JP4204435B2 - Transparent polyimide silicone resin containing thermosetting groups - Google Patents

Description

  The present invention relates to a thermosetting resin composition, particularly a thermosetting group capable of obtaining a cured film excellent in heat resistance, mechanical strength, solvent resistance and adhesion to various substrates by heat treatment in a low temperature for a short time. Furthermore, the present invention relates to a polyimide resin that is excellent in transparency in the visible light region and is soluble in a solvent.

  Polyimide resins are widely used as resin varnishes for electronic parts and the like because of their excellent heat resistance and electrical insulation. However, the polyimide resin only dissolves in a limited high boiling point organic solvent. Therefore, in general, it is a polyimide precursor, which is applied to a substrate in a polyamic acid state that is relatively easily soluble in various organic solvents, and then subjected to heat treatment at a temperature of 300 ° C. or higher for a long time, thereby dehydrating. , Imidize. However, this method requires heating at a high temperature for a long time in order to dehydrate the polyamic acid to form a polyimide. Therefore, the base material is likely to be thermally deteriorated. If the heating is insufficient, the polyamic acid remains in the structure of the resulting resin, which causes a decrease in moisture resistance, corrosion resistance, and the like.

On the other hand, after applying a solution of a polyimide resin soluble in an organic solvent instead of a polyamic acid to a substrate, a method of volatilizing the solvent by heating to form a polyimide resin film is known (for example, And Patent Documents 1 to 4). However, the resin film obtained by using a polyimide resin soluble in these organic solvents has a drawback of poor solvent resistance. Therefore, a thermosetting polyimide resin composition (see Patent Document 5) is obtained in which a cured polyimide resin film having good adhesion and solvent resistance can be obtained by heat treatment at a relatively low temperature for a short time.

  On the other hand, the polyimide resin has excellent physical properties, but is colored, so the usage is limited and there is a strong demand for a polyimide resin that is colorless and transparent. At present, transparent polyimide resins have been used for liquid crystal alignment films and the like, but these are all thermoplastic polyimide resins and have insufficient heat resistance.

JP 61-83228 A JP 61-118424 A Japanese Patent Laid-Open No. 61-118425 JP-A-2-36232 JP-A-10-195278

  Therefore, the present study contains a thermosetting group that can obtain a cured film excellent in heat resistance, mechanical strength, solvent resistance and adhesion to various substrates by heat treatment in a low temperature for a short time, and from a wavelength of 400 nm. An object of the present invention is to provide a polyimide silicone resin which is excellent in transparency in a so-called visible light region of 700 nm and is soluble in a solvent.

As a result of intensive studies to achieve the above object, the present inventors have found that the above object can be achieved by introducing a specific molecular structure into the polyimide resin. That is, the present invention contains a structural unit represented by the structural unit formula represented by the following general formula (1) (4), Ri soluble der in an organic solvent, the thickness on a glass plate having a thickness of 1mm The thermosetting polyimide silicone resin is characterized in that the light transmittance at a wavelength of 400 nm to 700 nm measured with a 10 μm film is 80% or more .

［式中、Ｘは、脂肪族テトラカルボン酸二無水物残基、芳香環を有する脂肪族テトラカルボン酸二無水物残基、または脂環式テトラカルボン酸二無水物残基であり、Ｙは一般式（２）で表されるジアミン残基である］

[Wherein, X is an aliphatic tetracarboxylic dianhydride residue, an aliphatic tetracarboxylic dianhydride residue having an aromatic ring , or an alicyclic tetracarboxylic dianhydride residue, and Y is It is a diamine residue represented by the general formula (2)]

（式中、Ｒ^１からＲ^６は水素原子または炭素数１から６のアルキル基であり、これらは同一でも異なっていてもよい。）

(Wherein R ¹ to R ⁶ are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and these may be the same or different.)

