WO2018124006A1 - Composition for forming substrate protection layer - Google Patents
Composition for forming substrate protection layer Download PDFInfo
- Publication number
- WO2018124006A1 WO2018124006A1 PCT/JP2017/046521 JP2017046521W WO2018124006A1 WO 2018124006 A1 WO2018124006 A1 WO 2018124006A1 JP 2017046521 W JP2017046521 W JP 2017046521W WO 2018124006 A1 WO2018124006 A1 WO 2018124006A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- substrate
- protective layer
- resin substrate
- resin
- composition
- Prior art date
Links
- 0 CC(C)(C)C(*C(N*NC(C)(C)C)=O)=O Chemical compound CC(C)(C)C(*C(N*NC(C)(C)C)=O)=O 0.000 description 1
Classifications
-
- 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
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/002—Pretreatement
-
- 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
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
-
- 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
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
-
- 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
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/12—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by mechanical means
-
- 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
-
- 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
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- 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
-
- 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
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
-
- 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
- B05D2201/00—Polymeric substrate or laminate
- B05D2201/02—Polymeric substrate
Definitions
- the present invention relates to a composition for forming a substrate protective 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 by hydrogen gas generated along with the 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.
- 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.
- a heat-resistant resin film such as a polyimide film
- ITO transparent electrodes, TFTs, etc. are formed and sealed on the film by a vacuum process, and finally the glass substrate is peeled off.
- the manufacturing process to remove is employ
- 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 step is equal to or higher than the glass transition temperature (hereinafter Tg) of the existing polymer.
- the existing polymer has improved adhesion when heated to a temperature of Tg or higher (see, for example, Patent Document 6), and the adhesion between the release layer, the substrate and the resin substrate after the heat treatment. In some cases, it becomes difficult to peel the resin substrate from the substrate.
- heat-resistant polymers applicable to such processes are limited to some high heat-resistant polymer compounds such as polyimide, but cannot be dissolved in a general solvent. For this reason, when the said polyimide was used for the peeling layer, it was difficult to remove the peeling layer remaining on the glass substrate after peeling the resin substrate and to reuse the glass 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
- the present invention has been made in view of the above circumstances, and can facilitate the reuse of the substrate, can be peeled from the substrate together with the resin substrate of the flexible electronic device, and can damage the resin substrate.
- An object of the present invention is to provide a composition for forming a substrate protective layer that does not significantly change the thickness of the substrate.
- the present inventor has formed a resin substrate on the substrate, and then peeled off the resin substrate to produce a resin substrate.
- a composition containing a polyamic acid and an organic solvent as a composition for forming a protective layer of a substrate that is interposed between the substrate and has an easy releasability from the substrate and functions as a protective layer for the resin substrate after peeling.
- the present invention 1. After the resin substrate is formed on the substrate, when the resin substrate is peeled from the substrate together with the resin substrate, the resin substrate is interposed between the substrate and the resin substrate, and has easy peelability from the substrate.
- 2 is a composition for forming a substrate protective layer, wherein Y is an aromatic group represented by the following formula (3): 4). 2 or 3 composition for forming a substrate protective layer, wherein Y is an aromatic group represented by the following formula (4): 5).
- a substrate protective layer forming composition 7).
- a substrate protective layer-forming composition of any one of 1 to 5 is applied onto a substrate and baked at a maximum temperature of 500 ° C. or higher to form a substrate protective layer, and then a resin substrate-forming composition is formed on the substrate protective layer
- a method for producing a resin substrate with a protective layer comprising: applying a product, firing at a maximum temperature of 500 ° C. or higher to form a resin substrate, and then peeling the resin substrate from the substrate together with the substrate protective layer; 11.
- the manufacturing method of 10 whose said resin substrate is a polyimide resin substrate is provided.
- the substrate protective layer forming composition of the present invention By using the substrate protective layer forming composition of the present invention, it is possible to obtain a substrate protective layer having appropriate adhesion to the substrate, appropriate peelability and excellent adhesion to the resin substrate with good reproducibility. Therefore, by using the composition for forming a substrate protective layer of the present invention, in the manufacturing process of the flexible electronic device, there is no damage to the resin substrate formed on the substrate or the circuit provided on the substrate. The resin substrate and the substrate protective layer can be separated from the substrate together with the circuit and the like. Therefore, the composition for forming a substrate protective layer of the present invention can promote reuse of the substrate, and can contribute to simplification of the production process of a flexible electronic device including a resin substrate, improvement of its yield, and the like.
- the composition for forming a substrate protective layer of the present invention contains a polyamic acid and an organic solvent.
- the substrate protective layer in the present invention is a layer provided directly on the glass substrate for a predetermined purpose, and a typical example thereof is a flexible electronic device comprising a substrate and a resin such as polyimide in a flexible electronic device manufacturing process.
- a layer provided for fixing the resin substrate in a predetermined process between the device and the resin substrate of the device is exemplified.
- the substrate protective layer is different from the conventional release layer in that after the electronic circuit or the like is formed on the resin substrate, the substrate protective layer is peeled from the substrate together with the resin substrate.
- the resin substrate has the property of peeling from the substrate together with the resin substrate after the above-described production process, that is, the resin substrate.
- the polyimide film which has adhesiveness with an aromatic diamine from a viewpoint of fully exhibiting the property of easy peelability from the said base
- a polyamic acid obtained by reacting a diamine component and an acid dianhydride component including an aromatic tetracarboxylic dianhydride is preferable, and in particular, a biphenyltetracarboxylic acid diacid represented by the following formula (1):
- a polyamic acid obtained using an anhydride and an aromatic diamine having a fluorine atom is preferred.
- X represents an aromatic group derived from biphenyltetracarboxylic acid represented by the following formula (2)
- Y represents a divalent fluorine atom-containing aromatic derived from an aromatic diamine having a fluorine atom. Represents a group.
- n represents a natural number, but an integer of 2 or more is preferable.
- Examples of the biphenyltetracarboxylic dianhydride that gives a divalent group derived from the biphenyltetracarboxylic acid represented by the above formula (2) include those represented by the following formulas (C1) to (C3).
- 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride represented by the formula (C1) is particularly suitable. Note that (C1) to (C3) may be used alone or in combination of two or more.
- tetracarboxylic dianhydride in addition to the said biphenyl tetracarboxylic dianhydride, other tetracarboxylic dianhydrides can also be used. Specific examples thereof include pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, naphthalene-1,2,3,4-tetracarboxylic dianhydride, naphthalene-1 , 2,5,6-tetracarboxylic dianhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride, naphthalene-1,2,7,8-tetracarboxylic dianhydride, naphthalene- 2,3,5,6-tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic
- the amount of biphenyltetracarboxylic dianhydride in the tetracarboxylic acid component is 70 mol% considering that the above-described easy peelability from the substrate and the adhesion to the resin substrate are compatible.
- the above is preferable, 80 mol% or more is more preferable, 90 mol% or more is more preferable, 95 mol% or more is further preferable, and 100 mol% is most preferable.
- aromatic diamine having a fluorine atom that gives Y are 5-trifluoromethylbenzene-1,3-diamine, 5-trifluoromethylbenzene-1,2-diamine, and 3,5-bis.
- diamines in addition to the aromatic diamine having a fluorine atom, other diamines can also be used. Specific examples thereof include 1,4-diaminobenzene (p-phenylenediamine), 1,3-diaminobenzene (m-phenylenediamine), 1,2-diaminobenzene (o-phenylenediamine), 2,4-diamino.
- the amount of the aromatic diamine having a fluorine atom in the diamine component is 70 mol% or more considering that the above-described easy peelability from the substrate and the adhesion to the resin substrate are compatible.
- 80 mol% or more is more preferable, 90 mol% or more is more preferable, 95 mol% or more is further preferable, and 100 mol% is most preferable.
- the polyamic acid contained in the composition for forming a substrate protective layer of the present invention can be obtained by reacting the diamine component and the tetracarboxylic dianhydride component described above in an organic solvent.
- the organic solvent used in this 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.
- N-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, Examples include 3-tert-butoxy-N, N-dimethylpropylamide and ⁇ -butyrolactone.
- an organic solvent can be used individually by 1 type or in combination of 2 or more types.
- the charge ratio (molar ratio) between the diamine component and the tetracarboxylic dianhydride component is determined appropriately in consideration of the target molecular weight, molecular weight distribution, diamine type, tetracarboxylic dianhydride type, etc.
- the diamine component is about 0.7 to 1.3, preferably about 0.8 to 1.2, and more preferably about 0.9 to 1.1. It is.
- 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 weight average molecular weight of the polyamic acid thus obtained is usually about 5,000 to 500,000, but preferably 10,000 to 200 from the viewpoint of improving the function of the resulting film as a substrate protective layer. About 30,000, more preferably about 30,000 to 150,000.
- a weight average molecular weight is a polystyrene conversion value by a gel permeation chromatography (GPC) measurement.
- one or both of the polymer chain ends may be further reacted with an amine having an anchor group or an acid anhydride having an anchor group.
