JP2017119821A - Polyimide material and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide polyimide materials having improved ultraviolet resistance while taking advantage of conventional characteristics of polyimide films.SOLUTION: The polyimide materials contain polyimides and ultraviolet absorbers, with the 0.5% weight loss temperature exceeding 200°C.SELECTED DRAWING: None

Description

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

  Polyimide films are widely used in fields such as the electric / electronic device field and the semiconductor field because they are excellent in heat resistance, chemical resistance, mechanical strength, electrical properties, dimensional stability, and the like. On the other hand, in recent years, with the arrival of an advanced information society, development of optical materials such as a liquid crystal alignment film and a protective film for a color filter in the display device field, such as an optical fiber and an optical waveguide in the optical communication field, is progressing. In particular, in the field of display devices, a plastic substrate that is lightweight and excellent in flexibility as a substitute for a glass substrate has been studied, and a display that can be bent and rolled has been actively developed. For this reason, there is a demand for higher performance optical materials that can be used for such applications.

  Aromatic polyimide is essentially yellowish brown due to intramolecular conjugation and the formation of charge transfer complexes. For this reason, as a means to suppress coloration, for example, introduction of fluorine atoms into the molecule, imparting flexibility to the main chain, introduction of bulky groups as side chains, etc. inhibits intramolecular conjugation and charge transfer complex formation. And the method of expressing transparency is proposed (for example, patent document 1).

  In addition, a method for expressing transparency by using a semi-alicyclic or fully alicyclic polyimide that does not form a charge transfer complex in principle has been proposed (for example, Patent Documents 2 to 5).

  Conventionally, applications utilizing the characteristics of polyimide have been developed. However, since polyimide generally has absorption in the ultraviolet region, light resistance, particularly durability to light in the ultraviolet region may be insufficient. Patent Document 6 (Japanese Patent Application Laid-Open No. 2004-258544) describes a retardation film obtained by applying a solution containing an ultraviolet absorber and a specific polyimide on a substrate.

Special table 2010-538103 gazette JP 2012-41529 A International Publication No. 2014/046064 JP 2009-286706 A JP 2014-92775 A JP 2004-258544 A

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

  An object of the present invention is to provide a polyimide material excellent in ultraviolet durability, a production method thereof, and a polyimide precursor composition used for the production while taking advantage of conventional characteristics of polyimide.

  The present invention relates to the following items.

1. Polyimide,
Containing a UV absorber,
A polyimide material having a 0.5% weight loss temperature exceeding 200 ° C.

  2. Item 2. The polyimide material according to Item 1, wherein the haze value is 15% or less.

3. Item 3. The polyimide material according to Item 1 or 2, wherein a yellowness change ΔYI before and after the ultraviolet irradiation test is 8 or less;
However, the conditions of the ultraviolet irradiation test are as follows: a QUV-313 lamp is used, the illuminance is 0.59 W / m ^{2 at} 310 nm, the temperature is 50 ° C., and the irradiation time is 24 hours.

  4). The said polyimide contains the repeating unit represented by following General formula (1), The polyimide material of any one of said claim | item 1-3 characterized by the above-mentioned.

（式中、Ｘ_１は芳香族環または脂環構造を有する４価の基であり、Ｙ_１は芳香族環または脂環構造を有する２価の基である。）
５． Ｘ_１が脂環構造を有する４価の基であり、Ｙ_１が脂環構造を有する２価の基である化学式（１）で表される繰り返し単位の含有量が、全繰り返し単位に対して、５０モル％以下であることを特徴とする上記項４に記載のポリイミド材料。

(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 content of the repeating unit represented by the chemical 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 based on the total repeating units. The polyimide material according to Item 4, wherein the content is 50 mol% or less.

6). A tetravalent radical X ₁ in Formula (1) has an aromatic ring, a polyimide material according to Item 4, wherein the Y ₁ is a divalent group having an aromatic ring.

7). A tetravalent radical X ₁ in Formula (1) has an alicyclic structure, a polyimide material according to Item 4, wherein the Y ₁ is a divalent group having an aromatic ring.

8). A tetravalent radical X ₁ in Formula (1) has an aromatic ring, a polyimide material according to Item 4, wherein the Y ₁ is a divalent group having an alicyclic structure.

  9. Item 9. The polyimide material according to any one of Items 1 to 8, which is in the form of a film or a coating layer.

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

  11. A polyimide characterized by heat-treating a polyimide precursor composition containing a polyimide precursor, an ultraviolet absorber and a solvent, or a polyimide solution composition containing a polyimide, an ultraviolet absorber and a solvent at a temperature exceeding 200 ° C. Material manufacturing method.

  12 The said polyimide precursor contained in the said polyimide precursor composition contains the repeating unit represented by the following general formula (A1), The manufacturing method of the polyimide material of the said claim | item 11 characterized by the above-mentioned.

（式中、Ｘ_１は芳香族環または脂環構造を有する４価の基であり、Ｙ_１は芳香族環または脂環構造を有する２価の基であり、Ｒ_１、Ｒ_２はそれぞれ独立に水素、炭素数１〜６、好ましくは炭素数１〜３のアルキル基、または炭素数３〜９のアルキルシリル基である。）
１３． 前記ポリイミド溶液組成物に含有される前記ポリイミドが、上記項４で定義された一般式（１）で表される繰り返し単位を含むことを特徴とする上記項１１に記載のポリイミド材料の製造方法。

Wherein X ₁ is a tetravalent group having an aromatic ring or alicyclic structure, Y ₁ is a divalent group having an aromatic ring or alicyclic structure, and R ₁ and R ₂ are each independently And hydrogen, an alkyl group having 1 to 6, preferably 1 to 3 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms.)
13. Item 12. The method for producing a polyimide material according to Item 11, wherein the polyimide contained in the polyimide solution composition contains a repeating unit represented by the general formula (1) defined in Item 4 above.

14 Applying the polyimide precursor composition or the polyimide solution composition onto a substrate;
The method for producing a polyimide material according to the above item 11, further comprising a step of heat-treating the polyimide precursor composition or the polyimide solution composition applied on the substrate.

  15. The said heat processing temperature is 250 degreeC or more, The manufacturing method of the polyimide material of any one of said Claims 11-14 characterized by the above-mentioned.

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

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

（式中、Ｒ_１１〜Ｒ_１８は有機基を表す。）

(In formula, R < ₁₁ > -R < ₁₈ > represents an organic group.)

（式中、Ｒ_３１〜Ｒ_３７およびＲ_４１〜Ｒ_４７は、Ｒ_１１〜Ｒ_１８について与えられる意味を表し、Ｘは２価の有機基である。）

(In the formula, R _{31 to} R ₃₇ and R _{41 to} R ₄₇ represent the meanings given for R _{11 to} R ₁₈ , and X is a divalent organic group.)

18. The benzotriazole compound is
(A) In the formula (100), R _{11 to} R ₁₈ are each independently substituted with H, aryl, or a substituted or unsubstituted maleimide group (the substitution position for alkyl is N). Optionally substituted with 1-20 carbon atoms, provided that the —CH ₂ — group in the alkyl may be replaced by —COO— or —OCO—; Cl is not present in the formula, R ₁₁ -R ₁₈ in total, a compound not containing two or more aromatic rings; and (b) represented by formula (101), wherein R ₃₁ -R ₃₇ and R ₄₁ -R ₄₇ are independently H , Aryl, or a substituted or unsubstituted maleimide group (the substitution position for alkyl is N), which is an alkyl having 1 to 20 carbon atoms, provided that the —CH ₂ — group in the alkyl is — COO- or -OCO X may be an alkylene having 1 to 20 carbon atoms, provided that the —CH ₂ — group in the alkyl may be replaced by —COO— or —OCO—; 18. It is selected from the group consisting of compounds that do not have a ring and R _{31 to} R ₃₇ , R _{41 to} R ₄₇ and X do not contain two or more aromatic rings in total. The manufacturing method of polyimide material.

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

  20. The polyimide precursor composition according to item 19, wherein the polyimide precursor is a polyimide precursor defined in item 12.

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

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

（式中、Ｒ_１１〜Ｒ_１８は有機基を表す。）

(In formula, R < ₁₁ > -R < ₁₈ > represents an organic group.)

（式中、Ｒ_３１〜Ｒ_３７およびＲ_４１〜Ｒ_４７は、Ｒ_１１〜Ｒ_１８について与えられる意味を表し、Ｘは２価の有機基である。）

(In the formula, R _{31 to} R ₃₇ and R _{41 to} R ₄₇ represent the meanings given for R _{11 to} R ₁₈ , and X is a divalent organic group.)

