WO2018105676A1 - 剥離層の製造方法 - Google Patents
剥離層の製造方法 Download PDFInfo
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- WO2018105676A1 WO2018105676A1 PCT/JP2017/043912 JP2017043912W WO2018105676A1 WO 2018105676 A1 WO2018105676 A1 WO 2018105676A1 JP 2017043912 W JP2017043912 W JP 2017043912W WO 2018105676 A1 WO2018105676 A1 WO 2018105676A1
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- group
- release layer
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- alkali
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- 0 CC(C)(*)N*NC(*C(I(C)C)=O)=O Chemical compound CC(C)(*)N*NC(*C(I(C)C)=O)=O 0.000 description 3
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on 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 C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use 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 C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Definitions
- the present invention relates to a method for producing a release layer.
- Patent Documents 1, 2, and 3 an amorphous silicon thin film layer is formed on a glass substrate, a plastic substrate is formed on the thin film layer, and then laser irradiation is performed from the glass substrate side to crystallize amorphous silicon.
- a method of peeling a plastic substrate from a glass substrate with hydrogen gas generated along with crystallization is disclosed.
- Patent Document 4 a layer to be peeled (described as “transfer target layer” in Patent Document 4) is attached to a plastic film by using the techniques disclosed in Patent Documents 1 to 3, and a liquid crystal display device is formed. A method of completion is disclosed.
- Patent Document 5 a current glass substrate is used as a substrate (hereinafter referred to as a glass substrate), and a release layer is formed on the glass substrate using a polymer such as a cyclic olefin copolymer. Then, after forming a heat-resistant resin film such as a polyimide film on the release layer, forming and sealing the ITO transparent electrode, TFT, etc. on the film by a vacuum process, finally peeling and removing the glass substrate Is adopted.
- a heat-resistant resin film such as a polyimide film
- TFT a low-temperature polysilicon TFT having a mobility twice as fast as that of an amorphous silicon TFT is currently used.
- This low-temperature polysilicon TFT needs to be subjected to dehydrogenation annealing at 400 ° C. or higher after amorphous silicon deposition, and irradiated with a pulse laser to crystallize silicon (hereinafter referred to as TFT process).
- the temperature of the annealing process is equal to or higher than the glass transition (hereinafter Tg) of the existing polymer.
- the existing polymer has improved adhesion when heated to a temperature equal to or higher than Tg (see, for example, Patent Document 6), and the adhesion between the release layer and the resin substrate is increased after the heat treatment. In some cases, it is difficult to peel the resin substrate from the substrate.
- JP 10-125929 A Japanese Patent Laid-Open No. 10-125931 International Publication No. 2005/050754 JP-A-10-125930 JP 2010-1111853 A JP 2008-188792 A
- This invention is made
- the present inventors used a composition containing a polyamic acid having an alkali-soluble group in the molecule and an organic solvent, and determined the firing temperature at the time of forming the release layer. It is found that a release layer having an appropriate adhesion to the substrate and an appropriate adhesion to the resin substrate used in the flexible electronic device and an appropriate release property can be formed by setting the temperature to the highest temperature of the present invention. Completed.
- the present invention 1. Including a step of applying a release layer-forming composition containing at least one polyamic acid represented by the following formulas (1A) to (1C) and an organic solvent on a substrate and baking at a maximum temperature of 450 to 550 ° C.
- X is independently a tetravalent aromatic group having two carboxylic acid derivatives
- Y is independently a divalent aromatic group
- Z 1 and Z 2 Are independently a monovalent organic group
- at least one of Y, Z 1 and Z 2 has an alkali-soluble group
- in formula (1B) Y and two Z 1 of at least one having an alkali-soluble group
- in the formula (1C) has a Y and two at least one alkali-soluble group Z 2
- m represents a natural number independently of each other.
- Y is a method for producing a release layer of 1 or 2 comprising an aromatic group represented by the following formulas (2) to (5):
- W independently represents a carboxy group or a hydroxyl group
- R 1 to R 3 each independently represents an alkylene group having 1 to 20 carbon atoms which may be substituted with a halogen atom, Represents an alkenylene group having 2 to 20 carbon atoms, an alkynylene group having 2 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms or a heteroarylene group having 2 to 20 carbon atoms, an ether group, an ester group, or an amide group; (Represents a bond.) 4).
- Y is a method for producing a release layer 3 comprising an aromatic group represented by the following formulas (6) to (9): (In the formula, it represents, ⁇ represents a bond.) 5).
- Z 2 is a monovalent organic group represented by the following formula (11): (In the formula, Z 3 represents a carboxy group or a hydroxyl group, and ⁇ represents a bond.) 7).
- a method for producing a flexible electronic device comprising a resin substrate, comprising using a release layer formed by using any one of production methods 1 to 8, 10.
- a flexible electronic device comprising a step of applying a composition for forming a resin substrate on a release layer formed using any one of manufacturing methods 1 to 8 and then firing the resin substrate at a maximum temperature of 450 ° C. or more to form a resin substrate Manufacturing method, 11.
- the method for producing a flexible electronic device according to 9 or 10 wherein the resin substrate is a polyimide resin substrate.
- the method for producing a release layer of the present invention it is possible to obtain a release layer having excellent adhesion to a substrate, moderate adhesion to a resin substrate, and moderate release with good reproducibility. Therefore, by implementing the manufacturing method of the present invention, in the manufacturing process of the flexible electronic device, the circuit or the like without damaging the resin substrate formed on the substrate or the circuit provided on the substrate. At the same time, the resin substrate can be separated from the substrate. Therefore, the manufacturing method of this invention can contribute to the simplification of the manufacturing process of a flexible electronic device provided with a resin substrate, the yield improvement, etc.
- a release layer forming composition containing at least one polyamic acid represented by the following formulas (1A) to (1C) and an organic solvent is applied on a substrate, It includes a step of baking at a maximum temperature of 450 to 550 ° C.
- the release layer in the present invention is a layer provided immediately above a glass substrate for a predetermined purpose.
- a flexible electronic made of a substrate and a resin such as polyimide is used.
- the resin substrate can be easily peeled from the substrate.
- a release layer may be used.
- X is a tetravalent aromatic group having two carboxylic acid derivatives independently of each other
- Y is a divalent aromatic group independently of each other
- Z 1 and Z 2 are , Independently of each other, a monovalent organic group, but in formula (1A), at least one of Y, Z 1 and Z 2 has an alkali-soluble group, and in formula (1B), Y and two Z1 At least one of them has an alkali-soluble group, and in formula (1C), at least one of Y and two Z2 has an alkali-soluble group.
- m represents a natural number independently of each other, and is preferably an integer of 2 or more.
- X is preferably a tetravalent aromatic ring containing 1 to 5 benzene rings, more preferably a tetravalent benzene ring, a tetravalent naphthalene ring, or a tetravalent biphenyl ring, more preferably a tetravalent benzene ring, a tetravalent benzene ring.
- a biphenyl ring is even more preferred.
