO, CdO, PbO, SiO ₂ , S
oxide fine particles such as b ₂ O ₅ , CdS, CdSe, ZnS
e, CdTe, ZnS, HgS, HgSe, PdS, S
Examples include sulfide such as bSe, selenide, and telluride fine particles.

The average particle diameter of 1~100nm inorganic fine particles used in the high refractive index material composition of the present invention there are various manufacturing methods for each compound but, for example, TiO ₂
, Journal of Chemical Engineering of Japan, Vol. 1, No. 1, pp. 21-28 (1998)
) Or ZnS, Journal of Physical Chemistry, Vol. 100, pp. 468-471 (1996).
) Can be used.

For example, according to these methods, titanium oxide having an average particle diameter of 5 nm can be converted to titanium tetraisopropoxy.
It can be easily produced by using de or titanium tetrachroride as a raw material and adding an appropriate surface modifier when hydrolyzing in an appropriate solvent. Zinc sulfide having an average particle diameter of 40 nm is dimethyl zinc or zinc per
It can be manufactured by adding a surface modifier when sulfide is used as a raw material and sulfurized with hydrogen sulfide or sodium sulfide. The high refractive index material composition of the present invention can be obtained by dispersing inorganic fine particles having an average particle diameter of 1 to 100 nm in a high molecular weight compound represented by the general formula (I) [Formula 9].

[0039]

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As a method for dispersing the inorganic fine particles, the inorganic fine particles are kneaded with the molten high molecular weight compound. After the inorganic fine particles are dispersed in the solution in which the high molecular weight compound is dissolved, the solvent is removed. Chemical bonding to high molecular weight compounds. Etc., but any of them is effective.

The glass transition temperature of the high refractive index material composition of the present invention is 150 ° C. or higher. In consideration of moldability, the temperature is more preferably 150 ° C. or more and 300 ° C. or less.

The method for obtaining an eyeglass lens, an optical lens, an optical element or the like using the high refractive index material composition in the present invention includes, for example, injection molding, extrusion molding, hot press molding of the high refractive index material composition. And a method of dissolving the high refractive index material composition in a solvent such as dimethylformamide, and then forming the solution into a film or the like by a casting method.

[0043]

The present invention will be further described with reference to Synthesis Examples, Examples and Comparative Examples.

<Synthesis Example 1> In a reactor equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen inlet tube, 20.02 g (0.10 mol) of 3,3'-diaminodiphenyl ether, 3,3 ', 4, Four'-
Charge 30.71 g (0.099 mol) of diphenyl ether tetracarbodianhydride, 0.296 g (0.002 mol) of phthalic anhydride and 280 g of N, N-dimethylacetamide and stir at room temperature under a nitrogen atmosphere for about 12 hours. did. The polyamic acid solution thus obtained was diluted with N, N-dimethylacetamide to a concentration of 0.5 g / dl, and the logarithmic viscosity η measured at 35 ° C. was 0.72 dl / g. After taking a part of this polyamic acid solution and casting it on a glass plate,
The resultant was heated at 250 ° C. for 2 hours to obtain a polyimide film. The glass transition temperature Tg of this polyimide film was 209 ° C. as measured using DSC (Shimadzu DT-40 Series, DSC-41M).

<Synthesis Example 2> 20.02 g (0.10 mol) of 3,3'-diaminodiphenyl ether in Synthesis Example 1 was 3,4 '
-Diaminodiphenyl ether 20.02 g (0.10 mol)
A polyamic acid was obtained in the same manner as in Synthesis Example 1 except that the polyamic acid was changed. The logarithmic viscosity η of the obtained polyamic acid was 0.60 dl / g. The Tg of the polyimide measured in the same manner as in Synthesis Example 1 was 233 ° C.

Synthesis Example 3 20.02 g (0.10 mol) of 3,3′-diaminodiphenyl ether in Synthesis Example 1 was 1,3-
Bis (3-aminophenoxy) benzene 29.23 g (0.1
0 mol) to obtain a polyamic acid in the same manner. Η of the obtained polyamic acid was 0.76 dl / g. The Tg of the polyimide obtained from this polyamic acid is 17
7 ° C.

Synthesis Example 4 20.02 g (0.10 mol) of 3,3′-diaminodiphenyl ether in Synthesis Example 1 was 1,3-
A polyamic acid was obtained in the same manner except that bis (4-aminophenoxy) benzene was changed to 29.23 g (0.10 mol).
Η of the obtained polyamic acid was 0.94 dl / g. The Tg of the polyimide obtained from this polyamic acid is 213 ° C.
Met.

Synthesis Example 5 20.02 g (0.10 mol) of 3,3′-diaminodiphenyl ether in Synthesis Example 1 was added to 2,6-
Bis (3-aminophenoxy) benzonitrile 31.74g
(0.10 mol), except that the polyamic acid was obtained. Η of the obtained polyamic acid was 0.91 dl / g. In addition, the polyimide obtained from this polyamic acid
Tg was 212 ° C.

