Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1003—Preparatory processes
  • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
  • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
  • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
  • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1003—Preparatory processes
  • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
  • C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
  • C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1075—Partially aromatic polyimides
  • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

• the present invention relates to a method for producing a polyimide resin varnish and a method for producing a polyimide-glass laminate.
• polyimide resin Since polyimide resin has excellent mechanical properties and heat resistance, its application to various uses is being considered. Recently, polyimide with excellent transparency has been developed, and products using polyimide film for image display devices such as liquid crystal displays and OLED displays have also been developed. Therefore, polyimide resins that satisfy the performance as optical materials are being developed. In the process of manufacturing a film, when coating an inorganic material on a support to form a film, adhesion to the support is required so that it does not peel off from the support during drying. In response to such demands, studies have been made to impart reactivity to polyimide precursors.
• Patent Document 1 discloses that an alkoxysilane compound containing an amino group, a tetracarboxylic dianhydride, and an aromatic diamine are used to form a thick film without peeling and to store it stably.
• An alkoxysilane-modified polyamic acid solution obtained by reaction with a polyamic acid obtained by reaction at a specific ratio is disclosed.
• a varnish containing a polyimide resin that is soluble in a solvent is desired.
• the present invention has been made in view of these circumstances, and an object of the present invention is to provide a method for producing a polyimide resin varnish, a polyimide resin, and a polyimide resin varnish that can produce a laminate with excellent adhesion between glass and polyimide resin. - To provide a method for manufacturing a glass laminate.
• the present inventors have developed a production method in which a raw material containing an aliphatic tetracarboxylic dianhydride and an aromatic diamine is polymerized at a specific temperature in a dry gas atmosphere, and an alkoxysilylamine compound is further reacted at a specific temperature to solve the above problems. He found a solution and completed his invention.
• a method for producing a polyimide resin varnish which includes the following step (A) and the following step (B), and is under a dry gas atmosphere from the start of step (A) to the end of step (B).
• Step (B) Step of reacting the polymer obtained in step (A) with an alkoxysilylamine compound at 60 to 130°C
• the tetracarboxylic acid component is a compound represented by the following formula (1) and the following: The method for producing a polyimide resin varnish according to the above [1], which contains at least one selected from the group consisting of compounds represented by formula (2). [3] The method for producing a polyimide resin varnish according to [1] or [2] above, wherein the diamine component contains a compound represented by the following formula (3).
• polyimide resin varnish obtained by the production method described in any one of [1] to [8] above is applied to the glass surface, heated and dried at 60 to 200°C, and polyimide-glass laminated.
• a method for producing a polyimide-glass laminate [10] The method for producing a polyimide-glass laminate according to [9] above, wherein the polyimide-glass laminate has a polyimide layer, and the polyimide layer has a thickness of 0.8 to 5 ⁇ m.
• X is a tetravalent aliphatic tetracarboxylic acid residue
• Y is a divalent aromatic diamine residue
• Z is an alkoxysilylamino group
• Z' is an alkoxysilylamino group. group or -OR 1
• n is a positive integer.
• R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
• the present invention it is possible to provide a method for producing a polyimide resin varnish, a polyimide resin, and a method for producing a polyimide-glass laminate, which can produce a laminate with excellent adhesion between glass and polyimide resin.
• the method for producing a polyimide resin varnish of the present invention includes the following step (A) and the following step (B), and the polyimide resin is under a dry gas atmosphere from the start of step (A) to the end of step (B).
• the process is carried out under a dry gas atmosphere from the start of step (A) to the end of step (B).
• the time point at which step (A) starts refers to the time point at which heating is started. In other words, it refers to the point at which the temperature of the solution containing the tetracarboxylic acid component, the diamine component, and the organic solvent starts to rise in order to polymerize the tetracarboxylic acid component and the diamine component. It is also preferable to charge the tetracarboxylic acid component, diamine component, organic solvent, etc. into the reaction vessel under a dry gas atmosphere.
• the end of step (B) refers to the time when the reaction between the polymer and the alkoxysilylamine compound is completed and the reaction solution does not change even if heated further. It is preferable to heat the reaction for a sufficient time to complete the reaction, and then conduct the reaction under a dry gas atmosphere until cooling is started.
• a dry gas atmosphere is used from the start of step (A) to the end of step (B), but a small amount of dry gas is used as long as the effect of the present invention is not impaired.
• the manufacturing method of the present invention also includes cases where gases other than those mentioned above are mixed.
• drying gas is preferably an inert gas, and more preferably nitrogen gas.
• dry gas in the production method of the present invention refers to a gas having a water concentration of 20 ppm or less.
• the moisture concentration of the drying gas is preferably 10 ppm or less.
• the method for producing a polyimide resin varnish of the present invention includes first polymerizing a tetracarboxylic acid component containing an aliphatic tetracarboxylic dianhydride and a diamine component containing an aromatic diamine at 100 to 210°C in an organic solvent. Obtain a polymer.
• the polymer is polyimide.
• this step by polymerizing and imidizing in an organic solvent, a varnish containing a polyimide resin soluble in a solvent can be efficiently obtained.
• the tetracarboxylic acid component subjected to polymerization in this step includes an aliphatic tetracarboxylic dianhydride.
• the tetracarboxylic acid component to be subjected to polymerization in this step is preferably a compound represented by the following formula (1) and a compound represented by the following formula (2). It contains at least one compound selected from the group consisting of, more preferably a compound represented by the following formula (1).
