JP2006206825A - Aromatic polyimide resin precursor and aromatic polyimide resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aromatic polyimide resin which is relatively inexpensive, has good heat resistance without being deteriorated, is little colored, has good light transmittance, and is soluble in organic solvents. <P>SOLUTION: This aromatic polyimide resin precursor is characterized by being obtained by reacting a tetracarboxylic dianhydride having a fluorene structure with a diamine component having a fluorene structure. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an aromatic polyimide resin that is transparent and soluble in an organic solvent. More specifically, it is a polyimide resin that is less colored, has a high light transmittance, and has high heat resistance and solubility in organic solvents, and is used for LCD peripheral materials such as liquid crystal alignment films or for photoresist applications. It relates to an aromatic polyimide resin that can be used.

  In general, an aromatic polyimide resin is obtained by a reaction between an aromatic tetracarboxylic dianhydride and an aromatic diamine. Such aromatic polyimide resins have excellent heat resistance and solvent resistance, and are therefore widely used in the electrical and electronics industry. However, on the other hand, general polyimide resin has a unique brown coloration, poor visible ultraviolet light permeability, and poor solubility in organic solvents, so it is used for applications that require high temperature treatment (molding, etc.) Therefore, it is not suitable for LCD peripheral materials.

In order to solve such problems, an alicyclic monomer is used for either the raw material tetracarboxylic dianhydride component or diamine component (see Patent Document 1), or a fluorine-containing monomer is used. (See Patent Document 2), however, they are difficult to industrially because they impair heat resistance and have problems such as manufacturing costs.
JP 2002-146021 A JP 2002-322274 A

  An object of the present invention is to provide an aromatic polyimide resin that is relatively inexpensive, does not impair heat resistance, has little coloration, has good light transmittance, and is soluble in an organic solvent.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that both the tetracarboxylic dianhydride component and the diamine component are derivatives having a fluorene structure, and both these components are obtained as raw materials. The inventors have found that an aromatic polyimide resin satisfies the above required characteristics, and have completed the present invention.

下記一般式（Ｃ）及び／又は（Ｄ）に示されるフルオレン構造を有するジアミン成分とを

反応させて得られたことを特徴とする芳香族ポリイミド樹脂前駆体。
（Ｒ₁〜Ｒ₆はそれぞれ独立に水素原子、水酸基、フェニル基、炭素数１〜３のアルキル基又はハロゲン原子を示す。）
（２）上記（１）に記載の少なくとも１種の芳香族ポリイミド樹脂前駆体を脱水閉環させて得られたことを特徴とする芳香族ポリイミド樹脂。
（３）厚さ２０μｍのフィルムとした時のＹＩ値（イエローネスインデックス）が１５以下、及び４００ｎｍにおける光透過率が５０％以上である上記（２）に記載の芳香族ポリイミド樹脂。
（４）ＮＭＰ（Ｎ−メチルピロリドン）に対する溶解度が１５．０質量％以上である上記（２）に記載の芳香族ポリイミド樹脂。
（５）下記一般式（Ａ）及び／又は（Ｂ）に示されるフルオレン構造を有するテトラカルボン酸二無水物成分と、

下記一般式（Ｃ）及び／又は（Ｄ）に示されるフルオレン構造を有するジアミン成分とを

反応させた後、脱水閉環させることを特徴とする下記一般式（Ｅ）〜（Ｈ）の繰返し単位を有する芳香族ポリイミド樹脂の製造方法。

（Ｒ₁〜Ｒ₆はそれぞれ独立に水素原子、水酸基、フェニル基、炭素数１〜３のアルキル基又はハロゲン原子を示す。） That is, the present invention has the following configuration.
(1) a tetracarboxylic dianhydride component having a fluorene structure represented by the following general formula (A) and / or (B);

A diamine component having a fluorene structure represented by the following general formula (C) and / or (D):

An aromatic polyimide resin precursor obtained by reacting.
(R _{1 to} R ₆ each independently represent a hydrogen atom, a hydroxyl group, a phenyl group, an alkyl group having 1 to 3 carbon atoms, or a halogen atom.)
(2) An aromatic polyimide resin obtained by dehydrating and ring-closing at least one aromatic polyimide resin precursor described in (1) above.
(3) The aromatic polyimide resin according to (2), wherein the YI value (yellowness index) when the film is 20 μm thick is 15 or less, and the light transmittance at 400 nm is 50% or more.
(4) The aromatic polyimide resin according to (2), wherein the solubility in NMP (N-methylpyrrolidone) is 15.0% by mass or more.
(5) a tetracarboxylic dianhydride component having a fluorene structure represented by the following general formula (A) and / or (B);

A diamine component having a fluorene structure represented by the following general formula (C) and / or (D):

A method for producing an aromatic polyimide resin having repeating units of the following general formulas (E) to (H), wherein the reaction is followed by dehydration and cyclization.

(R _{1 to} R ₆ each independently represent a hydrogen atom, a hydroxyl group, a phenyl group, an alkyl group having 1 to 3 carbon atoms, or a halogen atom.)

