JP2012193281A - Resin composition and molded body of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel highly-transparent heat resistant material excellent in solubility, transparency, low linear thermal expansion coefficient and heat resistance.SOLUTION: A resin composition includes: a first polyimide which is made of a repeated unit expressed by the general formula (1) and has a reduced viscosity (η) of 1.0 dL/g or more; and a specified second polyimide. Then, the resin composition comprises 0.05 to 99.95 pts.mass of the first polyimide and 99.95 to 0.05 pts.mass of the second polyimide, and satisfies the following conditions (a) and (b): (a) the first polyimide and the second polyimide are compatible to each other in the resin composition; and (b) a linear thermal expansion coefficient of the resin composition is 30 ppm/°C or less. In the formula, Ar is 4-24C tetravalent aromatic group and six-membered ring written as H is trans-1, 4-cyclohexane diyl group.

Description

  The present invention relates to a polyimide comprising an aromatic tetracarboxylic dianhydride and trans-1,4-cyclohexanediamine (in the present specification, “from aromatic tetracarboxylic dianhydride and trans-1,4-cyclohexanediamine”). "Polyimide" is also referred to as a first polyimide) and a polyimide comprising an aromatic tetracarboxylic dianhydride and isophorone diamine (in this specification, "polyimide comprising an aromatic tetracarboxylic dianhydride and isophorone diamine" And a molded product thereof. More specifically, the present invention relates to a novel resin composition excellent in solubility, transparency, low linear thermal expansion coefficient and heat resistance composed of a first polyimide and a second polyimide, and a molded body comprising the same. In addition, in this specification, a molded object includes a film-like thing besides what has a three-dimensional shape.

  In recent years, there is an urgent need to develop technology for transparent heat-resistant resins that have both flexibility and transparency as alternatives to glass and ceramics used in display substrates, solar cell substrates, mobile phones, etc., and are soluble in organic solvents. It has become. Polyimide obtained by ring-closing reaction of polyamic acid synthesized by these condensation reactions using aromatic tetralcarboxylic anhydride and aliphatic diamine as raw materials, represented by semi-aliphatic polyimide, has heat resistance and mechanical properties. The polyimide precursor solution is generally used because polyimide is not dissolved in a solvent. As this polyimide, a solution of polyamic acid is well known as a precursor solution.

A method for producing a polyisoimide of a polyimide precursor solution by reacting an aromatic tetracarboxylic dianhydride with a non-aromatic diamine such as cyclohexyldiamine has been reported (for example, Patent Document 1).
In addition, a method for producing a polyimide precursor solution obtained by reacting an aromatic tetracarboxylic acid anhydride with a non-aromatic diamine such as trans-1,4-diaminocyclohexane has been reported (for example, Patent Document 2). ).
Also, a polyimide precursor solution obtained by reacting a non-aromatic tetracarboxylic anhydride such as 1,2,4,5-cyclohexanetetracarboxylic acid with a non-aromatic diamine such as 1,4-diaminocyclohexane. A manufacturing method has been reported (for example, Patent Document 3).
A polyimide precursor solution obtained by reacting a non-aromatic tetracarboxylic anhydride such as 1,2,3,4-cyclobutanetetracarboxylic acid with a non-aromatic diamine such as 1,4-diaminocyclohexane A manufacturing method has been reported (for example, Patent Document 4).
Further, a polyimide precursor obtained by reacting an aromatic tetracarboxylic anhydride such as 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid with a non-aromatic diamine such as 1,4-diaminocyclohexane. A method for producing a body solution has been reported (for example, Patent Document 5).

In addition, a method for producing a polyimide precursor solution obtained by reacting an aromatic tetracarboxylic acid anhydride with a non-aromatic diamine such as 1,4-diaminocyclohexane has been reported (for example, Non-Patent Document 1). .
In addition, a method for producing a polyimide precursor solution obtained by reacting an aromatic tetracarboxylic acid anhydride with a non-aromatic diamine such as 1,4-diaminocyclohexane has been reported (for example, Non-Patent Document 2, 3).

In addition, a high molecular weight solvent-soluble ring-closed polyimide synthesis has been reported by reacting an aromatic tetracarboxylic acid anhydride with a non-aromatic diamine such as isophorone diamine (for example, Patent Document 6).
In addition, a method for producing an organic soluble polyimide by reacting an aromatic tetracarboxylic acid anhydride with a non-aromatic diamine such as isophorone diamine has been reported (for example, Patent Document 7).
Further, a production method has been reported in which an aromatic tetracarboxylic acid anhydride and a non-aromatic diamine such as isophorone diamine are reacted to produce an organic soluble polyimide, followed by further heat treatment under reduced pressure ( For example, Patent Document 8).

JP-A-8-3314 JP 2002-161136 A JP 2002-322274 A JP 2005-146072 A Japanese Patent Laying-Open No. 2005-163012 JP 56-36520 A JP 2000-169579 A JP 2000-327776 A

J. Polym. Sci., Part A. Polym. Chem., 31 P2345-2351 (1993) High Perfom.Polym.13 S93 ~ 106 (2001) High Perfom.Polym.15 P47-64 (2003)

  As a substitute material for glass and ceramic used in semiconductor elements, mobile phone devices, display substrates, solar cell substrates, etc., a resin composition having a soluble and transparent high heat resistance having both flexibility, heat resistance and mechanical strength, and its The object is to provide a molded body.

In order to solve the above problems, the present inventors have conducted intensive studies,
The specific first polyimide and the second polyimide are compatible with each other, and by mixing them, a novel resin composition excellent in solubility, transparency, low linear thermal expansion coefficient and heat resistance, and a molded body comprising the same are obtained. The present invention has been completed. The configuration of the present invention is shown below.

（上記一般式（１）において、Ａｒは炭素数４から２４の４価の芳香族基であり、Ｈと記された六員環はトランス−１，４−シクロヘキサンジイル基である。）
に表される繰り返し単位からなる還元粘度（η_ｓｐ／Ｃ）が１．０ｄＬ／ｇ以上の第一ポリイミドと、下記一般式（２）

（上記一般式（２）において、Ａｒは上記一般式（１）のＡｒと同じであり、Ｒは炭素数２〜２０の脂肪族基または炭素数３〜２０の脂環族基である。）
に表される繰り返し単位からなる還元粘度（η_ｓｐ／Ｃ）が０．８〜５．０ｄＬ／ｇの第二ポリイミドとからなる樹脂組成物であって、該第一ポリイミドと該第二ポリイミドとの合計１００質量部あたり、該第一ポリイミドが０．０５〜９９．９５質量部であり、該第二ポリイミドが９９．９５〜０．０５質量部であり、以下の（ａ）及び（ｂ）を満たすことを特徴とする樹脂組成物。
（ａ）樹脂組成物において第一ポリイミドと第二ポリイミドとが相溶していること。
（ｂ）樹脂組成物の線熱膨張係数が３０ｐｐｍ／℃以下であること。 1. The following general formula (1)

(In the general formula (1), Ar is a tetravalent aromatic group having 4 to 24 carbon atoms, and the six-membered ring denoted as H is a trans-1,4-cyclohexanediyl group.)
A first polyimide having a reduced viscosity (η _{sp / C} ) of 1.0 dL / g or more and comprising the repeating unit represented by formula (2):

(In the general formula (2), Ar is the same as Ar in the general formula (1), and R is an aliphatic group having 2 to 20 carbon atoms or an alicyclic group having 3 to 20 carbon atoms.)
A resin composition comprising a second polyimide having a reduced viscosity (η _{sp / C} ) of 0.8 to 5.0 dL / g comprising the repeating unit represented by The total amount of the first polyimide is 0.05 to 99.95 parts by mass, the second polyimide is 99.95 to 0.05 parts by mass, and the following (a) and (b) The resin composition characterized by satisfy | filling.
(A) The first polyimide and the second polyimide are compatible in the resin composition.
(B) The linear thermal expansion coefficient of the resin composition is 30 ppm / ° C. or less.