［式中、Ｘは上記のとおりであり、Ｚは一般式（５）で表されるジアミン残基である

[Wherein, X is as defined above, Z is is a diamine residue of the general formula (5)

（式中のＲ^９からＲ^１２は炭素数１から８の置換または非置換の一価の炭化水素基であり、これらは同一でも異なっていてもよい。また、ａは１以上１００以下の整数である。）］

(In the formula, R ⁹ to R ¹² are substituted or unsubstituted monovalent hydrocarbon groups having 1 to 8 carbon atoms, and these may be the same or different. A is an integer of 1 to 100. ]]]

In a preferred embodiment, the diamine residue represented by the general formula (2) or (3) is 5 mol% or more and 95 mol% or less with respect to the diamine residue , and the diamine residue represented by the general formula (5) is It is 5 mol% or more and 95 mol% or less. X is a group represented by the following formula.

Moreover, this invention is a semiconductor device using the said polyimide silicone resin , for example, a display apparatus.

  The solvent-soluble and thermosetting transparent polyimide silicone resin of the present invention is a cured polyimide resin film having excellent heat resistance, mechanical strength, solvent resistance, and adhesion to various substrates by low-temperature, short-time heat treatment. It is useful in color filters, light emitting diodes, laser diode protective films, liquid crystal alignment films, liquid crystal display devices, and other electronics and optical fields in semiconductor devices.

The present invention will be described in detail below.
The polyimide silicone resin of the present invention is a reaction product of tetracarboxylic dianhydride and diamine, and the reaction product structure contains a thermosetting group, is soluble in an organic solvent, is transparent. It is characterized by being.

  As the thermosetting group, a carboxyl group, an amino group, an epoxy group, a hydroxyl group, etc. are generally known, but a phenol group is selected because it does not easily react with a carboxyl group and an amino group in consideration of the production process of polyimide. Is done.

A diamine that is a raw material of the polyimide silicone resin synthesized in the present invention will be described. As a preferred embodiment of the present invention, a diamine residue containing a phenol group is used. For example, those represented by the general formula (A) or the general formula (B) and having a diamine residue are used in the present invention.

式中、Ｒ^１からＲ^６は水素原子または炭素数１から６のアルキル基であり、これらは同一でも異なっていてもよい。上記Ｒ^１〜Ｒ^６としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基基等のアルキル基が挙げられるが、中でもメチル基が好ましい。

In the formula, R ¹ to R ⁶ are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, which may be the same or different. Examples of R ^{1 to} R ⁶ include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and among them, a methyl group is preferable.

式中、Ｒ^７、Ｒ^８は水素原子または炭素数１から６のアルキル基であり、これらは同一でも異なっていてもよい。上記Ｒ^７〜Ｒ^８としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基基等のアルキル基が挙げられるが、中でもメチル基が好ましい。

In the formula, R ⁷ and R ⁸ are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and these may be the same or different. Examples of R ^{7 to} R ⁸ include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Among them, a methyl group is preferable.

  The diamine residue containing a phenol group may be contained in an amount of 5 mol% to 95 mol% in all diamine residues, and preferably 20 mol% to 80 mol%. If the content is as small as 5 mol% or less, for example, the crosslinking density when cured with epoxy or the like is lowered, so that the curing is insufficient and the solvent resistance is lowered. Moreover, when there is much content as 95 mol% or more, content of diaminosiloxane will decrease and the solubility to an organic solvent and the adhesiveness with respect to a base material will fall.

  The present invention is characterized in that a diamine residue further containing a diaminosiloxane residue is used as a preferred embodiment. For example, what is represented by the general formula (C) is used in the present invention.

式中のＲ^９からＲ^１２は非置換または置換の炭素原子数１〜８の１価炭化水素基、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基基等のアルキル基、シクロペンチル基、シクロヘキシル基等のシクロアルキル基、フェニル基、キシリル基等のアリール基、ベンジル基、フェネチル基等のアラルキル基、３，３，３−トリフルオロプロピル基、３−クロロプロピル基等のハロゲン化アルキル基、２−（トリメトキシシリル）エチル基等のトリアルコキシシリル化アルキル基等の他、メトキシ基、エトキシ基、プロポキシ基等のアルコキシ基、フェノキシ基等のアリーロキシ基、シアノ基等を挙げることができる。中でもメチル基、エチル基またはフェニル基が好ましい。また、ａは１以上１００以下の整数である。

