KR20160065806A - Heat-resistant resin film and method for menufacturing same, heating furnace and process for producing image display device - Google Patents

Abstract

The present invention relates to a heat resistant resin film having an outgass of 0.01 to 4 占 퐂 / cm < 2 > generated during heating at 450 占 폚 for 30 minutes under a stream of helium. The method for producing a heat-resistant resin film according to any one of claims 1 to 3, wherein the step of heating in a multi-step comprises (A) an oxygen concentration of 10 vol% (B) a second heating step of heating at a temperature higher than the first heating step in an atmosphere having an oxygen concentration of not more than 3% by volume in the above-described order Resistant resin film.

Description

TECHNICAL FIELD [0001] The present invention relates to a heat-resistant resin film, a method of manufacturing the same, a heating furnace, and a manufacturing method of an image display device.

The present invention relates to a heat-resistant resin film, a method of manufacturing the same, a heating furnace, and a method of manufacturing an image display device.

BACKGROUND ART Heat-resistant resins such as polyimide, polybenzoxazole, polybenzothiazole, and polybenzimidazole have been used in various fields including semiconductor applications due to their excellent electrical insulation, heat resistance, and mechanical properties. In recent years, application to substrates of image display apparatuses such as organic EL displays, electronic paper, and color filters has been expanded, and a flexible image display apparatus which is resistant to impact can be manufactured.

In order to use the heat-resistant resin as a substrate of an image display device, gas permeability such as oxygen or water vapor is high, and a gas barrier film such as a silicon nitride film is usually used. Although the method of forming this gas barrier film is variously studied, a vacuum process such as plasma chemical vapor deposition (PECVD) is often used. Therefore, it is preferable that the out gas from the heat resistant resin is minimized so that the film formation in the vacuum process is not defective.

Heat-resistant resins are generally insoluble in solvents and often are thermally insoluble, so that there is a difficulty in direct molding processing. Therefore, in forming the heat resistant resin film, it is common practice to apply a solution containing a precursor of a heat resistant resin (hereinafter referred to as varnish) to a support and convert the solution into a heat resistant resin film by heating. For example, in the case of polyimide, a polyimide film can be obtained by applying a solution containing a polyamic acid as a precursor on a support and heating at a temperature of 180 to 600 占 폚. As the heating method, there is a case where heating is performed in one step, and there is also a case where heating is performed in multiple steps. For example, in Patent Document 1, a method of heating in multiple stages has been reported.

Japanese Patent Application Laid-Open No. 2000-248077

In order to improve the mechanical properties of the heat-resistant resin film, it is often effective to increase the heating temperature within a range not exceeding the thermal decomposition temperature of the heat-resistant resin. However, when the heating temperature is raised in the atmosphere, oxygen molecules in the atmosphere cause oxidation of the resin and decomposition thereof, so that it is difficult to obtain good mechanical properties. For this reason, it is usually recommended to perform heating in an inert gas atmosphere such as nitrogen or argon, or in a vacuum atmosphere.

However, when heated in an inert atmosphere, outgas components are likely to remain in the heat-resistant resin film, making it difficult to reduce the out gas of the heat-resistant resin film. In addition, when heating in an inert atmosphere, the cost (power, gas) is required compared with the case of heating in air. Further, it takes time to replace the heating atmosphere with the inert gas or vacuum from the atmosphere before heating, and the productivity of the heat resistant resin film deteriorates.

An object of the present invention is to solve the above problems. That is, it is an object of the present invention to provide a heat-resistant resin film having a small out-gas and high mechanical properties. A further object of the present invention is to provide a method for producing a heat resistant resin film which does not deteriorate the mechanical characteristics of the heat resistant resin film and reduces the out gas even if the step of heating in an inert atmosphere is shortened.

One of the features of the present invention is a heat resistant resin film having an outgas of 0.01 to 4 占 퐂 / cm2 generated during heating at 450 占 폚 for 30 minutes under a current of helium.

Another feature of the present invention resides in a method of manufacturing a heat resistant resin film including a step of applying a solution containing a precursor of a heat resistant resin on a support and a step of heating in multiple steps, A) a first heating step of heating at a temperature higher than 200 ° C in an atmosphere of oxygen concentration of 10% by volume or more; (B) a second heating step of heating the substrate at a temperature higher than the first heating step And a heating step in the above-mentioned order.

According to another aspect of the present invention, there is provided an apparatus for measuring a temperature of a furnace, comprising: a temperature measuring unit for measuring a temperature in the furnace; a temperature adjusting unit for adjusting a temperature in the furnace; an oxygen concentration measuring unit for measuring an oxygen concentration in the furnace; A gas flow rate regulator for regulating the flow rate of the atmospheric gas; and a control unit for controlling the temperature regulator and the gas flow rate regulator, wherein the control unit controls the gas concentration regulator according to the oxygen concentration in the furnace, And controls the temperature adjusting unit so that the temperature in the furnace measured by the temperature measuring unit becomes a predetermined temperature after the oxygen concentration reaches a predetermined oxygen concentration.

(Effects of the Invention)

According to the present invention, it is possible to provide a heat resistant resin film having a low outgass and high mechanical properties.

1 is a schematic view of a heating furnace 1;

≪ Heat resistant resin film &

One of the features of the present invention is a heat resistant resin film having an outgas of 0.01 to 4 占 퐂 / cm2 generated during heating at 450 占 폚 for 30 minutes under a current of helium. The outgas generated during heating at 450 DEG C for 30 minutes under the above-mentioned helium air flow can be obtained by measuring under the following apparatus and conditions.

Measurement apparatus: "Small-4" (manufactured by Toray Research Center, Ltd.), GC / MS "QP5050A (7)" (manufactured by Shimadzu Seisakusho Co., Ltd.)

Heating conditions: The temperature was raised from room temperature to 10 占 폚 / min, maintained at 450 占 폚 for 30 minutes

Measurement atmosphere: Helium flow (50 mL / min).

The heat-resistant resin film of the present invention is required to have an outgas of 0.01 to 4 mu g / cm < 2 > measured during the time of reaching 450 DEG C and holding for 30 minutes by the above method. When the concentration is 4 占 퐂 / cm2 or less, it is less likely to cause poor film formation in a vacuum process such as plasma chemical vapor deposition (PECVD). More preferably 2 μg / cm 2 or less, and further preferably 1 μg / cm 2.

On the other hand, when the heat-resistant resin film formed on the glass substrate is peeled off from the glass substrate by using a laser, the outgas generated from the heat-resistant resin film sticks to the interface with the glass, thereby facilitating peeling. For this reason, it is necessary that the out gas of the heat-resistant resin film is 0.01 占 퐂 / cm2 or more. More preferably not less than 0.02 占 퐂 / cm2, and even more preferably not less than 0.04 占 퐂 / cm2.

The heat resistant resin film of the present invention preferably has a maximum tensile stress of 200 MPa or more. The maximum tensile stress referred to herein can be obtained by measuring in accordance with Japanese Industrial Standard (JIS K 7127: 1999) under the following apparatuses and conditions.

Measuring apparatus: Tensilon universal material tester "RTM-100" (manufactured by Orientech Co., Ltd.)

Measured sample shape: Ribbon shape

Measurement sample dimensions: length> 70 mm, width 10 mm

Tensile speed: 50 mm / min

Distance between chucks at start of test: 50 mm

Experiment temperature: 0 ~ 35 ℃

Number of samples: 10

Calculation method of measurement result: Arithmetic mean value of measurement values of 10 samples

When the maximum tensile stress is 200 MPa or more, appropriate mechanical properties are obtained as substrates for image display devices such as organic EL displays, electronic paper, and color filters. More preferably, it is 250 MPa or more. More preferably 800 MPa or less, and further preferably 600 MPa or less. If it is 800 MPa or less, flexibility as a flexible substrate is obtained.

≪ Heat resistant resin &

The heat-resistant resin in the present invention refers to a resin which does not have a melting point or a decomposition temperature at 300 占 폚 or lower and is a polyimide, polybenzoxazole, polybenzothiazole, polybenzimidazole, polyamide, polyether sulfone, poly Ether ether ketone, and the like. Among them, the heat-resistant resin preferably usable in the present invention is polyimide, polybenzoxazole, polybenzimidazole, polybenzothiazole, and more preferably polyimide. When the heat-resistant resin is a polyimide, the heat resistance (out gas characteristics, glass transition temperature, etc.) to the temperature of the production process and the mechanical characteristics suitable for imparting toughness to the image display device after the production of the image display device using the heat resistant resin film Lt; / RTI >

The polyimide is a resin having a structure represented by the formula (1).

In the formula (1), X represents a tetravalent tetracarboxylic acid residue having at least 2 carbon atoms, and Y represents a bivalent diamine residue having 2 or more carbon atoms. m represents a positive integer.

X is preferably a tetravalent hydrocarbon group having 2 to 80 carbon atoms. X may be a tetravalent organic group of 2 to 80 carbon atoms containing hydrogen and carbon as essential components and containing at least one atom selected from boron, oxygen, sulfur, nitrogen, phosphorus, silicon and halogen. Each atom of boron, oxygen, sulfur, nitrogen, phosphorus, silicon and halogen is independently preferably in the range of 20 or less, and more preferably in the range of 10 or less.