（上記一般式（３）において、Ｒは炭素数２〜２０の脂肪族基または炭素数３〜２０の脂環族基である。）
で表される１級ジアミンと、下記一般式（４）、（５）及び（６）

（上記一般式（４）、（５）及び（６）において、Ａｒは炭素数４〜２４の芳香族基である。上記一般式（５）において、Ｘ^１、Ｘ^２、Ｘ^３、およびＸ^４はそれぞれ独立にヒドロキシ基またはクロロ基である。上記一般式（６）において、Ｘ^５およびＸ^６はそれぞれ独立にヒドロキシ基またはクロロ基である。）
で表される芳香族テトラカルボン酸類からなる群より選ばれる少なくとも１種とを、有機溶媒中で重合反応させたものであることを特徴とする上記１項に記載の樹脂組成物。 2. The second polyimide of the general formula (2) is represented by the following general formula (3)

(In the general formula (3), R is an aliphatic group having 2 to 20 carbon atoms or an alicyclic group having 3 to 20 carbon atoms.)
And the following general formulas (4), (5) and (6)

(In the general formulas (4), (5), and (6), Ar is an aromatic group having 4 to 24 carbon atoms. In the general formula (5), X ¹ , X ² , X ³ , and X ⁴ is each independently a hydroxy group or a chloro group.In the general formula (6), X ⁵ and X ⁶ are each independently a hydroxy group or a chloro group.)
2. The resin composition as described in 1 above, wherein at least one selected from the group consisting of aromatic tetracarboxylic acids represented by the formula is polymerized in an organic solvent.

（上記一般式（４）、（５）及び（６）において、Ａｒは炭素数４〜２４の芳香族基である。上記一般式（５）において、Ｘ^１、Ｘ^２、Ｘ^３、およびＸ^４はそれぞれ独立にヒドロキシ基またはクロロ基である。上記一般式（６）において、Ｘ^５およびＸ^６はそれぞれ独立にヒドロキシ基またはクロロ基である。）
で表される芳香族テトラカルボン酸類からなる群より選ばれる少なくとも１種とを、有機溶媒中で重合反応させたものであることを特徴とする上記１項または２項に記載の樹脂組成物。 3. The first polyimide of the general formula (1) is trans-1,4-cyclohexanediamine and the following general formulas (4), (5) and (6)

(In the general formulas (4), (5), and (6), Ar is an aromatic group having 4 to 24 carbon atoms. In the general formula (5), X ¹ , X ² , X ³ , and X ⁴ is each independently a hydroxy group or a chloro group.In the general formula (6), X ⁵ and X ⁶ are each independently a hydroxy group or a chloro group.)
3. The resin composition as described in 1 or 2 above, wherein at least one selected from the group consisting of aromatic tetracarboxylic acids represented by the formula (1) is polymerized in an organic solvent.

4). 2. The resin composition as described in 1 above, wherein R in the general formula (2) is an isophoronediamine residue.
5. 3. The resin composition as described in 2 above, wherein the primary diamine of the general formula (3) is isophorone diamine.
6). A molded article comprising the resin composition according to any one of items 1 to 5 above.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition excellent in both the shaping | molding low linear thermal expansion coefficient and mechanical property and a molded object consisting thereof can be obtained.

Hereinafter, although the form for implementing this invention is illustrated, this invention is not limited to the following examples.
The 1st polyimide which is a component of the resin composition of this invention has a structure represented by the said General formula (1). In the general formula (1), Ar which is a tetravalent aromatic group having 4 to 24 carbon atoms is an aromatic tetracarboxylic acid which is a raw material of polyimide shown below, or a derivative thereof (hereinafter collectively referred to as aromatic tetra). Aromatic tetracarboxylic acids that are the same as Ar in the general formulas (3) to (5), which may be referred to as carboxylic acids), and are listed as preferred aromatic tetracarboxylic acids in the polyimide production method described below. Residues derived from acids are preferred, and among them, pyromellitic acids, 3,3 ′, 4,4′-biphenyltetracarboxylic acids (hereinafter sometimes abbreviated as s-BPDA), which have the following structural formula 2,3,3 ', 4'-biphenyltetracarboxylic acids, bis (3,4-dicarboxyphenyl) ethers, 3,3', 4,4'-benzophenone tetracarbo Acids, bis (3,4-carboxyphenyl) residues from one or more aromatic tetracarboxylic acid selected from the group consisting of sulfones are more preferable.

とを重合させて閉環反応を進行し、得られたポリマーを貧溶媒中に添加することによって固体状に析出させて第一ポリイミドを得ることができる。この第一ポリイミドを得る際、トランス−１,４−シクロヘキサンジアミン以外のジアミン、例えば、シス−１,４−シクロヘキサンジアミンなども、本発明の効果に支障が無い限り共重合させてもよいが、第一ポリイミドの原料であるジアミン成分の合計のうちトランス−１,４−シクロヘキサンジアミンの割合が９０ｍｏｌ％以上であると好ましく、９５ｍｏｌ％以上であるとより好ましく、９８ｍｏｌ％以上であると更に好ましい。 The first polyimide in the present invention has a polymer unit of the general formula (1), and in an organic solvent, aromatic tetracarboxylic acids, particularly preferably aromatic tetracarboxylic dianhydride, and trans-1,4- Cyclohexanediamine

The first polyimide can be obtained by precipitating in a solid state by adding the polymer obtained in a poor solvent. When obtaining this first polyimide, a diamine other than trans-1,4-cyclohexanediamine, such as cis-1,4-cyclohexanediamine, may be copolymerized as long as the effect of the present invention is not impaired. The ratio of trans-1,4-cyclohexanediamine is preferably 90 mol% or more, more preferably 95 mol% or more, and even more preferably 98 mol% or more in the total of diamine components that are raw materials of the first polyimide.

