JP6051653B2 - Polyimide resin, cured polyimide resin, and polyimide film - Google Patents

Description

The present invention relates to a polyimide resin having a specific structure, a cured polyimide resin and a polyimide film, which are obtained by irradiating and curing the polyimide resin by irradiating ultraviolet rays or electron beams, and have excellent transparency, heat resistance, and organic solvent resistance. . The polyimide film of the present invention is used for a transparent conductive film, a thin film transistor substrate, and a flexible printed wiring board.

  Traditionally, polyimide has excellent properties in terms of mechanical properties, chemical resistance, electrical properties, etc. in addition to its excellent heat resistance, so it can be used in fields such as molding materials, composite materials, and electrical / electronic components. Widely used. In recent years, electrical and electronic devices have made significant progress in miniaturization, thinning, and weight reduction, and even for plastic films that are one of the components, heat resistance, mechanical properties, Long-term reliability is required in terms of dimensional stability.

In recent years, with the advent of an advanced information society, materials having both heat resistance and transparency have been demanded in the fields of optical communication such as optical fibers and optical waveguides, and display devices such as liquid crystal alignment films and color filters. In particular, in the field of display devices, a glass substrate is being considered as an alternative to a lightweight and flexible plastic substrate, and displays that can be bent or rolled are being actively developed. In this field, development of a resin material having excellent toughness in addition to transparency and heat resistance is strongly demanded.
However, in general, a polyimide resin is essentially yellowish brown due to intramolecular conjugation or formation of a charge transfer complex. In order to solve such problems, Patent Document 1 discloses a colorless and transparent polyimide comprising a specific tetracarboxylic dianhydride and a linear or branched aliphatic diamine. Patent Document 2 discloses a transparent polyimide resin using a specific tetracarboxylic acid or a dianhydride thereof in a specific ratio or more. In Patent Document 3, a polyamic acid solution obtained by mixing and polymerizing a diamine component and an acid dianhydride component is heated under reduced pressure, a polyimide resin obtained by thermal imidization is dissolved again with a solvent, and cast coating is performed. A transparent polyimide film obtained by subsequent drying is disclosed. However, these polyimide resins have a problem of poor organic solvent resistance. Therefore, when used as a substrate or optical film, when exposed to a coating solution containing a polar solvent or solvent, its form changes due to elution or swelling of its surface, so that the film itself does not have a protective layer. Difficult to use.

Japanese Patent No. 3702579 Japanese Patent Laid-Open No. 2001-48983 International Publication No. 2002/66546

  An object of the present invention is to provide a transparent polyimide film having improved solvent resistance while having transparency and heat resistance.

As a result of intensive studies to solve the above problems, the present inventors have bonded a compound containing an acrylic group or a methacrylic group at the terminal, using a polyimide having a repeating unit containing an aliphatic tetracarboxylic acid structure as a skeleton, ultraviolet rays, etc. By curing and drying, the inventors found that a cured polyimide resin and a polyimide film having improved organic solvent resistance while having transparency and heat resistance were obtained, and the present invention was completed.

In this specification, “(meth) acryl group” means an acryl group or a methacryl group. Further, “(meth) acrylic monomer” means a monomer having an acrylic group or a methacrylic group.

That is, the present invention is as follows.
1. A polyimide resin represented by the following formula (I).

（式（Ｉ）中、Ｒは、環状構造、非環状構造、または環状構造と非環状構造を有する炭素数４〜１０の４価の基である。Φは、脂肪族構成単位、脂環族構成単位、芳香族構成単位、オルガノシロキサン構成単位、またはこれらの組み合わせあるいは繰り返しからなる炭素数２〜３９の２価の連結基であり、Φの主鎖には−Ｏ−、−ＳＯ_２−、−ＣＯ−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｃ_２Ｈ_４Ｏ−、および−Ｓ−からなる群から選ばれた少なくとも１種の基が介在していてもよい。ｎは繰り返し単位であることを示す。Ｘ１、Ｘ２は、式（II）または式（III）で示される基、若しくは水素原子のいずれかであって、前記Ｘ１およびＸ２の少なくとも一方は式（II）または式（III）で示される基である。式（II）、式（III）中、Ｘ３は炭素数２〜１０の基であり、エステル結合を有してもよい。Ｘ４は水素原子またはメチル基である。）
２．前記式（Ｉ）中のＲがシクロヘキサンから４個の水素原子を除いて形成される４価の基である上記１に記載のポリイミド樹脂。
３．テトラカルボン酸成分とジアミン成分を、前記ジアミン成分に対する前記テトラカルボン酸成分のモル比が０．８０以上０．９８以下の範囲において反応させる工程、前記工程を経て得られた化合物の末端に存在するアミノ基と、イソシアネート基またはエポキシ基を有する（メタ）アクリル化合物における前記イソシアネート基またはエポキシ基とを反応させることを特徴とする、式（Ｉ）で示されるポリイミド樹脂の製造方法。
４．上記１または２のいずれかに記載のポリイミド樹脂に、紫外線または電子線を照射して得られる、ポリイミド樹脂硬化物。
５．前記ポリイミド樹脂硬化物と、プラスチックフィルム、シリコンウェハー、金属箔およびガラスから選ばれる基材からなる積層体。
６．前記、基材が銅箔である、上記５に記載の積層体。
７．前記、ポリイミド樹脂硬化物からなる、ポリイミドフィルム。