Examples of the tetracarboxylic acid to which X is given include the following. Examples of the aromatic tetracarboxylic acid include monocyclic aromatic tetracarboxylic acid compounds such as pyromellitic acid and 2,3,5,6-pyridine tetracarboxylic acid;

Various isomers of biphenyltetracarboxylic acid such as 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyltetracarboxylic acid, 2,2 ', 3,3'-biphenyltetracarboxylic acid, 3,3', 4,4'-benzophenonetetracarboxylic acid, 2,2 ', 3,3'-benzophenonetetracarboxylic acid and the like;

Bis (3,4-dicarboxyphenyl) hexafluoropropane, 2,2-bis (2,3-dicarboxyphenyl) hexafluoropropane, 2 Bis (3,4-dicarboxyphenyl) propane, 2,2-bis (2,3-dicarboxyphenyl) propane, 1,1- Bis (2,3-dicarboxyphenyl) methane, bis (2,3-dicarboxyphenyl) ethane, bis (3,4-dicarboxyphenyl) ether and the like;

Bis (dicarboxyphenoxyphenol) compounds such as 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] hexafluoropropane, 2,2-bis [4- Dicarboxyphenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane, 2,2- Phenyl] propane, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] sulfone, 2,2-bis [4- Etc;

Naphthalene or various isomers of condensed polycyclic aromatic tetracarboxylic acids such as 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6, 7-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid and the like; (Trimellitic acid monoester anhydride) compounds such as p-phenylene bis (trimellitic acid monoester acid anhydride), p-biphenylene bis (trimellitic acid monoester acid anhydride), ethylene bis Mellitic acid monoester acid anhydride), and bisphenol A bis (trimellitic acid monoester acid anhydride).

Examples of the aliphatic tetracarboxylic acid include chain aliphatic tetracarboxylic acid compounds such as butanetetracarboxylic acid;

Alicyclic tetracarboxylic acid compounds such as cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, bicyclo [2.2.1.] Heptane tetracarboxylic acid, bicyclo [3.3.1.] Tetracarboxylic acid, bicyclo [3.1.1.] Hepto-2-enetracarboxylic acid, bicyclo [2.2.2. ] Octane tetracarboxylic acid, and adamantanetetracarboxylic acid.

These tetracarboxylic acids can be used as such or in the form of acid anhydrides, active esters, and active amides. Two or more of these may be used.

In applications where heat resistance is required, it is preferable to use an aromatic tetracarboxylic acid in an amount of 50 mol% or more of the entire tetracarboxylic acid. Among them, it is preferable that X is a tetravalent tetracarboxylic acid residue represented by the formula (2) or (3) as a main component.

That is, it is preferable to use pyromellitic acid or 3,3 ', 4,4'-biphenyltetracarboxylic acid as a main component. In the present invention, the main component is used in an amount of 50 mol% or more of the entire tetracarboxylic acid. More preferably, it is used in an amount of 80 mol% or more. The polyamic acid obtained from these tetracarboxylic acids has little deterioration even when heated in the air. Therefore, in the method for producing a heat resistant resin film, which is one of the features of the present invention, (A) the first heating step of heating at a temperature higher than 200 캜 in an atmosphere of 10% You can do it in.

Further, by using a silicon-containing tetracarboxylic acid such as dimethylsilanediphthalic acid and 1,3-bis (phthalic acid) tetramethyldisiloxane, it is possible to improve adhesion to a support, resistance to oxygen plasma used for cleaning, . These silicon-containing tetracarboxylic acids are preferably used in an amount of 1 to 30 mol% based on the total amount of the tetracarboxylic acid.

The tetracarboxylic acid exemplified above is a tetracarboxylic acid in which a part of the hydrogen contained in the residue of the tetracarboxylic acid is a fluoroalkyl group having 1 to 10 carbon atoms such as a hydrocarbon group having 1 to 10 carbon atoms such as a methyl group or an ethyl group or a trifluoromethyl group, , Cl, Br, I, or the like. Further, when it is substituted with an acidic group such as OH, COOH, SO ₃ H, CONH ₂ , or SO ₂ NH ₂ , the solubility of the resin in an aqueous alkali solution is improved, and therefore it is preferable when it is used as a photosensitive resin composition described below.

Y is preferably a divalent hydrocarbon group having 2 to 80 carbon atoms. Y may be a divalent organic group of 2 to 80 carbon atoms containing hydrogen and carbon as essential components and containing at least one atom selected from boron, oxygen, sulfur, nitrogen, phosphorus, silicon and halogen. Each atom of boron, oxygen, sulfur, nitrogen, phosphorus, silicon and halogen is independently preferably in the range of 20 or less, more preferably 10 or less.

Examples of the diamine to which Y is given include the following. As the diamine compound containing an aromatic ring, monocyclic aromatic diamine compounds such as m-phenylenediamine, p-phenylenediamine, 3,5-diaminobenzoic acid and the like;

Naphthalene or condensed polycyclic aromatic diamine compounds such as 1,5-naphthalene diamine, 2,6-naphthalene diamine, 9,10-anthracene diamine, 2,7-diaminofluorene and the like;

Bis (diaminophenyl) compounds or various derivatives thereof such as 4,4'-diaminobenzanilide, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3- Carboxy-4,4'-diaminodiphenyl ether, 3-sulfonic acid-4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'- Diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 4-aminobenzoic acid 4-aminophenyl ester, 9,9-bis (4-aminophenyl) fluorene, 1,3-bis (4-anilino) tetramethyldisiloxane and the like;

4,4'-diaminobiphenyl or various derivatives thereof such as 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-di Ethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2 , 3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3 ', 4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-di Trifluoromethyl) -4,4'-diaminobiphenyl and the like;

Bis (4-aminophenoxy) sulfone, bis (4-aminophenoxy) biphenyl, bis [4- (4 (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- Benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene and the like;

Bis (3-amino-4-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) Amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methylene, bis ) Biphenyl, 9,9-bis (3-amino-4-hydroxyphenyl) fluorene and the like;

Bis (aminobenzoyl) compounds such as 2,2'-bis [N- (3-aminobenzoyl) -3-amino-4-hydroxyphenyl] hexafluoropropane, 2,2'-bis [N- (3-aminobenzoyl) -3-amino-4-hydroxyphenyl] propane, 2,2'-bis [N- (3-aminobenzoyl) -3-amino-4-hydroxyphenyl] sulfone, bis [N- , Bis [N- (4-aminobenzoyl) -3-amino-4-hydroxyphenyl] sulfone, 9,9- (3-aminobenzoyl) -3-amino-4-hydroxyphenyl] fluorene, N, N'-bis N, N'-bis (3-aminobenzoyl) -2,5-diamino-1,4-dihydroxybenzene, N, N'- -4,4'-diamino-3,3-dihydroxybiphenyl, N, N'-bis (4-aminobenzoyl) -4,4 ' Diamino-3,3-dihydroxybiphenyl, N, N'-bis (3-aminobenzoyl) -3,3'-diamino- Bis (4-aminobenzoyl) -3,3'-diamino-4,4-dihydroxybiphenyl and the like;

(4-aminophenyl) -5-aminobenzoxazole, 2- (3-aminophenyl) -5-aminobenzoxazole, 2- Aminobenzooxazole, 1,4-bis (5-amino-2-benzoxazolyl) benzene, 1,4-bis Benzooxazolyl) benzene, 1,3-bis (5-amino-2-benzoxazolyl) benzene, 1,3- (3-aminophenyl) -5-benzooxazolyl] hexafluoro (2,2-bis (4-aminophenyl) benzobisoxazole, 2,6- Propane, bis [(3-aminophenyl) -5-benzoxazolyl], bis [(4-aminophenyl) -5-benzoxazolyl] hexafluoropropane, ) -5-benzoxazolyl], bis [(3-aminophenyl) -6-benzoxazolyl], bis [(4-aminophenyl) -6-benzoxazolyl] and the like;

Or a compound obtained by substituting a part of hydrogen bonded to aromatic rings contained in these diamine compounds with hydrocarbons or halogens.

Examples of the aliphatic diamine compounds include linear diamine compounds such as ethylenediamine, propylenediamine, butanediamine, pentanediamine, hexanediamine, octanediamine, nonanediamine, decanediamine, undecanediamine, dodecanediamine, tetramethylhexanediamine, 1,12- (4,9-dioxa) dodecanediamine, 1,8- (3,6-dioxa) octanediamine, 1,3-bis (3-aminopropyl) tetramethyldisiloxane and the like;

Alicyclic diamine compounds such as cyclohexanediamine, 4,4'-methylenebis (cyclohexylamine), isophoronediamine and the like;

Polyoxyethylene amines, polyoxypropylene amines, and their copolymer compounds known as Zephamine (trade name, manufactured by Huntsman Corporation).

These diamines can be used as such or as the corresponding trimethylsilylated diamines. Two or more of these may be used.

In applications where heat resistance is required, it is preferable to use an aromatic diamine compound in an amount of 50 mol% or more of the entire diamine compound. Among them, it is preferable that Y is a bivalent diamine residue represented by the formula (4) as a main component.

That is, it is preferable to use p-phenylenediamine as a main component. In the present invention, the main component is to use at least 50 mol% of the entire diamine compound. More preferably, it is used in an amount of 80 mol% or more. Polyamide acid obtained by using p-phenylenediamine has little deterioration even when heated in the air. Therefore, in the method for producing a heat resistant resin film, which is one of the features of the present invention, (A) the first heating step of heating at a temperature higher than 200 캜 in an atmosphere of 10% You can do it in.