• the tetracarboxylic acid component subjected to polymerization in this step is preferably an alicyclic tetracarboxylic dianhydride, more preferably a compound represented by the following formula (1) and a compound represented by the following formula (2). It is at least one selected from the group consisting of the compounds represented by the formula (1), and more preferably a compound represented by the following formula (1).
• the total ratio of the compound represented by the following formula (1) and the compound represented by the following formula (2) in the tetracarboxylic acid component used in this step is preferably 50 mol% or more, more preferably The content is 70 mol% or more, more preferably 90 mol% or more, even more preferably 95 mol% or more.
• the upper limit of the total ratio of the compound represented by the following formula (1) and the following formula (2) is not particularly limited, and may be 100 mol% or less.
• the ratio of the compound represented by the following formula (1) is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, even more preferably 95 mol%. That's all.
• the upper limit of the ratio of the compound represented by the following formula (1) is not particularly limited, and may be 100 mol% or less.
• Examples of the alicyclic tetracarboxylic dianhydride include 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, norbornane-2-spiro- ⁇ -Cyclopentanone- ⁇ '-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene- 2,3,5,6-tetracarboxylic dianhydride, dicyclohexyltetracarboxylic dianhydride, 5,5'-(1,4-phenylene)-bis[hexahydro-4,7-Methanoisobenzofuran-1,3- dione], 5,5'-bis-2-norbornene-5,5',6,6'-tetracarboxylic acid-5,5',6,6'-dianhydride,
• 1,2,4,5-cyclohexanetetracarboxylic dianhydride which is a compound represented by the above formula (1)
• 1,2,3, which is a compound represented by the above formula (2) 1,2,3, which is a compound represented by the above formula (2).
• ,4-cyclobutanetetracarboxylic dianhydride is preferred, and 1,2,4,5-cyclohexanetetracarboxylic dianhydride is more preferred.
• the resulting polyimide resin is soluble in a solvent, has excellent transparency, and also has excellent adhesion to glass.
• the resulting polyimide resin is soluble in a solvent and has excellent transparency. It has excellent adhesion to glass.
• the tetracarboxylic acid component to be subjected to polymerization in this step may include a tetracarboxylic dianhydride other than the alicyclic tetracarboxylic dianhydride.
• tetracarboxylic dianhydrides include, but are not particularly limited to, aromatic tetracarboxylic dianhydrides and aliphatic tetracarboxylic dianhydrides.
• aromatic tetracarboxylic dianhydride examples include biphenyltetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, pyromellitic dianhydride, 3,3', 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride Examples include anhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, and the like.
• aliphatic tetracarboxylic dianhydride examples include 1,2,3,4-butanetetracarboxylic dianhydride.
• the number of tetracarboxylic acid components subjected to polymerization in this step may be one or two or more.
• aromatic tetracarboxylic dianhydride means a tetracarboxylic dianhydride containing one or more aromatic rings
• alicyclic tetracarboxylic dianhydride means a tetracarboxylic dianhydride containing one or more alicyclic rings. It means a tetracarboxylic dianhydride that contains the above and does not contain an aromatic ring.
• Aliphatic tetracarboxylic dianhydride means tetracarboxylic dianhydride that does not contain an aromatic ring, but only when written together with alicyclic tetracarboxylic dianhydride, it includes both aromatic and alicyclic rings. Tetracarboxylic dianhydride.
• the diamine component subjected to polymerization in this step includes aromatic diamine.
• the diamine to be subjected to polymerization in this step preferably includes a compound represented by the following formula (3).
• the diamine component subjected to polymerization in this step is preferably an aromatic diamine, and more preferably a compound represented by the following formula (3).
• the ratio of the compound represented by the following formula (3) in the diamine component used in this step is preferably 20 mol% or more, more preferably 30 mol% or more, and still more preferably 50 mol% or more.
• the content is even more preferably 70 mol% or more, and even more preferably 90 mol% or more.
• the upper limit of the ratio of the compound represented by the following formula (3) is not particularly limited, and may be 100 mol% or less.
• Aromatic diamines include 1-(4-aminophenyl)-1,3,3-trimethylphenylindanamine, ⁇ , ⁇ '-bis(4-aminophenyl)-1,3-diisopropylbenzene, 4,4' -bis(4-aminophenoxy)biphenyl, 4-aminophenyl-4-aminobenzoate, 2,2'-bis(trifluoromethyl)benzidine, 3,5-diaminobenzoic acid, 9,9-bis(4-amino phenyl)fluorene, 1,4-phenylenediamine, p-xylylenediamine, 1,5-diaminonaphthalene, 2,2'-dimethylbiphenyl-4,4'-diamine, 4,4'-diaminodiphenylmethane, 1,4 -Bis[2-(4-aminophenyl)-2-propyl]benzene, 2,2-bis(4-aminoph
• 1-(4-aminophenyl)-1,3,3-trimethylphenylindanamine which is a compound represented by the above formula (3)
• the resulting polyimide resin is soluble in a solvent, has excellent transparency, and also has excellent adhesion to glass.
• the compound represented by the above formula (3) the resulting polyimide resin is soluble in a solvent, has very good transparency, and has very good adhesion to glass.