- the divalent aromatic group for Y is preferably an aromatic group containing 1 to 5 benzene rings, and more preferably those represented by the following formulas (2 ') to (5').
- R 1 to R 3 are each independently an alkylene group having 1 to 20 carbon atoms, which may be substituted with a halogen atom, or having 2 to 20 carbon atoms
- An alkenylene group, an alkynylene group having 2 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms or a heteroarylene group having 2 to 20 carbon atoms, an ether group, an ester group or an amide group is represented, and ⁇ represents a bond.
- halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
- the alkylene group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms may be linear, branched or cyclic.
- methylene, methylmethylene, dimethylmethylene, ethylene, trimethylene, propylene, tetramethylene, penta Examples include methylene and hexamethylene groups.
- the alkenylene group having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms may be linear, branched or cyclic.
- alkynylene group having 2 to 20 carbon atoms may be linear, branched or cyclic.
- ethynylene, propynylene, butynylene, pentynylene, hexynylene, heptynylene, octynylene, noninylene group and the like Is mentioned.
- Y is a divalent aromatic group having at least one alkali-soluble group
- it is preferably an organic group containing a benzene ring substituted with at least one alkali-soluble group, particularly at least one alkali-soluble group.
- An organic group containing two or more benzene rings substituted with a soluble group is more preferable, and an aromatic group represented by the following formulas (2) to (5) is more preferable, and in particular, the following formula (6)
- the structures represented by (9) to (9) are more preferred, and the structures represented by the formulas (6), (7) and (9) having a phenolic hydroxyl group in the ortho position with respect to the adjacent bond are optimal.
- W represents an alkali-soluble group, preferably a carboxy group or a phenolic hydroxyl group, and R 1 to R 3 and ⁇ have the same meaning as described above.
- the Y may contain both a divalent aromatic group having an alkali-soluble group and a divalent aromatic group not having an alkali-soluble group.
- the ratio of the divalent aromatic group having an alkali-soluble group in all Y can be about 0.1 to 99.9 mol%, preferably 1 to 50 mol%, and preferably 1 to 10 mol. % Is more preferable.
- Z 1 and Z 2 are monovalent organic groups, preferably monovalent organic groups containing a benzene ring, and monovalent organic groups containing one benzene ring.
- Z 1 bonded to the tetracarboxylic acid terminal side is preferably a monovalent organic group represented by the following formula (10A)
- Z 2 bonded to the diamine terminal side is represented by the following formula (11A).
- Monovalent organic groups are preferred.
- Z 1 and Z 2 are divalent aromatic groups having an alkali-soluble group
- the alkali-soluble group is preferably directly connected to the aromatic ring, and there is only one alkali-soluble group.
- Z 1 bonded to the tetracarboxylic acid terminal side is preferably a monovalent organic group represented by the following formula (10B), and an alkali-soluble group is present in the ortho position relative to NH:
- the monovalent organic group represented by 10) is more preferred
- Z 2 bonded to the diamine terminal side is preferably a monovalent organic group represented by the following formula (11B), wherein the alkali-soluble group is ortho to the CO.
- a monovalent organic group represented by the following formula (11) is more preferable.
- the polymer terminal has a hydroxyl group, the skeleton can be different from the flexible substrate used for the upper layer, so that the function of the obtained film as a release layer can be improved.
- Z 3 represents a carboxy group or a hydroxyl group, and ⁇ represents a bond.
- Z 3 represents a carboxy group or a hydroxyl group, and ⁇ represents a bond.
- the polyamic acid represented by the above formulas (1A) to (1C) can be obtained by reacting a predetermined aromatic tetracarboxylic dianhydride component and an aromatic diamine component at a predetermined ratio.
- aromatic tetracarboxylic dianhydride component and the aromatic diamine component used for the synthesis of the polyamic acid used in the production method of the present invention will be described.
- the aromatic tetracarboxylic dianhydride used for the synthesis of the polyamic acid represented by the above formulas (1A) to (1C) has two dicarboxylic anhydride sites in the molecule and has an aromatic ring.
- the aromatic tetracarboxylic dianhydride containing 1 to 5 benzene nuclei is preferred as long as it is contained.
- aromatic tetracarboxylic dianhydride examples include pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, naphthalene-1,2,3,4-tetra.
- the diamine component is preferably an aromatic diamine containing 1 to 5 benzene nuclei, more preferably an aromatic diamine substituted with at least one alkali-soluble group, and an aromatic ring having an aromatic ring having a carboxy group or a phenolic hydroxyl group.
- An aromatic diamine containing an aromatic group substituted with a phenolic hydroxyl group is more preferable.
- aromatic diamines having a phenolic hydroxyl group examples include 3,3′-diamino-4,4′-dihydroxybiphenyl (4BP), 3,3′-diamino-2,2′-dihydroxybiphenyl (2BP), 2 , 2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF), 2,2-bis (4-amino-3,5-dihydroxyphenyl) hexafluoropropane, 2,2-bis [4 — (3-Amino-4-hydroxyphenoxy) phenyl] hexafluoropropane, bis (3-amino-4-hydroxyphenyl) methane (BAPF), 3,3′-diamino-4,4′-dihydroxybenzophenone (AHPK) 3,3′-diamino-4,4′-dihydroxy-phenyl ether (AHPE), 3,3′-di Mino-4,4′-dihydroxy-thioph
- diamine components preferably 3,3′-diamino-4,4′-dihydroxybiphenyl (4BP), 3,3′-diamino-2,2′-dihydroxybiphenyl (2BP), 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF), 2,2-bis (4-amino-3,5-dihydroxyphenyl) hexafluoropropane, 2,2-bis [4- (3-amino -4-hydroxyphenoxy) phenyl] hexafluoropropane, bis (3-amino-4-hydroxyphenyl) methane (BAPF), 3,3'-diamino-4,4'-dihydroxybenzophenone (AHPK), 3,3 ' -Diamino-4,4'-dihydroxy-phenyl ether (AHPE), 3,3'-diamino-4,4'-dihydride Xyl-thiophenyl
- BAPF bis (3-amino-4-hydroxyphenyl) methane
- BAPA 2,2′-bis (3-amino-4-hydroxyphenyl) propane
- BAHF 2,2′-bis ( 3-amino-4-hydroxyphenyl) hexafluoropropane
- BAHF 3,3′-diamino-4,4′-dihydroxy-phenyl ether
- AHPK 3,3′-diamino-4,4′-dihydroxybenzophenone
- BSDA bis (3-amino-4-hydroxyphenyl) sulfide
- AHPA bis-N, N ′ -(P-aminobenzoyl) -hexafluoro-2,2'-bis (4-hydroxyphenyl) propane
- BABHB bis the like.