Particularly preferred are those wherein a tetravalent tetracarboxylic acid residue represented by the formula (2) or (3) is the main component of X in the formula (1) and Y is a bivalent diamine residue represented by the formula (4) . The polyamic acid which guides the polyimide of such a structure is particularly poor in deterioration even when heated in the air. Therefore, in the method for producing a heat resistant resin film, which is one of the features of the present invention, (A) the first heating step of heating at a temperature higher than 200 캜 in an atmosphere of 10% The maximum tensile stress of the obtained heat-resistant resin film can be maintained at a high level.

Further, by using a silicon-containing diamine such as 1,3-bis (3-aminopropyl) tetramethyldisiloxane or 1,3-bis (4-anilino) tetramethyldisiloxane as the diamine component, , Resistance to oxygen plasma and UV ozone treatment used for cleaning can be enhanced. These silicon-containing diamine compounds are preferably used in an amount of 1 to 30 mol% based on the total amount of the diamine compound.

The diamine compound exemplified above is a diamine compound in which part of the hydrogen contained in the diamine compound is a fluoroalkyl group having 1 to 10 carbon atoms such as a hydrocarbon group having 1 to 10 carbon atoms such as a methyl group or an ethyl group or a trifluoromethyl group or a fluoroalkyl group having F, Or the like. If also be substituted with acid, such as OH, COOH, SO ₃ H, CONH _2, SO ₂ NH ₂ since the enhanced solubility in an alkaline aqueous solution of a resin, it is preferred when used as a photosensitive resin composition which will be described later.

The weight average molecular weight of the precursor of the heat resistant resin in the present invention is preferably adjusted to 100,000 or less, more preferably 80,000 or less, and further preferably 50,000 or less in terms of polystyrene using gel permeation chromatography Do. Within this range, it is possible to further suppress the increase of the viscosity even at a high concentration of varnish. The weight average molecular weight is preferably 2000 or more, more preferably 3000 or more, and still more preferably 5000 or more. When the weight-average molecular weight is 2000 or more, the viscosity when the varnish is used does not deteriorate excessively, and better applicability can be maintained.

M in the formula (1) represents the number of repetitions of the polyimide unit and may be within a range that satisfies the weight average molecular weight of the heat-resistant resin in the present invention. m is preferably 5 or more, more preferably 10 or more. Further, it is preferably 500 or less, and more preferably 200 or less.

The precursor of the heat-resistant resin in the present invention can also be used as a varnish by dissolving it in a solvent. As described later, a film containing a precursor of a heat-resistant resin can be formed by applying such a varnish on various supports. The heat resistant resin film can be produced by converting the precursor of the heat resistant resin contained in this film into the heat resistant resin. Examples of the solvent include aprotic polar solvents such as N-methyl-2-pyrrolidone,? -Butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide and dimethylsulfoxide, tetrahydrofuran, Propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol ethyl methyl ether, and diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone , Ketones such as diisobutyl ketone, diacetone alcohol and cyclohexanone, esters such as ethyl acetate, propylene glycol monomethyl ether acetate and ethyl lactate, aromatic hydrocarbons such as toluene and xylene, etc., It can be mixed and used.

The preferable content of the solvent is preferably 50 parts by mass or more, more preferably 100 parts by mass or more, preferably 2,000 parts by mass or less, and more preferably 1,500 parts by mass or less based on 100 parts by mass of the precursor of the heat- . When the above conditions are satisfied, the viscosity becomes suitable for application, and the film thickness after application can be easily controlled.

The solution containing the precursor of the heat resistant resin in the present invention preferably contains at least one of (a) a photoacid generator, (b) a compound containing a phenolic hydroxyl group, and (c) a surfactant.

The varnish in the present invention can also be made into a photosensitive resin composition by containing (a) a photoacid generator. By containing the photoacid generator, an acid is generated in the light irradiated portion, the solubility of the irradiated portion in the aqueous alkaline solution is increased, and a positive relief pattern in which the irradiated portion is dissolved can be obtained. Incorporation of a photoacid generator and an epoxy compound or a thermal crosslinking agent to be described later promotes the crosslinking reaction of the epoxy compound or the thermal crosslinking agent with acid generated in the light irradiated region, and a negative relief pattern in which the irradiated portion is insoluble can be obtained.

Examples of the photoacid generator include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, iodonium salts and the like. Two or more of these may be contained, and a photosensitive resin composition with high sensitivity can be obtained.

Examples of the quinone diazide compound include 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 compound in which a sulfonic acid in quinone diazide is esterified with a polyhydroxypolyamine compound And / or a sulfonamide-bonded compound. It is preferable that at least 50 mol% of the functional groups of the polyhydroxy compound and the polyamino compound are substituted with quinone diazide.

In the present invention, the quinone diazide is preferably a 5-naphthoquinone diazide sulfonyl group or a 4-naphthoquinone diazide sulfonyl group. The 4-naphthoquinonediazidesulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. The 5-naphthoquinone diazidesulfonyl ester compound has increased absorption up to the g-line region of a mercury lamp, and is suitable for g-line exposure. In the present invention, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength to be exposed. The same molecule may contain a naphthoquinone diazide sulfonyl ester compound containing a 4-naphthoquinone diazidesulfonyl group and a 5-naphthoquinone diazide sulfonyl group. In the same resin composition, 4-naphthoquinone A diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound.

Among the photoacid generators, sulfonium salts, phosphonium salts, and diazonium salts are preferred because they properly stabilize acid components generated by exposure. Among them, sulfonium salts are preferable. In addition, a sensitizer or the like may be contained if necessary.

The content of the photoacid generator in the present invention is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the precursor of the heat resistant resin from the viewpoint of high sensitivity. Of these, the amount of the quinone diazide compound is preferably 3 to 40 parts by mass. The total amount of the sulfonium salt, phosphonium salt and diazonium salt is preferably 0.5 to 20 parts by mass.

The photosensitive resin composition of the present invention may contain a thermal crosslinking agent represented by the following chemical formula (31) or a thermal crosslinking agent comprising a structure represented by the following chemical formula (32) (hereinafter, also referred to as a thermal crosslinking agent). These heat-crosslinking agents can crosslink the heat-resistant resin, its precursor and other added components to increase the chemical resistance and hardness of the obtained heat-resistant resin film.

In the above formula (31), R ³¹ represents a 2 to 4-valent linking group. R ³² represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, Cl, Br, I or F; R ³³ and R ³⁴ each independently represent CH ₂ OR ³⁶ (R ³⁶ represents hydrogen or a monovalent hydrocarbon group having 1 to 6 carbon atoms). R ³⁵ represents hydrogen, a methyl group or an ethyl group. s represents an integer of 0 to 2, and t represents an integer of 2 to 4. The plurality of R ^{32 s} may be the same or different. The plurality of R ³³ and R ³⁴ may be the same or different. The plural R < ^{35 > s} may be the same or different. An example of connector R ³¹ is shown below.

In the above formulas, R ⁴¹ to R ⁶⁰ represent hydrogen, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group in which a part of hydrogen atoms of these hydrocarbon groups are substituted with Cl, Br, I or F.

In the above formula (32), R ³⁷ represents hydrogen or a monovalent hydrocarbon group of 1 to 6 carbon atoms. u represents 1 or 2, and v represents 0 or 1. Provided that u + v is 1 or 2;

In the above formula (31), R ³³ and R ³⁴ represent CH ₂ OR ³⁶ which is a thermally crosslinkable group. R ³⁶ is preferably a monovalent hydrocarbon group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group because it is suitable for the thermal crosslinking agent of the above chemical formula (31) and is excellent in storage stability.

Preferable examples of the thermosetting agent including the structure represented by the formula (31) are shown below.

In the formula (32), R ³⁷ is preferably a monovalent hydrocarbon group having 1 to 4 carbon atoms. From the viewpoints of the stability of the compound and the storage stability in the photosensitive resin composition, R ³⁷ is preferably a methyl group or an ethyl group, and the number of (CH ₂ OR ³⁷ ) groups contained in the compound is preferably 8 or less.

Preferable examples of the thermally crosslinking agent containing a group represented by the formula (32) are shown below.

The content of the heat crosslinking agent is preferably 10 parts by mass or more and 100 parts by mass or less based on 100 parts by mass of the precursor of the heat resistant resin. When the content of the heat crosslinking agent is 10 parts by mass or more and 100 parts by mass or less, the obtained heat resistant resin film has high strength and excellent storage stability of the photosensitive resin composition.

The varnish in the present invention may further contain a thermal acid generator. The thermal acid generator generates an acid by post-development heating, which will be described later, to accelerate the crosslinking reaction between the precursor of the heat resistant resin and the heat crosslinking agent, and accelerates the curing reaction of the precursor of the heat resistant resin. For this reason, the chemical resistance of the obtained heat-resistant resin film is improved, and film reduction can be reduced. The acid generated from the thermal acid generator is preferably a strong acid, for example, an arylsulfonic acid such as p-toluenesulfonic acid or benzenesulfonic acid, or an alkylsulfonic acid such as methanesulfonic acid, ethanesulfonic acid or butanesulfonic acid. In the present invention, the thermal acid generator is preferably an aliphatic sulfonic acid compound represented by the formula (33) or (34), and may contain two or more kinds thereof.