• the compound represented by formula (3), 1-(4-aminophenyl)-1,3,3-trimethylphenylindanamine is preferably 1-(4-aminophenyl)-1,3,3- At least one selected from the group consisting of trimethylphenylindan-6-amine and 1-(4-aminophenyl)-1,3,3-trimethylphenylindan-5-amine, and 1-(4-aminophenyl) It is more preferred to use both -1,3,3-trimethylphenylindan-6-amine and 1-(4-aminophenyl)-1,3,3-trimethylphenylindan-5-amine.
• ⁇ , ⁇ '-bis(4-aminophenyl)-1,3- which is a compound represented by the following formula (7) Diisopropylbenzene is preferred.
• the compound represented by formula (3) and the compound represented by formula (7) are used as the diamine component to be subjected to polycondensation in this step, the compound represented by formula (3) and The molar ratio [(3)/(7)] of the compound represented by formula (7) is preferably 5/95 to 70/30, more preferably 10/90 to 50/50, even more preferably is 20/80 to 40/60.
• the diamine component subjected to polymerization in this step may include diamines other than aromatic diamines.
• diamines include, but are not limited to, alicyclic diamines and aliphatic diamines.
• examples of the alicyclic diamine include 1,3-bis(aminomethyl)cyclohexane and 1,4-bis(aminomethyl)cyclohexane.
• examples of aliphatic diamines include ethylene diamine and hexamethylene diamine.
• the number of diamine components subjected to polymerization in this step may be one or two or more.
• aromatic diamine means a diamine containing one or more aromatic rings
• alicyclic diamine means a diamine containing one or more alicyclic rings and no aromatic ring
• Group diamine means a diamine containing neither aromatic ring nor alicyclic ring.
• This step is a step in which a tetracarboxylic acid component containing an aliphatic tetracarboxylic dianhydride and a diamine component containing an aromatic diamine are polymerized at 100 to 210°C in an organic solvent to obtain a polymer.
• the polymerization reaction in this step is preferably carried out as follows.
• the polymerization reaction in this step is performed in an organic solvent.
• the organic solvent used in the polymerization reaction may be any solvent as long as it can dissolve the polyimide produced, and examples include aprotic solvents, phenol solvents, ether solvents, carbonate solvents, etc. At least one selected from the group consisting of solvents, ether solvents, and carbonate solvents is preferred.
• the aprotic solvent include amide solvents such as cyclic amides and chain amides, phosphorus-containing amide solvents, sulfur-containing solvents, ketone solvents, and ester solvents containing cyclic esters.
• the organic solvent preferably contains at least one selected from the group consisting of a cyclic amide, a chain amide, and a cyclic ester, and more preferably at least one selected from the group consisting of a chain amide and a cyclic ester. , preferably a cyclic ester.
• the organic solvent is preferably at least one selected from the group consisting of a cyclic amide, a chain amide, and a cyclic ester, and more preferably at least one selected from the group consisting of a chain amide and a cyclic ester, Preferably it is a cyclic ester.
• Examples of the cyclic amide include N-methyl-2-pyrrolidone, N-methylcaprolactam, and 1,3-dimethylimidazolidinone, with N-methyl-2-pyrrolidone being preferred.
• Examples of the chain amide include N,N-dimethylformamide, N,N-dimethylacetamide, and tetramethylurea.
• Examples of the cyclic ester include ⁇ -butyrolactone and ⁇ -valerolactone.
• Other ester solvents include acetic acid (2-methoxy-1-methylethyl) and the like.
• Examples of the phosphorus-containing amide solvent include hexamethylphosphoric amide, hexamethylphosphine triamide, and the like.
• Examples of the sulfur-containing solvent include dimethylsulfone, dimethylsulfoxide, and sulfolane.
• Examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, methyl cyclohexanone, and the like.
• phenolic solvents include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4 -xylenol, 3,5-xylenol, etc.
• ether solvents include 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, 1,2-bis(2-methoxyethoxy)ethane, and bis[2-(2-methoxyethoxy)ethyl]. Examples include ether, tetrahydrofuran, 1,4-dioxane and the like.
• carbonate solvents include diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate, and the like.
• the organic solvent preferably contains at least one selected from the group consisting of ⁇ -butyrolactone, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone, and more preferably ⁇ -butyrolactone.
• - Contains at least one member selected from the group consisting of butyrolactone and N,N-dimethylacetamide, preferably ⁇ -butyrolactone.
• the organic solvent is preferably at least one selected from the group consisting of ⁇ -butyrolactone, N,N-dimethylacetamide and N-methyl-2-pyrrolidone, more preferably ⁇ -butyrolactone and N,N-dimethyl At least one selected from the group consisting of acetamides, preferably ⁇ -butyrolactone.
• the above organic solvents may be used alone or in combination of two or more.
• the method for polymerizing the tetracarboxylic acid component and the diamine component is not particularly limited, and any known method can be used.
• the specific reaction method is as follows: (1) A solution containing a diamine component and an organic solvent and a tetracarboxylic acid component are charged into a reactor, stirred at 10 to 110°C for 0.5 to 30 hours as necessary, and then (2) A method in which a solution containing a diamine component and an organic solvent and a tetracarboxylic acid component are charged into a reactor, and the temperature is immediately raised to conduct a polymerization reaction.
• the charging ratio of the tetracarboxylic acid component and the diamine component used for producing the polyimide resin is preferably 0.9 to 1.1 mol of the diamine component per 1 mol of the tetracarboxylic acid component.
