TWI758269B - Polyimide material, production method therefor, and polyimide precursor composition used in production thereof - Google Patents

Abstract

The present invention provides a polyimide material that has improved ultraviolet resistance while retaining the conventional characteristics of a polyimide film. This polyimide material contains a polyimide and an ultraviolet absorber, and has a 0.5% weight reduction temperature that exceeds 200°C.

Description

Polyimide material, method for producing the same, and polyimide precursor composition used in its production

The present invention relates to a polyimide material excellent in ultraviolet durability.

Polyimide films are widely used in the fields of electrical and electronic devices and semiconductors due to their excellent heat resistance, chemical resistance, mechanical strength, electrical properties, and dimensional stability. On the other hand, in recent years, with the advent of a highly information-based society, the development of optical materials such as liquid crystal alignment films and protective films for color filters in display devices such as optical fibers and optical waveguides in the field of optical communication has progressed. Especially in the field of display devices, the development of a light-weight plastic substrate with excellent flexibility and a display capable of being bent and rounded as a substitute for a glass substrate has been actively studied. Therefore, there is a need for higher performance optical materials that can be used in such applications.

Aromatic polyimides are inherently tan colored due to the formation of intramolecular conjugation or charge transfer complexes. In order to suppress the coloration, for example, introducing a fluorine atom into the molecule, introducing a fluorine atom into the main chain, A method of imparting flexibility, introducing a bulky group as a side chain, etc. to prevent intramolecular conjugation or formation of a charge transfer complex and to exhibit transparency (eg, Patent Document 1).

Moreover, the method of using semi-alicyclic or fully alicyclic polyimide which theoretically does not form a charge transfer complex, and making it exhibit transparency has also been proposed (for example, Patent Documents 2 to 5).

Conventionally, applications utilizing the properties of polyimide have been developed. However, since polyimide generally absorbs in the ultraviolet region, the light resistance, especially the durability against light in the ultraviolet region, is sometimes insufficient. Patent Document 6 (Japanese Patent Laid-Open No. 2004-258544 ) describes a retardation film obtained by coating a solution containing an ultraviolet absorber and a specific polyimide on a substrate.

Patent Document 7 (Chinese Patent Application Publication No. 103897391 specification) describes: mixing polyimide, nano-powder, light hardener, antioxidant, ultraviolet absorber and light stabilizer at 220~290°C. A photocurable polyimide film is produced by extrusion molding. It is also described that the performance of the solar cell is improved by using the photocurable polyimide film in the solar cell.

Patent Document 8 (Japanese Patent Laid-Open No. 10-148835 ) discloses a technique of adding an ultraviolet absorber to an alignment film in order to solve the problems of deterioration of electrical properties and image sticking caused by irradiation ([0006] etc.). The material of the alignment film is polyimide, and the embodiment records: in the combination of decamethylene bis-trimellitic acid dianhydride and 3,3',4,4'-biscyclohexyltetracarboxylic dianhydride in a ratio of 4/6 A tetracarboxylic acid component and a diamine component containing p-phenylenediamine and 4,4'-diaminodiphenylmethane are reacted in a proportion of 4,4'-diaminodiphenylmethane, and an ultraviolet absorber is added to the polyamide acid to prepare a liquid crystal alignment film. the polyamide solution, and using it to heat at 180°C to form an alignment film.

Patent Document 9 (Japanese Patent Laid-Open No. 62-184055 ) describes: a polyamide acid composition for producing a light-shielding film containing an ultraviolet absorber for a light-shielding film used in liquid crystal display elements, etc., and a method using the composition. Shading film.

Patent Document 10 describes a photosensitive resin composition containing a polyimide, a compound having a quinonediazide structure, and an ultraviolet absorber, and a protective film formed using the same.

[Prior Art Literature] [Patent Documents]

[Patent Document 1] Japanese Patent Publication No. 2010-538103

[Patent Document 2] Japanese Patent Application Laid-Open No. 2012-41529

[Patent Document 3] International Publication No. 2014/046064

[Patent Document 4] Japanese Patent Application Laid-Open No. 2009-286706

[Patent Document 5] Japanese Patent Application Laid-Open No. 2014-92775

[Patent Document 6] Japanese Patent Laid-Open No. 2004-258544

[Patent Document 7] Chinese Patent Application Publication No. 103897391

[Patent Document 8] Japanese Patent Application Laid-Open No. 10-148835

[Patent Document 9] Japanese Patent Laid-Open No. 62-184055

[Patent Document 10] Japanese Patent Application Laid-Open No. 2014-22951

However, Patent Document 6 focuses only on the optical anisotropy of polyimide, and is not a technique that fully utilizes the characteristics of polyimide such as heat resistance, chemical resistance, mechanical strength, electrical properties, and dimensional stability. In order to manufacture polyimide (film, coating) with sufficient heat resistance, chemical resistance, mechanical strength, electrical properties, dimensional stability, etc., high temperature heat treatment is required. However, Patent Document 6 only discloses heating at a relatively low temperature in the range of 40 to 200°C, which does not have sufficient heat resistance. Moreover, in the technique of patent document 6, the kind of polyimide is limited to a specific soluble polyimide, and the application is remarkably limited.

In Patent Document 7, as described above, it is described that by using a photocurable polyimide film containing an ultraviolet absorber, the performance of a solar cell is improved, but it is not suggested that the polyimide (itself) is made by an ultraviolet absorber. ) UV durability improvement. That is, Patent Document 7 does not teach anything about adding an ultraviolet absorber to polyimide other than the composition containing a photocuring agent. Furthermore, considering that the film is formed by extrusion molding in the range of 220 to 290°C, the polyimide contained is a low heat-resistant polyimide with a melting point of 290°C or lower. It is considered that the addition of an additive such as a photohardener reduces itself and physical properties, or reduces mechanical properties such as elongation at break due to crosslinking. Therefore, in order to fully utilize the characteristics of polyimide, it is preferable not to contain a light curing agent.

Patent Document 8, as described above, discloses a polyimide solution and an alignment film formed using the same in order to solve the problems peculiar to liquid crystal alignment films, but adding an ultraviolet absorber to polyimide for applications other than liquid crystal alignment films There is no teaching. Moreover, the temperature at which the alignment film was formed was as low as 180° C., and the heat resistance of the polyimide was insufficient. In addition, the disclosed polyimide itself is insufficient in terms of mechanical properties and heat resistance.

Patent Document 9 describes adding an ultraviolet absorber in order to form a light-shielding film, that is, to shield light (ultraviolet rays), but there is no teaching for improving the ultraviolet durability of polyimide. The purpose of Patent Document 9 is to form a light-shielding film, and there is no teaching at all about adding an ultraviolet absorber to polyimide to reduce haze and coloring (yellowness).

The purpose of Patent Document 10 is to reduce the influence of ultraviolet rays on the TFT of an organic EL display element, and it is described that an ultraviolet absorber (0218) is added to the protective film thereof, but it does not teach that the ultraviolet durability of polyimide is improved. That is, Patent Document 10 does not teach the addition of an ultraviolet absorber to polyimide in applications other than the photosensitive resin composition containing a polyimide resin and a compound having a quinonediazide structure.

As described above, the problem that the conventional properties of polyimide can be exhibited and ultraviolet durability can be improved has not been solved. Therefore, an object of the present invention is to provide a polyimide material capable of exhibiting the conventional properties of polyimide and at the same time excellent in ultraviolet durability, a production method thereof, and a polyimide precursor composition used for the production thereof.

The rights of the present invention are determined by the appended claims. On the other hand, the main disclosures of this application are summarized as follows.

1. A polyimide material comprising polyimide and a UV absorber, characterized in that: 0.5% weight reduction temperature exceeds 200°C.

2. The polyimide material according to 1. above, having a haze of 15% or less.

3. For the polyimide material of 1. or 2. above, the change △YI of the yellowness before and after the ultraviolet irradiation test is less than 8; however, the conditions for the aforementioned ultraviolet irradiation test are to use a QUV-313 lamp, and the The illumination at 310nm is 0.59W/m ² , the temperature is 50°C, and the irradiation time is 24 hours.

4. The polyimide material according to any one of 1. to 3. above, wherein the polyimide contains a repeating unit represented by the following general formula (1).

In the formula, X ₁ is a tetravalent group having an aromatic ring or alicyclic structure, and Y ₁ is a divalent group having an aromatic ring or alicyclic structure.

5. The polyimide material according to the above 4., wherein X ₁ is a tetravalent group having an alicyclic structure and Y ₁ is the content of the repeating unit represented by the general formula (1) of a bivalent group of an alicyclic structure, It is 50 mol% or less with respect to all repeating units.

6. The polyimide material according to 4., wherein X ₁ in the general formula (1) is a tetravalent group having an aromatic ring, and Y ₁ is a divalent group having an aromatic ring.

7. The polyimide material according to the above 4., wherein X ₁ in the general formula (1) is a tetravalent group having an alicyclic structure, and Y ₁ is a divalent group having an aromatic ring.

8. The polyimide material according to 4. above, wherein X ₁ in the general formula (1) is a tetravalent group having an aromatic ring, and Y ₁ is a divalent group having an alicyclic structure.

9. The polyimide material according to any one of the above 1. to 8., in the form of a film or a coating.

10. The polyimide material according to any one of 1. to 9. above, wherein the ultraviolet absorber is selected from a benzotriazole compound or a heat-modified product of a benzotriazole compound.

11. A manufacturing method of a polyimide material, characterized in that: the polyimide precursor composition containing polyimide precursor, ultraviolet absorber and solvent, or the polyimide precursor composition containing polyimide, ultraviolet absorber And the polyimide solution composition of the solvent is heat-treated at a temperature exceeding 200°C.

12. The method for producing a polyimide material according to 11. above, wherein the polyimide precursor contained in the polyimide precursor composition comprises a repeating unit represented by the following general formula (A1).

In the formula, X ₁ is a tetravalent group with an aromatic ring or alicyclic structure, Y ₁ is a divalent group with an aromatic ring or alicyclic structure, R ₁ , R ₂ are each independently hydrogen, carbon number 1~ 6. Preferably, it is an alkyl group with 1 to 3 carbon atoms, or an alkylsilyl group with 3 to 9 carbon atoms.

13. The method for producing a polyimide material according to 11. above, wherein the polyimide contained in the polyimide solution composition includes a repeating unit represented by the general formula (1) defined in the above 4..

14. The manufacturing method of the polyimide material according to the above 11. has the following steps: coating the aforementioned polyimide precursor composition or the aforementioned polyimide solution composition on a substrate; The polyimide precursor composition or the polyimide solution composition on the substrate is heat-treated.

15. The method for producing a polyimide material according to any one of 11. to 14. above, wherein the heat treatment temperature is 250°C or higher.

16. The method for producing a polyimide material according to any one of 11. to 15. above, wherein the ultraviolet absorber is selected from a benzotriazole compound or a heat-modified product of a benzotriazole compound.

17. The method for producing a polyimide material according to 16. above, wherein the benzotriazole compound is selected from compounds represented by formula (100) and formula (101).

In the formula, R ₁₁ to R ₁₈ represent an organic group.

In the formula, R ₃₁ to R ₃₇ and R ₄₁ to R ₄₇ represent the meanings given to R ₁₁ to R ₁₈ , and X is a divalent organic group.

18. The method for producing a polyimide material according to 17., wherein the benzotriazole compound is selected from the group consisting of (a) and (b): (a) a compound represented by formula (100) , at this time, R ₁₁ to R ₁₈ are independently of each other H, aryl, or carbon number 1 which can also be substituted by substituted or unsubstituted maleimide (the substitution position for alkyl is N) The alkyl group of ~20, but the -CH ₂ - group in the alkyl group can also be replaced by -COO- or -OCO-; the formula does not contain Cl, and R ₁₁ to R ₁₈ do not contain more than 2 aromatic rings in total (b) a compound represented by formula (101), at this time R ₃₁ ~ R ₃₇ and R ₄₁ ~ R ₄₇ are independently H, aryl, or may also be substituted or unsubstituted maleia An alkyl group with 1 to 20 carbon atoms substituted by an amino group (the substitution position for the alkyl group is N), but the -CH ₂ - group in the alkyl group can also be replaced with -COO- or -OCO-; X is a carbon number of 1 The alkylene group of ~20, but the -CH ₂ - group in the alkyl group can also be replaced by -COO- or -OCO-; there is no Cl in the formula, and in R ₃₁ ~R ₃₇ , R ₄₁ ~R ₄₇ and X A total of two or more aromatic rings are not contained.

19. A polyimide precursor composition, characterized by comprising a polyimide precursor, an ultraviolet absorber, and a solvent.

20. The polyimide precursor composition according to the above 19., wherein the polyimide precursor system of the above-mentioned polyimide precursor system is the polyimide precursor defined in the above 12..

21. The polyimide precursor composition according to 19. or 20. above, wherein the ultraviolet absorber is selected from a benzotriazole compound or a heat-modified product of a benzotriazole compound.

22. The polyimide precursor composition according to 21. above, wherein the benzotriazole compound is selected from compounds represented by formula (100) and formula (101).

In the formula, R ₁₁ to R ₁₈ represent an organic group.

In the formula, R ₃₁ to R ₃₇ and R ₄₁ to R ₄₇ represent the meanings given to R ₁₁ to R ₁₈ , and X is a divalent organic group.

23. The polyimide precursor composition according to 22. above, wherein the benzotriazole compound is selected from the group consisting of (a) and (b); (a) a compound represented by formula (100) , at this time R ₁₁ ~ R ₁₈ are independently H, aryl, or can also be substituted or unsubstituted maleimide group (the substitution position of the alkyl group is N) with carbon number 1 ~ The alkyl group of 20, but the -CH ₂ - group in the alkyl group can also be replaced by -COO- or -OCO-; the formula does not contain Cl, and R ₁₁ to R ₁₈ do not contain more than 2 aromatic rings in total; ( b) The compound represented by the formula (101), in this case, R ₃₁ ˜R ₃₇ and R ₄₁ ˜R ₄₇ are independently H, aryl, or maleimide which may also be substituted or unsubstituted Alkyl group (the substitution position of the alkyl group is N) substituted alkyl group with carbon number 1~20, but the -CH ₂ - group in the alkyl group can also be replaced by -COO- or -OCO-; X is carbon number 1~ Alkylidene of 20, but the -CH ₂ - group in the alkyl group can also be replaced with -COO- or -OCO-; Cl is not included in the formula, and the total of R ₃₁ ~R ₃₇ , R ₄₁ ~R ₄₇ and X is not Contains two or more aromatic rings.