- anchor groups include carboxylic acid groups, silyl groups (for example, alkylsilyl groups, alkoxysilyl groups, vinylsilyl groups, and allylsilyl groups), vinyl groups, maleimide groups, phenolic hydroxyl groups, and the like.
- Carboxylic acid groups and silyl groups are preferred.
- an alkyl group or aryl having a carbon number of about 1 to 10 that does not significantly reduce the peelability and heat resistance may be present.
- amine having an anchor group examples include 4-aminophenoxytrimethylsilane, 4-aminophenoxydimethylvinylsilane, 4-aminophenoxymethyldivinylsilane, 4-aminophenoxytrivinylsilane, 4-aminophenoxydimethylallylsilane, 4-amino Phenoxymethyldiallylsilane, 4-aminophenoxytriallylsilane, 4-aminophenoxydimethylphenylsilane, 4-aminophenoxymethyldiphenylsilane, 4-aminophenoxytriphenylsilane, 4-aminophenoxytrimethoxysilane, 4-aminophenoxydimethoxyvinylsilane 4-aminophenoxymethoxydivinylsilane, 4-aminophenoxytrivinylsilane, 4-aminophenoxydimethoxyallylsilane, 4 Aminophenoxymethoxydiallylsilane, 4-aminophenoxytrimethyl
- acid anhydride having an anchor group examples include trimellitic anhydride, vinylmaleic anhydride, 4-vinylnaphthalene-1,2-dicarboxylic anhydride, maleic anhydride, and 2,3-dimethylmaleic acid.
- examples thereof include, but are not limited to, anhydrides, 4-hydroxyphthalic anhydride, 3-hydroxyphthalic anhydride, and the like.
- the amount of the amine having an anchor group and the acid anhydride having an anchor group is about 0.01 to 0.6, preferably about 0.01 to 0.6, having an anchor group with respect to the tetracarboxylic dianhydride component 1 in terms of molar ratio.
- the substrate protective layer forming composition of the present invention contains an organic solvent in addition to the polyamic acid described above. Although it does not specifically limit as this organic solvent, The solvent chosen from the following is preferable.
- R 1 to R 8 independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
- R 9 and R 10 independently represent a hydrogen atom
- 10 represents an alkyl group or an acyl group having 1 to 10 carbon atoms
- b and m represent natural numbers
- alkyl group having 1 to 10 carbon atoms 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.
- acyl group having 1 to 10 carbon atoms examples include alkanoyl groups having 1 to 8 carbon atoms (for example, formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, and pivaloyl group), and 3 to 6 carbon atoms.
- Cycloalkylcarbonyl group for example, cyclopropylcarbonyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, etc.
- benzoyl group and the like and acetyl group is preferable.
- N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl- which dissolves polyamic acid well and is easy to prepare a highly uniform composition.
- 2-Imidazolidinone, N-ethyl-2-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 Propoxy) propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate and other solvents
- the method for preparing the composition for forming a substrate protective layer of the present invention is arbitrary.
- a preferable example of the preparation method includes a method of filtering the reaction solution containing the target polyamic acid obtained by the method described above. At this time, the filtrate may be diluted or concentrated if necessary for the purpose of adjusting the concentration.
- 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 above reaction.
- the solvent used for dilution can be used individually by 1 type or in combination of 2 or more types.
- the concentration of the polyamic acid in the composition for forming a substrate protective layer of the present invention is appropriately set in consideration of the thickness of the substrate protective layer to be produced, the viscosity of the composition, etc., but is usually about 1 to 30% by mass, The amount is preferably about 1 to 20% by mass. With such a concentration, a substrate protective layer having a thickness of about 0.05 to 5 ⁇ m can be obtained with good reproducibility.
- the concentration of the polyamic acid should be adjusted by adjusting the amount of diamine and tetracarboxylic dianhydride used as the raw material for the polyamic acid, adjusting the amount when the isolated polyamic acid is dissolved in the solvent, etc. Can do.
- the viscosity of the composition for forming a substrate protective layer of the present invention is appropriately set in consideration of the thickness of the substrate protective layer to be produced, etc., but a film having a thickness of about 0.05 to 5 ⁇ m is particularly reproducible. When it is intended to obtain, 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 substrate protective layer of the present invention may contain a crosslinking agent or the like in order to improve film strength, for example, in addition to the polyamic acid and the organic solvent.
- the polyamic acid is thermally imidized by a baking method including a step of baking at a maximum temperature of 500 ° C. or higher, thereby easily peeling from the substrate and A resin substrate protective layer made of a polyimide film having excellent adhesion to the resin substrate can be obtained.
- the maximum temperature during the baking is not particularly limited as long as it is in the range of 500 ° C. or more and not more than the heat resistant temperature of polyimide.
- the upper limit is usually about 550 ° C, preferably about 520 ° C, more preferably about 510 ° C.
- the heating time varies depending on the heating temperature, and cannot be generally defined, but is usually 5 minutes 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.
- the heating mode in the present invention there is a method of heating at 50 to 150 ° C., then raising the heating temperature stepwise and finally heating at 500 ° C. or higher.
- a method of heating at 50 to 100 ° C., heating above 100 ° C. to less than 500 ° C., and heating at 500 ° C. or more can be mentioned.
- the heating mode after heating at 50 to 100 ° C., heating at 200 to 300 ° C., heating at a temperature higher than 300 ° C. to less than 500 ° C., and finally heating at 500 to 510 ° C.
- a method 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 gradually increased as it is, and finally at 500 ° 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 500 ° C. for 5 minutes to 2 hours, and heating is performed at 500 ° C. or more for 30 minutes to 4 hours.
- the technique to do is mentioned.
- the heating mode after heating at 50 to 100 ° C. for 1 minute to 2 hours, 200 to 300 ° C. for 5 minutes to 2 hours, more than 300 ° C. to less than 500 ° C. for 5 minutes to 2 And a method of heating at 500 to 510 ° C. for 1 minute to 2 hours.
- the substrate protective layer When such a substrate protective layer of the present invention is formed on a substrate, the substrate protective layer may be formed on a part of the surface of the substrate or on the entire surface.
- a mode of forming a substrate protective layer on a part of the surface of the substrate a mode in which the substrate protective layer is formed only in a predetermined range on the surface of the substrate, a substrate in a pattern such as a dot pattern or a line and space pattern on the entire surface of the substrate.
- a protective layer is formed.
- substrate means what is used for manufacture of a flexible electronic device etc. by which the composition for board
- the substrate examples include glass, plastic (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene resin, etc.), metal (silicon wafer, etc.), Although wood, paper, slate, etc. are mentioned, since the board
- 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 composed of two or more materials, a certain range of the substrate surface is composed of a certain material, and the other surface is composed of other materials. A dot pattern is formed on the entire surface of the substrate. There is a mode in which a material in a pattern such as a line and space pattern is present in other materials.
- the method for applying the substrate protective layer-forming composition of the present invention to the substrate is not particularly limited, and examples thereof include cast coating, spin coating, blade coating, dip coating, roll coating, bar coating, and the like. Examples thereof include a coating method, a die coating method, an inkjet method, and a printing method (such as a relief plate, an intaglio plate, a lithographic plate, and a screen printing).
- Examples of the appliance 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 substrate protective layer is usually about 0.01 to 50 ⁇ m, and preferably about 0.05 to 20 ⁇ m from the viewpoint of productivity.
- desired thickness is implement
- the substrate protective layer described above has an appropriate adhesion to a substrate, particularly a glass substrate, an appropriate peelability, and an excellent adhesion to a resin substrate. Therefore, the substrate protective layer of the present invention, in the manufacturing process of the flexible electronic device, without damaging the resin substrate of the device, the resin substrate together with the circuit and the like formed on the resin substrate from the substrate. It can be suitably used for peeling.
- substrate protective layer is not specifically limited, From a heat resistant viewpoint, the thing whose 1% weight reduction temperature in a thermogravimetric analysis is 500 degreeC or more is suitable.
- a resin substrate include a resin substrate using a wholly aromatic polymer such as wholly aromatic polyimide, polybenzoxazole, polybenzothiazole, and polybenzimidazole.
- a hybrid film in which silica sol, titania sol or the like is added to the polymer may be used.
- a substrate protective layer is formed on a glass substrate by the method described above using the composition for forming a substrate protective layer of the present invention. Resin fixed to the glass substrate via the substrate protective layer of the present invention by applying a resin substrate forming solution for forming a resin substrate on the substrate protective layer and baking this coating film A substrate is formed.
- the firing temperature of the coating film is appropriately set according to the type of resin and the like.
- the maximum temperature during firing is preferably 500 ° C. or higher.
- the upper limit is usually about 550 ° C, preferably about 520 ° C, more preferably about 510 ° C.
- 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 raising the heating temperature stepwise and finally heating at 500 ° C. or higher.
- a method of heating at 50 to 100 ° C., heating above 100 ° C. to less than 500 ° C., and heating at 500 ° C. or more can be mentioned.
- the heating mode after heating at 50 to 100 ° C., heating at over 100 ° C. to 200 ° C., heating at over 200 ° C. to 300 ° C., over 300 ° C. to less than 500 ° C.