• water since water is produced by imidization, it is preferable to carry out the reaction while removing water produced during production using a Dean-Stark apparatus or the like. By performing such an operation, the degree of polymerization and the imidization rate can be further increased.
• imidization catalysts include base catalysts and acid catalysts.
• Base catalysts include pyridine, quinoline, isoquinoline, ⁇ -picoline, ⁇ -picoline, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine, triethylenediamine, imidazole, N,N
• organic base catalysts such as -dimethylaniline and N,N-diethylaniline
• inorganic base catalysts such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, and sodium hydrogen carbonate.
• examples of acid catalysts include crotonic acid, acrylic acid, trans-3-hexenoic acid, cinnamic acid, benzoic acid, methylbenzoic acid, oxybenzoic acid, terephthalic acid, benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, etc. can be mentioned.
• the above imidization catalysts may be used alone or in combination of two or more.
• base catalysts are preferred, organic base catalysts are more preferred, one or more selected from triethylamine and triethylenediamine are still more preferred, and triethylamine and triethylenediamine are even more preferred.
• the temperature of the polymerization reaction in the main polymerization step is 100 to 210°C, preferably 150 to 210°C, from the viewpoint of reaction rate and suppression of gelation and the like.
• the reaction time is preferably 0.5 to 20 hours, more preferably 2 to 20 hours, even more preferably 4 to 15 hours, even more preferably 6 to 6 hours after the start of distillation of the produced water. ⁇ 15 hours, more preferably 6 to 10 hours.
• the main polymerization step is performed in a dry gas atmosphere as described above. By setting the reaction time within the above range, the reaction rate is improved, so that the adhesion of the resulting polyimide resin to glass can be further improved.
• the concentration of the polymer (polyimide) in the reaction product (polymer solution) obtained after the polymerization reaction is preferably 1 to 50% by mass, more preferably 3 to 35% by mass, and still more preferably 5 to 50% by mass. It is 30% by mass.
• the weight average molecular weight (Mw) of the polymer (polyimide) obtained in this step is preferably 300,000 or more, more preferably 400,000 or more, and even more preferably is more than 500,000. Although there is no upper limit to the upper limit, it is preferably 1,000,000 or less, more preferably 700,000 or less. Further, from the same viewpoint, the number average molecular weight is preferably 50,000 to 500,000.
• the weight average molecular weight and number average molecular weight of the polymer can be determined from standard polystyrene equivalent values measured by gel filtration chromatography.
• a terminal capping agent may be used in addition to the above-mentioned tetracarboxylic acid component and diamine component.
• the terminal capping agent monoamines or dicarboxylic acids are preferable.
• the amount of the terminal capping agent to be introduced is preferably 0.0001 to 0.1 mol, more preferably 0.001 to 0.06 mol, per 1 mol of the tetracarboxylic acid component.
• Examples of monoamine terminal capping agents include methylamine, ethylamine, propylamine, butylamine, benzylamine, 4-methylbenzylamine, 4-ethylbenzylamine, 4-dodecylbenzylamine, 3-methylbenzylamine, 3- Ethylbenzylamine, aniline, 3-methylaniline, 4-methylaniline and the like are preferred. Among these, benzylamine and aniline can be preferably used.
• dicarboxylic acid terminal capping agent dicarboxylic acids are preferred, and a portion thereof may be ring-closed.
• phthalic acid, phthalic anhydride, 4-chlorophthalic acid, tetrafluorophthalic acid, 2,3-benzophenone dicarboxylic acid, 3,4-benzophenone dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, 4-cyclohexene-1 , 2-dicarboxylic acid and the like are preferred.
• phthalic acid and phthalic anhydride can be preferably used.
• the method for producing a polyimide resin varnish of the present invention includes, after step (A), which is a polymerization step, a step of reacting the polymer obtained in step (A) with an alkoxysilylamine compound at 60 to 130°C. include. By performing this step, it is possible to obtain a polyimide resin varnish that contains a polyimide resin that is soluble in a solvent and that does not reduce the adhesion of the polyimide resin to glass even when dried at low temperatures.
• alkoxysilylamine compound reacted with the polymer in this step is not particularly limited as long as it is an amine compound having an alkoxysilyl group in one molecule. Suitable alkoxysilylamine compounds will be explained below.
• the alkoxysilylamine compound has an alkoxysilyl group.
• the alkoxysilyl group is preferably at least one selected from the group consisting of a trialkoxysilyl group, a dialkoxy(alkyl)silyl group, and a monoalkoxy(dialkyl)silyl group, and a trialkoxysilyl group is more preferable.
• the trialkoxysilyl group at least one selected from the group consisting of trimethoxysilyl group and triethoxysilyl group is preferable, and trimethoxysilyl group is more preferable.
• the alkoxysilylamine compound may be any of a primary amine, a secondary amine, and a tertiary amine, but preferably at least one selected from the group consisting of primary amines and secondary amines, and more preferably secondary amines.
• the aliphatic tetracarboxylic dianhydride used in the production method of the present invention as a raw material for polyimide resin has lower reactivity toward amines than aromatic tetracarboxylic dianhydride, so the alkoxysilylamine compound High nucleophilicity is required.
• primary amines with high nucleophilicity may react with organic solvents depending on the type of organic solvent due to their high nucleophilicity.
• the alkoxysilylamine compound preferably contains a secondary amine having a trialkoxysilyl group, and more preferably the alkoxysilylamine compound is a secondary amine having a trialkoxysilyl group.