In addition to the above-mentioned disclosures, desirable embodiments of the present application have one or two or more of the features listed below.

Regarding the polyimide material, (a-1) does not contain a photosensitive component and a modified product derived from the photosensitive component; (a-2) the haze of the polyimide material is 15% or less, or the yellowness (YI ) Both before and after the ultraviolet irradiation test are 15 or less, or when the polyimide material forms a thin film or coating film with a thickness of at least one in the range of 5~100 μm, the haze is 15 % or less, or the yellowness (YI) before and after the ultraviolet irradiation test are both less than 15 (however, the conditions of the aforementioned ultraviolet irradiation test are to use a QUV-313 lamp, the illuminance at 310nm is 0.59W/m ² and the temperature is 50°C , irradiation time of 24 hours); (a-3) X ₁ of the general formula (1) is the content of repeating units with tetravalent groups with alicyclic structure, which is the ratio of more than 60% of all repeating units (only X ₁ The content of the repeating unit represented by the general formula (1), which is a tetravalent group with an alicyclic structure and Y ₁ is a divalent group with an alicyclic structure, is less than 50 mol% relative to all the repeating units); (a- 4) Y ₁ of the general formula (1) is the content of repeating units derived from at least one of 2,2'-bis(trifluoromethyl)benzidine and m-tolidine, and is all repeating (a-5) The melting point of the aforementioned polyimide is 300°C or higher; (a-6) The main chain of the aforementioned polyimide does not contain methylene groups with more than 4 carbon atoms Long chain; (a-7) is not an alignment film.

Regarding the polyimide precursor composition, (b-1) is not used for liquid crystal alignment films; (b-2) uses the polyimide precursor composition to form a polyimide having at least one thickness in the range of 5 to 100 μm In the case of an imine film or a polyimide coating film, a polyimide material with a haze of less than 15% or a yellowness (YI) of less than 15 before and after the ultraviolet irradiation test is obtained (except for the aforementioned ultraviolet irradiation test). The conditions are to use QUV-313 lamp, illuminance at 310nm of 0.59W/m ² , temperature of 50°C, and irradiation time of 24 hours); (b-3) In the polyimide precursor, X ₁ of the general formula (A1) It is the content of repeating units with tetravalent groups with alicyclic structure, and is the ratio of more than 60% of all repeating units (but X ₁ is a tetravalent group with an alicyclic structure and Y ₁ is a bivalent group with an alicyclic structure. (b-4) In the polyimide precursor, Y ₁ of the general formula (A1) is from The content of repeating units selected from groups derived from at least one of 2,2'-bis(trifluoromethyl)benzidine and m-tolidine is a ratio of 50% or more of all repeating units; (b-5) ) The main chain of the polyimide precursor does not contain a long methylene chain having more than 4 carbon atoms.

According to the present invention, in addition to the conventional properties of polyimide, a polyimide material excellent in ultraviolet durability can be provided.

The polyimide of the present invention is preferably in the form of a film or a coating. In particular, when a high-transparency polyimide is used, good UV resistance can be imparted to a polyimide film having excellent properties without sacrificing transparency. Thereby, the use of polyimide can be expanded extraordinarily.

In the present invention, the term "polyimide material" is used to distinguish it from "polyimide" in the form of a substance. That is, the term "polyimide material" is defined as one containing a polyimide and an ultraviolet absorber, and it means a solid state and does not contain a solution. For example: those that exist in the form of films, coatings (formed on other substrates), powders, and blocks. In addition, the polyimide precursor system refers to what is given to polyimide by treating it.

Hereinafter, the polyimide and the ultraviolet absorber contained in the polyimide material of the present invention, and the production method of the polyimide material will be described. The polyimide precursor composition of the present invention is described in the manufacturing method of the polyimide material.

<<Polyimide>>

The polyimide contained in the polyimide material of the present invention is not particularly limited, and the tetracarboxylic acid component and the diamine component are appropriately composed of polyimide selected from aromatic compounds and alicyclic compounds. For example: wholly aromatic polyimide, semi-alicyclic polyimide, fully alicyclic polyimide.

That is, the polyimide used in the present invention contains a repeating unit represented by the following general formula (1).

In the formula, X ₁ is a tetravalent group having an aromatic ring or alicyclic structure and Y ₁ is a divalent group having an aromatic ring or alicyclic structure.

The polyimide material obtained is not particularly limited, but X ₁ in the general formula (1) is preferably a tetravalent group having an aromatic ring and Y ₁ is a divalent group having an aromatic ring in order to obtain excellent heat resistance. Moreover, it is preferable that X ₁ is a tetravalent group having an alicyclic structure and Y ₁ is a divalent group having an aromatic ring in order to be excellent in heat resistance and transparency at the same time as the obtained polyimide material. In addition, in order to obtain a polyimide material having excellent heat resistance and excellent dimensional stability, X ₁ is preferably a tetravalent group having an aromatic ring and Y ₁ is a divalent group having an alicyclic structure.

Considering the properties of the obtained polyimide material, for example, from the viewpoint of transparency, mechanical properties, or heat resistance, X ₁ is a tetravalent group with an alicyclic structure and Y ₁ is a formula with a divalent group with an alicyclic structure The content of the repeating units represented by (1) is preferably 50 mol % or less, more preferably 30 mol % or less or less than 30 mol %, and still more preferably 10 mol % or less with respect to all repeating units.

In a certain embodiment, X ₁ is a tetravalent group having an aromatic ring, and Y ₁ is a content of one or more of the repeating units of the aforementioned formula (1) having a divalent group having an aromatic ring, relative to the total. The total repeating unit is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, still more preferably 90 mol% or more, particularly preferably 100 mol%. In this embodiment, especially when a polyimide material with high transparency is required, the polyimide preferably contains fluorine atoms. That is, the polyimide preferably contains the repeating unit of the aforementioned general formula (1) in which X ₁ is a tetravalent group having an aromatic ring containing a fluorine atom and/or Y ₁ is 2 that has an aromatic ring containing a fluorine atom. One or more kinds of the repeating units of the aforementioned general formula (1) of the valence group are preferred.

In one embodiment, X ₁ in the polyimide is a tetravalent group having an alicyclic structure, and Y ₁ is one or more repeating units of the aforementioned general formula (1) in which Y 1 is a divalent group having an aromatic ring. The content of the total amount of all repeating units is preferably 50 mol% or more, more preferably 70 mol% or more, more preferably 80 mol% or more, more preferably 90 mol% or more, especially is 100 mol%.

In one embodiment, X ₁ in the polyimide is a tetravalent group having an aromatic ring and Y ₁ is one or more of the repeating units of the aforementioned formula (1) wherein Y 1 is a bivalent group having an alicyclic structure. The content is preferably 50 mol % or more, more preferably 70 mol % or more, more preferably 80 mol % or more, more preferably 90 mol % or more, more preferably 90 mol % or more with respect to the total of the repeating units. 100 mol%.

The tetravalent group having an aromatic ring as X ₁ is preferably a tetravalent group having an aromatic ring having 6 to 40 carbon atoms.

The tetravalent group having an aromatic ring is, for example, listed below.

In the formula, Z ₁ is a direct bond, or any one of the following divalent groups:

In the formula, Z ₂ is a divalent organic group, Z ₃ and Z ₄ are each independently an amide bond, an ester bond, and a carbonyl bond, and Z ₅ is an aromatic ring-containing organic group.

Specific examples of Z ₂ include aliphatic hydrocarbon groups having 2 to 24 carbon atoms and aromatic hydrocarbon groups having 6 to 24 carbon atoms.

Specific examples of Z ₅ include aromatic hydrocarbon groups having 6 to 24 carbon atoms.

As the tetravalent group having an aromatic ring, the following are particularly desirable because they can achieve both high heat resistance and high transparency of the obtained polyimide material.

In the formula, Z ₁ is a direct bond or a hexafluoroisopropylidene bond.

Here, if Z ₁ is a direct bond, it is more desirable because high heat resistance, high transparency, and low coefficient of linear thermal expansion of the obtained polyimide material can be achieved.

A tetracarboxylic acid component to which X ₁ is a repeating unit of the general formula (1) having a tetravalent group of an aromatic ring, for example: 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 4- (2,5-Dioxytetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, pyromellitic acid, 3,3',4,4' - Benzophenone tetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 4,4'-oxydi-o-phenylene Dicarboxylic acid, bis(3,4-dicarboxyphenyl) bismuth, m-triphenyl-3,4,3',4'-tetracarboxylic acid, p-triphenyl-3,4,3',4'-tetra Carboxylic acid, biscarboxyphenyldimethylsilane, bisdicarboxyphenoxydiphenyl sulfide, sulfonyldiphthalic acid, tetracarboxylic dianhydrides of these, tetracarboxylate silicon ester, tetracarboxylate Derivatives such as acid esters, tetracarboxylate chloride, etc. X ₁ is a tetracarboxylic acid component that gives a repeating unit of the general formula (1) having a tetravalent group of an aromatic ring containing a fluorine atom, for example: 2,2-bis(3,4-dicarboxyphenyl)hexafluoro Propane, its tetracarboxylic dianhydride, tetracarboxylic silicon ester, tetracarboxylic acid ester, tetracarboxylic acid chloride and other derivatives. The tetracarboxylic acid component may be used alone or in combination of two or more.

The tetravalent group having an alicyclic structure of X ₁ is preferably a tetravalent group having an alicyclic structure having 4 to 40 carbon atoms, preferably at least one aliphatic 4 to 12-membered ring, more preferably having at least one 1 aliphatic 4-membered ring or aliphatic 6-membered ring. Desirable tetravalent groups having an aliphatic 4-membered ring or an aliphatic 6-membered ring are listed below.

In the formula, R ₃₁ to R ₃₈ are each independently a direct bond or a divalent organic group. R ₄₁ to R ₄₇ are independently selected from the group consisting of bases represented by the formulae: -CH ₂ -, -CH=CH-, -CH ₂ CH ₂ -, -O-, and -S-. R ₄₈ is an organic group containing an aromatic ring or an alicyclic structure.

R ₃₁ , R ₃₂ , R ₃₃ , R ₃₄ , R ₃₅ , R ₃₆ , R ₃₇ , and R ₃₈ specifically include a direct bond, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, or an oxygen atom (-O- ), sulfur atom (-S-), carbonyl bond, ester bond, amide bond.

Examples of the aromatic ring-containing organic group of R ₄₈ include, for example, the following.

In the formula, W ₁ is a direct bond or a divalent organic group, n ₁₁ to n ₁₃ each independently represent an integer of 0 to 4, and R ₅₁ , R ₅₂ , and R ₅₃ are each independently a carbon number of 1 to 6. Alkyl, halo, hydroxyl, carboxyl, or trifluoromethyl.

Specifically, W ₁ includes a direct bond, a divalent group represented by the following formula (5), and a divalent group represented by the following formula (6).

R ₆₁ to R ₆₈ in the formula (6) each independently represent a direct bond or any one of the divalent groups represented by the aforementioned formula (5).

When the tetravalent group having an alicyclic structure is one of the following, it is particularly preferable to achieve high heat resistance, high transparency, and low coefficient of linear thermal expansion of the obtained polyimide.

A tetracarboxylic acid component to which X ₁ is a repeating unit of formula (1) having a tetravalent group having an alicyclic structure, for example: 1,2,3,4-cyclobutanetetracarboxylic acid, isopropylidene diphenoxy diphthalic acid, cyclohexane-1,2,4,5-tetracarboxylic acid, [1,1'-bi(cyclohexane)]-3,3',4,4'-tetracarboxylic acid , [1,1'-bi(cyclohexane)]-2,3,3',4'-tetracarboxylic acid, [1,1'-bi(cyclohexane)]-2,2',3, 3'-tetracarboxylic acid, 4,4'-methylenebis(cyclohexane-1,2-dicarboxylic acid), 4,4'-(propane-2,2-diyl)bis(cyclohexane) -1,2-dicarboxylic acid), 4,4'-oxybis(cyclohexane-1,2-dicarboxylic acid), 4,4'-thiobis(cyclohexane-1,2-dicarboxylic acid) acid), 4,4'-sulfonylbis(cyclohexane-1,2-dicarboxylic acid), 4,4'-(dimethylsilanediyl)bis(cyclohexane-1,2-dicarboxylic acid) carboxylic acid), 4,4'-(tetrafluoropropane-2,2-diyl)bis(cyclohexane-1,2-dicarboxylic acid), octahydropentalyne-1,3,4,6- Tetracarboxylic acid, bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic acid, 6-(carboxymethyl)bicyclo[2.2.1]heptane-2,3,5-tricarboxylic acid , Bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic acid, Bicyclo[2.2.2]oct-5-ene-2,3,7,8-tetracarboxylic acid, Tricyclo[4.2 .2.02,5]decane-3,4,7,8-tetracarboxylic acid, tricyclo[4.2.2.02,5]dec-7-ene-3,4,9,10-tetracarboxylic acid, 9-oxo Heterotricyclo[4.2.1.02,5]nonane-3,4,7,8-tetracarboxylic acid, norbornane-2-spiro-α-cyclopentanone-α'-spiro-2"-norbornane 5,5",6,6"-tetracarboxylic acid, (4arH, 8acH)-decahydro-1t,4t: 5c,8c-dimethylnaphthalene-2c,3c,6c,7c-tetracarboxylic acid, (4arH , 8acH)-decahydro-1t,4t: 5c,8c-dimethylnaphthalene-2t,3t,6c,7c-tetracarboxylic acid, these tetracarboxylic dianhydrides, tetracarboxylic silicon esters, tetracarboxylic acids Derivatives such as esters, tetracarboxylate chloride, etc. The tetracarboxylic acid components may be used alone or in combination.

The divalent group having an aromatic ring of Y ₁ is preferably a divalent group having an aromatic ring having 6 to 40 carbon atoms, and more preferably a divalent group having an aromatic ring having 6 to 20 carbon atoms.

As a divalent group having an aromatic ring, for example, the following are mentioned.

In the formula, W ₁ is a direct bond or a divalent organic group, n ₁₁ to n ₁₃ each independently represent an integer of 0 to 4, and R ₅₁ , R ₅₂ , and R ₅₃ are each independently a carbon number of 1 to 6. Alkyl, halo, hydroxyl, carboxyl, or trifluoromethyl.