Although there is no restriction | limiting in particular about the molecular weight of the 1st polyimide in this invention, 0.12 g is E sol solvent (a mixture of 40 mass parts 1,1,2,2-tetrachloroethane and 60 mass parts phenol) 10mL. The reduced viscosity (η _{sp / C} ) measured using an Ubbelohde viscometer at 30 ° C. is in the range of 1.0 dL / g or more, preferably 1.5 dL / g or more, More preferably, it is 2.0 dL / g or more. If it is less than 1.0 dL / g, the film-forming property may be deteriorated, or the cast film may be cracked. When using polyimide for electronic materials, the upper limit is not particularly limited because the polyimide film is required to be sufficiently tough, but there is no problem as long as it is soluble in organic solvents, but practically Is preferably 5 dL / g or less.

  The first polyimide is soluble in many organic solvents. Soluble means that 5 g or more of the polyimide is dissolved in 100 g of the organic solvent. Preferably it is 10 g or more. A solubility of 5 g or less is not preferable because polyimide cannot be processed.

  Examples of the organic solvent in which the first polyimide is soluble include benzyl alcohol, α-amylcinnamyl alcohol, cinnamyl alcohol, cuminyl alcohol, p-cymen-8-ol, dehydrocumin alcohol, dihydrocinnamyl alcohol, 2 , 4-dimethylbenzyl alcohol, dimethylbenzyl carbinol, p-α-dimethylbenzyl alcohol, 2-ethoxybenzyl alcohol, 4-ethoxybenzyl alcohol, furfuryl alcohol, hydratropyl alcohol, 4-hydroxybenzyl alcohol, p-hydroxy Phenethyl alcohol, α-isobutylphenethyl alcohol, 2-methoxybenzyl alcohol, 3- (4-methoxyphenyl) propan-1-ol, methyl p-hydroxyphenyl carbinol, 4 Methyl-2-phenylpentanol, 2-methyl-3- (3,4-methylenedioxyphenyl) propanol, 2-methyl-4-phenyl-2-butanol, 2-methyl-5-hydroxymethylpyrazine, 4- Methylbenzyl alcohol, 5-methylfurfuryl alcohol, phenethyl alcohol, phenethylmethylethyl carbinol, 2-phenoxyethanol, phenylethyl carbinol, 2-phenyl-2-propanol, 4-phenylbutan-2-ol, piperonyl alcohol , Aromatic alcohol solvents such as styrylyl alcohol, sulfuryl, tenenyl alcohol, vanillyl alcohol, vanillyl alcohol methyl ether, 1-benzyl-2-methyl-2-propanol, 2,3-dimethoxybenzyl alcohol, Trimethylbenzenes of documene (1,2,4-trimethylbenzene), hemimeritene (1,2,3-trimethylbenzene), mesitylene (1,3,5-trimethylbenzene), cumene, n-propylbenzene, ethyltoluenes , Aromatic hydrocarbon solvents such as indene, indane, cymene, diethylbenzenes, ethylxylenes, phenolic solvents such as phenol and cresol, hetero compound solvents such as pyridine, or a mixture of two or more selected from these solvents Can be used. Besides the above mixed solvents, halogenated solvents such as dichloromethane, chloroform, tetrachloroethane, dichlorobenzene, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, 1,3 -Aprotic high-boiling and high-polarity solvents such as dimethyl-2-imidazolidinone, cyclic ether solvents such as dioxane, dioxolane, and tetrahydrofuran can be mixed and used.

  The 1st polyimide in this invention can be manufactured by a well-known method. For example, dianhydride of aromatic tetracarboxylic acid as the above aromatic tetracarboxylic acid, and polyamic acid is obtained from the above diamine and then ring-closed by heating, or acid anhydride and pyridine, carbodiimide, triphenyl phosphite, etc. Examples of such a method include chemical ring closure using the chemical ring closure agent.

一無水物

一無水物一酸塩化物

及び、一無水物二酸塩化物

（上記の芳香族テトラカルボン酸の塩化物〜一無水物二酸塩化物の各一般式において、Ａｒの定義は一般式（４）、（５）及び（６）におけるＡｒに同じである）
を含むものである。 The aromatic tetracarboxylic acids used in the method for producing the first polyimide are one or more selected from the group consisting of those represented by the general formulas (4), (5) and (6). . Examples of such aromatic tetracarboxylic acids include pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalene. Tetracarboxylic acid, 2,3,6,7-anthracenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3 ', 4'-biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3', 4,4'-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone , May be abbreviated as diphenylsulfonic acid), bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, , 1,3,3,3-hexafluoro-2,2-bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) ) Diphenylsilane, 2,3,4,5-pyridinetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 2,3,4,5-thiophenetetracarboxylic acid, 2,6-bis (3 , 4-dicarboxyphenyl) pyridine and other aromatic tetracarboxylic acids (including heteroaromatic tetracarboxylic acids), various aromatic tetracarboxylic acid dianhydrides listed above, Chlorides of various aromatic tetracarboxylic acids (monocarboxylic acid triacid chloride, dicarboxylic acid diacid chloride, tricarboxylic acid monoacid halide, tetrachloride), the various aromatic tetracarboxylic acids One or more selected from the group consisting of monoanhydrides of acid, monoanhydride monoacid chlorides of the various aromatic tetracarboxylic acids, and monoanhydride acid chlorides of the various aromatic tetracarboxylic acids are preferable As mentioned. As is clear from the above, the aromatic tetracarboxylic acid derivative encompassed by the term aromatic tetracarboxylic acid in the present application means the dianhydride of the aromatic tetracarboxylic acid (the general formula (4)), chloride object

Monoanhydride

Monoanhydride monoacid chloride

And monoanhydride diacid chloride

(In the above general formulas of aromatic tetracarboxylic acid chloride to monoanhydride diacid chloride, the definition of Ar is the same as Ar in the general formulas (4), (5) and (6))
Is included.

  Among the above aromatic tetracarboxylic acids, pyromellitic acids, 3,3 ′, 4,4′-biphenyltetracarboxylic acids, 2,3,3 ′, 4′-biphenyltetracarboxylic acids, bis (3,4- One or more aromatic tetracarboxylic acids selected from the group consisting of dicarboxyphenyl) ethers, 3,3 ′, 4,4′-benzophenonetetracarboxylic acids, bis (3,4-dicarboxyphenyl) sulfones Preferably, at least one selected from the group consisting of aromatic dianhydrides of these tetracarboxylic acids is more preferable, and pyromellitic dianhydride or 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride Is particularly preferred.

  In addition, as long as the production of the first polyimide of the present invention is not hindered, the tetracarboxylic acids other than the above aromatic tetracarboxylic acids, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2 , 3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 2,3,5-tricarboxycyclopentylacetic acid, 3,4-dicarboxy-1,2,3,4- Copolymer polyimide solution using non-aromatic tetracarboxylic acids such as alicyclic tetracarboxylic acids such as tetrahydro-1-naphthalene succinic acid and aliphatic tetracarboxylic acids such as 1,2,3,4-butanetetracarboxylic acid It is also good.