- a method of heating and finally heating at 500 to 510 ° C. can be 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 gradually increased as it is, and finally at 500 ° 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 500 ° C. for 5 minutes to 2 hours, and heating is performed at 500 ° C. or more for 30 minutes to 4 hours.
- the technique to do is mentioned.
- the heating mode after heating at 50 to 100 ° C.
- a desired circuit is formed on the resin substrate fixed to the base via the substrate protective layer of the present invention, and then, for example, the resin substrate is cut along the substrate protective layer.
- the substrate and the substrate protective layer are peeled from the substrate, and the resin substrate and the substrate protective layer are separated from the substrate. At this time, a part of the substrate may be cut together with the substrate protective layer.
- 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 substrate protective layer from the glass substrate without affecting the circuit or the like provided on the resin substrate, which determines the performance of the display.
- the composition for forming a substrate protective layer of the present invention has a feature of sufficiently absorbing light having a specific wavelength (for example, 308 nm) that allows application of the LLO method, and can therefore be used as a sacrificial layer for the LLO method. . Therefore, a desired circuit is formed on a resin substrate fixed to a glass substrate through a substrate protective layer formed using the composition according to the present invention, and then an LLO method is performed to irradiate a light beam of 308 nm. Then, only the substrate protective layer absorbs this light and evaporates (sublimates). As a result, the substrate protective 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
- Mw weight average molecular weight
- Mw molecular weight distribution of a polymer
- GPC apparatus manufactured by JASCO Corporation (column: KD801 and KD805 manufactured by Shodex; eluent: Dimethylformamide / LiBr.H 2 O (29.6 mM) / H 3 PO 4 (29.6 mM) / THF (0.1 wt%); flow rate: 1.0 mL / min; column temperature: 40 ° C .; Mw: standard polystyrene (Converted value).
- composition for forming substrate protective 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 the BCS was 20 mass% to obtain a composition for forming a substrate protective layer.
- Example 1-2 The reaction solution obtained in Synthesis Example L2 was directly used as the substrate protective layer forming composition.
- Example 2-1 Preparation of substrate protective layer and resin substrate [Example 2-1] Using a spin coater (condition: about 3,000 rpm for about 30 seconds), the substrate protective layer forming composition 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 80 ° C. for 10 minutes using a hot plate, and then heated at 300 ° C. for 30 minutes and at 400 ° C. for 30 minutes using an oven, and further at 500 ° C. for 10 minutes. The substrate was heated to form a substrate protective layer having a thickness of about 0.1 ⁇ m on the glass substrate, thereby obtaining a glass substrate with a substrate protective layer. The heating rate between the heating temperatures was 5 ° C./min. During the heating, the film-coated substrate was not removed from the oven and heated in the oven.
- a spin coater condition: about 3,000 rpm for about 30 seconds
- the composition for resin substrate formation was apply
- the obtained coating film was heated at 80 ° C. for 40 minutes using a hot plate, and then heated at 140 ° C., 210 ° C., 300 ° C. and 400 ° C. for 30 minutes using an oven, and then further heated to 500 ° C.
- the substrate was heated at 60 ° C. for 60 minutes to form a polyimide resin substrate having a thickness of about 10 ⁇ m on the substrate protective layer to obtain a glass substrate with a resin substrate / substrate protective layer.
- the temperature increase rate between each heating temperature was 2 degree-C / min, and it heated in oven, without taking out a board
- Example 2-2 The same composition as in Example 2-1 except that the composition for forming a substrate protective layer obtained in Example 1-2 was used in place of the composition for forming a substrate protective layer obtained in Example 1-1.
- a substrate protective layer and a polyimide resin substrate were formed, and a glass substrate with a substrate protective layer and a glass substrate with a resin substrate / substrate protective layer were obtained.
- Example 2 except that the substrate protective layer-forming composition obtained in Comparative Examples 1-1 to 1-2 was used in place of the substrate protective layer-forming composition obtained in Example 1-1.
- the substrate protective layer and the polyimide resin substrate were formed in the same manner as in -1, and a glass substrate with a substrate protective layer and a glass substrate with a resin substrate / substrate protective layer were obtained.
- ⁇ Evaluation criteria for releasability between glass substrate and substrate protective layer> ⁇ : The substrate protective layer is peeled off from the glass substrate. ⁇ : The resin substrate can be peeled off, but a part of the substrate protective layer remains on the glass substrate. X: The resin substrate and the substrate protective layer cannot be peeled from the glass substrate. Moreover, the surface of the glass surface of the peeled site
- the substrate protective layers of Examples 2-1 and 2-2 were easily peeled off together with the resin substrate, and it was confirmed that the substrate protective layer did not remain on the glass substrate.
- the resin substrates of Comparative Examples 2-1 and 2-2 were firmly attached to the glass substrate via the substrate protective layer and could not be peeled off from the glass substrate.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Encapsulation Of And Coatings For Semiconductor Or Solid State Devices (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Paints Or Removers (AREA)
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。この新世代ディスプレイに関する技術は、フレキシブルディスプレイや、フレキシブルスマートフォン、ミラーディスプレイ等の様々な分野への転用が期待されている。 In recent years, electronic devices have been required to have a function of being able to bend in addition to the characteristics of thinning and lightening. For this reason, it is required to use a lightweight flexible plastic substrate in place of the conventional glass substrate that is fragile and cannot be bent.
In particular, in the new generation display, development of an active matrix type full color TFT display panel using a lightweight flexible plastic substrate (hereinafter referred to as a resin substrate) is required. This new generation display technology is expected to be diverted to various fields such as flexible displays, flexible smartphones, and mirror displays.
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。 However, in the methods disclosed in Patent Documents 1 to 4, particularly the method disclosed in Patent Document 4, it is essential to use a highly light-transmitting substrate in order to transmit laser light, and the substrate passes through the substrate. In addition, it is necessary to irradiate laser light with a relatively large energy sufficient to release hydrogen contained in amorphous silicon, and the layer to be peeled may be damaged by the laser light irradiation. There is a problem.
In addition, when the layer to be peeled has a large area, it takes a long time for the laser treatment, and it is difficult to increase the productivity of device fabrication.
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基体および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。 By the way, as a 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 step is equal to or higher than the glass transition temperature (hereinafter Tg) of the existing polymer.
However, it is known that the existing polymer has improved adhesion when heated to a temperature of Tg or higher (see, for example, Patent Document 6), and the adhesion between the release layer, the substrate and the resin substrate after the heat treatment. In some cases, it becomes difficult to peel the resin substrate from the substrate.
1. 基体上に樹脂基板を形成した後、上記樹脂基板とともに上記樹脂基板を上記基体から剥離する際に、上記基体と上記樹脂基板との間に介在し、上記基体からの易剥離性を有するとともに、剥離後の上記樹脂基板の保護層として機能する基板保護層形成用組成物であって、ポリアミック酸と有機溶媒とを含むことを特徴とする基板保護層形成用組成物、
2. 下記式(1)で表されるポリアミック酸と有機溶媒とを含む1の基板保護層形成用組成物、
6. 上記樹脂基板上に、さらに電子デバイスを作製し、上記樹脂基板とともに電子デバイスを上記基体から剥離する際に、上記基体からの易剥離性を有するとともに剥離後の樹脂基板の保護層として機能する1の基板保護層形成用組成物、
7. 1~6のいずれかの基板保護層形成用組成物から得られる基板保護層、
8. 基体上に6の基板保護層形成用組成物を塗布し、最高温度500℃以上で焼成して上記基体からの易剥離性を有する基板保護層を形成する工程と、
該基板保護層の上に樹脂基板形成用組成物を塗布し、最高温度500℃以上で焼成して樹脂基板を形成する工程と、
この樹脂基板上に電子デバイスを作製する工程と、
上記基体から上記基板保護層および上記樹脂基板とともに上記電子デバイスを剥離する工程と、を含むことを特徴とするフレキシブル電子デバイスの製造方法、
9. 上記樹脂基板が、ポリイミド樹脂基板である8のフレキシブル電子デバイスの製造方法、
10. 基体上に1~5のいずれかの基板保護層形成用組成物を塗布し、最高温度500℃以上で焼成して基板保護層を形成した後、該基板保護層の上に樹脂基板形成用組成物を塗布し、最高温度500℃以上で焼成して、樹脂基板を形成した後、上記樹脂基板を上記基板保護層とともに基体から剥離することを特徴とする保護層付き樹脂基板の製造方法、
11. 上記樹脂基板が、ポリイミド樹脂基板である10の製造方法
を提供する。 That is, the present invention
1. After the resin substrate is formed on the substrate, when the resin substrate is peeled from the substrate together with the resin substrate, the resin substrate is interposed between the substrate and the resin substrate, and has easy peelability from the substrate. A composition for forming a protective layer of a substrate that functions as a protective layer for the resin substrate after peeling, comprising a polyamic acid and an organic solvent,
2. 1 composition for forming a substrate protective layer comprising a polyamic acid represented by the following formula (1) and an organic solvent;
6). When an electronic device is further produced on the resin substrate and the electronic device is peeled from the substrate together with the resin substrate, it has an easy releasability from the substrate and functions as a protective layer for the resin substrate after peeling. A substrate protective layer forming composition,
7). A substrate protective layer obtained from the substrate protective layer forming composition according to any one of 1 to 6,
8). A step of applying a composition for forming a substrate protective layer 6 on a substrate and firing at a maximum temperature of 500 ° C. or higher to form a substrate protective layer having easy peelability from the substrate;
Applying a composition for forming a resin substrate on the substrate protective layer, and baking at a maximum temperature of 500 ° C. or higher to form a resin substrate;
Producing an electronic device on the resin substrate;
Peeling the electronic device together with the substrate protective layer and the resin substrate from the substrate, and a method for producing a flexible electronic device,
9. The method for producing a flexible electronic device according to 8, wherein the resin substrate is a polyimide resin substrate,
10. A substrate protective layer-forming composition of any one of 1 to 5 is applied onto a substrate and baked at a maximum temperature of 500 ° C. or higher to form a substrate protective layer, and then a resin substrate-forming composition is formed on the substrate protective layer A method for producing a resin substrate with a protective layer, comprising: applying a product, firing at a maximum temperature of 500 ° C. or higher to form a resin substrate, and then peeling the resin substrate from the substrate together with the substrate protective layer;