In the formulas (33) and (34), R ⁶¹ to R ^{63, which} may be the same or different, each represent an organic group having 1 to 20 carbon atoms and preferably a hydrocarbon group having 1 to 20 carbon atoms. And an organic group having 1 to 20 carbon atoms containing hydrogen and carbon as essential components and containing at least one atom selected from boron, oxygen, sulfur, nitrogen, phosphorus, silicon and halogen.

Specific examples of the compound represented by the formula (33) include the following compounds.

Specific examples of the compound represented by the formula (34) include the following compounds.

The content of the thermal acid generator is preferably 0.5 parts by mass or more, more preferably 10 parts by mass or less based on 100 parts by mass of the precursor of the heat resistant resin from the viewpoint of further promoting the crosslinking reaction.

If necessary, a compound containing a phenolic hydroxyl group (b) may be contained for the purpose of supplementing the alkali developability of the photosensitive resin composition. Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z and BisOTBP-Z (trade names, manufactured by Honshu Kagaku Kogyo Co., BisOPP-CP, BisOPP-CP, BisOPP-CP, BisOPP-CP, BisOPP-CP, BisOPP-CP, BisOP-CP, BisP-EZ, BisP-PZ, BisP-PZ, BisP-IPZ, BisCRP-IPZ, BisOCPP- TrisP-PA, TrisP-SA, TrisOCR-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC- OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26X-OCHP, BisOCHP-OC, Bis236T-OCHP, methylene tris-FR-CR, BisRS-26X and BisRS-OCHP) BIP-PC, BIR-PCB, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP- Dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, Dihydroxynaphthalene, 2,4-dihydroxyquinoline, 2,6-di Hydroxyquinoline, 2,3-dihydroxyquinoxaline, anthracene-1,2,10-triol, anthracene-1,8,9-triol, 8-quinolinol and the like. The photosensitive resin composition obtained by containing such a compound containing a phenolic hydroxyl group is hardly dissolved in an alkali developing solution before exposure and is easily dissolved in an alkaline developing solution when exposed to light, so that film reduction due to development is small, So that the development can be easily performed. Therefore, the sensitivity tends to be improved.

The content of the compound containing a phenolic hydroxyl group is preferably 3 parts by mass or more and 40 parts by mass or less based on 100 parts by mass of the precursor of the heat-resistant resin.

The varnish in the present invention may contain an adhesion improver. Examples of the adhesion improver include vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane, titanium chelating agents, aluminum chelating agents, etc. . Besides these, there may be mentioned alkoxy silane-containing aromatic amine compounds and alkoxy silane-containing aromatic amide compounds as shown below.

A compound obtained by reacting an aromatic amine compound with an alkoxy group-containing silicon compound may also be used. As such a compound, for example, a compound obtained by reacting an aromatic amine compound with an alkoxysilane compound containing a group reacting with an amino group such as an epoxy group or a chloromethyl group. Two or more kinds of the adhesion improvers exemplified above may be contained. When the photosensitive resin film is developed by containing these adhesion improvers, adhesion to a base substrate such as a silicon wafer, ITO, SiO ₂ , and silicon nitride can be enhanced. Further, by increasing the adhesion between the heat-resistant resin film and the base material of the base, resistance to oxygen plasma or UV ozone treatment used for cleaning can be increased. The content of the adhesion improver is preferably 0.01 to 10 parts by mass relative to 100 parts by mass of the precursor of the heat-resistant resin.

The varnish in the present invention may contain inorganic particles for the purpose of improving heat resistance. Examples of the inorganic particles used for this purpose include metallic inorganic particles such as platinum, gold, palladium, silver, copper, nickel, zinc, aluminum, iron, cobalt, rhodium, ruthenium, tin, lead, bismuth, tungsten, Silica, etc.), titanium oxide, aluminum oxide, zinc oxide, tin oxide, tungsten oxide, zirconium oxide, calcium carbonate, barium sulfate and the like. The shape of the inorganic particles is not particularly limited, and examples thereof include a sphere, an ellipse, a flat shape, a lot shape, and a fiber shape. The average particle diameter of the inorganic particles is preferably 1 nm or more and 100 nm or less, more preferably 1 nm or more and 50 nm or less, and more preferably 1 nm or more And more preferably 30 nm or less.

The content of the inorganic particles is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the precursor of the heat resistant resin, Preferably 80 parts by mass or less, more preferably 50 parts by mass or less. When the content of the inorganic particles is 3 parts by mass or more, the heat resistance is sufficiently improved. When the content of the inorganic particles is 100 parts by mass or less, the toughness of the fired film is hardly lowered.

The varnish in the present invention preferably contains (c) a surfactant in order to improve the coatability. As the surfactant, "Fluorad" (registered trademark) of Sumitomo 3M Co., "Megapack" (registered trademark) of DIC Co., "Sulfuron" (registered trademark) of Asahi Glass Co., , KP341 of Shin-Etsu Chemical Co., Ltd., DBE of Thixso Co., Ltd., "Polyflow" (registered trademark), "GLORNOL" (trade name, manufactured by Kyoeisha Chemical Co., An organic siloxane surfactant such as BYK manufactured by BICKEMI Co., Ltd., and an acrylic polymer surfactant such as a polyflow manufactured by KYEI CHEMICAL CO., LTD. The surfactant is preferably contained in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the precursor of the heat-resistant resin.

Generally, a small amount of a photoacid generator (a), (b) a compound containing a phenolic hydroxyl group, and (c) a surfactant tend to cause outgas after heating as described later. However, according to the method for producing a heat-resistant resin film of the present invention, when a solution containing a precursor of a heat-resistant resin contains a surfactant, a heat-resistant resin film with less outgassing and excellent mechanical properties can be obtained.

The precursor of the heat-resistant resin can be polymerized by a known method. For example, in the case of a polyimide preferably used in the present invention, a tetracarboxylic acid, or a corresponding acid dianhydride, an active ester, an active amide, etc., is used as an acid component and a diamine or a corresponding trimethylsilylated diamine, As a diamine component, the polyamide acid as a precursor can be obtained by polymerization in a reaction solvent. The polyamic acid may also be one obtained by esterifying a carboxyl group with a hydrocarbon group having 1 to 10 carbon atoms or an alkylsilyl group having 1 to 10 carbon atoms.

Examples of the reaction solvent include aprotic polar solvents such as N-methyl-2-pyrrolidone,? -Butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, and dimethylsulfoxide, tetrahydrofuran, Ethers such as dioxane, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether diethylene glycol ethyl methyl ether and diethylene glycol dimethyl ether, acetone, methyl ethyl ketone , Ketones such as diisobutyl ketone, diacetone alcohol and cyclohexanone, esters such as ethyl acetate, propylene glycol monomethyl ether acetate and ethyl lactate, aromatic hydrocarbons such as toluene and xylene, etc., Can be used. Further, by using a solvent such as a solvent for use as a varnish, the desired varnish can be obtained without isolating the resin after the production.

Next, a method for producing a solution containing a precursor of a heat resistant resin film (hereinafter referred to as a varnish) in the present invention will be described. For example, a varnish can be obtained by dissolving a precursor of a heat-resistant resin and, if necessary, a photoacid generator, a dissolution regulator, an adhesion improver, an inorganic particle or a surfactant in a solvent. Examples of the dissolving method include stirring and heating. When a photoacid generator is contained, the heating temperature is preferably set within a range that does not impair the performance of the photosensitive resin composition, and is usually room temperature to 80 ° C. The order of dissolution of each component is not particularly limited, and for example, there is a method of sequentially dissolving the compound from a compound having a low solubility. In addition, with respect to components that are likely to generate bubbles during stirring and dissolving, such as a surfactant or a part of an adhesion improver, other components may be dissolved and then added at the end to prevent defective dissolution of other components due to generation of bubbles.

The obtained varnish is preferably filtered using a filter to remove foreign matter such as dust. The filter hole diameters are, for example, 10 mu m, 3 mu m, 1 mu m, 0.5 mu m, 0.2 mu m, 0.1 mu m, 0.07 mu m, 0.05 mu m, and the like. Examples of the material of the filter include polypropylene (PP), polyethylene (PE), nylon (NY), and polytetrafluoroethylene (PTFE). Polyethylene and nylon are preferred.

≪ Method of producing heat resistant resin film &

Next, a method for producing the heat-resistant resin film of the present invention will be described. A method for producing a heat resistant resin film, which is one of the features of the present invention, includes a step of applying a solution containing a precursor of a heat resistant resin on a support and a step of heating in multiple steps, (A) a first heating step of heating at a temperature higher than 200 deg. C in an atmosphere having an oxygen concentration of 10 vol% or more, (B) a step of heating the first heating step And a second heating step of heating the second heat-resistant resin film in the above-mentioned order.

First, a varnish containing a precursor of a heat-resistant resin is applied on a support. Examples of the support include wafer substrates such as silicon and gallium arsenide, glass substrates such as sapphire glass, soda lime glass, and alkali-free glass, metal substrates such as stainless steel and copper, metal foil and ceramics substrates.

