KR101921919B1 - Polyamic acid resin composition, polyimide resin composition, polyimide oxazole resin composition, and flexible substrate containing same - Google Patents

Polyamic acid resin composition, polyimide resin composition, polyimide oxazole resin composition, and flexible substrate containing same Download PDF

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KR101921919B1
KR101921919B1 KR1020147007050A KR20147007050A KR101921919B1 KR 101921919 B1 KR101921919 B1 KR 101921919B1 KR 1020147007050 A KR1020147007050 A KR 1020147007050A KR 20147007050 A KR20147007050 A KR 20147007050A KR 101921919 B1 KR101921919 B1 KR 101921919B1
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carbon atoms
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polyimide
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준지 와키타
다이치 미야자키
카즈토 미요시
마사오 토미카와
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도레이 카부시키가이샤
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/22Polybenzoxazoles
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/03Use of materials for the substrate
    • H05K1/0313Organic insulating material
    • H05K1/032Organic insulating material consisting of one material
    • H05K1/0346Organic insulating material consisting of one material containing N
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/03Use of materials for the substrate
    • H05K1/0393Flexible materials
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01Dielectrics
    • H05K2201/0104Properties and characteristics in general
    • H05K2201/0108Transparent
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01Dielectrics
    • H05K2201/0137Materials
    • H05K2201/0154Polyimide

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Abstract

A film after heat treatment is provided with a polyamic acid resin composition, polyimide resin composition and polyimide oxazole resin composition having excellent heat resistance, light transmittance and low birefringence, and a flexible substrate containing them.
(a) a polyamic acid containing as a main component a structural unit represented by the general formula (1) and (b) a solvent.

Figure 112014025457350-pct00092

(In the general formula (1), X 1 and X 2 each independently represent a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, R 1 represents a monocyclic or condensed polycyclic alicyclic structure having 4 to 40 carbon atoms A tetravalent organic group or a tetravalent organic group having 4 to 40 carbon atoms linked to each other through an organic group having a monocyclic alicyclic structure directly or via a crosslinking structure, R 2 represents a divalent organic group having 2 to 40 carbon atoms and at least two hydroxyl groups Lt; / RTI >

Description

FIELD OF THE INVENTION [0001] The present invention relates to a polyimide resin composition, a polyimide resin composition, a polyimide oxazole resin composition, and a flexible substrate containing the same. BACKGROUND OF THE INVENTION [0002]

The present invention relates to a polyamic acid resin composition, a polyimide resin composition, a polyimide oxazole resin composition and a flexible substrate containing them. More particularly, the present invention relates to a polyamic acid resin composition, a polyimide resin composition, a polyimide oxazole resin, and a polyimide resin composition, which are suitably used for a flat panel display, a touch panel, an electronic paper, a color filter substrate, And a flexible substrate containing them.

The organic film has an advantage that it is more flexible than glass, less fragile, and lightweight. In recent years, the movement of a display to be flexible by replacing a substrate of a flat panel display with an organic film is becoming active.

In the case of producing a display on an organic film, a process is generally used in which an organic film is formed on a supporting substrate, and after the device is formed, the organic film is peeled off from the supporting substrate. In order to form an organic film on a support substrate, the following methods are available. For example, there is a method of attaching an organic film to a glass substrate using an adhesive material or the like (see, for example, Patent Document 1). Or a solution containing a resin as a raw material of a film is coated on a support substrate and cured by heat or the like (see, for example, Patent Document 2). In the former, it is necessary to provide an adhesive material between the support substrate and the film, and the subsequent process temperature may be limited by the heat resistance of the adhesive. On the other hand, the latter is superior in terms of not using the pressure-sensitive adhesive, high surface smoothness of the film formed, and the like.

Examples of the resin used for the organic film include polyester, polyamide, polyimide, polycarbonate, polyether sulfone, acryl, epoxy and the like. Of these, polyimide is suitable as a display substrate as a high heat resistant resin. In particular, polyimide resins are widely used in the electric and electronic industries because they have excellent electrical properties such as high mechanical strength, abrasion resistance, dimensional stability, chemical resistance, and insulation as well as high heat resistance. In the case of forming the polyimide film by the coating method described above, a method of coating a solution containing a polyamic acid of the precursor and then curing it and converting it into polyimide is used. Generally, a polyamic acid can be easily synthesized by reacting an acid anhydride with a diamine in a solvent.

The aromatic polyimide derived from an aromatic dianhydride and an aromatic diamine has a high heat resistance. However, since there is an absorption band in the visible light wavelength range derived from intramolecular and intermolecular charge transfer complexes, the obtained polyimide film is colored in a yellow to brown color . In addition, it generally has a large birefringence. Therefore, it has been a problem that it can not be used as a display substrate requiring high transparency and low birefringence. In order to use it as a substitute material for a glass substrate, it is generally required to have a film thickness of 10 micrometers and a light transmittance of 400 nm of 80% or more, a glass transition temperature (Tg), a thermal decomposition initiation temperature of 300 ° C or more, To 800 nm) is required to have a low birefringence of 0.01 or less.

As a method of suppressing the charge transfer interaction of the polyimide and improving the light transmittance, a method of using an alicyclic monomer in at least one of the acid dianhydride and the diamine can be mentioned.

For example, Patent Document 3 discloses that polyimide obtained from alicyclic acid dianhydride and various aromatic or alicyclic diamines has high transparency and low birefringence.

Patent Document 4 discloses that polyimide obtained from 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic acid dianhydride and 2,2'-bis (trifluoromethyl) benzidine (TFMB) has high transparency and high Tg . Patent Document 4 discloses that a polyimide membrane using 2,2'-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane (HFBAPP) instead of 2,2'-bis (trifluoromethyl) And has high transparency.

Japanese Patent Application Laid-Open No. 2006-091822 Japanese Patent Publication No. 2007-512568 Japanese Patent Application Laid-Open No. 11-080350 Japanese Patent Application Laid-Open No. 2010-085992

However, the polyimide group described in Patent Document 3 has a sufficiently low Tg. Further, in the polyimide group described in Patent Document 4, Tg and birefringence do not satisfy general requirements.

As described above, a polyimide material satisfying all the requirements of high transparency, high heat resistance and low birefringence is not known at present.

SUMMARY OF THE INVENTION In view of the above problems, it is an object of the present invention to provide a polyamic acid resin composition, a polyimide resin composition, and a polyimide oxazole resin composition having excellent heat resistance, light transmittance and low birefringence after heat treatment and a flexible substrate containing them We do thing as problem.

In order to solve the above problems, a polyamic acid resin composition according to the present invention comprises (a) a polyamic acid containing as a main component a structural unit represented by the general formula (1), (b) .

Figure 112014025457350-pct00001

(In the general formula (1), X 1 and X 2 each independently represent a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, R 1 represents a monocyclic or condensed polycyclic alicyclic structure having 4 to 40 carbon atoms A tetravalent organic group or a tetravalent organic group having 4 to 40 carbon atoms linked to each other through an organic group having a monocyclic alicyclic structure directly or via a crosslinking structure, R 2 represents a divalent organic group having 2 to 40 carbon atoms and at least two hydroxyl groups Lt; / RTI >

The polyimide resin composition according to the present invention is characterized by containing (a ') a polyimide having a structural unit represented by the general formula (2) as a main component, and (b) a solvent.

Figure 112014025457350-pct00002

(In the general formula (2), R 1 is a divalent organic group having 4 to 40 carbon atoms and having an alicyclic or condensed polycyclic alicyclic structure or an organic group having a monocyclic alicyclic structure directly or through a crosslinking structure 4 to 40. R 2 represents a divalent organic group having 2 to 40 carbon atoms and at least two hydroxyl groups.)

The polyimide oxazole resin composition according to the present invention is characterized by containing (a ") a polyimide oxazole containing as a main component a structural unit represented by the general formula (3), and (b) a solvent.

Figure 112014025457350-pct00003

(In the general formula (3), R 1 represents a tetravalent organic group having 4 to 40 carbon atoms and having an alicyclic or condensed polycyclic alicyclic structure or an organic group having a monocyclic alicyclic structure directly or through a crosslinking structure, 4 to 40. R 3 represents a tetravalent organic group having 2 to 40 carbon atoms.)

(Effects of the Invention)

According to the present invention, it is possible to obtain a polyamic acid resin composition, a polyimide resin composition, and a polyimide oxazole resin composition each having excellent heat resistance, high light transmittance in a visible light region, and low birefringence, and a flexible substrate containing them .

Hereinafter, embodiments for carrying out the present invention will be described in detail. The present invention is not limited to the following embodiments. The drawings referred to in the following description are merely a schematic representation of the shape, size, and positional relationship to such an extent that the contents of the present invention can be understood. That is, the present invention is not limited to the shape, size, and positional relationship illustrated in the drawings.

A first aspect of the present invention is a polyamic acid resin composition characterized by containing (a) a polyamic acid having a structural unit represented by the general formula (1) as a main component and (b) a solvent. A second aspect of the present invention is a polyimide resin composition comprising (a ') a polyimide having a structural unit represented by the general formula (2) as a main component, and (b) a solvent. 3 is a polyimide oxazole resin composition containing polyimide oxazole as a main component (a ") represented by the general formula (3) and (b) a solvent.

Figure 112014025457350-pct00004

Figure 112014025457350-pct00005

Figure 112014025457350-pct00006

In the general formula (1), X 1 and X 2 each independently represent a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. In the general formulas (1) to (3), R 1 represents a monovalent or condensed polycyclic alicyclic organic group having 4 to 40 carbon atoms, or an organic group having a monocyclic alicyclic structure, Represents a tetravalent organic group having 4 to 40 carbon atoms linked to each other. In the general formulas (1) and (2), R 2 represents a divalent organic group having 2 to 40 carbon atoms and at least two hydroxyl groups. In the general formula (3), R 3 represents a tetravalent organic group having 2 to 40 carbon atoms.

The polyamic acid of the present invention may contain another structural unit as long as it contains the structural unit represented by the above general formula (1) as a main component. As other structural units, there may be mentioned polyamide acid, which is a polycondensate of acid dianhydride and diamine compound, polyhydroxyamide which is a polycondensate of dicarboxylic acid derivative and hydroxy diamine, polyimide which is a dehydration ring of polyamide acid, polyhydroxyamide in the dehydration ring-closure body poly benzoxazole may be mentioned a sol, such as, for example, the formula (2) structural unit represented by the structural unit, the above-mentioned formula (3) represented by the general formula (1) R 1 A polyimide which is an aromatic ring thereof, a polyimide in which R 1 in the general formula (2) is an aromatic ring, and polyimide benzoxazole in which R 1 in the general formula (3) is an aromatic ring. The structural unit represented by the general formula (1) is preferably contained in an amount of 50 mol% or more, more preferably 70 mol% or more, and still more preferably 90 mol% or more.

The polyamic acid can be synthesized by reacting a diamine compound with an acid dianhydride or a derivative thereof, as described later. Examples of the derivative include tetracarboxylic acid of the acid dianhydride, mono, di, tri, tetraester, and acid chloride of the tetracarboxylic acid.

The polyimide of the present invention may contain another structural unit as long as it contains a structural unit represented by the above general formula (2) as a main component. Examples of other structural units include polyamic acid, polyhydroxyamide, polyimide, polybenzoxazole, and the like. For example, a structural unit represented by the general formula (1), a structural unit represented by the general formula (3), a polyamic acid in which R 1 in the general formula (1) R 1 a may include a direction Whanin polyimide, the R 1 in the formula (3) direction Whanin polyimide benzoxazole of. The structural unit represented by the general formula (2) is preferably contained in an amount of 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more.

The polyimide can be synthesized by a thermal dehydration ring-closing reaction or a chemical dehydration ring-closing reaction of a polyamic acid synthesized by the reaction of a diamine compound and an acid dianhydride or a derivative thereof, as described later.

