JPWO2011027866A1 - Substrate manufacturing method and composition used therefor - Google Patents

Abstract

Disclosed is a method for producing a substrate at low cost and a composition used for the production method, which can more effectively avoid the occurrence of warping and twisting. (A) coating and drying a film-forming composition containing a precursor of a heterocyclic ring-containing polymer and an organic solvent on a support and forming a coating film; and (b) containing the coating film with a heterocyclic ring. A cyclization step of cyclizing the precursor of the heterocyclic ring-containing polymer by heating at a temperature 60 ° C. lower than the glass transition temperature of the polymer to 20 ° C. higher than the glass transition temperature of the heterocyclic ring-containing polymer; A step of forming an element on the film obtained by the cyclization step; and (d) a step of peeling the film on which the element is formed from a support. A method for producing a substrate, which is a polymer having at least one glass transition temperature selected from the group consisting of benzoxazole, polybenzothiazole and polybenzimidazole in a range of 230 to 420 ° C.

Description

  The present invention relates to a method for producing a substrate and a composition used therefor.

  In general, wholly aromatic polyimide obtained from aromatic tetracarboxylic dianhydride and aromatic diamine is due to the rigidity of the molecule, the fact that the molecule is resonance-stabilized, the strong chemical bond, etc. Excellent heat resistance, mechanical properties, electrical properties, oxidation resistance and hydrolysis resistance. Widely used as film, coating agent, molded part, insulation material in fields such as electricity, battery, automobile and aerospace industry. It is used.

  For example, polyimide obtained by polycondensation of pyromellitic dianhydride and 4,4'-oxydianiline is excellent in heat resistance and electrical insulation, has high dimensional stability, and is used for flexible printed circuit boards. The Specifically, a polyimide film is produced by removing a solvent from a polyamic acid solution obtained by reacting pyromellitic dianhydride and 4,4'-oxydianiline and performing a thermal imidization step. Usually, the polyimide film is generally formed on a relatively rigid substrate such as a stainless steel belt.

  Further, it is disclosed that polyimide synthesized from pyromellitic dianhydride, 4,4 "-oxydianiline and p-phenylenediamine is excellent in thermal dimensional stability (Patent Document 1 and Patent Document 2). .

  Furthermore, as a polyimide film having improved dimensional stability, tetracarboxylic dianhydride containing 4,4 "-oxydiphthalic dianhydride and pyromellitic dianhydride as essential components, p-phenylenediamine and 4, A polyimide film obtained from an aromatic diamine containing 4 "-oxydianiline is known (Patent Document 3).

JP-A-1-131241 JP-A-1-131242 JP 2009-518500 A

  However, it has been pointed out that the film obtained using the above conventional polyimide-forming composition has a problem that when the film is formed on a support, the substrate or the film itself is warped due to shrinkage deformation at the time of film formation. Yes.

  An object of the present invention is to provide a low-cost and simple method for producing a substrate and a composition used for the production method that can more effectively avoid the occurrence of warping and twisting.

  The present invention has been made in view of the above problems, and a coating film is formed by applying a film-forming composition containing a precursor of a specific heterocyclic-containing polymer and an organic solvent on a support and drying it. A step of forming, a cyclization step of cyclizing the precursor of the polymer at a specific temperature on the support, a step of forming an element on the film obtained by the cyclization step, and the element And a step of peeling the formed film from the support, the method for producing a substrate includes finding that a substrate with reduced warpage and twisting can be obtained, and further, adhesion to the support and peeling. As a result, the inventors have found a composition and a production method that are compatible with the properties, and have completed the present invention.

  That is, the present invention provides the following [1] to [8].

[1] (a) Applying and drying a film-forming composition containing a precursor of a heterocyclic ring-containing polymer and an organic solvent on a support to form a coating film;
(B) The coating film is heated at a temperature 60 ° C. lower than the glass transition temperature of the heterocyclic ring-containing polymer to 20 ° C. higher than the glass transition temperature of the heterocyclic ring-containing polymer. A cyclization step,
(C) forming a device on the film obtained by the cyclization step;
(D) peeling the film on which the element is formed from the support;
Including
Glass transition temperature (DSC, temperature increase rate 20 ° C./min) of at least one differential scanning calorimetry (DSC selected from the group consisting of polyimide, polybenzoxazole, polybenzothiazole and polybenzimidazole). Tg) is a polymer in the range of 230 to 420 ° C.

[2]
The method for producing a substrate according to [1], wherein the cyclization step (b) is performed at a temperature 60 ° C. lower than the glass transition temperature of the heterocyclic ring-containing polymer to the glass transition temperature of the heterocyclic ring-containing polymer.

  [3] The method for producing a substrate according to [1] or [2], wherein the cyclization step (b) is performed at 160 ° C to 420 ° C.

  [4] The method for manufacturing a substrate according to any one of [1] to [3], wherein the support is a silicon wafer or non-alkali glass.

  [5] The method for producing a substrate according to any one of [1] to [4], wherein the heterocyclic ring-containing polymer is polyimide.

  [6] The organic solvent includes at least one solvent selected from N, N′-dimethylimidazolidinone, γ-butyrolactone, N-methyl-2-pyrrolidone, and N, N-dimethylacetamide. The manufacturing method of the flexible substrate in any one of [1]-[5].

  [7] The method for producing a substrate according to any one of [1] to [6], wherein the film-forming composition has a viscosity (E-type viscometer, measured at 25 ° C.) of 5,000 to 50,000 cP.

[8] A film-forming composition used in the method for producing a substrate according to any one of [1] to [7],
Containing a precursor of a heterocyclic ring-containing polymer and an organic solvent,
Glass transition temperature (DSC, temperature increase rate 20 ° C./min) of glass transition temperature (DSC, at least one selected from the group consisting of polyimide, polybenzoxazole, polybenzothiazole, polybenzimidazole) A film-forming composition, which is a polymer having a Tg) in the range of 230 to 420 ° C.

  According to the substrate manufacturing method of the present invention, it is possible to easily manufacture a substrate with less warping and twisting.

  The film-forming composition of the present invention is a composition comprising a precursor of a polymer such as polyimide, polybenzoxazole, polybenzothiazole, polybenzimidazole and the like having a specific glass transition temperature (Tg) and an organic solvent. Therefore, it is possible to more effectively avoid the occurrence of warping and twisting when manufacturing the substrate.

  According to the present invention, it is possible to easily manufacture a substrate (film) that can achieve both adhesion to the support and peelability.

  In the present invention, “adhesiveness” refers to a property in which, for example, in the step (b) or step (c), the film formed on the support and the substrate and the support are difficult to peel off.

  In the present invention, “peelability” means, for example, a property that the substrate can be peeled from the support with few peeling marks in the step (d).

The method for producing a substrate of the present invention includes (a) applying a film forming composition containing a precursor of a heterocyclic ring-containing polymer and an organic solvent to a support and drying to form a coating film;
(B) The coating film is heated at a temperature 60 ° C. lower than the glass transition temperature of the heterocyclic ring-containing polymer to 20 ° C. higher than the glass transition temperature of the heterocyclic ring-containing polymer. A cyclization step,
(C) forming a device on the film obtained by the cyclization step;
(D) peeling the film on which the element is formed from the support;
Including
Glass transition temperature (DSC, temperature increase rate 20 ° C./min) of at least one differential scanning calorimetry (DSC selected from the group consisting of polyimide, polybenzoxazole, polybenzothiazole and polybenzimidazole). Tg) is a polymer in the range of 230-420 ° C.

[Step (a)]
First, the process of apply | coating and drying the composition for film formation containing the precursor of a heterocyclic containing polymer and an organic solvent on a support body, and forming a coating film is demonstrated.

  First, the film-forming composition used in this step is glass by differential scanning calorimetry (DSC, heating rate 20 ° C./min) selected from polyimide, polybenzoxazole, polybenzothiazole, and polybenzimidazole. It contains a precursor that can be a polymer having a transition temperature (Tg) in the range of 230 to 420 ° C. and an organic solvent. Each of the precursor and the organic solvent may be used alone or in combination of two or more.

  In addition, you may mix | blend additives, such as antioxidant, a ultraviolet absorber, and surfactant, with the said film formation composition in the range which does not impair the objective of this invention.

  First, the heterocyclic ring-containing polymer and the precursor of the heterocyclic ring-containing polymer will be described.

  The precursor of the heterocyclic ring-containing polymer preferably has a polystyrene-reduced weight average molecular weight by gel permeation chromatography (GPC) of 25,000 to 500,000, more preferably 50,000 to 400,000. is there. When the weight average molecular weight of the precursor of the heterocyclic ring-containing polymer is in the above range, a film-forming composition having excellent compatibility with an organic solvent and excellent coating properties can be obtained.