Examples of the application method of the varnish include a spin coating method, a slit coating method, a dip coating method, a spray coating method and a printing method, and these may be combined. Prior to application, the support may be pre-treated with the above-mentioned adhesion improver. For example, the adhesion improver may be dissolved in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate or diethyl adipate in an amount of 0.5 to 20 mass% , A method of treating the surface of the support by a spin coating method, a slit die cord, a bar coating, a dip coating, a spray coating, a steam treatment, or the like. If necessary, the reaction may be carried out under reduced pressure, and then the reaction between the support and the adhesion improver may proceed by heating at 50 ° C to 300 ° C.

After application, the varnish coating film is generally dried. As the drying method, it is possible to use it by reduced-pressure drying, heat drying, or a combination thereof. As a method of reduced-pressure drying, for example, a support having a coating film formed therein is placed in a vacuum chamber, and the pressure inside the vacuum chamber is reduced. The heating and drying is carried out by treating with an infrared ray, hot air or the like using a device such as a hot plate or an oven. When a hot plate is used, the coated film is held on a jig such as a proxy pin or the like directly on the plate, or heated and dried.

As the material of the proxy pin, there may be used 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 as long as it has heat resistance. The height of the proxy pin can be variously selected depending on the size of the support, the type of the solvent used in the varnish, the drying method, etc., but preferably about 0.1 to 10 mm. The heating temperature varies depending on the type and purpose of the solvent used in the varnish and is preferably from room temperature to 180 占 폚 for 1 minute to several hours.

When the varnish in the present invention contains a photoacid generator, a pattern can be formed from a coated film after drying by the following method. A mask having a desired pattern is passed over the coating film to irradiate an actinic ray and expose it. Examples of the actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, and X rays. In the present invention, it is preferable to use i line (365 nm), h line (405 nm), and g line (436 nm) Do. When having a positive type photosensitive property, the exposed portion dissolves in the developing solution. In the case of having a negative type photosensitive property, the exposed portion is cured and insoluble in the developer.

After exposure, a desired pattern is formed by removing an exposed portion in the case of the positive type and a non-visible portion in the case of the negative type using a developing solution. Examples of the developing solution include positive and negative types, and in the case of positive and negative types, any of tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, An aqueous solution of an alkaline compound such as dimethylaminoethyl acetate, dimethylaminoethanol, 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.

In the case of the negative type, the polar solvent, alcohols, esters, and ketones, which do not contain an aqueous alkali solution, may be used alone or in combination. After development, rinse treatment is generally performed with water. 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.

Followed by multi-step heating, which is a feature of the method for producing a heat-resistant resin film of the present invention. In the step of performing the multistage heating, heating is performed in a temperature range of 180 占 폚 or more, and the coated film is used as a heat resistant resin film. (A) a first heating step of heating at a temperature higher than 200 deg. C in an atmosphere of an oxygen concentration of 10 vol% or more, and (B) It is necessary to include a second heating step of heating at a higher temperature than the first heating step in the above-described order. The reasons are described below.

When the varnish of the present invention contains a component other than the precursor and the solvent of the heat-resistant resin, the component or the decomposition product thereof remains in the heat-resistant resin film and the outgas characteristics of the heat- . A compound containing a photoacid generator and a phenolic hydroxyl group is likely to cause outgas because it does not have a bonding point with a heat resistant resin or a substrate unlike a heat crosslinking agent or an adhesion improver. Further, as described above, the surfactant is often a resin such as an acrylic polymer, a polyoxyethylene alkyl ether, or the like. These cause the degradation of outgas characteristics of the heat resistant resin film while leaving the oligomer component and the monomer component decomposed in the heat resistant resin film. Therefore, it is preferable to oxidize a component causing outgas by heating in an atmosphere in which oxygen molecules are present in the first heating step, thereby promoting decomposition and vaporization.

The range of the oxygen concentration in the first heating step is 10% by volume or more, more preferably 15% by volume or more. When the range of the oxygen concentration is 10 vol% or more, the component causing the out-gas can be oxidized by the oxidation reaction, and decomposition and vaporization can be promoted. The oxygen concentration in the first heating step is preferably 22 vol% or less. If the range of the oxygen concentration is 22 vol% or less, the first heating step can be performed in the atmosphere, and there is little need to introduce oxygen gas into the heating atmosphere.

The heating temperature in the first step needs to be not lower than the temperature necessary for curing the precursor of the heat-resistant resin. Specifically, a temperature higher than 200 DEG C is required. It is preferable that the heating temperature in the first heating step is lower than the temperature at which the heat-resistant resin is oxidized. Specifically, the temperature is preferably 420 占 폚 or lower, more preferably 370 占 폚 or lower, and still more preferably 320 占 폚 or lower.

On the other hand, in order to improve the mechanical characteristics of the heat resistant resin film, it is preferable to increase the heating temperature. However, if the heating temperature is raised in an atmosphere in which oxygen molecules are present, oxidation of the heat resistant resin and decomposition thereof occur, and it becomes difficult to obtain good physical properties. Thus, by heating in an atmosphere having a low oxygen concentration in the second heating step, the mechanical properties can be improved while suppressing oxidation or decomposition of the heat resistant resin.

The range of the oxygen concentration in the second heating step is 3 vol% or less, more preferably 1 vol% or less, further preferably 0.1 vol% or less. If the range of the oxygen concentration is 3 vol% or less, the resin can be prevented from being deteriorated even if the heating temperature in the second step is 300 DEG C or more. The oxygen concentration in the second heating step is preferably 0.000001% by volume or more, more preferably 0.00001% by volume or more, and still more preferably 0.0001% by volume or more. When the range of the oxygen concentration is 0.000001 vol.% Or more, the use amount of the inert gas is extremely increased, and the burden on the vacuum pump can be prevented.

The heating temperature in the second step needs to be higher than the maximum temperature in the first heating step, specifically 300 DEG C or higher, more preferably 350 DEG C or higher, and even more preferably 400 DEG C or higher. On the other hand, it is preferable that the heating temperature in the second heating step does not exceed the decomposition temperature of the resin, specifically, 600 占 폚 or lower, and more preferably 550 占 폚 or lower.

In the method for producing a heat resistant resin film of the present invention, the step of heating in a multistage may include three or more heating steps. When an additional heating step is provided before the first heating step, it is preferable to perform heating at a temperature lower than that of the first heating step in an atmosphere equal to or higher than the oxygen concentration in the first heating step. When an additional step is provided after the second heating step, it is preferable to perform heating at a higher temperature than the second heating step in an atmosphere of oxygen concentration or lower in the second heating step.

As the heating method, any of the methods described in the above-mentioned heat drying can be suitably used. That is, it is preferable to use a device such as a hot plate or an oven and treat it with hot air or infrared rays.

After the collected heating process is completed, cooling is performed, and the heat resistant resin film is taken out from the apparatus. The cooling may be a method of cooling by natural cooling by stopping heating by the apparatus or forcibly cooling by a cooling unit installed in the apparatus. In the case of drawing by hand after cooling, it is preferable to cool to room temperature. However, in this case, drawing may be performed at a temperature higher than room temperature. However, it is preferable that the heat resistant resin film is formed in a range that does not significantly deteriorate the physical properties of the heat resistant resin film. The atmosphere in the apparatus at the time of cooling is preferably a state in which the atmosphere immediately after the end of the heating step is maintained, but the atmosphere in the apparatus may be replaced with air when the temperature in the apparatus is cooled to a predetermined temperature or lower. Also in this case, it is preferable to determine the temperature to be substituted into the atmosphere within a range in which the physical properties of the heat-resistant resin film are not significantly deteriorated.

<Heating Furnace>

Next, a heating furnace which is one of the features of the present invention will be described. In this heating furnace,

A temperature measuring unit for measuring the temperature in the furnace,

A temperature adjusting unit for adjusting the temperature in the furnace,

An oxygen concentration measuring unit for measuring an oxygen concentration in the furnace,

A gas flow rate regulating section for regulating the flow rate of the heating atmosphere gas into the furnace,

And a control unit for controlling the temperature adjusting unit and the gas flow rate adjusting unit,

Wherein,

The gas flow rate adjusting unit is controlled in accordance with the oxygen concentration in the furnace measured by the oxygen concentration measuring unit,

And controls the temperature adjusting unit so that the temperature in the furnace measured by the temperature measuring unit becomes a predetermined temperature after the oxygen concentration reaches a predetermined oxygen concentration.

One embodiment of the heating furnace of the present invention will be described with reference to the drawings. 1 is a schematic view of a heating furnace 10 which is one embodiment of the heating of the present invention.

Gas pipes (41 and 51) and an exhaust pipe (61) are connected to the furnace body (11) for arranging the heating target. The gas supply pipes 41 and 51 are provided with a gas flow rate adjusting unit and are provided with purge opening / closing valves 42 and 52, purge flow adjusting valves 43 and 53, running opening / closing valves 44 and 54, And flow rate adjusting valves 45 and 55. [ An exhaust opening / closing valve (62) and an exhaust flow rate adjusting valve (63) are also provided in the exhaust pipe (61).