R ⁹ to R ¹² in the formula are unsubstituted or substituted monovalent hydrocarbon groups having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. Group, cycloalkyl group such as cyclopentyl group and cyclohexyl group, aryl group such as phenyl group and xylyl group, aralkyl group such as benzyl group and phenethyl group, 3,3,3-trifluoropropyl group, 3-chloropropyl group and the like In addition to trialkoxysilylated alkyl groups such as 2- (trimethoxysilyl) ethyl group, alkoxy groups such as methoxy group, ethoxy group, and propoxy group, aryloxy groups such as phenoxy group, cyano group, etc. Can be mentioned. Of these, a methyl group, an ethyl group or a phenyl group is preferred. A is an integer of 1 to 100.

  The diaminosiloxane residue may be contained in the total diamine residue in an amount of 5 mol% to 95 mol%, and preferably 10 mol% to 90 mol%. If the content is as low as 5 mol% or less, the solubility in organic solvents is lowered, which is not preferable. On the other hand, when the content is as large as 95 mol% or more, it is difficult to handle as a polyimide silicone resin, and the content of the curable group is also reduced, so that a cured film having excellent adhesion cannot be obtained. By using diaminosiloxane, solubility in an organic solvent can be improved, and adhesion to various substrates can be improved.

  In these diamines, since the polyimide silicone resin of the present invention is transparent in the visible light region, it is preferable that the raw material diamine is not colored.

  As a synthetic raw material for the polyimide silicone resin of the present invention, known general diamines can be used at the same time as long as the transparency is not impaired. For example, aliphatic diamines such as tetramethylenediamine, 1,4-diaminocyclohexane and 4,4′-diaminodicyclohexylmethane, phenylenediamine, 4,4′-diaminodiphenyl ether, 2,2-bis (4-aminophenyl) propane Aromatic diamines such as these can be mentioned, and can be used alone or in combination of two or more.

  The tetracarboxylic dianhydride that is a raw material of the polyimide silicone resin synthesized in the present invention will be described. The polyimide silicone resin of the present invention is characterized in that it is transparent in the visible light region, the tetracarboxylic dianhydride as the raw material is not colored, and a charge transfer complex known as a cause of coloring Those that are difficult to form are preferred. Aliphatic tetracarboxylic dianhydrides or alicyclic tetracarboxylic dianhydrides are preferred in terms of excellent transparency, but aromatic tetracarboxylic dianhydrides that are superior in heat resistance within the range not colored may be used. Good.

  Examples of the aliphatic tetracarboxylic dianhydride include butane-1,2,3,4-tetracarboxylic dianhydride or pentane-1,2,4,5-tetracarboxylic dianhydride. Cyclic tetracarboxylic dianhydrides include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, dicyclohexyl-3,4,3. ', 4'-tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4. '-Gifeni Ether tetracarboxylic dianhydride, 4,4'-hexafluoro propylidene bis phthalic dianhydride, 3,3 ', and 4,4'-diphenylsulfone tetracarboxylic acid dianhydride. 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, Fragrances such as 3,3a, 4,5,9b-hexahydro-5-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione An aliphatic tetracarboxylic dianhydride having a ring may be used. These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

  The polyimide silicone resin can be produced by a one-step polymerization method in which diamine and tetracarboxylic dianhydride are used in approximately equimolar numbers in the presence of a solvent and polymerized only at a high temperature, or first, an amic acid is synthesized at a low temperature. Thereafter, any of two-stage polymerization methods in which imidization is performed at a high temperature may be used.

  The ratio of the diamine component to the tetracarboxylic dianhydride component is appropriately determined according to the adjustment of the molecular weight of the polyimide silicone resin, and is usually 0.95 to 1.05, preferably 0.98 to 1.02 in molar ratio. Range. In order to adjust the molecular weight of the polyimide silicone resin, a monofunctional raw material such as phthalic anhydride or aniline can be added. In this case, the addition amount is preferably 2 mol% or less with respect to the total imide skeleton.

  In the case of the single-stage polymerization method, the reaction temperature is 150 to 300 ° C., and the reaction time is achieved in 1 to 15 hours. When the two-stage polymerization method is used, the polyamic acid synthesis is performed at a temperature of 0 to 120 ° C. for 1 to 100 hours, and then imidization is performed at a temperature of 0 to 300 ° C. for 1 to 15 hours.