The polyimide oxazole of the present invention may contain another structural unit as long as it contains the structural unit represented by the above general formula (3) as a main component. Examples of other structural units include polyamic acid, polyhydroxyamide, polyimide, polybenzoxazole, and the like. Examples of the structural unit include a structural unit represented by the general formula (1), a structural unit represented by the general formula (2) A structural unit, a polyimide acid in which R 1 in the general formula (1) is an aromatic ring, polyimide in which R 1 in the general formula (2) is an aromatic ring, polyimide benzoxazine in which R 1 in the general formula (3) It may contain sol. The structural unit represented by the general formula (3) is preferably contained in an amount of 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more.

The polyimide oxazole can be synthesized by a thermal dehydration ring closure reaction or a chemical dehydration ring closure reaction of a polyamic acid synthesized by the reaction of a diamine compound having a hydroxyamide group and an acid dianhydride or a derivative thereof, as described later. Can be synthesized by thermal dehydration cyclization or chemical dehydration ring-closure reaction of a polyamic acid synthesized by the reaction of a diamine compound having an oxazole ring with an acid dianhydride or a derivative thereof.

R 1 in the general formulas (1) to (3) represents a structure of an acid component, and a quaternary organic group having 4 to 40 carbon atoms and having a monocyclic or condensed polycyclic alicyclic structure or a monocyclic alicyclic structure Represents a tetravalent organic group having 4 to 40 carbon atoms linked to each other through a direct or crosslinked structure. Here, in the alicyclic structure, a part of hydrogen atoms may be substituted with halogen. As the acid component, these acid components may be used singly or in combination.

Examples of the acid dianhydride having an alicyclic structure usable in the present invention include 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride , 1,2,3,4-cyclohexanetetracarboxylic acid dianhydride, 1,2,4,5-cyclopentanetetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2, Cyclobutane tetracarboxylic acid dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4- Cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-cycloheptane tetracarboxylic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dianhydride, 3,4-dicarboxy Cyclohexylsuccinic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid dianhydride, bicyclo [4.3.0] nonane- Tetracarboxylic acid dianhydride, bicyclo [4.4.0] decane-2,4,7,9-tetracarboxylic acid dianhydride, bicyclo [4.4.0] decan- Tetracarboxylic acid dianhydride, tricyclo [6.3.0.0 < 2,6 >] undecane-3,5,9,11-tetracarboxylic acid dianhydride, bicyclo [2.2.2] Tetracarboxylic acid dianhydride, bicyclo [2.2.2] octo-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, bicyclo [2.2.1] heptanetetracarboxylic acid Acid anhydride, bicyclo [2.2.1] heptane-5-carboxymethyl-2,3,6-tricarboxylic acid dianhydride, 7-oxabicyclo [2.2.1] heptane-2,4,6,8 -Tetracarboxylic acid dianhydride, octahydronaphthalene-1,2,6,7-tetracarboxylic acid dianhydride, tetradecahydroanthracene-1,2,8,9-tetracarboxylic acid dianhydride, 3,3 ', 4,4'-dicyclohexanetetracarboxylic acid dianhydride, 3,3', 4,4'-oxydicyclohexanetetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro- 3-furanyl) -3-methyl-3-cy The like-1,2-dicarboxylic anhydride, and "Rikacid (Rikacid)" (TM) BT-100 (or more, trade name, manufactured products to whether or Shin-Nippon Rika) and their derivatives are exemplified by.

Preferred as R 1 in the formula (1) to (3) in the structure of, for example the following can be given a structure represented by formula (4) to (10).

Figure 112014025457350-pct00007

Figure 112014025457350-pct00008

Figure 112014025457350-pct00009

Figure 112014025457350-pct00010

Figure 112014025457350-pct00011

Figure 112014025457350-pct00012

Figure 112014025457350-pct00013

In the general formulas (4) to (10), R 4 to R 79 independently represent a monovalent organic group having 1 to 3 carbon atoms which may be substituted with a hydrogen atom, a halogen atom or a halogen atom. Examples of the alicyclic structures represented by the general formulas (4) to (6) include cyclobutane, cyclopentane, cyclohexane and the like. In the general formula (7), X 3 is a divalent organic group having 1 to 3 carbon atoms which may be substituted with an oxygen atom, a sulfur atom, a sulfonyl group or a halogen atom, or a divalent crosslinked structure formed by connecting two or more thereof. Examples of such alicyclic structures include bicyclo [2.2.1] heptane, bicyclo [2.2.1] octa-2-ene, and 7-oxabicyclo [2.2.1] heptane. Examples of the alicyclic structures of the general formula (8) and the general formula (9) include decahydronaphthalene and tetradecahydroanthracene, respectively. In the general formula (10), X 4 represents a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, a divalent organic group having 1 to 3 carbon atoms which may be substituted with a hydrogen atom by a halogen atom, an arylene group which may be substituted with a hydrogen atom by a halogen atom, An oxygen atom, a sulfur atom, a sulfonyl group, a bivalent organic group having 1 to 3 carbon atoms which may be substituted with a hydrogen atom by a halogen atom, and an arylene group which may be substituted with a halogen atom. Examples of such alicyclic structures include 1,1-bicyclohexane, oxydicycohexane, and the like.

Examples of the acid dianhydride include 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 1,2,3,4- Cyclohexanetetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2-dimethyl-1,2,3,4 -Cyclobutane tetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cycloheptanetetracarboxylic acid dianhydride, Bicyclo [2.2.2] octo-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, bicyclo [2.2.1] heptane tetracarboxylic acid dianhydride, 7-oxabicyclo [2.2 .1] heptane-2,4,6,8-tetracarboxylic acid dianhydride, octahydronaphthalene-1,2,6,7-tetracarboxylic acid dianhydride, tetradecahydroanthracene- Tetracarboxylic acid dianhydride, 3,3 ', 4,4'-dicyclohexanetetracarboxylic acid dianhydride, 3,3', 4,4'-oxydicyclohexanetetracar Acids may be mentioned the anhydride or the like.

Among these, are commercially available in hand Easy loading point of view, and from the viewpoint of the reactivity with the diamine compound represented by the general formula (1) to the R 1 of which is represented by formula (11) ~ (13) 1S , 2S, 4R, 5R- Cyclohexanetetracarboxylic acid dianhydride, 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic acid dianhydride and 3,3 ', 4,4'-dicyclohexanetetracarboxylic acid dianhydride are preferable. These acid dianhydrides are commercially available from Iwatani Gas Co. under the product names "PMDA-HH", "PMDA-HS" and "BPDA-H". These acid dianhydrides may be used alone or in combination of two or more.

Figure 112014025457350-pct00014

Figure 112014025457350-pct00015

Figure 112014025457350-pct00016

In addition, a part of the acid dianhydride may be substituted with another acid dianhydride so long as the effect of the present invention is not hindered. Examples of other acid dianhydrides include aromatic acid dianhydrides and aliphatic acid dianhydrides. Examples of the aromatic acid dianhydride include pyromellitic acid dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3', 4'-biphenyltetracarboxylic acid Acid dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-terphenyltetracarboxylic acid dianhydride, 3,3 ', 4,4 Oxyphthalic acid dianhydride, diphenylsulfone-3,3 ', 4,4', 4'-oxyphthalic acid dianhydride, 2,3 ', 3'- -Tetracarboxylic acid dianhydride, benzophenone-3,3 ', 4,4'-tetracarboxylic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2- Bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1- Bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4- -1,3-dihydroisobenzofuran-5-carboxyl (4-aminophenoxy) phenyl) propane, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7- 7,9-naphthalene tetracarboxylic acid dianhydride, 2,3,5,6-pyridine tetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 2,2-bis (3 , 4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis (4- (3,4-dicarboxyphenoxy) phenyl) hexafluoropropane dianhydride, Dicarboxybenzoyloxy) phenyl) hexafluoropropane dianhydride, 1,6-difluoropyromellitic dianhydride, 1-trifluoromethyl pyromellitic acid dianhydride, 1,6-ditrifluoro (3,4-dicarboxyphenoxy) biphenyl dianhydride, 2,2'-bis (trifluoromethyl) -4,4'-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride, Aromatic tetracarboxylic acid dianhydrides such as TMEG-100 (trade name, manufactured by Shin-Nippon Rikagaku Co., Ltd.) and derivatives thereof And the like. Examples of the aliphatic acid dianhydride include 1,2,3,4-butanetetracarboxylic acid dianhydride, 1,2,3,4-pentanetetracarboxylic acid dianhydride and derivatives thereof, and the like. It is not. These other acid anhydrides may be used alone or in combination of two or more.

R 2 in the general formulas (1) and (2) is a divalent organic group having 2 to 40 carbon atoms and at least two hydroxyl groups, and examples thereof include the structures represented by the formulas (14) to (23) have.

Figure 112014025457350-pct00017

Figure 112014025457350-pct00018

Figure 112014025457350-pct00019

Figure 112014025457350-pct00020

Figure 112014025457350-pct00021

Figure 112014025457350-pct00022

Figure 112014025457350-pct00023

Figure 112014025457350-pct00024

Figure 112014025457350-pct00025

Figure 112014025457350-pct00026

Among them, the structure of the formula (14) is preferable from the viewpoint of transparency, and it is preferable to use a diamine represented by the formula (24).

Figure 112014025457350-pct00027

R 3 in the general formula (3) represents a tetravalent organic group having 2 to 40 carbon atoms, and examples thereof include the structures represented by the chemical formulas (25) to (34). Among them, the structure of the formula (25) is preferable from the viewpoint of transparency.

Figure 112014025457350-pct00028

Figure 112014025457350-pct00029

Figure 112014025457350-pct00030

Figure 112014025457350-pct00031

Figure 112014025457350-pct00032

Figure 112014025457350-pct00033

Figure 112014025457350-pct00034

Figure 112014025457350-pct00035

Figure 112014025457350-pct00036

Figure 112014025457350-pct00037

Further, the formula (3) R 3 is represented by formula (25) in jineu polyimide oxazole is, a polyamic acid represented by formula (1), which is synthesized from a diamine represented by the above formula (24), and general Is a polyimide dehydrating ring member represented by the formula (2).

In addition, a part of the diamine compound may be substituted by another diamine compound within the range not hindering the effect of the present invention. Examples of other diamine compounds include aromatic diamine compounds, alicyclic diamine compounds, and aliphatic diamine compounds. Examples of the aromatic diamine compound include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl Methane, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2- 4-methylphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 3,3'- diaminodiphenylsulfide, 4,4'- Bis (trifluoromethyl) benzidine, 2,2'-bis (trifluoromethyl) benzidine, 3,3'-bis (trifluoromethyl) benzidine, Dimethylbenzidine, 2,2 ', 3,3'-tetramethylbenzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6 Bis (4-aminophenoxy)} sulfone, bis {4- (3-aminophenoxyphenyl)} sulfone, bis Bis (4-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4 (4-aminophenoxy) phenyl] hexafluoropropane, 4,4-diaminobenzanilide, 3,4-diaminobenzene Anilide, 4,4-diaminobenzophenone, 3,3-diaminobenzophenone, or a diamine compound in which these aromatic rings are substituted with an alkyl group, an alkoxy group, a halogen atom or the like, but the present invention is not limited thereto.

Examples of the alicyclic diamine compound include cyclobutanediamine, isophoronediamine, bicyclo [2.2.1] heptanebismethylamine, tricyclo [3.3.1.13,7] decane-1,3-diamine, 1,2-cyclohexyldiamine, 1,3-cyclohexyldiamine, 1,4-cyclohexyldiamine, 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, -Diethyl-4,4'-diaminodicyclohexyl methane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodicyclohexyl methane, 3,3', 5,5 -Tetraethyl-4,4'-diaminodicyclohexylmethane, 3,5-diethyl-3 ', 5'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'- 3,3'-dimethyl-4,4'-diaminodicyclohexyl ether, 3,3'-diethyl-4,4'-diaminodicyclohexyl ether, 3,3 '-dimethyldicyclohexyl ether, 5,5'-tetramethyl-4,4'-diaminodicyclohexyl ether, 3,3 ', 5,5'-tetraethyl-4,4'-diaminodicyclohexyl ether, 3,5-di Ethyl-3 ', 5'-dimethyl-4,4'-diamine Bis (3-ethyl-4-aminocyclohexyl) propane, 2,2-bis Propane, 2,2-bis (3,5-dimethyl-4-aminocyclohexyl) (3,5-diethyl-3 ', 5'-dimethyl-4,4'-diaminodicyclohexyl) propane, 2,2'-bis (4-aminocyclohexyl) hexafluoropropane, 2,2 (Dimethylaminophenyl) -4,4'-diaminobicyclohexane, 2,2'-bis (trifluoromethyl) -4,4'-diaminobicyclohexane, or an alicyclic hydrocarbon group such as an alkyl group, an alkoxy group, a halogen And the like, but the present invention is not limited thereto.