The purge opening / closing valve is opened when the atmosphere in the furnace 12 filled with the gas different from the supply gas is rapidly replaced with the supply gas. Therefore, it is necessary that the gas flow rate sufficiently large enough to replace the furnace 12 with the supply gas is set by the purge flow rate adjusting valve. On the other hand, the running on / off valve is opened when gas is supplied to maintain the atmosphere of the furnace 12 in particular. Therefore, it is only necessary to set the gas flow rate as much as possible to maintain the atmosphere of the furnace 12 by the running flow rate adjusting valve, and normally, the gas flow rate less than the flow rate set by the purge flow rate control valve is set.

The furnace body 11 is provided with a temperature measuring section 22 and a heating section 23. The temperature measuring unit 22 and the heating unit 23 are connected to the temperature adjusting unit 21 through an electrical connection indicated by a broken line. The temperature adjusting unit 21 is electrically connected to the control unit 71. [

The heating furnace 10 is provided with an oxygen concentration measuring section for measuring the oxygen concentration and comprises an oxygen concentration meter 31 and a gas sampling port 32 for collecting the gas in the furnace 12. The oxygen concentration meter 31 is also connected to the control unit 71 through an electrical connection indicated by a broken line. A user interface 81 capable of automatically setting a program in order to automatically execute a heating process under predetermined conditions is also provided and is also electrically connected to the control unit 71. [

The opening and closing of the opening / closing valves 42, 44, 52, 54 and 62 is performed by an electric signal from the control unit 71 . Although not shown, a door for opening and closing the object to be heated is provided in the roto- ley 11.

The control unit 71 controls at least the temperature adjusting unit 21 and the gas flow rate adjusting unit. Specifically, the gas flow rate adjusting unit is controlled in accordance with the oxygen concentration of the in-furnace 12 measured by the oxygen concentration measuring unit, and the oxygen concentration in the furnace 12 reaches a predetermined oxygen concentration, And controls the temperature adjusting unit 21 so that the temperature of the furnace 12 in the furnace 12 becomes a predetermined temperature.

At this time, it is preferable that the control unit 71 can control the temperature adjusting unit 21 and the gas flow rate adjusting unit so as to continuously perform the multi-step heating process. For example, at least a first heating step of heating at a first temperature in a first oxygen concentration atmosphere and a second heating step of heating at a second temperature in a second oxygen concentration atmosphere may be performed in a multi-stage In the heating process, it is preferable that the control unit 71 can control the gas flow rate adjusting unit and the temperature adjusting unit 21 so as to continuously perform the first heating process and the second heating process.

Hereinafter, the case where the heat resistant resin film of the present invention is produced using the heating furnace 10 will be described, and the action of each part will be described. For example, a two-stage heating process is performed, and the first heating process and the second heating process are respectively performed under the atmosphere (oxygen concentration: 21% by volume) and under nitrogen (oxygen concentration is 0.01% by volume or less).

First, the gas supply pipes 41 and 51 are connected to a supply line for nitrogen and air, respectively. Subsequently, a coating film formed by applying a solution containing the precursor of the above-mentioned heat-resistant resin film on the substrate and drying the coating film is placed in the rosette 11. And sets the program of the heating process through the user interface 81. [

After the above preparation is completed, the heating process is started. At the start time, the first heating process is started because the furnace 12 is filled with the atmosphere. If the oxygen concentration in the furnace 12 is not the same as atmospheric air, the oxygen concentration meter 31 detects the oxygen concentration and the signal is sent from the control unit 71 to the purge switching valve 52 to open the valve 12 ). When the in-furnace 12 is filled with air and the oxygen concentration meter 31 detects it, the valve of the purging on-off valve 52 is closed by the signal from the control unit 71, and the supply of air stops. During the first heating process, the purge opening / closing valve 42 and the running opening / closing valve 44 provided in the gas supply pipe 41 for supplying nitrogen are all closed.

A signal is sent from the control unit 71 to the temperature regulating unit 21 in a state in which the furnace 12 is filled with air and the temperature rise is started according to a preset program. During heating, the temperature measuring unit 22 always monitors the temperature of the furnace 12 and the temperature adjusting unit 21 controls the heating unit 23 so that heating can be performed in accordance with the program. Since out gas is generated from the coating film during the first heating process, the atmosphere is always supplied from the gas supply pipe 51 for supplying air to the inside of the furnace 12, and the out gas from the coating film is supplied to the inside of the furnace 12, (61). Therefore, during heating, it is preferable that the running on / off valve 54 of the gas supply pipe 51 is open.

It is more preferable that the running flow regulating valve 55 and the exhaust flow regulating valve 63 are adjusted so that the atmosphere in the furnace 12 is always positive. When the in-furnace 12 is at a negative pressure, there is a possibility that the outside air enters the furnace 12 from a gap or the like of the opening / closing door.

During the first heating process, the oxygen concentration meter 31 can always monitor the oxygen concentration in the furnace 12. If a decrease in the oxygen concentration is detected, a signal is sent from the control unit 71 to the gas flow rate regulating unit, and the purge opening / closing valve 52 is opened to purged the atmosphere. When the oxygen concentration in the furnace 12 returns to a predetermined concentration and the oxygen concentration meter 31 can detect it, a signal is sent from the control unit 71 to the gas flow rate adjusting unit, the purge opening / closing valve 52 is closed, .

While the purge opening / closing valve 52 is opened and the air is purged, the running opening / closing valve 54 may be in a closed state. However, at the time when the purging on-off valve 52 is closed and purging of the atmosphere is stopped, it is preferable to open the running on-off valve 54 to continuously supply air.

A signal is sent from the control unit 71 to the gas flow rate adjusting unit to lower the oxygen concentration in the furnace 12 to a predetermined concentration before the second heating process is started after the completion of the first heating process. By this signal, both the purge opening / closing valve 52 and the running opening / closing valve 54 of the gas supply pipe 51 are closed, and the supply of the air stops. On the other hand, the purge opening / closing valve 42 of the gas supply pipe 41 opens to supply nitrogen into the furnace 12. The supply of nitrogen is continued until the furnace 12 becomes the predetermined oxygen concentration or less, and the start of the second heating process is temporarily put in a standby state.

When the oxygen concentration meter 31 detects that the oxygen concentration in the furnace 12 has become equal to or lower than the predetermined oxygen concentration level, the signal is sent to the control unit 71 to be supplied from the control unit 71 to the purge opening / 42 are closed. Simultaneously with this, a signal for starting the second heating process is sent from the control unit 71 to the temperature adjusting unit 21 to start heating.

In this second heating step, since out gas is generated from the coating film during heating, nitrogen is always supplied from the gas supply pipe 41 to the inside of the furnace 12, and the out gas from the coating film is supplied to the inside of the furnace 12 61). Therefore, during heating, it is preferable that the running on / off valve 44 of the gas supply pipe 41 is open. It is more preferable that the running flow regulating valve 45 and the exhaust flow regulating valve 63 are adjusted so that the atmosphere in the furnace 12 is always positive. When the in-furnace 12 is at a negative pressure, there is a possibility that the outside air enters the furnace 12 from a gap or the like of the opening / closing door.

The oxygen concentration meter 31 can always monitor the oxygen concentration in the furnace 12 during the second heating process. If an increase in the oxygen concentration is detected, a signal is sent from the control section 71 to the gas flow rate regulating section, and the purge opening / closing valve 42 is opened to purge the nitrogen. When the oxygen concentration in the furnace 12 returns to a predetermined concentration or less and the oxygen concentration meter 31 detects it, a signal is sent from the control section 71 to the gas flow rate regulating section and the purge opening / closing valve 42 is closed, Stop the purge.

After the second heating process is completed, cooling of the furnace 12 is started. A signal is sent from the control unit 71 to the temperature regulating unit 21, and when the heating in the heating unit 23 is stopped accordingly, cooling is naturally started. In some cases, a cooling section (not shown) electrically connected to the temperature regulating section 21 may be provided in the furnace body 11 as a heating furnace. The temperature of the furnace 12 can be forcibly lowered by the action of the cooling section.

When the temperature of the furnace 12 falls below a predetermined temperature, the operation of replacing the atmosphere of the furnace 12 with the atmosphere is started. The work is performed, for example, as follows. The temperature measuring unit 22 detects that the temperature of the furnace 12 is lower than the predetermined temperature in accordance with the program set in the user interface 81. [ And the signal is transmitted to the control unit 71 through the temperature adjusting unit 21. [ Subsequently, a signal is sent from the control section 71 to the gas flow rate regulating section, and the purge opening / closing valve 42 and the running opening / closing valve 44 provided in the gas supply pipe 41 are closed to supply the nitrogen into the furnace 12 Stop. At the same time, the purge opening / closing valve 52 provided in the gas supply pipe 51 is opened, and supply of air to the furnace 12 is started.

The temperature and the oxygen concentration in the furnace 12 are monitored by the temperature measuring unit 22 and the oxygen concentration meter 31 while the furnace is cooling and the temperature of the furnace 12 falls below a predetermined temperature set in the program, All the processes are completed when the atmosphere of the oxygen concentration sensor 12 reaches approximately the same oxygen concentration as the atmosphere. Thereafter, the coating film is taken out from the opening / closing door provided on the furnace body 11. During the heating process, it is preferable that the opening and closing door is in a locked state, and it is preferable that the lock is released at the time when all the processes are completed, so that the object to be heated can be drawn out.