  In the polymerization reaction in the first polyimide production method described above, the ratio of the total number of moles of aromatic tetracarboxylic acids to the total number of moles of trans 1,4-cyclohexanediamine is 1: 0.9 to 1.1. Is preferable, 1: 0.95 to 1.05 is more preferable, and 1: 0.98 to 1.02 is particularly preferable.

  In the production method of the first polyimide, the polymerization reaction for obtaining the polyimide is a high-boiling / high-polarity solvent such as N-methylpyrrolidone, N, N-dimethylacetamide or dimethylsulfoxide, a phenolic solvent such as phenol or m-cresol, Various organic solvents such as cyclic ether solvents such as dioxane, dioxolane, and tetrahydrofuran can be used. Among them, from the group consisting of aprotic high boiling high polarity solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone. It is preferable to mix at least one selected from at least one selected from the group consisting of aromatic hydrocarbons having 6 to 12 carbon atoms in a mass ratio of 1:99 to 99: 1 and use it as a solvent for the polymerization reaction. .

  In the polymerization reaction for obtaining the first polyimide, the reaction is carried out by mixing one or more aromatic alcohols and one or more aromatic hydrocarbons having 9 to 12 carbon atoms to such an extent that the polymerization reactivity is not hindered. It may be used as a solvent. In this case, the mixing ratio of one or more aromatic alcohols and one or more aromatic hydrocarbons having 9 to 12 carbon atoms is preferably a mass ratio of 90:10 to 10:90, and the mass ratio is 80. : 20 to 30:70 is more preferable, and 60:40 to 40:60 is even more preferable. In the above mixed solvent, if the amount of the aromatic hydrocarbon having 9 to 12 carbon atoms exceeds 90% by mass in the mixed solvent, the polyimide may be difficult to dissolve, and if it is 10% by mass or less, the storage stability of the polyimide solution is decreased. May get worse.

  Examples of the aromatic alcohol used in the first polyimide polymerization reaction solvent include benzyl alcohol, α-amylcinnamyl alcohol, cinnamyl alcohol, cuminyl alcohol, p-cymen-8-ol, dehydrocumin alcohol, and dihydrocinna. Mil alcohol, 2,4-dimethylbenzyl alcohol, dimethylbenzylcarbinol, p-α-dimethylbenzyl alcohol, 2-ethoxybenzyl alcohol, 4-ethoxybenzyl alcohol, furfuryl alcohol, hydratropyl alcohol, 4-hydroxybenzyl alcohol P-hydroxyphenethyl alcohol, α-isobutylphenethyl alcohol, 2-methoxybenzyl alcohol, 3- (4-methoxyphenyl) propan-1-ol, methyl p-hydroxy Phenylcarbinol, 4-methyl-2-phenylpentanol, 2-methyl-3- (3,4-methylenedioxyphenyl) propanol, 2-methyl-4-phenyl-2-butanol, 2-methyl-5- Hydroxymethylpyrazine, 4-methylbenzyl alcohol, 5-methylfurfuryl alcohol, phenethyl alcohol, phenethylmethylethyl carbinol, 2-phenoxyethanol, phenylethyl carbinol, 2-phenyl-2-propanol, 4-phenylbutane-2- All, piperonyl alcohol, styryl alcohol, sulfuryl, tenyl alcohol, vanillyl alcohol, vanillyl alcohol methyl ether, 1-benzyl-2-methyl-2-propanol, 2,3-dimethoxybenzyl alcohol 1 or more preferably selected from the group, especially benzyl alcohol.

  Examples of the aromatic hydrocarbon having 9 to 12 carbon atoms used in the first polyimide solution include pseudocumene (1,2,4-trimethylbenzene), hemimelliten (1,2,3-trimethylbenzene), mesitylene (1 , 3,5-trimethylbenzene) is preferably one or more selected from the group consisting of trimethylbenzenes, cumene, n-propylbenzene, ethyltoluenes, indene, indane, cymene, diethylbenzenes, ethylxylenes, More preferably, it is at least one selected from the group consisting of aromatic hydrocarbons having 9 carbon atoms, consisting of benzenes, cumene, n-propylbenzene, ethyltoluenes, indane, and indene, and further trimethylbenzenes. Pseudocumene or mesitylene is particularly preferred. Arbitrariness.

  In the method for producing the first polyimide, the polymerization reaction is performed by dissolving the trans 1,4-cyclohexanediamine and the aromatic tetracarboxylic acid in the organic mixed solvent at room temperature or under ice cooling. The reaction is carried out for a predetermined time while the mixed solvent is heated to reflux. As reaction temperature, 150 to 400 degreeC is preferable, and it is more preferable in it being 180 to 350 degreeC. The reaction time is preferably 0.1 hours to 72 hours, more preferably 0.2 hours to 12 hours, and particularly preferably 0.3 hours to 5 hours.

  In the present invention, a known catalyst can be used in the polymerization reaction for obtaining the first polyimide. However, depending on the application to be used, it is preferable to carry out the reaction in the absence of a catalyst from the viewpoint of the stability and coloring of the polyimide because a trace amount of the catalyst remains.

When using a catalyst, for example, as a base catalyst, quinoline, isoquinoline, α-picoline, β-picoline, 2,4-lutidine, 2,6-lutidine, triethylamine, trimethylamine, propylamine, tributylamine, Illustrative are organic base catalysts such as imidazole, N-dimethylaniline, N, N-diethylaniline, pyridine, and inorganic base catalysts such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, sodium carbonate. .
Examples of the acid catalyst include benzoic acid, methylbenzoic acid, oxybenzoic acid, terephthalic acid, cinnamic acid, crotonic acid, acrylic acid, benzenesulfonic acid, paratoluenesulfonic acid, naphthalenesulfonic acid and the like.

  The monomer concentration during the polymerization reaction (the ratio of the total amount of the trans 1,4-cyclohexanediamine and the aromatic tetracarboxylic acid to the total amount of the reaction solution) is preferably 5 to 50% by mass, more preferably Is 10-30 mass%. By carrying out the polymerization in the range of the monomer concentration, a more uniform and highly polymerized polyimide solution can be obtained. When the polymerization is performed at a monomer concentration of 5% by mass or less, the degree of polymerization of the polyimide does not increase, and the polyimide polymer may become brittle. In addition, when the polymerization reaction is performed at a monomer concentration exceeding 50% by mass, an amine salt is formed, and a longer reaction time is required until the amine salt dissolves and disappears, resulting in problems such as reduced productivity. There is not preferable.

  In the polymerization reaction, it is preferable to remove water generated by the reaction from the reaction solution in order to efficiently obtain a high molecular weight polyimide. Methods for removing water include a method in which a molecular sieve is present in the reaction system, a method in which heated reflux vapor is brought into contact with the molecular sieve to return it to the reaction solution, a condensed liquid produced by cooling the heated reflux vapor, and a molecular sieve. And a method of bringing the reaction solution back into the reaction solution, cooling the heated reflux steam, separating water with a separation tank or Dean Stark apparatus, etc., and returning only the solvent into the reaction solution.