  The heterocycle-containing polymer preferably includes a component (A) containing a compound having four functional groups such as a carboxyl group, an acid chloride group, an ester group, an amino group, an isocyanate group, a hydroxy group, and a mercapto group; The heterocyclic ring-containing polymer obtained by making the component (B) containing the compound which has these two functional groups react can be mentioned. The component (A) includes a compound having two acid anhydride groups.

<Polyimide>
When the heterocyclic ring-containing polymer is a polyimide, the glass transition temperature (Tg) of the polyimide by differential scanning calorimetry (DSC, heating rate 20 ° C./min) is 230 to 420 ° C., preferably 240 to 400. ° C, more preferably 250-380 ° C.

  As a precursor capable of forming a polyimide having a glass transition temperature (Tg) of 230 to 420 ° C. by differential scanning calorimetry (DSC, heating rate 20 ° C./min), for example, tetracarboxylic Examples thereof include polyamic acid obtained by reacting acid, tetracarboxylic dianhydride, tetracarboxylic acid diester dichloride, and the like and diamine, diisocyanate compound, trimethylsilylated diamine and the like as the component (B).

  As the polyimide precursor, specifically, as the component (A), at least one acyl compound selected from (A1) (A-1) 4,4′-oxydiphthalic dianhydride and reactive derivatives thereof. (Hereinafter also referred to as “compound (A-1)”), and (A-2) at least one acyl compound selected from pyromellitic dianhydride and a reactive derivative thereof (hereinafter referred to as “compound (A-2)”. And a component (B1) containing an aromatic imino-forming compound represented by the following general formula (1) as the component (B), and a component containing at least one compound selected from the group consisting of: And polyamic acid obtained by reacting.

[(A1) component]
The component (A1) includes at least one acyl compound (A-1) selected from 4,4′-oxydiphthalic dianhydride and reactive derivatives thereof, pyromellitic dianhydride and reactive derivatives thereof. It is a component comprising at least one compound selected from the group consisting of at least one acyl compound (A-2) selected from the above.

  By using such an acid dianhydride, a flexible substrate excellent in the balance between adhesion and peelability and smoothness without warping can be obtained.

  In particular, when the component (A1) contains the compounds (A-1) and (A-2), the glass transition temperature is changed to the cyclization temperature by reacting the component (A1) with the component (B1). Since a polymer (polyimide) close to (approximately 250 ° C.) can be easily obtained, it has excellent adhesion and releasability to a support, particularly a support such as a silicon wafer or non-alkali glass, and warpage or twisting occurs. A film and a substrate with a small amount can be manufactured.

  When the component (A1) contains the compounds (A-1) and (A-2), the compounding ratio of the compound (A-1) and the compound (A-2) (compound (A-1): compound (A -2), (molar ratio)) is preferably 10:90 to 90:10, more preferably 20:80 to 50:50 (however, the sum of both is 100 mol).

  A compound and a substrate with a compounding ratio of the compound (A-1) and the compound (A-2) in the above-mentioned range, which are more easily excellent in adhesion and peelability to the support and are less likely to be warped or twisted. Can be manufactured.

  Examples of the reactive derivative of 4,4′-oxydiphthalic dianhydride include 4,4′-oxydiphthalic acid alkyl ester. Specifically, 4,4′-oxydiphthalic acid monomethyl ester, 4 , 4'-oxydiphthalic acid dimethyl ester, 4,4'-oxydiphthalic acid trimethyl ester, 4,4'-oxydiphthalic acid tetramethyl ester, 4,4'-oxydiphthalic acid monoethyl ester, 4,4'-oxydiphthalic acid diethyl ester 4,4′-oxydiphthalic acid triethyl ester, 4,4′-oxydiphthalic acid tetraethyl ester, and the like.

  Examples of the reactive derivative of pyromellitic dianhydride include pyromellitic acid alkyl ester. Specifically, pyromellitic acid monomethyl ester, pyromellitic acid dimethyl ester, pyromellitic acid trimethyl ester, pyromellitic acid Examples include meritic acid tetramethyl ester, pyromellitic acid monoethyl ester, pyromellitic acid diethyl ester, pyromellitic acid triethyl ester, and pyromellitic acid tetraethyl ester.

  Further, 4,4'-oxydiphthalic acid and pyromellitic acid unsubstituted phenyl ester or para-substituted phenyl ester are also included.

  Other reactive derivatives include 4,4′-oxydiphthalic acid tetrachloride, 4,4′-oxydiphthalic acid dichloride diester, pyromellitic acid tetrachloride, pyromellitic acid dichloride diester (this ester is the same alkyl ester as above) And non-substituted phenyl ester or para-substituted phenyl ester).

  As the component (A1), 4,4′-oxydiphthalic dianhydride and pyromellitic dianhydride are preferably used. When 4,4'-oxydiphthalic dianhydride or pyromellitic dianhydride, which is an anhydride, is used as the component (A1), a polyamic acid is synthesized at a lower temperature than when a non-anhydride compound is used. be able to.

  In addition, these (A1) components can be used individually by 1 type or in mixture of 2 or more types.

  The amount of at least one acylated compound (A-1) selected from 4,4′-oxydiphthalic dianhydride and its reactive derivative is selected from the viewpoint of obtaining a substrate excellent in smoothness without warping. It is preferable that it is 10-50 mol% with respect to the whole quantity ((A1) component whole quantity), and it is more preferable that it is 15-45 mol%.

  Moreover, the usage-amount of the at least 1 sort (s) of acylated compound (A-2) chosen from a pyromellitic dianhydride and its reactive derivative is 50- with respect to the whole quantity of an acyl compound from a heat resistant and peelable viewpoint. It is preferably 90 mol%, more preferably 55 to 85 mol%.

  In addition to the 4,4'-oxydiphthalic dianhydride, pyromellitic dianhydride, and reactive derivatives thereof, other acyl compounds may be further used as the acyl compound. Other acyl compounds include aromatic tetracarboxylic dianhydrides (except 4,4′-oxydiphthalic dianhydride, pyromellitic dianhydride, and reactive derivatives thereof), aliphatic tetracarboxylic Examples thereof include at least one selected from the group consisting of acid dianhydrides, alicyclic tetracarboxylic dianhydrides, and reactive derivatives thereof.

Specific examples include butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3, 5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4 , 5,9b-Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 5- (2,5-dioxotetrahydrofura L) -3-Methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride Such as Aliphatic tetracarboxylic acid dianhydride or an alicyclic tetracarboxylic acid dianhydride, and reactive derivatives thereof;
3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride Anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ′, 4,4′-tetra Phenylsilanetetracarboxylic dianhydride, 2,3,4,5-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4 ′ -Bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoro Isopropyl Redene diphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride , M-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4′-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride Aromatic tetracarboxylic dianhydrides such as products, and reactive derivatives thereof.

  Of these, aliphatic tetracarboxylic dianhydride or alicyclic tetracarboxylic dianhydride is preferably used from the viewpoint of excellent transparency and good solubility in an organic solvent. In addition, aromatic tetracarboxylic dianhydrides are preferably used from the viewpoint of low linear expansion coefficient (dimensional stability) and low water absorption.

[(B1) component]
The component (B1) is an aromatic imino forming compound represented by the following formula (1).

(In the formula (1), X is independently —NH ₂ or —N═C═O, —NHSi (R ²⁵ ) (R ²⁶ ) (R ²⁷ ), and Y is independently a direct bond ( single _{bond), - CH 2 -, -} O -, - S -, - C (CH 3) 2 - from a single group selected, Z is a direct _{bond, -CH 2 -, - O -} , - S —, —C (CH ₃ ) ₂ —,> C═O, —SO ₂ —, wherein R ^{1 to} R ¹⁶ are each independently hydrogen, carbon atoms of 1 to 12 carbon atoms. (It is a group selected from a hydrogen group and halogen, and R ^{25 to} R ²⁷ are each independently an alkyl group having 1 to 15 carbon atoms.)
Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms include a linear or branched hydrocarbon (alkyl) group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and 6 carbon atoms. -12 aromatic hydrocarbon (aryl) groups and the like.

  The linear or branched hydrocarbon group having 1 to 12 carbon atoms is preferably a linear or branched hydrocarbon group having 1 to 8 carbon atoms, and the linear or branched carbon group having 1 to 5 carbon atoms. A hydrogen group is more preferable.

  Preferable specific examples of the linear or branched hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, and n-pentyl. Group, n-hexyl group, n-heptyl group and the like.

