JP7388296B2 - Silicon-containing tetracarboxylic dianhydride, its production method and polyimide resin - Google Patents

Description

The present invention relates to a silicon-containing tetracarboxylic dianhydride, and more specifically, to a silicon-containing tetracarboxylic dianhydride useful as a raw material for polyamic acid and polyimide, a method for producing the same, and a polyimide resin.

Conventionally, polyimide resins have been known as resins having heat resistance, flame resistance, electrical and mechanical properties, etc., and are used as composite materials such as copper-clad laminates and multilayer printed wiring board materials. Polyimide resins are also used as varnishes for passivation films for multilayer wiring in LSIs, α-ray blocking films for memory devices, multilayer wiring insulating films for magnetic heads, liquid crystal wiring alignment films, and as films for flexible printed wiring board substrates. is also used.
However, common polyimide resins are made from aromatic tetracarboxylic dianhydride, and while they have high heat resistance, they have the problem of poor light transmittance and poor solubility in organic solvents.
In this regard, polyimides made from alicyclic tetracarboxylic dianhydrides have been proposed for use in the optical field in order to improve light transmittance (Patent Documents 1 and 2), but these Polyimide also has problems in that it has insufficient solubility in organic solvents, and the synthesis method is complicated and expensive.

Japanese Patent Application Publication No. 2005-336244 Japanese Patent Application Publication No. 2010-70721

The present invention was made in view of the above circumstances, and aims to provide a tetracarboxylic dianhydride that provides a polyimide resin with excellent solubility in organic solvents and light transmittance, a method for producing the same, and a polyimide resin. .

As a result of intensive studies aimed at solving the above problems, the inventors of the present invention discovered that a certain silicon atom-containing tetracarboxylic dianhydride provides a polyimide resin with excellent solubility in organic solvents and light transmittance. , completed the invention.

（式中、Ｒ¹は、それぞれ独立に炭素原子数１～１２の一価炭化水素基であり、Ｒ²は、それぞれ独立に水素原子または炭素原子数１～１２の一価炭化水素基であり、Ａは、下記構造式（２）

で表される二価の基であり、破線は、結合手を表す。）
２． 下記一般式（３）で表されるシラン化合物と、下記一般式（４）で表される酸無水物とをヒドロシリル化反応させる１記載のケイ素含有テトラカルボン酸二無水物の製造方法、

（式中、Ｒ¹およびＲ²は、上記と同じである。）
３． １記載のケイ素含有テトラカルボン酸二無水物を含む単量体の重合物であるポリイミド樹脂
を提供する。 That is, the present invention
1. A silicon-containing tetracarboxylic dianhydride represented by the following general formula (1),

(In the formula, R ¹ is each independently a monovalent hydrocarbon group having 1 to 12 carbon atoms, and R ² is each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. , A is the following structural formula (2)

It is a divalent group represented by , and the broken line represents a bond. )
2. The method for producing a silicon-containing tetracarboxylic dianhydride according to 1, in which a silane compound represented by the following general formula (3) and an acid anhydride represented by the following general formula (4) are subjected to a hydrosilylation reaction,

(In the formula, R ¹ and R ² are the same as above.)
3. The present invention provides a polyimide resin which is a polymer of a monomer containing the silicon-containing tetracarboxylic dianhydride described in 1 above.

The silicon-containing tetracarboxylic dianhydride of the present invention can be used as a raw material for polyimide. The polyimide using the silicon-containing tetracarboxylic dianhydride of the present invention as a raw material has excellent solubility in organic solvents and light transmittance, and is useful for optical applications.

This is an IR spectrum of the silicon-containing tetracarboxylic dianhydride obtained in Example 1-1. This is a ¹ H-NMR spectrum of the silicon-containing tetracarboxylic dianhydride obtained in Example 1-1. This is an IR spectrum of the polyimide resin obtained in Example 2-1.

The present invention will be explained in more detail below.
The silicon-containing tetracarboxylic dianhydride of the present invention is represented by the following general formula (1).

In formula (1), R ¹ is each independently a monovalent hydrocarbon group having 1 to 12 carbon atoms, and R ² is each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. It is.
The monovalent hydrocarbon group having 1 to 12 carbon atoms for R ¹ and R ² may be linear, branched, or cyclic, and specific examples include methyl, ethyl, n-propyl, isopropyl, and n-butyl. Examples include alkyl groups such as , isobutyl, n-octyl, and cyclohexyl groups, and aryl groups such as phenyl, tolyl, and naphthyl groups. Among these, from the viewpoint of raw material availability, R ¹ and R ² are preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group.

A is a divalent group represented by the following structural formula (2), and the broken line represents a bond.