• the alkoxysilylamine compound contains at least one selected from the group consisting of a compound represented by the following formula (4) and a compound represented by the following formula (5); It is more preferable that the compound represented by (4) is included. Further, it is more preferable that the alkoxysilylamine compound is at least one selected from the group consisting of a compound represented by the following formula (4) and a compound represented by the following formula (5), and the alkoxysilylamine compound is preferably at least one compound represented by the following formula (4). It is more preferable to include a compound represented by: When the alkoxysilylamine compound is a compound represented by the following formula (4), the resulting polyimide resin has high stability. Me in the following formulas (4) and (5) is a methyl group.
• the amount of the alkoxysilylamine compound used in this step is preferably 0.01 to 2.00 parts by mass based on 100 parts by mass of the total amount of the tetracarboxylic acid component and the diamine component used in step (A). and more preferably 0.01 to 1.00 parts by mass, still more preferably 0.10 to 1.00 parts by mass, even more preferably 0.15 to 1.00 parts by mass, and more preferably The amount is more preferably 0.30 to 1.00 parts by weight, even more preferably 0.50 to 1.00 parts by weight, and even more preferably 0.50 to 0.80 parts by weight.
• the amount of the alkoxysilylamine compound used is within the above range, the adhesion of the resulting polyimide resin to glass can be further improved.
• the alkoxysilylamine compound is preferably added to the solution of the polymer obtained in step (A), and the alkoxysilylamine compound is added to the solution of the polymer obtained in step (A) simultaneously with the organic solvent or as an organic solvent solution. It is more preferable to add it to a solution of the polymer.
• the organic solvent used here is preferably the organic solvent used in the polymerization reaction, and more preferably the organic solvent contained in the polymer solution is the same organic solvent.
• reaction temperature in this step (B) of reacting the polymer and the alkoxysilylamine compound is 60 to 130°C, preferably 70 to 130°C, more preferably 80 to 130°C, and preferably 80 to 130°C. ⁇ 110°C.
• reaction time of this step (B) in which the polymer and the alkoxysilylamine compound are reacted may be changed depending on the reaction temperature and the type of alkoxysilylamine compound, but is preferably 0.5 to 50 hours, and more Preferably it is 1 to 30 hours, preferably 2 to 10 hours.
• the polyimide resin varnish obtained by the method for producing a polyimide resin varnish contains a polyimide resin.
• the polyimide resin includes a structural unit derived from the tetracarboxylic acid component and a structural unit derived from the diamine component.
• the polyimide resin preferably contains a structural unit derived from an alicyclic tetracarboxylic dianhydride, more preferably a structural unit derived from a compound represented by the following formula (1), and the following: It contains at least one structural unit selected from the group consisting of structural units derived from the compound represented by the formula (2), and more preferably contains a structural unit derived from the compound represented by the following formula (1).
• the total ratio of the structural units derived from the compound represented by the following formula (1) and the structural units derived from the compound represented by the following formula (2) in the structural units derived from the tetracarboxylic acid component is , preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, even more preferably 95 mol% or more.
• the upper limit of the total ratio of the structural units derived from the compound represented by the following formula (1) and the structural units derived from the compound represented by the following formula (2) is not particularly limited, and is 100 mol% or less That's fine.
• the polyimide resin is soluble in a solvent by containing either or both of the structural unit derived from the compound represented by the above formula (1) and the structural unit derived from the compound represented by the above formula (2). Therefore, it has excellent transparency and adhesion to glass.
• the structural unit derived from a tetracarboxylic acid component may include a structural unit derived from a tetracarboxylic dianhydride other than the structural unit derived from an alicyclic tetracarboxylic dianhydride.
• Such structural units derived from tetracarboxylic dianhydrides are not particularly limited, but include structural units derived from aromatic tetracarboxylic dianhydrides, and structural units derived from aliphatic tetracarboxylic dianhydrides. Examples include structural units that The number of structural units derived from tetracarboxylic dianhydride may be one or more, and may be one or two or more.
• the polyimide preferably contains a structural unit derived from an aromatic diamine, and more preferably contains a structural unit derived from a compound represented by the following formula (3).
• the ratio of the structural unit derived from the compound represented by the following formula (3) in the structural unit derived from diamine is preferably 20 mol% or more, more preferably 30 mol% or more, and even more preferably is 50 mol% or more, more preferably 70 mol% or more, even more preferably 90 mol% or more.
• the upper limit of the ratio of the structural units derived from the compound represented by the following formula (3) is not particularly limited, and may be 100 mol% or less.
• the polyimide resin becomes a polyimide resin that is soluble in a solvent, has very good transparency, and has very good adhesion to glass. Further, it may contain a structural unit derived from a compound represented by the following formula (7). When it contains both a structural unit derived from the compound represented by the formula (3) and a structural unit derived from the compound represented by the formula (7), the compound represented by the formula (3) is derived from the compound represented by the formula (3).
• the molar ratio [(3)/(7)] of the structural unit and the structural unit derived from the compound represented by formula (7) is preferably 5/95 to 70/30, more preferably 10 /90 to 50/50, more preferably 20/80 to 40/60.
• the structural unit derived from a diamine may include a structural unit derived from a diamine other than the structural unit derived from an aromatic diamine.