Examples of the aliphatic diamine compound include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7- (Aminomethyl) ether, bis (2-aminoethyl) ether, bis (3-aminopropyl) ), And ethylene glycol diamines such as 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis Aminopropyl) polydimethylsiloxane, and the like, but the present invention is not limited thereto.

These aromatic diamine compounds, alicyclic diamine compounds, or aliphatic diamine compounds may be used alone or in combination of two or more.

Of these, 9,9-bis (4-aminophenyl) fluorenediamine represented by the following chemical formula (35) is preferably used, and the glass transition temperature is elevated while maintaining transparency and mechanical properties of the fired film, And found that birefringence can be reduced.

Figure 112014025457350-pct00038

The structural unit represented by the following general formula (36) or the following general formula (37) can be introduced into the molecular chain by using the diamine represented by the general formula (35).

Figure 112014025457350-pct00039

Figure 112014025457350-pct00040

(36), X 1 and X 2 each independently represent a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. In the general formulas (36) and (37), R 1 represents a monocyclic or A tetravalent organic group having 4 to 40 carbon atoms having a condensed polycyclic alicyclic structure or a tetravalent organic group having 4 to 40 carbon atoms connected to each other through an organic group having a monocyclic alicyclic structure directly or via a crosslinking structure.

In general, the polyimide film using the diamine represented by the chemical formula (35) is often colored. As described later (Comparative Example 8), 4,4 '- (hexafluoroisopropylidene) diphthalic anhydride used as a raw material monomer for the transparent polyimide and polyimide using the diamine represented by the above formula (35) In the film, the transparency deteriorates as compared with the polyimide of the present invention and the polyimide oxazene film. Since the aliphatic acid dianhydride is used for the polyimide and the polyimide oxazole film of the present invention, the coloring can be suppressed.

The diamine represented by the above formula (35) is preferably contained in an amount of 10 mol% or more and 50 mol% or less, more preferably 30 mol% or more and 50 mol% or less, Mol% or more and 50 mol% or less. Thus, the polyimide acid, the polyimide and the polyimide oxazole of the present invention contain 10 mol% to 50 mol% of the structural unit represented by the general formula (36) or the general formula (37).

The polyamic acid, polyimide and polyimide oxazole of the present invention may be sealed at both ends by a terminal sealing agent to adjust the molecular weight to a preferable range. Examples of the terminal sealing agent reacting with the acid dianhydride include monoamine and monohydric alcohol. Examples of the terminal sealing agent which reacts with the diamine compound include an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, and a mono-active ester compound. Further, various organic groups can be introduced as a terminal group by reacting the terminal sealing agent.

Examples of the monoamine used in the end sealant include 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxy-8-aminonaphthalene, 1-hydroxy- Aminonaphthalene, 1-hydroxy-3-aminonaphthalene, 1-hydroxy-2-aminonaphthalene, 1-hydroxy- Amino-naphthalene, 2-hydroxy-4-aminonaphthalene, 2-hydroxy-4-aminonaphthalene, 2-hydroxy- Amino-2-hydroxynaphthalene, 1-carboxy-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy- Amino-naphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-3-aminonaphthalene, Aminonaphthalene, 2-carboxy-3-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2- Amino nicotinic acid, 6-aminonicotinic acid, 4-aminonicotric acid, 5-aminosalicylic acid, 6-aminosalicylic acid, amelide, 2-aminobenzoic acid, Aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3- amino Aminophenol, 5-amino-8-mercaptoquinoline, 4-amino-8-mercaptoquinoline, 1-mercapto-8-aminonaphthalene, 1-mercapto- Aminophthalene, 1-mercapto-5-aminonaphthalene, 1-mercapto-4-aminonaphthalene, 1-mercapto-3- Aminonaphthalene, 2-mercapto-6-aminonaphthalene, 2-mercapto-5-aminaphthalene, 2-mercapto- Naphthalene, 2-mercapto-4-aminonaphthalene, 2-mercapto-3-aminonaphthalene, 1-amino-2-mercaptonaphthalene, 3-amino-4,6-dimercaptopyrimidine, 2-ethylaniline, 2-ethylaniline, 4-ethylaniline, 2,4-diethylaniline, 2,5-diethylaniline, 2-aminothiophenol Diethynylaniline, 3,5-diethynylaniline, 1-ethynyl-2-aminonaphthalene, 1-ethynyl-3-aminonaphthalene, 1- Amino-naphthalene, 1-ethynyl-5-aminonaphthalene, 1-ethynyl-6-aminonaphthalene, Amino naphthalene, 2-ethynyl-3-aminonaphthalene, 2-ethynyl- Aminonaphthalene, 2-ethynyl-8-aminonaphthalene, 3,5-diethynyl-6-aminonaphthalene, 2-ethynyl- Aminonaphthalene, 3,6-diethynyl-2-aminonaphthalene, 3,7-diethynyl-1-aminonaphthalene, Amino naphthalene, 3,7-diethynyl-2-aminonaphthalene, 4,8-diethynyl-1-aminonaphthalene and 4,8-diethynyl-2-aminonaphthalene. .

Examples of monohydric alcohols used as a terminal sealing agent include aliphatic alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, Butanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, 2-heptanol, 1-decanol, 1-undecanol, 1-dodecanol, 2-dodecanol, 1-tridecanol, 2-tridecanol, 1-tetradecanol, 2-pentadecanol, 1-hexadecanol, 2-hexadecanol, 1-heptadecanol, 2-heptadecanol, 1-octadecanol, 2- Propanol, 2-methyl-1-butanol, 3-methyl-1-pentanol, Butanol, 3-methyl-2-butanol, 2-propyl-1-pentanol, 2-ethyl- 2-heptanol, 2,4,4-trimethyl-1-hexanol, 2,6-dimethyl- 2-heptylundecanol, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether, 1-methyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether cyclopentanol, cyclohexanol, cyclopentane monomethylol, dicyclopentane monomethylol, tricyclodecane mono Methylol, norbornole, terpineol, and the like, but are not limited thereto.

Examples of the acid anhydride, monocarboxylic acid, monoacid chloride compound and mono-active ester compound used as a terminal sealing agent include phthalic anhydride, maleic anhydride, anhydrous nadic acid, cyclohexanedicarboxylic acid anhydride, 3-hydroxyphthalic anhydride Carboxyphenol, 4-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-8-carboxynaphthalene, 1- 1-hydroxy-4-carboxynaphthalene, 1-hydroxy-3-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1- Carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 1-mercapto- Mercapto-4-carboxynaphthalene, 1-mercapto-3- Carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 2-ethynylbenzoic acid, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, Diethynylbenzoic acid, 2,5-diethynylbenzoic acid, 2,6-diethynylbenzoic acid, 3,4-diethynylbenzoic acid, 3,5-diethynylbenzoic acid, 1-naphthoic acid, 3-ethynyl-1-naphthoic acid, 4-ethynyl-1-naphthoic acid, 2-naphthoic acid, 3-ethynyl-2-naphthoic acid, 4-ethynyl-2-naphthoic acid, 5-ethynyl- Monocarboxylic acids such as 6-ethynyl-2-naphthoic acid, 7-ethynyl-2-naphthoic acid and 8-ethynyl-2-naphthoic acid, monoacid chloride compounds in which these carboxyl groups are acid chloride- Terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid, 5-norbornene- 3-dicarboxylic acid, 1,2-dicarboxy naphthalene, 1,3-dicarboxy naphthalene, 1,4-dicarboxy naphthalene, 1,5-dicarboxy naphthalene, 1,6- - only monocarboxylic groups of dicarboxylic acids such as dicarboxy naphthalene, 1,8-dicarboxy naphthalene, 2,3-dicarboxy naphthalene, 2,6-dicarboxy naphthalene and 2,7- A monoacid chloride compound, an active ester compound obtained by reacting a monoacid chloride compound with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboxyimide.

The introduction ratio of monoamine and monohydric alcohol used in the terminal sealing agent is preferably in the range of 0.1 to 60 mol%, particularly preferably 5 to 50 mol%, based on the total amine component. The introduction ratio of the acid anhydride, the monocarboxylic acid, the monoacid chloride compound and the monoactive ester compound used as the terminal sealing agent is preferably in the range of 0.1 to 100 mol%, particularly preferably in the range of 5 to 90 mol% to be. A plurality of other end groups may be introduced by reacting a plurality of end sealants.

The end sealant introduced into polyamic acid, polyimide and polyimide oxazole can be easily detected by the following method. For example, a polymer having an end-capping agent introduced therein is dissolved in an acidic solution, and decomposed into an amine component and an acid anhydride component, which are constituent units of the polymer, and the resultant is easily subjected to gas chromatography (GC) Can be detected. In addition, the polymer into which the end sealant is introduced can be easily detected directly by pyrolysis gas chromatography (PGC), infrared spectroscopy and 13 C NMR spectroscopy.

The polyamide acid resin composition, the polyimide resin composition and the polyimide oxazole resin composition of the present invention contain (b) a solvent. Examples of the solvent include polar aprotic solvents such as N-methyl-2-pyrrolidone,? -Butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, and dimethylsulfoxide, tetrahydrofuran, Ethers such as tetrahydrofuran, dioxane and propylene glycol monomethyl ether, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone and diacetone alcohol, esters such as ethyl acetate, propylene glycol monomethyl ether acetate and ethyl lactate, And aromatic hydrocarbons such as xylene. These may be used singly or in combination of two or more.

The content of the solvent (b) is preferably 50 parts by weight or more, more preferably 100 parts by weight or more, and preferably 2,000 parts by weight or less, based on 100 parts by weight of polyamic acid, polyimide or polyimide oxazole. More preferably 1,500 parts by weight or less. When the amount is in the range of 50 to 2,000 parts by weight, the viscosity becomes suitable for application, and the film thickness after application can be easily controlled.

Hereinafter, a method for producing a polyamic acid having (a) a structural unit represented by the general formula (1) as a main component will be described. The reaction method of the polymerization reaction is not particularly limited as long as the desired polyamic acid can be produced, and a known reaction method can be used.

Specific examples of the reaction method include a method in which a predetermined amount of all the diamine components and a reaction solvent are added to a reactor to dissolve the mixture, a predetermined amount of an acid anhydride component is added, and the mixture is stirred at room temperature to 80 ° C for 0.5 to 30 hours have.

The diamine compound represented by the formula (24), the 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic acid dianhydride, the 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic acid dianhydride, Examples of the structural unit of the polyamic acid obtained from 4,4'-dicyclohexanetetracarboxylic dianhydride include the following structural formulas (38) to (42).

Figure 112014025457350-pct00041

Figure 112014025457350-pct00042

Figure 112014025457350-pct00043

Figure 112014025457350-pct00044

Figure 112014025457350-pct00045

Next, a method for producing a polyimide having a structural unit represented by the general formula (2) as the main component (a ') will be described. The polyamic acid represented by the general formula (1) There is no particular limitation on the production method that can be imidized, and a known reaction method can be used.

Specific examples of the reaction method include a method of stirring the polyamide acid solution obtained as described above at room temperature to 200 占 폚 for 0.5 to 30 hours, and the like.

The diamine compound represented by the formula (24), the 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic acid dianhydride, the 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic acid dianhydride, Examples of the structural unit of the polyimide obtained from 4,4'-dicyclohexanetetracarboxylic dianhydride include the following structural formulas (43) to (45).