23. The benzotriazole compound is
(A) In the formula (100), R _{11 to} R ₁₈ are each independently substituted with H, aryl, or a substituted or unsubstituted maleimide group (the substitution position for alkyl is N). Optionally substituted with 1-20 carbon atoms, provided that the —CH ₂ — group in the alkyl may be replaced by —COO— or —OCO—; Cl is not present in the formula, R ₁₁ -R ₁₈ in total, a compound not containing two or more aromatic rings; and (b) represented by formula (101), wherein R ₃₁ -R ₃₇ and R ₄₁ -R ₄₇ are independently H , Aryl, or a substituted or unsubstituted maleimide group (the substitution position for alkyl is N), which is an alkyl having 1 to 20 carbon atoms, provided that the —CH ₂ — group in the alkyl is — COO- or -OCO X may be an alkylene having 1 to 20 carbon atoms, provided that the —CH ₂ — group in the alkyl may be replaced by —COO— or —OCO—; Item 22. The above item 22, wherein the compound is selected from the group consisting of compounds that do not have two or more aromatic rings in total in R _{31 to} R ₃₇ , R _{41 to} R ₄₇ and X. Polyimide precursor composition.

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

  The polyimide of the present invention is particularly preferably in the form of a film or a coating layer. In particular, when a highly transparent polyimide is used, good ultraviolet resistance can be imparted to a polyimide film having excellent characteristics without impairing transparency. Thereby, the use of a polyimide can be extended greatly.

  In the present invention, the term “polyimide material” is used to distinguish it from “polyimide” as a substance. That is, the term “polyimide material” is defined as containing polyimide and an ultraviolet absorber, and means a solid material and does not include a solution. For example, it exists in the form of a film, a coating layer (formed on another substrate), a powder, or a lump. Moreover, a polyimide precursor means what gives a polyimide by processing it.

  Below, the polyimide and ultraviolet absorber contained in the polyimide material of this invention, and the manufacturing method of a polyimide material are demonstrated. The polyimide precursor composition of this invention is demonstrated in the manufacturing method of a 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 a polyimide selected from an aromatic compound and an alicyclic compound. For example, a wholly aromatic polyimide, a semi-alicyclic polyimide, and a wholly alicyclic polyimide may be mentioned.

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

（式中、Ｘ_１は芳香族環または脂環構造を有する４価の基であり、Ｙ_１は芳香族環または脂環構造を有する２価の基である。）

(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.)

Although not particularly limited, since the obtained polyimide material is excellent in heat resistance, X ₁ in the general formula (1) is a tetravalent group having an aromatic ring, and Y ₁ has an aromatic ring. A divalent group is preferred. Moreover, since the obtained polyimide material is excellent in heat resistance and excellent in transparency, X ₁ is a tetravalent group having an alicyclic structure, and Y ₁ is a divalent group having an aromatic ring. preferable. Moreover, since the obtained polyimide material is excellent in heat resistance and excellent in dimensional stability, X ₁ is a tetravalent group having an aromatic ring, and Y ₁ is a divalent group having an alicyclic structure. Is preferred.

From the characteristics of the obtained polyimide material, for example, transparency, mechanical properties, heat resistance, etc., X ₁ is a tetravalent group having an alicyclic structure, and Y ₁ is a divalent group having an alicyclic structure. The content of the repeating unit represented by the formula (1) as a group is preferably 50 mol% or less, more preferably 30 mol% or less or less than 30 mol%, more preferably 10 mol, based on all repeating units. % Or less is preferable.

In one embodiment, X ₁ is a tetravalent group having an aromatic ring, and Y ₁ is a divalent group having an aromatic ring. However, the total is preferably 50 mol% or more, more preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, particularly preferably 100 mol%, based on all repeating units. Preferably there is. In this embodiment, when a highly transparent polyimide material is particularly required, the polyimide preferably contains a fluorine atom. That is, the polyimide is a divalent group in which X ₁ is a tetravalent group having an aromatic ring containing a fluorine atom and / or Y ₁ has an aromatic ring containing a fluorine atom. It is preferable that 1 type or more of the repeating unit of the said Chemical formula (1) which is group of is included.

In one embodiment, the polyimide is one or more repeating units of the above chemical formula (1), wherein X ₁ is a tetravalent group having an alicyclic structure and Y ₁ is a divalent group having an aromatic ring. The total content is preferably 50 mol% or more, more preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, particularly preferably 100 mol, based on all repeating units. It is preferable that it is mol%.

In one embodiment, the polyimide is one or more repeating units of the above formula (1), wherein X ₁ is a tetravalent group having an aromatic ring and Y ₁ is a divalent group having an alicyclic structure. The total content is preferably 50 mol% or more, more preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, particularly preferably 100 mol, based on all repeating units. It is preferable that it is mol%.

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

  Examples of the tetravalent group having an aromatic ring include the following.

（式中、Ｚ_１は直接結合、または、下記の２価の基：

(In the formula, Z ₁ is a direct bond or the following divalent group:

のいずれかである。ただし、式中のＺ_２は、２価の有機基、Ｚ_３、Ｚ_４はでそれぞれ独立にアミド結合、エステル結合、カルボニル結合であり、Ｚ_５は芳香環を含む有機基である。）

One of them. 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 organic group containing an aromatic ring. )

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

The Z _5, specifically, an aromatic hydrocarbon group having 6 to 24 carbon atoms.

  As the tetravalent group having an aromatic ring, since the high heat resistance and high transparency of the obtained polyimide material can be compatible, the following are particularly preferable.

（式中、Ｚ_１は直接結合、または、へキサフルオロイソプロピリデン結合である。）

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

Here, since the high heat resistance, high transparency, and low linear thermal expansion coefficient of the obtained polyimide material can be compatible, Z ₁ is more preferably a direct bond.

Examples of the tetracarboxylic acid component that gives a repeating unit of the chemical formula (1) in which X ₁ is a tetravalent group having an aromatic ring include, for example, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, pyromellitic acid, 3,3 ′, 4,4′-benzophenonetetra Carboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 4,4′-oxydiphthalic acid, bis (3,4-dicarboxyphenyl) ) Sulfone, m-terphenyl-3,4,3 ′, 4′-tetracarboxylic acid, p-terphenyl-3,4,3 ′, 4′-tetracarboxylic acid, biscarboxyphenyldimethylsilane, Streaks carboxyphenoxy diphenyl sulfide, or sulfonyl di phthalate, these tetracarboxylic dianhydrides, tetracarboxylic acid silyl ester, tetracarboxylic acid esters, derivatives of such tetracarboxylic acid chloride. Examples of the tetracarboxylic acid component that gives a repeating unit of the chemical formula (1) in which X ₁ is a tetravalent group having an aromatic ring containing a fluorine atom include 2,2-bis (3,4-dicarboxyphenyl). ) Derivatives such as hexafluoropropane, tetracarboxylic dianhydrides, tetracarboxylic acid silyl esters, tetracarboxylic acid esters, and tetracarboxylic acid chlorides thereof. A tetracarboxylic acid component may be used independently and can also be used in combination of multiple types.

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, more preferably at least one aliphatic 4- to 12-membered ring, more preferably aliphatic. More preferably, it has a 4-membered ring or an aliphatic 6-membered ring. The following are mentioned as a tetravalent group which has a preferable aliphatic 4-membered ring or an aliphatic 6-membered ring.

（式中、Ｒ_３１〜Ｒ_３８は、それぞれ独立に直接結合、または、２価の有機基である。Ｒ_４１〜Ｒ_４７は、それぞれ独立に 式：−ＣＨ_２−、−ＣＨ＝ＣＨ−、−ＣＨ_２ＣＨ_２−、−Ｏ−、−Ｓ−で表される基よりなる群から選択される１種を示す。Ｒ_４８は芳香環もしくは脂環構造を含む有機基である。）

(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 each independently a formula: —CH ₂ —, —CH═CH—, This is one selected from the group consisting of groups represented by —CH ₂ CH ₂ —, —O—, and —S—, and R ₄₈ is an organic group containing an aromatic ring or alicyclic structure.

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

Examples of the organic group containing an aromatic ring as R ₄₈ include the following.

（式中、Ｗ_１は直接結合、または、２価の有機基であり、ｎ_１１〜ｎ_１３は、それぞれ独立に０〜４の整数を表し、Ｒ_５１、Ｒ_５２、Ｒ_５３は、それぞれ独立に炭素数１〜６のアルキル基、ハロゲン基、水酸基、カルボキシル基、またはトリフルオロメチル基である。）

(In the formula, W ₁ is a direct bond or a divalent organic group, n _{11 to} n ₁₃ each independently represents an integer of 0 to 4, and R ₅₁ , R ₅₂ , and R ₅₃ are each independent. And an alkyl group having 1 to 6 carbon atoms, a halogen group, a hydroxyl group, a carboxyl group, or a trifluoromethyl group.)

Specific examples of W ₁ include a direct bond, a divalent group represented by the following formula (5), and a divalent group represented by the following formula (6).

（式（６）中のＲ_６１〜Ｒ_６８は、それぞれ独立に直接結合または前記式（５）で表される２価の基のいずれかを表す。）

(R _{61 to} R ₆₈ in the formula (6) each independently represent a direct bond or a divalent group represented by the formula (5).)