(In Formula (I), R is a C4-C10 tetravalent group which has a cyclic structure, an acyclic structure, or a cyclic structure and an acyclic structure. (PHI) is an aliphatic structural unit, an alicyclic group. A divalent linking group having 2 to 39 carbon atoms composed of a structural unit, an aromatic structural unit, an organosiloxane structural unit, or a combination or repetition thereof, and the main chain of Φ has —O—, —SO ₂ —, At least one group selected from the group consisting of —CO—, —CH ₂ —, —C (CH ₃ ) ₂ —, —C ₂ H ₄ O—, and —S— may intervene. n represents a repeating unit, X1 and X2 are either a group represented by formula (II) or formula (III), or a hydrogen atom, and at least one of X1 and X2 is represented by formula (II) Or a group represented by formula (III): In formula (II) and formula (III), X3 Is a group having 2 to 10 carbon atoms and may have an ester bond, and X4 is a hydrogen atom or a methyl group.)
2. 2. The polyimide resin according to 1 above, wherein R in the formula (I) is a tetravalent group formed by removing four hydrogen atoms from cyclohexane.
3. A step of reacting a tetracarboxylic acid component and a diamine component in a range where the molar ratio of the tetracarboxylic acid component to the diamine component is 0.80 or more and 0.98 or less; A method for producing a polyimide resin represented by the formula (I), comprising reacting an amino group and the isocyanate group or epoxy group in a (meth) acrylic compound having an isocyanate group or an epoxy group.
4). A cured polyimide resin obtained by irradiating the polyimide resin according to either 1 or 2 with ultraviolet rays or electron beams.
5. A laminate comprising the polyimide resin cured product and a base material selected from a plastic film, a silicon wafer, a metal foil, and glass.
6). 6. The laminate according to 5 above, wherein the substrate is a copper foil.
7). The polyimide film which consists of said polyimide resin hardened | cured material.

The polyimide film of the present invention is characterized by being excellent in organic solvent resistance such that it does not change in shape even when exposed to a coating agent containing an organic solvent, etc. while having heat resistance and transparency.

  The polyimide resin of the present invention is represented by the following formula (I).

（式（Ｉ）中、Ｒは、環状構造、非環状構造、または環状構造と非環状構造を有する炭素数４〜１０の４価の基である。Φは、脂肪族炭化水素基、脂環族炭化水素基、芳香族炭化水素基、およびオルガノシロキサン基からなる群より選ばれる少なくとも１種の基を有する、炭素数２〜３９の２価の基であり、Φの主鎖には−Ｏ−、−ＳＯ_２−、−ＣＯ−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｃ_２Ｈ_４Ｏ−、および−Ｓ−からなる群から選ばれる少なくとも１種の基が介在していてもよい。ｎは繰り返し単位であることを示す。Ｘ１、Ｘ２は、式（II）または式（III）で示される基、若しくは水素原子のいずれかであって、前記Ｘ１およびＸ２の少なくとも一方は式（II）または式（III）で示される基である。式（II）、式（III）中、Ｘ３は炭素数２〜１０の基であり、エステル結合を有してもよい。Ｘ４は水素原子またはメチル基である。）

(In the formula (I), R represents a cyclic structure, an acyclic structure, or a tetravalent group having 4 to 10 carbon atoms having a cyclic structure and an acyclic structure. Φ represents an aliphatic hydrocarbon group or an alicyclic ring. A divalent group having 2 to 39 carbon atoms having at least one group selected from the group consisting of an aromatic hydrocarbon group, an aromatic hydrocarbon group, and an organosiloxane group. _{-, - SO 2 -, -} CO -, - CH 2 -, - C (CH 3) 2 -, - C 2 H 4 O-, and at least one group intervening selected from the group consisting of -S- N represents a repeating unit, X1 and X2 are either a group represented by formula (II) or formula (III), or a hydrogen atom, and each of X1 and X2 At least one is a group represented by the formula (II) or the formula (III): In the formula (II) or the formula (III), X 3 is a group having 2 to 10 carbon atoms and may have an ester bond, and X4 is a hydrogen atom or a methyl group.)