Figure 112014025457350-pct00046

Figure 112014025457350-pct00047

Figure 112014025457350-pct00048

Next, a method for producing polyimide oxazole having as a main component a structural unit represented by the general formula (a ") will be described. As the first method, there is a method of producing a polyimide oxazole represented by the general formula (2) As a specific reaction method, the polyimide powder is subjected to heat treatment at 300 to 400 DEG C for 0.5 to 30 hours, and then the polyimide powder is heat- A method in which an acid catalyst such as a thermal acid generator is added to the polyimide solution and stirring is carried out at room temperature to 250 ° C for 0.5 to 30 hours.

As the second method, imidization of a diamide including an oxazole ring represented by the following general formula (46) and a polyamic acid obtained from an acid dianhydride can be exemplified. As a specific reaction method, a predetermined amount of an acid anhydride component is added, followed by stirring at room temperature to 80 ° C for 0.5 to 30 hours and then at room temperature to 200 ° C for 0.5 to 30 hours.

Figure 112014025457350-pct00049

(In the general formula (46), R 3 represents a tetravalent organic group having 2 to 40 carbon atoms.)

The diamine compound represented by the formula (24), the 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic acid dianhydride, the 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic acid dianhydride, When the polyamic acid obtained from 4,4'-dicyclohexanetetracarboxylic dianhydride is subjected to dehydration ring closure, the diamine represented by the formula (47) and 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic acid 2 A polyamic acid obtained from anhydride, 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic acid dianhydride and 3,3 ', 4,4'-dicyclohexanetetracarboxylic acid dianhydride is subjected to dehydration ring closure Examples of the structural unit of the polyimide oxazole include the following structural formulas (48) to (50).

Figure 112014025457350-pct00050

Figure 112014025457350-pct00051

Figure 112014025457350-pct00052

Figure 112014025457350-pct00053

The polyamide acid resin composition, the polyimide resin composition and the polyimide oxazole resin composition of the present invention may contain a surfactant. Examples of the surfactant include fluorosurfactants such as fluororad (trade name, manufactured by Sumitomo 3M Limited), Megapack (trade name, manufactured by DIC Corp.) and sulfuron (trade name, available from Asahi Glass Co., Ltd.) have. (Trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), DBP (trade name, manufactured by Chisso Corporation), polyfluoro, ganol (trade name, available from Kyoeisha Kagaku Kogyo Co., Ltd.) (Manufactured by KEMIPO Co., Ltd.), and the like. And acrylic polymer surfactants such as Polyflow (trade name, manufactured by Kyoeisha Chemical Co., Ltd.).

The surfactant is preferably contained in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of polyamic acid, polyimide or polyimide oxazole.

The polyamic acid resin composition, the polyimide resin composition and the polyimide oxazole resin composition of the present invention may contain an internal mold release agent. Examples of the internal release agent include long-chain fatty acids.

The polyamide acid resin composition, the polyimide resin composition and the polyimide oxazole resin composition of the present invention may contain a heat crosslinking agent. As the thermal cross-linking agent, a compound having at least two epoxy compounds, alkoxymethyl groups or methylol groups is preferable. By having at least two of these groups, a cross-linking structure is formed by condensation reaction with the resin and homologous molecules, and mechanical strength and chemical resistance can be improved.

Preferable examples of the epoxy compound include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polymethyl (glycidyloxypropyl) Epoxy group-containing silicon, and the like. However, the present invention is not limited to these. Particularly, it is possible to use an EPCLON 850-S, Epiclon HP-4032, Epiclon HP-7200, Epiclon HP-820, Epiclon HP-4700, Epiclon EXA-4710, Epiclon HP- Epiclon EXA-4816, Epiclon EXA-4822 (all trade names, available from Dainippon Ink &amp; Kagaku Co., Ltd.) (Available from Shin-Nippon Rikagaku Co., Ltd.), EP-4003S, EP-4000S (available from Shin-Etsu Chemical Co., Ltd.), Rica resin BEO-60E, Rica resin BPO-20E, Rica resin HBE-100 NC-3000 (trade name, available from Nippon Kayaku Co., Ltd.), PG-100, CG-500 and EG-200 (trade names, available from Osaka Gas Chemical Co., ), EPOX-MK R508, EPOX-MK R540, EPOX-MK R710, EPOX-MK R1710, VG3101L, VG3101M80 (trade names, available from K.K. Printech), Celloxide 2021P, Celloxide 2081, (Trade name, available from Daicel Chemical Industries, Ltd.), and the like.

Examples of the compound having at least two alkoxymethyl groups or methylol groups include DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML- PML, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP- TML-BP-BPM, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BP, TML-BP, TML- HMM-TPHAP (trade name, manufactured by Honshu Kagaku Kogyo K.K.), NIKALAC (registered trademark) MX (registered trademark) NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM and NIKALAC MX-750LM (trade names, available from Sanwa Chemical Co., Ltd.) Maybe.

The polyamic acid resin composition, the polyimide resin composition and the polyimide oxazole resin composition of the present invention may contain a coloring agent. By adding a coloring agent, the color taste of polyamic acid, polyimide, and polyimide oxazine can be controlled.

As the colorant, a dye, an organic pigment, an inorganic pigment and the like can be used. From the viewpoint of heat resistance and transparency, an organic pigment is preferable. Among them, it is preferable to have high transparency, excellent light resistance, heat resistance and chemical resistance. A specific example of a representative organic pigment is represented by a color index (CI) number, the following is preferably used, but not limited thereto.

Examples of the yellow pigment include Pigment Yellow (hereinafter abbreviated as PY) 12,13,17,20,24,83,86,93,95,109,111, 117,125,129,137,138,139,147 , 148, 150, 153, 154, 166, 168, 185, etc. are used. Pigment orange (hereinafter abbreviated as PO) 13, 36, 38, 43, 51, 55, 59, 61, 64, 65, 71 and the like are used as orange pigments. Examples of the red pigment include Pigment Red (hereinafter referred to as PR) 9, 48, 97, 122, 123, 144, 149, 166, 168, 177, 179, 180, 192, 209, 215, 216, 217 , 220, 223, 224, 226, 227, 228, 240, and 254 are used. Examples of purple pigments include pigment violet (hereinafter abbreviated as PV) 19, 23, 29, 30, 32, 37, 40, 50 and the like. 15, 15: 3, 15: 4, 15: 6, 22, 60, 64 and the like are used as pigment blue (hereinafter abbreviated as PB). Examples of the green pigment include pigment green (hereinafter abbreviated as PG) 7, 10, 36, 58 and the like. These pigments may be subjected to surface treatment such as rosin treatment, acidic group treatment and basic treatment, if necessary.

The polyamic acid resin composition, the polyimide resin composition and the polyimide oxazole resin composition of the present invention may contain an inorganic filler. Examples of the inorganic filler include silica fine particles, alumina fine particles, titania fine particles, and zirconia fine particles.

The shape of the inorganic filler is not particularly limited, and examples thereof include a spherical shape, an elliptical shape, a flat shape, a lot shape, and a fibrous shape.

The contained inorganic filler preferably has a small particle diameter in order to prevent light scattering. The average particle diameter is 0.5 to 100 nm, preferably 0.5 to 30 nm.

The content of the inorganic filler is preferably 1 to 50% by weight, more preferably 10 to 30% by weight, based on the polyamic acid, the polyimide or the polyimide oxazole. As the content increases, flexibility and abrasion resistance are lowered.

As a method for containing an inorganic filler in a polyamic acid resin composition, a polyimide resin composition or a polyimide oxazole resin composition, various known methods can be used. For example, the organo-inorganic filler sol may be mixed with polyamic acid, polyimide or polyimide oxazole. The organo-inorganic filler sol is prepared by dispersing an inorganic filler in an organic solvent in an amount of about 30% by weight. Examples of the organic solvent include methanol, isopropanol, n-butanol, ethylene glycol, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl acetate Propylene glycol monomethyl ether, N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, .

The organo inorganic filler sol may be treated with a silane coupling agent in order to improve the dispersibility of the inorganic filler to polyamic acid, polyimide or polyimide oxazole. When the end functional group of the silane coupling agent has an epoxy group or an amino group, the compatibility with the polyamic acid, the polyimide or the polyimide oxazole is enhanced by bonding with the carboxylic acid of the polyamic acid, and more effective dispersion can be achieved.

Examples of compounds having an epoxy group include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- glycidoxypropyl Methyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and the like.

Examples of the compound having an amino group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine and N-phenyl-3-aminopropyltrimethoxysilane.

As a method for treating the organo inorganic filler sol with the silane coupling agent, various known methods can be used. For example, a silane coupling agent may be added to an organo-inorganic filler sol whose concentration is adjusted, and the mixture may be stirred at room temperature to 80 ° C for 0.5 to 2 hours.

The polyamic acid resin composition, the polyimide resin composition and the polyimide oxazole resin composition of the present invention may contain a photoacid generator. When a light is irradiated through a mask in which an exposure pattern is drawn by containing a photoacid generator, acid is generated in the exposed portion and the solubility of the exposed portion in an alkali aqueous solution is increased, so that the composition can be used as a positive photosensitive resin composition.

Examples of the photoacid generator used in the present invention include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts. Among them, a quinone diazide compound is preferably used since it exhibits excellent dissolution inhibiting effect and can obtain a positive photosensitive resin composition having a high sensitivity and a reduced film thickness. In addition, two or more photoacid generators may be contained. As a result, the ratio of the dissolution rate between the exposed portion and the unexposed portion can be increased, and a positive photosensitive resin composition with high sensitivity can be obtained.

As the quinone diazide compound, there may be mentioned a compound in which a sulfonic acid of quinone diazide is bonded to a polyhydroxy compound with an ester, a compound in which a sulfonic acid of quinone diazide is sulfonamide bonded to a polyamino compound, a sulfonic acid ester of quinone diazide is bonded to a polyhydroxypolyamino compound Bonded and / or sulfonamide-bonded. Although not all the functional groups of the polyhydroxy compound and the polyamino compound may be substituted with quinone diazide, it is preferable that at least 50 mol% of the entire functional groups are substituted with quinone diazide. By using such a quinone diazide compound, it is possible to obtain a positive photosensitive resin composition that reacts with an i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of a mercury lamp which is general ultraviolet light.

In the present invention, the quinone diazide compound is preferably a 5-naphthoquinone diazide sulfonyl group or a 4-naphthoquinone diazide sulfonyl group. A compound having both of these groups in the same molecule may be used, or a compound using another group may be used in combination.

The quinone diazide compound used in the present invention is synthesized from a specific phenol compound by the following method. For example, a method of reacting a 5-naphthoquinonediazide sulfonyl chloride with a phenol compound in the presence of triethylamine. A method for synthesizing a phenol compound includes a method of reacting an? - (hydroxyphenyl) styrene derivative with a polyhydric phenol compound under an acid catalyst.

The content of the photoacid generator is preferably 3 to 40 parts by weight based on 100 parts by weight of polyamic acid, polyimide or polyimide oxazole. By setting the content of the photoacid generator within this range, higher sensitivity can be achieved. In addition, a sensitizer or the like may be contained if necessary.

In order to form a pattern of a positive photosensitive resin, a varnish of a positive photosensitive resin is applied on a substrate, and after exposure, the exposed portion is removed using a developer. Examples of the developer include aqueous solutions such as tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethyl An aqueous solution of a compound showing alkalinity such as aminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and the like is preferable. Further, in some cases, an aqueous solution of an alkali thereof may be added to an aqueous solution of an alkali in the presence of N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, , Alcohols such as methanol, ethanol and isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone, Or a combination of several species may be added. After development, rinsing with water is preferred. Here, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water and rinsed.

Hereinafter, a method for producing a heat resistant resin film using the polyamide acid resin composition, the polyimide resin composition, and the polyimide oxazole resin composition of the present invention will be described.