  As a method for producing the first polyimide, the mixed solution after the polymerization reaction is heated, decompressed, or further subjected to melt heat treatment of the isolated polyimide by distilling off the solvent under heating and decompressing. Thus, there is a method in which the polyimide is made to have a higher degree of polymerization and is dissolved again in the above mixed solvent. The melting heat treatment temperature at this time is equal to or lower than the thermal decomposition temperature of the polyimide. In the case of crystalline polyimide, the melting point is preferably 10 ° C. or higher, and in the case of amorphous polyimide, the glass transition temperature is preferably 10 ° C. or higher. More preferably, it is a melting point of 30 ° C. or higher in the case of crystalline polyimide, and a glass transition temperature of 30 ° C. or higher in the case of amorphous polyimide. When the temperature difference is less than 10 ° C., the viscosity of the polyimide is too high, and it is difficult to obtain the effect of increasing the degree of polymerization by heat treatment.

  As a manufacturing method of said 1st polyimide, after precipitating in a poor solvent after a pre-polymerization reaction, it can be made to melt | dissolve in another solvent, and can be used. Furthermore, a polyimide can also be obtained by melt-heat-treating the solid thing obtained by the above-mentioned method with solid.

The 2nd polyimide which is a component of the resin composition of this invention has a structure represented by the said General formula (2). R in the general formula (2) which is an aliphatic group having 2 to 20 carbon atoms or an alicyclic group having 3 to 20 carbon atoms represents a residue derived from a primary diamine which is a raw material of the polyimide. And a residue derived from a primary diamine listed as a preferred primary diamine in the method for producing the polyimide described below is preferred, and a residue derived from an alicyclic primary diamine having 3 to 15 carbon atoms is more preferred. Preferably, a residue derived from an alicyclic primary diamine having 6 to 15 carbon atoms is more preferable, such as isophorone diamine (hereinafter sometimes abbreviated as IPDA), 1,3-cyclohexanediamine, 1,4-cyclohexanediamine. 1,4-cyclohexanedimethylamine, 2-methyl-1,3-cyclohexanediamine, norbornanediamine, bis (4-aminocyclohexyl) methane, bis 4-amino-3-methylcyclohexyl) methane, hexahydro-4,7-meth Noin mite range diamine, tricyclo [6.2.1.0 ^2,7] - 1 kind selected from the group consisting of a undecylenate range methyl-diamine The residues derived from the above primary diamines are more preferable, and the following residues derived from isophorone diamine, that is, isophorone diamine residues are particularly preferable.

  Ar which is a tetravalent aromatic group having 4 to 24 carbon atoms in the general formula (2) is Ar in the general formula (1) for the first polyimide, and an aromatic which is a raw material of the polyimide. It is the same as Ar in the general formulas (3) to (5) representing tetracarboxylic acid or a derivative thereof (hereinafter sometimes referred to as aromatic tetracarboxylic acids), and the preferred one is also related to the first polyimide. The same as described above.

  The second polyimide in the present invention has a polymerization unit of the general formula (2), and polymerizes an aromatic tetracarboxylic acid such as aromatic tetracarboxylic dianhydride with a primary diamine in an organic solvent. It can be obtained by allowing the ring closure reaction to proceed.

The molecular weight of the second polyimide is not particularly limited, but 0.12 g is added to 10 mL of E sol solvent (a mixture of 40 parts by mass of 1,1,2,2-tetrachloroethane and 60 parts by mass of phenol). The reduced viscosity (η _{sp / C} ) measured using an Ubbelohde viscometer at 30 ° C. is in the range of 0.8 to 5.0 dL / g, and is 0.8 dL / g or more. Preferably, it is 1.0 dL / g or more. If it is less than 0.8, the film forming property may be deteriorated, and the cast film may be cracked. The upper limit is not particularly limited, but there is no problem as long as it is soluble in an organic solvent, but practically it is preferably 5 dL / g or less.

As a manufacturing method of the 2nd polyimide of this invention, it can manufacture by well-known methods, such as a heat ring closure method and a chemical ring closure method, like the above-mentioned 1st polyimide.
In the production method of the second polyimide used in the present invention, it is selected from the group consisting of diaminoclay, diaminosilica, diaminoceramic nanofiber, diaminocellulose, modified diaminocellulose, etc. whose surface is modified with an amine group to the extent that the present invention is not hindered. One or more types may be mixed.

  The aromatic tetracarboxylic acids used in the method for producing the second polyimide are those represented by the same general formulas (4), (5) and (6) as described above for the method for producing the first polyimide. One or more kinds selected from the group consisting of the above-described aromatic tetracarboxylic acids are also the same as in the case of the first polyimide.

  In addition, if the second polyimide is of an extent that does not hinder its production, in addition to the above aromatic tetracarboxylic acids as tetracarboxylic acids, non-aromatic such as 1,2,3,4-cyclobutanetetracarboxylic acid It is the same as the first polyimide that a copolymerized polyimide using tetracarboxylic acids may also be used.

が特に好ましい。 The primary diamine used in the production of the second polyimide is represented by the general formula (3). Such primary diamines include ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,2-cyclopropanediamine, 1,4-butanediamine, 1,2-cyclobutanediamine, 1,3. -Cyclobutanediamine, 1,2-cyclopentanediamine, 1,3-cyclopentanediamine, 2,2-dimethyl-1,3-propanediamine, 1,6-hexamethylenediamine, 1,8-octamethylenediamine, 1 , 9-nonamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethyl Hexamethylene diamine, isophorone diamine, 1,3-cyclohexane diamine, 1,4-cyclohexanediamine, 1,4-cyclohexanedimethylamine, 2-methyl-1,3-cyclohexanediamine, norbornanediamine, bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) ) Methane, hexahydro-4,7-methanoin danylene dimethylene diamine, tricyclo [6.2.1.0 ^2,7 ] -undecylenedimethyl diamine, diaminosiloxane, diaminoclay with surface modification of amine groups, diaminosilica, diamino One or more types selected from the group consisting of ceramic nanofibers, diaminocellulose, modified diaminocellulose and the like are preferred. Of these primary diamines, 2,2-dimethyl-1,3-propanediamine, 1,6-hexamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, , 10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, isophoronediamine, 1 , 3-cyclohexanediamine, cis-1,4-cyclohexanediamine, 1,4-cyclohexanedimethylamine, 2-methyl-1,3-cyclohexanediamine, norbornanediamine, bis (4-aminocyclohexyl) methane, bis (4- Amino-3-methylcyclohexyl) methane, hex Hydro-4,7-meth Noin mite range diamine, tricyclo [6.2.1.0 ^2,7] - one or more kinds of primary diamines selected from the group consisting undecylenate range methyl diamines, the general formula ( It is more preferable that R in 3) is a primary diamine which is an alicyclic group having 3 to 15 carbon atoms. Especially, primary diamine whose R in the said General formula (3) is a C6-C15 alicyclic group is preferable, and isophorone diamine, 1, 3- cyclohexane diamine, cis 1, 4- cyclohexane diamine, 1,4-cyclohexanedimethylamine, 2-methyl-1,3-cyclohexanediamine, norbornanediamine, bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, hexahydro-4,7- One or more primary diamines selected from the group consisting of methanoin danylene dimethylene diamine, tricyclo [6.2.1.02,7] -undecylenedimethyl diamine and the like are more preferable, and isophorone diamine

Is particularly preferred.