  Preferable R in the above formula (I) includes cyclohexane, cyclopentane, cyclobutane, bicyclopentane, and tetravalent groups formed by removing four hydrogen atoms from these stereoisomers. More specifically, a tetravalent group represented by the following structural formula can be given.

中でもシクロヘキサンから４個の水素原子を除いて形成される４価の基がより好ましい。

Among these, a tetravalent group formed by removing four hydrogen atoms from cyclohexane is more preferable.

Φ in the above formula (I) is an aliphatic structural unit, alicyclic structural unit, aromatic structural unit, organosiloxane structural unit, or a divalent linking group having 2 to 39 carbon atoms composed of a combination or repetition thereof. And the main chain of Φ is a group consisting of —O—, —SO ₂ —, —CO—, —CH ₂ —, —C (CH ₃ ) ₂ —, —C ₂ H ₄ O—, and —S—. At least one group selected from may be interposed. Where Φ is cyclohexane, dicyclohexylmethane, dimethylcyclohexane, isophorone, norbornane, and their alkyl substituents, halogen substituents; benzene, naphthalene, biphenyl, diphenylmethane, diphenyl ether, diphenylsulfone, benzophenone, and their alkyl substituents, halogen Substituted body: a divalent group formed by removing two hydrogen atoms from a compound such as organo (poly) siloxane. More specifically, a divalent group having 6 to 27 carbon atoms represented by the following structural formula is preferable.

Below, the manufacturing method of the polyimide resin of this invention is shown. The polyimide resin of the present invention is
Step 1: a step of reacting a tetracarboxylic acid component and a diamine-based component to obtain a polyimide having an amino group at the terminal,
Step 2: reacting a polyimide having an amino group at the terminal obtained in Step 1 with a compound having either an isocyanate group or an epoxy group and a (meth) acryl group,
It is obtained through

The process of Step 1 will be described. Examples of the tetracarboxylic acid component include cyclohexanetetracarboxylic acid, cyclohexanetetracarboxylic acid esters, cyclohexanetetracarboxylic dianhydride, cyclobutanetetracarboxylic acid, cyclobutanetetracarboxylic acid esters, cyclobutanetetracarboxylic dianhydride, cyclopentanetetra Examples thereof include carboxylic acid, cyclopentanetetracarboxylic acid esters, cyclopentanetetracarboxylic dianhydride, bicyclopentanetetracarboxylic dianhydride, and the like. Preferred are cyclohexanetetracarboxylic dianhydride and cyclobutanetetracarboxylic dianhydride. Anhydrous, cyclopentanetetracarboxylic dianhydride. More preferred is cyclohexanetetracarboxylic dianhydride. The tetracarboxylic acid component includes positional isomers.

Preferred examples of the tetracarboxylic acid component include 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetra. Carboxylic acid methyl ester, 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic acid methyl ester, 1 , 2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid methyl ester, 1,2,4,5 -Cyclopentanetetracarboxylic acid, 1,2,4,5-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclopentanetetracarboxylic acid Ester, 3-carboxymethyl-1,2,4-cyclopentanetricarboxylic acid, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid, bicyclo [2.2. 2] Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid methyl ester , Dicyclohexyltetracarboxylic acid, dicyclohexyltetracarboxylic dianhydride, and dicyclohexyltetracarboxylic acid methyl ester.
Among them, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid methyl ester are polyimide resins. It is particularly preferable because it is easy to increase the molecular weight during production and is advantageous in that a flexible film can be easily obtained.

  The tetracarboxylic acid component may be other tetracarboxylic acid or a derivative thereof such as pyromellitic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, as long as the flexibility and thermocompression bonding property of the film are not impaired. 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) propane, 2,2-bis (2,3-dicarboxyphenyl) propane, 2,2 -Bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3 , 3,3-hexafluoropropane, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) ether, bis (2,3-dicarboxyphenyl) ether 3,3 ′, 4,4′-benzophenone tetracarboxylic acid, 2,2 ′, 3,3′-benzophenone tetracarboxylic acid, 4,4- (p-phenylenedioxy) diphthalic acid, 4,4- (M-phenylenedioxy) diphthalic acid, ethylenetetracarboxylic acid, 1,1-bis (2,3-dicarboxyphenyl) ethane, bis (2,3-dicarboxyphenyl) methane, bis (3,4-di It may contain at least one compound selected from (carboxyphenyl) methane and derivatives thereof.

  Examples of the diamine component include diamines, diisocyanates, and diaminodisilanes, with diamines being preferred. The diamine content in the diamine-based component is preferably 50 mol% or more (including 100 mol%).

  The diamine may be an aliphatic diamine, an aromatic diamine, or a mixture thereof. In the present invention, “aromatic diamine” means a diamine in which an amino group is directly bonded to an aromatic ring, and an aliphatic group, an alicyclic group, and other substituents are included in a part of the structure. May be. The “aliphatic diamine” represents a diamine in which an amino group is directly bonded to an aliphatic group or an alicyclic group, and an aromatic group and other substituents may be included in a part of the structure.