- aromatic diamine having a carboxy group examples include 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,6-diamino-1,3-benzenedicarboxylic acid, 5-diamino-1,4-benzenedicarboxylic acid, bis (4-amino-3-carboxyphenyl) ether, bis (4-amino-3,5-dicarboxyphenyl) ether, bis (4-amino-3-carboxy) Phenyl) sulfone, bis (4-amino-3,5-dicarboxyphenyl) sulfone, 4,4′-diamino-3,3′-dicarboxybiphenyl, 4,4′-diamino-3,3′-dicarboxy -5,5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dicarboxy-5,5-
- the aromatic diamine which does not have an alkali-soluble group can also be used as a diamine component used for the synthesis
- the aromatic diamine having no alkali-soluble group include p-phenylenediamine, m-phenylenediamine, 2,4,6-trimethyl-1,3-phenylenediamine, and 2,3,5,6-tetramethyl.
- the charge ratio of the diamine component to the tetracarboxylic dianhydride component cannot be specified unconditionally because it is determined appropriately in consideration of the target molecular weight and molecular weight distribution, the type of diamine and the type of tetracarboxylic dianhydride, etc.
- 1 1 (molar ratio) based on the desired molecular chain ends, and a ratio of both ends of the molecular chain derived from tetracarboxylic acid (formula (1B)), with respect to 1 mole of the diamine component
- the tetracarboxylic dianhydride component is preferably 1.05 to 3.0 mol, more preferably 1.07 to 2.5 mol, even more preferably 1.1 to 2.0 mol, and the molecular chain derived from diamine.
- the diamine component is preferably 1.00 to 2.5 mol, more preferably 1.01 to 1.5 mol, relative to 1 mol of the tetracarboxylic dianhydride component. 1.02 to 1.3 mol Even more preferably.
- the organic solvent used in such a reaction is not particularly limited as long as it does not adversely affect the reaction.
- Specific examples thereof include m-cresol, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2- Pyrrolidone, N-vinyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, 3-methoxy-N, N-dimethylpropylamide, 3-ethoxy-N, N-dimethylpropylamide, 3- Propoxy-N, N-dimethylpropylamide, 3-isopropoxy-N, N-dimethylpropylamide, 3-butoxy-N, N-dimethylpropylamide, 3-sec-butoxy-N, N-dimethylpropylamide, 3 -Tert-butoxy-N, N-dimethylpropylamide, ⁇ -butyrolactone and the like.
- amides represented by formula (S1), amides represented by formula (S2) and formula ( At least one selected from amides represented by S3) is preferred.
- R 1 and R 2 each independently represent an alkyl group having 1 to 10 carbon atoms.
- R 3 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
- h represents a natural number, preferably 1 to 3, more preferably 1 or 2.
- alkyl group having 1 to 10 carbon atoms examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, n- Examples include hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like. Of these, alkyl groups having 1 to 3 carbon atoms are preferable, and alkyl groups having 1 or 2 carbon atoms are more preferable.
- the reaction temperature may be appropriately set in the range from the melting point to the boiling point of the solvent used, and is usually about 0 to 100 ° C., but it prevents imidization in the solution of the resulting polyamic acid and contains a high content of polyamic acid units. In order to maintain the amount, it is preferably about 0 to 70 ° C, more preferably about 0 to 60 ° C, and still more preferably about 0 to 50 ° C.
- the reaction time depends on the reaction temperature and the reactivity of the raw material, and cannot be specified unconditionally, but is usually about 1 to 100 hours.
- the end-capping compound or alkali-soluble group having an alkali-soluble group which further gives Z 1 and / or Z 2 to the polyamic acid obtained by reacting the tetracarboxylic dianhydride component and the diamine component described above.
- the polyamic acid represented by the formulas (1A) to (1C) can be obtained by reacting an end-capping compound that does not have. More specifically, an aromatic monoamine can be suitably used as the end-capping compound that gives Z 1 bonded to the terminal side of the tetracarboxylic acid.
- the aromatic monoamine preferably has an aromatic ring having 6 to 30 carbon atoms, preferably has an aromatic ring having 6 to 15 carbon atoms, and more preferably has an aromatic ring having 6 to 10 carbon atoms. As described above, those containing one benzene ring are preferred.
- aromatic monoamine having no alkali-soluble group examples include aniline, 1-naphthylamine, 2-naphthylamine, 1-aminoanthracene, 2-aminoanthracene, 9-aminoanthracene, 9-aminophenanthracene and 2-amino.
- Biphenyl, 3-aminobiphenyl, 4-aminobiphenyl and the like can be mentioned.
- aromatic monoamine having an alkali-soluble group examples include aromatic monoamines having a phenolic hydroxyl group such as 2-aminophenol, 3-aminophenol and 4-aminophenol; 2-aminobenzoic acid, 3-aminobenzoic acid And aromatic monoamines having a carboxy group such as 4-aminobenzoic acid.
- the end-capping compound that gives Z 1 is preferably an aromatic monoamine having an alkali-soluble group, more preferably an aromatic monoamine having a phenolic hydroxyl group, and even more preferably 2-aminophenol.
- an aromatic carboxylic acid can be suitably used as the end-capping compound that gives Z 2 bonded to the diamine terminal side.
- the aromatic carboxylic acid preferably has an aromatic ring having 6 to 30 carbon atoms, preferably has an aromatic ring having 6 to 15 carbon atoms, more preferably has an aromatic ring having 6 to 10 carbon atoms, As described above, those containing one benzene ring are preferred.
- aromatic carboxylic acid having no alkali-soluble group after end-capping include benzoic acid, 1-naphthalene carboxylic acid, 2-naphthalene carboxylic acid, 1-anthracene carboxylic acid, 2-anthracene carboxylic acid, and 9-anthracene.
- Aromatic monocarboxylic acids such as carboxylic acid, 2-phenylbenzoic acid, 3-phenylbenzoic acid and 4-phenylbenzoic acid can be mentioned.
- aromatic carboxylic acids having an alkali-soluble group after end-capping include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid; phenols such as salicylic acid, 3-hydroxybenzoic acid, and 4-hydroxybenzoic acid.
- the carboxylic acid may be in the form of an acid halide or an acid anhydride.
- an aromatic carboxylic acid having an alkali-soluble group after end-capping is preferred, an aromatic dicarboxylic acid is preferred, and phthalic acid is even more preferred.
- the polyamic acid represented by the formulas (1A) to (1C) of the present invention uses only a diamine component that does not have an alkali-soluble group as the diamine component (that is, when all Y have no alkali-soluble group).
- Z 1 and / or Z 2 must have an alkali-soluble group.
- either or both of the molecular chain ends of the synthesized polyamic acid are substituted with the above-described monoamine having an alkali-soluble group, What is necessary is just to seal with carboxylic acid.
- the charge amount of the end-capping compound may be 1 mol or more per 1 mol of the polyamic acid, but it is preferably 2 mol or more, more preferably 2 to 4 mol, and further preferably 2 to 3 mol.
- the addition amount is preferably 0.1 mol or more, more preferably 0.2 to 4 with respect to 1 mol of tetracarboxylic dianhydride used for the synthesis of the polyamic acid. Molar, more preferably 0.2 to 3 moles.