Although the example of the heating furnace which is one of the features of the present invention has been described above, the present invention is not limited only to this example. In the above example, the gas flow rate regulating section is controlled by the control section 71 and automatically opens / closes the opening / closing valves 42, 44, 52, 54 and 62 in accordance with the program previously set through the user interface 81 Structure. The flow rate regulating valves 43, 45, 53, 55, and 63 may be adjusted in advance, unchanged during the heating process, or automatically adjusted.

In order to monitor the oxygen concentration during heating, it is necessary to always keep the oxygen concentration meter 31 operating. However, there is a possibility that it is difficult to accurately measure the oxygen concentration by the outgas from the object to be heated, or the oxygen concentration meter 31 may be contaminated. In order to prevent this, it is preferable to provide a cold trap between the gas sampling port 32 and the oxygen concentration meter 31. By installing the cold trap, it is possible to trap the out gas from the object to be heated and to measure the accurate oxygen concentration. Also, the possibility of contamination of the oxygen concentration meter 31 is also reduced.

The heat-resistant resin film obtained by the present invention can be applied to a surface protective film or an interlayer insulating film of a semiconductor element, an insulating layer or a spacer layer of an organic electroluminescence element (organic EL element), a planarizing film of a thin film transistor substrate, A substrate for a flexible display, a substrate for a flexible electronic paper, a substrate for a flexible solar cell, a substrate for a flexible color filter, and the like. Particularly, for an image display apparatus such as an organic EL, an electronic paper, and a color filter, the heat resistance (outgas characteristics, glass transition temperature, etc.) to the temperature of the manufacturing process and the mechanical characteristics suitable for imparting toughness to the image display apparatus after production Heat-resistant resin films, they can be preferably used as their substrates.

 A method of using the heat resistant resin film obtained by the manufacturing method of the present invention as a substrate of an image display apparatus will be described. First, the heat resistant resin film is formed on a support such as a glass substrate by the production method of the present invention.

Subsequently, a pixel driving element or a colored pixel is formed on the heat resistant resin film. For example, in the case of an organic EL display, a TFT serving as an image driving device, a first electrode, an organic EL light emitting element, a second electrode, and a sealing film are sequentially formed. In the case of a color filter, a black matrix is formed as needed, and colored pixels such as red, green, and blue are formed.

The gas barrier film may be formed between the heat-resistant resin film and the pixel-driving element or the colored pixel, if necessary. By forming the gas barrier film, it is possible to prevent moisture or oxygen from passing from the outside of the image display device through the heat-resistant resin film to deteriorate the pixel driving element or the colored pixel. As the gas barrier film, an inorganic film such as a silicon oxide film (SiOx), a silicon nitride film (SiNy), or a silicon oxynitride film (SiOxNy) is used as a film or a laminate of plural kinds of inorganic films. These gas barrier films are formed by a method such as chemical vapor deposition (CVD) or physical vapor deposition (PVD). As the gas barrier film, an inorganic film and an organic film such as polyvinyl alcohol may be alternately laminated.

Finally, peeling is performed at the interface between the support and the heat-resistant resin film to obtain an image display device including the heat-resistant resin film. Examples of the method of peeling at the interface between the support and the heat resistant resin film include a method using a laser, a mechanical peeling method, and a method of etching a support. In the method using a laser, peeling can be performed without damaging the image display element by irradiating a laser beam from a side on which an image display element is not formed with respect to a support such as a glass substrate. Further, a primer layer for facilitating peeling may be formed between the support and the heat-resistant resin film.

(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. Further, in the case where there is no particular conflict with the number of measurements, the measurement was performed only once.

(1) Measurement of maximum tensile elongation and maximum tensile stress

The glass substrate on which the heat resistant resin films obtained in each of the examples and the comparative examples were laminated was immersed in hydrofluoric acid for 4 minutes and the heat resistant resin film was peeled from the glass substrate and air dried in air at 50 캜 for 1 hour. Subsequently, the maximum tensile elongation and the maximum tensile stress were determined by measurement under the following apparatus and conditions.

Measuring apparatus: Tensilon universal material tester "RTM-100" (manufactured by Orientech Co., Ltd.)

Measured sample shape: Ribbon shape

Measurement sample dimensions: length> 70 mm, width 10 mm

Tensile speed: 50 mm / min

Distance between chucks at start of test: 50 mm

Experiment temperature: 0 ~ 35 ℃

Number of samples: 10

Calculation method of measurement result: An arithmetic average value of the measurement values of 10 samples was obtained.

(2) Measurement of outgas occurring during heating at 450 DEG C for 30 minutes under a stream of helium

The heat-resistant resin film obtained in each of the Examples and Comparative Examples was measured for outgas measured during the period from reaching 450 캜 to holding for 30 minutes by the following apparatus and conditions.

Measurement apparatus: "Small-4" (manufactured by Toray Research Center, Ltd.), GC / MS "QP5050A (7)" (manufactured by Shimadzu Seisakusho Co., Ltd.)

Heating conditions: The temperature was raised from room temperature to 10 占 폚 / min, maintained at 450 占 폚 for 30 minutes

Measurement atmosphere: Helium flow (50 mL / min).

The abbreviations of the compounds used in Synthesis Examples and Examples will be described below.

p-PDA: p-phenylenediamine

DAE: 4,4'-diaminodiphenyl ether

HAB: 3,3'-dihydroxybenzidine

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

PMDA: pyromellitic acid dianhydride

ODPA: 4,4'-oxydiphthalic acid dianhydride

TPC: terephthalic acid dichloride

NMP: N-methyl-2-pyrrolidone

THPE: 1,1,1-tris (4-hydroxyphenyl) ethane

Surfactant b: BYK-350 (manufactured by BYK-Chemie GmbH)

Surfactant c: Megafac F-444 (DIC Co., Ltd.)

Surfactant d: Polyflow 77 (manufactured by Kyoeisha Chemical Co., Ltd.).

In a 200 mL four-necked flask, a stirrer bar equipped with a thermometer and a stirring blade was set. Subsequently, 90 g of NMP was added in a dry nitrogen stream, and the temperature was raised to 60 占 폚. After heating, 5.407 g (50.00 mmol) of p-PDA was added while stirring, and the mixture was washed with 15 g of NMP. After confirming that the p-PDA is dissolved, 14.49 g (49.25 mmol) of BPDA is added and the solution is washed with 15 g of NMP.

Synthesis Example 2:

In a 200 mL four-necked flask, a stirrer bar equipped with a thermometer and a stirring blade was set. Subsequently, 90 g of NMP was charged into a dry nitrogen stream, and the temperature was raised to 40 占 폚. After warming, 10.01 g (50.00 mmol) of DAE is added while stirring, and the mixture is washed with 15 g of NMP. 10.7 g (49.25 mmol) of PMDA is added to the solution, and the solution is washed with 15 g of NMP. After 4 hours, it was cooled.

Synthesis Example 3:

In a 200 mL four-necked flask, a stirrer bar equipped with a thermometer and a stirring blade was set. Subsequently, 90 g of NMP was added in a dry nitrogen stream, and the temperature was raised to 60 占 폚. After heating, 5.407 g (50.00 mmol) of p-PDA was added while stirring, and the mixture was washed with 15 g of NMP. After confirming that the p-PDA is dissolved, 15.28 g (49.25 mmol) of ODPA is added, and the solution is washed with 15 g of NMP.

Synthesis Example 4:

In a 200 mL four-necked flask, a stirrer bar equipped with a thermometer and a stirring blade was set. Subsequently, 90 g of NMP was introduced into a dry nitrogen gas stream and cooled to 10 캜 or lower. After cooling, 10.81 g (50.00 mmol) of HAB and 13.22 g (150.0 mmol) of glycidyl methyl ether are added while stirring, and the mixture is washed with 15 g of NMP. Subsequently, 10.15 g (50.00 mmol) of TPC diluted with 15 g of NMP was added dropwise. After completion of the dropwise addition, the mixture was stirred overnight at room temperature.

Synthesis Example 5:

In a 200 mL four-necked flask, a stirrer bar equipped with a thermometer and a stirring blade was set. Subsequently, 90 g of NMP was added in a dry nitrogen stream, and the temperature was raised to 60 占 폚. After heating, 6.488 g (60.00 mmol) of p-PDA is added while stirring, and the mixture is washed with 15 g of NMP. 7.061 g (24.00 mmol) of BPDA and 7.525 g (34.50 mmol) of PMDA are introduced, and the solution is washed with 15 g of NMP. After 4 hours, it was cooled. After cooling, 0.100 g of Surfactant d was added to make a varnish.

Synthesis Example 6: Synthesis of photoacid generator a

A stirring rod with a thermometer and stirring blade was set in a 1000 mL four-necked flask. Subsequently, 15.31 g (50.00 mmol) of 1,1,1-tris (4-hydroxyphenyl) ethane and 20.15 g (75.00 mmol) of 5-naphthoquinonediazide sulfonyl chloride were added to a 1,4- -Dioxane (450 g) and the temperature was brought to room temperature. 7.59 g (75.00 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise to the reaction system so that the temperature did not exceed 35 占 폚. After dropwise addition, the mixture was stirred at 30 ° C for 2 hours. The triethylamine salt was filtered, and the solution was poured into water. After that, precipitated precipitate was collected by filtration. This precipitate was dried with a vacuum drier to obtain a photoacid generator a. The esterification rate of the naphthoquinone diazide compound was 50%.