  The solvent that can be used at the time of synthesis may be any one that is compatible with the raw material diamine, tetracarboxylic dianhydride, and the product polyimide silicone. Phenols such as phenol, 4-methoxypheno 4-methoxyphenol, 2,6-dimethylphenol, m-cresol, ethers such as tetrahydrofuran, anisole, cyclohexanone, 2-butanone, methyl isobutyl ketone, 2-heptanone, 2- Ketones such as octanone and acetophenone, esters such as butyl acetate, methyl benzoate and γ-butyrolactone, cellosolves such as butyl cellosolve acetate and propylene glycol monomethyl ether acetate, N, N-dimethylformamide, N, N-dimethylacetamide, Examples include amides such as N-methyl-2-pyrrolidone.

  Moreover, it is also possible to make it easy to remove water generated during imidization by azeotropy by using together aromatic hydrocarbons such as toluene and xylene. These solvents may be used alone or in combination of two or more.

    When using at least one of diamine and tetracarboxylic dianhydride, the reaction method is not particularly limited, for example, a method of co-condensation after mixing all the raw materials in advance, or two or more types used. There is a method of sequentially adding diamine or tetracarboxylic dianhydride while reacting individually.

  Moreover, you may use the method of imidating by adding a dehydrating agent and an imidation catalyst in an imidation process, and heating as needed. In this method, as the dehydrating agent, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used. The amount of the dehydrating agent used is preferably 1 to 10 mol per 1 mol of diamine.

  Moreover, as an imidation catalyst, tertiary amines, such as a pyridine, a collidine, a lutidine, a triethylamine, can be used, for example. The amount of the imidization catalyst used is preferably 0.5 to 10 mol with respect to 1 mol of the dehydrating agent to be used.

  Since the polyimide silicone resin of the present invention is excellent in solubility, it can be adjusted to an appropriate viscosity by dissolving in an organic solvent so that it can be easily coated on various substrates.

  The organic solvent that can be used to dissolve the polyimide silicone resin of the present invention may be the above-mentioned organic solvent that can be used when synthesizing a generally known polyimide silicone resin, an aromatic hydrocarbon solvent that is different from the synthesis, Any solvent may be used as long as it is soluble, such as a ketone solvent.

  In particular, if you want to dissolve in a low-boiling aromatic hydrocarbon solvent or ketone solvent, re-dissolve the purified polyimide resin by a method such as adding a poor solvent to the synthesized polyimide silicone resin solution and reprecipitating it. At that time, the solvent may be used for dissolution.

  The substrate on which the polyimide silicone resin of the present invention can be coated may be a metal such as iron, copper, nickel, or aluminum, an inorganic material such as glass, or an organic resin such as an epoxy resin or an acrylic resin.

  Furthermore, it is possible to further improve the thermosetting property by adding a substance that reacts with a phenol group in the polyimide silicone resin. Here, examples of the substance that reacts with the phenol group include a polyfunctional organic compound such as a resin or an oligomer including two or more functional groups capable of reacting with a phenol group such as a carboxyl group, an amino group, and an epoxy group.

    The polyimide silicone resin of the present invention has excellent heat resistance, mechanical strength, solvent resistance, and adhesion to various substrates by thermosetting.

  Curing conditions are not particularly limited, but curing is performed in the range of 80 ° C. to 300 ° C., preferably 100 ° C. to 250 ° C. When it is cured at 80 ° C. or less, it takes too much time for thermal curing, which is not practical, or there is a problem of storage stability when a mechanism that cures at a low temperature is selected. Moreover, unlike the conventional polyamic acid solution, the thermal deterioration of the substrate can be suppressed without requiring heating at a high temperature of 300 ° C. or higher for a long time after coating.

  The polyimide silicone resin of the present invention has a transmittance in the wavelength region of 400 nm to 700 nm, so-called visible light region, in an ultraviolet / visible light absorption spectrum measured on a 10 μm thick film on a 1 mm thick glass plate. % Or more.