  In the polymerization reaction in the second polyimide production method, the ratio of the total number of moles of aromatic tetracarboxylic acids to the total number of moles of primary diamine is preferably 1: 0.9 to 1.1. 1: 0.95 to 1.05 is more preferable, and 1: 0.98 to 1.02 is particularly preferable.

  In the production method of the present invention, the polymerization reaction for obtaining the second polyimide is preferably carried out in a mixed solvent of one or more aromatic alcohols and one or more aromatic hydrocarbons having 9 to 12 carbon atoms. About the aromatic alcohol which comprises the mixed solvent used for the polymerization reaction which obtains a 2nd polyimide, a C9-C12 aromatic hydrocarbon, and those mixing ratios are preferable regarding the mixed solvent of a 1st polyimide solution. Those mentioned above are likewise suitable. At this time, N-methylpyrrolidone or the like as a solvent in which the polyimide contained in the polyimide solution of the present invention is soluble may be mixed to such an extent that the polymerization reactivity and the storage stability of the polyimide solution are not hindered. .

  In the method for producing the second polyimide of the present invention, the polymerization reaction is performed by dissolving the diamine such as isophorone diamine and the aromatic tetracarboxylic acid in the organic mixed solvent at room temperature or under ice cooling. Accordingly, the reaction is performed for a predetermined time while the mixed solvent is heated to reflux. As reaction temperature, 150 to 400 degreeC is preferable, and it is more preferable in it being 180 to 350 degreeC. The reaction time is preferably 0.1 hours to 72 hours, more preferably 0.2 hours to 12 hours, and particularly preferably 0.3 hours to 5 hours.

In the polymerization reaction for obtaining the second polyimide used in the present invention, a known catalyst can be used. However, depending on the application to be used, it is preferable to carry out the reaction in the absence of a catalyst from the viewpoint of the stability and coloring of the polyimide because a trace amount of the catalyst remains.
When the catalyst is used, as described above with respect to the first polyimide, an organic base catalyst such as quinoline or an inorganic base catalyst such as sodium hydroxide can be used as the base catalyst.
Further, as described above for the first polyimide, benzoic acid, methylbenzoic acid, or the like can be used as the acid catalyst.

  The monomer concentration during the polymerization reaction (ratio of the total amount of the diamine with the isophoronediamine and the aromatic tetracarboxylic acid to the total amount of the reaction solution) is preferably 5 to 50% by mass, more preferably It is 10-30 mass%. By carrying out the polymerization in the range of the monomer concentration, a more uniform and highly polymerized polyimide solution can be obtained. When the polymerization is performed at a monomer concentration of 5% by mass or less, the degree of polymerization of the polyimide does not increase, and the polyimide polymer may become brittle. In addition, when the polymerization reaction is performed at a monomer concentration exceeding 50% by mass, an amine salt is formed, and a longer reaction time is required until the amine salt dissolves and disappears, resulting in problems such as reduced productivity. There is not preferable.

  In the polymerization reaction, it is preferable to remove water generated by the reaction from the reaction solution in order to efficiently obtain a high molecular weight polyimide. Methods for removing water include a method in which a molecular sieve is present in the reaction system, a method in which heated reflux vapor is brought into contact with the molecular sieve to return it to the reaction solution, a condensed liquid produced by cooling the heated reflux vapor, and a molecular sieve. And a method of bringing the reaction solution back into the reaction solution, cooling the heated reflux steam, separating water with a separation tank or Dean Stark apparatus, etc., and returning only the solvent into the reaction solution.

  As a method for producing the above-mentioned second polyimide, heating the mixed liquid after the polymerization reaction, depressurizing, or distilling off the solvent under heating and depressurizing and further subjecting the isolated polyimide to a heat treatment under reduced pressure. Thus, there is a method in which the polyimide is made to have a higher degree of polymerization and is dissolved again in the above mixed solvent. The melting heat treatment temperature at this time is equal to or lower than the thermal decomposition temperature of the polyimide. In the case of crystalline polyimide, the melting point is preferably 10 ° C. or higher, and in the case of amorphous polyimide, the glass transition temperature is preferably 10 ° C. or higher. More preferably, it is a melting point of 30 ° C. or higher in the case of crystalline polyimide, and a glass transition temperature of 30 ° C. or higher in the case of amorphous polyimide. When the temperature difference is less than 10 ° C., the viscosity of the polyimide is too high, and it is difficult to obtain the effect of increasing the degree of polymerization by heat treatment.

  As a manufacturing method of said 2nd polyimide, after precipitating in a poor solvent after a pre-polymerization reaction, it can be made to melt | dissolve in another solvent, and can be used. Furthermore, a polyimide can also be obtained by melt-heat-treating the solid thing obtained by the above-mentioned method with solid.

  The reaction solution of the above polymerization reaction can be used as it is as the polyimide solution of the present invention, but the polymerization reaction solution may be concentrated by heating or the like, or diluted by adding a solvent to the polymerization reaction solution. It is good also as a polyimide solution. As the solvent for dilution, the same composition as the mixed solvent used for the polymerization reaction with a mixed solvent of one or more aromatic alcohols and one or more aromatic hydrocarbons having 9 to 12 carbon atoms is preferable. It may be of a different composition. If the composition of the mixed solvent after dilution falls within a mass ratio of 90:10 to 10:90 of one or more aromatic alcohols and one or more aromatic hydrocarbons having 9 to 12 carbon atoms. You may dilute with only 1 or more types of aromatic alcohol, or only 1 or more types of C9-C12 aromatic hydrocarbon. Furthermore, as long as the storage stability of the polyimide solution is not hindered, the polyimide contained in the polyimide solution of the present invention such as N-methylpyrrolidone may be diluted with the above-described solvent.

  The resin composition of the present invention is 0.05 to 99.95 parts by mass of the first polyimide and 0.05 to 99.95 parts by mass of the first polyimide and the second polyimide. 99.95-0.05 parts by mass), preferably 1-99 parts by mass (second polyimide is 99-1 parts by mass), more preferably 5-95 parts by mass (second polyimide is 95-5 parts by mass). ). When the amount of the first polyimide is less than 0.05 parts by mass, there is a possibility that a sufficient reduction in linear thermal expansion coefficient may not be obtained, which is not preferable. When the amount of the first polyimide is more than 99.95 parts by mass, the solubility of the resin composition in the solvent may be insufficient, which is not preferable.

  The polyimide resin composition in the present invention includes a halogenated solvent such as dichloromethane, chloroform, tetrachloroethane, dichlorobenzene, a phenolic solvent such as phenol, m-cresol, o-chlorophenol, tetrahydrofuran, 1,3-dioxolane, 1, It is preferable to be soluble in cyclic ether solvents such as 4-dioxane, amide solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide and N, N-dimethylformamide, and organic solvents such as pyridine. .