First, a polyamic acid resin composition, a polyimide resin composition or a polyimide oxazole resin composition is applied on a substrate. As the substrate, for example, a silicon wafer, ceramics, gallium arsenide, soda lime glass, alkali-free glass, and the like can be used, but the present invention is not limited thereto. Examples of the application method include a slit die coating method, a spin coating method, a spray coating method, a roll coating method and a bar coating method, and these methods may be applied in combination.

Subsequently, the substrate coated with the polyamide acid resin composition, the polyimide resin composition or the polyimide oxazole resin composition is dried to obtain a polyamic acid resin composition, a polyimide resin composition or a polyimide oxazole resin composition coating. Use a hot plate, oven, infrared, or vacuum chamber for drying. When using a hot plate, heat the object to be heated directly on the plate or on a jig such as a proxy pin provided on the plate. As the material of the proxy pin, there is a metal material such as aluminum or stainless steel, or a synthetic resin such as polyimide resin or " Teflon (registered trademark) ", and a proxy pin of any material may be used. The height of the proxy pin varies depending on the size of the substrate, the type of the resin layer to be heated, the purpose of heating, and the like. However, when the resin layer coated on a glass substrate having a size of 300 mm x 350 mm x 0.7 mm is heated, The height of the pin is preferably about 2 to 12 mm. The heating temperature varies depending on the kind and purpose of the object to be heated, and is preferably from room temperature to 180 占 폚 for one minute to several hours.

Subsequently, a temperature is applied in a range of 180 ° C to 400 ° C to convert it into a heat-resistant resin film. In order to peel off the heat-resistant resin film from the substrate, a method of immersing it in a chemical liquid such as hydrofluoric acid or a method of irradiating a laser to the interface between the heat-resistant resin film and the substrate may be used.

The polyamic acid and polyimide of the present invention containing the structural unit represented by the general formula (1) and the general formula (2) as the main component are subjected to the heat treatment as described above to convert the structural unit represented by the general formula (2) Or a polyimide oxazole containing as a main component a structural unit represented by the general formula (3) is obtained.

The heat resistant resin film thus obtained has high transparency, high heat resistance, low birefringence, and flexibility, and can be suitably used as a flexible substrate. As for the transparency, the transmittance at a wavelength of 400 nm is preferably 85% or more, more preferably 90% or more, and even more preferably 95% or more. The glass transition temperature is preferably 250 占 폚 or higher, more preferably 300 占 폚 or higher, and still more preferably 350 占 폚 or higher. The birefringence is preferably 0.01 or less, more preferably 0.005 or less, still more preferably 0.003 or less.

The flexible substrate containing the resin composition of the present invention can be used for a flexible device such as a liquid crystal display, an organic EL display, a display device such as a touch panel, an electronic paper, a color filter, a light receiving device such as a solar cell and a CMOS.

The manufacturing process of the flexible device includes a step of forming a circuit necessary for the display device and the light receiving device on the heat-resistant resin film formed on the substrate. For example, a TFT of amorphous silicon can be formed on a flexible substrate. Further, a structure necessary for the device may be formed thereon by a well-known method. As described above, the heat-resistant resin film in the form of a solid on which a circuit or the like is formed on the surface can be peeled from the substrate by a known method such as laser irradiation to obtain a flexible device.

(Example)

Hereinafter, the present invention will be described by way of examples and the like, but the present invention is not limited to these examples.

(1) Production of a heat-resistant resin film

Varnish was spin-coated on a 6-inch mirror silicon wafer using a coating and developing apparatus Mark-7 manufactured by Tokyo Electron Limited, so that the film thickness after pre-baking at 140 占 폚 for 4 minutes was 15 占 0.5 占 퐉. Thereafter, similarly, a pre-baking treatment at 140 ° C for 4 minutes was carried out using a hot plate of Mark-7. The prebaked film was heated to 300 DEG C or 350 DEG C at 3.5 DEG C / min under nitrogen flow (oxygen concentration of 20 ppm or less) using an inner oven (INH-21CD manufactured by Goyoso System Co., Ltd.) Lt; 0 &gt; C / min to 50 deg. C to prepare a heat-resistant resin film. Subsequently, the substrate was immersed in hydrofluoric acid for 1 to 4 minutes to peel off the heat resistant resin film from the substrate, and dried by air to obtain a heat resistant resin film.

(2) Production of a heat-resistant resin film (on a glass substrate)

A glass substrate (TEMPAX) having a thickness of 50 mm x 50 mm x 1.1 mm was spin coated with a spin coater MS-A200 manufactured by Mikasa Co., Ltd. to a thickness of 15 +/- 0.5 mu m after baking at 140 DEG C for 4 minutes. Was spin-coated. Thereafter, pre-baking treatment was performed at 140 占 폚 for 4 minutes using a hot plate D-SPIN manufactured by Dainippon Screen Corporation. The prebaked film was heated to 300 DEG C or 350 DEG C at 3.5 DEG C / min under nitrogen flow (oxygen concentration of 20 ppm or less) using an inner oven (INH-21CD manufactured by Goyoso System Co., Ltd.) And cooled to 50 deg. C at a cooling rate of 0 deg. C / minute to prepare a heat-resistant resin film (on a glass substrate).

(3) Production of a heat-resistant resin film (on a silicon substrate)

The varnish was spin-coated on a 4-inch silicon substrate cut to 1/4 using a spin coater MS-A200 manufactured by Mikasa K.K., so that the film thickness after pre-baking at 140 ° C for 4 minutes was 5 ± 0.5 μm. Thereafter, pre-baking treatment was performed at 140 占 폚 for 4 minutes using a hot plate D-SPIN manufactured by Dainippon Screen Corporation. The prebaked film was heated to 300 DEG C or 350 DEG C at 3.5 DEG C / min under nitrogen flow (oxygen concentration of 20 ppm or less) using an inner oven (INH-21CD manufactured by Goyoso System Co., Ltd.) And cooled to 50 deg. C at a cooling rate of 0 deg. C / minute to prepare a heat-resistant resin film (on a silicon substrate).

(4) Measurement of light transmittance (T)

The light transmittance at 400 nm was measured using an ultraviolet visible spectrophotometer (MultiSpec 1500 manufactured by Shimadzu Seisakusho Co., Ltd.). The heat resistant resin film prepared in (2) was used for the measurement.

(5) Measurement of total light transmittance (Tt)

The total light transmittance of the heat-resistant resin film prepared in (1) was measured using Hayes computer (HGM2DP, C light source, manufactured by Suga Shikenki K.K.) directly. In addition, the value of one measurement was used as Tt.

(6) Measurement of refractive index, in-plane / out-plane birefringence

TE refractive index (n (TE)) and TM refractive index (n (TM)) at a wavelength of 632.8 nm were measured using a prism coupler (manufactured by METRICON Inc., PC2010). n (TE) and n (TM) are refractive indices parallel to the polyimide film surface and in the vertical direction, respectively. The average refractive index n AV is calculated from ((2 x n (TE) 2 + n (TM) 2 ) / 3) ^ 0.5 and the in- (TE) -n (TM)). The heat-resistant resin film prepared in (3) was used for the measurement.

(7) Measurement of glass transition temperature (Tg) and coefficient of linear expansion (CTE)

The measurement was carried out in a nitrogen gas stream using a thermomechanical analyzer (EXSTAR6000 TMA / SS6000 manufactured by SII ANA Nanotechnology Co., Ltd.). The temperature rising method was performed under the following conditions. In the first step, the temperature of the sample was raised to 150 占 폚 at a heating rate of 5 占 폚 / min to remove the adsorbed water of the sample, and in the second step, the sample was air-cooled to room temperature at a cooling rate of 5 占 폚 / min. In the third step, this measurement was carried out at a heating rate of 5 캜 / min to obtain a glass transition temperature. The coefficient of linear expansion (CTE) was determined from the average of the linear expansion coefficients at 50 to 200 캜 in the third step. The heat resistant resin film prepared in (1) was used for the measurement.

(8) Measurement of 1% weight loss temperature (Td1)

Measurement was carried out in a nitrogen gas stream using a thermogravimetric analyzer (TGA-50 manufactured by Shimadzu Seisakusho Co., Ltd.). The temperature rising method was performed under the following conditions. In the first step, the temperature of the sample was raised to 350 캜 at a temperature raising rate of 3.5 캜 / min to remove the adsorbed water of the sample, and cooled to room temperature at a temperature lowering rate of 10 캜 / min in the second step. In the third step, this measurement was performed at a heating rate of 10 캜 / min to obtain a 1% thermogravimetric temperature. The heat resistant resin film prepared in (1) was used for the measurement.

(9) Measurement of breaking stress, elongation at break, Young's modulus

And the measurement was carried out using Tensilon (Orientech RTM-100 manufactured by Kabushiki Kaisha). Measurements of 10 samples or more were performed on each sample, and the JIS average value was calculated using the JIS number average (JIS K-6301). The heat resistant resin film prepared in (1) was used for the measurement.

(10) Measurement of b * value

The b * value of CIELAB, which is a representative color space, was measured using an SM color computer (SM-7-CH manufactured by Suga Shikeki Co., Ltd.). The C light source was used as the light source, and measurement was performed in the transmission light mode. In the CIELAB, the b * value is a coordinate of yellow and blue, near yellow at b * > 0, and near blue at b * <0. The heat resistant resin film prepared in (1) was used for the measurement.

(11) Fabrication of relief pattern

The photosensitive resin composition (varnish) prepared in the examples was spin-coated on an 8-inch silicon wafer, and then heat-treated at 120 ° C for 3 minutes using a hot plate (Coating / Developing Device Mark-7 available from Tokyo Electron Limited) (Pre-baking) to prepare a prebaked film having a thickness of 2 to 4 mu m. The obtained prebaked film was exposed using an i-line stepper (DSC-8000 manufactured by GCA) at an exposure amount of 20 to 320 mJ / cm 2 in 10 mJ / cm 2 steps. The line and space patterns used for exposure are 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 30, 50, After exposure, the resist film was developed with a 2.38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution (ELM-D, manufactured by Mitsubishi Gas Kagaku Co., Ltd.) for 60 seconds and rinsed with pure water to obtain a relief pattern. The film thickness after the prebaking and after the development was measured with a refractive index of 1.63 using a film thickness measuring apparatus Lambda Ace STM-602 manufactured by DAINIPPON SCREEN SEISAKUSHI CO., LTD.

(12) Calculation of reduction in developing film

The reduction amount of the developed film was calculated according to the following formula.

(탆) = film thickness after pre-baking-film thickness after development

(13) Calculation of sensitivity

After exposure and development, the minimum amount of exposure in which line and space patterns (1L / 1S) of 10 mu m and 20 mu m are formed one by one is called sensitivity.

The abbreviations of the compounds used in the examples are described below.

PMDA-HH: 1S, 2S, 4R, 5R-cyclohexanetetracarboxylic acid dianhydride

PMDA-HS: 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic acid dianhydride

BPDA-H: 3,3 ', 4,4'-dicyclohexanetetracarboxylic acid dianhydride

PMDA: pyromellitic acid dianhydride

BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride

ODPA: 3,3 ', 4,4'-oxydiphthalic acid dianhydride

6FDA: 4,4 '- (hexafluoroisopropylidene) diphthalic anhydride

HFHA: 2,2-bis [3- (3-aminobenzamide) -4-hydroxyphenyl] hexafluoropropane

FDA: 9,9-bis (4-aminophenyl) fluorene

CHDA: trans-1,4-diaminocyclohexane

PDA: p-phenylenediamine

m-TB: 2,2'-dimethyl-4,4'-diaminobiphenyl

TFMB: 2,2'-bis (trifluoromethyl) benzidine

m-BAPS: bis [4- (3-aminophenoxy) phenyl] sulfone

SiDA: 1,3-bis (3-aminopropyl) tetramethyldisiloxane

MAP: m-Aminophenol

NMP: N-methyl-2-pyrrolidone

GBL:? -Butyrolactone

EL: Ethyl lactate

DFA: Dimethylformamide dimethylacetal

Example 1

2.7704 g (12 mmol) of PMDA-HH, 7.4706 g (12 mmol) of HFHA and 50 g of NMP were added to a 100 mL four-necked flask under a dry nitrogen gas stream and the mixture was heated and stirred at 80 占 폚. After 8 hours, it was cooled to a varnish.