Specifically, W ₁ includes a direct bond, a divalent group represented by the following formula (5), and a divalent group represented by the following formula (6).

R ₆₁ to R ₆₈ in the formula (6) each independently represent a direct bond or any one of the divalent groups represented by the aforementioned formula (5).

Here, considering the high heat resistance, high transparency and low coefficient of linear thermal expansion of the obtained polyimide, W ₁ is preferably a direct bond, or selected from the following formulas: -NHCO-, -CONH-, -COO- , One of the groups represented by the base represented by -OCO- is particularly preferred. In addition, W ₁ represents that R ₆₁ to R ₆₈ are a direct bond, or one of the aforementioned formulas (6 ) is also particularly desirable.

、2,4-雙(4-胺基苯胺基)-6-甲胺基-1,3,5-三

、2,4-雙(4-胺基苯胺基)-6-乙胺基-1,3,5-三

、2,4-雙(4-胺基苯胺基)-6-苯胺基-1,3,5-三

。給予Y₁係具有含氟原子之芳香族環的2價基的通式(1)的重複單元之二胺成分，例如：2,2’-雙(三氟甲基)聯苯胺、3,3’-雙(三氟甲基)聯苯胺、2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷、2,2-雙(4-胺基苯基)六氟丙烷、2,2’-雙(3-胺基-4-羥基苯基)六氟丙烷。二胺成分可以單獨使用也可組合使用多種。 A diamine component to which Y ₁ is a repeating unit of the general formula (1) having a divalent group of an aromatic ring, for example: p-phenylenediamine, m-phenylenediamine, benzidine, 3,3'-diamino- Biphenyl, 2,2'-bis(trifluoromethyl)benzidine, 3,3'-bis(trifluoromethyl)benzidine, m-tolidine, 4,4'-diaminobenzidine , 3,4'-diaminobenzidine, N,N'-bis(4-aminophenyl)terephthalamide, N,N'-p-phenylene bis(p-aminobenzene) Carboxamide), 4-aminophenoxy-4-diaminobenzoate, bis(4-aminophenyl)terephthalate, biphenyl-4,4'-dicarboxylic acid Bis(4-aminophenyl)ester, p-phenylene bis(p-aminobenzoate), bis(4-aminophenyl)-[1,1'-biphenyl]-4,4' -Dicarboxylate, [1,1'-biphenyl]-4,4'-diylbis(4-aminobenzoate), 4,4'-oxydiphenylamine, 3,4'- Oxydiphenylamine, 3,3'-oxydiphenylamine, p-methylenebis(phenylenediamine), 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3- Aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3 -Aminophenoxy)biphenyl, 2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane , bis(4-aminophenyl) bismuth, 3,3'-bis(trifluoromethyl)benzidine, 3,3'-bis((aminophenoxy)phenyl)propane, 2,2' -Bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(4-(4-aminophenoxy)diphenyl) bis(4-(3-aminophenoxy) diphenyl) bismuth, octafluorobenzidine, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl , 3,3'-difluoro-4,4'-diaminobiphenyl, 2,4-bis(4-aminoanilino)-6-amino-1,3,5-triphenyl

, 2,4-bis(4-aminoanilino)-6-methylamino-1,3,5-tri

, 2,4-bis(4-aminoanilino)-6-ethylamino-1,3,5-tri

, 2,4-bis(4-aminoanilino)-6-anilino-1,3,5-tri

. A diamine component that gives Y ₁ a repeating unit of the general formula (1) having a divalent group of an aromatic ring containing a fluorine atom, for example: 2,2'-bis(trifluoromethyl)benzidine, 3,3 '-Bis(trifluoromethyl)benzidine, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexa Fluoropropane, 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane. The diamine component may be used alone or in combination of two or more.

As the divalent group with an alicyclic structure of Y ₁ , it is preferably a divalent group with an alicyclic structure with a carbon number of 4 to 40. Preferably, it has at least one aliphatic 4 to 12-membered ring, more preferably has at least 1 An aliphatic 6-membered ring is more ideal.

As a divalent group which has an alicyclic structure, the following are mentioned, for example.

In the formula, V ₁ and V ₂ are each independently a direct bond or a divalent organic group, n ₂₁ to n ₂₆ are each independently an integer of 0 to 4, and R ₈₁ to R ₈₆ are each independently a carbon number of 1 ~6 alkyl group, halogen group, hydroxyl group, carboxyl group, or trifluoromethyl group, R ₉₁ , R ₉₂ , R ₉₃ are each independently selected from the formula: -CH ₂ -, -CH=CH-, -CH ₂ CH _2. One of the groups of bases represented by -, -O-, and -S-.

Specific examples of V ₁ and V ₂ include a direct bond and a divalent group represented by the aforementioned formula (5).

As the divalent group having an alicyclic structure, considering both the high heat resistance and the low coefficient of linear thermal expansion of the obtained polyimide, the following is particularly preferable.

As a divalent group having an alicyclic structure, the following are preferable.

A diamine component to which Y ₁ is a repeating unit of the general formula (1) having a divalent group having an alicyclic structure, for example: 1,4-diaminocyclohexane, 1,4-diamino-2-methyl cyclohexane, 1,4-diamino-2-ethylcyclohexane, 1,4-diamino-2-n-propylcyclohexane, 1,4-diamino-2-isopropyl cyclohexane, 1,4-diamino-2-n-butylcyclohexane, 1,4-diamino-2-isobutylcyclohexane, 1,4-diamino-2-diaminocyclohexane Dibutylcyclohexane, 1,4-diamino-2-tert-butylcyclohexane, 1,2-diaminocyclohexane, 1,3-diaminocyclobutane, 1,4 - Bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, diaminobicycloheptane, diaminomethylbicycloheptane, diaminooxybicycloheptane , diaminomethoxybicycloheptane, isophorone diamine, diaminotricyclodecane, diaminomethyltricyclodecane, bis(aminocyclohexyl)methane, bis(aminocyclohexyl) Hexyl) isopropylidene, 6,6'-bis(3-aminophenoxy)-3,3,3',3'-tetramethyl-1,1'-spiroindene, 6, 6'-bis(4-aminophenoxy)-3,3,3',3'-tetramethyl-1,1'-spiroindene. The diamine component may be used alone or in combination of two or more.

The polyimide containing at least one of the repeating units represented by the aforementioned general formula (1) may include other repeating units other than the repeating units represented by the aforementioned general formula (1).

The tetracarboxylic acid component and the diamine component which give other repeating units are not particularly limited, and other well-known aliphatic tetracarboxylic acids and well-known aliphatic diamines can also be used. Other tetracarboxylic acid components may be used alone or in combination of two or more. Other diamine components may be used alone or in combination.

The content of other repeating units other than the repeating units represented by the aforementioned formula (1) is preferably 30 mol % or less or less than 30 mol % relative to all repeating units, more preferably 20 mol % or less, and even more Preferably, it is 10 mol% or less.

Among the above, in a preferred embodiment of the present invention, X ₁ of the general formula (1) is the content of the repeating unit having a tetravalent group having an alicyclic structure, which is more than 60% of all repeating units, more preferably 70%. It is more than mol%, more preferably more than 80 mol%, more preferably more than 90 mol%, especially preferably 100 mol%. When the alicyclic structure is less than 100%, the rest is preferably X ₁ is a tetravalent group having an aromatic ring. Desirable tetravalent groups having an alicyclic structure and tetravalent groups having an aromatic ring are as described above. In addition, Y ₁ may be any of a divalent group having an aromatic ring and a divalent group having an alicyclic structure, but as described above, X ₁ is a tetravalent group having an alicyclic structure and Y ₁ is an aliphatic group The content of the repeating unit represented by the formula (1) of the divalent group of the ring structure is preferably 50 mol % or less, more preferably 30 mol % or less, or less than 30 mol %, relative to all repeating units. Preferably, it is 10 mol% or less.

In addition, in a different desirable embodiment of the present invention, Y ₁ of the general formula (1) includes a compound derived from at least one selected from the group consisting of 2,2'-bis(trifluoromethyl)benzidine and m-tolidine The structure and content are preferably more than 50% of all repeating units, more preferably more than 50%, still more preferably more than 60%, more preferably more than 70%, 100% is also ideal. When this structure is not 100%, the remaining Y ₁ may be, for example, a divalent group having an aromatic ring. In addition, X ₁ may be either a tetravalent group having an aromatic ring or a tetravalent group having an alicyclic structure, and in a certain embodiment, a tetravalent group having an aromatic ring is more preferable, and in different In an embodiment, a tetravalent group having an alicyclic structure is more preferable. The ideal basis is as described above.

Furthermore, in the present invention, the polyimide preferably does not contain a long methylene chain in the main chain. Patent Document 8 (Japanese Patent Laid-Open No. 10-148835) uses a component containing a long-chain methylene group (decamethylene group) such as decamethylene bis-trimellitic dianhydride, but if the main chain contains a long-chain methylene group. A methyl group reduces mechanical strength and heat resistance. Therefore, in the present invention, the length of the methylene chain which may also exist in the main chain is not more than 4 carbon atoms (tetramethylene), preferably not more than 3 carbon atoms (propylene group), more preferably carbon atoms The number of carbon atoms is not more than 2 (ethylidene group), more preferably not more than 1 (methylene group), and it is also preferable that there is no methylene chain in the main chain.

In addition, in another preferred embodiment of the present invention, a polyimide (and a polyimide material) having a breaking strength of 100 MPa or more when formed into a thin film is preferable. The breaking strength can use a value obtained from a film having a thickness of, for example, about 5 to 100 μm. In addition, this breaking strength is a value obtained for a film obtained by heating a polyimide precursor solution composition or a coating film of the polyimide solution composition at preferably a maximum temperature of 260°C.

Furthermore, in a different embodiment of the present invention, the polyimide (and the polyimide material) preferably has a melting point above 300°C. Here, the melting point can be determined using differential scanning calorimetry. Moreover, it is more preferable to have a melting point of 400°C or higher. Here, "having a melting point of xx°C or higher" includes the case where the polyimide does not exhibit a melting point (they decompose due to high temperature before exhibiting a melting point).

、2,4-雙(4-胺基苯胺基)-6-甲胺基-1,3,5-三

、2,4-雙(4-胺基苯胺基)-6-乙胺基-1,3,5-三

、2,4-雙(4-胺基苯胺基)-6-苯胺基-1,3,5-三

、2,4-雙(4-胺基苯胺基)-6-苯胺基-1,3,5-三

、1,4-二胺基環己烷、1,4-二胺基-2-甲基環己烷、1,4-二胺基-2-乙基環己烷、1,4-二胺基-2-正丙基環己烷、1,4-二胺基-2-異丙基環己烷、1,4-二胺基-2-正丁基環己烷、1,4-二胺基-2-異丁基環己烷、1,4-二胺基-2-第二丁基環己烷、1,4-二胺基-2-第三丁基環己烷、1,2-二胺基環己烷、1,3-二胺基環丁烷、1,4-雙(胺基甲基)環己烷、1,3-雙(胺基甲基)環己烷、二胺基雙環庚烷、二胺基甲基雙環庚烷、二胺氧基雙環庚烷、二胺基甲氧基雙環庚烷、異佛爾酮二胺者。又，實施例合成之聚醯亞胺皆有300℃以上之熔點。 Examples of the polyimide exhibiting a melting point of 300°C or higher include tetracarboxylic acid components selected from the group consisting of 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, pyromellitic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 4,4'- Oxydiphthalic acid, bis(3,4-dicarboxyphenyl) bismuth, m-triphenyl-3,4,3',4'-tetracarboxylic acid, p-triphenyl-3,4,3',4'-tetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, cyclohexane-1,2,4,5-tetracarboxylic acid, [1,1'-bi(cyclohexane) )]-3,3',4,4'-tetracarboxylic acid, [1,1'-bi(cyclohexane)]-2,3,3',4'-tetracarboxylic acid, [1,1'- -Bi(cyclohexane)]-2,2',3,3'-tetracarboxylic acid, octahydropentalevene-1,3,4,6-tetracarboxylic acid, bicyclo[2.2.1]heptane- 2,3,5,6-tetracarboxylic acid, 6-(carboxymethyl)bicyclo[2.2.1]heptane-2,3,5-tricarboxylic acid, bicyclo[2.2.2]octane-2,3 ,5,6-tetracarboxylic acid, bicyclo[2.2.2]oct-5-ene-2,3,7,8-tetracarboxylic acid, tricyclo[4.2.2.02,5]decane-3,4,7 ,8-tetracarboxylic acid, tricyclo[4.2.2.02,5]dec-7-ene-3,4,9,10-tetracarboxylic acid, 9-oxatricyclo[4.2.1.02,5]nonane- 3,4,7,8-Tetracarboxylic acid, norbornane-2-spiro-α-cyclopentanone-α'-spiro-2"-norbornane 5,5",6,6"-tetracarboxylic acid , (4arH,8acH)-decahydro-1t,4t:5c,8c-dimethylnaphthalene-2c,3c,6c,7c-tetracarboxylic acid, (4arH,8acH)-decahydro-1t,4t:5c, 8c-dimethylnaphthalene-2t,3t,6c,7c-tetracarboxylic acid and derivatives of these tetracarboxylic dianhydrides, tetracarboxylic silicon esters, tetracarboxylic acid esters, tetracarboxylic acid chlorides, etc., and diamine components are Selected from p-phenylenediamine, m-phenylenediamine, benzidine, 3,3'-diamino-biphenyl, 2,2'-bis(trifluoromethyl)benzidine, 3,3'-bis(trifluoromethyl)benzidine Fluoromethyl)benzidine, m-tolidine, 4,4'-diaminobenzidine, 3,4'-diaminobenzidine, N,N'-bis(4-aminobenzene base) terephthalamide, N,N'-p-phenylene bis(p-aminobenzamide), 4-aminophenoxy-4-diaminobenzoate, bis(4 - aminophenyl) terephthalate, biphenyl-4,4'-dicarboxylate bis(4-aminophenyl) ester, p-phenylene bis(p-aminobenzoate), Bis(4-aminophenyl)-[1,1'-biphenyl]-4,4'-dicarboxylate, [1,1'-biphenyl]-4,4'-diylbis(4 -aminobenzoate), 4,4'-oxydiphenylamine, 3,4'-oxydiphenylamine, 3,3'-oxydiphenylamine, p-methylenebis(phenylenediamine), 1,3-bis(4-aminophenoxy)benzene, 1,3 -Bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4 '-Bis(3-aminophenoxy)biphenyl, 2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane, 2,2-bis(4-aminobenzene) base) hexafluoropropane, bis(4-aminophenoxy)phenyl), 3,3'-bis(trifluoromethyl)benzidine, 3,3'-bis((aminophenoxy)phenyl)propane , 2,2'-bis(3-amino-4-hydroxyphenyl) hexafluoropropane, bis(4-(4-aminophenoxy)diphenyl) bis(4-(3-amine) phenoxy) diphenyl) benzene, octafluorobenzidine, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'- Diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 2,4-bis(4-aminoanilino)-6-amino-1,3,5- three

, 2,4-bis(4-aminoanilino)-6-methylamino-1,3,5-tri

, 2,4-bis(4-aminoanilino)-6-ethylamino-1,3,5-tri

, 2,4-bis(4-aminoanilino)-6-anilino-1,3,5-tri

, 2,4-bis(4-aminoanilino)-6-anilino-1,3,5-tri

, 1,4-diaminocyclohexane, 1,4-diamino-2-methylcyclohexane, 1,4-diamino-2-ethylcyclohexane, 1,4-diamine yl-2-n-propylcyclohexane, 1,4-diamino-2-isopropylcyclohexane, 1,4-diamino-2-n-butylcyclohexane, 1,4-diamino Amino-2-isobutylcyclohexane, 1,4-diamino-2-tert-butylcyclohexane, 1,4-diamino-2-tert-butylcyclohexane, 1,4-diamino-2-tert-butylcyclohexane 2-diaminocyclohexane, 1,3-diaminocyclobutane, 1,4-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, Diaminobicycloheptane, diaminomethylbicycloheptane, diaminooxybicycloheptane, diaminomethoxybicycloheptane, and isophoronediamine. In addition, the polyimides synthesized in the examples all have melting points above 300°C.