  As said C3-C12 alicyclic hydrocarbon group, a C3-C8 alicyclic hydrocarbon group is preferable, and a C3-C4 alicyclic hydrocarbon group is more preferable.

  Preferable specific examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group; cyclobutenyl group, cyclopentenyl group, and cyclohexenyl group. And the like. The bonding site of the alicyclic hydrocarbon group may be any carbon on the alicyclic ring.

  Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms include a phenyl group, a biphenyl group, and a naphthyl group. The bonding site of the aromatic hydrocarbon group may be any carbon on the aromatic ring.

Examples of the alkyl group having 1 to 15 carbon atoms represented by R ^{25 to} R ²⁷ include a linear or branched alkyl group having 1 to 15 carbon atoms, and a linear or branched alkyl group having 1 to 12 carbon atoms. Group, a linear or branched alkyl group having 1 to 8 carbon atoms is more preferable, and a linear or branched alkyl group having 1 to 5 carbon atoms is more preferable.

  Preferred examples of the linear or branched alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group. , N-hexyl group, n-heptyl group and the like.

  By using the aromatic imino forming compound represented by such a specific formula, a film (film) with less warpage can be obtained. Here, the “imino forming compound” refers to a compound for reacting with the component (A) to form an imino (group).

  Examples of the aromatic imino-forming compound include bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, and bis [4- (3-aminophenoxy) phenyl] ketone. Bis [4- (4-aminophenoxy) phenyl] ketone, 4,4 "-bis (3-aminophenoxy) biphenyl, 4,4" -bis (4-aminophenoxy) biphenyl, bis [4- (3- Aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, etc. Can be mentioned. Of these, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 4,4 "-bis (3-aminophenoxy) biphenyl, 4,4 ' -Bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] propane, and 2,2-bis [4- (4-aminophenoxy) phenyl] propane are preferably used.

  In addition, as the component (B1), an aromatic imino-forming compound in which the bonding groups represented by X, Y, and Z are bonded to each other at the para position of the benzene ring in the above formula (1), that is, the following formula The aromatic imino forming compound represented by (2) is preferred. By using such a compound, a film (film) having more excellent heat resistance and less warpage can be obtained. Among the above-mentioned aromatic imino forming compounds, bis [4- (4-aminophenoxy) phenyl] sulfone, 4,4′-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-amino) Phenoxy) phenyl] propane is more preferably used.

(In the formula (2), R ^{1 to} R ¹⁶ , X, Y, and Z are the same as those in the above formula (1).)
In addition, these imino forming compounds (B1) can be used individually by 1 type or in combination of 2 or more types.

  The polyimide precursor is a compound having a structure containing —CO—NH— and —CO—OH or a derivative thereof (specifically, for example, —CO—NH— and —CO—OR). (Wherein R is an alkyl group or the like)), etc., and by heating, etc., H of —CO—NH— and OH of —CO—OH are dehydrated to form a cyclic A polyimide having a chemical structure (—CO—N—CO— (hereinafter also referred to as an imide ring structure)) (hereinafter, a structure containing —CO—NH— and —CO—OH or —CO—NH—). And a structure containing —CO—OR (where R is an alkyl group or the like) is also referred to as an amic acid structure).

<Polybenzoxazole>
When the heterocycle-containing polymer is polybenzoxazole, the glass transition temperature (Tg) of the polybenzoxazole by differential scanning calorimetry (DSC, heating rate 20 ° C./min) is 230 to 420 ° C., preferably Is 240-400 degreeC, More preferably, it is 250-380 degreeC.

  A precursor capable of forming polybenzoxazole having a glass transition temperature (Tg) of 230 to 420 ° C. by differential scanning calorimetry (DSC, heating rate of 20 ° C./min) is, for example, bisamino as the component (A). Obtained by reacting the hydroxy compound (A2) with the component (B2) containing at least one compound selected from the group consisting of dicarboxylic acid, dicarboxylic acid chloride, dicarboxylic acid ester and the like as the component (B). Can do. In general, a polyhydroxyamide, which is one of the polybenzoxazole precursors, can be obtained by reacting a bisaminohydroxy compound with a dicarboxylic acid, and polybenzoxazole can be obtained by dehydrating and cyclizing this by heating or the like. be able to.

[(A2) component]
As the bisaminohydroxy compound (A2), specifically, 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2′-bis (3-amino-4-hydroxy-) 5-trifluoromethylphenyl) hexafluoropropane, 2,4-diaminoresorcinol, 4,6-diaminoresorcinol, 2,2′-bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 2,2′- Bis (3-amino-4-hydroxyphenyl) propane, 2,2′-bis (4-amino-3-hydroxyphenyl) propane, 3,3′-diamino-4,4′-dihydroxydiphenylsulfone, 4,4 '-Diamino-3,3'-dihydroxydiphenylsulfone, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-dia -3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4 '-Dihydroxy-2,2'-trifluoromethylbiphenyl, 4,4'-diamino-3,3'-dihydroxy-2,2'-trifluoromethylbiphenyl, 3,3'-diamino-4,4'- Dihydroxy-5,5′-trifluoromethylbiphenyl, 4,4′-diamino-3,3′-dihydroxy-5,5′-trifluoromethylbiphenyl, 3,3′-diamino-4,4′-dihydroxy- 6,6′-trifluoromethylbiphenyl, 4,4′-diamino-3,3′-dihydroxy-6,6′-trifluoromethylbiphenyl, 4,4′-diamino-3,3′-di Droxy-5,5′-trifluoromethylbiphenyl, 4,4′-diamino-3,3′-dihydroxy-5,5′-pentafluoroethylbiphenyl, 4,4′-diamino-3,3′-dihydroxy- 6,6′-pentafluoroethylbiphenyl, 3,3′-diamino-4,4′-dihydroxy-5,5′-pentafluoroethylbiphenyl, 3,3′-diamino-4,4′-dihydroxy-6 6'-pentafluoroethylbiphenyl, 3,4'-diamino-4,3'-dihydroxy-5,5'-trifluoromethylbiphenyl, 3,4'-diamino-4,3'-dihydroxy-5,5 ' -Pentafluoroethylbiphenyl, 3,4'-diamino-4,3'-dihydroxy-6,6'-trifluoromethylbiphenyl, 3,4'-diamino-4,3'-dihydroxy-6,6 ' Pentafluoroethylbiphenyl, 1,3-diamino-4,6-dihydroxydifluorobenzene, 1,4-diamino-3,6-dihydroxydifluorobenzene, 1,4-diamino-2,3-dihydroxydifluorobenzene, 1,2 -Diamino-3,6-dihydroxydifluorobenzene, 1-trifluoromethyl-2,4-diamino-3,5-dihydroxybenzene, 1-trifluoromethyl-2,5-diamino-3,6-dihydroxybenzene, 1 -Trifluoromethyl-2,4-diamino-3,5-dihydroxyfluorobenzene, 1-trifluoromethyl-2,5-diamino-3,6-dihydroxyfluorobenzene, 1,4-bis (trifluoromethyl)- 2,5-diamino-3,6-dihydroxybenzene, 1-pentaph Oroethyl-2,5-diamino-3,6-dihydroxybenzene, 1-perfluorocyclohexyl-2,5-diamino-3,6-dihydroxybenzene, 2,7-diamino-3,6-dihydroxytetrafluoronaphthalene, 2, , 6-Diamino-3,7-dihydroxytetrafluoronaphthalene, 1,6-diamino-2,5-dihydroxytetrafluoronaphthalene, 2,7-diamino-1,8-dihydroxytetrafluoronaphthalene, 1-trifluoromethyl- 3,6-diamino-2,7-dihydroxynaphthalene, 1,5-bis (trifluoromethyl) -3,7-diamino-2,6-dihydroxynaphthalene, 1-pentafluoroethyl-3,6-diamino-2 , 7-Dihydroxynaphthalene, 1-perfluorocyclohexyl- 3,6-diamino-2,7-dihydroxynaphthalene, 1,5-bis (trifluoromethyl) -3,7-diamino-2,6-dihydroxydifluoronaphthalene, 1,4,5,8-tetra (trifluoro Methyl) -2,5-diamino-3,6-dihydroxynaphthalene, 1,4-bis (3-amino-4-hydroxyphenyl) tetrafluorobenzene, 2,4-diamino-1,5-benzenediol, bis ( 3-amino-4-hydroxyphenyl) ketone, bis (3-amino-4-hydroxyphenyl) sulfide, bis (3-amino-4-hydroxyphenyl) ether, bis (3-hydroxy-4-aminophenyl) sulfone, Bis (3-hydroxy-4-aminophenyl) methane, bis (3-amino-4-hydroxyphenyl) diflu Aromatic bis-amino hydroxy compounds such Rometan like. These can be used alone or in combination of two or more.