  As the tetravalent group having an alicyclic structure, the following are particularly preferable because the polyimide obtained can have both high heat resistance, high transparency, and a low linear thermal expansion coefficient.

Examples of the tetracarboxylic acid component that gives the repeating unit of the formula (1) in which X ₁ is a tetravalent group having an alicyclic structure include 1,2,3,4-cyclobutanetetracarboxylic acid, isopropylidenediphenoxybis Phthalic acid, cyclohexane-1,2,4,5-tetracarboxylic acid, [1,1′-bi (cyclohexane)]-3,3 ′, 4,4′-tetracarboxylic acid, [1,1′-bicarboxylic acid (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), 4,4'-sulfonylbis (cyclohexane-1,2-dicarboxylic acid), 4,4 '-(dimethylsilanediyl) bis (cyclohexane-1,2-dicarboxylic acid) ), 4,4 ′-(tetrafluoropropane-2,2-diyl) bis (cyclohexane-1,2-dicarboxylic acid), octahydropentalene-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-oxa Tricyclo [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-dimethananaphthalene-2c, 3c, 6c, 7c-tetracarboxylic acid, (4arH, 8acH) -decahydro-1t, 4t: 5c, 8c-dimethanonaphthalene-2t, 3t, 6c, 7c-tetracarboxylic acid, these tetracarboxylic dianhydrides, tetracarboxylic silyl esters, tetracarboxylic acids Le, include derivatives such as tetracarboxylic acid chloride. A tetracarboxylic acid component may be used independently and can also be used in combination of multiple types.

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, more preferably 6 to 20 carbon atoms.

  Examples of the divalent group having an aromatic ring include the following.

（式中、Ｗ_１は直接結合、または、２価の有機基であり、ｎ_１１〜ｎ_１３は、それぞれ独立に０〜４の整数を表し、Ｒ_５１、Ｒ_５２、Ｒ_５３は、それぞれ独立に炭素数１〜６のアルキル基、ハロゲン基、水酸基、カルボキシル基、またはトリフルオロメチル基である。）

(In the formula, W ₁ is a direct bond or a divalent organic group, n _{11 to} n ₁₃ each independently represents an integer of 0 to 4, and R ₅₁ , R ₅₂ , and R ₅₃ are each independent. And an alkyl group having 1 to 6 carbon atoms, a halogen group, a hydroxyl group, a carboxyl group, or a trifluoromethyl group.)

Specific examples of W ₁ include a direct bond, a divalent group represented by the following formula (5), and a divalent group represented by the following formula (6).

（式（６）中のＲ_６１〜Ｒ_６８は、それぞれ独立に直接結合または前記式（５）で表される２価の基のいずれかを表す。）

(R _{61 to} R ₆₈ in the formula (6) each independently represent a direct bond or a divalent group represented by the formula (5).)

Here, since high heat resistance, high transparency, and a low linear thermal expansion coefficient of the obtained polyimide can be compatible, W ₁ is a direct bond or a formula: —NHCO—, —CONH—, —COO—, —OCO—. Particularly preferred is one selected from the group consisting of: W ₁ is _one of R _{61 to} R ₆₈ directly selected from the group consisting of a direct bond, or a group represented by the formula: —NHCO—, —CONH—, —COO—, —OCO—. It is also particularly preferable that it is any of the divalent groups represented by formula (6).

Examples of the diamine component that gives a repeating unit of the chemical formula (1) in which Y ₁ is a divalent group having an aromatic ring include p-phenylenediamine, m-phenylenediamine, benzidine, and 3,3′-diamino-biphenyl. 2,2′-bis (trifluoromethyl) benzidine, 3,3′-bis (trifluoromethyl) benzidine, m-tolidine, 4,4′-diaminobenzanilide, 3,4′-diaminobenzanilide, N , N′-bis (4-aminophenyl) terephthalamide, N, N′-p-phenylenebis (p-aminobenzamide), 4-aminophenoxy-4-diaminobenzoate, bis (4-aminophenyl) terephthalate, biphenyl -4,4'-dicarboxylic acid bis (4-aminophenyl) ester, p-phenylenebis (p-aminobenzo) ), Bis (4-aminophenyl)-[1,1′-biphenyl] -4,4′-dicarboxylate, [1,1′-biphenyl] -4,4′-diyl bis (4-amino) Benzoate), 4,4′-oxydianiline, 3,4′-oxydianiline, 3,3′-oxydianiline, 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-amino) Phenyl) sulfone, 3,3′-bis (trifluoromethyl) benzidine, 3,3′-bis ((aminophenoxy) phenyl) propane, 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoro Propane, bis (4- (4-aminophenoxy) diphenyl) sulfone, bis (4- (3-aminophenoxy) diphenyl) sulfone, 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- Triazine, 2,4-bis (4-aminoanilino) -6-methylamino-1,3,5-triazine, 2,4-bis (4-aminoanilino) 6-ethyl-1,3,5-triazine, 2,4-bis (4-aminoanilino) -6-anilino-1,3,5-triazine. Examples of the diamine component that gives the repeating unit of the chemical formula (1) in which Y ₁ is a divalent group having an aromatic ring containing a fluorine atom include 2,2′-bis (trifluoromethyl) benzidine, 3, 3′-bis (trifluoromethyl) benzidine, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2 ′ -Bis (3-amino-4-hydroxyphenyl) hexafluoropropane. A diamine component may be used independently and can also be used in combination of multiple types.

The divalent group having an alicyclic structure of Y ₁ is preferably a divalent group having an alicyclic structure having 4 to 40 carbon atoms, more preferably at least one aliphatic 4- to 12-membered ring, more preferably aliphatic. More preferably, it has a 6-membered ring.

  Examples of the divalent group having an alicyclic structure include the following.

（式中、Ｖ_１、Ｖ_２は、それぞれ独立に直接結合、または、２価の有機基であり、ｎ_２１〜ｎ_２６は、それぞれ独立に０〜４の整数を表し、Ｒ_８１〜Ｒ_８６は、それぞれ独立に炭素数１〜６のアルキル基、ハロゲン基、水酸基、カルボキシル基、またはトリフルオロメチル基であり、Ｒ_９１、Ｒ_９２、Ｒ_９３は、それぞれ独立に 式：−ＣＨ_２−、−ＣＨ＝ＣＨ−、−ＣＨ_２ＣＨ_２−、−Ｏ−、−Ｓ−で表される基よりなる群から選択される１種である。）

(In the formula, V ₁ and V ₂ are each independently a direct bond or a divalent organic group, n _{21 to} n ₂₆ each independently represents an integer of 0 to 4, and R _{81 to} R _86. Are each independently an alkyl group having 1 to 6 carbon atoms, a halogen group, a hydroxyl group, a carboxyl group, or a trifluoromethyl group, and R ₉₁ , R ₉₂ , and R ₉₃ are each independently represented by the formula: —CH ₂ —, It is one selected from the group consisting of groups represented by —CH═CH—, —CH ₂ CH ₂ —, —O—, and —S—.

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

  As the divalent group having an alicyclic structure, the following can be particularly preferred since both the high heat resistance and low linear thermal expansion coefficient of the resulting polyimide can be achieved.

脂環構造を有する２価の基としては、中でも、下記のものが好ましい。

Among the divalent groups having an alicyclic structure, the following are preferable.

Examples of the diamine component that gives the repeating unit of the chemical formula (1) in which Y ₁ is a divalent group having an alicyclic structure include 1,4-diaminocyclohexane, 1,4-diamino-2-methylcyclohexane, 1,4-diamino-2-ethylcyclohexane, 1,4-diamino-2-n-propylcyclohexane, 1,4-diamino-2-isopropylcyclohexane, 1,4-diamino-2-n-butylcyclohexane, 1, 4-diamino-2-isobutylcyclohexane, 1,4-diamino-2-sec-butylcyclohexane, 1,4-diamino-2-tert-butylcyclohexane, 1,2-diaminocyclohexane, 1,3-diaminocyclobutane 1,4-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane Sun, diaminobicycloheptane, diaminomethylbicycloheptane, diaminooxybicycloheptane, diaminomethyloxybicycloheptane, isophoronediamine, diaminotricyclodecane, diaminomethyltricyclodecane, bis (aminocyclohexyl) methane, bis (aminocyclohexyl) Isopropylidene, 6,6′-bis (3-aminophenoxy) -3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane, 6,6′-bis (4-aminophenoxy) -3 3,3 ′, 3′-tetramethyl-1,1′-spirobiindane. A diamine component may be used independently and can also be used in combination of multiple types.

  The polyimide containing at least one repeating unit represented by the chemical formula (1) can contain other repeating units other than the repeating unit represented by the chemical formula (1).