<<UV Absorber>>

系紫外線吸收劑、受阻胺系紫外線吸收劑、無機粒子系紫外線吸收劑、其他、草酸苯胺化物系紫外線吸收劑、丙二酸酯系紫外線吸收劑等有機系紫外線吸收劑。本發明中，紫外線吸收劑可僅使用1種，也可併用2種以上。其中，苯并三唑系紫外線吸收劑及三

系紫外線吸收劑較理想，苯并三唑系紫外線吸收劑更理想。苯并三唑系化合物之中，理想結構依後述式(100)及式(101)。 As the ultraviolet absorber contained in the present invention, any appropriate ultraviolet absorber can be used as long as the object of the present invention can be achieved. For example: benzotriazole-based UV absorbers, benzophenone-based UV absorbers, benzoate-based UV absorbers,

Organic UV absorbers such as UV absorbers, hindered amine UV absorbers, inorganic particle UV absorbers, others, oxalate aniline UV absorbers, and malonate UV absorbers. In the present invention, only one type of ultraviolet absorber may be used, or two or more types may be used in combination. Among them, benzotriazole-based ultraviolet absorbers and three

A UV absorber is preferable, and a benzotriazole-based UV absorber is more preferable. Among the benzotriazole-based compounds, ideal structures are as described below by formula (100) and formula (101).

Benzotriazole-based UV absorbers, such as: 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5' -Methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-pentylphenyl)benzotriazole, 2-(2'-hydroxyl -5'-Third-octylphenyl)benzotriazole, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-tert-octylphenol], 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2'-hydroxy-5'-tert-butylbenzene base)-2H-benzotriazole, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H- Benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3,-tetramethylbutyl)phenol, 2,2' - Methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2-(3,5-di- tert-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(2H-benzotriazole-2 -yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-benzotriazol-2-yl-4,6-di-tert-butylphenol, 2-[ 5-Chloro(2H)-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol, 2-(2H-benzotriazol-2-yl)-4,6 -Di-tert-butylphenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H-benzoyl) Triazol-2-yl)-4-methyl-6-(3,4,5,6-tetrahydrophthalimidomethyl)phenol, methyl 3-(3-(2H-benzene 2-(2H-benzotriazol-2-yl)- 6-(Linear and side-chain dodecyl)-4-methylphenol.

Specific examples of benzotriazole-based UV absorbers include Tinuvin PS, Tinuvin 109, Tinuvin 1130, Tinuvin 171, Tinuvin 326, Tinuvin 328, Tinuvin 384-2, Tinuvin 99-2, Tinuvin 900, Tinuvin 928, Tinuvin Carboprotect, Sumisorb 200, Sumisorb 250, Sumisorb 300, Sumisorb 340, Sumisorb 350 from Sumikachemtex, LA-29, LA-31, LA-32, LA-36 from ADEKA, JF-77, JF- 79, JF-80, JF-83, JF-832, JAST-500, KEMISORB 71 of Chemipro Kasei Company, KEMISORB 73, KEMISORB 74, KEMISORB 79, KEMISORB 279, SEESORB of Ciprokasei Company 701, SEESORB 703, SEESORB 704, SEESORB 706, SEESORB 707, SEESORB 709, etc.

The benzotriazole-based ultraviolet absorber is not particularly limited, and can be represented by the following general formula (100).

In the formula, R ₁₁ to R ₁₈ represent an organic group.

Preferably, R ₁₁ to R ₁₈ are independently of each other H, Cl, or an alkyl group having 1 to 20 carbon atoms which may also be substituted by a substituent, preferably an alkyl group having at most 10 carbon atoms. As the substituent of the alkyl group, an aryl group such as a phenyl group, a substituted or unsubstituted maleimide group (the substitution position of the alkyl group is N), and the like can be mentioned. However, the -CH ₂ - group in the alkyl group can also be replaced by -COO- or -OCO-. The alkyl group is preferably a branched alkyl group or a substituted group.

R ₁₁ to R ₁₄ are more preferably H. More preferably, R ₁₅ and R ₁₇ are H. R ₁₆ and R ₁₈ are more preferably H, independently of each other, an alkyl group as defined above, preferably an alkyl group having at most 10 carbon atoms.

In addition, the benzotriazole compound may have a structure in which two or more of the structures represented by the formula (100) are connected in common with one of each of R ₁₁ to R ₁₈ . For example, one of R ₁₁ to R ₁₈ in the first structure represented by the formula (100) and one of R ₁₁ to R ₁₈ in the second structure represented by the formula (100) may be common to represent a divalent organic base, and the first structure and the second structure are bonded. The common organic group is preferably an alkylene group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. An example of a compound obtained by linking two structures represented by the formula (100) is represented by the formula (101).

In the formula, R ₃₁ to R ₃₇ and R ₄₁ to R ₄₇ represent the meanings given to R ₁₁ to R ₁₈ , and X is a divalent organic group.

The ideal meanings of R ₃₁ -R ₃₇ and R ₄₁ -R ₄₇ are as given above for R ₁₁ -R ₁₈ . In particular, R ₃₁ to R ₃₄ and R ₄₁ to R ₄₄ are more preferably H, and R ₃₅ , R ₃₇ , R ₄₅ and R ₄₇ are more preferably H. More preferably, R ₃₆ and R ₄₆ are independently of each other H, an alkyl group as defined above, and preferably an alkyl group having at most 10 carbon atoms. X corresponds to the structure linked by R ₁₈ in the formula (100), and is preferably an alkylene group having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms.

An example of this structure is LA-31 described later.

The benzotriazole-based ultraviolet absorber is not particularly limited, and from the viewpoint of heat resistance and transmittance, among R ₁₁ to R ₁₈ of formula (100), R ₃₁ to R 37 of formula (101) to R ₃₇ , R ₄₁ to R ₄₇ and X preferably do not contain Cl, more preferably.

Not particularly limited, for benzotriazole-based ultraviolet absorbers, considering the compatibility with polyimide, among R ₁₁ to R ₁₈ of formula (100), for R ₃₁ of formula (101) Among ~R ₃₇ , R ₄₁ , ~R ₄₇ and X, it is more preferable not to contain two or more aromatic rings in total. When two or more aromatic rings are contained in these groups in one compound in total, the obtained polyimide film may be fogged. More preferably, among R ₁₁ to R ₁₈ of formula (100), R ₃₁ to R ₃₇ , R ₄₁ to R ₄₇ and X of formula (101) do not contain an aromatic ring.

系紫外線吸收劑而言，可列舉2-(4,6-二苯基-1,3,5-三

-2-基)-5-[(己基)氧基]-苯酚、2-(4,6-雙(2,4-二甲基苯基)-1,3,5-三

-2-基)-5-羥基苯基、2,4-雙[2-羥基-4-丁氧基苯基]-6-(2,4-二丁氧基苯基)-1,3,5-三

、2-(4,6-二苯基-1,3,5-三

-2-基)-5-[2-(2-乙基己醯氧基)乙氧基]苯酚、2,4,6-參(2-羥基-4-己氧基-3-甲基苯基)-1,3,5-三

。 just three

As an ultraviolet absorber, 2-(4,6-diphenyl-1,3,5-triphenylene

-2-yl)-5-[(hexyl)oxy]-phenol, 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-tris

-2-yl)-5-hydroxyphenyl, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3, 5-Three

, 2-(4,6-diphenyl-1,3,5-triphenylene

-2-yl)-5-[2-(2-ethylhexyloxy)ethoxy]phenol, 2,4,6-paraben(2-hydroxy-4-hexyloxy-3-methylbenzene base)-1,3,5-three

.

系抗紫外線劑可列舉BASF公司之Tinuvin 460、Tinuvin 479、Tinuvin 477、Tinuvin 400、Tinuvin 405、Tinuvin 1577ED、ADEKA公司之LA-46、LA-F70等。 three specific

Examples of the anti-ultraviolet agent include Tinuvin 460, Tinuvin 479, Tinuvin 477, Tinuvin 400, Tinuvin 405, Tinuvin 1577ED, LA-46, LA-F70 from ADEKA, etc. from BASF.

系紫外線吸收劑不特別限定，亦可如下列通式所示。 three

The ultraviolet absorber is not particularly limited, and may be represented by the following general formula.

【Chemistry 23】

In the formula, R ₁₉ to R ₂₄ represent an organic group.

Preferably, R ₁₉ to R ₂₄ are independently H, an alkyl group having 1 to 30 carbon atoms which may be substituted by a substituent, or an aryl group such as a phenyl group. As a substituent of an alkyl group and an aryl group, -OH etc. are mentioned. However, the -CH ₂ - group in the alkyl group can also be replaced by -O-, -COO- or -OCO-. The alkyl group is preferably a branched alkyl group or a substituted group.

R ₁₉ and R ₂₀ preferably include aromatic rings. More preferably, the aromatic ring is substituted with -OH. R ₂₁ to R ₂₄ are preferably independently H, alkyl or aryl as defined above.

Examples of benzophenone-based ultraviolet absorbers include 2-hydroxy-4-n-octyloxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 4-decyloxybenzone. yl-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4' -Dimethoxybenzophenone, 1,4-bis(4-benzyl-3-hydroxyphenoxy)-butane, etc.

Specific examples of benzophenone-based anti-ultraviolet agents include Chimassorb 81 from BASF, Chimassorb 90, 1413 from ADEKA, SEESORB 100 from Ciprokasei, SEESORB 101, SEESORB 101S, SEESORB 102, SEESORB 103, SEESORB 105, SEESORB 106, SEESORB 107, SEESORB 151, Sumisorb 130 from Sumikachemtex, KEMISORB 10, KEMISORB 11, KEMISORB 11S, KEMISORB 12 from Chemipro Kasei, etc.

The addition amount of the ultraviolet absorber is preferably 0.01 to 5 parts, more preferably 0.1 to 4 parts, and particularly preferably 0.5 to 2 parts with respect to 100 parts by mass of the obtained polyimide. When the amount of the ultraviolet absorber is too large, the properties of the polyimide such as optical properties and heat resistance may be deteriorated, or the film may be fogged.

In the present invention, the ultraviolet absorber is the one that can achieve the effect of the ultraviolet absorber in the polyimide material. Therefore, the above-mentioned compound can exist in the polyimide material in its original structure, or the above-mentioned compound can be modified by heat treatment into a modified product which still has the effect of absorbing ultraviolet rays.

It is better to mix the UV absorber and the polyimide homogeneously. Therefore, as explained in the following item, it is preferable to prepare a polyimide precursor composition or a polyimide solution composition and heat-treating them to prepare a polyimide material.

The polyimide material of the present invention as described above has improved ultraviolet durability and less coloration due to ultraviolet irradiation. That is, when the UV durability is evaluated by using the change ΔYI of the yellowness (YI) before and after the UV irradiation test, the polyimide of the present invention is less than the ΔYI of the polyimide material (control material) without an ultraviolet absorber. The imine material preferably achieves an improvement of 20% or more (meaning that the ΔYI is improved to be less than 80% of the ΔYI of the control material), and more preferably achieves an improvement of 30% or more (ΔYI is 70% of the ΔYI of the control material. % or less), and more preferably an improvement of 40% or more (ΔYI is 60% or less of the ΔYI of the control material). Here, the ultraviolet irradiation test conditions used Q-LAB's QUV-313 lamp, the illuminance at 310 nm was 0.59 W/m ² , the temperature was 50° C., and the irradiation time was 24 hours.

The value of ΔYI also depends on the type of polyimide and is not limited, but is preferably 10 or less, more preferably 8 or less, still more preferably 7 or less, more preferably 6 or less, and most preferably 5 or less . Preferably it is 0 or more.

Moreover, about the value of yellowness (YI), both before and after an ultraviolet irradiation test are 15 or less, Preferably it is 10.5 or less. Preferably it is 0 or more.

Regarding the degree of improvement of ΔYI, the value of ΔYI and the value of YI, when the polyimide material is in the form of a film or a coating, the polyimide material of the present invention that is a film or a coating should not matter. Thickness, to achieve the above improvement, the value is better. The polyimide material as a substance, when forming a film or coating with at least one thickness in the range of 5 μm to 100 μm, should achieve the above improvement, and the value is better.

In addition, the haze of the polyimide material of the present invention is preferably 15% or less, more preferably 10% or less, still more preferably 5% or less, and most preferably 2% or less. The value of haze, when the polyimide material is in the form of a film or a coating, the polyimide material of the present invention, which is a film or a coating, preferably has nothing to do with the thickness, and it is better to achieve the above haze value. When the polyimide material as the substance is formed into a film or coating having at least one thickness in the range of 5 μm to 100 μm, it is preferable to achieve the above-mentioned value.