- the amount of the aromatic carboxylic acid added is preferably 0.1 mol or more, more preferably 0.2 to 4 mol, and still more preferably 0.1 mol, per 1 mol of the diamine component used for the synthesis of the polyamic acid. A standard of 2 to 3 moles may be used.
- the organic solvent used for sealing the molecular chain terminal of the polyamic acid is not particularly limited as long as it does not adversely affect the reaction, and the same solvents as those exemplified in the above polyamic acid synthesis can be used.
- the reaction temperature at the time of sealing the molecular chain end of the polyamic acid may be appropriately set in the range from the melting point to the boiling point of the solvent used, as in the synthesis of the polyamic acid, and is usually about 0 to 100 ° C. From the viewpoint of securely sealing the molecular chain terminal of the synthesized polyamic acid, the temperature can be preferably about 0 to 70 ° C, more preferably about 0 to 60 ° C, and still more preferably about 0 to 50 ° C.
- the reaction time depends on the reaction temperature and the reactivity of the raw material, it cannot be defined unconditionally, but is usually about 1 to 100 hours.
- the weight average molecular weight of the polyamic acid thus obtained is usually about 5,000 to 500,000. From the viewpoint of improving the function, the range is preferably about 6,000 to 200,000, more preferably about 7,000 to 150,000.
- a weight average molecular weight is a polystyrene conversion value by a gel permeation chromatography (GPC) measurement.
- the reaction solution after end-capping can be used as it is, or a solution obtained by diluting or concentrating can be used as the release layer forming composition of the present invention.
- the solvent in this case include organic solvents used in the above-described reaction.
- the solvent used for dilution is not particularly limited, and specific examples thereof include those similar to the specific examples of the reaction solvent for the reaction.
- the solvent used for dilution may be used singly or in combination of two or more.
- N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethyl-2 are used because they dissolve polyamic acid well.
- -Pyrrolidone and ⁇ -butyrolactone are preferred, and N-methyl-2-pyrrolidone is more preferred.
- ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy -2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxy A solvent having a low surface tension such as propoxy) propanol, methyl lactate, ethyl lactate, n-propyl lactate, n
- the concentration of the polyamic acid in the composition for forming a release layer of the present invention is appropriately set in consideration of the thickness of the release layer to be produced, the viscosity of the composition, etc., but is usually about 1 to 30% by mass, preferably It is about 1 to 20% by mass. By setting such a concentration, a release layer having a thickness of about 0.05 to 5 ⁇ m can be obtained with good reproducibility.
- the concentration of polyamic acid is adjusted to adjust the amount of diamine and tetracarboxylic dianhydride used as raw materials for polyamic acid, and after filtering the reaction solution, the filtrate is diluted or concentrated, and the isolated polyamic acid is used as a solvent. The amount can be adjusted by, for example, adjusting the amount when dissolved in the aqueous solution.
- the viscosity of the composition for forming the release layer is appropriately set in consideration of the thickness of the release layer to be produced, etc., but in particular, a film having a thickness of about 0.05 to 5 ⁇ m can be obtained with good reproducibility. When it is intended, it is usually about 10 to 10,000 mPa ⁇ s, preferably about 20 to 5,000 mPa ⁇ s at 25 ° C.
- the viscosity can be measured using a commercially available liquid viscosity measurement viscometer, for example, with reference to the procedure described in JIS K7117-2 at a temperature of the composition of 25 ° C. .
- a conical plate type (cone plate type) rotational viscometer is used as the viscometer, and preferably the composition temperature is 25 ° C. using 1 ° 34 ′ ⁇ R24 as a standard cone rotor. It can be measured under the condition of ° C.
- An example of such a rotational viscometer is TVE-25L manufactured by Toki Sangyo Co., Ltd.
- composition for forming a release layer according to the present invention may contain a component such as a crosslinking agent in addition to the polyamic acid and the organic solvent, for example, in order to improve the film strength.
- a component such as a crosslinking agent in addition to the polyamic acid and the organic solvent, for example, in order to improve the film strength.
- the polyamic acid is thermally imidized by a baking method including a step of baking at a maximum temperature of 450 to 550 ° C. It is possible to obtain a release layer made of a polyimide film that has appropriate adhesion and appropriate adhesion to the resin substrate and appropriate release properties.
- the maximum temperature at the time of firing is not particularly limited as long as it is in the range of 450 to 550 ° C. and not higher than the heat resistant temperature of polyimide, but the adhesion to the substrate and the resin substrate are not limited. In view of improving moderate adhesion and peelability, 500 ° C. or higher is preferable.
- the upper limit is usually about 550 ° C., preferably about 510 ° C.
- the heating time varies depending on the heating temperature and cannot be defined generally, but is usually 1 minute to 5 hours.
- the imidization rate may be in the range of 50 to 100%.
- the temperature at the time of the said baking may include the process baked at the temperature below it.
- a preferred example of the heating mode in the present invention is a method of heating at 50 to 150 ° C., then increasing the heating temperature stepwise and finally heating at 450 to 550 ° C.
- a more preferable example of the heating mode is a method of heating at 50 to 100 ° C., heating at a temperature higher than 100 ° C. to less than 450 ° C., and heating at 450 ° C. or higher.
- heating mode after heating at 50 to 150 ° C., heating at 150 to 350 ° C., then heating at 350 to 450 ° C., and finally 450 to 550 ° C.
- the method of heating with is mentioned.
- the heating mode in consideration of the firing time, after heating at 50 to 150 ° C. for 1 minute to 2 hours, the heating temperature is increased stepwise, and finally at 400 ° C. or higher for 30 minutes.
- a method of heating for up to 4 hours can be mentioned.
- heating is performed at 50 to 100 ° C. for 1 minute to 2 hours, heating is performed above 100 ° C. to less than 450 ° C. for 5 minutes to 2 hours, and heating is performed at 450 ° C. or higher for 30 minutes to 4 hours.
- the technique to do is mentioned.
- the peeling layer of this invention when forming the peeling layer of this invention on a base
- a release layer is formed in a pattern such as a dot pattern or a line and space pattern on the entire surface of the substrate.
- substrate means what is used for manufacture of a flexible electronic device etc. by which the composition for peeling layer formation of this invention is applied to the surface.
- the substrate examples include glass, metal (silicon wafer, etc.), slate, and the like.
- the release layer obtained from the release layer forming composition according to the present invention has sufficient adhesion to it. From the viewpoint of glass, glass is preferable.
- substrate surface may be comprised with the single material and may be comprised with two or more materials. As an aspect in which the substrate surface is constituted by two or more materials, a certain range of the substrate surface is constituted by a certain material, and the other surface is constituted by another material. A dot pattern is formed on the entire substrate surface. There is a mode in which a material in a pattern such as a line and space pattern is present in other materials.
- the coating method is not particularly limited.