• Such structural units derived from diamines include, but are not particularly limited to, structural units derived from alicyclic diamines and structural units derived from aliphatic diamines.
• the number of structural units derived from diamine may be one or more, and may be one or two or more.
• the polyimide resin of the present invention includes a polyimide resin having a structure represented by the following general formula (6).
• X is a tetravalent aliphatic tetracarboxylic acid residue
• Y is a divalent aromatic diamine residue
• Z is an alkoxysilylamino group
• Z' is an alkoxysilylamino group. group or -OR 1
• n is a positive integer.
• R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
• X is a tetravalent aliphatic tetracarboxylic acid residue.
• "Aliphatic tetracarboxylic acid residue” refers to a portion obtained by removing two acid anhydride groups (four carboxy groups) from a corresponding aliphatic tetracarboxylic dianhydride.
• the aliphatic tetracarboxylic dianhydride corresponding to X preferably contains at least one selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2), More preferably, it includes a compound represented by the following formula (1).
• the alicyclic tetracarboxylic dianhydride corresponding to X is preferably at least one selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2). More preferably, it is a compound represented by the following formula (1).
• the total ratio of the compound represented by the following formula (1) and the compound represented by the following formula (2) in the aliphatic tetracarboxylic dianhydride corresponding to X is preferably 50 mol% or more, The content is more preferably 70 mol% or more, still more preferably 90 mol% or more, even more preferably 95 mol% or more.
• the upper limit of the total ratio of the compound represented by the following formula (1) and the following formula (2) is not particularly limited, and may be 100 mol% or less.
• the resulting polyimide resin is soluble in a solvent, has excellent transparency, and also has excellent adhesion to glass.
• the polyimide resin becomes resistant to solvents. It is soluble, has excellent transparency, and has excellent adhesion to glass.
• Y is a divalent aromatic diamine residue.
• "Aromatic diamine residue” refers to a portion obtained by removing two amino groups from a corresponding aromatic diamine.
• the aromatic diamine corresponding to Y preferably includes a compound represented by the following formula (3).
• the aromatic diamine corresponding to Y is more preferably a compound represented by the following formula (3).
• the ratio of the compound represented by the following formula (3) in the aromatic diamine corresponding to Y is preferably 20 mol% or more, more preferably 30 mol% or more, and still more preferably 50 mol% or more.
• the content is even more preferably 70 mol% or more, and even more preferably 90 mol% or more.
• the upper limit of the ratio of the compound represented by the following formula (3) is not particularly limited, and may be 100 mol% or less.
• the polyimide resin is soluble in solvents, has excellent transparency, and also has excellent adhesion to glass.
• the aromatic diamine corresponding to Y may include a compound represented by the following formula (7).
• the aromatic diamine corresponding to Y contains both the compound represented by the formula (3) and the compound represented by the formula (7), the compound represented by the formula (3) and the compound represented by the formula (7)
• the molar ratio [(3)/(7)] of the represented compounds is preferably 5/95 to 70/30, more preferably 10/90 to 50/50, even more preferably 20/80 to It is 40/60.
• Z is an alkoxysilylamino group.
• Z' is an alkoxysilylamino group or -OR 1 .
• R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
• the alkoxysilylamino group has a structure in which an adjacent carbon and the nitrogen of the amino group are bonded. That is, the terminal of the polyimide resin of the present invention has at least one alkoxysilylamino group.
• the polyimide resin contained in the polyimide resin varnish obtained by the above-mentioned manufacturing method usually has a structure represented by the general formula (6), in which both Z and Z' are -OR 1 . Also included are polyimide resins having a structure.
• the alkoxysilyl group contained in the alkoxysilylamino group is preferably at least one selected from the group consisting of a trialkoxysilyl group, a dialkoxy(alkyl)silyl group, and a monoalkoxy(dialkyl)silyl group, and the trialkoxysilyl group is More preferred.
• the trialkoxysilyl group at least one selected from the group consisting of trimethoxysilyl group and triethoxysilyl group is preferable, and trimethoxysilyl group is more preferable.
• the amino group of the alkoxysilylamino group may be either a secondary amino group or a tertiary amino group, but a tertiary amino group is more preferable. Since the amino group of the alkoxysilylamino group is a tertiary amino group, the polyimide resin is soluble in a solvent and does not lose its adhesiveness to glass even when dried at a low temperature. Therefore, the alkoxysilylamino group is preferably an alkoxysilylamino group corresponding to a secondary amine having a trialkoxysilyl group.
• the alkoxysilylamine compound corresponding to the alkoxysilylamino group preferably contains at least one selected from the group consisting of a compound represented by the following formula (4) and a compound represented by the following formula (5). , more preferably contains a compound represented by the following formula (4). Further, the alkoxysilylamine compound corresponding to the alkoxysilylamino group may be at least one selected from the group consisting of a compound represented by the following formula (4) and a compound represented by the following formula (5). It is more preferable that the compound represented by the following formula (4) is included. When the alkoxysilylamine compound is a compound represented by the following formula (4), the resulting polyimide resin has high stability. Me in the following formulas (4) and (5) is a methyl group.
• Z' may be -OR1 .
• R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
• R 1 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom. That is, when Z' is -OR 1 , Z' is preferably at least one selected from the group consisting of a hydroxyl group and an alkoxy group having 1 to 4 carbon atoms.
• n is a positive integer. n can be appropriately adjusted depending on the molecular weight of the polyimide resin, and differs depending on each molecule. The average value of n is preferably 10 to 10,000, more preferably 100 to 1,000.