In addition, the polyimide material of the present invention has high light transmittance, and the transmittance at 400 nm is preferably 50% or more, more preferably 60% or more, still more preferably 70% or more, and most preferably 80% or more. . The value of light transmittance, when the polyimide material is in the form of film or coating, the polyimide material of the present invention, which is a film or coating, should preferably achieve the above light transmittance value regardless of thickness . As the polyimide material of the substance, when a film or coating having at least one thickness in the range of 5 μm to 100 μm is formed, it is preferable to achieve the above value.

In the present invention, the polyimide is selected so as to have its own desirable mechanical properties, heat resistance, and other properties. Therefore, the polyimide material of the present invention does not contain photosensitive components (that is, photosensitive components), such as photohardeners (photoradical generators, photocation generators, photoanion generators, etc.), photosensitizer components (with Compounds of quinonediazide structure, such as photosensitive compounds used in other photoresists, etc.), and other photosensitive components or modified products derived from these photosensitive components (introduced into decomposed products, polymers, etc.) . The reason is that the original performance of the intended polyimide is impaired by including such a component.

In addition, the polyimide material of the present invention is intended to be used in applications that require mechanical strength, such as films and coatings, and is not intended to be used in applications such as alignment films of liquid crystal display devices that require thinness but do not require mechanical properties and/or heat resistance. use. In the present invention, for example, the film thickness is preferably a predetermined thickness which will be described later. In addition, the present invention is not intended to be used for an alignment film unless it includes a component (as described above) containing a long-chain methylene group such as decamethylene bis-trimellitic dianhydride for alignment.

In addition, the polyimide material of the present invention is preferably used as a light-transmitting film or coating, and preferably has a small light shielding property. In particular, it should not contain dyes, pigments and carbon black that absorb in the visible light region.

<<Polyimide Precursor Composition, Polyimide Solution Composition and Manufacturing Method of Polyimide Material>>

Next, the manufacturing method of the polyimide material of the present invention is explained. The polyimide material of the present invention is obtained by subjecting the polyimide precursor composition or the polyimide solution composition to heat treatment. The polyimide precursor composition of the present invention contains a polyimide precursor, an ultraviolet absorber and a solvent. The polyimide precursor and the UV absorber are preferably dissolved in a solvent. Moreover, the polyimide solution composition contains polyimide, an ultraviolet absorber, and a solvent. The polyimide and the ultraviolet absorber should preferably be dissolved in the solvent.

The polyimide precursor has a chemical structure that gives the aforementioned polyimide. That is, the polyimide precursor contains repeating units represented by the following general formula (A1).

In the formula, X ₁ is a tetravalent group with an aromatic ring or an alicyclic structure, Y ₁ is a divalent group with an aromatic ring or an alicyclic structure, and R ₁ and R ₂ are each independently hydrogen and carbon number. 1 to 6, preferably an alkyl group with 1 to 3 carbon atoms, or an alkylsilyl group with 3 to 9 carbon atoms.

In formula (A1), ideal definitions and combinations of X ₁ and Y ₁ are the same as those described for formula (1). In addition, the polyimide precursor may include repeating units other than the repeating unit represented by the formula (A1), and the structure and ratio thereof are the same as those described for the polyimide.

In formula (A1), when R ₁ and R ₂ are hydrogen, the production of polyimide tends to be easy. R ₁ and R ₂ can be changed according to the production method described later, by changing the type of functional group and the introduction rate of the functional group.

The polyimide precursor used in the present invention (the polyimide precursor containing at least one of the repeating units represented by the aforementioned formula (A1)) can be classified according to the chemical structures taken by R ₁ and R ₂ into As follows: 1) Polyamic acid (R ₁ and R ₂ are hydrogen), 2) Polyamic acid ester (At least a part of R ₁ and R ₂ is an alkyl group), 3) 4) Polyamic acid silicone ester ( At least a part of R ₁ and R ₂ is alkylsilyl).

In addition, the polyimide precursor can be easily produced by the following production methods according to its classification. However, the manufacturing method of the polyimide precursor used in the present invention is not limited to the following manufacturing methods.

1) Polyamide

The polyimide precursor can be obtained by mixing the tetracarboxylic dianhydride as the tetracarboxylic acid component and the diamine component in a solvent at approximately equal molar ratios, preferably the molar ratio of the diamine component to the tetracarboxylic acid component. more than [diamine component The ratio of ear number/molar number of tetracarboxylic acid component] is preferably 0.90 to 1.10, more preferably 0.95 to 1.05. For example, at a relatively low temperature of 120°C or lower, the reaction is suppressed while the imidization is desired, and ideally A polyimide precursor solution was obtained.

Although not limited, more specifically, by dissolving diamine in an organic solvent or water, slowly adding tetracarboxylic dianhydride to this solution while stirring, and at 0~120°C, preferably 5~80°C. The range of ℃ is stirred for 1 to 72 hours to obtain a polyimide precursor. When the reaction is performed at 80° C. or higher, the molecular weight varies depending on the temperature history during the polymerization, and imidization progresses due to heat, so there is a possibility that a polyimide precursor cannot be stably produced. In the above-mentioned production method, the order of addition of the diamine and the tetracarboxylic dianhydride tends to increase the molecular weight of the polyimide precursor, which is preferable. In addition, the order of addition of the diamine and the tetracarboxylic dianhydride in the above-mentioned production method may be reversed, which is preferable because the precipitates are reduced. When water is used as the solvent, the amount of imidazoles such as 1,2-dimethylimidazole or bases such as triethylamine is preferably 0.8 times the carboxyl group of the polyimide (polyimide precursor) produced. It is preferable to add an amount of equivalent or more.

2) Polyurethane

The tetracarboxylic dianhydride is reacted with an arbitrary alcohol to obtain a diester dicarboxylic acid, and then it is reacted with a chlorinating reagent (thionine chloride, oxalic chloride, etc.) to obtain a diester dicarboxylate chloride. The diester dicarboxylate chloride and diamine are stirred at -20 to 120°C, preferably -5 to 80°C for 1 to 72 hours to obtain a polyimide precursor. When the reaction is performed at 80° C. or higher, the molecular weight varies depending on the temperature history during the polymerization, and imidization proceeds by heat, so that the polyimide precursor may not be stably produced. In addition, a polyimide precursor can also be easily obtained by dehydrating and condensing a diester dicarboxylic acid and a diamine using a phosphorus-based condensing agent, a carbodiimide condensing agent, or the like.

The polyimide precursor obtained by this method is stable, so it is also possible to add a solvent such as water or alcohol for purification such as reprecipitation.

3) Polyamide silicone ester (indirect method)

The diamine is reacted with a silylating agent in advance to obtain a silylated diamine. If necessary, purification of the silylated diamine is performed by distillation or the like. The silylated diamine is first dissolved in the dehydrated solvent, and tetracarboxylic dianhydride is added while stirring, and stirring is performed at 0~120°C, preferably 5~80°C for 1~72 hours. , the polyimide precursor can be obtained. When the reaction is performed at 80° C. or higher, the molecular weight varies depending on the temperature history during the polymerization, and imidization proceeds by heat, so that the polyimide precursor may not be stably produced.

4) Polyamide silicone ester (direct method)

Mix the polyimide solution obtained by the method 1) with the silylizing agent, and stir at 0~120°C, preferably 5~80°C for 1~72 hours, to obtain the polyimide precursor. When the reaction is carried out at 80° C. or higher, the molecular weight varies depending on the temperature history during the polymerization, and imidization proceeds by heat, and there is a possibility that the polyimide precursor cannot be stably produced.

The method 3) and the silylizing agent used in the method 4), if a chlorine-free silylizing agent is used, it is not necessary to silylize the polyamide acid or the obtained polyimide. Refined is ideal. Examples of silylizing agents that do not contain chlorine atoms include N,O-bis(trimethylsilyl)trifluoroacetamide, N,O-bis(trimethylsilyl)acetamide, and hexamethyldisilazide. Azane. From the viewpoint of no fluorine atom and low cost, N,O-bis(trimethylsilyl)acetamide and hexamethyldisilazane are particularly preferred.

In addition, in the silylation reaction of diamine in the method of 3), in order to accelerate the reaction, an amine-based catalyst such as pyridine, piperidine, and triethylamine can be used. This catalyst can be directly used as the polymerization catalyst of the polyimide precursor.

The solvent used in the preparation of the polyimide precursor is preferably water, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1, Aprotic solvents such as 3-dimethyl-2-imidazolidinone and dimethyl sulfoxide are ideal. If the raw material monomer components and the polyimide precursor produced are soluble, any type of solvent can be used without It is used because of the problem, and its structure is not specially limited. Solvents are preferably water, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and other amide solvents, γ-butyrolactone, γ-valerolactone, δ - Cyclic ester solvents such as valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, carbonate solvents such as ethylidene carbonate and propylidene carbonate, triethylene Glycol-based solvents such as alcohols, phenol-based solvents such as m-cresol, p-cresol, 3-chlorophenol, and 4-chlorophenol, acetophenone, 1,3-dimethyl-2-imidazolidinone, cyclobutane , dimethyl sulfite, etc. are ideal. Furthermore, other general organic solvents can also be used, namely phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl serosol, butyl serosol Thr, 2-Methyl-Saloxol Acetate, Ethyl-Saloxol Acetate, Butyl-Saloxol Acetate, Tetrahydrofuran, Dimethoxyethane, Diethoxyethane, Dibutyl Ether , Diethylene glycol dimethyl ether, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, butanol, ethanol, xylene, toluene, chlorobenzene, terpenes, mineral spirits , Petroleum naphtha solvents, etc. In addition, the solvent may be used in combination of two or more.

The logarithmic viscosity of the polyimide precursor is not particularly limited, and the logarithmic viscosity in a N,N-dimethylacetamide solution with a concentration of 0.5g/dL at 30°C is 0.2dL/g or more, more preferably 0.3dL /g or more, more preferably 0.4 dL/g or more. When the logarithmic viscosity is 0.2 dL/g or more, the molecular weight of the polyimide precursor is high, and the obtained polyimide has excellent mechanical strength and heat resistance.

The solvent contained in the polyimide precursor composition of the present invention is not particularly limited as long as the polyimide precursor and the ultraviolet absorber are soluble. Specific examples of the solvent include those used in the production of the above-mentioned polyimide precursor, and the solvent used in the production of the polyimide precursor can be used as it is.

As the ultraviolet absorber contained in the polyimide precursor composition of the present invention, the ultraviolet absorber described in the item of polyimide material can be used, and ideally the same. The timing of adding the ultraviolet absorber is not particularly limited, and the ultraviolet absorber is usually added after preparing the solution of the polyimide precursor, but the ultraviolet absorber may also be added to the solvent before the diamine component and the tetracarboxylic acid component are reacted. . In addition, it is preferable to add a solution prepared by dissolving the ultraviolet absorber in a solvent in advance.

The polyimide precursor composition of the present invention may contain chemical imidizing agents (acid anhydrides such as acetic anhydride, amine compounds such as pyridine and isoquinoline), antioxidants, fillers (inorganic particles such as silica), as needed etc.), dyes, pigments, coupling agents such as silane coupling agents, primers, flame retardants, defoaming agents, leveling agents, rheology control agents (flow aids), release agents, etc. However, for applications requiring transparency, it is better not to contain dyes and pigments that will reduce light transmittance and haze. For other additives, it is preferable to appropriately select the type and amount thereof so as not to reduce the light transmittance and haze.

In the case of the composition of the polyimide solution, the polyimide contained therein is a polyimide which is soluble in a solvent as described in "Polyimide material of the present invention". The solvent can be appropriately selected in combination with polyimide from among those already described for the solvent used in the production of the aforementioned polyimide precursor. In addition, the ultraviolet absorber contained is also the ultraviolet absorber described in the item of polyimide material.

For the preparation method of the polyimide solution composition, the solution of the aforementioned polyimide precursor (preferably without UV absorber) can be subjected to imidization treatment (thermal imidization) in the solution. , chemical imidization), convert the polyimide precursor into polyimide, and use it directly in the form of polyimide solution, or put the reaction mixture after the imidization reaction into a poor solvent to make After the polyimide is precipitated, the obtained polyimide is dissolved in a solvent. In addition, the solution of the aforementioned polyimide precursor (containing an imidization catalyst and a dehydrating agent if necessary) can also be cast on, for example, a substrate, heat-treated and dried, and imidized (thermal imidization). chemical imidization), and the obtained polyimide is dissolved in a solvent. The UV absorber is preferably added after preparing the solution of polyimide.

In a specific embodiment, the polyimide contained in the polyimide solution composition is preferably in the formula (1) in consideration of transparency, mechanical strength, etc., where (i) X ₁ is 4 having an alicyclic structure valent group and Y ₁ is a divalent group with an alicyclic structure, or (ii) X ₁ is a tetravalent group with an alicyclic structure and Y ₁ is a divalent group with an aromatic ring, or (iii) X ₁ is A tetravalent group with an aromatic ring and Y ₁ is a bivalent group with an alicyclic structure, or (iv) X ₁ is a tetravalent group with an F-containing aromatic ring and a 4-valent group with an aromatic ring without F It is preferable that Y ₁ is a divalent group having an aromatic ring.

The polyimide material of the present invention can be obtained by heating the above-mentioned polyimide precursor composition or polyimide solution composition at a temperature exceeding 200°C. When a polyimide precursor composition is used, the imidization proceeds while removing the solvent, and is converted into polyimide (solid, eg, thin film, coating). In the case of the polyimide solution composition, it is also heat treated at a high temperature to remove the solvent and obtain polyimide (solid, eg, film, coating). In either case, heat treatment is performed at a high temperature exceeding 200°C, Therefore, a polyimide material having stable thermal and mechanical properties and having the original excellent characteristics of polyimide can be obtained. The heat treatment temperature is preferably 250°C or higher.

Heating at high temperature is necessary to obtain polyimide with excellent properties (especially thin films and coatings), but there are concerns about the evaporation and decomposition of the ultraviolet absorber. However, the fact that a polyimide material with sufficient ultraviolet durability can be obtained even when heated at a high temperature in a state containing an ultraviolet absorber was not foreseen by the inventors of the present application.

An example of a method for producing a polyimide film which is an ideal form of the polyimide material will be described.