Example 2

2.7704 g (12 mmol) of PMDA-HS, 7.4706 g (12 mmol) of HFHA and 50 g of NMP were placed in a 100-mL four-necked flask under dry nitrogen flow and the mixture was heated and stirred at 80 占 폚. After 8 hours, it was cooled to a varnish.

Example 3

Under a dry nitrogen gas stream, 3.4441 g (11 mmol) of BPDA-H, 6.7969 g (11 mmol) of HFHA and 50 g of NMP were added to a 100 mL four-necked flask and the mixture was heated and stirred at 80 占 폚. After 8 hours, it was cooled to a varnish.

Example 4

2.7704 g (12 mmol) of PMDA-HH, 6.5286 g (10.8 mmol) of HFHA, 0.4181 g (1.2 mmol) of FDA and 50 g of NMP were placed in a 100 mL four-necked flask and heated and stirred at 80 占 폚. After 8 hours, it was cooled to a varnish.

Example 5

(3.48 mmol) of BPDA, 1.9099 g (8.52 mmol) of PMDA-HH, 0.4110 g (3.60 mmol) of CHDA, 5.0778 g (8.40 mmol) of HFHA and 50 g of NMP were placed in a 100 mL four- . After 8 hours, it was cooled to a varnish.

Example 6

3.4345 g (15.3 mmol) of PMDA-HS, 8.7985 g (14.5 mmol) of HFHA, 0.2669 g (0.8 mmol) of FDA and 50 g of NMP were placed in a 100 mL four-necked flask under dry nitrogen flow and the mixture was heated and stirred at 30 占 폚. After 6 hours, it was cooled to a varnish.

Example 7

3.4893 g (15.6 mmol) of PMDA-HS, 8.4683 g (14.0 mmol) of HFHA, 0.5424 g (1.6 mmol) of FDA and 50 g of NMP were placed in a 100 mL four-necked flask under a dry nitrogen flow. After 8 hours, it was cooled to a varnish.

Example 8

3.6042 g (16.1 mmol) of PMDA-HS, 7.7753 g (12.9 mmol) of HFHA, 1.1204 g (3.2 mmol) of FDA and 50 g of NMP were placed in a 100 mL four-necked flask under dry nitrogen flow and the mixture was heated and stirred at 30 占 폚. After 6 hours, it was cooled to a varnish.

Example 9

3.7270 g (16.6 mmol) of PMDA-HS, 7.0351 g (11.6 mmol) of HFHA, 1.7379 g (5.0 mmol) of FDA and 50 g of NMP were placed in a 100 mL four-necked flask under dry nitrogen flow and the mixture was heated and stirred at 30 占 폚. After 6 hours, it was cooled to a varnish.

Example 10

3.8584 g (17.2 mmol) of PMDA-HS, 6.2427 g (10.3 mmol) of HFHA, 2.3989 g (6.9 mmol) of FDA and 50 g of NMP were placed in a 100 mL four-necked flask under dry nitrogen flow and the mixture was heated and stirred at 30 占 폚. After 6 hours, it was cooled to a varnish.

Example 11

3.9994 g (17.8 mmol) of PMDA-HS, 5.3924 g (8.9 mmol) of HFHA, 3.1082 g (8.9 mmol) of FDA and 50 g of NMP were placed in a 100 mL four-necked flask under dry nitrogen flow and the mixture was heated and stirred at 30 占 폚. After 6 hours, it was cooled to a varnish.

Comparative Example 1

Under a dry nitrogen gas stream, 2.7154 g (12 mmol) of PMDA, 7.5255 g (12 mmol) of HFHA and 50 g of NMP were added to a 100 mL four-necked flask and the mixture was heated and stirred at 50 ° C. After 2 hours, it was cooled to a varnish.

Comparative Example 2

Under a dry nitrogen gas stream, 3.3527 g (11 mmol) of BPDA, 6.8883 g (11 mmol) of HFHA and 50 g of NMP were added to a 100 mL four-necked flask and the mixture was heated and stirred at 50 ° C. After 2 hours, it was cooled to a varnish.

Comparative Example 3

In a dry nitrogen gas stream, 3.4731 g (11 mmol) of ODPA, 6.7679 g (11 mmol) of HFHA and 50 g of NMP were added to a 100 mL four-necked flask, and the mixture was heated and stirred at 50 占 폚. After 2 hours, it was cooled to a varnish.

Comparative Example 4

5.2599 g (23 mmol) of PMDA-HH, 4.9811 g (23 mmol) of m-TB and 50 g of NMP were added to a 100 mL four-necked flask under dry nitrogen flow and the mixture was heated and stirred at 50 占 폚. After 2 hours, it was cooled to a varnish.

Comparative Example 5

Under a dry nitrogen stream, 7.0599 g (15.9 mmol) of 6FDA, 9.6068 g (15.9 mmol) of HFHA and 50 g of NMP were added to a 100 mL four-necked flask and the mixture was heated and stirred at 30 ° C. After 6 hours, it was cooled to a varnish.

Comparative Example 6

7.2639 g (16.4 mmol) of 6FDA, 5.2361 g (16.4 mmol) of TFMB and 50 g of NMP were added to a 100 mL four-necked flask under a dry nitrogen flow, and the mixture was heated and stirred at 30 ° C. After 6 hours, it was cooled to a varnish.

Comparative Example 7

8.4450 g (19.0 mmol) of 6FDA, 8.2216 g (19.0 mmol) of m-BAPS and 50 g of NMP were added to a 100 mL four-necked flask under a dry nitrogen gas stream and the mixture was heated and stirred at 30 占 폚. After 6 hours, it was cooled to a varnish.

Comparative Example 8

7.824 g (17.6 mmol) of 6FDA, 2.4547 g (7.0 mmol) of FDA, 6.3879 g (10.6 mmol) of HFHA and 50 g of NMP were added to a 100 mL four-necked flask under dry nitrogen flow and the mixture was heated and stirred at 30 占 폚. After 6 hours, it was cooled to a varnish.

Comparative Example 9

Under a dry nitrogen atmosphere, 5.1472 g (23 mmol) of PMDA-HH, 7.3528 g (23 mmol) of TFMB and 50 g of NMP were added to a 100 mL four-necked flask and the mixture was heated and stirred at 50 占 폚. After 6 hours, it was cooled to a varnish.

Comparative Example 10

5.6897 g (25.4 mmol) of PMDA-HS, 10.9770 g (25.4 mmol) of m-BAPS and 50 g of NMP were added to a 100 mL four-necked flask under dry nitrogen flow and the mixture was heated and stirred at 50 占 폚. After 6 hours, it was cooled to a varnish.

Comparative Example 11

9.2384 g (30.2 mmol) of BPDA-H, 3.2616 g (30.2 mmol) of PDA and 50 g of NMP were added to a 100 mL four-necked flask under dry nitrogen flow, and the mixture was heated and stirred at 50 占 폚. After 6 hours, it was cooled to a varnish.

Comparative Example 12

4.1511 g (18.5 mmol) of PMDA-HS, 4.4776 g (7.4 mmol) of HFHA, 3.8714 g (11.1 mmol) of FDA and 50 g of NMP were added to a 100 mL four-necked flask under dry nitrogen flow and the mixture was heated and stirred at 30 占 폚. After 6 hours, it was cooled to a varnish.

The compositions of the varnishes synthesized in Examples 1 to 11 and Comparative Examples 1 to 12 are shown in Table 1. The transmittance T, the total light transmittance Tt, the TE refractive index n (TE), the TM refractive index n (TM), and the average refractive index (n) of the heat resistant resin film obtained by firing at 350 deg. plane birefringence, glass transition temperature (Tg), linear expansion coefficient (CTE), and 1% thermogravimetric reduction temperature (Td1)

Figure 112014025457350-pct00054

Example 12

Under a dry nitrogen gas stream, 121.5804 g (0.201 mol) of HFHA was dissolved in 400 g of NMP. 45.5372 g (0.203 mol) of PMDA-HS was added thereto together with 100 g of NMP, and the mixture was stirred at 30 캜 for 6 hours. Thereafter, the mixture was stirred at room temperature for 12 hours. Thereafter, the mixture was stirred at 180 占 폚 for 4 hours. After the completion of the stirring, the solution was poured into 3 L of water, and the precipitate of the polymer solid was collected by filtration. And further washed 5 times with 3 L of water, and the collected polymer solid was dried in a dryer at 50 캜 for 72 hours to obtain a polyimide powder. To 15 g of the obtained polyimide powder, 47.5 g of GBL was added to obtain a polyimide varnish.

Example 13

Under a dry nitrogen gas stream, 62.4272 g (0.103 mol) of HFHA and 23.9891 g (0.069 mol) of FDA were dissolved in 400 g of NMP. 38.9695 g (0.174 mol) of PMDA-HS was added to 100 g of NMP, followed by stirring at 30 DEG C for 6 hours. Thereafter, the mixture was stirred at room temperature for 12 hours. Thereafter, the mixture was stirred at 180 占 폚 for 4 hours. After the completion of the stirring, the solution was poured into 3 L of water, and the precipitate of the polymer solid was collected by filtration. And further washed 5 times with 3 L of water, and the collected polymer solid was dried in a dryer at 50 캜 for 72 hours to obtain a polyimide powder. To 15 g of the obtained polyimide powder, 47.5 g of GBL was added to obtain a polyimide varnish.

The total light transmittance Tt, the TE refractive index n (TE), and the TM refractive index n (TM) of the heat-resistant resin film obtained by firing at 350 deg. C using the varnish of Examples 12 and 13 Table 2 shows the results of measuring the average refractive index n (AV), the in-plane / out-of-plane birefringence, the glass transition temperature (Tg), the linear expansion coefficient (CTE) and the 1%

Figure 112014025457350-pct00055

Example 14

Under a dry nitrogen gas stream, 121.5804 g (0.201 mol) of HFHA was dissolved in 400 g of NMP. 45.5372 g (0.203 mol) of PMDA-HS was added thereto together with 100 g of NMP, and the mixture was stirred at 30 캜 for 6 hours. Thereafter, the mixture was stirred at room temperature for 12 hours. Thereafter, the mixture was stirred at 180 占 폚 for 4 hours. After the completion of the stirring, the solution was poured into 3 L of water, and the precipitate of the polymer solid was collected by filtration. And further washed 5 times with 3 L of water, and the collected polymer solid was dried in a dryer at 50 캜 for 72 hours to obtain a polyimide powder. The obtained polyimide powder was heat-treated in an oven at 350 캜 for 30 minutes in a nitrogen stream to obtain a polyimide oxazole powder. To 15 g of the obtained polyimide oxazole powder, 47.5 g of NMP was added to obtain a polyimide oxazole varnish.

Example 15

Under a dry nitrogen gas stream, 62.4272 g (0.103 mol) of HFHA and 23.9891 g (0.069 mol) of FDA were dissolved in 400 g of NMP. 38.9695 g (0.174 mol) of PMDA-HS was added to 100 g of NMP, followed by stirring at 30 DEG C for 6 hours. Thereafter, the mixture was stirred at room temperature for 12 hours. Thereafter, the mixture was stirred at 180 占 폚 for 4 hours. After the completion of the stirring, the solution was poured into 3 L of water, and the precipitate of the polymer solid was collected by filtration. And further washed 5 times with 3 L of water, and the collected polymer solid was dried in a dryer at 50 캜 for 72 hours to obtain a polyimide powder. The obtained polyimide powder was heat-treated in an oven at 350 캜 for 30 minutes in a nitrogen stream to obtain a polyimide oxazole powder. To 15 g of the obtained polyimide oxazole powder, 47.5 g of NMP was added to obtain a polyimide oxazole varnish.