- a cast coating method for example, a cast coating method, a spin coating method, a blade coating method, a dip coating method, a roll coating method, a bar coating method, a die coating method, an ink jet method, a printing method (a relief plate, an intaglio plate, a planographic plate). , Screen printing, etc.).
- Examples of equipment used for heating include a hot plate and an oven.
- the heating atmosphere may be under air or under an inert gas, and may be under normal pressure or under reduced pressure.
- the thickness of the release layer is usually about 0.01 to 50 ⁇ m, and preferably about 0.05 to 20 ⁇ m, more preferably about 0.05 to 5 ⁇ m from the viewpoint of productivity. To achieve the desired thickness.
- the release layer described above has excellent adhesion to a substrate, particularly a glass substrate, moderate adhesion to a resin substrate, and moderate release. Therefore, the release layer of the present invention peels the resin substrate from the substrate together with the circuit formed on the resin substrate without damaging the resin substrate of the device in the manufacturing process of the flexible electronic device. Therefore, it can be suitably used.
- a release layer is formed on a glass substrate by the method described above.
- a resin substrate forming solution for forming a resin substrate is applied, and this coating film is baked, so that the resin substrate fixed to the glass substrate via the release layer of the present invention is obtained.
- the firing temperature of the coating film is appropriately set according to the type of resin and the like. In the present invention, the maximum temperature during firing is preferably 450 to 550 ° C. or higher, and preferably 480 ° C. or higher. More preferably, the temperature is set to 490 ° C.
- the maximum temperature during firing at the time of resin substrate production within this range, the adhesiveness between the release layer and the substrate as the base, and the appropriate adhesiveness and peelability between the release layer and the resin substrate are further improved be able to.
- a step of baking at a temperature lower than that may be included.
- the heating mode at the time of preparing the resin substrate there is a method of heating at 50 to 150 ° C., then increasing the heating temperature stepwise and finally heating at 450 to 550 ° C.
- a more preferable example of the heating mode is a method of heating at 50 to 100 ° C., heating at a temperature higher than 100 ° C. to less than 450 ° C., and heating at 450 ° C. or higher.
- the heating mode after heating at 50 to 100 ° C., heating is performed at over 100 ° C. to 200 ° C., then over 200 ° C. to less than 300 ° C., and heating is performed at 300 ° C. to less than 400 ° C. And heating at 400 to 450 ° C., and finally heating at 450 to 550 ° C. can be mentioned.
- the heating mode in consideration of the firing time, after heating at 50 to 150 ° C. for 5 minutes to 2 hours, the heating temperature is increased stepwise and finally at 450 to 550 ° C.
- a method of heating for minutes to 4 hours can be mentioned.
- heating is performed at 50 to 100 ° C. for 5 minutes to 2 hours, heating is performed above 100 ° C. to less than 450 ° C. for 5 minutes to 2 hours, and heating is performed at 450 ° C. or more for 30 minutes to 4 hours.
- the technique to do is mentioned.
- after heating at 50 to 100 ° C. for 5 minutes to 2 hours after heating at over 100 ° C.
- the resin substrate is formed so as to cover the entire release layer and to have a larger area than the area of the release layer.
- the resin substrate include a resin substrate made of polyimide, which is a typical resin substrate for flexible electronic devices, and examples of the resin solution for forming the resin substrate include a polyimide solution and a polyamic acid solution.
- the method for forming the resin substrate may follow a conventional method.
- a desired circuit is formed on the resin substrate fixed to the base via the release layer of the present invention, and then the resin substrate is cut along the release layer, for example. It peels from a peeling layer, and a resin substrate and a base
- the LLO method is characterized in that light having a specific wavelength, for example, light having a wavelength of 308 nm, is irradiated from the surface opposite to the surface on which a circuit or the like is formed from the glass substrate side.
- the irradiated light passes through the glass substrate, and only the polymer (polyimide) in the vicinity of the glass substrate absorbs this light and evaporates (sublimates).
- the polymer polyimide
- the release layer of the present invention has a feature of sufficiently absorbing light having a specific wavelength (for example, 308 nm) that enables application of the above LLO method, and therefore can be used as a sacrificial layer of the LLO method. Therefore, when a desired circuit is formed on a resin substrate fixed to a glass substrate through a release layer formed by using the composition according to the present invention, and then an LLO method is performed to irradiate a light beam of 308 nm. Only the release layer absorbs this light and evaporates (sublimates). Thereby, the release layer is sacrificed (acts as a sacrifice layer), and the resin substrate can be selectively peeled from the glass substrate.
- a specific wavelength for example, 308 nm
- NMP N-methylpyrrolidone
- BCS butyl cellosolve
- p-PDA p-phenylenediamine
- 6FAP 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane
- 2AP 2-aminophenol
- BPDA 3,3-4,4-biphenyltetracarboxylic dianhydride
- TFMB 2,2′-bis (trifluoromethyl) benzidine
- PMDA pyromellitic dianhydride
- PA phthalic anhydride
- CBDA 1,2, 3,4-cyclobutanetetracarboxylic acid-1,2: 3,4-dianhydride
- Mw polymer weight average molecular weight
- Mw polymer weight average molecular weight
- Mw molecular weight distribution
- a GPC apparatus Shidex (registered trademark) columns KF803L and KF805L
- dimethylformamide was measured under the conditions of a flow rate of 1 ml / min and a column temperature of 50 ° C.
- Mw was made into the polystyrene conversion value.
- composition for forming release layer [Example 1-1] BCS and NMP were added to the reaction solution obtained in Synthesis Example L1, and diluted such that the polymer concentration was 5 wt% and BCS was 20 mass%, to obtain a release layer forming composition.
- Examples 1-2 to 1-4 A release layer-forming composition was obtained in the same manner as in Example 1-1 except that the reaction solutions obtained in Synthesis Examples L2 to L4 were used instead of the reaction solution obtained in Synthesis Example L1. It was.
- Example 2-1 Production of release layer and resin substrate [Example 2-1] Using a spin coater (conditions: about 3,000 rpm for about 30 seconds), the release layer forming composition L1 obtained in Example 1-1 was used as a glass substrate of 100 mm ⁇ 100 mm glass substrate (hereinafter the same). It was applied on top. The obtained coating film was heated at 100 ° C. for 2 minutes using a hot plate, and then heated at 300 ° C. for 30 minutes using an oven, and the heating temperature was raised to 400 ° C. (10 ° C./min. And then heated to 400 ° C. for 30 minutes, further heated to 500 ° C. (10 ° C./min), and heated at 500 ° C. for 10 minutes to form a release layer having a thickness of about 0.1 ⁇ m on the glass substrate. A glass substrate with a release layer was obtained. During the temperature increase, the film-coated substrate was not removed from the oven but heated in the oven.