As an example of the manufacturing method of the polyimide film, for example, the polyimide precursor composition is cast on the substrate, and the polyimide precursor composition on the substrate is, for example, 100-500 ℃. ℃, preferably 200~500℃, more preferably about 250~450℃, heat treatment is performed, and the polyimide precursor is imidized while removing the solvent. In addition, the heating profile is not particularly limited, and can be appropriately selected.

In addition, by casting the polyimide precursor composition on the substrate, preferably drying at a temperature range below 180°C, a film of the polyimide precursor composition is formed on the substrate, and the obtained The film of the polyimide precursor composition is peeled off from the substrate, and the end of the film is fixed, or the end of the film is not fixed, and the temperature is for example 100~500 ℃, preferably 200~500 ℃ , More preferably, heat treatment is performed at a temperature of about 250~450°C, and the polyimide precursor is imidized, and the polyimide film can also be ideally produced.

In addition, the same is true when using the polyimide solution composition, by casting the polyimide solution composition on the substrate, for example, at a temperature exceeding 200 to 500° C., preferably 250 to 500° C., more preferably The temperature of about 250~450℃ is heated to remove the solvent, so as to ideally manufacture the polyimide film. In addition, the heating profile in this case is not particularly limited, and can be appropriately selected.

The polyimide film (and the polyimide coating film) is not particularly limited, and the linear thermal expansion coefficient at 100°C to 250°C is preferably 60 ppm/K or less, more preferably 50 ppm/K or less.

The polyimide film (and the polyimide coating film) is not particularly limited, and the total light transmittance (average light transmittance at a wavelength of 380 nm to 780 nm) is preferably 68% or more, more preferably 70% or more, and even better 75% or more, preferably 80% or more. When used in display applications, etc., if the total light transmittance is low, the light source needs to be strong, and there is a problem of energy consumption.

The index of the heat resistance of the polyimide film (and the polyimide coating film), that is, the 5% weight reduction temperature is not particularly limited, but is preferably 400°C or higher, more preferably 430°C or higher, and more preferably 450°C or higher .

In addition, the 0.5% weight reduction temperature is also important as an index of the heat resistance of the polyimide film (and the polyimide coating film). The 0.5% weight reduction temperature is an index of the temperature at which the contained components and decomposed components are released from the material. When the 0.5% weight reduction temperature of the polyimide material is high (for example, the temperature exceeds 200° C.), it means that in the production process using the polyimide material, almost no contained components and decomposed components are released. Therefore, in the manufacturing steps of products using polyimide materials (such as polyimide films), it is possible to reduce equipment, Contamination of other parts. For example, in steps such as vapor deposition, device pollution can be reduced, which is beneficial to simplification of manufacturing steps, reduction of manufacturing costs, and improvement of yield.

In addition, the thickness of the polyimide film (and the polyimide coating film), although it depends on the application, is preferably 0.1 μm to 250 μm, more preferably 1 μm to 150 μm, still more preferably 3 μm to 120 μm, particularly preferably 5μm~100μm. When the polyimide film is used for light transmission, if the polyimide film is too thick, the light transmittance may decrease.

[Example]

Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples. In addition, the present invention is not limited to the following examples.

<Evaluation of Varnish>

The solution in which the ultraviolet absorber was dissolved was added to the polyimide precursor solution or the polyimide solution, and the uniformity of the varnish after stirring was visually evaluated. Uniform: ○ Non-uniform (dissolved residue, etc.): ×

<Evaluation of Polyimide Films>

[400nm light transmittance]

Using a UV-Vis spectrophotometer/V-650DS (manufactured by JASCO Corporation), the light transmittance of the polyimide film at a wavelength of 400 nm was measured.

[YI]

Using UV-Vis spectrophotometer/V-650DS (manufactured by Japan Spectrophotometer), according to the specification of ASTEM E313, the YI of the polyimide film was measured. The light source is D65 and the viewing angle is set to 2°.

[Change in YI before and after UV irradiation △YI]

△YI=YI _A -YI _B

YI _A : YI of polyimide film after UV irradiation test

YI _B : YI of polyimide film before UV irradiation test

[Haze]

The haze of the polyimide film was measured using a turbidimeter/NDH2000 (manufactured by Nippon Denshoku Industries) according to the specification of JIS K7136.

[Tensile modulus of elasticity, elongation at break point, strength at break point]

The polyimide film was punched into a dumbbell shape of IEC-540(S) standard, and as a test piece (width: 4 mm), TENSILON manufactured by ORIENTEC Co., Ltd. was used. Tensile modulus of elasticity, elongation at break point.

[0.5% weight reduction temperature]

The polyimide film was used as a test piece, and the temperature was raised from 25°C to 600°C at a heating rate of 10°C/min in a nitrogen stream using a calorimeter measuring device (Q5000IR) from TA INSTRUMENT. The 0.5% weight loss temperature was obtained from the obtained weight curve.

[Ultraviolet irradiation test]

Use the QUV weathering tester (weather meter) Q-UV SE type (Q screen) made by Q-LAB company, the light source is UVB-313, the test temperature is 50 ° C (black screen temperature), and the test illuminance is 0.59W/m ² (310nm ), the test time is 24h.

The abbreviations, purities, etc. of the raw materials used in the following examples are as follows.

[Diamine component]

4,4'-ODA: 4,4'-oxydiphenylamine [purity: 99.9% (GC analysis)]

BAFL: 9,9-bis(4-aminophenyl)pyrene

m-TD: 2,2'-dimethyl-4,4'-diaminobiphenyl [purity: 99.85% (GC analysis)]

TFMB: 2,2'-bis(trifluoromethyl)benzidine [Purity: 99.83% (GC analysis)]

tra-DACH: trans-1,4-diaminocyclohexane [Purity: 99.1% (GC analysis)]

DABAN: 4,4'-Diaminobenzidine [Purity: 99.90% (GC analysis)]

PPD: p-phenylenediamine [purity: 99.9% (GC analysis)]

BAPB: 4,4'-bis(4-aminophenoxy)biphenyl

TPE-Q: 1,4-bis(4-aminophenoxy)benzene

[Tetracarboxylic acid component]

CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride [Purity: 99.9% (GC analysis)]

6FDA: 4,4'-(2,2-hexafluoroisopropylidene) diphthalic dianhydride [purity 99.77% (H-NMR analysis)

PPHT: (octahydro-1,3-dioxy-5-isobenzofuran carboxylic acid) 1,4-phenylenediamide

CpODA: norbornane-2-spiro-α-cyclopentanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride

PMDA-HS: 1R,2S,4S,5R-cyclohexanetetracarboxylic dianhydride [purity: 99.9% (GC analysis)]

s-BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride [purity 99.9% (H-NMR analysis)]

a-BPDA: 2,3,3',4'-biphenyltetracarboxylic dianhydride [purity 99.9% (H-NMR analysis)]

DNDAxx: (4arH, 8acH)-decahydro-1t,4t:5c,8c-dimethylnaphthalene-2t,3t,6c,7c-tetracarboxylic dianhydride

[Purity for DNDAxx: 99.2% (GC analysis)]

[Solvent]

DMAc: N,N-Dimethylacetamide

NMP: N-methyl-2-pyrrolidone

MIBK: methyl isobutyl ketone

[Ultraviolet absorber]

【Table 1】

The structural formulas of the tetracarboxylic acid component and the diamine component are shown below.

【Chemical 25】

The structural formula of the ultraviolet absorber is shown below.

【Hua 27】

[Polyamic acid solution 1]

In a reaction vessel substituted with nitrogen, 2.12 g (10 mmoles) of m-TD was charged, and 31.33 g of DMAc was added in such an amount that the total mass of the fed monomers (the sum of the diamine component and the carboxylic acid component) became 12 % by mass, and stirred at room temperature for 1 hour. To this solution was slowly added CBDA 1.76g (9 mmol) and CpODA 0.38g (1 mmol) Ear). Stir at room temperature for 12 hours. To this solution, a mixed solution of 0.096 g of 1,2-dimethylimidazole and 0.096 g of DMAc was added, and stirred at room temperature for 1 hour to obtain a uniform and viscous polyimide precursor solution (polyamide acid solution 1) .

[Polyamic acid solution 2]

A nitrogen-substituted reaction vessel was charged with 4,4'-ODA 1.40 g (7 mmol) and BAFL 1.05 g (3 mmol), and NMP 39.21 g was added in such an amount as to make the total mass of the fed monomers (The sum of the diamine component and the carboxylic acid component) was adjusted to an amount of 15% by mass, and the mixture was stirred at room temperature for 1 hour. To this solution was slowly added PPHT 3.51 g (7.5 mmol) and CpODA 0.96 g (2.5 mmol). Stir at room temperature for 12 hours to obtain a homogeneous and viscous polyimide precursor solution (polyamide solution 2).

[Polyimide solution 1]

A nitrogen-substituted reaction vessel was charged with 3.20 g (10 mmol) of TFMB, and 30.58 g of DMAc was added in such an amount that the total mass of the fed monomers (the sum of the diamine component and the carboxylic acid component) was 20% by mass amount, and stirred at room temperature for 1 hour. To this solution was slowly added 6FDA 4.44 g (10 mmol). The mixture was stirred at room temperature for 12 hours, at 160°C for 12 hours, cooled to 50°C, 30.58 g of DMAc was added, and the mixture was stirred at 50°C for 3 hours. This solution was slowly added dropwise to 500 mL of water to precipitate polyimide. The polyimide was recovered, dried, and dissolved in MIBK to obtain a 20 mass % uniform and viscous polyimide solution (polyimide solution 1).

[Polyamic acid solution 3]

In a reaction vessel substituted with nitrogen, 2.12 g (10 mmoles) of m-TD was charged, and 31.33 g of DMAc was added in such an amount that the total mass of the fed monomers (the sum of the diamine component and the carboxylic acid component) became 12 % by mass, and stirred at room temperature for 1 hour. To this solution was slowly added CBDA 1.76 g (9 mmol) and CpODA 0.38 g (1 mmol). Stir at room temperature for 12 hours. To this solution, a mixed solution of 0.192 g of 1,2-dimethylimidazole and 0.192 g of DMAc was added, and stirred at room temperature for 1 hour to obtain a uniform and viscous polyimide precursor solution (polyamide acid solution 3) .

[Polyamic acid solution 4]

In a reaction vessel substituted with nitrogen, 2.12 g (10 mmoles) of m-TD was charged, and 31.33 g of DMAc was added in such an amount that the total mass of the fed monomers (the sum of the diamine component and the carboxylic acid component) became 12 % by mass, and stirred at room temperature for 1 hour. To this solution was slowly added CBDA 1.76 g (9 mmol) and CpODA 0.38 g (1 mmol). Stir at room temperature for 12 hours. To this solution, a mixed solution of 0.384 g of 1,2-dimethylimidazole and 0.384 g of DMAc was added, and stirred at room temperature for 1 hour to obtain a uniform and viscous polyimide precursor solution (polyamide acid solution 4) .

[Polyamic acid solution 5]

20.02 g (0.100 mol) of 4,4'-ODA was charged into the reaction vessel substituted with nitrogen, and 207.21 g of DMAc was added, the amount being the total mass of the fed monomers (the sum of the diamine component and the carboxylic acid component) It became 17 mass %, and it stirred at room temperature for 1 hour. To this solution was slowly added PMDA-HS 22.41 g (0.100 moles). After stirring at room temperature for 12 hours, a homogeneous and viscous polyimide precursor solution (polyamide solution 5) was obtained.

[Polyamic acid solution 6]

10.81 g (0.100 mol) of tra-DACH was charged into the reaction vessel substituted with nitrogen, and 2950.64 g of DMAc was added in such an amount that the total mass of the feed monomers (the sum of the diamine component and the carboxylic acid component) became 12 mass % amount, stirred at room temperature for 1 hour. To this solution was slowly added s-BPDA 28.69 g (0.0975 mol) and a-BPDA 0.74 g (0.0025 mol). It was stirred at 50° C. for 12 hours to obtain a homogeneous and viscous polyimide precursor solution (polyimide solution 6).

[Polyamic acid solution 7]

20.02 g (0.100 mol) of 4,4'-ODA was charged into the reaction vessel substituted with nitrogen, and 233.85 g of DMAc was added, the amount being the total mass of the fed monomers (the sum of the diamine component and the carboxylic acid component) It became 20 mass %, and it stirred at room temperature for 1 hour. To this solution was slowly added CpODA 38.44 g (0.100 moles). After stirring at room temperature for 12 hours, a homogeneous and viscous polyimide precursor solution (polyamide solution 5) was obtained.

[Polyamic acid solution 8]

In a reaction vessel substituted with nitrogen, 1.87 g (8.8 mmol) of m-TD and 0.35 g (1.2 mmol) of TPE-Q were charged, and 24.37 g of DMAc was added, the amount being the total mass of the feed monomer ( The total amount of the diamine component and the carboxylic acid component) was adjusted to 15% by mass, and the mixture was stirred at room temperature for 1 hour. To this solution was slowly added CBDA 1.76 g (9 mmol) and CpODA 0.38 g (1 mmol). Stir at room temperature for 12 hours. To this solution, a mixed solution of 0.384 g of 1,2-dimethylimidazole and 0.384 g of DMAc was added, and stirred at room temperature for 1 hour to obtain a uniform and viscous polyimide precursor solution (polyimide solution 8) .

[Polyamic acid solution 9]

In a nitrogen-substituted reaction vessel, m-TD 1.61 g (7.6 mmol). and TPE-Q 0.70 g (1.2 mmol) were charged, and DMAc 24.91 g was added, which was the total mass of the monomers fed. (The sum of the diamine component and the carboxylic acid component) was adjusted to an amount of 15% by mass, and the mixture was stirred at room temperature for 1 hour. To this solution was slowly added CBDA 1.76 g (9 mmol) and CpODA 0.38 g (1 mmol). Stir at room temperature for 12 hours. To this solution, a mixed solution of 0.384 g of 1,2-dimethylimidazole and 0.384 g of DMAc was added, and stirred at room temperature for 1 hour to obtain a uniform and viscous polyimide precursor solution (polyamide acid solution 9) .