  The tetracarboxylic acid component and the diamine component that give other repeating units are not particularly limited, and any other known aliphatic tetracarboxylic acids and known aliphatic diamines can 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 of two or more.

  The content of other repeating units other than the repeating unit represented by the formula (1) is preferably 30 mol% or less or less than 30 mol%, more preferably 20 mol% or less, based on all repeating units. More preferably, it is 10 mol% or less.

<< UV absorber >>
Arbitrary suitable ultraviolet absorbers can be employ | adopted for the ultraviolet absorber contained in this invention in the range which can achieve the objective of this invention. For example, benzotriazole UV absorbers, benzophenone UV absorbers, benzoate UV absorbers, triazine UV absorbers, hindered amine UV absorbers, inorganic particle UV absorbers, other oxalic anilide UV absorbers and malon Organic ultraviolet absorbers such as acid ester ultraviolet absorbers may be mentioned. In the present invention, only one ultraviolet absorber may be used, or two or more ultraviolet absorbers may be used in combination. Of these, benzotriazole ultraviolet absorbers and triazine ultraviolet absorbers are preferred, and benzotriazole ultraviolet absorbers are more preferred. Among the benzotriazole compounds, preferred structures will be described later with the formula (100) and the formula (101).

  Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl). ) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-amylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-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-butylphenyl) -2H-benzotriazo 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-benzotriazol-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-benzotriazole-2- Yl) -4-methyl-6- (3,4,5,6-tetrahydrophthalimidylmethyl) phenol, methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4 -Hydroxyphenyl) propionate / polyethylene glycol 300 reaction product, 2- (2H-benzotriazol-2-yl) -6- (linear and side) Chain dodecyl) -4-methylphenol.

  Specific examples of the benzotriazole-based UV absorber include Tinuvin PS, Tinuvin 109, Tinuvin 1130, Tinuvin 171, Tinuvin 326, Tinuvin 328, Tinuvin 384-2, Tinuvin 99-2, Tinuvin 900-2, Tinuvin 900-2, Tinuvin 900, 28 Carboprotect, Sumikab Chemistex, Sumisorb 200, Sumisorb 250, Sumisorb 300, Sumisorb 340, Sumisorb 350, ADEKA LA-29, LA-31, LA-32, LA-36, Johoku Chemical Industries JF-77, JF-79, JF-80, JF-83, JF-832, JAST-500, K of Kemipro Kasei MISORB 71, KEMISORB 73, KEMISORB 74, KEMISORB 79, KEMISORB 279, SEESORB 701 of Cipro Kasei Co., SEESORB 703, SEESORB 704, SEESORB 706, mention may be made of SEESORB 707, SEESORB 709, and the like.

  Although it does not specifically limit as a benzotriazole type ultraviolet absorber, It can also represent with the following general formula (100).

（式中、Ｒ_１１〜Ｒ_１８は有機基を表す。）

(In formula, R < ₁₁ > -R < ₁₈ > represents an organic group.)

Preferably, R _{11 to} R ₁₈ are each independently alkyl having 1 to 20 carbon atoms, preferably up to 10 carbon atoms, optionally substituted with H, Cl or a substituent. Examples of the substituent for alkyl include aryl such as phenyl, a substituted or unsubstituted maleimide group (the substitution position on alkyl is N), and the like. However, the —CH ₂ — group in alkyl may be replaced with —COO— or —OCO—. Alkyl is preferably branched alkyl or has a substituent.

R _{11 to} R ₁₄ are more preferably H. R ₁₅ and R ₁₇ are more preferably H. R ₁₆ and R ₁₈ are more preferably independently of each other H, alkyl as defined above, preferably alkyl having up to 10 carbon atoms.

Further, the benzotriazole compound may have a structure in which two or more of the structures represented by the formula (100) are bonded in common with one of R _{11 to} R ₁₈ . For example, one of _R 11 _{to R 18} of the first structure represented by the formula (100), one of commonly divalent _R 11 _{to R 18} of the second structure of the formula (100) And the first structure and the second structure may be bonded to each other. The common organic group is preferably an alkylene having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. One example of a compound in which two of the structures represented by formula (100) are linked is represented by formula (101).

（式中、Ｒ_３１〜Ｒ_３７およびＲ_４１〜Ｒ_４７は、Ｒ_１１〜Ｒ_１８について与えられる意味を表し、Ｘは２価の有機基である。）

(In the formula, R _{31 to} R ₃₇ and R _{41 to} R ₄₇ represent the meanings given for R _{11 to} R ₁₈ , and X is a divalent organic group.)

Preferred meanings of R _{31 to} R ₃₇ and R _{41 to} R ₄₇ are as given above for R _{11 to} 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. R ₃₆ and R ₄₆ are more preferably H, independently of each other, alkyl as defined above, preferably alkyl having up to 10 carbon atoms. X corresponds to the structure in which R ₁₈ in formula (100) is linked, and is preferably alkylene having 1 to 20 carbons, more preferably 1 to 10 carbons.

  One example of this structure is LA-31 described below.

Is not particularly limited, Examples of the benzotriazole-based ultraviolet absorber, among _R 11 _{to R 18} for Formula (100) from the viewpoint of heat resistance and transmittance, for formula (101) _R 31 _{~R 37, R 41} ~ More preferably, R ₄₇ and X do not contain Cl.

Is not particularly limited, Examples of the benzotriazole-based ultraviolet absorber, among _R 11 _{to R 18} for Formula (100) from the viewpoint of compatibility with polyimide, for formula (101) _R 31 _{~R 37, R 41} ~ More preferably, R ₄₇ and X do not contain two or more aromatic rings in total. When the total of these groups of one compound contains two or more aromatic rings, haze may occur in the resulting polyimide film. More preferably, the aromatic ring is not contained in R _{11 to} R ₁₈ for the formula (100) and R _{31 to} R ₃₇ , R _{41 to} R ₄₇ and X for the formula (101).

  Examples of triazine ultraviolet absorbers include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- (4,6-bis). (2,4-Dimethylphenyl) -1,3,5-triazin-2-yl) -5-hydroxyphenyl, 2,4-bis [2-hydroxy-4-butoxyphenyl] -6- (2,4- Dibutoxyphenyl) -1,3,5-triazine, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- [2- (2-ethylhexanoyloxy) ethoxy] Mention may be made of phenol and 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine.

  Specific examples of the triazine UV inhibitor include Tinuvin 460, Tinuvin 479, Tinuvin 477, Tinuvin 400, Tinuvin 405, Tinuvin 1577ED from BASF, LA-46, LA-F70 from ADEKA, and the like.

  Although it does not specifically limit as a triazine type ultraviolet absorber, It can also represent like the following general formula.

（式中、Ｒ_１９〜Ｒ_２４は有機基を表す。）

_(Wherein, R 19 _{to R 24} represents an organic group.)

Preferably, R _{19 to} R ₂₄ are independently of each other H, alkyl having 1 to 30 carbon atoms which may be substituted with a substituent, or aryl such as phenyl. Examples of the substituent for alkyl and aryl include —OH and the like. However, the —CH ₂ — group in the alkyl may be replaced by —O—, —COO— or —OCO—. Alkyl is preferably branched alkyl or has a substituent.

R ₁₉ and R ₂₀ preferably contain an aromatic ring. More preferably, the aromatic ring is substituted with —OH. R _{21 to} R ₂₄ are preferably H, independently of one another, alkyl or aryl as defined above.

  Examples of benzophenone ultraviolet absorbers include 2-hydroxy-4-n-octoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2. -Hydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 1,4-bis (4-benzoyl-3-hydroxyphenoxy) -butane

  Specific examples of benzophenone-based UV inhibitors include: BASF Chimassorb 81, Chimassorb 90, ADEKA 1413, Sipro Kasei SEESORB 100, SEESORB 101, SEESORB 101S, SEESORB 103, SEESORB 105, SEESORB 105, SEESORB 105, SEESORB 105, 107, SEESORB 151, Sumisorb 130 of Sumika Chemtex, KEMISORB 10, KEMISORB 11, KEMISORB 11S, and KEMISORB 12 of Chemipro Kasei.

  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 large, polyimide characteristics such as optical characteristics and heat resistance may deteriorate, or haze may occur in the film.

  In the present invention, the ultraviolet absorber can achieve the effect of the ultraviolet absorber in the polyimide material. Therefore, the above compound may be present in the polyimide material as it is, or the above compound may be modified by a heat treatment into a modified product that still has an ultraviolet absorption effect.

  It is preferable that the ultraviolet absorber is uniformly mixed with the polyimide. For this purpose, as explained in the next section, it is preferable to prepare a polyimide precursor composition or a polyimide solution composition, and heat-treat this to produce a polyimide material.