<Synthesis Example 6> 20.02 g (0.10 mol) of 3,3'-diaminodiphenyl ether in Synthesis Example 1 was 1,3-
Bis (3-aminophenoxy) -5-chlorobenzene 32.68 g
(0.10 mol), except that the polyamic acid was obtained. Η of the obtained polyamic acid was 0.69 dl / gd. The Tg of the polyimide obtained from this polyamic acid was 182 ° C.

Synthesis Example 7 20.02 g (0.10 mol) of 3,3′-diaminodiphenyl ether in Synthesis Example 1 was 4,4 ′
36.85 g of bis- (4-aminophenoxy) biphenyl (0.1
0 mol) to obtain a polyamic acid in the same manner. Η of the obtained polyamic acid was 1.33 dl / g. The Tg of the polyimide obtained from this polyamic acid is 24
7 ° C.

<Synthesis Example 8> 20.02 g (0.10 mol) of 3,3'-diaminodiphenyl ether in Synthesis Example 1 was 4,4 '
36.85 g of -bis (3-aminophenoxy) biphenyl (0.
10 mol) to obtain a polyamic acid in the same manner. Η of the obtained polyamic acid was 0.93 dl / g.
The Tg of the polyimide obtained from this polyamic acid is 2
It was 11 ° C.

Synthesis Example 9 20.02 g (0.10 mol) of 3,3′-diaminodiphenyl ether in Synthesis Example 1 was 4,4 ′
-Bis (4-aminophenoxy) diphenyl sulfide 40.05
Polyamide acid was obtained in the same manner except that the amount was changed to g (0.10 mol). Η of the obtained polyamic acid was 0.82 dl / g. The Tg of the polyimide obtained from this polyamic acid was 212 ° C.

Synthesis Example 10 20.03 g (0.01 mol) of 3,3′-diaminodiphenyl ether in Synthesis Example 1 was added to 4,
4'-bis (3-aminophenoxy) diphenyl sulfide 4
A polyamic acid was obtained in the same manner except that the amount was changed to 0.05 g (0.01 mol). Η of the obtained polyamic acid is 0.91 dl
/ g. The Tg of the polyimide obtained from this polyamic acid was 179 ° C.

<Synthesis Example 11> A container equipped with a stirrer, a reflux condenser, a water separator, a thermometer and a nitrogen inlet tube was charged with 1,3-bis.
(3-aminophenoxy) benzene 29.23 g (0.10 mol), 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride 28.81 g (0.098 mol), phthalic anhydride 0.59
4 g (0.004 mol) and 262 g of m-cresol were charged,
The mixture was heated to 202 ° C. while stirring under a nitrogen atmosphere. During this time, outflow of about 3.5 cc of water was confirmed. Further, the reaction was performed at 202 ° C. for 4 hours. Thereafter, the mixture was cooled to room temperature and discharged into about 3 liters of methanol, and then the polyimide powder was separated by filtration. After washing this polyimide powder with methanol, it was dried at 200 ° C. under a nitrogen atmosphere.
5 g (99.0% yield) of polyimide powder was obtained. The logarithmic viscosity η of the polyimide thus obtained was 0.51 dl / g. still,
This logarithmic viscosity is obtained by mixing 0.50 g of polyimide powder with 100 ml of a mixed solvent of p-chlorophenol / phenol (weight ratio: 9/1).
This is a value measured at 35 ° C. after heating and dissolving in water.
The Tg of this polyimide powder measured by DSC was 175 ° C.
Met. The obtained polyimide powder was dissolved in cyclopentanone at a concentration of 20% by weight, and a thin film of about 10 μm was obtained on a silicon wafer by a usual spin coating method. The refractive index at 633 nm of this thin film measured by the prism coupling method was 1.68.

<Synthesis Example 12> Japanese Journal of Appl
ied Physics, 37 (1998), 4603-46
9.2 mol of TiOCl ₂ by the method described on page 08
/ L aqueous solution is prepared. ₂ m of the obtained TiOCl ₂ solution
is dissolved in 17.4 ml of ion-exchanged water. This solution 1
0 ml of tridecanoic acid 0.96 g and 12-aminododecanoic acid 0.11 g of ethanol 150 ml and ion-exchanged water 1
Dissolve in 00ml and add to the solution heated to 60 ° C and stir for 30 minutes. The resulting gel precipitate is centrifuged (400
0 rpm, 2 minutes) and take out ethyl acetate 15m
l, stirred and centrifuged again (4000 rpm, 2 minutes) to obtain about 7% by weight of the surface amino-modified TiO ₂ fine particles.
Was obtained. The average particle diameter was 5 nm as a result of observation with an electron microscope.