  According to the present invention, it is possible to obtain an aromatic polyimide resin and a precursor thereof that do not impair heat resistance, have little coloration, have good light transmittance, and are soluble in an organic solvent.

Next, the present invention will be described in more detail with reference to preferred embodiments.
As the tetracarboxylic dianhydride component of the aromatic polyimide resin in the present invention, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride and 9,9-bis [4- (3,4- Dicarboxyphenoxy) phenyl] fluorene dianhydride, and diamine components include 9,9-bis (4-aminophenyl) fluorene and 9,9-bis [4- (4-aminophenoxy) phenyl] fluorene. And derivatives thereof. These and derivatives are those having a bonding group of R ₁ ~ _R6 shown in the general formula (A) ~ (D), each independently represent a hydrogen atom _R1-R6, a hydroxyl group, a phenyl group, the carbon number 1 to 3 alkyl groups or halogen atoms are shown.

  The precursor of the aromatic polyimide resin in the present invention is a polyamic acid obtained by the reaction of the tetracarboxylic dianhydride component and the diamine component. An aromatic polyimide resin is obtained by dehydration and ring closure of polyamic acid.

  The means for producing the aromatic polyimide resin in the present invention is not particularly limited. For example, (a.1) the reaction product is heated after reacting the tetracarboxylic dianhydride component and the diamine component in an organic solvent. (A.2) reaction of a tetracarboxylic dianhydride component and a diamine component, and chemical dehydration and ring closure in an organic solvent in the presence of a dehydrating agent. A publicly known method such as a method for converting to a conventional method can be used.

  Solvents used for the reaction of the tetracarboxylic dianhydride component and the diamine component include aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone, and cresols And glycol solvents such as diglyme and the like. These solvents can be used alone or in admixture of two or more. Although there is no restriction | limiting in particular in the usage-amount of a solvent, The usage-amount so that the content of the precursor of the aromatic polyimide resin to produce | generate will be 5-40 mass% is desirable.

A predetermined amount of a diamine component is dissolved in these organic solvents, a predetermined amount of tetracarboxylic dianhydride component is added to the diamine component solution, and the reaction proceeds by stirring. The aromatic polyimide resin in the present invention An organic solvent solution of the precursor can be obtained.
The polymerization temperature is generally -10 to 120 ° C, preferably 5 to 30 ° C.
The polymerization time varies depending on the raw material components used, but is usually 3 to 24 hours.
The intrinsic viscosity of the precursor solution of aromatic polyimide resin (in N, N-dimethylacetamide) obtained under the above conditions is preferably 0.1 to 3.0 dl / g, more preferably 0.2 to 1.5 dl. / G.

  The precursor solution of the aromatic polyimide resin obtained under the above conditions is put into a non-soluble solvent such as methanol, and the precursor of the aromatic polyimide resin is precipitated, filtered and dried to obtain a solid fragrance. A precursor of a group polyimide resin can be obtained.

  Moreover, the obtained precursor solution of the aromatic polyimide resin is coated on a substrate such as a glass plate with a bar coater, a spin coater or the like, and the coated material is dried at a temperature of 50 ° C. to 150 ° C. for 0.5 to 24 hours. Thus, a precursor of a film-like aromatic polyimide resin can also be obtained.

  The aromatic polyimide resin precursor in the present invention can be imidized by dehydration ring closure by heat treatment or reaction with a dehydrating agent to obtain the aromatic polyimide resin in the present invention.

  When dehydrating and cyclizing the precursor of the aromatic polyimide resin by heat treatment, for example, in the case of a film-like aromatic polyimide resin precursor, in an inactive gas atmosphere or under reduced pressure while being peeled off from the substrate. Usually, heat treatment is performed at a temperature of 200 ° C. to 400 ° C., preferably 250 ° C. to 350 ° C. for 0.5 to 15 hours, preferably 1 to 5 hours.

  In the case of dehydrating and ring-closing by reacting with a dehydrating agent, for example, in the case of a precursor of a film-like aromatic polyimide resin, it is immersed in a solution containing the dehydrating agent while being peeled off from the substrate or chemically. The dehydration ring is closed. Examples of the dehydrating agent used for dehydration ring closure include acetic anhydride and pyridine, and trifluoroacetic anhydride and pyridine.

  The aromatic polyimide resin in this invention can mix 1 or more types of the aromatic polyimide resin which has a repeating unit of general formula (E)-(H). As a mixing method, after mixing an organic solvent solution of a precursor of an aromatic polyimide resin, a method of obtaining a mixed aromatic polyimide resin by dehydration and ring closure, or a method of mixing an aromatic polyimide resin by dissolving it in an organic solvent Any one of them may be used.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. The physical properties of the aromatic polyimide resin films of Examples and Comparative Examples are as follows: [1] Light transmission and YI value, [2] NMP solubility, [3] Glass transition temperature (Tg) and thermal weight reduction start The temperature (Td) was measured and summarized in Table 1.