Specific examples of the silicon-containing tetracarboxylic dianhydride of the present invention include the following.

The silicon-containing tetracarboxylic dianhydride of the present invention can be obtained, for example, by subjecting a silane compound represented by the following general formula (3) to a hydrosilylation reaction with an acid anhydride represented by the following general formula (4). can get.

In formulas (3) and (4), R ¹ and R ² are the same as R ¹ and R ² in formula (1) above.

Specific examples of the silane compound (3) include 1,4-bis(dimethylsilyl)benzene, 1,4-bis(diethylsilyl)benzene, 1,4-bis(diphenylsilyl)benzene, 1,3-bis( Examples include dimethylsilyl)benzene.

Specific examples of the acid anhydride (4) include 5-norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, and ethyl-5-norbornene-2,3-dicarboxylic anhydride. Examples include dicarboxylic acid anhydrides.

The amount of the silane compound (3) and the acid anhydride (4) to be used is such that the amount of carbon-carbon double bonds in the acid anhydride is 1.0 to 3.0 to 3.0% per mole of Si--H groups in the silane compound. The amount is preferably 0 mol.

As the hydrosilylation reaction catalyst, all conventionally known catalysts can be used. For example, carbon powder supporting platinum metal, platinum black, platinum chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohol, complexes of platinum and vinyl siloxanes such as divinyltetramethyldisiloxane; Examples include platinum-based catalysts such as complexes of chloroplatinic acid and olefins, platinum bisacetoacetate; palladium-based catalysts; and platinum group metal-based catalysts such as rhodium-based catalysts.

The amount of the catalyst to be used may be an effective amount as a catalyst, and is not particularly limited, but it is usually preferably 1 to 500 ppm, particularly preferably 1 to 500 ppm based on the mass of the platinum group metal, based on the total mass of the silane compound and acid anhydride. It is preferable to mix about 2 to 200 ppm.

Although the above addition reaction (hydrosilylation reaction) proceeds without using a solvent, the reaction can be carried out under mild conditions by using a solvent. Examples of the solvent include aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as hexane and octane; and ether solvents such as tetrahydrofuran and dioxane. Two or more types can be used in combination.

The reaction temperature is preferably 20 to 150°C, more preferably 50 to 120°C, and the reaction time is preferably 1 to 24 hours.

The silicon-containing tetracarboxylic dianhydride of the present invention thus obtained is useful as a raw material for polyamic acid, polyimide, and the like. By producing the above resin using the silicon-containing tetracarboxylic dianhydride of the present invention as a monomer, a resin having high transparency and solubility in organic solvents can be obtained.

The diamine compound used when synthesizing the polyimide resin is not particularly limited, and can be appropriately selected from conventionally known diamine compounds. Specific examples include tetramethylene diamine, 1,4 - Aliphatic diamines such as diaminodicyclohexane, 4,4'-diaminodicyclohexylmethane; o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenyl ether, 2,2-bis(4-amino Examples include aromatic diamines such as phenyl)propane and 2,2-bis[4-(4-aminophenoxy)phenyl]propane, which may be used alone or in combination of two or more. good.
In the present invention, a known tetracarboxylic dianhydride used in the production of polyimide may be used in combination with the silicon-containing tetracarboxylic dianhydride described above, but transparency and solubility in organic solvents may be From the viewpoint of increasing the temperature, it is preferable to use the silicon-containing tetracarboxylic dianhydride of the present invention alone.

Moreover, the polyimide resin of the present invention can be manufactured by a known method.
For example, first, a silicon-containing tetracarboxylic dianhydride and a diamine compound are placed in a solvent and reacted at about 20 to 50°C to produce polyamic acid, which is a precursor of polyimide resin. Next, the temperature of the obtained polyamic acid solution is preferably raised to 60 to 200°C, and the acid amide of the polyamic acid is subjected to a dehydration ring-closing reaction to obtain a polyimide resin solution. A polyimide resin can be obtained by pouring the resin into a solvent such as , ethanol, acetonitrile, etc. to precipitate it, and drying the resulting precipitate.

The weight average molecular weight of the polyimide resin of the present invention is not particularly limited, but considering the balance between the strength of the film obtained from the resin and the solubility in solvents, it is between 5,000 and 100,000. Preferably, 10,000 to 50,000 is more preferable.
Note that the weight average molecular weight in the present invention is a polystyrene equivalent value determined by gel permeation chromatography (hereinafter sometimes abbreviated as GPC) using tetrahydrofuran (THF) as a solvent.

The present invention will be specifically described below using Examples and Comparative Examples, but the present invention is not limited thereto.