The total light transmittance (Tt), the TE refractive index (n (TE)) and the TM refractive index (n (TM) Table 3 shows the results of measuring the average refractive index n (AV), the in-plane / out-of-plane birefringence, the glass transition temperature (Tg), the linear expansion coefficient (CTE) and the 1%

Figure 112014025457350-pct00056

Example 16

(Trade name: PMA-ST, particle diameter 10-30 nm) was added to the polyamic acid varnish so that the amount of the silica fine particles was 10 parts by weight based on 100 parts by weight of the varnish obtained in Example 1, Was added to obtain a polyamic acid-silica nanoparticle varnish.

Example 17

(Trade name: PMA-ST, particle diameter: 10 to 30 nm) was added to the polyamic acid varnish so that the amount of the silica fine particles was 20 parts by weight based on 100 parts by weight of the varnish obtained in Example 1, Was added to obtain a polyamic acid-silica nanoparticle varnish.

Example 18

(Trade name: PMA-ST, particle diameter 10-30 nm) was added to the polyamic acid varnish so that the amount of the silica fine particles was 30 parts by weight based on 100 parts by weight of the varnish obtained in Example 1, Was added to obtain a polyamic acid-silica nanoparticle varnish.

The compositions of the varnishes prepared in Examples 16 to 18 are shown in Table 4. The transmittance T, the total light transmittance Tt, the TE refractive index n (TE), the TM refractive index n (TM), and the average refractive index n (TM) of the heat resistant resin film obtained by firing at 350 deg. (Tg), the coefficient of linear expansion (CTE), and the 1% thermogravimetric reduction temperature (Td1) were measured.

Figure 112014025457350-pct00057

Example 19

To 4 g of the polyimide powder obtained in Example 13, 0.044 g of surfactant polyflow 77 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and 13.47 g of GBL were added to obtain polyimide varnish.

Example 20

To 4 g of the polyimide powder obtained in Example 13 were added 0.044 g of a surfactant polyflow 77 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), 0.2 g of Epiclon 850-S (trade name, manufactured by Dainippon Ink and Chemicals, Incorporated) g and 13.47 g of GBL were added to obtain a polyimide varnish.

Example 21

0.044 g of Surfactant polyflow 77 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), 0.044 g of Epiclon 850-S (trade name, manufactured by Dainippon Ink and Chemicals, Incorporated), 0.4 g of polyimide powder obtained in Example 13 g and 13.47 g of GBL were added to obtain a polyimide varnish.

Example 22

To 4 g of the polyimide powder obtained in Example 13 were added 0.044 g of a surfactant polyflow 77 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), 0.84 g of Epiclon 850-S (trade name, manufactured by Dainippon Ink and Chemicals, Incorporated) g and 13.47 g of GBL were added to obtain a polyimide varnish.

The total light transmittance Tt, the TE refractive index n (TE), and the TM refractive index n (TM) of the heat-resistant resin film obtained by firing at 300 ° C using the varnish of Examples 19 to 22, , The average refractive index (n AV), the in-plane / out-of-plane birefringence, the glass transition temperature (Tg), the coefficient of linear expansion (CTE), the 1% thermogravimetric reduction temperature (Td1), the fracture stress, Table 5 shows the results.

Figure 112014025457350-pct00058

Reference Example 1

117 g of PB 15: 6 (average primary diameter: 30 nm), 140 g of a solution of propylene glycol monomethyl ether acetate (30% by weight) of Ajinomoto Fine Techno product "Ajisper" PB821, A 45% by weight solution of "Cyclomer" ACA250 (product of Shikisai Co., Ltd.) and 627 g of propylene glycol monomethyl ether acetate were stirred with homodisperser to prepare a slurry. The beaker containing the slurry was connected with a circulating bead mill disperser ("Dynomill" KDL-A manufactured by Willy Bacopen Co., Ltd.) by a tube, and dispersed for 3 hours at 3200 rpm using zirconia beads having a diameter of 0.3 mm as a medium To obtain a blue pigment dispersion. To 0.4167 g of the obtained blue pigment dispersion, 49.5833 g of GBL was added to obtain a diluted solution.

Example 23

To 13 g of the polyimide powder obtained in Example 13, 0.013 g of surfactant polyflow 77 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and 36.3 g of GBL were added to obtain polyimide varnish.

Example 24

To 13 g of the polyimide powder obtained in Example 13 were added 0.013 g of the surfactant polyflow 77 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), 0.325 g of the blue pigment dispersion obtained in Reference Example 1, and 36.3 g of GBL to obtain polyimide I got a varnish.

Example 25

To 13 g of the polyimide powder obtained in Example 13 were added 0.013 g of the surfactant polyflow 77 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), 0.650 g of the blue pigment dispersion obtained in Reference Example 1 and 36.3 g of GBL to obtain polyimide I got a varnish.

Example 26

To 13 g of the polyimide powder obtained in Example 13 was added 0.013 g of the surfactant polyflow 77 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), 0.975 g of the blue pigment dispersion obtained in Reference Example 1 and 36.3 g of GBL to obtain polyimide I got a varnish.

Example 27

To 13 g of the polyimide powder obtained in Example 13 was added 0.013 g of the surfactant polyflow 77 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), 1.300 g of the blue pigment dispersion obtained in Reference Example 1 and 36.3 g of GBL to obtain polyimide I got a varnish.

Example 28

To 13 g of the polyimide powder obtained in Example 13 were added 0.013 g of the surfactant polyflow 77 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), 1.625 g of the blue pigment dispersion obtained in Reference Example 1 and 36.3 g of GBL to obtain polyimide I got a varnish.

Example 29

To 13 g of the polyimide powder obtained in Example 13, 0.013 g of the surfactant polyflow 77 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), 2.600 g of the blue pigment dispersion obtained in Reference Example 1 and 36.3 g of GBL were added to obtain polyimide I got a varnish.

The light transmittance (T), b * value, TE refractive index (n) (TE), TM refractive index (n)) of the heat resistant resin film obtained by firing at 350 deg. The average refractive index (n (AV)) and the in-plane / out-of-plane birefringence were measured.

Figure 112014025457350-pct00059

Example 30

In a dry nitrogen stream, 22.4 g (0.037 mol) of HFHA and 0.58 g (0.0023 mol) of SiDA were dissolved in 105 g of NMP. 5.75 g (0.018 mol) of ODPA was added thereto together with 20 g of NMP, followed by stirring at 40 DEG C for 1 hour. Then, 6.23 g of PMDA-HH was added together with 20 g of NMP, and the mixture was stirred at 80 ° C for 8 hours and then at room temperature for 11 hours. Then, 1.011 g of MAP was added together with 15 g of NMP and the mixture was stirred at 60 캜 for 1 hour. Thereafter, a solution prepared by diluting 4.60 g (0.038 mol) of DFA with 10 g of NMP was added dropwise, followed by dropwise addition, followed by stirring at 60 ° C for 1 hour. Thereafter, the same operation was performed twice. Thereafter, 16.69 g of acetic acid was added at room temperature, and the mixture was stirred for 1 hour. After completion of the stirring, the solution was poured into 2 L of water, and the precipitate of the polymer solid was collected by filtration. And further washed five times with 2 liters of water, and the collected polymer solids were dried in a dryer at 50 DEG C for 72 hours to obtain polyamide acid ester powder.

0.455 g of quinone diazide compound TP-250 (manufactured by Toyo Kosei Kabushiki Kaisha), 0.455 g of HAP-170 (manufactured by Toyo Kosei Kabushiki Kaisha), 4 g of dissolution accelerator Tris-HAP (Trade name, manufactured by Kyoeisha Chemical Co., Ltd.) 0.182 g, EL 9.3 g, GBL 6.9 g (trade name, available from Kyoeisha Chemical Co., Ltd.), 0.421 g of a thermosetting agent HMOM (manufactured by Honshu Kagaku K. K.) To obtain a varnish of a photosensitive resin composition. Using the obtained varnish, a relief pattern was prepared by the method of (9) above, and the photosensitivity was evaluated. As a result, the amount of decrease in the developed film was as small as 0.17 mu m and the sensitivity was 300 mJ / cm2.

Example 31

0.929 g of a quinone diazide compound HAP-170 (manufactured by Toyo Kosei K. K.), 0.664 g of a thermal cross-linking agent HMOM (manufactured by Honshu Kagaku Kogyo Co., Ltd.), 0.649 g of a surfactant poly-flow 77 0.011 g, trade name, produced by Kyoeisha Chemical Co., Ltd.) and 18.75 g of GBL were added to obtain a varnish of photosensitive resin composition. Using the varnish thus obtained, a relief pattern was prepared by the method of (9) above, and the photosensitivity was evaluated. As a result, the reduction amount of the developed film was 1.27 탆 and the sensitivity was 125 mJ / cm 2.

(Industrial availability)

According to the present invention, it is possible to provide a polyamic acid resin composition, a polyimide resin composition, and a polyimide oxazole resin composition, each having a heat-treated film having excellent heat resistance, light transmittance and low birefringence. The film after heat treatment can be applied to a flexible substrate such as a flat panel display, a touch panel, an electronic paper, a color filter substrate, and a solar cell, a surface protective film of a semiconductor element, an interlayer insulating film, an insulating layer of an organic electroluminescence element (organic EL element) A flattening film of a thin film transistor substrate, an insulating layer of an organic transistor, a flexible printed substrate, and the like.

Claims (17)

A flexible substrate comprising a polyamic acid containing at least 50 mol% of structural units represented by the general formula (1).
Figure 112018053573567-pct00060

[In the general formula (1), X 1 and X 2 each independently represent a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. R 1 is a quaternary organic group having 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure or a tetravalent organic group having 4 to 40 carbon atoms linked to each other through an organic group having a monocyclic alicyclic structure directly or via a crosslinking structure . R 2 represents a divalent organic group having 2 to 40 carbon atoms and having at least two hydroxyl groups.
The method according to claim 1,
R 1 in the general formula (1) is at least one selected from the following general formulas (4) to (10).
Figure 112018053573567-pct00061

Figure 112018053573567-pct00062

Figure 112018053573567-pct00063

Figure 112018053573567-pct00064

Figure 112018053573567-pct00065

Figure 112018053573567-pct00066

Figure 112018053573567-pct00067

[In formulas (4) to (10), R 4 to R 79 each independently represent a monovalent organic group having 1 to 3 carbon atoms which may be substituted with a hydrogen atom, a halogen atom or a halogen atom. In the general formula (7), X 3 is a divalent organic group having 1 to 3 carbon atoms which may be substituted with an oxygen atom, a sulfur atom, a sulfonyl group or a halogen atom, or a divalent crosslinked structure formed by connecting two or more thereof. In the general formula (10), X 4 represents a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, a divalent organic group having 1 to 3 carbon atoms which may be substituted with a hydrogen atom by a halogen atom, an arylene group which may be substituted with a hydrogen atom by a halogen atom, An oxygen atom, a sulfur atom, a sulfonyl group, a bivalent organic group having 1 to 3 carbon atoms which may be substituted with a hydrogen atom by a halogen atom, and an arylene group which may be substituted with a halogen atom. ]
The method according to claim 1,
A flexible substrate characterized in that R 2 in the general formula (1) is represented by the following formula (14).
Figure 112018053573567-pct00068
The method according to claim 1,
Wherein the polyamic acid containing 50 mol% or more of the structural unit represented by the general formula (1) contains 10 mol% to 50 mol% of the structural unit represented by the general formula (36).