• formula (6) shows only one end of the molecule constituting the polyimide resin
• the other end of the molecule constituting the polyimide resin also contains an aliphatic tetracarboxylic acid derived from an aliphatic tetracarboxylic acid.
• a residue may be bonded, and a substituent similar to Z or Z' may also be bonded.
• the polyimide resin varnish of the present invention is a polyimide resin varnish obtained by the above method for producing a polyimide resin varnish, and contains a polyimide resin and an organic solvent.
• the polyimide resin varnish of the present invention also includes a polyimide resin varnish containing the polyimide resin and an organic solvent. Specifically, polyimide resin varnishes containing a polyimide resin having a structure represented by the general formula (6) and an organic solvent are also included.
• the organic solvent contained in the polyimide resin varnish is the same as the organic solvent used in the step (A) or the step (B).
• the solution obtained in the step (B) may be used as it is as a polyimide resin varnish, or by adjusting the polyimide concentration (solid content) suitable for the polyimide resin varnish in the step (B), the solution obtained in the step (B)
• the solution obtained can be used as it is as a polyimide resin varnish.
• the polyimide resin varnish has polyimide dissolved therein uniformly, and the concentration (solid content) of the polyimide is preferably 5 to 40% by mass, more preferably 10 to 30% by mass.
• the viscosity (25° C.) of the polyimide varnish is preferably 1 to 200 Pa ⁇ s, more preferably 1 to 100 Pa ⁇ s.
• the polyimide resin varnish may contain inorganic fillers, adhesion promoters, release agents, flame retardants, ultraviolet stabilizers, surfactants, leveling agents, antifoaming agents, and optical brighteners within the range that does not impair the effects of the present invention. , a crosslinking agent, a polymerization initiator, a photosensitizer, and other various additives.
• the polyimide-glass laminate of the present invention is preferably a polyimide-glass laminate obtained by applying a polyimide resin varnish to a glass surface, heating and drying it.
• the polyimide-glass laminate of the present invention also includes a polyimide-glass laminate formed by laminating the polyimide resin and glass. Specifically, it also includes a polyimide-glass laminate formed by laminating a polyimide resin having a structure represented by the general formula (6) and glass.
• the polyimide-glass laminate of the present invention has excellent adhesion of the polyimide layer to glass.
• the glass included in the polyimide-glass laminate has a plate shape. That is, it has a shape in which the thickness (length in the thickness direction) is shorter than the length and width.
• the thickness of the glass may be appropriately selected depending on the application, but is preferably 0.05 to 50 mm, more preferably 0.1 to 30 mm, still more preferably 0.3 to 20 mm, and even more preferably is 0.5 to 10 mm.
• the type of glass is not particularly limited, and non-alkali glass (borosilicate glass), alkali glass, soda glass, non-fluorescent glass, phosphate glass, boric acid glass, quartz, etc. can be used.
• the top surface of the glass substrate has high flatness. Specifically, the surface roughness Rmax is preferably 10 ⁇ m or less, and more preferably 1 ⁇ m or less.
• the polyimide-glass laminate has a polyimide layer.
• the polyimide layer is made of polyimide contained in the polyimide resin or the polyimide resin varnish obtained by the manufacturing method.
• the thickness of the polyimide layer may be appropriately selected depending on the application, but is preferably 0.1 to 20 ⁇ m, more preferably 0.5 to 10 ⁇ m, still more preferably 0.8 to 5 ⁇ m, and more preferably More preferably, it is 1 to 2 ⁇ m.
• the polyimide-glass laminate of the present invention is preferably a polyimide-glass laminate obtained by applying a polyimide resin varnish to the glass surface, heating and drying it.
• the polyimide resin varnish used here is preferably the polyimide resin varnish described in the section [Polyimide resin varnish] above, and the polyimide resin varnish obtained by the production method of the present invention, or the polyimide resin varnish having the structure represented by formula (6).
• a polyimide resin varnish containing a polyimide resin and an organic solvent is more preferable, and a polyimide resin varnish obtained by the production method of the present invention is even more preferable.
• a glass rod, a coater, or the like can be used to apply the polyimide resin varnish to the glass surface.
• the organic solvent is removed by heating and drying.
• a polyimide layer can be formed on the glass surface.
• the drying temperature is preferably 50 to 250°C, more preferably 60 to 200°C, even more preferably 80 to 190°C, even more preferably 120 to 180°C.
• Preheating may be performed to equalize the applied varnish before drying, and the temperature during preheating is preferably 50 to 120°C, more preferably 60 to 100°C.
• the polyimide resin varnish of the present invention contains a polyimide resin that is soluble in a solvent, and the adhesion of the polyimide resin to glass does not deteriorate even when dried at low temperatures. A polyimide-glass laminate with excellent adhesion between glass and glass can be obtained.
• the polyimide resin varnish obtained by the production method of the present invention also contains a polyimide resin that is soluble in a solvent, and the adhesion of the polyimide resin to glass does not decrease even when dried at low temperatures. Even at high temperatures, a polyimide-glass laminate with excellent adhesion between the polyimide layer and glass can be obtained.
• the polyimide resin varnish obtained by the above-mentioned production method is applied to the glass surface, heated at 60 to 200°C and dried, and the polyimide-glass laminate is produced.
• One example is how to get a body.