  The polyimide silicone resin of the present invention that is excellent in transparency, is soluble in solvent, and is thermosetting is, for example, a color filter or a light emitting diode in a semiconductor device, a protective film for a laser diode, a liquid crystal alignment film, a liquid crystal display device, and others It is considered useful in the fields of electronics and optics.

Example 1 (Synthesis of imide silicone resin)
1,3,3a, 4,5,9b-Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,1,3,3a, 4,5,9b in a flask equipped with a stirrer, thermometer and nitrogen displacement apparatus. 2-c] 30.0 g (0.1 mol) of furan-1,3-dione and 250 g of N, N-dimethylacetamide were charged and dissolved by stirring. Next, 17.3 g (0.035 mol) of 2,2′-methylenebis {6- (4-amino-3,5-dimethylbenzyl) -4-methyl} phenol was added into the flask, and the temperature of the reaction system was adjusted. Hold at 50 ° C. for 3 hours. Further, 56.2 g (0.065 mol) of diaminosiloxane (however, the average of a in formula (C) was 9.5) was added dropwise at room temperature, and the mixture was stirred at room temperature for 12 hours after completion of the addition.

  Next, after attaching a reflux condenser with a moisture receiver to the flask, 50 g of toluene was added, the temperature was raised to 170 ° C. and the temperature was maintained for 6 hours, and an almost transparent solution was obtained.

  The obtained solution was poured into methanol as a poor solvent to reprecipitate the resin. The result of measuring the infrared absorption spectrum of this resin is shown in FIG. Absorption based on polyamic acid indicating the presence of unreacted functional groups did not appear, and absorption based on imide groups was confirmed at 1770 cm −1 and 1710 cm −1. The resulting resin has a repeating unit represented by Formula 1.

  Formula 1

  Where X is

  Y is

  Z is

    Moreover, it was 11000 when the weight average molecular weight (polystyrene conversion) of this resin was measured by the gel permeation chromatography (GPC) which uses tetrahydrofuran as a solvent. This resin was dissolved in methyl isobutyl ketone, applied onto a glass substrate having a thickness of 1 mm, a width of 25 mm, and a length of 75 mm and dried to prepare a film having a thickness of 70 μm. The light transmittance of the film on this glass substrate was measured, and the result is shown in FIG. The light transmittance from a wavelength of 400 nm to 700 nm was 80% or more.

Example 2 (Synthesis of imide silicone resin)
1,3,3a, 4,5,9b-Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,1,3,3a, 4,5,9b in a flask equipped with a stirrer, thermometer and nitrogen displacement apparatus. 2-c] Furan-1,3-dione (30.0 g, 0.1 mol) and N, N-dimethylacetamide (250 g) were charged. Subsequently, 34.6 g (0.07 mol) of 2,2′-methylenebis {6- (4-amino-3,5-dimethylbenzyl) -4-methyl} phenol was added into the flask, and the temperature of the reaction system was increased. Was held at 50 ° C. for 3 hours. Furthermore, 26.0 g (0.03 mol) of diaminosiloxane (however, the average of a in formula (C) is 9.5) was added dropwise at room temperature, and the mixture was stirred at room temperature for 12 hours after completion of the addition.

Next, after attaching a reflux condenser with a moisture receiver to the flask, 50 g of toluene was added, the temperature was raised to 170 ° C. and the temperature was maintained for 6 hours, and an almost transparent solution was obtained.

  The obtained solution was poured into methanol as a poor solvent to reprecipitate the resin. When the infrared absorption spectrum of this resin was measured, absorption based on polyamic acid indicating that there was an unreacted functional group did not appear, and absorption based on imide groups was confirmed at 1770 cm −1 and 1710 cm −1. The obtained resin has a repeating unit represented by Formula 2.

  Formula 2

Where X is

Y is

Z is

  Moreover, it was 7000 when the weight average molecular weight (polystyrene conversion) of this resin was measured by the gel permeation chromatography (GPC) which uses tetrahydrofuran as a solvent. This resin was dissolved in methyl isobutyl ketone, applied onto a glass substrate and dried to prepare a film having a thickness of 30 μm. When the light transmittance of this film was measured, the light transmittance from a wavelength of 400 nm to 700 nm was 80% or more.