11. The manufacturing method of 10 whose said resin substrate is a polyimide resin substrate is provided.
本発明の基板保護層形成用組成物は、ポリアミック酸と有機溶媒とを含む。ここで、本発明における基板保護層とは、所定の目的でガラス基体直上に設けられる層であり、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る層が挙げられる。なお、この基板保護層は、上記樹脂基板上に電子回路等を形成した後において、当該樹脂基板とともに当該基体から剥離される点において従来の剥離層とは異なるものである。 Hereinafter, the present invention will be described in more detail.
The composition for forming a substrate protective layer of the present invention contains a polyamic acid and an organic solvent. Here, the substrate protective layer in the present invention is a layer provided directly on the glass substrate for a predetermined purpose, and a typical example thereof is a flexible electronic device comprising a substrate and a resin such as polyimide in a flexible electronic device manufacturing process. A layer provided for fixing the resin substrate in a predetermined process between the device and the resin substrate of the device is exemplified. The substrate protective layer is different from the conventional release layer in that after the electronic circuit or the like is formed on the resin substrate, the substrate protective layer is peeled from the substrate together with the resin substrate.
nは、自然数を表すが、2以上の整数が好ましい。 In the formula (1), X represents an aromatic group derived from biphenyltetracarboxylic acid represented by the following formula (2), and Y represents a divalent fluorine atom-containing aromatic derived from an aromatic diamine having a fluorine atom. Represents a group.
n represents a natural number, but an integer of 2 or more is preferable.
その具体例としては、ピロメリット酸二無水物、ベンゼン-1,2,3,4-テトラカルボン酸二無水物、ナフタレン-1,2,3,4-テトラカルボン酸二無水物、ナフタレン-1,2,5,6-テトラカルボン酸二無水物、ナフタレン-1,2,6,7-テトラカルボン酸二無水物、ナフタレン-1,2,7,8-テトラカルボン酸二無水物、ナフタレン-2,3,5,6-テトラカルボン酸二無水物、ナフタレン-2,3,6,7-テトラカルボン酸二無水物、ナフタレン-1,4,5,8-テトラカルボン酸二無水物、アントラセン-1,2,3,4-テトラカルボン酸二無水物、アントラセン-1,2,5,6-テトラカルボン酸二無水物、アントラセン-1,2,6,7-テトラカルボン酸二無水物、アントラセン-1,2,7,8-テトラカルボン酸二無水物、アントラセン-2,3,6,7-テトラカルボン酸二無水物、フェナントレン-1,2,3,4-テトラカルボン酸二無水物、フェナントレン-1,2,5,6-テトラカルボン酸二無水物、フェナントレン-1,2,6,7-テトラカルボン酸二無水物、フェナントレン-1,2,7,8-テトラカルボン酸二無水物、フェナントレン-1,2,9,10-テトラカルボン酸二無水物、フェナントレン-2,3,5,6-テトラカルボン酸二無水物、フェナントレン-2,3,6,7-テトラカルボン酸二無水物、フェナントレン-2,3,9,10-テトラカルボン酸二無水物、フェナントレン-3,4,5,6-テトラカルボン酸二無水物、フェナントレン-3,4,9,10-テトラカルボン酸二無水物等が挙げられ、これらは単独でも、2種以上を組み合わせて用いることもできる。 Moreover, in this invention, in addition to the said biphenyl tetracarboxylic dianhydride, other tetracarboxylic dianhydrides can also be used.
Specific examples thereof include pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, naphthalene-1,2,3,4-tetracarboxylic dianhydride, naphthalene-1 , 2,5,6-tetracarboxylic dianhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride, naphthalene-1,2,7,8-tetracarboxylic dianhydride, naphthalene- 2,3,5,6-tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, anthracene -1,2,3,4-tetracarboxylic dianhydride, anthracene-1,2,5,6-tetracarboxylic dianhydride, anthracene-1,2,6,7-tetracarboxylic dianhydride, Anthracene-1,2,7 8-tetracarboxylic dianhydride, anthracene-2,3,6,7-tetracarboxylic dianhydride, phenanthrene-1,2,3,4-tetracarboxylic dianhydride, phenanthrene-1,2,5 , 6-tetracarboxylic dianhydride, phenanthrene-1,2,6,7-tetracarboxylic dianhydride, phenanthrene-1,2,7,8-tetracarboxylic dianhydride, phenanthrene-1,2, 9,10-tetracarboxylic dianhydride, phenanthrene-2,3,5,6-tetracarboxylic dianhydride, phenanthrene-2,3,6,7-tetracarboxylic dianhydride, phenanthrene-2,3 , 9,10-tetracarboxylic dianhydride, phenanthrene-3,4,5,6-tetracarboxylic dianhydride, phenanthrene-3,4,9,10-tetracarboxylic dianhydride Anhydride, and the like. These alone, it may be used in combination of two or more.
したがって、式(1)における好適なYとしては、式(3)および(4)で表される2価の芳香族基が挙げられる。 Among these, in consideration of achieving both the above-described easy peelability from the substrate and adhesion to the resin substrate, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl (2,2 ′) -Bis (trifluoromethyl) benzidine), 3,3′-bis (trifluoromethyl) -4,4′-diaminobiphenyl (3,3′-bis (trifluoromethyl) benzidine) is preferred, and 2,2 ′ -Bis (trifluoromethyl) -4,4'-diaminobiphenyl (2,2'-bis (trifluoromethyl) benzidine) is even more preferred.
Therefore, as suitable Y in Formula (1), the bivalent aromatic group represented by Formula (3) and (4) is mentioned.
その具体例としては、1,4-ジアミノベンゼン(p-フェニレンジアミン)、1,3-ジアミノベンゼン(m-フェニレンジアミン)、1,2-ジアミノベンゼン(o-フェニレンジアミン)、2,4-ジアミノトルエン、2,5-ジアミノトルエン、2,6-ジアミノトルエン、4,6-ジメチル-m-フェニレンジアミン、2,5-ジメチル-p-フェニレンジアミン、2,6-ジメチル-p-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-p-フェニレンジアミン、m-キシリレンジアミン、p-キシリレンジアミン等のベンゼン核が1つのジアミン;1,2-ナフタレンジアミン、1,3-ナフタレンジアミン、1,4-ナフタレンジアミン、1,5-ナフタレンジアミン、1,6-ナフタレンジアミン、1,7-ナフタレンジアミン、1,8-ナフタレンジアミン、2,3-ナフタレンジアミン、2,6-ナフタレンジアミン、4,4’-ビフェニルジアミン、3,3’-ジメチル-4,4’-ジアミノジフェニルメタン、3,3’-ジカルボキシ-4,4’-ジアミノジフェニルメタン、3,3’,5,5’-テトラメチル-4,4’-ジアミノジフェニルメタン、4,4’-ジアミノベンズアニリド、3,3’-ジクロロベンジジン、3,3’-ジメチルベンジジン、2,2’-ジメチルベンジジン、3,3’-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、4,4’-ジアミノジフェニルメタン、2,2-ビス(3-アミノフェニル)プロパン、2,2-ビス(4-アミノフェニル)プロパン、3,3’-ジアミノジフェニルスルホキシド、3,4’-ジアミノジフェニルスルホキシド、4,4’-ジアミノジフェニルスルホキシド、2-(3-アミノフェニル)-5-アミノベンズイミダゾール、2-(4-アミノフェニル)-5-アミノベンゾオキゾール等のベンゼン核が2つのジアミン;1,5-ジアミノアントラセン、2,6-ジアミノアントラセン、9,10-ジアミノアントラセン、1,8-ジアミノフェナントレン、2,7-ジアミノフェナントレン、3,6-ジアミノフェナントレン、9,10-ジアミノフェナントレン、1,3-ビス(3-アミノフェニル)ベンゼン、1,3-ビス(4-アミノフェニル)ベンゼン、1,4-ビス(3-アミノフェニル)ベンゼン、1,4-ビス(4-アミノフェニル)ベンゼン、1,3-ビス(3-アミノフェニルスルフィド)ベンゼン、1,3-ビス(4-アミノフェニルスルフィド)ベンゼン、1,4-ビス(4-アミノフェニルスルフィド)ベンゼン、1,3-ビス(3-アミノフェニルスルホン)ベンゼン、1,3-ビス(4-アミノフェニルスルホン)ベンゼン、1,4-ビス(4-アミノフェニルスルホン)ベンゼン、1,3-ビス〔2-(4-アミノフェニル)イソプロピル〕ベンゼン、1,4-ビス〔2-(3-アミノフェニル)イソプロピル〕ベンゼン、1,4-ビス〔2-(4-アミノフェニル)イソプロピル〕ベンゼン、4,4’’-ジアミノ-p-ターフェニル、4,4’’-ジアミノ-m-ターフェニル等のベンゼン核が3つのジアミンなどが挙げられ、これらは単独で用いても、2種以上を組み合わせて用いてもよい。 In the present invention, in addition to the aromatic diamine having a fluorine atom, other diamines can also be used.