The polyimide material of the present invention as described above has improved ultraviolet durability and is less colored by ultraviolet irradiation. That is, when the ultraviolet durability is evaluated by a change in yellowness (YI) before and after the ultraviolet irradiation test ΔYI, the polyimide material of the present invention is compared with ΔYI of a polyimide material not containing an ultraviolet absorber (control material). , Preferably 20% or more improvement (ΔYI means 80% or less of ΔYI of control material), more preferably 30% or more improvement (ΔYI is 70% or less of ΔYI of control material) More preferably, an improvement of 40% or more (ΔYI is 60% or less of ΔYI of the control material) is achieved. Here, the ultraviolet irradiation test conditions were a QUV-313 lamp manufactured by Q-LAB, an illuminance of 0.59 W / m ^{2 at} 310 nm, a temperature of 50 ° C., and an irradiation time of 24 hours.

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

  The yellowness (YI) value is 15 or less, preferably 10.5 or less both before and after the ultraviolet irradiation test. 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 layer, the polyimide material of the present invention that is a film or a coating layer is independent of the thickness. Preferably the above improvements and values are achieved. In the polyimide material as the substance, it is preferable that the above improvement and value are achieved when a film or coating layer having at least one thickness in the range of 5 μm to 100 μm is formed.

  The polyimide material of the present invention preferably has a haze value of 15% or less, more preferably 10% or less, still more preferably 5% or less, and most preferably 2% or less. When the polyimide material is in the form of a film or a coating layer, the haze value of the polyimide material of the present invention, which is a film or a coating layer, is preferably achieved regardless of the thickness. In the polyimide material as the substance, the above value is preferably achieved when a film or coating layer having at least one thickness in the range of 5 μm to 100 μm is formed.

<< Polyimide precursor composition, polyimide solution composition and method for producing polyimide material >>
Next, the manufacturing method of the polyimide material of this invention is demonstrated. The polyimide material of the present invention can be obtained by heat-treating a polyimide precursor composition or a polyimide solution composition. The polyimide precursor composition of the present invention contains a polyimide precursor, an ultraviolet absorber and a solvent. It is preferable that the polyimide precursor and the ultraviolet absorber are dissolved in a solvent. Moreover, a polyimide solution composition contains a polyimide, a ultraviolet absorber, and a solvent. It is preferable that the polyimide and the ultraviolet absorber are dissolved in a solvent.

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

（式中、Ｘ_１は芳香族環または脂環構造を有する４価の基であり、Ｙ_１は芳香族環または脂環構造を有する２価の基であり、Ｒ_１、Ｒ_２はそれぞれ独立に水素、炭素数１〜６、好ましくは炭素数１〜３のアルキル基、または炭素数３〜９のアルキルシリル基である。）

Wherein X ₁ is a tetravalent group having an aromatic ring or alicyclic structure, Y ₁ is a divalent group having an aromatic ring or alicyclic structure, and R ₁ and R ₂ are each independently And hydrogen, an alkyl group having 1 to 6, preferably 1 to 3 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms.)

In formula (A1), preferred definitions and combinations of X ₁ and Y ₁ are all the same as those described for formula (1). In addition, the polyimide precursor can contain other 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 the formula (A1), when R ₁ and R ₂ are hydrogen, polyimide tends to be easily produced. R ₁ and R ₂ can change the type of functional group and the introduction rate of the functional group by the production method described later.

The polyimide precursor (polyimide precursor containing at least one repeating unit represented by the formula (A1)) used in the present invention has a chemical structure taken by R ₁ and R ₂ .
1) Polyamic acid (R ₁ and R ₂ are hydrogen),
2) Polyamic acid ester (at least part of R ₁ and R ₂ is an alkyl group),
3) 4) Polyamic acid silyl ester (at least a part of R ₁ and R ₂ is an alkylsilyl group),
Can be classified. And a polyimide precursor can be easily manufactured with the following manufacturing methods for every classification. However, the manufacturing method of the polyimide precursor used by this invention is not limited to the following manufacturing methods.

1) Polyamic acid A polyimide precursor is prepared by mixing a tetracarboxylic dianhydride as a tetracarboxylic acid component and a diamine component in a solvent in an approximately equimolar amount, preferably a molar ratio of the diamine component to the tetracarboxylic acid component [mol of diamine component. Number / number of moles 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 less to suppress imidization. The reaction can be suitably obtained as a polyimide precursor solution.

  Although it does not limit, more specifically, diamine is melt | dissolved in an organic solvent or water, Tetracarboxylic dianhydride is gradually added to this solution, stirring, 0-120 degreeC, Preferably 5 is added. A polyimide precursor is obtained by stirring for 1 to 72 hours in a range of ˜80 ° C. When the reaction is carried out at 80 ° C. or higher, the molecular weight varies depending on the temperature history at the time of polymerization, and imidization proceeds due to heat, so there is a possibility that the polyimide precursor cannot be produced stably. The order of addition of diamine and tetracarboxylic dianhydride in the above production method is preferable because the molecular weight of the polyimide precursor is likely to increase. Moreover, it is also possible to reverse the order of addition of the diamine and tetracarboxylic dianhydride in the above production method, and this is preferable because precipitates are reduced. When water is used as a solvent, an imidazole such as 1,2-dimethylimidazole or a base such as triethylamine is preferably 0.8 times equivalent to the carboxyl group of the polyamic acid (polyimide precursor) to be produced. It is preferable to add in the above amount.

2) Polyamic acid ester After reacting tetracarboxylic dianhydride with an arbitrary alcohol to obtain a diester dicarboxylic acid, it is reacted with a chlorinating reagent (thionyl chloride, oxalyl chloride, etc.) to obtain a diester dicarboxylic acid chloride. The polyimide precursor is obtained by stirring the diester dicarboxylic acid chloride and the diamine in the range of -20 to 120 ° C, preferably -5 to 80 ° C for 1 to 72 hours. When the reaction is carried out at 80 ° C. or higher, the molecular weight varies depending on the temperature history at the time of polymerization, and imidization proceeds due to heat, so there is a possibility that the polyimide precursor cannot be produced stably. Alternatively, a polyimide precursor can be easily obtained by dehydrating and condensing diester dicarboxylic acid and diamine using a phosphorus condensing agent or a carbodiimide condensing agent.

  Since the polyimide precursor obtained by this method is stable, it can be purified by reprecipitation by adding a solvent such as water or alcohol.

3) Polyamide acid silyl ester (indirect method)
A diamine and a silylating agent are reacted in advance to obtain a silylated diamine. If necessary, the silylated diamine is purified by distillation or the like. Then, the silylated diamine is dissolved in the dehydrated solvent, and tetracarboxylic dianhydride is gradually added while stirring, and the temperature is 0 to 120 ° C., preferably 5 to 80 ° C. A polyimide precursor is obtained by stirring for 72 hours. When the reaction is carried out at 80 ° C. or higher, the molecular weight varies depending on the temperature history at the time of polymerization, and imidization proceeds due to heat, so there is a possibility that the polyimide precursor cannot be produced stably.

4) Polyamide acid silyl ester (direct method)
The polyimide precursor is obtained by mixing the polyamic acid solution obtained by the method 1) and the silylating agent and stirring for 1 to 72 hours in the range of 0 to 120 ° C, preferably 5 to 80 ° C. When the reaction is carried out at 80 ° C. or higher, the molecular weight varies depending on the temperature history at the time of polymerization, and imidization proceeds due to heat, so there is a possibility that the polyimide precursor cannot be produced stably.

  Since the use of a silylating agent not containing chlorine as the silylating agent used in the method 3) and the method 4) does not require purification of the silylated polyamic acid or the resulting polyimide, Is preferred. Examples of the silylating agent not containing a chlorine atom include N, O-bis (trimethylsilyl) trifluoroacetamide, N, O-bis (trimethylsilyl) acetamide, and hexamethyldisilazane. N, O-bis (trimethylsilyl) acetamide and hexamethyldisilazane are particularly preferred because they do not contain fluorine atoms and are low in cost.

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

  The solvent used in preparing the polyimide precursor is water, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone. An aprotic solvent such as dimethyl sulfoxide is preferable, and any type of solvent can be used without any problem as long as the raw material monomer component and the polyimide precursor to be produced are dissolved, and the structure is not particularly limited. As a solvent, water, amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone , Cyclic ester solvents such as α-methyl-γ-butyrolactone, carbonate solvents such as ethylene carbonate and propylene carbonate, glycol solvents such as triethylene glycol, m-cresol, p-cresol, 3-chlorophenol, 4-chlorophenol Phenol solvents such as acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide and the like are preferably employed. Furthermore, other common organic solvents such as phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cellosolve, butyl cellosolve, 2-methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve 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 spirit, petroleum A naphtha solvent can also be used. In addition, a solvent can also be used in combination of multiple types.

  The logarithmic viscosity of the polyimide precursor is not particularly limited, but the logarithmic viscosity in an N, N-dimethylacetamide solution having a concentration of 0.5 g / dL at 30 ° C. is 0.2 dL / g or more, more preferably 0.3 dL / g. As described above, it is particularly 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 mechanical strength and heat resistance of the resulting polyimide are excellent.