[Polyamic acid solution 10]

In a reaction vessel substituted with nitrogen, 1.27 g (6.0 mmol) of m-TD and 1.17 g (1.2 mmol) of TPE-Q were charged, and 25.64 g of DMAc was added, this amount being the total mass of the fed monomer ( The total amount of the diamine component and the carboxylic acid component) was adjusted to 15% by mass, and the mixture was stirred at room temperature for 1 hour. To this solution was slowly added CBDA 1.76 g (9 mmol) and CpODA 0.38 g (1 mmol). Stir at room temperature for 12 hours. To this solution, a mixed solution of 0.384 g of 1,2-dimethylimidazole and 0.384 g of DMAc was added, and stirred at room temperature for 1 hour to obtain a uniform and viscous polyimide precursor solution (polyimide solution 10) .

[Polyamic acid solution 11]

In a reaction vessel substituted with nitrogen, 2.12 g (10 mmol) of m-TD was charged, and 24.71 g of DMAc was added, so that the total mass of the monomers to be fed (the sum of the diamine component and the carboxylic acid component) became 20 % by mass, and stirred at room temperature for 1 hour. To this solution was slowly added PMDA-HS 2.24 g (10 mmol). It was stirred at room temperature for 12 hours to obtain a homogeneous and viscous polyimide precursor solution (polyamide solution 11).

[Polyamic acid solution 12]

A nitrogen-substituted reaction vessel was charged with 3.20 g (10 mmol) of TFMB, and 23.66 g of DMAc was added in such an amount that the total mass of the monomers to be fed (the sum of the diamine component and the carboxylic acid component) was 25% by mass amount, and stirred at room temperature for 1 hour. To this solution was slowly added PPHT 4.69 g (10 mmol). Stir at room temperature for 12 hours to obtain a homogeneous and viscous polyimide precursor solution (polyamide solution 12).

[Polyamic acid solution 13]

In a nitrogen-substituted reaction vessel, 3.20 g (10 mmol) of TFMB was charged, and 20.64 g of DMAc was added in such an amount that the total mass of the fed monomers (the sum of the diamine component and the carboxylic acid component) became 20% by mass amount, and stirred at room temperature for 1 hour. To this solution was slowly added CBDA 1.96 g (10 mmol). It was stirred at room temperature for 12 hours to obtain a homogeneous and viscous polyimide precursor solution (polyamide solution 13).

[Polyamic acid solution 14]

A nitrogen-substituted reaction vessel was charged with DABAN 1.59 g (7 mmol), PPD 0.14 g (1 mmol) and BAPB 0.93 g (2 mmol), and NMP 24.85 g was added, which was the amount to make the The total mass of the monomers (the sum of the diamine component and the carboxylic acid component) was adjusted to 22% by mass, and the mixture was stirred at room temperature for 1 hour. To this solution was slowly added DNDAxx 3.95 g (10 mmol). After stirring at room temperature for 12 hours, a homogeneous and viscous polyimide precursor solution (polyamide solution 14) was obtained.

[Polyamic acid solution 15]

In a nitrogen-substituted reaction vessel, 3.20 g (10 mmol) of TFMB was charged, and 28.16 g of DMAc was added in such an amount that the total mass of the fed monomers (the sum of the diamine component and the carboxylic acid component) became 20% by mass Of amount, and stirred at room temperature for 1 hour. To this solution was slowly added CpODA 3.84 g (10 mmol). Stir at room temperature for 12 hours to obtain a homogeneous and viscous polyimide precursor solution (polyamide solution 15).

[Polyamic acid solution 16]

A nitrogen-substituted reaction vessel was charged with 3.20 g (10 mmol) of TFMB, and 28.76 g of DMAc was added in such an amount that the total mass of the fed monomers (the sum of the diamine component and the carboxylic acid component) became 20% by mass amount, and stirred at room temperature for 1 hour. To this solution was slowly added 6FDA 3.11 g (7 mmol) and s-BPDA 0.88 g (3 mmol). After stirring at room temperature for 12 hours, a homogeneous and viscous polyimide precursor solution (polyamide solution 16) was obtained.

[Example 1]

The solution obtained by dissolving LA-46 in DMAc was added to the polyimide solution 1 in an amount of 2 parts by weight relative to 100 parts by weight of the obtained polyimide, and stirred at room temperature for 1 hour to obtain a uniform and viscous solution. The polyimide precursor composition. The evaluation results of the varnish are shown in Table 2.

The polyimide precursor composition filtered by a PTFE membrane was coated on a glass substrate, and heated directly on it from room temperature to 260°C in a nitrogen atmosphere for thermal imidization to obtain a colorless and transparent polyimide. Imide film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film. Table 2 shows the evaluation results of the polyimide film.

[Examples 2 to 19, Comparative Example 2, Reference Examples 1 to 3]

The same operation as in Example 1 was carried out, except that LA-46 was used as the ultraviolet absorber described in the table, and added to the polyamic acid solution 1 in the amount described in the table. The evaluation results of the varnish and the polyimide film are shown in Table 2.

[Comparative Example 1]

The polyamide solution 1 filtered by the PTFE filter membrane was coated on a glass substrate, and heated directly on it from room temperature to 260°C under nitrogen atmosphere for thermal imidization to obtain a colorless and transparent polyamide Amine film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film. Table 2 shows the evaluation results of the polyimide film.

[Example 20]

The solution obtained by dissolving Sumisorb 340 in NMP was added to the polyimide solution 2 in an amount of 2 parts by weight relative to 100 parts by weight of the obtained polyimide, and stirred at room temperature for 1 hour to obtain a uniform and viscous solution. The polyimide precursor composition. The evaluation results of the varnish are shown in Table 2.

The polyimide precursor composition filtered through a PTFE membrane was coated on a glass substrate, and heated directly on it from room temperature to 350°C in a nitrogen atmosphere for thermal imidization to obtain a colorless and transparent Polyimide film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film. Table 2 shows the evaluation results of the polyimide film.

[Comparative Example 3]

The polyamide solution 2 filtered through a PTFE membrane was coated on a glass substrate, and heated directly on it in a nitrogen atmosphere from room temperature to 350°C for thermal imidization to obtain a colorless and transparent polyamide Amine film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film. Table 2 shows the evaluation results of the polyimide film.

[Comparative Examples 4 and 5]

The solution obtained by dissolving Tinuvin 384-2 in MIBK was added to the polyimide solution 1 in an amount of 1 part by weight relative to 100 parts by weight of the obtained polyimide, and stirred at room temperature for 1 hour to obtain a uniform And viscous polyimide solution composition. The evaluation results of the varnish are shown in Table 2.

The polyimide solution composition filtered through a PTFE membrane was coated on a glass substrate, and directly heated on it from room temperature to 130°C and 200°C in a nitrogen atmosphere (comparative examples 4 and 5, respectively), for Thermal imidization to obtain a colorless and transparent polyimide film/glass laminate. Next, the obtained polyimide film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film. Table 2 shows the evaluation results of the polyimide film.

[Examples 21 to 23]

The ultraviolet absorber (Tinuvin PS) described in Table 3 was used instead of LA-46, and it was added to the polyamic acid solution 1 in the amount (2 parts by weight) described in Table 3, and other than that 1 do the same. However, as a result of changing the coating amount of the polyimide precursor composition, the thickness of the polyimide film is as shown in Table 3 (the same applies to other examples and comparative examples). Table 3 shows the evaluation results of the varnish and the polyimide film.

[Example 24]

The same operation as in Example 21 was carried out, except that the polyamic acid solution 1 was replaced with the polyamic acid solution 3. Table 3 shows the evaluation results of the varnish and the polyimide film.

[Examples 25 and 26]

The same operation as in Example 1 was carried out except that the amount of the ultraviolet absorber (Tinuvin PS) was changed to the amount described in Table 3, and the polyamic acid solution 4 was used. Table 3 shows the evaluation results of the varnish and the polyimide film.

[Comparative Examples 6 to 8]

Without using an ultraviolet absorber, the same procedure as in Example 1 was carried out by using the polyamic acid solution 1 (comparative example 8), the polyamic acid solution 3 (comparative example 9), and the polyamic acid solution 4 (comparative example 10), respectively. operation. Table 3 shows the evaluation results of the varnish and the polyimide film.

[Example 27, 28]

The ultraviolet absorber (Tinuvin PS) and the polyimide solution described in Table 3 were used in the amounts described in Table 3, and the same operation as in Example 1 was carried out to obtain a uniform and viscous polyimide precursor composition. Table 3 shows the evaluation results of the varnishes. A polyimide film was obtained in the same manner as in Example 1, except that it was heated to a temperature of 350° C. and imidized. Table 3 shows the evaluation results of the polyimide film.

[Comparative Examples 9, 10]

Without using the ultraviolet absorber, the same operation as in Example 1 was carried out using the polyamic acid solution 5 (Comparative Example 9) and the polyamic acid solution 6 (Comparative Example 10) to obtain a uniform and viscous polyimide precursor. Composition. The evaluation results of the varnish are shown in Table 3. Except that the heating temperature was 350°C and imidization was carried out, it was carried out in the same manner as in Example 1 to obtain a polyimide film. Evaluation of the polyimide film The results are shown in Table 3.

[Example 29]

The ultraviolet absorber (Tinuvin PS) and the polyamic acid solution (polyamic acid solution 7) described in Table 3 were used in the amounts described in Table 3, and the same operation as in Example 1 was carried out to obtain a uniform and viscous polymer. Imide precursor composition. Table 3 shows the evaluation results of the varnishes. Except heating to 400 degreeC and carrying out imidization, it carried out similarly to Example 1, and obtained the polyimide film. Table 3 shows the evaluation results of the polyimide film.

[Comparative Example 11]

A uniform and viscous polyimide precursor composition was obtained in the same manner as in Example 1 using the polyimide solution 7 without using the ultraviolet absorber. Table 3 shows the evaluation results of the varnishes. Except heating to 400 degreeC and carrying out imidization, it carried out similarly to Example 1, and obtained the polyimide film. Table 3 shows the evaluation results of the polyimide film.

[Example 30]

A solution obtained by dissolving an ultraviolet absorber (Tinuvin PS) in DMAc was added to the polyimide solution 8 in an amount of 2 parts by weight relative to 100 parts by weight of the obtained polyimide, and stirred at room temperature for 1 hour , to obtain a uniform and viscous polyimide precursor composition. The evaluation results of the varnish are shown in Table 4.

The polyimide precursor composition filtered through a PTFE membrane was coated on UPILEX (registered trademark)-125S, and heated directly on it in a nitrogen atmosphere from room temperature to 260°C for thermal imidization. , to obtain a colorless and transparent polyimide film/UPILEX (registered trademark)-125S laminate. Next, the polyimide film was peeled off from the obtained polyimide film/UPILEX (registered trademark)-125S laminate. Moreover, peeling can be easily peeled off even if it is not immersed in water or the like. Table 4 shows the evaluation results of the obtained polyimide films.

[Comparative Example 12]

The same operation as in Example 30 was carried out using the polyamic acid solution 8 without using the ultraviolet absorber. Table 4 shows the evaluation results of the varnish and the polyimide film.

[Examples 31 to 33]

The same operation as in Example 30 was carried out, except that the amount of the ultraviolet absorber (Tinuvin PS) was the amount described in Table 4 and the polyamic acid solution 9 was used. Table 4 shows the evaluation results of the varnish and the polyimide film.

[Comparative Example 13]

The same operation as in Example 30 was carried out using the polyamic acid solution 9 without using the ultraviolet absorber. Table 4 shows the evaluation results of the varnish and the polyimide film.

[Example 34]

The same operation as in Example 30 was carried out, except that the amount of the ultraviolet absorber (Tinuvin PS) was the amount described in Table 4 and the polyamic acid solution 10 was used. Table 4 shows the evaluation results of the varnish and the polyimide film.

[Comparative Example 14]

The same operation as in Example 30 was carried out using the polyamic acid solution 10 without using the ultraviolet absorber. Table 4 shows the evaluation results of the varnish and the polyimide film.

[Example 35]

The solution obtained by dissolving Sumisorb 250 in DMAc was added to the polyimide solution 11 in an amount of 2 parts by weight relative to 100 parts by weight of the obtained polyimide, and stirred at room temperature for 1 hour to obtain a uniform and viscous Polyimide precursor composition. Table 4 shows the evaluation results of the varnishes.

The polyimide precursor composition filtered through a PTFE membrane was coated on UPILEX (registered trademark)-125S, and heated directly on it from room temperature to 350°C in a nitrogen atmosphere for thermal imidization. , to obtain a colorless and transparent polyimide film/UPILEX (registered trademark)-125S laminate. Next, the polyimide film was peeled off from the obtained polyimide film/UPILEX (registered trademark)-125S laminate. In addition, peeling can be easily peeled off even if it is not immersed in water or the like. Table 4 shows the evaluation results of the obtained polyimide films.

[Comparative Example 15]

The same operation as in Example 35 was carried out using the polyamic acid solution 11 without using the ultraviolet absorber. Table 4 shows the evaluation results of the varnish and the polyimide film.

[Example 36]

The solution obtained by dissolving Sumisorb 250 in DMAc was added to the polyimide solution 12 in an amount of 2 parts by weight relative to 100 parts by weight of the obtained polyimide, and stirred at room temperature for 1 hour to obtain a uniform and viscous solution. The polyimide precursor composition. The evaluation results of the varnish are shown in Table 4.

The polyimide precursor composition filtered through a PTFE membrane was coated on UPILEX (registered trademark)-125S, and heated directly on it from room temperature to 350°C in a nitrogen atmosphere for thermal imidization. , to obtain a colorless and transparent polyimide film/UPILEX (registered trademark)-125S laminate. Next, the polyimide film was peeled off from the obtained polyimide film/UPILEX (registered trademark)-125S laminate. In addition, peeling can be easily peeled off even if it is not immersed in water or the like. Table 4 shows the evaluation results of the obtained polyimide films.

[Comparative Example 16]

The same operation as in Example 36 was carried out using the polyamic acid solution 12 without using the ultraviolet absorber. Table 4 shows the evaluation results of the varnish and the polyimide film.

[Example 37]

The solution obtained by dissolving Sumisorb 250 in DMAc was added to the polyimide solution 13 in an amount of 2 parts by weight relative to 100 parts by weight of the obtained polyimide, and stirred at room temperature for 1 hour to obtain a uniform and viscous solution. Polyimide precursor composition. The evaluation results of the varnish are shown in Table 4.

The polyimide precursor composition filtered through a PTFE membrane was coated on UPILEX (registered trademark)-125S, and heated directly on it from room temperature to 350°C in a nitrogen atmosphere for thermal imidization. , to obtain a colorless and transparent polyimide film/UPILEX (registered trademark)-125S laminate. Next, the polyimide film was peeled off from the obtained polyimide film/UPILEX (registered trademark)-125S laminate. In addition, peeling can be easily peeled off even if it is not immersed in water or the like. Table 4 shows the evaluation results of the obtained polyimide films.