Specific examples thereof include 1,4-diaminobenzene (p-phenylenediamine), 1,3-diaminobenzene (m-phenylenediamine), 1,2-diaminobenzene (o-phenylenediamine), 2,4-diamino. Toluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 4,6-dimethyl-m-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2 1,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, etc., one diamine nucleus; 1,2-naphthalenediamine, 1,3-naphthalenediamine, 1,4-naphthalenediamine, 1,5-naphthalene Amine, 1,6-naphthalenediamine, 1,7-naphthalenediamine, 1,8-naphthalenediamine, 2,3-naphthalenediamine, 2,6-naphthalenediamine, 4,4'-biphenyldiamine, 3,3'- Dimethyl-4,4′-diaminodiphenylmethane, 3,3′-dicarboxy-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylmethane, 4,4 '-Diaminobenzanilide, 3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine, 2,2'-dimethylbenzidine, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4' -Diaminodiphenylmethane, 2,2-bis (3-aminophenyl) propane, 2,2-bis (4-aminophenyl) propane, , 3'-diaminodiphenyl sulfoxide, 3,4'-diaminodiphenyl sulfoxide, 4,4'-diaminodiphenyl sulfoxide, 2- (3-aminophenyl) -5-aminobenzimidazole, 2- (4-aminophenyl)- A diamine having two benzene nuclei such as 5-aminobenzoxazole; 1,5-diaminoanthracene, 2,6-diaminoanthracene, 9,10-diaminoanthracene, 1,8-diaminophenanthrene, 2,7-diaminophenanthrene, 3,6-diaminophenanthrene, 9,10-diaminophenanthrene, 1,3-bis (3-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (3-aminophenyl) ) Benzene, 1,4-bis (4-aminophenyl) benzene, 1, 3-bis (3-aminophenyl sulfide) benzene, 1,3-bis (4-aminophenyl sulfide) benzene, 1,4-bis (4-aminophenyl sulfide) benzene, 1,3-bis (3-aminophenyl) Sulfone) benzene, 1,3-bis (4-aminophenylsulfone) benzene, 1,4-bis (4-aminophenylsulfone) benzene, 1,3-bis [2- (4-aminophenyl) isopropyl] benzene, 1,4-bis [2- (3-aminophenyl) isopropyl] benzene, 1,4-bis [2- (4-aminophenyl) isopropyl] benzene, 4,4 ″ -diamino-p-terphenyl, 4 , 4 ″ -diamino-m-terphenyl, etc., and diamine nuclei with three diamines. These may be used alone or in combination of two or more. May be used.
この反応に用いる有機溶媒は、反応に悪影響を及ぼさない限り特に限定されるものではなく、その具体例としては、m-クレゾール、2-ピロリドン、N-メチル-2-ピロリドン、N-エチル-2-ピロリドン、N-ビニル-2-ピロリドン、N,N-ジメチルアセトアミド、N,N-ジメチルホルムアミド、3-メトキシ-N,N-ジメチルプロピルアミド、3-エトキシ-N,N-ジメチルプロピルアミド、3-プロポキシ-N,N-ジメチルプロピルアミド、3-イソプロポキシ-N,N-ジメチルプロピルアミド、3-ブトキシ-N,N-ジメチルプロピルアミド、3-sec-ブトキシ-N,N-ジメチルプロピルアミド、3-tert-ブトキシ-N,N-ジメチルプロピルアミド、γ-ブチロラクトン等が挙げられる。なお、有機溶媒は1種単独で又は2種以上を組み合わせて使用することができる。 The polyamic acid contained in the composition for forming a substrate protective layer of the present invention can be obtained by reacting the diamine component and the tetracarboxylic dianhydride component described above in an organic solvent.
The organic solvent used in this 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, Examples include 3-tert-butoxy-N, N-dimethylpropylamide and γ-butyrolactone. In addition, an organic solvent can be used individually by 1 type or in combination of 2 or more types.
このようなアンカー基としては、カルボン酸基、シリル基(例えば、アルキルシリル基、アルコキシシリル基、ビニルシリル基及びアリルシリル基等)、ビニル基、マレイミド基、フェノール性水酸基等が挙げられるが、中でも、カルボン酸基、シリル基(特にアルコキシ基、ビニル基及びアリル基から選ばれる基がケイ素原子に1つ以上結合したシリル基)が好ましい。
また、ジアミン成分及びテトラカルボン酸二無水物成分から得られるポリアミック酸と、アンカー基との間には、炭素数1~10程度の剥離性や耐熱性を著しく低下させない炭素数のアルキル基、アリール基等のスペーサー基が存在してもよい。 In the polyamic acid used in the present invention, one or both of the polymer chain ends may be further reacted with an amine having an anchor group or an acid anhydride having an anchor group.
Examples of such anchor groups include carboxylic acid groups, silyl groups (for example, alkylsilyl groups, alkoxysilyl groups, vinylsilyl groups, and allylsilyl groups), vinyl groups, maleimide groups, phenolic hydroxyl groups, and the like. Carboxylic acid groups and silyl groups (particularly silyl groups in which one or more groups selected from alkoxy groups, vinyl groups and allyl groups are bonded to silicon atoms) are preferred.
Further, between the polyamic acid obtained from the diamine component and the tetracarboxylic dianhydride component and the anchor group, an alkyl group or aryl having a carbon number of about 1 to 10 that does not significantly reduce the peelability and heat resistance. Spacer groups such as groups may be present.
炭素数1~10のアルキル基としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、s-ブチル基、t-ブチル基、n-ペンチル基、n-ヘキシル基、n-ヘプチル基、n-オクチル基、n-ノニル基、n-デシル基等が挙げられる。これらのうち、炭素数1~3のアルキル基が好ましく、炭素数1又は2のアルキル基がより好ましい。
炭素数1~10のアシル基としては、炭素数1~8のアルカノイル基(例えば、ホルミル基、アセチル基、プロピオニル基、ブチリル基、イソブチリル基、バレリル基、ピバロイル基等)、炭素数3~6のシクロアルキルカルボニル基(例えば、シクロプロピルカルボニル基、シクロペンチルカルボニル基、シクロヘキシルカルボニル基等)、ベンゾイル基等が挙げられ、アセチル基が好ましい。 b and m represent natural numbers, preferably 1 to 3, more preferably 1 or 2.
Examples of the alkyl group having 1 to 10 carbon atoms 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.
Examples of the acyl group having 1 to 10 carbon atoms include alkanoyl groups having 1 to 8 carbon atoms (for example, formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, and pivaloyl group), and 3 to 6 carbon atoms. Cycloalkylcarbonyl group (for example, cyclopropylcarbonyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, etc.), benzoyl group and the like, and acetyl group is preferable.
本発明において、上記焼成時の最高温度は500℃以上、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。また、その上限は通常550℃程度であるが、好ましくは520℃、より好ましくは510℃程度である。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5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。 After applying the composition for forming a release layer described above on a substrate, the polyamic acid is thermally imidized by a baking method including a step of baking at a maximum temperature of 500 ° C. or higher, thereby easily peeling from the substrate and A resin substrate protective layer made of a polyimide film having excellent adhesion to the resin substrate can be obtained.
In the present invention, the maximum temperature during the baking is not particularly limited as long as it is in the range of 500 ° C. or more and not more than the heat resistant temperature of polyimide. The upper limit is usually about 550 ° C, preferably about 520 ° C, more preferably about 510 ° C. By making heating temperature into the said range, it becomes possible to fully advance an imidation reaction, preventing weakening of the film | membrane obtained.
The heating time varies depending on the heating temperature, and cannot be generally defined, but is usually 5 minutes to 5 hours. The imidization rate may be in the range of 50 to 100%.