[1] Light transmittance and coloring degree (YI value)
The light transmittance of the obtained aromatic polyimide resin film was measured in the range of 200 nm to 1000 nm with a visible ultraviolet spectrometer UV-1650PC manufactured by Shimadzu. Further, the degree of coloring was measured by yellowness (yellowness index = YI value) with OME-2000 manufactured by Nippon Denshoku.

[2] Solubility The obtained aromatic polyimide resin film was dissolved in N-methylpyrrolidone at 80 ° C as much as possible, and after cooling, the solubility was measured from the nonvolatile content of 300 ° C or higher of the solution layer. The solubility was calculated by the following formula.
Nonvolatile content (g) / solution layer (g) × 100 = solubility

[3] Measurement of glass transition temperature (Tg) and thermogravimetric decrease start temperature (Td) (measurement of Tg)
Using a differential scanning calorimeter (DSC), the aromatic polyimide resin film was heated in a nitrogen atmosphere under the temperature rising rate of 20 ° C./min, and the temperature at the change point of the specific heat was measured to obtain Tg.
(Measurement of Td)
Using a thermobalance, the aromatic polyimide resin film was heated in a nitrogen atmosphere at a temperature rising rate of 10 ° C./min, and the temperature at which the weight loss was 3% from the initial weight was measured to obtain Td.

Example 1
Nitrogen gas was allowed to flow into a vessel equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube, and after charging 35.22 g of N, N′-dimethylacetamide (DMAc), 9,9-bis [4- (4-amino Phenoxy) -phenyl] fluorene (5.32 g) was added and sufficiently dissolved. Thereafter, 6.42 g of 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene dianhydride was added and reacted at 10 ° C. for 5.0 hours to obtain an intrinsic viscosity of 0.55 ( dl / g) of 46.96 g of a polyamic acid solution (25% by mass DMAc) was obtained.
Thereafter, it was uniformly coated on a smooth glass plate with a bar coater, dehydrated and closed by heating, imidized to obtain an aromatic polyimide resin film. Table 1 shows the physical properties of the obtained aromatic polyimide resin film.

Example 2
An aromatic polyimide resin film was produced in the same manner except that the diamine used in Example 1 was replaced with 3.48 g of 9,9-bis (4-aminophenyl) fluorene. Table 1 shows the physical properties of the obtained aromatic polyimide resin film.

Example 3
An aromatic polyimide resin film was produced in the same manner except that the diamine used in Example 1 was replaced with 3.76 g of 9,9-bis (4-amino-3-methylphenyl) fluorene. Table 1 shows the physical properties of the obtained aromatic polyimide resin film.

Example 4
An aromatic polyimide resin film was produced in the same manner except that the tetracarboxylic dianhydride used in Example 1 was replaced with 4.58 g of 9,9-bis (3,4-dicarboxyphenyl) fluorene. Table 1 shows the physical properties of the obtained aromatic polyimide resin film.

Comparative Example 1
An aromatic polyimide resin film was prepared in the same manner as in Example 1 except that the diamine of Example 1 was used and 3.10 g of 4,4′-oxydiphthalic dianhydride was used as the tetracarboxylic dianhydride. Table 1 shows the physical properties of the obtained aromatic polyimide resin film.
It is a polyimide resin having a low light transmittance and a high YI value.

Comparative Example 2
An aromatic polyimide resin film was prepared in the same manner as in Example 1 except that the tetracarboxylic dianhydride of Example 1 was used and 2.00 g of 4,4′-diaminodiphenyl ether was used as the diamine. Table 1 shows the physical properties of the obtained aromatic polyimide resin film.
It is a polyimide resin having a low light transmittance and a high YI value.

According to the present invention, it is possible to provide an aromatic polyimide resin that is soluble in an organic solvent with a low degree of coloring and good light transmittance without impairing heat resistance.

Claims (5)

A tetracarboxylic dianhydride component having a fluorene structure represented by the following general formula (1) and / or (2):

A diamine component having a fluorene structure represented by the following general formula (3) and / or (4):

An aromatic polyimide resin precursor obtained by reacting.
(R _{1 to} R ₆ each independently represent a hydrogen atom, a hydroxyl group, a phenyl group, an alkyl group having 1 to 3 carbon atoms, or a halogen atom.)   An aromatic polyimide resin obtained by dehydrating and ring-closing at least one aromatic polyimide resin precursor according to claim 1.   The aromatic polyimide resin according to claim 2, wherein the YI value (yellowness index) when the film is 20 μm thick is 15 or less, and the light transmittance at 400 nm is 50% or more.   The aromatic polyimide resin according to claim 2, wherein the solubility in NMP (N-methylpyrrolidone) is 15.0% by mass or more. A tetracarboxylic dianhydride component having a fluorene structure represented by the following general formula (1) and / or (2):

A diamine component having a fluorene structure represented by the following general formula (3) and / or (4):

A process for producing an aromatic polyimide resin having repeating units of the following general formulas (5) to (8), wherein the reaction is followed by dehydration and ring closure.

(R _{1 to} R ₆ each independently represent a hydrogen atom, a hydroxyl group, a phenyl group, an alkyl group having 1 to 3 carbon atoms, or a halogen atom.)