  In general, when an aliphatic diamine is used as a constituent component, the polyamic acid as an intermediate product and the aliphatic diamine form a strong complex, and thus it is difficult to obtain a high molecular weight polyimide. Therefore, it is necessary to devise such as using a solvent having a relatively high solubility of the complex, such as cresol. However, when cyclohexanetetracarboxylic acid or a derivative thereof and an aliphatic diamine are used as components, a complex in which the bond between the polyamic acid and the aliphatic diamine is relatively weak is formed, so that the polyimide can be easily increased in molecular weight.

  Examples of the aliphatic diamine include 4,4′-diaminodicyclohexylmethane, ethylenediamine, hexamethylenediamine, polyethylene glycol bis (3-aminopropyl) ether, polypropylene glycol bis (3-aminopropyl) ether, and 1,3- Examples thereof include bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, m-xylylenediamine, p-xylylenediamine, isophorone diamine, norbornane diamine, and siloxane diamines.

  Examples of the aromatic diamine include 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, m-phenylenediamine, p-phenylenediamine, diaminobenzophenone, and 2,6. -Diaminonaphthalene, 1,5-diaminonaphthalene, etc. are mentioned.

In Step 1, the organic solvent used when the tetracarboxylic acid component and the diamine component are reacted is a solvent containing at least one structure selected from the group consisting of cyclic ether, cyclic ketone, cyclic ester, amide, and urea. preferable. Specific examples include, but are not limited to, γ-butyrolactone, N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylphosphoramide, cyclopentanone, cyclohexanone, It is preferable to contain at least one selected from aprotic polar organic solvents such as 1,3-dioxolane, 1,4-dioxane, tetramethylurea and tetrahydrofuran. Among these, one or more selected from γ-butyrolactone, N, N-dimethylacetamide, N, N-dimethylformamide and N-methyl-2-pyrrolidone is more preferable.

In step 1, an imidization catalyst may be used when the tetracarboxylic acid component and the diamine component are reacted. As the imidization catalyst, a tertiary amine compound is preferable, and specifically, trimethylamine, triethylamine (TEA), tripropylamine, tributylamine, triethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine. , Triethylenediamine, N-methylpyrrolidine, N-ethylpyrrolidine, N-methylpiperidine, N-ethylpiperidine, imidazole, pyridine, quinoline, isoquinoline and the like, and the reaction is performed in the presence of at least one catalyst selected from these. be able to.

The reaction temperature in Step 1 is usually in the range of 160 to 200 ° C, preferably in the range of 170 to 190 ° C, more preferably in the range of 180 to 190 ° C. If it is lower than 160 ° C., imidation and high molecular weight may not sufficiently proceed due to insufficient temperature, and if it exceeds 200 ° C., a problem such as the resin scorching on the wall of the reaction vessel when the solution viscosity increases remarkably. May occur. In some cases, an azeotropic dehydrating agent such as toluene or xylene may be used. The reaction pressure is usually atmospheric pressure, but the reaction can also be carried out under pressure as necessary. The holding time for the reaction temperature is at least 1 hour, more preferably 3 hours or more. If it is less than 1 hour, imidization and high molecular weight may not proceed sufficiently. Although there is no upper limit in particular about reaction time, it is normally performed in 3 to 10 hours.

  The tetracarboxylic acid component A mole and the diamine component B mole are preferably reacted in a range of 0.80 ≦ A / B ≦ 0.98, more preferably 0.85 ≦ A / B ≦ 0.95. is there. If 0.80 ≦ A / B, the flexibility is good, and if A / B ≦ 0.98, a polyimide resin having sufficient organic solvent resistance can be obtained.

Step 2 reacts the polyimide having an amino group at the terminal obtained in Step 1 with a compound having either an isocyanate group or an epoxy group and a (meth) acrylic group, and a (meth) acrylic group at the terminal. It is the process of obtaining the polyimide resin which has.

  Examples of the compound having an amino group and a (meth) acryl group used in the present invention include 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, 1,1- (bisacryloyloxymethyl) ethyl isocyanate. , Glycidyl methacrylate, allyl glycidyl ether, 2-hydroxyethyl methacrylate, and the like. These may be used alone or in combination of two or more.

The reaction temperature in Step 2 is preferably 30 to 100 ° C., and the reaction time is preferably 1 to 5 hours.

Although the polyimide resin hardened | cured material and polyimide film of this invention are not restrict | limited in particular, it is manufactured by the following method.
You may mix a photoinitiator with respect to the solution containing the polyimide which has the (meth) acryl group at the terminal obtained in step 2.
Examples of the photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane- 1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2- Hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl 2-Dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-mol Pholinyl) phenyl] -1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, etc., and these are used alone. Alternatively, two or more components may be mixed and used. It is preferable to mix a photoinitiator in the ratio of 0.1-10 weight part with respect to solid content in the solution containing the polyimide resin which has a (meth) acryl group at the terminal.