[(B2) component]
As the component (B2), o-phthalic acid, terephthalic acid, 4,4′-dicarboxydiphenyl ether, benzophenone-4,4′-dicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 2,2′-biphenyl Dicarboxylic acid, 4,4'-dicarboxydiphenyl sulfone, 2,2'-bis (4-carboxyphenyl) propane, 2,2'-bis (4-carboxyphenyl) hexafluoropropane, 2,6-naphthalenedicarboxylic acid 1,5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, bis (4-carboxyphenyl) methane, 5,5'-dithiobis (2-nitrobenzoic acid), 1,10-bis (4-carboxyphenoxy) ) Decane, ethylene glycol bis (4-carboxyphenyl) ether, and combinations thereof Chloro compound of or ester thereof. These can be used alone or in combination of two or more.

  The polybenzoxazole precursor is a compound having a structure containing —CO—NH— and —OH or a derivative thereof (specifically, for example, —CO—NH— and —OR (however, , R is an alkyl group or the like), and is dehydrated by heating or the like to form a cyclic chemical structure (—O—C═N— (hereinafter also referred to as an oxazole ring structure). )) (Hereinafter, a structure containing —CO—NH— and —OH or —CO—NH— and —OR (where R is an alkyl group or the like). The structure is also called a hydroxyamide structure.)

<Polybenzothiazole>
When the heterocyclic ring-containing polymer is polybenzothiazole, the glass transition temperature (Tg) of the polybenzothiazole by differential scanning calorimetry (DSC, heating rate 20 ° C./min) is 230 to 420 ° C., preferably Is 240-400 degreeC, More preferably, it is 250-380 degreeC.

  A precursor capable of forming a polybenzothiazole having a glass transition temperature (Tg) of 230 to 420 ° C. by differential scanning calorimetry (DSC, heating rate 20 ° C./min) is, for example, bismercapto as the component (A). Obtained by reacting the amino compound (A3) with the component (B3) containing at least one compound selected from the group consisting of dicarboxylic acid, dicarboxylic acid chloride, dicarboxylic acid active ester and the like as the component (B). be able to. In general, polymercaptoamide, which is one of polybenzothiazole precursors, can be obtained by reacting a bismercaptoamino compound with a dicarboxylic acid, and polybenzothiazole is obtained by dehydrating cyclization by heating or the like. be able to.

[(A3) component]
Specific examples of the bismercaptoamino compound (A3) include 2,2′-bis (3-amino-4-mercaptophenyl) hexafluoropropane, 2,2′-bis (3-amino-4-mercapto5). -Trifluoromethylphenyl) hexafluoropropane, 2,2'-bis (4-amino-3-mercaptophenyl) hexafluoropropane, 2,2'-bis (3-amino-4-mercaptophenyl) propane, 2, 2′-bis (4-amino-3-mercaptophenyl) propane, 3,3′-diamino-4,4′-dimercaptodiphenyl sulfone, 4,4′-diamino-3,3′-dimercaptodiphenyl sulfone, 3,3′-diamino-4,4′-dimercaptobiphenyl, 4,4′-diamino-3,3′-dimercaptobiphenyl, 3,3′-diamino-4,4′- Mercaptodiphenyl ether, 4,4′-diamino-3,3′-dimercaptodiphenyl ether, 3,3′-diamino-4,4′-dimercapto 2,2′-trifluoromethylbiphenyl, 4,4′-diamino-3 , 3'-dimercapto 2,2'-trifluoromethylbiphenyl, 3,3'-diamino-4,4'-dimercapto 5,5'-trifluoromethylbiphenyl, 4,4'-diamino-3,3'- Dimercapto 5,5′-trifluoromethylbiphenyl, 3,3′-diamino-4,4′-dimercapto 6,6′-trifluoromethylbiphenyl, 4,4′-diamino-3,3′-dimercapto 6,6 '-Trifluoromethylbiphenyl, 4,4'-diamino-3,3'-dimercapto 5,5'-trifluoromethylbiphenyl, 4,4'-diamino-3,3'-di Lucapto 5,5′-pentafluoroethylbiphenyl, 4,4′-diamino-3,3′-dimercapto 6,6′-pentafluoroethylbiphenyl, 3,3′-diamino-4,4′-dimercapto 5,5 '-Pentafluoroethylbiphenyl, 3,3'-diamino-4,4'-dimercapto 6,6'-pentafluoroethylbiphenyl, 3,4'-diamino-4,3'-dimercapto 5,5'-trifluoro Methyl biphenyl, 3,4'-diamino-4,3'-dimercapto 5,5'-pentafluoroethylbiphenyl, 3,4'-diamino-4,3'-dimercapto 6,6'-trifluoromethylbiphenyl, 3, , 4′-diamino-4,3′-dimercapto 6,6′-pentafluoroethylbiphenyl, 1,3-diamino-4,6-dimercaptodifluorobenzene, 1, -Diamino-3,6-dimercaptodifluorobenzene, 1,4-diamino-2,3-dimercaptodifluorobenzene, 1,2-diamino-3,6-dimercaptodifluorobenzene, 1-trifluoromethyl-2, 4-diamino-3,5-dimercaptobenzene, 1-trifluoromethyl-2,5-diamino-3,6-dimercaptobenzene, 1-trifluoromethyl-2,4-diamino-3,5-dimercapto Fluorobenzene, 1-trifluoromethyl-2,5-diamino-3,6-dimercaptofluorobenzene, 1,4-bis (trifluoromethyl) -2,5-diamino-3,6-dimercaptobenzene, 1 -Pentafluoroethyl-2,5-diamino-3,6-dimercaptobenzene, 1-perfluorocyclohexyl-2 5-diamino-3,6-dimercaptobenzene, 2,7-diamino-3,6-dimercaptotetrafluoronaphthalene, 2,6-diamino-3,7-dimercaptotetrafluoronaphthalene, 1,6-diamino- 2,5-dimercaptotetrafluoronaphthalene, 2,7-diamino-1,8-dimercaptotetrafluoronaphthalene, 1-trifluoromethyl-3,6-diamino-2,7-dimercaptonaphthalene, 1,5- Bis (trifluoromethyl) -3,7-diamino-2,6-dimercaptonaphthalene, 1-pentafluoroethyl-3,6-diamino-2,7-dimercaptonaphthalene, 1-perfluorocyclohexyl-3, 6-Diamino-2,7-dimercaptonaphthalene, 1,5-bis (trifluoromethyl) -3,7-di Amino-2,6-dimercaptodifluoronaphthalene, 1,4,5,8-tetra (trifluoromethyl) -2,5-diamino-3,6-dimercaptonaphthalene, 1,4-bis (3-amino- 4-mercaptophenyl) tetrafluorobenzene, 2,4-diamino-1,5-benzenediol, bis (3-amino-4-mercaptophenyl) ketone, bis (3-amino-4-mercaptophenyl) sulfide, bis ( Such as 3-amino-4-mercaptophenyl) ether, bis (3-mercapto-4-aminophenyl) sulfone, bis (3-mercapto-4-aminophenyl) methane, bis (3-amino-4-mercaptophenyl) difluoromethane, etc. Aromatic bisaminomercapto compounds are mentioned. These can be used alone or in combination of two or more.

[(B3) component]
As said (B3) component, the compound similar to the compound quoted by said (B2) can be mentioned. In addition, these (B3) components can be used individually by 1 type or in mixture of 2 or more types.

  The polybenzothiazole precursor is a compound having a structure containing —CO—NH— and —SH, or a derivative thereof (specifically, for example, —CO—NH— and —SR (however, , R is an alkyl group or the like), and is dehydrated by heating or the like to form a cyclic chemical structure (—S—C═N— (hereinafter also referred to as a thiazole ring structure). )) (Hereinafter, a structure containing -CO-NH- and -SH or -CO-NH- and -SR (where R is an alkyl group or the like)). The structure is also referred to as a mercaptoamide structure.)

<Polybenzimidazole>
When the polymer is polybenzimidazole, the glass transition temperature (Tg) by differential scanning calorimetry (DSC, heating rate 20 ° C./min) of the polybenzimidazole is 230 to 420 ° C., preferably 240 to 400. ° C, more preferably 250-380 ° C.