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500℃以上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~500℃未満で加熱し、500℃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、50~100℃で加熱した後に、200~300℃で加熱し、300℃超~500℃未満で加熱し、最後に500~510℃で加熱する手法が挙げられる。 Moreover, as long as the maximum temperature becomes the said range, the temperature at the time of the said baking may include the process baked at the temperature below it.
As a preferred example of the heating mode in the present invention, there is a method of heating at 50 to 150 ° C., then raising the heating temperature stepwise and finally heating at 500 ° C. or higher. In particular, as a more preferable example of the heating mode, a method of heating at 50 to 100 ° C., heating above 100 ° C. to less than 500 ° C., and heating at 500 ° C. or more can be mentioned. Furthermore, as another more preferable example of the heating mode, after heating at 50 to 100 ° C., heating at 200 to 300 ° C., heating at a temperature higher than 300 ° C. to less than 500 ° C., and finally heating at 500 to 510 ° C. A method is mentioned.
このような樹脂基板としては、全芳香族系ポリイミド、ポリベンゾオキサゾール、ポリベンゾチアゾール、ポリベンゾイミダゾールのような、全芳香族系ポリマーを用いた樹脂基板が挙げられる。また、上記ポリマーにシリカゾル、チタニアゾル等が添加されたハイブリッドフィルムであってもよい。 Although the resin substrate formed on the said board | substrate protective layer is not specifically limited, From a heat resistant viewpoint, the thing whose 1% weight reduction temperature in a thermogravimetric analysis is 500 degreeC or more is suitable.
Examples of such a resin substrate include a resin substrate using a wholly aromatic polymer such as wholly aromatic polyimide, polybenzoxazole, polybenzothiazole, and polybenzimidazole. Further, a hybrid film in which silica sol, titania sol or the like is added to the polymer may be used.
本発明の基板保護層形成用組成物を用いて、上述の方法によって、ガラス基体上に基板保護層を形成する。この基板保護層の上に、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、本発明の基板保護層を介して、ガラス基体に固定された樹脂基板を形成する。 Hereinafter, an example of the manufacturing method of the flexible electronic device using the board | substrate protective layer of this invention is demonstrated.
A substrate protective layer is formed on a glass substrate by the method described above using the composition for forming a substrate protective layer of the present invention. Resin fixed to the glass substrate via the substrate protective layer of the present invention by applying a resin substrate forming solution for forming a resin substrate on the substrate protective layer and baking this coating film A substrate is formed.
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、下地である保護層と基体との剥離性や、基板保護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。 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 500 ° C. or higher. The upper limit is usually about 550 ° C, preferably about 520 ° C, more preferably about 510 ° C.
By setting the maximum temperature during firing during resin substrate preparation within this range, the peelability between the protective layer and the substrate as the base, and the appropriate adhesion and peelability between the substrate protective layer and the resin substrate are further improved. Can be made.
樹脂基板作製時の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500℃以上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~500℃未満で加熱し、500℃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、50~100℃で加熱した後に、100℃超~200℃で加熱し、200℃超~300℃で加熱し、300℃超~500℃未満で加熱し、最後に500~510℃で加熱する手法が挙げられる。 In this case, as long as the maximum temperature falls within the above range, a step of baking at a temperature lower than that may be included.
As a preferred example of the heating mode at the time of preparing the resin substrate, there is a method of heating at 50 to 150 ° C., then raising the heating temperature stepwise and finally heating at 500 ° C. or higher. In particular, as a more preferable example of the heating mode, a method of heating at 50 to 100 ° C., heating above 100 ° C. to less than 500 ° C., and heating at 500 ° C. or more can be mentioned. Furthermore, as another more preferable example of the heating mode, after heating at 50 to 100 ° C., heating at over 100 ° C. to 200 ° C., heating at over 200 ° C. to 300 ° C., over 300 ° C. to less than 500 ° C. A method of heating and finally heating at 500 to 510 ° C. can be mentioned.
p-PDA:p-フェニレンジアミン
TFMB:2,2’-ビス(トリフルオロメチル)ベンジジン
BPDA:3,3’,4,4’-ビフェニルテトラカルボン酸二無水物
PMDA:ピロメリット酸二無水物
CBDA:1,2,3,4-シクロブタンテトラカルボン酸二無水物
NMP:N-メチル-2-ピロリドン
BCS:ブチルセロソルブ
PGME:プロピレングリコールモノメチルエーテル [1] Abbreviations of compounds p-PDA: p-phenylenediamine TFMB: 2,2′-bis (trifluoromethyl) benzidine BPDA: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride PMDA: pyro Mellitic acid dianhydride CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride NMP: N-methyl-2-pyrrolidone BCS: Butyl cellosolve PGME: Propylene glycol monomethyl ether
ポリマーの重量平均分子量(以下Mwと略す)及び分子量分布の測定は、日本分光(株)製GPC装置(カラム:Shodex製 KD801及びKD805;溶離液:ジメチルホルムアミド/LiBr・H2O(29.6mM)/H3PO4(29.6mM)/THF(0.1wt%);流量:1.0mL/分;カラム温度:40℃;Mw:標準ポリスチレン換算値)を用いて行った。 [2] Measuring method of weight average molecular weight and molecular weight distribution The weight average molecular weight (hereinafter abbreviated as Mw) and molecular weight distribution of a polymer are measured by GPC apparatus manufactured by JASCO Corporation (column: KD801 and KD805 manufactured by Shodex; eluent: Dimethylformamide / LiBr.H 2 O (29.6 mM) / H 3 PO 4 (29.6 mM) / THF (0.1 wt%); flow rate: 1.0 mL / min; column temperature: 40 ° C .; Mw: standard polystyrene (Converted value).
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基板保護層形成用組成物を調製した。 [3] Synthesis of polymer Polyamic acid was synthesized by the following method.
In addition, the polymer was not isolated from the obtained polymer containing reaction liquid, but the resin liquid formation composition or the composition for board | substrate protective layer formation was prepared by diluting a reaction liquid as mentioned later.
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。 <Synthesis Example S1 Synthesis of Polyamic Acid (S1)>
3.176 g (0.02937 mol) of p-PDA was dissolved in 88.2 g of NMP, and 8.624 g (0.02931 mol) of BPDA was added, followed by reaction at 23 ° C. for 24 hours in a nitrogen atmosphere. Mw of the obtained polymer was 107,300, and the molecular weight distribution was 4.6.
TFMB23.7g(74.2mmol)をNMP352gに溶解させた。得られた溶液に、BPDA24.2g(82.5mmol)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76,400、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。 <Synthesis Example L1 Synthesis of polyamic acid (L1)>
23.7 g (74.2 mmol) of TFMB was dissolved in 352 g of NMP. To the obtained solution, 24.2 g (82.5 mmol) of BPDA was added and reacted at 23 ° C. for 24 hours under a nitrogen atmosphere. Mw of the obtained polymer was 76,400 and molecular weight distribution 2.2. The resulting solution was soluble in PGME.
TFMB9.89g(30.9mmol)をPGME380gに溶解させた。得られた溶液に、BPDA10.0g(34.3mmol)を加え、窒素雰囲気下、50℃で72時間反応させた。得られたポリマーのMwは76,400、分子量分布2.2であった。 <Synthesis Example L2 Synthesis of polyamic acid (L2)>
9.89 g (30.9 mmol) of TFMB was dissolved in 380 g of PGME. To the resulting solution, 10.0 g (34.3 mmol) of BPDA was added and reacted at 50 ° C. for 72 hours under a nitrogen atmosphere. Mw of the obtained polymer was 76,400 and molecular weight distribution 2.2.
TFMB2.73g(8.53mmol)をNMP38.5gに溶解させた。得られた溶液に、PMDA2.06g(9.47mmol)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76,400、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。 <Synthesis of Comparative Synthesis Example HL1 Polyamic Acid (HL1)>
2.73 g (8.53 mmol) of TFMB was dissolved in 38.5 g of NMP. To the obtained solution, 2.06 g (9.47 mmol) of PMDA was added and reacted at 23 ° C. for 24 hours under a nitrogen atmosphere. Mw of the obtained polymer was 76,400 and molecular weight distribution 2.2. The resulting solution was soluble in PGME.
TFMB2.86g(8.91mmol)をNMP35.2gに溶解させた。得られた溶液に、CBDA1.94g(9.91mmol)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。 <Synthesis of Comparative Synthesis Example HL2 Polyamic Acid (HL2)>
2.86 g (8.91 mmol) of TFMB was dissolved in 35.2 g of NMP. CBDA 1.94 g (9.91 mmol) was added to the resulting solution, and the mixture was reacted at 23 ° C. for 24 hours under a nitrogen atmosphere. Mw of the obtained polymer was 69,200 and molecular weight distribution 2.2. The resulting solution was soluble in PGME.
[調製例1]
合成例S1で得られた反応液をそのまま樹脂基板形成用組成物として用いた。 [4] Preparation of resin substrate forming composition [Preparation Example 1]
The reaction solution obtained in Synthesis Example S1 was used as it was as a resin substrate forming composition.