  Moreover, you may mix a bifunctional or more (meth) acryl monomer with respect to the solution containing the polyimide which has the (meth) acryl group at the terminal obtained in step 2. FIG. Flexibility and heat resistance can be controlled by the structure of the (meth) acrylic monomer to be mixed. Examples of the (meth) acrylic monomer include tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, polypropylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tris- (2-acrylic). Roxyethyl) isocyanurate, ditrimethylolpropane tetraacrylate, and the like may be used, and these may be used alone or in combination of two or more components. These bifunctional or higher functional (meth) acrylic monomers are preferably mixed in a ratio of 1/2 to 4 times the solid content in the solution containing the polyimide having a (meth) acrylic group at the terminal.

  Then, the solution containing the polyimide which has a (meth) acryl group at the terminal is apply | coated on a base material. As a method of coating on a substrate, inkjet method, spin coating method, casting method, micro gravure method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen A printing method, a flexographic printing method, a large coating method and the like can be mentioned, but the method is not particularly limited. When apply | coating on a board | substrate, it is preferable to adjust the solid content concentration of the solution containing the polyimide which has a (meth) acryl group at the terminal so that it may become the range of 5 to 20 weight%. If necessary, it may be diluted with an organic solvent. As the organic solvent for dilution, the organic solvent described in paragraph 0030 can be used.

  Examples of the substrate include glass, silicon wafer, metal foil, and plastic film. Among the metal foils, copper foil is particularly preferably used.

  Then, an ultraviolet-ray is irradiated to the coating film obtained by apply | coating on a base material, and polyimide resin hardened | cured material (cured film) is obtained. The ultraviolet irradiation amount is preferably such that the cumulative irradiation amount is 500 mJ / cm 2 or more.

  Next, heat treatment is performed to evaporate the solvent contained in the cured polyimide resin (cured film). As heat treatment conditions, the heating temperature is preferably 250 ° C. or higher, and the heating time is preferably 1 to 5 hours. Thereafter, the cured polyimide resin (cured film) after the heat treatment is peeled off from the base material to obtain a polyimide film. The thickness of the polyimide film is preferably in the range of 20 μm to 500 μm.

  Hereinafter, the present invention will be described specifically by way of examples. However, this invention is not restrict | limited at all by these Examples.

Evaluation of the polyimide films obtained in Examples and Comparative Examples was performed as follows.
-Glass transition temperature DSC measurement was performed using a differential scanning calorimeter device (DSC6200) manufactured by SII Nano Technology Co., Ltd. under the condition of a heating rate of 10 ° C / min to obtain a glass transition temperature.
-Total light transmittance, haze It measured using the Nippon Denshoku Industries Co., Ltd. color and turbidity simultaneous measuring device (COH400).
(3) Organic solvent resistance 0.1 g of polyimide film and 20 mL of each organic solvent were placed in a 50 mL Erlenmeyer flask and stirred with a magnetic stirrer for 24 hours to evaluate organic solvent resistance. ○: not dissolved ×: dissolved

<Reference Example 1>
Synthesis of 1,2,4,5-cyclohexanetetracarboxylic dianhydride Catalyst with 552 g of pyromellitic acid in a 5 liter Hastelloy (HC22) autoclave and rhodium on activated carbon (N.E. NE Chemcat Corporation) 200 g and water 1656 g were charged, and the inside of the reactor was replaced with nitrogen gas while stirring. Next, the inside of the reactor was replaced with hydrogen gas, and the temperature of the reactor was increased to 60 ° C. with a hydrogen pressure of 5.0 MPa. The reaction was carried out for 2 hours while maintaining the hydrogen pressure at 5.0 MPa. The hydrogen gas in the reactor was replaced with nitrogen gas, the reaction solution was extracted from the autoclave, and the reaction solution was filtered while hot to separate the catalyst. The filtrate was concentrated by evaporating water under reduced pressure using a rotary evaporator to precipitate crystals. The precipitated crystals were separated into solid and liquid at room temperature and dried to obtain 481, g (yield: 85.0%) of 1,2,4,5-cyclohexanetetracarboxylic acid.
Subsequently, 450 g of the obtained 1,2,4,5-cyclohexanetetracarboxylic acid and 4000 g of acetic anhydride were charged into a 5-liter glass separable flask (with Dimroth condenser), and the inside of the reactor was stirred. Replaced with nitrogen gas. The temperature was raised to the reflux temperature of the solvent under a nitrogen gas atmosphere, and the solvent was refluxed for 10 minutes. While stirring, the mixture was cooled to room temperature to precipitate crystals. The precipitated crystals were separated into solid and liquid and dried to obtain primary crystals. Further, the separated mother liquor was concentrated under reduced pressure using a rotary evaporator to precipitate crystals. The crystals were separated into solid and liquid and dried to obtain secondary crystals. The primary crystal and the secondary crystal were combined to obtain 375 g of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (anhydrous yield of 96.6%).