  In the resin composition of the present invention, the first polyimide and the second polyimide are compatible. Here, the term “compatible” means that the glass composition has only one glass transition temperature when measured by differential scanning calorimetry (DSC) at a heating rate of 10 ° C./min, or in dynamic viscoelasticity measurement. When present, it refers to a case where the composition light transmittance satisfies either the same or a high transmittance as compared with the light transmittance of a single component.

  The resin composition of the present invention has a linear thermal expansion coefficient of 30 ppm / ° C. or less, and more preferably 20 ppm / ° C. or less. As the linear thermal expansion coefficient, a test piece having a width of 4 mm, a length of 40 mm, and a thickness of 18 μm, obtained by thermomechanical analysis under the conditions of a load of 0.2 N, a temperature rising rate of 10 ° C./min, and a distance between chucks of 16 mm. An average value of elongation in the range of 40 ° C. to 180 ° C. can be adopted.

In the resin composition of the present invention, the glass transition temperature is preferably 300 ° C. or higher, and more preferably 310 ° C. or higher. When the glass transition temperature is 300 ° C. or lower, the heat resistance of the polyimide resin composition is not used, and the resin characteristics are not sufficiently obtained, which is not preferable.
Even if the glass transition temperature is 300 ° C or higher, there is no problem in application to the industrial field. Applications for electronic materials such as protective films for flexible printed circuits, semiconductor passivation films, buffer coat films, interlayer insulation films for multilayer integrated circuits, etc. Useful as.

  In the present invention, as a method for producing a resin composition, when both the first polyimide and the second polyimide are soluble in an organic solvent, the resin composition is prepared by dissolving and mixing with an organic solvent and removing the organic solvent after molding. Can do. This method is very effective particularly when the glass transition temperature of the resin composition in the present invention is high. If the temperature does not cause decomposition of the polymer and at least one of the polymers flows, it can be mixed using a ruder.

  Furthermore, the polyimide resin composition of the present invention includes, for example, a silane coupling agent, clay, filler, cellulose, plant-derived biopolymer powder or fiber, ultraviolet absorber, antioxidant, photosensitive agent, light as necessary. In addition to a polymerization initiator and a sensitizer, known additives can be added as long as the effects of the present invention are not impaired, and these additives can also be mixed and used. In addition, in addition to the use such as solubility and heat resistance, a polymer other than the polyimide may be added within a range not impairing the effects of the present invention.

The resin composition of the present invention can be suitably used for applications such as molded articles as described below, and is particularly suitable for forming a coating film or a plastic substrate as a polyimide varnish. The polyimide composition of the present invention can be obtained by molding the above resin composition resin composition. As a method for forming, a conventionally known method can be used without particular limitation, and typical examples include solution forming, solution casting, dry spinning, wet spinning and the like.
Although there is no limitation in the form of a molded object, A film | membrane, a film, a sheet | seat, a fiber, a hollow fiber, a tube, a pipe, a bottle etc. are illustrated.

  The polyimide molded body of the present invention is a plastic substrate for replacing glass substrates such as for liquid crystal displays, for organic electroluminescence displays, for electronic paper, for solar cells, and for electrical insulating films of electronic devices, and further, a solar cell protective film, Suitable for electrical / electronic parts and optical materials such as glass substrate substitute plastics such as protective films for color filters, transparent conductive film substrates, TFT substrates, optical disk substrates, optical fibers, lenses, touch panels and the like. For use in these electric / electronic parts and optical materials, the polyimide molded body of the present invention in the form of a film, film or sheet is suitable. Insulating films are particularly useful.

As a method for producing a molded body in the form of the above film, film, or sheet, a production method characterized by applying a polyimide solution on a substrate and removing the solvent is preferable.
-A method of obtaining a polyimide molded body as a film by applying a polyimide solution to a substrate by screen printing, spin coating method, spray coating method spin coating, etc. (application step) and then drying (drying step),
・ Extrude the polyimide solution from the slit-like nozzle or use a bar coater to apply to the substrate (application process), dry (drying process), and then remove the polyimide molding from the substrate (exfoliation process) ) To obtain a polyimide molded body that is a film or a sheet,
Etc. are exemplified.

  In the above application step, the thickness to which the polyimide solution of the present invention is applied is appropriately adjusted according to the dimensions of the target molded article, but is usually about 0.01 to 1000 μm, more preferably. It is 0.1-500 micrometers, More preferably, it is 0.3-100 micrometers, Most preferably, it is 0.5-50 micrometers. The coating step is usually performed at room temperature, but the polyimide varnish may be heated in the range of 40 to 80 ° C. for the purpose of reducing the viscosity and improving operability.

  In the above drying step, the drying temperature is usually 50 to 250 ° C., preferably 60 to 230 ° C., more preferably 100 to 190 ° C., although it depends on the type of the mixed solvent. May be dried. In addition, the drying temperature over 250 degreeC may cause the yellowing of the polyimide molded body of this invention, and the fall of transparency. Examples of the heating method used in the drying step include warm air heating, infrared heating, microwave heating, and EB heating. Although the drying process can be performed in an air atmosphere, it is recommended to perform in an inert gas atmosphere from the viewpoint of safety and prevention of oxidation. Examples of the inert gas include nitrogen and argon. It is also possible to dry under reduced pressure.

  Said peeling process is normally implemented after cooling this molded object on a base material to about room temperature-about 50 degreeC. Since the resin composition of the present invention has high adhesiveness, a release agent may be applied to the substrate as necessary before applying the polyimide solution of the present invention in order to easily perform the peeling operation. Examples of the mold release agent include vegetable oils, silicons, and fluorines.

  Since the film formed as described above using the resin composition of the present invention is in a state of being bonded to the base material, it is also effective as a component of the adhesive, and includes the resin composition of the present invention. The material is suitable for bonding an electric / electronic component to form an electric / electronic component device, and is particularly suitable as an adhesive between semiconductor wafers used during three-dimensional semiconductor mounting.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention does not receive any limitation by this. The measurement in each Example and the comparative example was calculated | required with the following method.

[Reduced viscosity: η _{sp / C} ]
Using an Ubbelohde viscometer at 30 ° C., 0.12 g of polymer was dissolved in 10 mL of E sol solvent (a mixture of 40 parts by mass of 1,1,2,2-tetrachloroethane and 60 parts by mass of phenol), The reduced viscosity (η _{sp / C} ) at 30 ° C. of the polyimide solution was determined.

[Solubility]
The solubility evaluation of the resin composition was performed at room temperature.
◎: No sediment ○: Very small sediment △: Small amount of sediment X: No change

[Glass-transition temperature]
As the glass transition temperature (Tg), Tg at a heating rate of 10 ° C./min was determined by DSC (DSC2920 manufactured by TA Instruments).