  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 dissolved. Specific examples of the solvent include a solvent used when preparing the polyimide precursor described above, and the solvent used when producing the polyimide precursor can be used as it is.

  As an ultraviolet absorber contained in the polyimide precursor composition of this invention, the ultraviolet absorber demonstrated by the term of the polyimide material can be used, and a preferable thing is also the same. The timing of adding the UV absorber is not particularly limited. Usually, the UV absorber is added after preparing the polyimide precursor solution, but before the diamine component and the tetracarboxylic acid component are reacted, the UV absorber is absorbed in the solvent. An agent may be added. In addition, it is preferable to add a solution prepared by dissolving an ultraviolet absorber in a solvent in advance.

  In the polyimide precursor composition of the present invention, a chemical imidizing agent (an acid anhydride such as acetic anhydride or an amine compound such as pyridine or isoquinoline), an antioxidant, or a filler (inorganic particles such as silica) is included as necessary. Etc.), dyes, pigments, coupling agents such as silane coupling agents, primers, flame retardants, antifoaming agents, leveling agents, rheology control agents (flow aids), release agents and the like.

  In the case of the polyimide solution composition, the contained polyimide is the polyimide described in the “polyimide material of the present invention” and is a polyimide that can be dissolved in a solvent. A solvent can be suitably selected according to a polyimide from what was demonstrated as a solvent used when manufacturing the above-mentioned polyimide precursor. Moreover, the ultraviolet absorber contained also uses the ultraviolet absorber demonstrated in the term of the polyimide material.

  As a method for preparing a polyimide solution composition, the above polyimide precursor solution (UV absorber is preferably not contained) is imidized in the solution (thermal imidization, chemical imidization), and polyimide. The precursor may be converted into polyimide and used as it is as a polyimide solution, or the reaction mixture after the imidization reaction may be poured into a poor solvent to precipitate the polyimide, and then the obtained polyimide may be dissolved in the solvent. Also, the polyimide precursor solution (containing an imidization catalyst and a dehydrating agent if necessary) is cast on a substrate, for example, and heat-treated to dry and imidize (thermal imidization, chemical imidization). ), The obtained polyimide may be dissolved in a solvent. The ultraviolet absorber is preferably added after preparing a polyimide solution.

In a specific embodiment, the polyimide contained in the polyimide solution composition is a tetravalent group in which (i) X ₁ has an alicyclic structure in the formula (1) from the viewpoints of transparency and mechanical strength. Y ₁ is a divalent group having an alicyclic structure, or (ii) X ₁ is a tetravalent group having an alicyclic structure, and Y ₁ is a divalent group having an aromatic ring. Or (iii) X ₁ is a tetravalent group having an aromatic ring, Y ₁ is a divalent group having an alicyclic structure, or (iv) X ₁ is an aromatic ring containing F And a tetravalent group having an aromatic ring not containing F, and Y ₁ is preferably a divalent group having an aromatic ring.

  The polyimide material of the present invention can be obtained by heat-treating the above-described polyimide precursor composition or polyimide solution composition at a temperature exceeding 200 ° C. When the polyimide precursor composition is used, the solvent is removed and imidization proceeds to be converted into a polyimide (solid, for example, a film or a coating layer). Also in the case of a polyimide solution composition, the solvent is removed by heat treatment at a high temperature, and polyimide (solid, for example, a film or a coating layer) is obtained. In either case, since the heat treatment is finally performed at a high temperature exceeding 200 ° C., the thermal characteristics and mechanical characteristics are stabilized, and a polyimide material having excellent characteristics inherent to polyimide can be obtained. The heat treatment temperature is preferably 250 ° C. or higher.

  Heating at a high temperature is indispensable for obtaining a polyimide having excellent characteristics (particularly, a film or a coating layer), but there has been a concern about evaporation and decomposition of the ultraviolet absorber. However, it was unexpected for the present inventor that a polyimide material having sufficient ultraviolet durability was obtained even when heated at a high temperature in a state containing an ultraviolet absorber.

  An example of the manufacturing method of the polyimide film which is 1 preferable form of a polyimide material is demonstrated.

  As an example of the manufacturing method of a polyimide film, a polyimide precursor composition is cast on a base material, for example, The polyimide precursor composition on this base material is 100-500 degreeC, for example, Preferably 200-500 degreeC, More preferably, a method of imidizing the polyimide precursor while removing the solvent by heat treatment at a temperature of about 250 to 450 ° C. can be mentioned. In addition, a heating profile is not specifically limited, It can select suitably.

  Also, the polyimide precursor composition is cast on a substrate, and preferably dried in a temperature range of 180 ° C. or less to form a polyimide precursor composition film on the substrate, and the resulting polyimide precursor is obtained. The film of the composition is peeled off from the substrate and the end of the film is fixed, or the end of the film is not fixed, for example, 100 to 500 ° C., preferably 200 to 500 ° C., more preferably Can be suitably produced also by heat treatment at a temperature of about 250 to 450 ° C. to imidize the polyimide precursor.

  Similarly, when a polyimide solution composition is used, the polyimide solution composition is cast on a substrate, for example, more than 200 to 500 ° C., preferably 250 to 500 ° C., more preferably about 250 to 450 ° C. A polyimide film can be suitably manufactured by heat-processing at temperature and removing a solvent. In this case, the heating profile is not particularly limited and can be selected as appropriate.

  Although a polyimide film is not specifically limited, The linear thermal expansion coefficient from 100 degreeC to 250 degreeC becomes like this. Preferably it is 60 ppm / K or less, More preferably, it can be 50 ppm / K or less.

  The polyimide film is not particularly limited, but 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, more preferably 75% or more, and particularly preferably 80. % Or more. When used for a display application or the like, if the total light transmittance is low, it is necessary to strengthen the light source, which may cause a problem that energy is applied.

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

  Further, a 0.5% weight loss temperature is also important as an index of heat resistance of the polyimide film. The 0.5% weight loss temperature is an index of the temperature at which the contained components and decomposition product components are released from the material. If the polyimide material has a high 0.5% weight loss temperature (for example, a temperature exceeding 200 ° C.), it means that there is almost no release of contained components or decomposed components in the production process using the polyimide material. Therefore, in a manufacturing process of a product using a polyimide material (for example, a polyimide film), contamination of the device and other parts can be reduced. For example, in a process such as vapor deposition, the contamination of the apparatus is reduced, which is advantageous in terms of simplifying the manufacturing process, reducing the manufacturing cost, and improving the yield.

  The thickness of the polyimide film is preferably 0.1 μm to 250 μm, more preferably 1 μm to 150 μm, still more preferably 3 μm to 120 μm, and particularly preferably 5 μm to 100 μm, although it depends on the application. When the polyimide film is used for light transmission, if the polyimide film is too thick, the light transmittance may be lowered.

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

<Evaluation of varnish>
A polyimide precursor solution or a solution obtained by dissolving an ultraviolet absorber in a polyimide solution was added, and the uniformity of the varnish after stirring was visually evaluated. Uniformity: ○ Nonuniformity (such as undissolved residue): ×

<Evaluation of polyimide film>
[400 nm light transmittance]
Using a UV-visible spectrophotometer / V-650DS (manufactured by JASCO), the light transmittance of the polyimide film at a wavelength of 400 nm was measured.

[YI]
Using a UV-visible spectrophotometer / V-650DS (manufactured by JASCO Corporation), YI of the polyimide film was measured based on the standard of ASTM E313. The light source was D65 and the viewing angle was 2 °.

[YI change ΔYI before and after UV irradiation]
ΔYI ₌ YI A -YI _B
YI _A: YI of the polyimide film after the ultraviolet irradiation test
YI _B: YI of the polyimide film before the ultraviolet irradiation test

[Haze]
Using a turbidimeter / NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.), the haze of the polyimide film was measured based on the standard of JIS K7136.

[Tensile modulus, elongation at break, strength at break]
The polyimide film is punched into a IEC-540 (S) standard dumbbell shape to obtain a test piece (width: 4 mm). Using ENSILON manufactured by ORIENTEC, the initial tensile elastic modulus is 30 mm between chucks and the tensile speed is 2 mm / min. The elongation at break was measured.

[0.5% weight loss temperature]
The polyimide film was used as a test piece, and the temperature was increased from 25 ° C. to 600 ° C. at a temperature increase rate of 10 ° C./min in a nitrogen stream using a calorimeter measuring device (Q5000IR) manufactured by TA Instruments. A 0.5% weight loss temperature was determined from the obtained weight curve.

[UV irradiation test]
Using a QUV weather meter Q-UV SE type (Q panel) manufactured by Q-LAB, the light source is UVB-313, the test temperature is 50 ° C. (black panel temperature), and the test illuminance is 0.59 W / m ² (310 nm ), The test time was 24 hours.

  Abbreviations, purity, etc. of raw materials used in the following examples are as follows.