<Reference Example 2>
In a 500 mL five-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, dropping funnel with side tube, Dean Stark, and condenser tube, 2,2-bis [4- (4-aminophenoxy) phenyl] under a nitrogen stream After charging 48.9 g (0.119 mol) of propane and 91.6 g of γ-butyrolactone and 22.9 g of N, N-dimethylacetamide as solvents, 1, 2, 4, synthesized in Reference Example 1 were dissolved. 24.1 g (0.107 mol) of 5-cyclohexanetetracarboxylic dianhydride and 0.5 g (0.005 mol) of triethylamine as an imidization catalyst were added all at once. After completion of the dropwise addition, the temperature was raised to 180 ° C. and refluxed for 5 hours while distilling off the distillate as needed to obtain a solution containing a polyimide having an amino group at the terminal.

<Reference Example 3>
In a 500 mL five-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, dropping funnel with side tube, Dean Stark, and condenser tube, 2,2-bis [4- (4-aminophenoxy) phenyl] under a nitrogen stream After charging 48.7 g (0.119 mol) of propane, 91.6 g of γ-butyrolactone and 22.9 g of N, N-dimethylacetamide as solvents, 1,2,4 synthesized in Reference Example 1 were dissolved. 25.3 g (0.113 mol) of 5-cyclohexanetetracarboxylic dianhydride and 0.5 g (0.005 mol) of triethylamine as an imidization catalyst were added all at once. After completion of the dropwise addition, the temperature was raised to 180 ° C. and refluxed for 5 hours while distilling off the distillate as needed to obtain a solution containing a polyimide having an amino group at the terminal.

<Reference Example 4>
In a 500 mL five-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, dropping funnel with side tube, Dean Stark, and condenser tube, 35.5 g (0.177 mol) of 4,4′-diaminodiphenyl ether under nitrogen flow Then, 94.1 g of γ-butyrolactone and 23.5 g of N, N-dimethylacetamide as a solvent were added and dissolved, and then 1,2,4,5-cyclohexanetetracarboxylic dianhydride 35 synthesized in Reference Example 1 was used. 0.8 g (0.160 mol) and 0.8 g (0.005 mol) triethylamine as an imidization catalyst were added all at once. After completion of the dropwise addition, the temperature was raised to 180 ° C. and refluxed for 5 hours while distilling off the distillate as needed to obtain a solution containing a polyimide having an amino group at the terminal.

<Reference Example 5>
In a 500 mL five-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, dropping funnel with side tube, Dean Stark, and condenser tube, 4,4′-bis (4-aminophenoxy) biphenyl (BAPB) under a nitrogen stream 35.6 g (0.097 mol) and 69.0 g of γ-butyrolactone and 17.2 g of N, N-dimethylacetamide as a solvent were added and dissolved, then 1,2,4,5 synthesized in Reference Example 1 -20.6 g (0.092 mol) of cyclohexanetetracarboxylic dianhydride and 0.5 g (0.005 mol) of triethylamine as an imidization catalyst were added all at once. After completion of the dropwise addition, the temperature was raised to 180 ° C. and refluxed for 5 hours while distilling off the distillate as needed to obtain a solution containing a polyimide having an amino group at the terminal.

<Example 1>
3.4 g (0.024 mol) of 2-isocyanatoethyl acrylate was added to the solution containing the amino group-terminated polyimide synthesized in Reference Example 2 and reacted at 60 ° C. for 3 hours. A solution containing a polyimide having a group was obtained. To the obtained polyimide solution, 0.1 part by weight of a photopolymerization initiator in terms of resin solid content was added. Subsequently, a polyimide solution was applied onto a glass plate, irradiated with ultraviolet rays at an integrated irradiation amount of 4,800 mJ / cm2, and then heated at 250 ° C. for 2 hours in a hot air dryer to evaporate the solvent to obtain a polyimide film having a thickness of 100 μm. . The results are shown in Table 1.

<Example 2>
The same as Example 1 except that 8.0 g (0.024 mol) of tricyclodecane dimethanol diacrylate was added to the solution containing the polyimide having an acrylic group at the terminal obtained in Example 1. Thus, a polyimide film having a thickness of 100 μm was obtained. The results are shown in Table 1.

<Example 3>
The same method as in Example 1 except that 4.7 g (0.016 mol) of trimethylolpropane triacrylate was added to the solution containing the polyimide having an acrylic group at the terminal obtained in Example 1. A polyimide film having a thickness of 100 μm was obtained. The results are shown in Table 1.