  A precursor that can be a polybenzimidazole having a glass transition temperature (Tg) of 230 to 420 ° C. by differential scanning calorimetry (DSC, heating rate 20 ° C./min) is, for example, tetraamine (A4) as the component (A). And the component (B) can be obtained by reacting the component (B4) containing at least one compound selected from the group consisting of dicarboxylic acid, dicarboxylic acid chloride, dicarboxylic acid ester and the like. In general, polyaminoamide, which is one of the polybenzimidazole precursors, can be obtained by reacting an aromatic tetraamine compound with dicarboxylic acid, and polybenzimidazole can be obtained by dehydrating cyclization by heating or the like. Can do.

[(A4) component]
Specific examples of the tetraamine (A4) include 1,2,4,5-tetraaminobenzene, 1,2,5,6-tetraaminonaphthalene, 2,3,6,7-tetraaminonaphthalene, 3, 3 ', 4,4'-tetraaminodiphenylmethane, 3,3', 4,4'-tetraaminodiphenylethane, 3,3 ', 4,4'-tetraaminodiphenyl, 3,3 Mention may be made of aromatic tetraamines such as ', 4,4'-tetraaminodiphenylthioether and 3,3', 4,4'-tetraaminodiphenylsulfone. In addition, these (A4) components can be used individually by 1 type or in mixture of 2 or more types.

[(B4) component]
Examples of (B4) include the same compounds as those mentioned in (B2) above. In addition, these (B4) components can be used individually by 1 type or in mixture of 2 or more types.

The polybenzimidazole precursor is a compound having a structure containing —CO—NH— and —NH ₂ or a derivative thereof (specifically, for example, —CO—NH— and —NR _2). (Where R is an alkyl group or the like) and the like, and is dehydrated by heating or the like to form a cyclic chemical structure (—NH—C═N— (hereinafter also referred to as an imidazole ring structure). (Hereinafter, a structure containing —CO—NH— and —NH ₂ , or —CO—NH— and —NR ₂ (where R is an alkyl group or the like)). A structure including.) Is also referred to as an aminoamide structure.

[Composition for film formation]
The film-forming composition containing the precursor of the heterocyclic ring-containing polymer and the organic solvent has components (A) (components (A1) to (A4)) and components (B) ((B1) to (B4), respectively. It can be obtained by reacting the component) in an organic solvent. As a specific method for reacting the component (A) and the component (B), at least one component (B) is dissolved in an organic solvent, and then the resulting solution is mixed with at least one component (A). And the like, and a method of stirring at a temperature of 0 to 100 ° C. for 1 to 60 hours.

  Examples of the organic solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, N, N′-dimethylimidazolidinone, and tetramethyl. Aprotic polar solvents such as urea; phenolic solvents such as cresol, xylenol, and halogenated phenol; Among these, N, N′-dimethylimidazolidinone, γ-butyrolactone, N-methyl-2-pyrrolidone, and N, N-dimethylacetamide are preferable. Further, at least one organic solvent selected from N, N′-dimethylimidazolidinone, γ-butyrolactone, N-methyl-2-pyrrolidone, and N, N-dimethylacetamide is used as the total amount of organic solvent (100% by weight). On the other hand, it is preferable to contain 50% by weight or more, preferably 70 to 100% by weight.

  These solvents can be used alone or in combination of two or more.

  In addition, it is preferable that the total amount of (A) component and (B) component in a reaction liquid is 5-30 mass% of reaction liquid whole quantity.

  (A) component and (B) component are made to react so that molar ratio ((A) component / (B) component) of (A) component and (B) component may be 0.8-1.2. It is preferable to make it react so that it may become 0.95-1.0. When the molar ratio of the component (A) to the component (B) is less than 0.8 equivalent or more than 1.2 equivalent, the molecular weight may be low and it may be difficult to form a film (film).

  Further, the composition containing the obtained heterocyclic-containing precursor and the organic solvent can be used as it is as the film-forming composition, but the film-forming composition is obtained from the obtained heterocyclic-containing precursor. It can also be obtained by isolating the body as a solid and then re-dissolving it in an organic solvent. In addition, as an organic solvent which redissolves, the compound similar to the said organic solvent is mentioned. As a method for isolating a precursor of a heterocyclic ring-containing polymer, a solution containing a precursor of a heterocyclic ring-containing polymer and an organic solvent is used as a poor solution for a precursor of a heterocyclic ring-containing polymer such as methanol or isopropanol. Examples thereof include a method in which a polymer precursor is precipitated by being poured into a solvent, and each polymer precursor is separated as a solid component by filtration, washing, drying, or the like.

  The film-forming composition preferably has a viscosity (E-type viscometer, measured at 25 ° C.) of 5,000 to 50,000 cP, more preferably 7,500 to 30,000 cP. When the viscosity of the film-forming composition is in the above range, a composition having excellent coating properties can be obtained.

  In addition, after forming a coating film in a process (a), it is also possible to partially cyclize the precursor used before a process (b), such as imidation.

  By performing partial cyclization before the step (b), a substrate having more excellent heat resistance can be obtained.

  Examples of this method include a method using a dehydrating agent (chemical partial cyclization such as chemical imidation) and the like. Since partial cyclization can be performed by heating at a lower temperature, chemical imidization and other chemicals are possible. Partial cyclization is preferred.

  Examples of dehydrating agents that can be used for chemical partial cyclization such as chemical imidization include acid anhydrides such as acetic anhydride, propionic anhydride, and benzoic anhydride, or acid chlorides corresponding to these compounds, dicyclohexylcarbodiimide, etc. And carbodiimide compounds. In the case of chemical partial cyclization, it is preferable to heat at a temperature at which partial cyclization occurs, specifically at a temperature of 60 to 120 ° C.

  In the partial cyclization such as partial imidization, a base catalyst such as pyridine, isoquinoline, trimethylamine, triethylamine, N, N-dimethylaminopyridine, or imidazole can be used as necessary. The dehydrating agent or the base catalyst is preferably used in an amount of 0.1 to 8 moles per 1 mole of component (A).

  When partial cyclization such as partial imidization is performed, 100 mol% of a precursor structure such as an amic acid structure, a hydroxyamide structure, a mercaptoamide structure, and an aminoamide structure in the precursor of the heterocyclic ring-containing polymer. At least a part, preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and particularly preferably 20 to 50 mol% of the compound is partially cyclized by partial imidization.

  Examples of the support to which the film forming composition is applied include a silicon wafer and non-alkali glass. The alkali-free glass is a glass that does not contain an alkaline component such as potassium or sodium.

  Since such a support has high dimensional stability under heating conditions, there is little dimensional change even when heat is applied in the step (a) or the step (b). For this reason, the film (film) provided on the support also has less dimensional change, and the element can be easily formed at a desired position.

  Further, by using such a support, it is possible to prevent warping or twisting of the substrate after the support is removed. For this reason, it is preferable to form a film on such a support and further form an element.

  As a method for applying the film-forming composition onto the support, a roll coating method, a gravure coating method, a spin coating method, a method using a doctor blade, or the like can be used.

  Moreover, the process of drying the said coating material can be specifically performed by heating the said coating material. By heating the coating film, the organic solvent in the coating film can be evaporated and removed. The heating condition is not particularly limited as long as the organic solvent evaporates. For example, the heating condition is 60 to 250 ° C. for 1 to 5 hours. Heating may be performed in two stages. For example, after heating at 100 ° C. for 30 minutes, heating at 150 ° C. for 1 hour. Further, if necessary, drying may be performed under a nitrogen atmosphere or under reduced pressure.

  Although the thickness of a coating film is not specifically limited, For example, it is 1-250 micrometers, Preferably it is 2-150 micrometers, More preferably, it is 5-125 micrometers.

[Step (b)]
Next, the coating film obtained in step (a) is at a temperature 60 ° C. lower than the glass transition temperature of the heterocyclic ring-containing polymer to 20 ° C. higher than the glass transition temperature of the heterocyclic ring-containing polymer, preferably the glass transition temperature. The heterocyclic ring-containing polymer is cyclized by heating at a temperature 60 ° C. lower than the temperature to the glass transition temperature of the heterocyclic ring-containing polymer, preferably 160 to 420 ° C. The heating in the step (b) is desirably a temperature higher than the temperature at which the drying (evaporating the organic solvent) in the step (a) is performed by heating.

  Furthermore, when the cyclization step (b) is carried out near the glass transition temperature (Tg) (± 10 ° C.) of the heterocyclic ring-containing polymer, the resulting film or substrate has good adhesion to the support and peelability. This is preferable.

  In the present invention, when two or more kinds of precursors are used as the precursor of the heterocyclic ring-containing polymer, the heating temperature in the step (b) is the glass transition temperature of the polymer obtained from those precursors. Decide on the basis of the lowest temperature.