[Diamine component]
4,4′-ODA: 4,4′-oxydianiline [Purity: 99.9% (GC analysis)]
BAFL: 9,9-bis (4-aminophenyl) fluorene 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)]
[Tetracarboxylic acid component]
CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride [purity: 99.9% (GC analysis)]
6FDA: 4,4 ′-(2,2-hexafluoroisopropylene) diphthalic dianhydride [purity 99.77% (H-NMR analysis)]
PPHT: (Octahydro-1,3-dioxo-5-isobenzofurancarboxylic 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)]
[solvent]
DMAc: N, N-dimethylacetamide NMP: N-methyl-2-pyrrolidone MIBK: methyl isobutyl ketone

[Ultraviolet absorber]

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

  The structural formula of the UV absorber is shown below.

[Polyamic acid solution 1]
In a reaction vessel substituted with nitrogen gas, 2.12 g (10 mmol) of m-TD was placed, and DMAc was charged in an amount of 31.33 g so that the total monomer weight (total of diamine component and carboxylic acid component) was 12% by mass. And stirred at room temperature for 1 hour. To this solution, 1.76 g (9 mmol) of CBDA and 0.38 g (1 mmol) of CpODA were gradually added. 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 (polyamic acid solution 1).

[Polyamic acid solution 2]
In a reaction vessel substituted with nitrogen gas, 1.40 g (7 mmol) of 4,4′-ODA and 1.05 g (3 mmol) of BAFL were added, NMP was charged, and the total mass of monomers (total of diamine component and carboxylic acid component) ) Was added in an amount of 15% by mass, and the mixture was stirred at room temperature for 1 hour. To this solution, 3.51 g (7.5 mmol) of PPHT and 0.96 g (2.5 mmol) of CpODA were gradually added. The mixture was stirred at room temperature for 12 hours to obtain a uniform and viscous polyimide precursor solution (polyamic acid solution 2).

[Polyimide solution 1]
TFMB 3.20 g (10 mmol) is put into a reaction vessel substituted with nitrogen gas, and DMAc is added, and 30.58 g of the total amount of monomers added (total of diamine component and carboxylic acid component) is 20% by mass. And stirred at room temperature for 1 hour. To this solution, 4.44 g (10 mmol) of 6FDA was gradually added. The mixture was stirred at room temperature for 12 hours and at 160 ° C. for 12 hours, the temperature was lowered 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 dropped into 500 mL of water to precipitate polyimide. The polyimide was recovered, dried and dissolved in MIBK to obtain a 20% by mass uniform and viscous polyimide solution (polyimide solution 1).

[Polyamic acid solution 3]
In a reaction vessel substituted with nitrogen gas, 2.12 g (10 mmol) of m-TD was placed, and DMAc was charged in an amount of 31.33 g so that the total monomer weight (total of diamine component and carboxylic acid component) was 12% by mass. And stirred at room temperature for 1 hour. To this solution, 1.76 g (9 mmol) of CBDA and 0.38 g (1 mmol) of CpODA were gradually added. 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 (polyamic acid solution 3).

[Polyamide acid solution 4]
In a reaction vessel substituted with nitrogen gas, 2.12 g (10 mmol) of m-TD was placed, and DMAc was charged in an amount of 31.33 g so that the total monomer weight (total of diamine component and carboxylic acid component) was 12% by mass. And stirred at room temperature for 1 hour. To this solution, 1.76 g (9 mmol) of CBDA and 0.38 g (1 mmol) of CpODA were gradually added. Stir at room temperature for 12 hours. To this solution was added a mixed solution of 0.384 g of 1,2-dimethylimidazole and 0.384 g of DMAc, and the mixture was stirred at room temperature for 1 hour to obtain a uniform and viscous polyimide precursor solution (polyamic acid solution 4).

[Polyamic acid solution 5]
In a reaction vessel substituted with nitrogen gas, 20.42 g (0.100 mol) of 4,4′-ODA is put, DMAc is charged, and the total mass of monomers (total of diamine component and carboxylic acid component) is 17% by mass. An amount of 207.21 g was added and stirred at room temperature for 1 hour. To this solution, 22.41 g (0.100 mol) of PMDA-HS was gradually added. The mixture was stirred at room temperature for 12 hours to obtain a uniform and viscous polyimide precursor solution (polyamide acid solution 5).

[Polyamic acid solution 6]
In a reaction vessel substituted with nitrogen gas, 10.81 g (0.100 mol) of tra-DACH was added, and DMAc was charged in 2950 in such an amount that the charged monomer total mass (total of diamine component and carboxylic acid component) was 12% by mass. .64 g was added and stirred at room temperature for 1 hour. To this solution, 28.69 g (0.0975 mol) of s-BPDA and 0.74 g (0.0025 mol) of a-BPDA were gradually added. The mixture was stirred at 50 ° C. for 12 hours to obtain a uniform and viscous polyimide precursor solution (polyamic acid solution 6).

[Polyamic acid solution 7]
In a reaction vessel substituted with nitrogen gas, 20.42 g (0.100 mol) of 4,4′-ODA is placed, DMAc is charged, and the total mass of monomers (total of diamine component and carboxylic acid component) is 20 mass%. An amount of 233.85 g was added and stirred at room temperature for 1 hour. To this solution, 38.44 g (0.100 mol) of CpODA was gradually added. The mixture was stirred at room temperature for 12 hours to obtain a uniform and viscous polyimide precursor solution (polyamide acid solution 5).

[Example 1]
A solution in which LA-46 is dissolved in DMAc is added to the polyamic acid solution 1 in an amount of 2 parts by weight with respect 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. A body composition was obtained. The evaluation results of the varnish are shown in Table 2.

  A polyimide precursor composition filtered through a PTFE membrane filter is applied to a glass substrate, heated in a nitrogen atmosphere as it is from room temperature to 260 ° C., and thermally imidized to form a colorless and transparent polyimide film / glass laminate. Got the body. Next, the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film. The evaluation results of the polyimide film are shown in Table 2.

[Examples 2 to 19, Comparative Example 2, Reference Examples 1 to 3]
The same operation as in Example 1 was performed except that the ultraviolet absorber described in the table was used in place of LA-46 and added to the polyamic acid solution 1 so as to have the amount described in the table. Table 2 shows the evaluation results of the varnish and the polyimide film.

[Comparative Example 1]
A polyamic acid solution 1 filtered through a PTFE membrane filter is applied to a glass substrate, heated in a nitrogen atmosphere as it is from room temperature to 260 ° C., and thermally imidized to form a colorless transparent polyimide film / glass laminate. Got. Next, the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film. The evaluation results of the polyimide film are shown in Table 2.

Example 20
A solution in which Sumisorb 340 is dissolved in NMP is added to the polyamic acid solution 2 in an amount of 2 parts by weight with respect 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. A composition was obtained. The evaluation results of the varnish are shown in Table 2.

  A polyimide precursor composition filtered through a PTFE membrane filter is applied to a glass substrate, heated in a nitrogen atmosphere as it is from room temperature to 350 ° C., and thermally imidized to form a colorless and transparent polyimide film / glass laminate. Got the body. Next, the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film. The evaluation results of the polyimide film are shown in Table 2.

  [Comparative Example 3]

  A polyamic acid solution 2 filtered through a PTFE membrane filter is applied to a glass substrate, heated in a nitrogen atmosphere as it is from room temperature to 350 ° C., and thermally imidized to form a colorless transparent polyimide film / glass laminate. Got. Next, the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film. The evaluation results of the polyimide film are shown in Table 2.

[Comparative Examples 4 and 5]
A solution in which Tinuvin 384-2 is dissolved in MIBK is added to polyimide solution 1 in an amount of 1 part by weight with respect 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. A composition was obtained. The evaluation results of the varnish are shown in Table 2.

  A polyimide solution composition filtered through a PTFE membrane filter is applied to a glass substrate, and heated from room temperature to 130 ° C. and 200 ° C. (Comparative Examples 4 and 5 respectively) under a nitrogen atmosphere to thermally imidize. A colorless and transparent polyimide film / glass laminate was obtained. Next, the obtained polyimide film / glass laminate was immersed in water and then peeled off and dried to obtain a polyimide film. The evaluation results of the polyimide film are shown in Table 2.

[Examples 21 to 23]
Example except that UV absorber (Tinuvin PS) described in Table 3 was used instead of LA-46 and added to the polyamic acid solution 1 so as to have the amount (2 parts by weight) described in Table 3. The same operation as 1 was performed. However, as a result of changing the coating amount of the polyimide precursor composition, the thickness of the polyimide film became 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 performed except that the polyamic acid solution 3 was used instead of the polyamic acid solution 1. Table 3 shows the evaluation results of the varnish and the polyimide film.

[Examples 25 and 26]
The same procedure as in Example 1 was performed except that the amount of the ultraviolet absorber (Tinvin PS) was adjusted to the amount shown 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 6-8]
The same operation as in Example 1 was carried out 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) without using an ultraviolet absorber. went. Table 3 shows the evaluation results of the varnish and the polyimide film.