<Example 4>
1.6 g (0.012 mol) of 2-isocyanatoethyl acrylate was added to the solution containing the amino group-terminated polyimide synthesized in Reference Example 3 and reacted at 60 ° C. for 3 hours. A solution containing a polyimide having a group was obtained. To the obtained polyimide solution, 0.1 part by weight of a photopolymerization initiator in terms of resin solid content was added. Subsequently, a polyimide solution was applied onto a glass plate, irradiated with ultraviolet rays at an integrated irradiation amount of 4,800 mJ / cm2, and then heated at 250 ° C. for 2 hours in a hot air dryer to evaporate the solvent to obtain a polyimide film having a thickness of 100 μm. . The results are shown in Table 1.

<Example 5>
The same method as in Example 4 except that 2.4 g (0.008 mol) of trimethylolpropane triacrylate was added to the solution containing the polyimide having an acrylic group at the terminal obtained in Example 4. A polyimide film having a thickness of 100 μm was obtained. The results are shown in Table 1.

<Example 6>
3.4 g (0.024 mol) of 2-isocyanatoethyl acrylate was added to the solution containing the amino group-terminated polyimide synthesized in Reference Example 4 and reacted at 60 ° C. for 3 hours. A solution containing a polyimide having a group was obtained. To the obtained polyimide solution, 0.1 part by weight of a photopolymerization initiator in terms of resin solid content was added. Subsequently, a polyimide solution was applied onto a glass plate, irradiated with ultraviolet rays at an integrated dose of 4,800 mJ / cm2, and then heated in a hot air dryer at 280 ° C. for 2 hours to evaporate the solvent to obtain a polyimide film having a thickness of 100 μm. . The results are shown in Table 1.

<Example 7>
Polyimide having a thickness of 100 μm in the same manner as in Example 6 except that 7.3 g (0.035 mol) of 1,1- (bisacryloyloxymethyl) ethyl isocyanate was used instead of 2-isocyanatoethyl acrylate. A film was obtained. The results are shown in Table 1.

<Example 8>
The same as Example 6 except that 11.6 g (0.035 mol) of tricyclodecane dimethanol diacrylate was added to the solution obtained in Example 6 containing a polyimide having an acrylic group at the terminal. Thus, a polyimide film having a thickness of 100 μm was obtained. The results are shown in Table 1.

<Example 9>
The same method as in Example 6 except that 6.8 g (0.023 mol) of trimethylolpropane triacrylate was added to the solution containing the polyimide having an acrylic group at the terminal obtained in Example 6. A polyimide film having a thickness of 100 μm was obtained. The results are shown in Table 1.

<Example 10>
1.4 g (0.010 mol) of 2-isocyanatoethyl acrylate was added to the solution containing the amino group-terminated polyimide synthesized in Reference Example 5 and reacted at 60 ° C. for 3 hours. 0.1 part by weight of a photopolymerization initiator was added to obtain a solution containing a polyimide having an acrylic group at the terminal. To the obtained polyimide solution, 0.1 part by weight of a photopolymerization initiator in terms of resin solid content was added. Subsequently, the obtained polyimide solution was applied onto a glass plate, irradiated with ultraviolet rays at an integrated irradiation amount of 4,800 mJ / cm 2, heated at 280 ° C. for 2 hours in a hot air dryer to evaporate the solvent, and a polyimide film having a thickness of 100 μm. Got. The results are shown in Table 1.

<Comparative Example 1>
In a 500 mL five-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, dropping funnel with side tube, Dean Stark, and condenser tube, 2,2-bis [4- (4-aminophenoxy) phenyl] under a nitrogen stream 13.5 g (0.060 mol) of propane, 45.8 g of γ-butyrolactone and 11.5 g of N, N-dimethylacetamide as a solvent were added and dissolved, and then 1,2,4 synthesized in Reference Example 1 13.5 g (0.06 mol) of 5-cyclohexanetetracarboxylic dianhydride and 0.5 g (0.005 mol) of triethylamine as an imidization catalyst were added all at once. After completion of the dropwise addition, the temperature was raised to 180 ° C., refluxed for 5 hours while distilling off the distillate as needed, the reaction was terminated, air-cooled until the internal temperature reached 100 ° C., and N, N-dimethyl as a diluent solvent. 86.8 g of acetamide was added and cooled with stirring to obtain a polyimide solution having a solid content concentration of 20% by weight. Subsequently, the obtained polyimide solution was applied onto a glass plate, held at 100 ° C. for 60 minutes on a hot plate, and the solvent was volatilized to obtain a colorless and transparent primary dry film having self-supporting property. This film was fixed to a stainless steel frame, heated in a hot air dryer at 250 ° C. for 2 hours to evaporate the solvent, and a film having a thickness of 100 μm was obtained. The results are shown in Table 1.