- the resin substrate forming composition S2 was applied on the release layer (resin thin film) on the glass substrate obtained above. Then, the obtained coating film was heated at 80 ° C. for 30 minutes using a hot plate, and then the atmosphere was changed to a nitrogen atmosphere using an oven, followed by heating at 140 ° C. for 30 minutes, and the heating temperature was raised to 210 ° C. (2 ° C / min, the same applies hereinafter), heated at 210 ° C for 30 minutes, heated to 300 ° C, heated at 300 ° C for 30 minutes, heated to 400 ° C, heated to 400 ° C The temperature was raised to 500 ° C. for 30 minutes, and heated at 500 ° C.
- Example 2-2 to 2-4 Except that the release layer forming compositions L2 to L4 obtained in Examples 1-2 to 1-4 were used in place of the release layer forming composition L1 obtained in Example 1-1, respectively.
- a release layer and a polyimide substrate were produced in the same manner as in Example 2-1, and a glass substrate with a release layer and a glass substrate with a resin substrate / release layer were obtained.
Abstract
Description
特に、新世代ディスプレイでは、軽量なフレキシブルプラスチック基板(以下、樹脂基板と表記する)を用いたアクティブマトリクス型フルカラーTFTディスプレイパネルの開発が求められている。
しかも、被剥離層が大面積である場合には、レーザー処理に長時間を要するため、デバイス作製の生産性を上げることが難しい。
しかしながら、既存のポリマーは、Tg以上の温度に加熱された場合、密着性が高まることが知られており(例えば、特許文献6参照)、加熱処理後に剥離層と樹脂基板との密着性が高まり、樹脂基板を基体から剥離することが困難となることがあった。
1. 下記式(1A)~(1C)で表されるポリアミック酸の少なくとも1種と有機溶剤とを含む剥離層形成用組成物を基体上に塗布し、最高温度450~550℃で焼成する工程を含む剥離層の製造方法、
2. 上記アルカリ可溶性基が、カルボキシ基又はフェノール性水酸基である1の剥離層の製造方法、
3. 上記Yが、下記式(2)~(5)で表される芳香族基を含む1又は2の剥離層の製造方法、
4. 上記Yが、下記式(6)~(9)で表される芳香族基を含む3の剥離層の製造方法、
5. 上記Z1が、下記式(10)で表される1価の有機基である1~4のいずれかの剥離層の製造方法、
6. 上記Z2が、下記式(11)で表される1価の有機基である1~5のいずれかの剥離層の製造方法、
7. 上記Yが、さらにアルカリ可溶性基を有しない芳香族基を含む3~6のいずれかの剥離層の製造方法、
8. 上記アルカリ可溶性基を有しない芳香族基が、フェニレン基、ビフェニレン基又はターフェニレン基である7の剥離層の製造方法、
9. 1~8のいずれかの製造方法を用いて形成される剥離層を用いることを特徴とする、樹脂基板を備えるフレキシブル電子デバイスの製造方法、
10. 1~8のいずれかの製造方法を用いて形成した剥離層上に、樹脂基板形成用組成物を塗布した後、最高温度450℃以上で焼成して樹脂基板を形成する工程を含むフレキシブル電子デバイスの製造方法、
11. 前記樹脂基板が、ポリイミド樹脂基板である9又は10のフレキシブル電子デバイスの製造方法
を提供する。
本発明に係る剥離層の製造方法は、下記式(1A)~(1C)で表されるポリアミック酸の少なくとも1種と、有機溶媒とを含む剥離層形成用組成物を基体上に塗布し、最高温度450~550℃で焼成する工程を含むことを特徴とする。
ここで、本発明における剥離層とは、所定の目的でガラス基体直上に設けられる層であって、その典型例としては、フレキシブル電子デバイスの製造プロセスにおいて、基体と、ポリイミドといった樹脂からなるフレキシブル電子デバイスの樹脂基板との間に当該樹脂基板を所定のプロセス中において固定するために設けられ、且つ、当該樹脂基板上に電子回路等の形成した後において当該樹脂基板が当該基体から容易に剥離できるようにするために設けられる剥離層が挙げられる。
mは、互いに独立して自然数を表すが、2以上の整数が好ましい。
炭素数1~20、好ましくは炭素数1~10のアルキレン基としては、直鎖、分岐、環状のいずれでもよく、例えば、メチレン、メチルメチレン、ジメチルメチレン、エチレン、トリメチレン、プロピレン、テトラメチレン、ペンタメチレン、ヘキサメチレン基等が挙げられる。
炭素数2~20、好ましくは炭素数2~10のアルケニレン基としては、直鎖、分岐、環状のいずれでもよく、例えば、エテニレン、プロペニレン、ブテニレン、ペンテニレン、へキセニレン、ヘプテニレン、オクテニレン、ノネニレン基等が挙げられる。
炭素数2~20、好ましくは炭素数2~10のアルキニレン基としては、直鎖、分岐、環状のいずれでもよく、例えば、エチニレン、プロピニレン、ブチニレン、ペンチニレン、へキシニレン、ヘプチニレン、オクチニレン、ノニニレン基等が挙げられる。
この場合、全Yにおけるアルカリ可溶性基を有する2価の芳香族基の割合は、0.1~99.9モル%程度とすることができるが、1~50モル%が好ましく、1~10モル%がより好ましい。
より具体的には、テトラカルボン酸末端側に結合するZ1は、下記式(10B)で示される1価の有機基が好ましく、アルカリ可溶性基がNHに対してオルト位に存在する下記式(10)で示される1価の有機基がより好ましく、ジアミン末端側に結合するZ2は、下記式(11B)で示される1価の有機基が好ましく、アルカリ可溶性基がCOに対してオルト位に存在する下記式(11)で示される1価の有機基がより好ましい。
特に、重合体末端が水酸基を有することで、上層に用いるフレキシブル基板と骨格の相違ができるために、得られる膜の剥離層としての機能の向上を図ることができる。
以下、本発明の製造方法で使用するポリアミック酸の合成に用いる芳香族テトラカルボン酸二無水物成分と芳香族ジアミン成分について説明する。