  In addition, when the precursor of the heterocyclic ring-containing polymer is a polyimide precursor, a polyimide film, and when the precursor of the heterocyclic ring-containing polymer is a polybenzoxazole precursor, a polybenzoxazole film, A polybenzothiazole film is obtained when the precursor of the heterocyclic ring-containing polymer is a polybenzothiazole precursor, and a polybenzimidazole film is obtained when the precursor of the heterocyclic ring-containing polymer is a polybenzimidazole precursor. .

  When the precursor of the heterocyclic ring-containing polymer is a polyamic acid, specifically, the obtained coating film is subjected to dehydration cyclization (imidization) by heat treatment at, for example, 160 ° C. to 420 ° C. (Thermal imidization). The temperature of thermal imidization is preferably 160 to 350 ° C from the viewpoint of peelability, preferably 200 to 350 ° C, preferably 230 to 270 ° C, and 240 to 250 ° C. Is more preferable. Further, the thermal imidization temperature is particularly preferably not higher than the glass transition temperature of the precursor used from the viewpoint of peelability.

  In the imidization, the ratio of the imide ring structure (hereinafter also referred to as the cyclization rate) is preferably 75 mol% or more, more preferably 85 mol% or more, in a total of 100 mol% of the amic acid structure and the imide ring structure. Particularly preferably, it is carried out so as to be 90 mol% or more. When the ratio of the imide ring structure is less than 75 mol%, the water absorption rate of the obtained polyimide film or substrate may be increased, or the durability may be lowered.

  The imide group concentration of the polyimide is preferably 2.5 to 3.7 mmol / g, and preferably 3.0 to 3.7 mmol / g, assuming that the imidization rate is 100 mol%. More preferably, it is 3.0-3.5 mmol / g.

  When the precursor of the heterocyclic ring-containing polymer is a polybenzoxazole precursor, specifically, the obtained coating film is subjected to dehydration cyclization by heat treatment at, for example, 160 ° C. to 420 ° C. The cyclization temperature is preferably 160 ° C. to 350 ° C., preferably 200 ° C. to 340 ° C., and more preferably 230 ° C. to 330 ° C. from the viewpoint of peelability. Furthermore, the cyclization temperature is particularly preferably not higher than the glass transition temperature of the polybenzoxazole precursor used from the viewpoint of peelability.

  In the cyclization of the polybenzoxazole precursor, the ratio of the oxazole ring structure (hereinafter also referred to as ring closure rate) is preferably 75 mol% or more, more preferably 85, out of the total 100 mol% of the hydroxyamide structure and the oxazole ring structure. It is carried out so as to be at least mol%, particularly preferably at least 90 mol%. When the proportion of the oxazole ring structure is less than 75 mol%, the water absorption rate of the obtained polybenzoxazole-based film or substrate may be increased or the durability may be decreased.

  When the polymer precursor is a polybenzothiazole precursor, specifically, the obtained coating film is subjected to dehydration cyclization by heat treatment at, for example, 160 ° C. to 420 ° C. The cyclization temperature is preferably 160 ° C. to 350 ° C., preferably 200 ° C. to 340 ° C., and more preferably 230 ° C. to 330 ° C. from the viewpoint of peelability. Furthermore, the cyclization temperature is particularly preferably not higher than the glass transition temperature of the polybenzothiazole precursor from the viewpoint of peelability.

  The cyclization of the polybenzothiazole precursor is carried out in such a manner that the ratio of the thiazole ring structure (hereinafter also referred to as the ring closure ratio) is 100 mol% in the total 100 mol% of the mercaptoamide structure and the thiazole ring structure. Preferably, it is carried out so as to be 75 mol% or more, more preferably 85 mol% or more, particularly preferably 90 mol% or more. When the ratio of the thiazole ring structure is less than 75 mol%, the water absorption rate of the obtained polybenzothiazole-based film or substrate may be increased or the durability may be decreased.

  When the polymer precursor is a polybenzimidazole precursor, specifically, the obtained coating film is subjected to dehydration cyclization by heat treatment at, for example, 160 ° C. to 420 ° C. The cyclization temperature is preferably 160 ° C. to 350 ° C., preferably 200 ° C. to 340 ° C., and more preferably 230 ° C. to 330 ° C. from the viewpoint of peelability. Furthermore, the cyclization temperature is particularly preferably not higher than the glass transition temperature of the polybenzimidazole precursor from the viewpoint of peelability.

  In the cyclization of the polybenzimidazole precursor, the ratio of the imidazole ring structure (hereinafter also referred to as the ring closure rate) in the total 100 mol% of the aminoamide structure and the imidazole ring structure is preferably 75 mol. % Or more, more preferably 85 mol% or more, particularly preferably 90 mol% or more. When the proportion of the imidazole ring structure is less than 75 mol%, the water absorption rate of the obtained polybenzimidazole film or substrate may be increased, or the durability may be lowered.

  In the present invention, the thickness of a film (film) such as a polyimide film is preferably 1 to 250 μm, more preferably 2 to 150 μm, and particularly preferably 10 to 125 μm.

[Step (c)]
Then, a board | substrate is manufactured by forming an element on the film | membrane (film) obtained by the said process (b). Examples of the element to be formed include light-emitting elements such as organic electroluminescence (EL) elements and thin film transistor (TFT) elements, modules such as metal wirings and semiconductor integrated circuits.

  When a light emitting element such as an organic EL element or a TFT element is formed on the film (film) obtained by the step (b), it can be used as a flexible display substrate or the like. When a module such as a circuit is formed, it can be used as a flexible wiring board.

  As a method for forming the TFT element, specifically, a gate electrode is provided by forming a film of metal, metal oxide or the like on the film by sputtering or the like and then etching. What is necessary is just to select suitably the temperature at the time of forming films | membranes, such as a metal and a metal oxide, by the sputtering method etc. according to the precursor to be used or the element to form, It is preferable that it is 210 to 400 degreeC, 220 to More preferably, it is 370 degreeC, and it is preferable that it is 230-350 degreeC. Next, a gate insulating film such as a silicon nitride film is formed on the film provided with the gate electrode by a plasma CVD method or the like. Further, an active layer made of an organic semiconductor or the like is formed on the gate insulating film by a plasma CVD method or the like. The temperature at which a film such as a gate insulating film or an organic semiconductor is formed by plasma CVD or the like may be appropriately selected according to the precursor to be used and the element to be formed, but is preferably 210 ° C to 400 ° C. It is more preferable that it is 220-370 degreeC, and it is preferable that it is 230-350 degreeC. Next, a source electrode and a drain electrode are provided by forming a film of metal, metal oxide, or the like on the active layer by sputtering or the like and then etching. Finally, a thin film transistor element can be manufactured by forming a silicon nitride film or the like by a plasma CVD method or the like as a protective film as necessary.

  Although the bottom gate type thin film transistor element has been described above, the thin film transistor element of the present invention is not limited to this structure, and may be a top gate type.

  The gate electrode, the source electrode, and the drain electrode are not particularly limited as long as they are formed of a conductive material, and examples thereof include metals and metal oxides.

Examples of metals include platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony lead, tantalum, indium, aluminum, zinc, magnesium, and alloys thereof, and examples of metal oxides , ITO, IZO, ZnO and In ₂ O ₃ . In addition, a conductive polymer may be used as the conductive material in consideration of adhesiveness with the film.

  Among these, it is preferable to use a metal oxide because a transparent electrode can be formed.

  Moreover, as a method of forming the organic EL element, for example, a method of forming an insulating layer, a first electrode, an organic semiconductor layer, a second electrode, and a protective layer on the film in order from the film surface side. It is done.

  Furthermore, as a method of forming the metal wiring, for example, a copper layer is provided on the film by a lamination method, a metalizing method, or the like, and the metal wiring can be provided by processing the copper layer by a known method. In the case of the laminating method, a copper layer can be provided by, for example, hot pressing a metal foil such as a copper foil on the film using a roll press machine or the like. In the case of the metalizing method, for example, a seed layer made of a Ni-based metal bonded to the film is formed by a vapor deposition method or a sputtering method. Then, a copper layer having a predetermined thickness can be provided by a wet plating method. In the case of using the metalizing method, it is possible to modify the surface of the film in advance in order to develop an affinity with the metal.

  Since the film (film) is excellent in heat resistance and excellent in adhesion to the support, a temperature range that can be applied when forming an element on the film (film) is wide, and a substrate having excellent performance can be obtained. .

[Step (d)]
Next, the substrate obtained in the step (c) is peeled from the support. Since the substrate obtained in the step (c) is excellent in releasability, the entire substrate can be easily peeled from the support.