<Comparative example 2>
In a 500 mL five-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, dropping funnel with side tube, Dean Stark, and condenser tube, 18.6 g (0.093 mol) of 4,4′-diaminodiphenyl ether in a nitrogen stream Then, 47.2 g of γ-butyrolactone and 11.8 g of N, N-dimethylacetamide as a solvent were added and dissolved, and then 1,2,4,5-cyclohexanetetracarboxylic dianhydride 20 synthesized in Reference Example 1 was used. 0.8 g (0.093 mol) and 0.5 g (0.005 mol) of triethylamine as an imidization catalyst were added all at once. After completion of the dropwise addition, the temperature was raised to 180 ° C., refluxed for 5 hours while distilling off the distillate as needed, the reaction was terminated, air-cooled until the internal temperature reached 100 ° C., and N, N-dimethyl as a diluent solvent. 85.0 g of acetamide was added and cooled with stirring to obtain a polyimide solution having a solid content concentration of 20% by weight. Subsequently, the obtained polyimide solution was applied onto a glass plate, held at 100 ° C. for 60 minutes on a hot plate, and the solvent was volatilized to obtain a colorless and transparent primary dry film having self-supporting property. This film was fixed to a stainless steel frame, heated in a hot air dryer at 250 ° C. for 2 hours to evaporate the solvent, and a film having a thickness of 100 μm was obtained. The results are shown in Table 1.

<Comparative Example 3>
In a 500 mL five-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, dropping funnel with side tube, Dean Stark, and condenser tube, 4,4′-bis (4-aminophenoxy) biphenyl (BAPB) under a nitrogen stream 23.9 g (0.065 mol) and 46.0 g of γ-butyrolactone and 11.5 g of N, N-dimethylacetamide as a solvent were added and dissolved, and then 1,2,4,5 synthesized in Reference Example 1 -14.5 g (0.065 mol) of cyclohexanetetracarboxylic dianhydride and 0.5 g (0.005 mol) of triethylamine as an imidization catalyst were added all at once. After completion of the dropwise addition, the temperature was raised to 180 ° C., refluxed for 5 hours while distilling off the distillate as needed, the reaction was terminated, air-cooled until the internal temperature reached 100 ° C., and N, N-dimethyl as a diluent solvent. 86.5 g of acetamide was added and cooled with stirring to obtain a polyimide solution having a solid content concentration of 20% by weight. Subsequently, the obtained polyimide solution was applied onto a glass plate, held at 100 ° C. for 60 minutes on a hot plate, and the solvent was volatilized to obtain a colorless and transparent primary dry film having self-supporting property. This film was fixed to a stainless steel frame, heated in a hot air dryer at 250 ° C. for 2 hours to evaporate the solvent, and a film having a thickness of 100 μm was obtained. The results are shown in Table 1.

ＮＭＰ：Ｎ−メチル−２−ピロリドン
ＤＭＡｃ：Ｎ，Ｎ−ジメチルアセトアミド
ＧＢＬ：γ―ブチロラクトン

NMP: N-methyl-2-pyrrolidone DMAc: N, N-dimethylacetamide GBL: γ-butyrolactone

Claims (6)

A polyimide resin represented by the following formula (I).

(In the formula (I), R is a tetravalent group formed by removing four hydrogen atoms from cyclohexane. Φ is an aliphatic structural unit, alicyclic structural unit, aromatic structural unit, organo A siloxane structural unit, or a divalent linking group having 2 to 39 carbon atoms composed of a combination or repetition thereof, and the main chain of Φ has —O—, —SO ₂ —, —CO—, —CH ₂ —, At least one group selected from the group consisting of —C (CH ₃ ) ₂ —, —C ₂ H ₄ O—, and —S— may intervene, and n represents a repeating unit. .X1, X2 is any one of groups represented by the formula (II), or a hydrogen atom, at least one of the X1 and X2 is a group represented by the formula (II) in. formula (II), X3 is a group having 2 to 10 carbon atoms and may have an ester bond. Is a hydrogen atom or a methyl group.) A step of reacting a tetracarboxylic acid component and a diamine component in a range where the molar ratio of the tetracarboxylic acid component to the diamine component is 0.80 or more and 0.98 or less; The method for producing a polyimide resin according to claim 1, wherein the amino group and the isocyanate group in the (meth) acrylic compound having an isocyanate group are reacted.   A cured polyimide resin obtained by irradiating the polyimide resin according to claim 1 with ultraviolet rays or electron beams. The laminated body which consists of a base material chosen from the polyimide resin hardened | cured material of Claim 3, and a plastic film, a silicon wafer, metal foil, and glass.   The laminate according to claim 4, wherein the substrate is a copper foil. A polyimide film comprising the cured polyimide resin according to claim 3 .