[Examples 27 and 28]
Using the ultraviolet absorber (Tinuvin PS) and the polyamic acid solution shown in Table 3 in the amounts shown in Table 3, the same operation as in Example 1 was performed to obtain a uniform and viscous polyimide precursor composition. Got. Table 3 shows the evaluation results of the varnish. A polyimide film was obtained in the same manner as in Example 1 except that imidization was performed by heating the temperature to 350 ° C. Table 3 shows the evaluation results of the polyimide film.

[Comparative Examples 9 and 10]
Using a polyamic acid solution 5 (Comparative Example 9) and a polyamic acid solution 6 (Comparative Example 10 using the same procedure as in Example 1 without using an ultraviolet absorber, a uniform and viscous polyimide precursor was obtained. An evaluation result of the varnish is shown in Table 3. A polyimide film was obtained in the same manner as in Example 1 except that the imidization was performed by heating the temperature to 350 ° C. Evaluation result of the polyimide film Is shown in Table 3.

Example 29
Using the UV absorber (Tinuvin PS) and the polyamic acid solution (polyamic acid solution 7) shown in Table 3 in the amounts shown in Table 3, the same operation as in Example 1 was carried out to obtain a uniform and viscous solution. A polyimide precursor composition was obtained. Table 3 shows the evaluation results of the varnish. A polyimide film was obtained in the same manner as in Example 1 except that imidization was performed by heating the temperature to 400 ° C. Table 3 shows the evaluation results of the polyimide film.

[Comparative Example 11]
The same operation as in Example 1 was performed using the polyamic acid solution 7 without using an ultraviolet absorber, to obtain a uniform and viscous polyimide precursor composition. Table 3 shows the evaluation results of the varnish. A polyimide film was obtained in the same manner as in Example 1 except that imidization was performed by heating the temperature to 400 ° C. Table 3 shows the evaluation results of the polyimide film.

  According to the present invention, polyimide having improved UV durability while taking advantage of conventional characteristics of polyimide materials (for example, polyimide films and coating materials) such as chemical resistance, mechanical strength, electrical properties, and dimensional stability. Material can be provided. This polyimide material can be suitably used particularly as a substrate for a display, a touch panel, a solar cell, a protective film, a protective layer or the like.

Claims (23)

Polyimide,
Containing a UV absorber,
A polyimide material having a 0.5% weight loss temperature exceeding 200 ° C.   The haze value is 15% or less, The polyimide material according to claim 1. The polyimide material according to claim 1 or 2, wherein a change in yellowness ΔYI before and after the ultraviolet irradiation test is 8 or less;
However, the conditions of the ultraviolet irradiation test are as follows: a QUV-313 lamp is used, the illuminance is 0.59 W / m ^{2 at} 310 nm, the temperature is 50 ° C., and the irradiation time is 24 hours. The said polyimide contains the repeating unit represented by following General formula (1), The polyimide material of any one of Claims 1-3 characterized by the above-mentioned.

(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 content of the repeating unit represented by the chemical 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 based on the total repeating units. The polyimide material according to claim 4, wherein the content is 50 mol% or less. 5. The polyimide material according to claim 4, wherein X ₁ in the chemical formula (1) is a tetravalent group having an aromatic ring, and Y ₁ is a divalent group having an aromatic ring. 5. The polyimide material according to claim 4, wherein X ₁ in the chemical formula (1) is a tetravalent group having an alicyclic structure, and Y ₁ is a divalent group having an aromatic ring. 5. The polyimide material according to claim 4, wherein X ₁ in the chemical formula (1) is a tetravalent group having an aromatic ring, and Y ₁ is a divalent group having an alicyclic structure.   It is a form of a film or a coating layer, The polyimide material of any one of Claims 1-8.   The polyimide material according to any one of claims 1 to 9, wherein the ultraviolet absorber is selected from a benzotriazole compound or a heat-modified product of a benzotriazole compound.   A polyimide characterized by heat-treating a polyimide precursor composition containing a polyimide precursor, an ultraviolet absorber and a solvent, or a polyimide solution composition containing a polyimide, an ultraviolet absorber and a solvent at a temperature exceeding 200 ° C. Material manufacturing method. The method for producing a polyimide material according to claim 11, wherein the polyimide precursor contained in the polyimide precursor composition contains a repeating unit represented by the following general formula (A1).

Wherein X ₁ is a tetravalent group having an aromatic ring or alicyclic structure, Y ₁ is a divalent group having an aromatic ring or alicyclic structure, and R ₁ and R ₂ are each independently And hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms.)   The said polyimide contained in the said polyimide solution composition contains the repeating unit represented by General formula (1) defined in Claim 4, The manufacturing method of the polyimide material of Claim 11 characterized by the above-mentioned. Applying the polyimide precursor composition or the polyimide solution composition onto a substrate;
It has the process of heat-processing the polyimide precursor composition apply | coated on the base material or a polyimide solution composition, The manufacturing method of the polyimide material of Claim 11 characterized by the above-mentioned.   The said heat processing temperature is 250 degreeC or more, The manufacturing method of the polyimide material of any one of Claims 11-14 characterized by the above-mentioned.   The method for producing a polyimide material according to any one of claims 11 to 15, wherein the ultraviolet absorber is selected from a benzotriazole compound or a heat-modified product of a benzotriazole compound. The said benzotriazole compound is chosen from the compound represented by Formula (100) and Formula (101), The manufacturing method of the polyimide material of Claim 16 characterized by the above-mentioned.

(In formula, R < ₁₁ > -R < ₁₈ > represents an organic group.)

(In the formula, R _{31 to} R ₃₇ and R _{41 to} R ₄₇ represent the meanings given for R _{11 to} R ₁₈ , and X is a divalent organic group.) The benzotriazole compound is
(A) In the formula (100), R _{11 to} R ₁₈ are each independently substituted with H, aryl, or a substituted or unsubstituted maleimide group (the substitution position for alkyl is N). Optionally substituted with 1-20 carbon atoms, provided that the —CH ₂ — group in the alkyl may be replaced by —COO— or —OCO—; Cl is not present in the formula, R ₁₁ -R ₁₈ in total, a compound not containing two or more aromatic rings; and (b) represented by formula (101), wherein R ₃₁ -R ₃₇ and R ₄₁ -R ₄₇ are independently H , Aryl, or a substituted or unsubstituted maleimide group (the substitution position for alkyl is N), which is an alkyl having 1 to 20 carbon atoms, provided that the —CH ₂ — group in the alkyl is — COO- or -OCO X may be an alkylene having 1 to 20 carbon atoms, provided that the —CH ₂ — group in the alkyl may be replaced by —COO— or —OCO—; 18. It is selected from the group consisting of compounds that do not have a ring and R _{31 to} R ₃₇ , R _{41 to} R ₄₇ and X do not contain two or more aromatic rings in total. The manufacturing method of polyimide material. Polyimide precursor,
A polyimide precursor composition comprising an ultraviolet absorber and a solvent.   The polyimide precursor composition according to claim 19, wherein the polyimide precursor is a polyimide precursor defined in claim 12.   The polyimide precursor composition according to claim 19 or 20, wherein the ultraviolet absorber is selected from a benzotriazole compound or a heat-modified product of a benzotriazole compound. The polyimide precursor composition according to claim 21, wherein the benzotriazole compound is selected from compounds represented by formula (100) and formula (101).

(In formula, R < ₁₁ > -R < ₁₈ > represents an organic group.)

(In the formula, R _{31 to} R ₃₇ and R _{41 to} R ₄₇ represent the meanings given for R _{11 to} R ₁₈ , and X is a divalent organic group.) The benzotriazole compound is
(A) In the formula (100), R _{11 to} R ₁₈ are each independently substituted with H, aryl, or a substituted or unsubstituted maleimide group (the substitution position for alkyl is N). Optionally substituted with 1-20 carbon atoms, provided that the —CH ₂ — group in the alkyl may be replaced by —COO— or —OCO—; Cl is not present in the formula, R ₁₁ -R ₁₈ in total, a compound not containing two or more aromatic rings; and (b) represented by formula (101), wherein R ₃₁ -R ₃₇ and R ₄₁ -R ₄₇ are independently H , Aryl, or a substituted or unsubstituted maleimide group (the substitution position for alkyl is N), which is an alkyl having 1 to 20 carbon atoms, provided that the —CH ₂ — group in the alkyl is — COO- or -OCO X may be an alkylene having 1 to 20 carbon atoms, provided that the —CH ₂ — group in the alkyl may be replaced by —COO— or —OCO—; It is selected from the group consisting of compounds that are not contained in R _{31 to} R ₃₇ , R _{41 to} R ₄₇ and X and that do not contain two or more aromatic rings in total. Polyimide precursor composition.