  As a peeling method, a masking tape is previously applied to the edge of the substrate, the steps (a) to (c) are performed, and then the substrate is peeled off by peeling off the masking tape. Examples thereof include a method of making an incision at the end to make a starting point and peeling off, a method of peeling by immersing in a solvent such as water and alcohol, and the like. The temperature at the time of peeling is usually 0 to 100 ° C, preferably 10 to 70 ° C, more preferably 20 to 50 ° C.

Hereinafter, the present invention will be specifically described by way of examples.
(1) Glass transition temperature (Tg)
Using the films obtained in the following examples or comparative examples, the glass transition temperature of each heterocyclic ring-containing polymer was measured using a Rigaku 8230 type DSC measuring apparatus at a heating rate of 20 ° C./min.

(2) Viscosity The polyamic acid solution (composition) obtained in the following examples or comparative examples was measured at 25 ° C. using a RE-100 type viscosity measuring device manufactured by Toki Sangyo Co., Ltd.

(3) Thick film coatability [○] was given when there was no coating failure during coating with a spin coater, and [x] was given when the surface was rough or could not be applied over the entire surface.

(4) Peelability In the cyclization process (after drying at 250 ° C.), [◎] indicates that the entire surface can be peeled from the support, [○] indicates that the entire surface can be peeled and remains partially peeled [○], and partially peeled. Alternatively, [x] indicates that the entire surface cannot be peeled.

(5) Self-supporting In the cyclization step (after completion of drying at 250 ° C.), a film having no cracks and the like and having a self-supporting property was designated as “◯” and the others were designated as “X”.

(6) Film warp The film peeled off from the support is cut into 40 × 40 mm, the warp is less than 1.0 mm [［], the warp is 1.0 mm or more and less than 2.0 mm [◯], the warp is The thing of 2.0 mm or more was set as [x].

(7) Imido group concentration (theoretical value assuming that the imidization rate is 100 mol%)
Assuming that the imidization rate is 100 mol%, the molecular weight of the repeating unit in the obtained polymer is (molecular weight of (A) component) + (molecular weight of (B) component) −2 × (molecular weight of water) Is required. Since each of these repeating units contains two imide groups, the imide group concentration (theoretical value assuming that the imidization rate is 100 mol%) of the polymer obtained in the following Examples or Comparative Examples is Was determined by the following formula.
[Imide group concentration] (unit: mmol / g) = 2 / {(molecular weight of component (A)) + (molecular weight of component (B)) − 2 × (molecular weight of water)} × 1000
(8) Weight average molecular weight The weight average molecular weight of the polyamic acid or polybenzoxazole precursor obtained in the following examples or comparative examples was measured using an HLC-8020 GPC apparatus manufactured by TOSOH. As the solvent, N-methyl-2-pyrrolidone (NMP) to which lithium bromide and phosphoric acid were added was used, and the molecular weight in terms of polystyrene was determined at a measurement temperature of 40 ° C.

[Example 1]
A 2,2-bis [4- (4-aminophenoxy) phenyl] propane (hereinafter also referred to as “BAPP”) as a component (B) was added to a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube. .) 9.48 g (23.1 mmol) was added. Next, after the flask was purged with nitrogen, 58 ml of N, N-dimethylacetamide (hereinafter also referred to as “DMAc”) was added and stirred until uniform. In the obtained solution, as component (A), pyromellitic dianhydride (hereinafter also referred to as “PMDA”) 3.74 g (17.2 mmol) and 4,4 ”-oxydiphthalic dianhydride (hereinafter referred to as“ ODPA ”). 1.77 g (5.7 mmol) was added at room temperature (about 25 ° C.), and stirring was continued at that temperature for 24 hours to obtain a polyamic acid solution (composition).

  The viscosity of the obtained composition was measured. Moreover, the polyamic acid was isolated from this composition using a part of obtained composition. The weight average molecular weight of the isolated polyamic acid was evaluated. In addition, the weight average molecular weight was measured about the polyamic acid before imidation. The results are shown in Table 1.

  Next, the obtained polyamic acid solution was applied on an alkali-free glass support using a spin coater at an arbitrary rotation number and time (5 seconds at 300 rpm, then 10 seconds at 1000 rpm), and 30 minutes at 70 ° C. Subsequently, the coating film was obtained by drying at 120 degreeC for 30 minutes. Then, the coating film obtained as a cyclization (imidation) step was further dried at 250 ° C. for 2 hours, and then peeled off from the alkali-free glass support to obtain a film (film) having a thickness of 0.1 mm. . As a result of measuring IR (ATR method, FT-IR, 6700, manufactured by NICOLET) spectrum of the obtained film (film), it was confirmed that the amic acid structure disappeared and imidized.

  The evaluation results of the obtained film are shown in Table 1.

[Example 2]
As component (B), 9.29 g (22.5 mmol) of BAPP was used instead of 9.48 g of BAPP, and 2.93 g (13.4 mmol) of PMDA instead of 3.74 g of PMDA and 1.77 g of ODPA as component (A), and 2.78 g of ODPA A polyamic acid solution (composition) was obtained in the same manner as in Example 1 except that (9.0 mmol) was used. Next, a membrane (film) was obtained in the same manner as in Example 1 except that the obtained polyamic acid solution was applied at an arbitrary rotation speed and time so as to obtain a membrane (film) having a thickness of 0.1 mm. . As a result of measuring the IR spectrum of the obtained film (film) in the same manner as in Example 1, it was confirmed that the amic acid structure was lost and imidized. Table 1 shows the physical properties of the resulting composition, polymer, and membrane (film).

[Example 3]
As component (B), 9.33 g (22.7 mmol) of BAPP was used instead of 9.48 g of BAPP, and 2.91 g (13.4 mmol) of PMDA and 2.76 g of ODPA instead of 3.74 g of PMDA and 1.77 g of ODPA as component (A) ( 8.9 mmol) was used in the same manner as in Example 1 to obtain a polyamic acid solution (composition). Next, a membrane (film) was obtained in the same manner as in Example 1 except that the obtained polyamic acid solution was applied at an arbitrary rotation speed and time so as to obtain a membrane (film) having a thickness of 0.1 mm. . As a result of measuring the IR spectrum of the obtained film (film) in the same manner as in Example 1, it was confirmed that the amic acid structure was lost and imidized. Table 1 shows the physical properties of the resulting composition, polymer, and membrane (film).

[Example 4]
As component (B), 8.81 g (23.9 mmol) of 4,4′-bis (4-aminophenoxy) biphenyl (hereinafter also referred to as “BAPB”) is used instead of BAPP 9.48 g, and PMDA3 is used as component (A). A polyamic acid solution (composition) was obtained in the same manner as in Example 1 except that PMDA 2.56 g (11.7 mmol) and ODPA 3.64 g (11.7 mmol) were used instead of .74 g and ODPA 1.77 g. . Next, a membrane (film) was obtained in the same manner as in Example 1 except that the obtained polyamic acid solution was applied at an arbitrary rotation speed and time so as to obtain a membrane (film) having a thickness of 0.1 mm. . As a result of measuring the IR spectrum of the obtained film (film) in the same manner as in Example 1, it was confirmed that the amic acid structure was lost and imidized. Table 1 shows the physical properties of the resulting composition, polymer, and membrane (film).

[Example 5]
As component (B), 9.40 g (22.9 mmol) of BAPP was used instead of 9.48 g of BAPP, and 2.73 g (13.2 mmol) of PMDA and 1.07 g of ODPA instead of 3.74 g of PMDA and 1.77 g of ODPA as component (A) ( 8.8 mmol) was used in the same manner as in Example 1 to obtain a polyamic acid solution (composition). Next, a membrane (film) was obtained in the same manner as in Example 1 except that the obtained polyamic acid solution was applied at an arbitrary rotation speed and time so as to obtain a membrane (film) having a thickness of 0.1 mm. . As a result of measuring the IR spectrum of the obtained film (film) in the same manner as in Example 1, it was confirmed that the amic acid structure was lost and imidized. Table 1 shows the physical properties of the resulting composition, polymer, and membrane (film).

[Example 6]
As component (B), BAPB 8.94 g (24.3 mmol) was used instead of BAPP 9.48 g, and as component (A), PMDA 3.11 g (14.3 mmol) and ODPA 2.95 g instead of PMDA 3.74 g and ODPA 1.77 g ( A polyamic acid solution (composition) was obtained in the same manner as in Example 1 except that 9.5 mmol) was used. Next, a membrane (film) was obtained in the same manner as in Example 1 except that the obtained polyamic acid solution was applied at an arbitrary rotation speed and time so as to obtain a membrane (film) having a thickness of 0.1 mm. . As a result of measuring the IR spectrum of the obtained film (film) in the same manner as in Example 1, it was confirmed that the amic acid structure was lost and imidized. Table 1 shows the physical properties of the resulting composition, polymer, and membrane (film).