• the polyimide-glass laminate thus obtained has excellent adhesion of the polyimide layer to the glass.
• the polyimide-glass laminate of the present invention has excellent adhesion of the polyimide layer to glass, it can be suitably used in various applications such as optical materials.
• the peeled area of the polyimide resin is more than 0% and less than 5%.
• 3 The peeled area of the polyimide resin is 5% or more and less than 15%.
• 2 The peeled area of the polyimide resin is 15% or more and less than 35%.
• 1 The peeled area of the polyimide resin is 35% or more and less than 65%.
• 0 The peeled area of the polyimide resin is 65% or more.
• the polyimide resin peeled off after immersion in hot water and before evaluation of adhesion.
• the laminate using the varnish of Example 2 was rated 3 based on the following evaluation criteria, the laminate using the varnish of Examples 3 and 4 was rated 5 based on the following evaluation criteria, and the laminate using the varnish of Example 5 was rated 5 based on the following evaluation criteria.
• the peeled area of the polyimide resin is more than 0% and less than 5%.
• 3 The peeled area of the polyimide resin is 5% or more and less than 15%.
• 2 The peeled area of the polyimide resin is 15% or more and less than 35%.
• 1 The peeled area of the polyimide resin is 35% or more and less than 65%.
• 0 The peeled area of the polyimide resin is 65% or more.
• tetracarboxylic acid component and diamine component used in Examples and Comparative Examples, and their abbreviations are as follows.
• HPMDA 1,2,4,5-cyclohexanetetracarboxylic dianhydride (compound represented by formula (1), manufactured by Mitsubishi Gas Chemical Co., Ltd.)
• CBDA cyclobutanetetracarboxylic dianhydride (compound represented by formula (2))
• BisAP ⁇ , ⁇ '-bis(4-aminophenyl)-1,3-diisopropylbenzene (compound represented by formula (7), manufactured by Mitsui Chemicals Fine Co., Ltd.)
• TMDA 1-(4-aminophenyl)-1,3,3-trimethylphenylindan-6-amine/1-(4-aminophenyl)-1,3,3-trimethylphenylindan-5-amine mixture (formula Compound represented by (3), manufactured by Nippon Junryo Pharmaceutical Co
• solvents and catalysts used in Examples and Comparative Examples are as follows.
• GBL ⁇ -butyrolactone (manufactured by Mitsubishi Chemical Corporation)
• TEA Triethylamine (manufactured by Kanto Kagaku Co., Ltd.)
• TEDA Triethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
• Example 1 (Step (A): Polymerization step) 35.1958 g (0.1318 mol) of TMDA and 77.7159 g of GBL was added, the system temperature was set to 80° C. under an atmosphere of dry nitrogen (moisture concentration: 10 ppm or less), and the system was stirred at a rotational speed of 200 rpm to obtain a solution. Note that dry nitrogen was introduced through the nitrogen introduction tube until a polyimide resin varnish was obtained.
• Examples 2 to 9 and Comparative Examples 5 to 6 The types and amounts of the tetracarboxylic acid component and diamine component used in step (A) are as described in Table 1, the reaction conditions of step (A) are as described in Table 1, and step (B) is performed. In the same manner as in Example 1, except that the type and amount of the alkoxysilylamine compound used in Step (B) were as described in Table 1, and the reaction conditions of step (B) were as described in Table 1. A polyimide resin varnish was obtained.
• Comparative examples 1 to 3 In the same manner as in Example 1, except that the types and amounts of the tetracarboxylic acid component and diamine component used in step (A) were changed as listed in Table 1, and step (B) was not performed. A polyimide resin varnish was obtained.
• Comparative example 4 A polyimide resin varnish was obtained in the same manner as in Example 1, except that in step (A), KBM-573 was added at the same time as TMDA, and in step (B), KBM-573 was not used.
• step (B) after adding GBL to the polymer solution, a polyimide resin varnish was prepared in the same manner as in Example 1, except that the nitrogen introduced from the nitrogen introduction tube was changed to water-containing nitrogen (water concentration: 176 ppm). I got it.
• polyimide-glass laminate ⁇ Production of polyimide-glass laminate>
• the polyimide resin varnishes obtained in Examples and Comparative Examples were applied onto a glass substrate by spin coating, held at 80°C for 20 minutes on a hot plate, and then heated at 160°C for 60 minutes in a hot air dryer in an air atmosphere. The solvent was evaporated to obtain a polyimide-glass laminate.
• the thickness of the polyimide layer made of polyimide resin formed on the glass substrate was 5 ⁇ m.
• the glass substrate used here was AN100 glass (alkali-free glass, manufactured by AGC Co., Ltd., size 100 mm x 100 mm x 0.7 mm), which was cleaned with water and a 1% (w/v) potassium hydroxide aqueous solution. , those irradiated with UV were used.
• the polyimide-glass laminate produced using the polyimide resin varnish of the example has excellent adhesion between the polyimide resin and the glass even though it was dried at a low temperature. Further, it can be seen that the polyimide resin varnish of the example is uniform, and the polyimide resin contained in the varnish is soluble in the solvent. Therefore, it can be seen that the polyimide resin varnish of the present invention can provide a laminate with excellent adhesion between glass and polyimide resin. Moreover, it can be seen that the polyimide resin varnish obtained by the production method of the present invention can provide a laminate with excellent adhesion between glass and polyimide resin.

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• 2023
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