[Linear thermal expansion coefficient]
A test piece having a width of 4 mm, a length of 40 mm, and a thickness of 18 μm under the conditions of a load of 0.2 N, a heating rate of 10 ° C./min, and a distance between chucks of 16 mm by thermomechanical analysis using a TMA2940 thermomechanical analyzer manufactured by TA instruments. The average value of the elongation in the range of 40 ° C. to 180 ° C. was obtained and used as the linear thermal expansion coefficient.

[Production Example 1: First polyimide]
In a 0.5 L separable flask, trans-1,4-cyclohexanediamine (t-CHDA, purity 98 mol%) 2.8548 parts by mass (0.025 mol part) N-methyl 2-pyrrolidone 36.7571 parts by mass / Biphenyltetracarboxylic dianhydride (s-BPDA) 7.3555 parts by mass (0.025 mol part) was charged into 4.084 parts by mass of toluene (manufactured by Wako) (mass ratio 90:10). First, the reaction exotherm was confirmed while stirring for 0.5 hr at 50 rpm with a stirring speed of 50 rpm in a nitrogen atmosphere at room temperature, and the reaction solution was heated to 190 ° C. over 6.5 hr. The polymerization and the ring closure reaction were allowed to proceed while removing them from the system. The amount of water distilled during the reaction was the same as the theoretical amount of imide bond formation by the cyclization reaction, and the formation of polyimide was confirmed. Thereafter, the temperature was raised to 200 ° C. over 0.5 hours at a stirring rotational speed of 150 rpm, held at the same temperature for 0.5 hours, allowed to cool, and when the reaction solution dropped to 80 ° C., the reaction solution was mixed with water / acetone (volume). Ratio 3/2) Opened to 200 parts by mass, the deposited first polyimide (white solid) was collected by filtration. When the reduced viscosity (η _{sp / C} ) of the obtained first polyimide was measured, it was 2.05 dL / g.

[Production Example 2: Second polyimide]
In a 0.5 L separable flask, 4.2575 parts by mass of isophoronediamine (IPDA) (0.025 mol parts), 36.7571 parts by mass of benzyl alcohol / pseudocumene (manufactured by Wako), 4.084 parts by mass (mass ratio 90:10) ) A mixed solvent was charged with 7.3555 parts by mass (0.025 mol parts) of biphenyltetracarboxylic dianhydride (s-BPDA). First, the reaction exotherm was confirmed while stirring for 0.5 hr at 50 rpm with a stirring speed of 50 rpm in a nitrogen atmosphere at room temperature, and the reaction solution was heated to 190 ° C. over 6.5 hr. The polymerization and the ring closure reaction were allowed to proceed while removing them from the system. The amount of water distilled during the reaction was the same as the theoretical amount of imide bond formation by the cyclization reaction, and the formation of polyimide was confirmed. Thereafter, the temperature was raised to 200 ° C. over 0.5 hours at a stirring rotational speed of 150 rpm, held at the same temperature for 0.5 hours, allowed to cool, and when the reaction solution dropped to 80 ° C., the reaction solution was mixed with water / acetone (volume). Ratio 3/2) The mixture was opened at 200 parts by mass, and the precipitated second polyimide (white solid) was collected by filtration. When the reduced viscosity (η _{sp / C} ) of the obtained second polyimide was measured, it was 2.52 dL / g.

[Examples 1 to 3]
The first polyimide obtained by the method of Production Example 1 and the second polyimide obtained by the method of Production Example 2 were dissolved in m-cresol at a mass ratio shown in the following table to prepare a 10% by mass dope, After casting on a glass substrate, it was dried at 200 ° C. to obtain a transparent and uniform film. Various physical properties of the obtained film were measured. The results are shown in Table 1.

[Comparative Example 1]
Using only the first polyimide obtained by the method of Production Example 1, an attempt was made to obtain a film in the same manner as in Examples 1 to 3, but the first polyimide did not dissolve in m-cresol, so the film Could not make. The results are shown in Table 1.

[Comparative Example 2]
The same operation as in Examples 1 to 3 was performed using only the second polyimide obtained by the method of Production Example 2. The results are shown in Table 1.

  The resin composition of the present invention is useful as a material for a plastic substrate as a substitute for a glass substrate used in the field of electric and electronic components, and is used for liquid crystal displays, organic electroluminescence displays, electronic papers, and solar cells. It can be used for various applications such as plastic substrates for glass substrates, electrical insulating films for electronic devices, optical materials, protective films for solar cell panels, and optical waveguides.

Claims (6)

The following general formula (1)

(In the general formula (1), Ar is a tetravalent aromatic group having 4 to 24 carbon atoms, and the six-membered ring denoted as H is a trans-1,4-cyclohexanediyl group.)
A first polyimide having a reduced viscosity (η _{sp / C} ) of 1.0 dL / g or more and comprising the repeating unit represented by formula (2):

(In the general formula (2), Ar is the same as Ar in the general formula (1), and R is an aliphatic group having 2 to 20 carbon atoms or an alicyclic group having 3 to 20 carbon atoms.)
A resin composition comprising a second polyimide having a reduced viscosity (η _{sp / C} ) of 0.8 to 5.0 dL / g comprising the repeating unit represented by The total amount of the first polyimide is 0.05 to 99.95 parts by mass, the second polyimide is 99.95 to 0.05 parts by mass, and the following (a) and (b) The resin composition characterized by satisfy | filling.
(A) In the resin composition, the first polyimide and the second polyimide are compatible.
(B) The linear thermal expansion coefficient of the resin composition is 30 ppm / ° C. or less. The second polyimide of the general formula (2) is represented by the following general formula (3)

(In the general formula (3), R is an aliphatic group having 2 to 20 carbon atoms or an alicyclic group having 3 to 20 carbon atoms.)
And the following general formulas (4), (5) and (6)

(In the general formulas (4), (5), and (6), Ar is an aromatic group having 4 to 24 carbon atoms. In the general formula (5), X ¹ , X ² , X ³ , and X ⁴ is each independently a hydroxy group or a chloro group.In the general formula (6), X ⁵ and X ⁶ are each independently a hydroxy group or a chloro group.)
The resin composition according to claim 1, wherein at least one selected from the group consisting of aromatic tetracarboxylic acids represented by the formula (1) is polymerized in an organic solvent. The first polyimide of the general formula (1) is trans-1,4-cyclohexanediamine and the following general formulas (4), (5) and (6)

(In the general formulas (4), (5), and (6), Ar is an aromatic group having 4 to 24 carbon atoms. In the general formula (5), X ¹ , X ² , X ³ , and X ⁴ is each independently a hydroxy group or a chloro group.In the general formula (6), X ⁵ and X ⁶ are each independently a hydroxy group or a chloro group.)
The resin composition according to claim 1 or 2, wherein at least one selected from the group consisting of aromatic tetracarboxylic acids represented by the formula (I) is polymerized in an organic solvent.   The resin composition according to claim 1, wherein R in the general formula (2) is an isophoronediamine residue.   The resin composition according to claim 2, wherein the primary diamine of the general formula (3) is isophorone diamine.   A molded article comprising the resin composition according to any one of claims 1 to 5.