[In the formula (36), X 1 and X 2 each independently represent a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. R 1 is a quaternary organic group having 4 to 40 carbon atoms having a monocyclic or condensed polycyclic alicyclic structure or a tetravalent organic group having 4 to 40 carbon atoms linked to each other through an organic group having a monocyclic alicyclic structure directly or via a crosslinking structure .]
5. The method according to any one of claims 1 to 4,
Wherein the in-plane / out-plane birefringence is 0.01 or less.
A flexible substrate comprising a polyimide containing at least 50 mol% of structural units represented by the general formula (2).
Figure 112018053573567-pct00070

[In the general formula (2), R 1 represents a monovalent or condensed polycyclic alicyclic organic group having 4 to 40 carbon atoms having a cycloaliphatic structure or an organic group having a monocyclic alicyclic structure directly or via a crosslinking structure Represents a tetravalent organic group having 4 to 40 carbon atoms. R 2 represents a divalent organic group having 2 to 40 carbon atoms and having at least two hydroxyl groups.
The method according to claim 6,
R 1 in the general formula (2) is at least one selected from the following general formulas (4) to (10).
Figure 112018053573567-pct00071

Figure 112018053573567-pct00072

Figure 112018053573567-pct00073

Figure 112018053573567-pct00074

Figure 112018053573567-pct00075

Figure 112018053573567-pct00076

Figure 112018053573567-pct00077

[In formulas (4) to (10), R 4 to R 79 each independently represent a monovalent organic group having 1 to 3 carbon atoms which may be substituted with a hydrogen atom, a halogen atom or a halogen atom. In the general formula (7), X 3 is a divalent organic group having 1 to 3 carbon atoms which may be substituted with an oxygen atom, a sulfur atom, a sulfonyl group or a halogen atom, or a divalent crosslinked structure formed by connecting two or more thereof. In the general formula (10), X 4 represents a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, a divalent organic group having 1 to 3 carbon atoms which may be substituted with a hydrogen atom by a halogen atom, an arylene group which may be substituted with a hydrogen atom by a halogen atom, An oxygen atom, a sulfur atom, a sulfonyl group, a bivalent organic group having 1 to 3 carbon atoms which may be substituted with a hydrogen atom by a halogen atom, and an arylene group which may be substituted with a halogen atom. ]
The method according to claim 6,
A flexible substrate characterized in that R 2 in the general formula (2) is represented by the following formula (14).
Figure 112018053573567-pct00078
The method according to claim 6,
Wherein the polyimide comprising 50 mol% or more of the structural unit represented by the general formula (2) contains 10 mol% to 50 mol% of the structural unit represented by the general formula (37).
Figure 112018053573567-pct00079

[In the formula (37), R 1 represents a divalent organic group having 4 to 40 carbon atoms and having an alicyclic or condensed polycyclic alicyclic structure or an organic group having a monocyclic alicyclic structure directly or via a crosslinking structure Represents a tetravalent organic group having 4 to 40 carbon atoms.
10. The method according to any one of claims 6 to 9,
Wherein the in-plane / out-plane birefringence is 0.01 or less.
A polyimide oxazole containing a structural unit represented by the general formula (3) in an amount of 50 mol% or more.
Figure 112018053573567-pct00080

[In the general formula (3), R &lt; 1 &gt; is a divalent organic group having 4 to 40 carbon atoms and having an alicyclic or condensed polycyclic alicyclic structure, or an organic group having a monocyclic alicyclic structure, Represents a tetravalent organic group having 4 to 40 carbon atoms. And R 3 represents a tetravalent organic group having 2 to 40 carbon atoms.
12. The method of claim 11,
R 1 in the general formula (3) is at least one selected from the following general formulas (4) to (10).
Figure 112018053573567-pct00081

Figure 112018053573567-pct00082

Figure 112018053573567-pct00083

Figure 112018053573567-pct00084

Figure 112018053573567-pct00085

Figure 112018053573567-pct00086

Figure 112018053573567-pct00087

[In formulas (4) to (10), R 4 to R 79 each independently represent a monovalent organic group having 1 to 3 carbon atoms which may be substituted with a hydrogen atom, a halogen atom or a halogen atom. In the general formula (7), X 3 is a divalent organic group having 1 to 3 carbon atoms which may be substituted with an oxygen atom, a sulfur atom, a sulfonyl group or a halogen atom, or a divalent crosslinked structure formed by connecting two or more thereof. In the general formula (10), X 4 represents a direct bond, an oxygen atom, a sulfur atom, a sulfonyl group, a divalent organic group having 1 to 3 carbon atoms which may be substituted with a hydrogen atom by a halogen atom, an arylene group which may be substituted with a hydrogen atom by a halogen atom, An oxygen atom, a sulfur atom, a sulfonyl group, a bivalent organic group having 1 to 3 carbon atoms which may be substituted with a hydrogen atom by a halogen atom, and an arylene group which may be substituted with a halogen atom. ]
12. The method of claim 11,
R 3 in the general formula (3) is represented by the following formula (25).
Figure 112018053573567-pct00088
12. The method of claim 11,
Wherein the polyimide oxazole containing 50 mol% or more of the structural unit represented by the general formula (3) comprises 10 mol% to 50 mol% of the structural unit represented by the general formula (37).
Figure 112018053573567-pct00089

[In the formula (37), R 1 represents a divalent organic group having 4 to 40 carbon atoms and having an alicyclic or condensed polycyclic alicyclic structure or an organic group having a monocyclic alicyclic structure directly or via a crosslinking structure Represents a tetravalent organic group having 4 to 40 carbon atoms.
15. The method according to any one of claims 11 to 14,
Wherein the in-plane / out-plane birefringence is 0.01 or less.
The method according to claim 6,
And a polyimide comprising 100 mol% of the structural unit represented by the general formula (2).
Figure 112018053573567-pct00090

[In the general formula (2), R 1 represents a monovalent or condensed polycyclic alicyclic organic group having 4 to 40 carbon atoms having a cycloaliphatic structure or an organic group having a monocyclic alicyclic structure directly or via a crosslinking structure Represents a tetravalent organic group having 4 to 40 carbon atoms. R 2 represents a divalent organic group having 2 to 40 carbon atoms and having at least two hydroxyl groups.
12. The method of claim 11,
A polyimide oxazole comprising 100 mol% of the structural unit represented by the general formula (3).
Figure 112018053573567-pct00091

[In the general formula (3), R &lt; 1 &gt; is a divalent organic group having 4 to 40 carbon atoms and having an alicyclic or condensed polycyclic alicyclic structure, or an organic group having a monocyclic alicyclic structure, Represents a tetravalent organic group having 4 to 40 carbon atoms. And R 3 represents a tetravalent organic group having 2 to 40 carbon atoms.
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Families Citing this family (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012124664A1 (en) * 2011-03-11 2012-09-20 宇部興産株式会社 Polyimide precursor and polyimide
JP6477469B2 (en) 2013-07-05 2019-03-06 三菱瓦斯化学株式会社 Polyimide resin
TWI504641B (en) * 2013-12-16 2015-10-21 Taimide Technology Inc White polyimide film
JP6724363B2 (en) * 2014-09-02 2020-07-15 東レ株式会社 Resin and photosensitive resin composition
KR102656566B1 (en) * 2015-03-26 2024-04-12 도레이 카부시키가이샤 Resin laminated film, laminated body containing the same, TFT substrate, organic EL device color filter, and method for manufacturing the same
WO2016158672A1 (en) * 2015-03-30 2016-10-06 東レ株式会社 Colored resin composition, colored film, decorative substrate and touch panel
CN104830169A (en) * 2015-05-11 2015-08-12 黄强 Wear resistant paint used for automobile engines
CN107849362B (en) * 2015-10-23 2020-09-15 东丽株式会社 Resin composition for display substrate, heat-resistant resin film using same, organic EL display substrate, and method for producing organic EL display
JP6718678B2 (en) * 2015-12-25 2020-07-08 ソマール株式会社 Polyimide copolymer and molded product using the same
KR102503173B1 (en) * 2016-03-31 2023-02-23 동우 화인켐 주식회사 Flexible color filter
KR102127033B1 (en) * 2016-04-26 2020-06-25 주식회사 엘지화학 Negative type photosensitive resin composition and organic light emitting device black matrix comprising the same
TWI788288B (en) * 2016-05-06 2023-01-01 日商三菱瓦斯化學股份有限公司 Polyimide resin
JP6768234B2 (en) * 2016-05-09 2020-10-14 三菱瓦斯化学株式会社 Polyimide and polyimide film
WO2017221776A1 (en) * 2016-06-24 2017-12-28 東レ株式会社 Polyimide resin, polyimide resin composition, touch panel using same, method for producing said touch panel, color filter, method for producing color filter, liquid crystal element, method for producing liquid crystal element, organic el element, and method for producing organic el element
CN109311297A (en) * 2016-07-15 2019-02-05 宇部兴产株式会社 The manufacturing method of polyimides laminated body and the manufacturing method of flexible circuit board
WO2018029766A1 (en) * 2016-08-09 2018-02-15 東レ株式会社 Laminated resin film, laminated body including laminated resin film, tft substrate, organic el element color filter, and methods for manufacturing same
JP7186617B2 (en) * 2016-09-30 2022-12-09 住友化学株式会社 Method for producing polyimide polymer varnish, method for producing polyimide polymer film, and transparent polyimide polymer film
TWI600168B (en) 2016-11-02 2017-09-21 律勝科技股份有限公司 Laminate structure of thin film transistor
JP6847221B2 (en) 2016-12-09 2021-03-24 エルジー・ケム・リミテッド Sealing material composition
CN116891571A (en) * 2017-09-18 2023-10-17 嘉兴山蒲照明电器有限公司 Organosilicon modified polyimide resin composition and application thereof
CN111133034B (en) * 2017-09-29 2022-08-09 三菱瓦斯化学株式会社 Polyimide resin, polyimide varnish, and polyimide film
JP7248394B2 (en) * 2017-09-29 2023-03-29 日鉄ケミカル&マテリアル株式会社 Polyimide film and metal-clad laminate
WO2020071415A1 (en) * 2018-10-03 2020-04-09 コニカミノルタ株式会社 Resin composition and electronic device
JP7384037B2 (en) * 2018-11-09 2023-11-21 東レ株式会社 Polyimide precursors, polyimides, polyimide resin films, and flexible devices
TW202035527A (en) * 2018-12-28 2020-10-01 日商住友化學股份有限公司 Optical film, flexible display device and polyamide-imide resin
CN111621260B (en) * 2020-06-18 2022-01-25 株洲时代新材料科技股份有限公司 Polyamide acid coating adhesive and preparation method thereof
CN112708134B (en) * 2020-12-28 2021-08-03 深圳瑞华泰薄膜科技股份有限公司 Colorless transparent copolyamide-imide film and preparation method thereof
TWI806308B (en) * 2021-07-14 2023-06-21 南韓商可隆股份有限公司 Optical film having improved visibility and display device comprising the same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008184558A (en) 2007-01-30 2008-08-14 Asahi Kasei Corp Polyimide precursor and polyimide having ester group and oxazole structure and process for producing the same
WO2010087238A1 (en) * 2009-01-29 2010-08-05 東レ株式会社 Resin composition and display device formed using same
JP2011020399A (en) 2009-07-17 2011-02-03 Toyobo Co Ltd Peelable polyimide film laminate
WO2011030744A1 (en) 2009-09-10 2011-03-17 東レ株式会社 Photosensitive resin composition and method for producing photosensitive resin film

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3168827B2 (en) * 1994-05-20 2001-05-21 信越化学工業株式会社 Polyimide copolymer and method for producing the same
JP2004134487A (en) * 2002-10-09 2004-04-30 Toray Ind Inc Semiconductor device and its manufacturing method
JP5370884B2 (en) * 2008-08-29 2013-12-18 Jnc株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
JP5556482B2 (en) * 2009-09-15 2014-07-23 Jnc株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
WO2012124664A1 (en) * 2011-03-11 2012-09-20 宇部興産株式会社 Polyimide precursor and polyimide
JP6792358B2 (en) * 2016-07-07 2020-11-25 サッポロビール株式会社 How to predict the turbidity of beer-taste beverages

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008184558A (en) 2007-01-30 2008-08-14 Asahi Kasei Corp Polyimide precursor and polyimide having ester group and oxazole structure and process for producing the same
WO2010087238A1 (en) * 2009-01-29 2010-08-05 東レ株式会社 Resin composition and display device formed using same
JP2011020399A (en) 2009-07-17 2011-02-03 Toyobo Co Ltd Peelable polyimide film laminate
WO2011030744A1 (en) 2009-09-10 2011-03-17 東レ株式会社 Photosensitive resin composition and method for producing photosensitive resin film

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