[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、基板保護層形成用組成物を得た。 [5] Preparation of composition for forming substrate protective 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 the BCS was 20 mass% to obtain a composition for forming a substrate protective layer.
合成例L2で得られた反応溶液をそのまま基板保護層形成用組成物とした。 [Example 1-2]
The reaction solution obtained in Synthesis Example L2 was directly used as the substrate protective layer forming composition.
比較合成例HL1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、基板保護層形成用組成物を得た。 [Comparative Example 1-1]
BCS and NMP were added to the reaction solution obtained in Comparative Synthesis Example HL1, and diluted such that the polymer concentration was 5 wt% and the BCS was 20 mass% to obtain a composition for forming a substrate protective layer.
比較合成例HL2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、基板保護層形成用組成物を得た。 [Comparative Example 1-2]
BCS and NMP were added to the reaction solution obtained in Comparative Synthesis Example HL2, and diluted such that the polymer concentration was 5 wt% and BCS was 20 mass% to obtain a composition for forming a substrate protective layer.
[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で得られた基板保護層形成用組成物を、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80℃で10分間加熱し、その後、オーブンを用いて、300℃で30分間、400℃で30分間加熱した後、更に500℃で10分間加熱し、ガラス基板上に厚さ約0.1μmの基板保護層を形成し、基板保護層付きガラス基板を得た。なお、各加熱温度間の昇温速度は5℃/分とし、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。 [6] Preparation of substrate protective layer and resin substrate [Example 2-1]
Using a spin coater (condition: about 3,000 rpm for about 30 seconds), the substrate protective layer forming composition 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 80 ° C. for 10 minutes using a hot plate, and then heated at 300 ° C. for 30 minutes and at 400 ° C. for 30 minutes using an oven, and further at 500 ° C. for 10 minutes. The substrate was heated to form a substrate protective layer having a thickness of about 0.1 μm on the glass substrate, thereby obtaining a glass substrate with a substrate protective layer. The heating rate between the heating temperatures was 5 ° C./min. During the heating, the film-coated substrate was not removed from the oven and heated in the oven.
実施例1-1で得られた基板保護層形成用組成物の代わりに、実施例1-2で得られた基板保護層形成用組成物を用いた以外は、実施例2-1と同様の方法で、基板保護層及びポリイミド樹脂基板を形成し、基板保護層付きガラス基板及び樹脂基板・基板保護層付きガラス基板を得た。 [Example 2-2]
The same composition as in Example 2-1 except that the composition for forming a substrate protective layer obtained in Example 1-2 was used in place of the composition for forming a substrate protective layer obtained in Example 1-1. By the method, a substrate protective layer and a polyimide resin substrate were formed, and a glass substrate with a substrate protective layer and a glass substrate with a resin substrate / substrate protective layer were obtained.
実施例1-1で得られた基板保護層形成用組成物の代わりに、それぞれ比較例1-1~1-2で得られた基板保護層形成用組成物を用いた以外は、実施例2-1と同様の方法で、基板保護層及びポリイミド樹脂基板を形成し、基板保護層付きガラス基板及び樹脂基板・基板保護層付きガラス基板を得た。 [Comparative Examples 2-1 and 2-2]
Example 2 except that the substrate protective layer-forming composition obtained in Comparative Examples 1-1 to 1-2 was used in place of the substrate protective layer-forming composition obtained in Example 1-1. The substrate protective layer and the polyimide resin substrate were formed in the same manner as in -1, and a glass substrate with a substrate protective layer and a glass substrate with a resin substrate / substrate protective layer were obtained.
実施例2-1~2-2及び比較例2-1~2-2で得られた樹脂基板・基板保護層付きガラス基板の樹脂基板及び基板保護層を、カッターを用いて幅2cm、長さ5cmの短冊状にカットした。そして、カットした樹脂基板の端部に粘着テープを貼り付け、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170°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。
<ガラス基板と基板保護層の剥離性 評価基準>
○:基板保護層がガラス基体から全て剥離する。
△:樹脂基板を剥離できるが、一部、ガラス基体上に基板保護層が残る。
×:ガラス基体から樹脂基板及び基板保護層を剥離できない。
また、剥離した部位のガラス面の表面をカッターで削り、以下の基準に基づき、残膜性を評価した。結果を表1に示す。
<ガラス基板への基板保護層の残膜性 評価基準>
○:基板保護層が残膜しない。
△:一部、基板保護層が残る。
×:基板保護層が残る。
―:樹脂基板が剥離しないため、評価不能。 [7] Evaluation of peelability The resin substrate and the substrate protective layer of the resin substrate and the glass substrate with the substrate protective layer obtained in Examples 2-1 to 2-2 and Comparative Examples 2-1 to 2-2 were cut with a cutter. It was cut into strips with a width of 2 cm and a length of 5 cm. And the adhesive tape was affixed on the edge part of the cut resin substrate, and this was made into the test piece. The test piece was subjected to a peel test using an Atonic Co., Ltd. push-pull tester so that the peel angle was 170 °, and peelability was evaluated based on the following criteria. The results are shown in Table 1.
<Evaluation criteria for releasability between glass substrate and substrate protective layer>
○: The substrate protective layer is peeled off from the glass substrate.
Δ: The resin substrate can be peeled off, but a part of the substrate protective layer remains on the glass substrate.
X: The resin substrate and the substrate protective layer cannot be peeled from the glass substrate.
Moreover, the surface of the glass surface of the peeled site | part was shaved with the cutter, and the remaining film property was evaluated based on the following references | standards. The results are shown in Table 1.
<Evaluation criteria of remaining film property of substrate protective layer on glass substrate>
○: The substrate protective layer does not remain.
Δ: A part of the substrate protective layer remains.
X: The substrate protective layer remains.
―: Evaluation is not possible because the resin substrate does not peel off.
実施例2-1で得られた樹脂基板の機械特性を測定した。なお、比較として、基板保護層を形成せず樹脂基板形成用組成物S1を基体上に直接塗布して、焼成して作製した樹脂基板を用いた。その際、基体をガラス基板からシリコン基板に変更し、それ以外は実施例2-1と同様の方法で樹脂基板を形成した。得られた樹脂膜をSF1とした。 [9] Physical properties of resin film The mechanical properties of the resin substrate obtained in Example 2-1 were measured. For comparison, a resin substrate prepared by directly applying the resin substrate-forming composition S1 on a substrate and baking it without forming a substrate protective layer was used. At that time, the substrate was changed from a glass substrate to a silicon substrate, and a resin substrate was formed by the same method as in Example 2-1. The obtained resin film was designated as SF1.
上記で得られたフィルムから、20mm×5mmの短冊状の試験片を作製し、TMA-4000SA(ブルカー・エイエックスエス(株)製)を用いて、50℃から500℃までの線膨張係数を測定した。結果を表2に示す。 <Linear expansion coefficient>
A 20 mm × 5 mm strip-shaped test piece was prepared from the film obtained above, and the coefficient of linear expansion from 50 ° C. to 500 ° C. was measured using TMA-4000SA (manufactured by Bruker AXS Co., Ltd.). It was measured. The results are shown in Table 2.
上記で得られたフィルムから、20mm×3mmの短冊状の試験片を作製し、TGA-DTA-2000SR(ブルカー・エイエックスエス(株)製)を用いて、50℃から600℃までの重量減少を測定し、1%の重量減少が認められた温度を確認した。結果を表2に示す。 <Weight reduction>
A 20 mm × 3 mm strip test piece was prepared from the film obtained above, and the weight was reduced from 50 ° C. to 600 ° C. using TGA-DTA-2000SR (manufactured by Bruker AXS Co., Ltd.). The temperature at which 1% weight loss was observed was confirmed. The results are shown in Table 2.
Claims (11)
- 基体上に樹脂基板を形成した後、上記樹脂基板とともに上記樹脂基板を上記基体から剥離する際に、上記基体と上記樹脂基板との間に介在し、上記基体からの易剥離性を有するとともに、剥離後の上記樹脂基板の保護層として機能する基板保護層形成用組成物であって、ポリアミック酸と有機溶媒とを含むことを特徴とする基板保護層形成用組成物。 After the resin substrate is formed on the substrate, when the resin substrate is peeled from the substrate together with the resin substrate, the resin substrate is interposed between the substrate and the resin substrate, and has easy peelability from the substrate. A composition for forming a protective layer of a substrate, which functions as a protective layer for the resin substrate after peeling, comprising a polyamic acid and an organic solvent.
- 下記式(1)で表されるポリアミック酸と有機溶媒とを含む請求項1記載の基板保護層形成用組成物。
- 上記有機溶媒が、下記式(S1)~(S7)で表される構造を有するものから選ばれる少なくとも1種である請求項1~4のいずれか1項記載の基板保護層形成用組成物。
- 上記樹脂基板上に、さらに電子デバイスを作製し、上記樹脂基板とともに電子デバイスを上記基体から剥離する際に、上記基体からの易剥離性を有するとともに剥離後の樹脂基板の保護層として機能する請求項1記載の基板保護層形成用組成物。 An electronic device is further produced on the resin substrate, and when the electronic device is peeled from the substrate together with the resin substrate, it has an easy peelability from the substrate and functions as a protective layer for the resin substrate after peeling. Item 2. The substrate protective layer-forming composition according to Item 1.