[Example 1-1] Production of silicon-containing tetracarboxylic dianhydride 5-norbornene-2,3-dicarboxylic anhydride was placed in a 500 mL four-necked flask equipped with a stirring device, cooling tube, dropping funnel, and thermometer. 25.0 g (152 mmol) of C. and 62.5 g of toluene were added thereto, and the mixture was heated to 80.degree. C. using an oil bath while stirring. To this was added 0.22 g of a 2% by mass chloroplatinic acid solution in ethanol, and 8.88 g (45.7 mmol) of 1,4-bis(dimethylsilyl)benzene was added dropwise over 15 minutes while stirring. After the dropwise addition was completed, the mixture was further heated and stirred at 90° C. for 2 hours, and then cooled to room temperature. The precipitated white precipitate was filtered off, 40 g of toluene was added to the filtrate, and the mixture was stirred at 130°C for 30 minutes. After cooling to room temperature, the precipitated white precipitate was filtered off. The obtained filter material was dried in an environment of 50° C. and 0.4 kPa to obtain 15.3 g (yield: 64%) of a white solid.
As a result of analyzing this white solid by IR and ¹ H-NMR, it was confirmed that it was a silicon-containing tetracarboxylic dianhydride represented by the following structural formula (5). The results of IR and ¹ H-NMR measurements are shown in FIGS. 1 and 2.

¹ H-NMR: 7.46 ppm (4H, s, H _i ), 2.96 to 2.89 ppm (4H, m, H _b,c ), 2.83 to 2.77 ppm (4H, m, H _{a, d} ), 1.69 to 1.54 ppm (4H, m, H _f,g ), 1.18 to 1.11 ppm (4H, m, H _f,g ), 0.94 to 0.86 ppm (2H, m , H _e ), 0.31 ppm, and 0.30 ppm (12H,s,H _h )

[Example 2-1] Production of polyimide resin 1.57 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane was placed in a 100 mL three-necked flask equipped with a stirrer, a cooling tube, and a thermometer. (3.82 mmol) and 14.3 g of N,N-dimethylacetamide (DMAc) were added and stirred until the mixture became homogeneous. Then, 2.00 g (3.83 mmol) of the compound obtained in Example 1-1 was added. ) and continued stirring at room temperature for 17 hours. Next, 1.16 g (11.5 mmol) of triethylamine and 1.17 g (11.5 mmol) of acetic anhydride were added in this order, and imidization was performed at 80° C. for 3 hours. After the solution was cooled to room temperature, it was added dropwise to 50 g of methanol to precipitate. The precipitate was filtered, washed with 50 g of methanol, and dried at 80° C. and 0.4 kPa to obtain 2.96 g of white powdery resin (87% yield). The weight average molecular weight (in terms of polystyrene) of this resin was measured by GPC using THF as a solvent and found to be 21,000.
The IR spectrum of the obtained resin is shown in FIG. Since C═O stretching vibrations derived from imidocarbonyl were observed at 1706 and 1774 cm ⁻¹ , it was confirmed that it was a polyimide resin.

The resulting resin was dissolved in chloroform, THF, and DMAc.

The resulting resin was made into a 10% by mass THF solution, spread on a slide glass provided with a frame, and exposed to an environment of 40° C. for 1 hour and then 80° C. for 1 hour to produce a 15 μm thick film. The light transmittance of the glass with this film attached and the light transmittance of the glass itself were measured using a spectrophotometer (Model U3310 (manufactured by Hitachi, Ltd.)), and the transmittance of the film was calculated from the difference. However, it was 98% or more in the wavelength range of 400 to 800 nm.

As described above, it has been shown that the polyimide resin using the silicon-containing tetracarboxylic dianhydride of the present invention as a raw material is a material with excellent solubility in organic solvents and excellent light transmittance.

Claims (4)

A silicon-containing tetracarboxylic dianhydride represented by the following general formula (1).

(In the formula, R ¹ is each independently a methyl group, ethyl group, or phenyl group, R ² is a hydrogen atom, and R ² ' is each independently a hydrogen atom , methyl group, or ethyl group , A is the following structural formula (2)

It is a divalent group represented by , and the broken line represents a bond. ) The silicon-containing tetracarboxylic dianhydride according to claim 1, which is represented by any of the following formulas .

The production of silicon-containing tetracarboxylic dianhydride according to claim 1 or 2 , wherein a silane compound represented by the following general formula (3) and an acid anhydride represented by the following general formula (4) are subjected to a hydrosilylation reaction. Method.

(In the formula, R ¹ , R ² and R ² ' are the same as above.) A polyimide resin which is a polymer of a monomer containing the silicon-containing tetracarboxylic dianhydride according to claim 1 or 2 .