[Example 7]
BPP 9.16 g (22.3 mmol) was used instead of BAPP 9.48 g as component (B), PMDA 2.41 g (11.0 mmol) and ODPA 3.43 g instead of PMDA 3.74 g and ODPA 1.77 g as component (A) ( 11.0 mmol) was used in the same manner as in Example 1 to obtain a polyamic acid solution (composition). Next, a membrane (film) was obtained in the same manner as in Example 1 except that the obtained polyamic acid solution was applied at an arbitrary rotation speed and time so as to obtain a membrane (film) having a thickness of 0.1 mm. . As a result of measuring the IR spectrum of the obtained film (film) in the same manner as in Example 1, it was confirmed that the amic acid structure was lost and imidized. Table 1 shows the physical properties of the resulting composition, polymer, and membrane (film).

[Example 8]
BPP 9.658 g (23.5 mmol) was used instead of BAPP 9.48 g as component (B), PMDA 4.27 g (19.6 mmol) and ODPA 1.07 g (PM) instead of PMDA 3.74 g and ODPA 1.77 g as component (A) A polyamic acid solution (composition) was obtained in the same manner as in Example 1 except that 3.5 mmol) was used. Next, a membrane (film) was obtained in the same manner as in Example 1 except that the obtained polyamic acid solution was applied at an arbitrary rotation speed and time so as to obtain a membrane (film) having a thickness of 0.1 mm. . As a result of measuring the IR spectrum of the obtained film (film) in the same manner as in Example 1, it was confirmed that the amic acid structure was lost and imidized. Table 1 shows the physical properties of the resulting composition, polymer, and membrane (film).

[Example 9]
To a 300 mL four-necked flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube, 6.41 g (29.1 mmol) of 4,4 "-diamino-3,3" -dihydroxybiphenyl was added. Next, the atmosphere in the flask was replaced with nitrogen, and then 58 ml of DMAc was added and stirred until uniform. To the resulting solution, 8.58 g (29.7 mmol) of diphenyl ether 4,4 "-dicarbonyl chloride and 5.86 g of triethylamine were added at room temperature (about 25 ° C.), and stirring was continued at that temperature for 24 hours. An oxazole precursor solution was obtained, and the resulting solution was filtered to remove the precipitated triethylamine hydrochloride, and then poured into 1000 ml of distilled water for reprecipitation, and the resulting precipitate was vacuum-dried at 80 ° C. for 12 hours. As a result, a light yellow solid polybenzoxazole precursor was obtained.

  The obtained pale yellow solid was dissolved in DMAc to obtain a 20% solution (composition). A coating film was formed on a non-alkali glass support in the same manner as in Example 1 except that the composition was used for coating at an arbitrary rotation speed and time so as to obtain a film having a thickness of 0.1 mm. . As a cyclization step, a film (film) having a thickness of 0.1 mm was obtained by the same operation as in Example 1 except that the obtained coating film was heated at 300 ° C. for 2 hours. As a result of measuring the IR spectrum of the obtained film (film) in the same manner as in Example 1, it was confirmed that the hydroxyamide structure disappeared and was cyclized. Table 1 shows the physical properties of the resulting composition, polymer, and membrane (film).

[Comparative Example 1]
BPP 9.83 g (23.9 mmol) was used instead of BAPP 9.48 g as component (B), PMDA 5.17 g (23.7 mmol) was used instead of PMDA 3.74 g and ODPA 1.77 g as component (A) In the same manner as in Example 1, a polyamic acid solution (composition) was obtained. Next, the same procedure as in Example 1 was performed except that the obtained polyamic acid solution was applied at an arbitrary rotation speed and time so as to obtain a 0.1 mm thick film (film). A membrane was obtained. Table 1 shows the physical properties of the resulting composition, polymer, and membrane (film).

[Comparative Example 2]
(B) 8.58 g (20.9 mmol) of BAPP was used instead of 9.48 g of BAPP as component, and 6.42 g (20.7 mmol) of ODPA was used instead of 3.74 g of PMDA and 1.77 g of ODPA as component (A). In the same manner as in Example 1, a polyamic acid solution (composition) was obtained. Next, a membrane (film) was obtained in the same manner as in Example 1 except that the obtained polyamic acid solution was applied at an arbitrary rotation speed and time so as to obtain a membrane (film) having a thickness of 0.1 mm. . Table 1 shows the physical properties of the resulting composition, polymer, and membrane (film).

[Comparative Example 3]
As component (B), 7.29 g (36.4 mmol) of 4,4′-diaminodiphenyl ether (hereinafter also referred to as “ODA”) was used instead of 9.48 g of BAPP, and 3.74 g of PMDA and 1.77 g of ODPA were used as component (A). A polyamic acid solution (composition) was obtained in the same manner as in Example 1 except that 7.71 g (35.3 mmol) of PMDA was used instead of. Next, a membrane (film) was obtained in the same manner as in Example 1 except that the obtained polyamic acid solution was applied at an arbitrary rotation speed and time so as to obtain a membrane (film) having a thickness of 0.1 mm. . Table 1 shows the physical properties of the resulting composition, polymer, and membrane (film).

[Example 10]
The polyamic acid solution (composition) prepared in Example 1 was cast and applied by a spin coater so that the thickness of the coating film obtained on the alkali-free glass support was 25 μm, and 30 minutes at 70 ° C. Subsequently, it dried at 120 degreeC for 30 minutes, and obtained the coating film. Then, the coating film obtained as a cyclization (imidation) step was further dried at 250 ° C. for 2 hours. Next, the rolled copper foil (film thickness: 18 μm) having the same width as the obtained coating film is laminated so that the roughened surface is in contact with the obtained coating film, and using a roll press machine at a pressure of 5 MPa, 250 ° C., 20 ° C. A copper foil was provided as an element by thermocompression bonding for a minute. Thereafter, the polyimide film provided with the copper foil was peeled from the alkali-free glass support to obtain a flexible substrate. The flexible substrate could be peeled from the entire surface of the support, and no warping was observed.

Claims (8)

(A) applying to a support a film-forming composition containing a precursor of a heterocyclic ring-containing polymer and an organic solvent and drying to form a coating film;
(B) The coating film is heated at a temperature 60 ° C. lower than the glass transition temperature of the heterocyclic ring-containing polymer to 20 ° C. higher than the glass transition temperature of the heterocyclic ring-containing polymer, and the precursor of the heterocyclic ring-containing polymer is heated. A cyclization step for cyclization;
(C) forming a device on the film obtained by the cyclization step;
(D) peeling the film on which the element is formed from the support;
Including
Glass transition temperature (DSC, temperature increase rate 20 ° C./min) of at least one differential scanning calorimetry (DSC selected from the group consisting of polyimide, polybenzoxazole, polybenzothiazole and polybenzimidazole). Tg) is a polymer in the range of 230 to 420 ° C.   The method for producing a substrate according to claim 1, wherein the cyclization step (b) is performed at a temperature that is 60 ° C. lower than the glass transition temperature of the heterocyclic ring-containing polymer to the glass transition temperature of the heterocyclic ring-containing polymer.   The manufacturing method of the board | substrate of Claim 1 or 2 which performs the said cyclization process (b) at 160 to 420 degreeC.   The manufacturing method of the board | substrate of any one of Claims 1-3 whose said support body is a silicon wafer or an alkali free glass.   The manufacturing method of the board | substrate of any one of Claims 1-4 whose said heterocyclic containing polymer is a polyimide.   The organic solvent includes at least one solvent selected from N, N′-dimethylimidazolidinone, γ-butyrolactone, N-methyl-2-pyrrolidone, and N, N-dimethylacetamide. 6. The method for producing a flexible substrate according to any one of 5 above.   The manufacturing method of the board | substrate of any one of Claims 1-6 whose viscosity (E-type viscosity meter, 25 degreeC measurement) of the said film formation composition is 5,000-50,000 cP. It is the composition for film formation used for the manufacturing method of the board | substrate of any one of Claims 1-7,
Containing a precursor of a heterocyclic ring-containing polymer and an organic solvent,
Glass transition temperature (DSC, temperature increase rate 20 ° C./min) of glass transition temperature (DSC, at least one selected from the group consisting of polyimide, polybenzoxazole, polybenzothiazole, polybenzimidazole) A film-forming composition, which is a polymer having a Tg) in the range of 230 to 420 ° C.