[Comparative Example 17]

The same operation as in Example 37 was carried out using the polyamic acid solution 13 without using the ultraviolet absorber. Table 4 shows the evaluation results of the varnish and the polyimide film.

[Example 38]

The solution obtained by dissolving Tinuvin PS in NMP was added to the polyimide solution 14 in an amount of 2 parts by weight relative to 100 parts by weight of the obtained polyimide, and stirred at room temperature for 1 hour to obtain a uniform and viscous solution. Polyimide precursor composition. The evaluation results of the varnish are shown in Table 4.

The polyimide precursor composition filtered through a PTFE membrane was coated on UPILEX (registered trademark)-125S, and heated directly on it from room temperature to 430°C in a nitrogen atmosphere for thermal imidization. , to obtain a colorless and transparent polyimide film/UPILEX (registered trademark)-125S laminate. Next, the polyimide film was peeled off from the obtained polyimide film/UPILEX (registered trademark)-125S laminate. In addition, peeling can be easily peeled off even if it is not immersed in water or the like. Table 4 shows the evaluation results of the obtained polyimide films.

[Comparative Example 18]

The same operation as in Example 38 was carried out using the polyamic acid solution 14 without using the ultraviolet absorber. The evaluation results of the varnish and the polyimide film are shown in Table 4.

[Industrial Availability]

According to the present invention, it is possible to provide a polymer that utilizes the conventional properties of polyimide materials (eg, polyimide films, coatings), such as chemical resistance, mechanical strength, electrical properties, dimensional stability, etc., and improves UV durability. imide material. This polyimide material is particularly suitable as substrates, protective films, protective layers, etc. for displays, touch panels, solar cells, and the like.

Claims (20)

A polyimide material, comprising only polyimide and a UV absorber as polymer components, and meeting the following conditions: (i) 0.5% weight reduction temperature exceeds 200°C; (ii) no photosensitive components and Modified from photoreceptive components; (iii) haze of 15% or less, or yellowness (YI) of 15 or less both before and after the ultraviolet irradiation test, or formed from the same polyimide material with 5 The haze is 15% or less, or the yellowness (YI) is 15 or less both before and after the ultraviolet irradiation test when the film or coating has at least one thickness in the range of ~100μm, but the conditions of the ultraviolet irradiation test are to use QUV-313 lamp, and the illuminance at 310nm is 0.59W/m ² , the temperature is 50°C, and the irradiation time is 24 hours; (iv) The change in yellowness before and after the ultraviolet irradiation test △YI is less than 10, or from the same polyamide When the amine material is used to form a film or coating with at least one thickness in the range of 5 to 100 μm, the change in yellowness △YI is less than 10, but the conditions of the ultraviolet irradiation test are as defined in the above (iii); (v) ) Yellowness (YI) is 0 or more before and after the UV irradiation test, or when a film or coating with at least one thickness in the range of 5 to 100 μm is formed from the same polyimide material, the yellowness ( YI) both before and after the ultraviolet irradiation test are 0 or more, but the conditions of the ultraviolet irradiation test are as defined in the aforementioned (iii); wherein, the polyimide contains the repeating unit represented by the following general formula (1); [ 1]

In the formula, X ₁ is a 4-valent group with an aromatic ring or an alicyclic structure, and Y ₁ is a 2-valent group with an aromatic ring or an alicyclic structure, but when both X ₁ and Y ₁ are aromatic. In the case of a ring group, X ₁ is a tetravalent group of an aromatic ring containing a fluorine atom, and Y ₁ is a divalent group of an aromatic ring containing a fluorine atom; only the polyimide is related to the following formula (501) The tetracarboxylic dianhydride shown is different from the polyimide obtained by reacting the diamines of formula (502) and (503):

In the form of a film or coating with a thickness of 1 to 250 μm; wherein the ultraviolet absorber is selected from: the benzotriazole compound represented by formula (100) or formula (101), the benzotriazole compound represented by formula (200) Show three

Compounds and their heating modifications; [Chemical 2]

In the formula, R ₁₁ ~R ₁₈ represent organic groups without aromatic rings;

In the formula, R ₃₁ to R ₃₇ and R ₄₁ to R ₄₇ represent the meanings given to R ₁₁ to R ₁₈ , and X is a divalent organic group without an aromatic ring;

In the formula, R ₁₉ to R ₂₄ represent an organic group. The polyimide material according to claim 1, wherein X ₁ is a tetravalent group having an alicyclic structure and Y ₁ is a content of the repeating unit represented by the general formula (1) having a divalent group having an alicyclic structure , is 50 mol% or less relative to all repeating units. The polyimide material according to claim 1, wherein X ₁ in the general formula (1) is a tetravalent group with an aromatic ring and Y ₁ is a divalent group with an aromatic ring, but X ₁ is The tetravalent group having a fluorine atom-containing aromatic ring and/or Y ₁ is a divalent group having a fluorine atom-containing aromatic ring. The polyimide material according to claim 1, wherein X ₁ in the general formula (1) is a tetravalent group having an alicyclic structure, and Y ₁ is a divalent group having an aromatic ring. The polyimide material according to claim 1, wherein X ₁ in the general formula (1) is a tetravalent group having an aromatic ring, and Y ₁ is a divalent group having an alicyclic structure. The polyimide material according to claim 1, wherein X ₁ of the general formula (1) is the content of repeating units with a tetravalent group having an alicyclic structure, which is a proportion exceeding 60% of all repeating units, The content of the repeating unit represented by the general formula (1) in which X ₁ is a tetravalent group having an alicyclic structure and Y ₁ is a divalent group having an alicyclic structure is 50 mol % or less with respect to all repeating units. The polyimide material according to claim 1, wherein Y ₁ of the general formula (1) is selected from at least one selected from 2,2'-bis(trifluoromethyl)benzidine and m-tolidine The content of the repeating unit of the derived group is a ratio of 50% or more of all the repeating units. The polyimide material according to claim 1, wherein the melting point of the polyimide is 300°C or higher. The polyimide material according to claim 1, wherein the polyimide does not contain a long methylene chain having more than 4 carbon atoms in the main chain. The polyimide material according to claim 1 is not an alignment film. The polyimide material according to claim 1, wherein the benzotriazole compound is selected from the group consisting of (a) and (b): (a) a compound represented by formula (100), and at this time R ₁₁ to R ₁₈ are independently H, or an alkyl group having 1 to 20 carbon atoms which may also be substituted by a substituted or unsubstituted maleimide group (the substitution position for the alkyl group is N), but only The -CH ₂ - group in the alkyl group can also be replaced by -COO- or -OCO-; there is no Cl in the formula, and R ₁₁ to R ₁₈ do not contain an aromatic ring; (b) the compound represented by the formula (101), here , R ₃₁ to R ₃₇ and R ₄₁ to R ₄₇ are independently H, or the number of carbon atoms that may be substituted by a substituted or unsubstituted maleimido group (the substitution position for an alkyl group is N) 1~20 alkyl groups, but the -CH ₂ - group in the alkyl group can also be replaced by -COO- or -OCO-; X is an alkyl group with 1~20 carbon atoms, but the -CH ₂ - group in the alkyl group The group can also be replaced by -COO- or -OCO-; there is no Cl in the formula, and R ₃₁ -R ₃₇ , R ₄₁ -R ₄₇ and X do not contain an aromatic ring. A method for manufacturing a polyimide material, characterized in that: a polyimide precursor composition containing a polyimide precursor, an ultraviolet absorber and a solvent, or a polyimide precursor composition containing a polyimide, an ultraviolet absorber and a solvent The polyimide solution composition is heat-treated at a temperature exceeding 200° C., and the polyimide material according to any one of claims 1 to 10 is produced. The method for producing a polyimide material according to claim 12, wherein the polyimide precursor contained in the polyimide precursor composition comprises a repeating unit represented by the following general formula (A1); 5]

In the formula, X ₁ is a 4-valent group with an aromatic ring or an alicyclic structure, and Y ₁ is a 2-valent group with an aromatic ring or an alicyclic structure, but when both X ₁ and Y ₁ are aromatic. In the case of a ring group, X ₁ is a tetravalent group of an aromatic ring containing a fluorine atom and/or Y ₁ is a divalent group of an aromatic ring containing a fluorine atom, and R ₁ and R ₂ are each independently hydrogen , an alkyl group with 1 to 6 carbon atoms, or an alkyl silicon group with 3 to 9 carbon atoms. The method for producing a polyimide material according to claim 12, wherein the polyimide contained in the polyimide solution composition is represented by general formula (1) as defined in claim 1 of the scope of the application. the repeating unit. The method for producing a polyimide material according to claim 12, comprising the following steps: coating the polyimide precursor composition or the polyimide solution composition on a substrate; The polyimide precursor composition or the polyimide solution composition on the substrate is heat-treated. The method for producing a polyimide material according to claim 12, wherein the heat treatment temperature is 250°C or higher. A polyimide precursor composition, comprising a polyimide precursor, an ultraviolet absorber, and a solvent, and meets the following conditions (i) to (v): (i) is not used for liquid crystal alignment films, and the polymer The imide precursor does not have a long methylene chain with more than 4 carbon atoms in the main chain; (ii) when the polyimide precursor composition is used to form a polyimide having at least one thickness in the range of 5 to 100 μm When the imine film or polyimide coating is used, the yellowness (YI) of the polyimide material before and after the ultraviolet irradiation test is less than 15, but the condition of the ultraviolet irradiation test is to use QUV-313 lamp, and the illumination at 310nm is 0.59W/m ² , the temperature is 50°C, and the irradiation time is 24 hours; (iii) when the polyimide precursor composition is used to form a polyimide having at least one thickness in the range of 5~100μm In the case of an imine film, a polyimide material with a breaking strength of 100 MPa or more is obtained; (iv) when a polyimide precursor composition is used to form a polyimide film with at least one thickness in the range of 5 to 100 μm or In the case of polyimide coating, the yellowness (YI) is above 0 before and after the ultraviolet irradiation test, but the conditions of the ultraviolet irradiation test are as defined in (ii) above; (v) no photosensitive components or Modified products derived from these photosensitive components; the polyimide precursor includes repeating units represented by the following general formula (A1), and the content of repeating units other than the repeating units represented by the following general formula (A1) is relative to the total The repeating unit is less than 10 mol%;

In the formula, X ₁ is a tetravalent group having an aromatic ring or an alicyclic structure or a tetravalent group having an alicyclic structure represented by the following general formula (10), and Y ₁ is 2 represented by the following general formula (4) valence, but when both X ₁ and Y ₁ are groups with an aromatic ring, X ₁ is a tetravalent group with an aromatic ring containing a fluorine atom and/or Y ₁ is an aromatic group with a fluorine atom The divalent group of the ring, R ₁ and R ₂ are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms.

In the formula, R ₃₁ to R ₃₈ are each independently a direct bond or a divalent organic group. R ₄₁ to R ₄₇ are independently selected from the group consisting of bases represented by the formulae: -CH ₂ -, -CH=CH-, -CH ₂ CH ₂ -, -O-, and -S-. R ₄₈ is an organic group containing an aromatic ring or an alicyclic structure;

In the formula, W ₁ is a direct bond, a divalent group represented by the following general formula (5) or a divalent group represented by the following general formula (6), n ₁₁ to n ₁₃ each independently represent an integer of 0 to 4, R ₅₁ , R ₅₂ and R ₅₃ are each independently an alkyl group with 1 to 6 carbon atoms, a halogen group, a hydroxyl group, a carboxyl group, or a trifluoromethyl group;

R ₆₁ to R ₆₈ in the formula (6) each independently represent a direct bond or any one of the divalent groups represented by the aforementioned formula (5); only the polyimide is represented by the following formula (501) The polyimides obtained by the reaction of tetracarboxylic dianhydrides with diamines represented by formulas (502) and (503) are different:

Wherein the ultraviolet absorber is selected from: the benzotriazole compound represented by the formula (100) or the formula (101), the third one represented by the formula (200)

Compounds and their thermal modifications;

In the formula, R ₁₁ ~R ₁₈ represent organic groups without aromatic rings;

In the formula, R ₃₁ to R ₃₇ and R ₄₁ to R ₄₇ represent the meanings given to R ₁₁ to R ₁₈ , and X is a divalent organic group without an aromatic ring;

In the formula, R ₁₉ to R ₂₄ represent an organic group. The polyimide precursor composition according to claim 17, wherein, in the polyimide precursor, X ₁ of the general formula (A1) is the content of repeating units having a tetravalent group of an alicyclic structure, It is the proportion of more than 60% of all repeating units, but X ₁ is a tetravalent group with an alicyclic structure and Y ₁ is a 2-valent group with an alicyclic structure. The content of the repeating units represented by the general formula (A1), relative to It is 50 mol% or less in all repeating units. The polyimide precursor composition according to claim 17, wherein, in the polyimide precursor, Y ₁ of the general formula (A1) is selected from 2,2'-bis(trifluoromethyl) ) The content of the repeating unit of the group derived from at least one of benzidine and m-tolidine is a ratio of 50% or more in all repeating units. The polyimide precursor composition according to claim 17, wherein the benzotriazole compound is selected from the group consisting of (a) and (b): (a) a compound represented by formula (100), In this case, R ₁₁ to R ₁₈ are independently H, or an alkane having 1 to 20 carbon atoms which may be substituted with a substituted or unsubstituted maleimide group (the substitution position for the alkyl group is N). group, but the -CH ₂ - group in the alkyl group can also be replaced by -COO- or -OCO-; there is no Cl in the formula, and R ₁₁ to R ₁₈ do not contain an aromatic ring; (b) Formula (101) represents Compounds, in this case, R ₃₁ -R ₃₇ and R ₄₁ -R ₄₇ are independently H, or may be substituted or unsubstituted maleimido group (the substitution position for alkyl is N) X is an alkyl group with 1~20 carbon atoms, but the -CH ₂ - group in the alkyl group can also be replaced by -COO- or -OCO-; X is an alkyl group with a carbon number of 1~20, but the - in the alkyl group The CH ₂ - group can also be replaced by -COO- or -OCO-; in the formula, it does not have Cl, R ₃₁ to R ₃₇ , R ₄₁ to R ₄₇ and X does not contain an aromatic ring.