Example 3 (Synthesis of imide silicone resin)
1,3,3a, 4,5,9b-Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,1,3,3a, 4,5,9b in a flask equipped with a stirrer, thermometer and nitrogen displacement apparatus. 2-c] Furan-1,3-dione (30.0 g, 0.1 mol), N, N-dimethylacetamide (250 g), and toluene (100 g) were charged. Subsequently, 12.35 g (0.025 mol) of 2,2′-methylenebis {6- (4-amino-3,5-dimethylbenzyl) -4-methyl} phenol was added to the flask, and the temperature of the reaction system was increased. Was held at 50 ° C. for 3 hours. Further, 64.88 g (0.075 mol) of diaminosiloxane (however, the average of a in formula (C) is 9.5) was added dropwise at room temperature, and the mixture was stirred at room temperature for 12 hours after completion of the addition.

Next, after attaching a reflux condenser with a moisture receiver to the flask, 20.4 g of acetic anhydride and 26.4 g of pyridine were added, the temperature was raised to 50 ° C., and the temperature was maintained for 3 hours.

  The obtained solution was poured into methanol as a poor solvent to reprecipitate the resin. When the infrared absorption spectrum of this resin was measured, absorption based on polyamic acid indicating that there was an unreacted functional group did not appear, and absorption based on imide groups was confirmed at 1770 cm −1 and 1710 cm −1. The resulting resin has a repeating unit represented by Formula 3.

  Formula 3

  Where X is

  Y is

  Z is

    Moreover, it was 24000 when the weight average molecular weight (polystyrene conversion) of this resin was measured by the gel permeation chromatography (GPC) which uses tetrahydrofuran as a solvent. This resin was dissolved in methyl isobutyl ketone, coated on a glass substrate and dried to form a film having a thickness of 50 μm. When the light transmittance of this film was measured, the light transmittance from a wavelength of 400 nm to 700 nm was 80% or more.

Example 4 (Evaluation of thermoset)
10 parts by weight of epoxy resin N, N-diglycidyl-4-glycidyloxyaniline is added to 100 parts by weight of the polyimide silicone resin synthesized in Example 1 and dissolved in methyl isobutyl ketone. A bar coater is used on a copper plate. It was applied and heat cured at 150 ° C. for 2 hours. The obtained coating film was subjected to an environmental test at 85 ° C. and 85% RH for one week. However, it did not peel off over time and the copper plate was not corroded. Moreover, although it was immersed in methyl ethyl ketone for 5 minutes, the surface was not attacked.

2 is an infrared absorption spectrum of an imide silicone resin synthesized in Example 1. 2 is a transmittance spectrum of an imide silicone resin synthesized in Example 1. FIG.

Claims (4)

It contains a structural unit represented by the following general formula (1) and a structural unit represented by the general formula (4), is soluble in an organic solvent, and measured as a 10 μm thick film on a 1 mm thick glass plate. A thermosetting polyimide silicone resin having a light transmittance of 80% or more at a wavelength of 400 nm to 700 nm.

[Wherein, X is an aliphatic tetracarboxylic dianhydride residue, an aliphatic tetracarboxylic dianhydride residue having an aromatic ring , or an alicyclic tetracarboxylic dianhydride residue, and Y is It is a diamine residue represented by the general formula (2)

(Wherein R ¹ to R ⁶ are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, which may be the same or different.)]

[Wherein, X is as described above, and Z is a diamine residue represented by the general formula (5)

(In the formula, R ⁹ to R ¹² are substituted or unsubstituted monovalent hydrocarbon groups having 1 to 8 carbon atoms, and these may be the same or different. A is an integer of 1 to 100. ]]]   The diamine residue represented by general formula (2) is 5 mol% or more and 95 mol% or less, and the diamine residue represented by general formula (5) is 5 mol% or more and 95 mol% or less with respect to all diamine residues. The polyimide silicone resin according to claim 1. The polyimide silicone resin according to claim 1, wherein X is a group represented by the following formula.

  The semiconductor device formed using the polyimide silicone resin of any one of Claims 1-3.

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