アルカリ可溶性基を有しない芳香族ジアミンの具体例としては、p-フェニレンジアミン、m-フェニレンジアミン、2,4,6-トリメチル-1,3-フェニレンジアミン、2,3,5,6-テトラメチル-1,4-フェニレンジアミン、4,4’-ジアミノジフェニルエーテル(ODA)、3,4’-ジアミノジフェニルエーテル、3,3’-ジアミノジフェニルエーテル、4,4’-ジアミノジフェニルスルフィド、4,4’-ジアミノジフェニルメタン、3,4’-ジアミノジフェニルメタン、3,3’-ジアミノジフェニルメタン、4,4-メチレン-ビス(2-メチルアニリン)、4,4’-メチレン-ビス(2,6-ジメチルアニリン)、4,4-メチレン-ビス(2,6-ジエチルアニリン)、4,4’-メチレン-ビス(2-イソプロピル-6-メチルアニリン)、4,4’-メチレン-ビス(2,6-ジイソプロピルアニリン)、4,4’-ジアミノジフェニルスルホン、3,3’-ジアミノジフェニルスルホン、ベンジジン、o-トリジン、m-トリジン、3,3’,5,5’-テトラメチルベンジジン、1,4-ビス(4-アミノフェノキシ)ベンゼン、1,3-ビス(4-アミノフェノキシ)ベンゼン、1,3-ビス(3-アミノフェノキシ)ベンゼン、ビス[4-(4-アミノフェノキシ)フェニル]スルホン、ビス[4-(3-アミノフェノキシ)フェニル]スルホン、2,2-ビス[4-(4-アミノフェノキシ)フェニル]プロパン、2,2-ビス[4-(3-アミノフェノキシ)フェニル]プロパンが挙げられる。
より具体的には、テトラカルボン酸末端側に結合するZ1を与える末端封止化合物としては、芳香族モノアミンを好適に用いることができる。
芳香族モノアミンは、炭素数6~30の芳香環を有するものが好ましく、炭素数6~15の芳香環を有するものが好ましく、炭素数6~10の芳香環を有するものがより一層好ましく、上述のとおり、ベンゼン環を1つ含むものが好ましい。
アルカリ可溶性基を有する芳香族モノアミンの具体例としては、2-アミノフェノール、3-アミノフェノール、4-アミノフェノール等のフェノール性水酸基を有する芳香族モノアミン;2-アミノ安息香酸、3-アミノ安息香酸、4-アミノ安息香酸等のカルボキシ基を有する芳香族モノアミンなどが挙げられる。
これらの中でも、Z1を与える末端封止化合物としては、アルカリ可溶性基を有する芳香族モノアミンが好ましく、フェノール性水酸基を有する芳香族モノアミンがより好ましく、2-アミノフェノールがより一層好ましい。
芳香族カルボン酸は、炭素数6~30の芳香環を有するものが好ましく、炭素数6~15の芳香環を有するものが好ましく、炭素数6~10の芳香環を有するものがより一層好ましく、上述のとおり、ベンゼン環を1つ含むものが好ましい。
末端封止後にアルカリ可溶性基を有する芳香族カルボン酸の具体例としては、フタル酸、イソフタル酸、テレフタル酸等の芳香族ジカルボン酸;サリチル酸、3-ヒドロキシ安息香酸、4-ヒドロキシ安息香酸等のフェノール性水酸基を有する芳香族モノカルボン酸などが挙げられる。
なお、上記カルボン酸は、酸ハロゲン化物や、酸無水物の形態であってもよい。
これらの中でも、Z2を与える末端封止化合物としては、末端封止後にアルカリ可溶性基を有する芳香族カルボン酸が好ましく、芳香族ジカルボン酸が好ましく、フタル酸がより一層好ましい。
ポリアミック酸の分子鎖末端を封止する際の反応温度は、ポリアミック酸の合成時と同様に、用いる溶媒の融点から沸点までの範囲で適宜設定すればよく、通常0~100℃程度であるが、合成したポリアミック酸の分子鎖末端を確実に封止する観点から、好ましくは0~70℃程度、より好ましくは0~60℃程度、更に好ましくは0~50℃程度とすることができる。反応時間は、反応温度や原料物質の反応性に依存するため一概に規定できないが、通常1~100時間程度である。
本発明において、上記焼成時の最高温度は450~550℃、かつ、ポリイミドの耐熱温度以下の範囲であれば特に限定されるものではないが、上述した基体との密着性や、樹脂基板との適度な密着性及び剥離性を向上させることを考慮すると、500℃以上が好ましい。また、その上限は通常550℃程度であるが、510℃程度が好ましい。加熱温度を上記範囲とすることで、得られる膜の脆弱化を防ぎつつ、イミド化反応を十分に進行させることも可能となる。
加熱時間は、加熱温度によって異なるため一概に規定できないが、通常1分~5時間である。また、イミド化率は、50~100%の範囲であればよい。
本発明における加熱態様の好ましい一例としては、50~150℃で加熱した後に、そのまま段階的に加熱温度を上昇させて最終的に450~550℃で加熱する手法が挙げられる。特に、加熱態様のより好ましい一例としては、50~100℃で加熱し、100℃超~450℃未満で加熱し、450℃以上で加熱する手法が挙げられる。更に、加熱態様のより好ましい他の一例としては、50~150℃で加熱した後に、150℃超~350℃で加熱し、次いで350℃超~450℃未満で加熱し、最後に450~550℃で加熱する手法が挙げられる。
本発明の剥離層形成用組成物を用いて、上述の方法によって、ガラス基体上に剥離層を形成する。この剥離層の上に、樹脂基板を形成するための樹脂基板形成用溶液を塗布し、この塗膜を焼成することで、本発明の剥離層を介して、ガラス基体に固定された樹脂基板を形成する。
上記塗膜の焼成温度は、樹脂の種類等に応じて適宜設定されるものであるが、本発明では、この焼成時の最高温度を450~550℃以上とすることが好ましく、480℃以上とすることがより好ましく、490℃以上とすることがより一層好ましく、500℃以上とすることがさらに好ましい。樹脂基板作製の際の焼成時の最高温度をこの範囲とすることで、下地である剥離層と基体との密着性や、剥離層と樹脂基板との適度な密着性及び剥離性をより向上させることができる。
この場合も、最高温度が上記範囲となる限り、それ以下の温度で焼成する工程を含んでいてもよい。
NMP:N-メチルピロリドン
BCS:ブチルセロソルブ
p-PDA:p-フェニレンジアミン
6FAP:2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン
2AP:2-アミノフェノール
BPDA:3,3-4,4-ビフェニルテトラカルボン酸二無水物
TFMB:2,2’-ビス(トリフルオロメチル)ベンジジン
PMDA:ピロメリット酸二無水物
PA:フタル酸無水物
CBDA:1,2,3,4-シクロブタンテトラカルボン酸-1,2:3,4-二無水物
ポリマーの重量平均分子量(以下Mwと略す)と分子量分布は、日本分光(株)製GPC装置(Shodex(登録商標)カラムKF803LおよびKF805L)を用い溶出溶媒としてジメチルホルムアミドを流量1ml/分、カラム温度50℃の条件で測定した。なお、Mwはポリスチレン換算値とした。
以下の方法によって、ポリアミック酸を合成した。
なお、得られたポリマー含有反応液からポリマーを単離せず、後述の通りに、反応液を希釈することで、樹脂基板形成用組成物又は剥離層形成用組成物を調製した。
p-PDA3.176g(0.02937モル)をNMP88.2gに溶解し、BPDA8.624g(0.02931モル)を添加した後、窒素雰囲気下、23℃で24時間反応させた。得られたポリマーのMwは107,300、分子量分布4.6であった。