<Synthesis Example 13> 100 ml of 3 × 10 ⁻⁴ M zinc perchlorate hexahydrate in alkaline acetonitrile
Through 5% hydrogen sulfide gas helium dilution, 5 × 10 ^-4
M dodecanethiol in acetonitrile 100 ml
Was added. 200 ml of hexane was added thereto, and after removing the solvent and drying, surface-modified ZnS (0.3 g of net ZnS) was obtained. From the measurement of the infrared spectrum and the X-ray diffraction spectrum, it was confirmed that zinc sulfide fine particles whose surface was modified with dodecanethiol were obtained. Average particle diameter is 40
nm.

Example 1 1 g of the surface-modified titanium oxide synthesized in Synthesis Example 12 was weighed in a net amount of titanium oxide and 200 ml.
Was dissolved in dimethylacetamide. The polyamic acid (1 g of imide equivalent) synthesized in Synthesis Example 1 was mixed with the solution and stirred for 5 hours. After confirming that it became a homogeneous solution,
The solution was concentrated to 10 ml using a rotary evaporator. This solution was applied on a silicon wafer by a usual spin coating method. Thereafter, by heating at 250 ° C. for 2 hours, about 10 μm
Thus, a thin film having a thickness of m was obtained. Using this thin film, the refractive index at 633 nm was measured by the prism coupling method to be 1.88. This solution was applied on a glass plate and heated at 250 ° C. for 2 hours to obtain a film having a thickness of about 50 μm. This film was colorless and transparent. When the glass transition temperature Tg of this film was measured in the same manner as in Synthesis Example 1, it was 209 ° C.

<Example 2> 1 g of the surface-modified zinc sulfide synthesized in Synthesis Example 13 was weighed,
Dissolved in ml of dimethylacetamide. Similarly, 1 g of the polyimide synthesized in Synthesis Example 11 was dissolved in 200 ml of dimethylacetamide, and these solutions were mixed and stirred for 5 hours. Then, after concentrating using a rotary evaporator, it was discharged into 500 ml of methanol to obtain a polymer powder. After the polymer powder was separated by filtration, the polymer powder was dried under reduced pressure at 100 ° C. for 5 hours. Obtained polymer powder at 300 ° C., 9.8 MP
a) to give a film. This film was colorless and transparent. After dissolving this polymer in cyclopentanone, it is applied on a silicon wafer by a usual spin coating method, and after drying, 633 nm is obtained by a prism coupling method.
The measured refractive index at m was 1.84. The glass transition temperature Tg of this film was 175 ° C. as measured in the same manner as in Synthesis Example 1.

<Examples 3 to 11> Using the polyamic acid obtained in Synthesis Examples 2 to 10, the refractive index, the transparency of the film, and the glass transition temperature Tg were evaluated according to the method of Example 1. Table 1 summarizes the results depending on the type of inorganic fine particles used, the average particle diameter, and the amount added.

<Comparative Examples 1 to 5> Using the polyamic acids of Synthesis Examples 2 and 3, the refractive index, the transparency of the film, and the glass transition temperature Tg were evaluated according to the method of Example 1. Table 1 also shows the results depending on the type of the inorganic particles used, the average particle diameter, and the amount added.

[0061]

According to the present invention, a polyimide composed of diphenyl ether tetracarboxylic dianhydride, a diamine compound having a specific structure, and inorganic fine particles having an average particle diameter of 1 to 100 nm have a refractive index of 1.70 or more and a glass transition temperature of 150 ° C. The above high refractive index material composition is provided.

[0062]

[Table 1]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G02B 1/04 G02B 1/04 G02C 7/02 G02C 7/02 (72) Inventor Yoshihiro Sakata Mayor of Sodegaura, Chiba Prefecture 580-32 Uraji Takuji 32 Mitsui Chemicals, Inc. (72) Inventor Yuichi Okawa Takuji Nagaura, Sodegaura-shi, Chiba 580-32 Mitsui Chemicals, Inc. No. 580 32 Mitsui Chemicals, Inc. F-term (reference) 4J002 CM041 DE096 DE106 DE126 DE136 DE156 DG026 DG066 DJ016

Claims (7)

[Claims] 1. A refractive index 1 comprising 100 parts by weight of a high molecular weight compound having a repeating unit structure represented by the general formula (I) [Formula 1] and 10 to 400 parts by weight of inorganic fine particles having an average particle diameter of 1 to 100 nm. A high-refractive-index material composition having a glass transition temperature of 150 ° C. or higher and 70 to 2.50. Embedded image 2. The high refractive index material composition according to claim 1, wherein the inorganic fine particles are oxide fine particles. 3. The high refractive index material composition according to claim 1, wherein the inorganic fine particles are sulfide fine particles. 4. The high refractive index material composition according to claim 1, wherein the inorganic fine particles are selenide fine particles. 5. The high refractive index material composition according to claim 1, wherein the inorganic fine particles are telluride fine particles. 6. The high refractive index material composition according to claim 2, wherein the oxide fine particles are titanium oxide. 7. The sulfide fine particle is zinc sulfide.
The high refractive index material composition described in the above.