Example 1:

The resin solution obtained in Synthesis Example 1 was filtered under pressure using a 1 탆 filter to remove foreign matter. Spin coating was carried out on a 6-inch glass substrate using a coating and developing apparatus Mark-7 (manufactured by Tokyo Electron Limited) so that the film thickness after pre-baking became 15 占 퐉, and then pre-baking was performed at 140 占 폚 for 5 minutes Respectively. The pre-baking film was heated in accordance with the following first condition using a gas oven (INH-21CD manufactured by Koyo Thermo Systems Co., Ltd.) and then heated according to the second condition below to prepare a heat resistant resin film on the glass substrate. Heating in the first condition and heating in the second condition were performed continuously.

Step 1: Heating was carried out at 350 占 폚 for 30 minutes in an air atmosphere (oxygen concentration: about 21% by volume).

Second step: The sample was heated at 400 占 폚 for 30 minutes in a nitrogen atmosphere having an oxygen concentration of less than 20 ppm.

However, in the first step, the temperature was raised from room temperature, and the rate of temperature rise was set at 5 占 폚 / min. In the second step, the temperature was raised from the maximum heating temperature in the first step, and the rate of temperature rise was 5 ° C / min.

Examples 2 to 10c, Comparative Examples 1 to 12:

As shown in Table 1, using the resin solution obtained in Synthesis Examples 1 to 5, a prebaking film was produced in the same manner as in Example 1. [ However, for Examples 6 to 9 and Comparative Examples 6 to 9, those to which the additives described in Table 1 were added were used. Subsequently, a heat-resistant resin film was produced in the same manner as in Example 1, except that the maximum heating temperature and the heating atmosphere in the first step and the second step were set as shown in Table 1. However, for Comparative Example 12, the following third step was added.

Step 3: The sample was heated at 450 占 폚 for 30 minutes in an air atmosphere.

However, in the third step, the temperature was raised from room temperature, and the rate of temperature rise was set at 5 占 폚 / min.

The maximum tensile elongation, the maximum tensile stress and the outgas measurement results of the heat-resistant resin films obtained in Examples 1 to 10c and Comparative Examples 1 to 12 are shown in Tables 1 and 2.

Example 11

On the heat resistant resin film obtained in Example 10a, a gas barrier film composed of a lamination of SiO ₂ and Si ₃ N ₄ was formed by CVD. Subsequently, a TFT was formed, and an insulating film made of Si ₃ N ₄ was formed while covering the TFT. Subsequently, a contact hole was formed in the insulating film, and a wiring connected to the TFT was formed through the contact hole.

Further, a planarization film was formed to planarize irregularities due to formation of wiring lines. Then, a first electrode made of ITO was connected to the wiring on the obtained planarization film. Thereafter, the resist was applied, pre-baked, exposed through a mask of a desired pattern, and developed. Using this resist pattern as a mask, patterning was carried out by wet etching using ITO etchant. Thereafter, the resist pattern was peeled off using a resist stripping solution (a mixture of monoethanolamine and diethylene glycol monobutyl ether). The substrate after peeling was washed with water and dehydrated by heating to obtain an electrode substrate having a flattening film. Then, an insulating film having a shape covering the periphery of the first electrode was formed.

Further, a hole transporting layer, an organic light emitting layer, and an electron transporting layer were sequentially deposited through a desired pattern mask in a vacuum evaporation apparatus. Then, a second electrode made of Al / Mg was formed on the entire upper surface of the substrate. Further, a sealing film composed of a lamination of SiO ₂ and Si ₃ N ₄ was formed by CVD. Finally, a laser (wavelength: 308 nm) was irradiated from the side where the heat-resistant resin film was not formed on the glass substrate, and peeling was performed at the interface with the heat-resistant resin film.

Thus, an organic EL display device formed on the heat-resistant resin film was obtained. When a voltage was applied through the driving circuit, good light emission was exhibited.

Comparative Example 13

A gas barrier film was formed on the heat resistant resin film obtained in Comparative Example 10 by CVD in the same manner as in Example 11. [ The formation of the TFT was continued. However, due to the visible cause of outgassing of the heat-resistant resin film, the adhesion between the heat-resistant resin film and the gas barrier film deteriorated and peeling occurred.

(Industrial availability)

According to the present invention, it is possible to provide a method for producing a heat-resistant resin film that does not deteriorate the mechanical properties of the heat-resistant resin film and has excellent out-gas characteristics. The heat-resistant resin film thus obtained can be used as an insulating layer or a spacer layer of a surface protective film or interlayer insulating film of a semiconductor element, an organic electroluminescence element (organic EL element), a planarization film of a thin film transistor substrate, an insulating layer of an organic transistor, A substrate for a flexible electronic paper, a substrate for a flexible solar cell, a substrate for a flexible color filter, and the like.

10: heating furnace 11:
12: furnace 21: temperature adjusting section
22: temperature measuring part 23: heating part
31: oxygen concentration meter 32: gas sampling port
41 · 51: gas supply pipe 42 · 52: purge opening / closing valve
43 · 53: purge flow adjusting valve 44 · 54: opening / closing valve for running
45 占 55: Flow regulating valve for running 61: Exhaust pipe
62: exhaust opening / closing valve 63: exhaust flow regulating valve
71: control unit 81: user interface

Claims (17)

Wherein the outgas generated during heating at 450 DEG C for 30 minutes in a helium air flow is 0.01 to 4 mu g / cm &lt; 2 &gt;. The method according to claim 1,
Wherein the maximum tensile stress is 200 MPa or more. 3. The method according to claim 1 or 2,
A heat-resistant resin film characterized by having a structure represented by the formula (1).

(In the formula (1), X represents a tetravalent tetracarboxylic acid residue having at least 2 carbon atoms, Y represents a bivalent diamine residue having at least 2 carbon atoms, and m represents a positive integer.) 4. The method according to any one of claims 1 to 3,
Characterized in that X in the formula (1) is a tetravalent tetracarboxylic acid residue represented by the formula (2) or (3) as a main component and Y is a bivalent diamine residue represented by the formula (4) Resistant resin film.

A method of manufacturing a heat resistant resin film comprising a step of applying a solution containing a precursor of a heat resistant resin on a support and a step of heating in a multistage manner, wherein the step of heating in a multistage comprises: (A) (B) a second heating step of heating at a temperature higher than the first heating step in an atmosphere having an oxygen concentration of not more than 3% by volume in this order Wherein the heat-resistant resin film has a thickness of 10 to 100 angstroms. 6. The method of claim 5,
Wherein the first heating step is performed at 420 DEG C or less. The method according to claim 5 or 6,
Wherein the heat-resistant resin is a resin having a structure represented by the formula (1).

(In the formula (1), X represents a tetravalent tetracarboxylic acid residue having at least 2 carbon atoms, Y represents a bivalent diamine residue having at least 2 carbon atoms, and m represents a positive integer.) 8. The method according to any one of claims 5 to 7,
Characterized in that X in the formula (1) is a tetravalent tetracarboxylic acid residue represented by the formula (2) or (3) as a main component and Y is a bivalent diamine residue represented by the formula (4) Resistant resin film.

9. The method according to any one of claims 5 to 8,
Wherein the solution containing the precursor of the heat-resistant resin comprises at least one of (a) a photoacid generator, (b) a compound containing a phenolic hydroxyl group, and (c) a surfactant. A temperature measuring unit for measuring the temperature in the furnace,
A temperature adjusting unit for adjusting the temperature in the furnace,
An oxygen concentration measuring unit for measuring an oxygen concentration in the furnace,
A gas flow rate regulating section for regulating the flow rate of the heating atmosphere gas into the furnace,
And a control unit for controlling the temperature adjusting unit and the gas flow rate adjusting unit,
Wherein,
The gas flow rate adjusting unit is controlled in accordance with the oxygen concentration in the furnace measured by the oxygen concentration measuring unit,
And controls the temperature adjusting unit so that the temperature in the furnace measured by the temperature measuring unit becomes a predetermined temperature after the oxygen concentration reaches a predetermined oxygen concentration. 11. The method of claim 10,
Wherein,
A first heating step of heating at a first temperature in at least a first oxygen concentration atmosphere,
And a second heating step of performing heating at a second temperature in a second oxygen concentration atmosphere in the above-
And controls the gas flow rate adjusting unit and the temperature adjusting unit to continuously perform the first heating process and the second heating process. The method according to claim 10 or 11,
Wherein the oxygen concentration measuring unit comprises:
A gas collecting port for collecting gas in the furnace,
An oxygen concentration meter for measuring an oxygen concentration in the gas sampling port,
And a cold trap positioned between the oxygen concentration meter and the gas sampling port. 10. The method according to any one of claims 5 to 9,
The method for producing a heat-resistant resin film according to any one of claims 10 to 12, wherein the step of heating in the multistage is performed using the heating furnace. An image display apparatus comprising the heat resistant resin film according to any one of claims 1 to 4. A process for producing a heat resistant resin film by the process for producing a heat resistant resin film according to any one of claims 5 to 9 and a process for forming a pixel driving element or a colored pixel on the heat resistant resin film Wherein the step of forming the first electrode is performed after the step of forming the second electrode. 16. The method of claim 15,
And peeling the heat-resistant resin film from the support. 17. The method according to claim 15 or 16,
Wherein the image display device is an organic EL display.

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