p-PDA1.507g(0.0139モル)をNMP43.2gに溶解し、PMDA3.166g(0.01452モル)を添加した後、窒素雰囲気下、23℃で2時間反応させた。その後、更に2AP0.127g(0.0012モル)を添加し、窒素雰囲気下、23℃で24時間反応させた。得られたポリマーのMwは48,500、分子量分布2.08であった。
p-PDA1.119g(0.01103モル)をNMP35.2gに溶解し、PMDA3.006g(0.01378モル)を添加した後、窒素雰囲気下、23℃で2時間反応させた。その後、更に2AP0.602g(0.00551モル)を添加し、窒素雰囲気下、23℃で24時間反応させた。得られたポリマーのMwは11,700、分子量分布1.76であった。
p-PDA0.681g(0.00629モル)をNMP35.2gに溶解し、PMDA2.746g(0.01259モル)を添加した後、窒素雰囲気下、23℃で2時間反応させた。その後、更に2AP1.373g(0.012588モル)を添加し、窒素雰囲気下、23℃で24時間反応させた。得られたポリマーのMwは8,000、分子量分布1.57であった。
p-PDA1.5206g(0.01406モル)と6FAP0.105g(0.00287モル)をNMP35.2gに溶解し、PMDA3.004g(0.01377モル)を添加した後、窒素雰囲気下、23℃で22時間反応させた。その後、更にPA0.170g(0.00115モル)を添加した後、窒素雰囲気下、23℃で22時間反応させた。得られたポリマーのMwは22,100、分子量分布1.93であった。
p-PDA1.29g(0.00107モル)をNMP43.2gに溶解し、BPDA3.509g(0.00119モル)を添加した後、窒素雰囲気下、23℃で24時間反応させた。得られたポリマーのMwは34,000、分子量分布2.03であった。
TFMB2.86g(0.0089モル)をNMP35.2gに溶解し、CBDA1.944g(0.00991モル)を加え、窒素雰囲気下、23℃で24時間反応させた。得られたポリマーのMwは69,200、分子量分布2.2であった。得られた溶液は、PGMEに可溶であった。
合成例S1で得られた反応液を、それぞれ、そのまま樹脂基板形成用組成物として用いた。
[実施例1-1]
合成例L1で得られた反応液に、BCSとNMPを加え、ポリマー濃度が5wt%、BCSが20質量%となるように希釈し、剥離層形成用組成物を得た。
合成例L1で得られた反応液の代わりに、それぞれ合成例L2~L4で得られた反応液を用いた以外は、実施例1-1と同様の方法で、剥離層形成用組成物を得た。
合成例L1で得られた反応液の代わりに、それぞれ比較合成例B1及びB2で得られた反応液を用いた以外は、実施例1-1と同様の方法で、剥離層形成用組成物を得た。
[実施例2-1]
スピンコーター(条件:回転数3,000rpmで約30秒)を用いて、実施例1-1で得られた剥離層形成用組成物L1を、ガラス基体としての100mm×100mmガラス基板(以下同様)の上に塗布した。
そして、得られた塗膜を、ホットプレートを用いて100℃で2分間加熱し、その後、オーブンを用いて、300℃で30分間加熱し、加熱温度を400℃まで昇温(10℃/分)し、400℃で30分間加熱し、更に、500℃まで昇温(10℃/分)し、500℃で10分間加熱し、ガラス基板上に厚さ約0.1μmの剥離層を形成し、剥離層付きガラス基板を得た。なお、昇温の間、膜付き基板をオーブンから取り出すことはせず、オーブン内で加熱した。
実施例1-1で得られた剥離層形成用組成物L1の代わりに、それぞれ実施例1-2~1-4で得られた剥離層形成用組成物L2~L4を用いた以外は、実施例2-1と同様の方法で、剥離層及びポリイミド基板を作製し、剥離層付きガラス基板及び樹脂基板・剥離層付きガラス基板を得た。
実施例1-1で得られた剥離層形成用組成物L1の代わりに、それぞれ比較例1-1~1-2で得られた剥離層形成用組成物B1及びB2を用いた以外は、実施例2-1と同様の方法で、剥離層及びポリイミド基板を作製し、剥離層付きガラス基板及び樹脂基板・剥離層付きガラス基板を得た。
上記実施例2-1~2-4及び比較例2-1~2-2で得られた剥離層付きガラス基板について、剥離層とガラス基板との剥離性を、下記手法にて確認した。なお、下記の試験は、同一のガラス基板で行った。
実施例2-1~2-4及び比較例2-1~2-2で得られた剥離層付きガラス基板上の剥離層をクロスカット(縦横1mm間隔、以下同様)し、100マスカットを行った。すなわち、このクロスカットにより、1mm四方のマス目を100個形成した。
そして、この100マスカット部分に粘着テープを貼り付けて、そのテープを剥がし、以下の基準に基づき、剥離性を評価した。結果を表1に示す。
<判定基準>
5B:0%剥離(剥離なし)
4B:5%未満の剥離
3B:5~15%未満の剥離
2B:15~35%未満の剥離
1B:35~65%未満の剥離
0B:65%~80%未満の剥離
B:80%~95%未満の剥離
A:95%~100%未満の剥離
AA:100%剥離(すべて剥離)
実施例2-1~2-4及び比較例2-1~2-2で得られた樹脂基板・剥離層付きガラス基板の樹脂基板を、カッターを用いて25mm幅の短冊状にカットした。そして、カットした樹脂基板の先端にセロハンテープを貼り付け、これを試験片とした。この試験片を、(株)アトニック製プッシュプルテスターを用いて剥離角度が90°となるように剥離試験を行い、下記の基準に基づいて剥離性を評価した。結果を表1に示す。
<判定基準>
5B:0%剥離(剥離なし)
4B:5%未満の剥離
3B:5~15%未満の剥離
2B:15~35%未満の剥離
1B:35~65%未満の剥離
0B:65%~80%未満の剥離
B:80%~95%未満の剥離
A:95%~100%未満の剥離
AA:100%剥離(すべて剥離)
Claims (11)
- 下記式(1A)~(1C)で表されるポリアミック酸の少なくとも1種と有機溶剤とを含む剥離層形成用組成物を基体上に塗布し、最高温度450~550℃で焼成する工程を含む剥離層の製造方法。
- 上記アルカリ可溶性基が、カルボキシ基又はフェノール性水酸基である請求項1記載の剥離層の製造方法。
- 上記Yが、さらにアルカリ可溶性基を有しない芳香族基を含む請求項3~6のいずれか1項記載の剥離層の製造方法。
- 上記アルカリ可溶性基を有しない芳香族基が、フェニレン基、ビフェニレン基又はターフェニレン基である請求項7記載の剥離層の製造方法。
- 請求項1~8のいずれか1項記載の製造方法を用いて形成される剥離層を用いることを特徴とする、樹脂基板を備えるフレキシブル電子デバイスの製造方法。
- 請求項1~8のいずれか1項記載の製造方法を用いて形成した剥離層上に、樹脂基板形成用組成物を塗布した後、最高温度450℃以上で焼成して樹脂基板を形成する工程を含むフレキシブル電子デバイスの製造方法。
- 前記樹脂基板が、ポリイミド樹脂基板である請求項9又は10記載のフレキシブル電子デバイスの製造方法。
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