- 請求項1~6のいずれか1項記載の基板保護層形成用組成物から得られる基板保護層。 A substrate protective layer obtained from the composition for forming a substrate protective layer according to any one of claims 1 to 6.
- 基体上に請求項6記載の基板保護層形成用組成物を塗布し、最高温度500℃以上で焼成して上記基体からの易剥離性を有する基板保護層を形成する工程と、
該基板保護層の上に樹脂基板形成用組成物を塗布し、最高温度500℃以上で焼成して樹脂基板を形成する工程と、
この樹脂基板上に電子デバイスを作製する工程と、
上記基体から上記基板保護層および上記樹脂基板とともに上記電子デバイスを剥離する工程と、を含むことを特徴とするフレキシブル電子デバイスの製造方法。 Applying a composition for forming a substrate protective layer according to claim 6 on a substrate and firing at a maximum temperature of 500 ° C. or higher to form a substrate protective layer having easy peelability from the substrate;
Applying a composition for forming a resin substrate on the substrate protective layer, and baking at a maximum temperature of 500 ° C. or higher to form a resin substrate;
Producing an electronic device on the resin substrate;
And a step of peeling the electronic device together with the substrate protective layer and the resin substrate from the substrate. - 上記樹脂基板が、ポリイミド樹脂基板である請求項8記載のフレキシブル電子デバイスの製造方法。 The method of manufacturing a flexible electronic device according to claim 8, wherein the resin substrate is a polyimide resin substrate.
- 基体上に請求項1~5のいずれか1項記載の基板保護層形成用組成物を塗布し、最高温度500℃以上で焼成して基板保護層を形成した後、該基板保護層の上に樹脂基板形成用組成物を塗布し、最高温度500℃以上で焼成して、樹脂基板を形成した後、上記樹脂基板を上記基板保護層とともに基体から剥離することを特徴とする保護層付き樹脂基板の製造方法。 A substrate protective layer-forming composition according to any one of claims 1 to 5 is applied onto a substrate and baked at a maximum temperature of 500 ° C or higher to form a substrate protective layer. A resin substrate with a protective layer, wherein a resin substrate forming composition is applied and baked at a maximum temperature of 500 ° C. or more to form a resin substrate, and then the resin substrate is peeled off from the substrate together with the substrate protective layer. Manufacturing method.
- 上記樹脂基板が、ポリイミド樹脂基板である請求項10記載の製造方法。 The manufacturing method according to claim 10, wherein the resin substrate is a polyimide resin substrate.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201780080618.5A CN110099974B (en) | 2016-12-27 | 2017-12-26 | Composition for forming protective layer on substrate |
KR1020197019440A KR102500563B1 (en) | 2016-12-27 | 2017-12-26 | Composition for Forming a Substrate Protection Layer |
JP2018559483A JP7063273B2 (en) | 2016-12-27 | 2017-12-26 | Composition for forming a substrate protective layer |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016-253112 | 2016-12-27 | ||
JP2016253112 | 2016-12-27 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2018124006A1 true WO2018124006A1 (en) | 2018-07-05 |
Family
ID=62710673
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2017/046521 WO2018124006A1 (en) | 2016-12-27 | 2017-12-26 | Composition for forming substrate protection layer |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP7063273B2 (en) |
KR (1) | KR102500563B1 (en) |
CN (1) | CN110099974B (en) |
TW (1) | TWI773715B (en) |
WO (1) | WO2018124006A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018225825A1 (en) * | 2017-06-08 | 2018-12-13 | 日産化学株式会社 | Method for producing substrate for flexible device |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20130161864A1 (en) * | 2011-12-26 | 2013-06-27 | Chi Mei Corporation | Substrate structure and method for making the same |
WO2015152120A1 (en) * | 2014-03-31 | 2015-10-08 | 日産化学工業株式会社 | Composition for forming releasing layer |
WO2016140238A1 (en) * | 2015-03-04 | 2016-09-09 | 日産化学工業株式会社 | Peeling layer forming composition |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5520960A (en) * | 1994-08-03 | 1996-05-28 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Electrically conductive polyimides containing silver trifluoroacetylacetonate |
JP4619462B2 (en) | 1996-08-27 | 2011-01-26 | セイコーエプソン株式会社 | Thin film element transfer method |
JP3809681B2 (en) | 1996-08-27 | 2006-08-16 | セイコーエプソン株式会社 | Peeling method |
JP4619461B2 (en) | 1996-08-27 | 2011-01-26 | セイコーエプソン株式会社 | Thin film device transfer method and device manufacturing method |
JP2001316622A (en) | 2000-05-11 | 2001-11-16 | Jsr Corp | Composition for film formation and material for insulation film formation |
JP3882817B2 (en) * | 2001-09-26 | 2007-02-21 | 日産化学工業株式会社 | Positive photosensitive polyimide resin composition |
US20070106056A1 (en) | 2003-03-28 | 2007-05-10 | Pi R&D Co., Ltd. | Crosslinked polyimide, composition comprising the same and method for producing the same |
GB0327093D0 (en) | 2003-11-21 | 2003-12-24 | Koninkl Philips Electronics Nv | Active matrix displays and other electronic devices having plastic substrates |
JP5119401B2 (en) | 2007-02-01 | 2013-01-16 | 倉敷紡績株式会社 | Flexible laminate having thermoplastic polyimide layer and method for producing the same |
TWI354854B (en) | 2008-09-15 | 2011-12-21 | Ind Tech Res Inst | Substrate structures applied in flexible electrica |
JP2010202729A (en) | 2009-03-02 | 2010-09-16 | Hitachi Chemical Dupont Microsystems Ltd | Polyimide precursor resin composition for flexible device substrates and method for producing flexible device using the same, and flexible device |
JP5667392B2 (en) | 2010-08-23 | 2015-02-12 | 株式会社カネカ | Laminated body and use thereof |
KR20140122677A (en) * | 2013-04-09 | 2014-10-20 | 주식회사 엘지화학 | Polyimide-based film and mehtod for preparing same |
JP6206071B2 (en) | 2013-10-15 | 2017-10-04 | 東レ株式会社 | RESIN COMPOSITION, POLYIMIDE RESIN FILM USING THE SAME, COLOR FILTER CONTAINING THE SAME, TFT SUBSTRATE, DISPLAY DEVICE AND METHOD FOR PRODUCING THEM |
CN113136103B (en) * | 2015-03-13 | 2024-05-03 | 旭化成株式会社 | Polyimide precursor resin composition |
-
2017
- 2017-12-26 JP JP2018559483A patent/JP7063273B2/en active Active
- 2017-12-26 KR KR1020197019440A patent/KR102500563B1/en active IP Right Grant
- 2017-12-26 WO PCT/JP2017/046521 patent/WO2018124006A1/en active Application Filing
- 2017-12-26 CN CN201780080618.5A patent/CN110099974B/en active Active
- 2017-12-27 TW TW106145941A patent/TWI773715B/en active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20130161864A1 (en) * | 2011-12-26 | 2013-06-27 | Chi Mei Corporation | Substrate structure and method for making the same |
WO2015152120A1 (en) * | 2014-03-31 | 2015-10-08 | 日産化学工業株式会社 | Composition for forming releasing layer |
WO2016140238A1 (en) * | 2015-03-04 | 2016-09-09 | 日産化学工業株式会社 | Peeling layer forming composition |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018225825A1 (en) * | 2017-06-08 | 2018-12-13 | 日産化学株式会社 | Method for producing substrate for flexible device |
JPWO2018225825A1 (en) * | 2017-06-08 | 2020-05-21 | 日産化学株式会社 | Method for manufacturing flexible device substrate |
JP7116366B2 (en) | 2017-06-08 | 2022-08-10 | 日産化学株式会社 | Method for manufacturing substrate for flexible device |
Also Published As
Publication number | Publication date |
---|---|
JP7063273B2 (en) | 2022-05-09 |
KR102500563B1 (en) | 2023-02-17 |
CN110099974A (en) | 2019-08-06 |
CN110099974B (en) | 2022-02-25 |
JPWO2018124006A1 (en) | 2019-10-31 |
TW201833224A (en) | 2018-09-16 |
KR20190100228A (en) | 2019-08-28 |
TWI773715B (en) | 2022-08-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6939941B2 (en) | Manufacturing method of flexible electronic device | |
KR102602473B1 (en) | Composition for forming release layer | |
JP7131385B2 (en) | COMPOSITION FOR FORMING RELEASE LAYER FOR TRANSPARENT RESIN SUBSTRATE | |
WO2021125308A1 (en) | Release layer forming composition | |
JP6705444B2 (en) | Release layer | |
WO2018025955A1 (en) | Composition for forming releasing layer | |
JP7063273B2 (en) | Composition for forming a substrate protective layer | |
JP6962323B2 (en) | Composition for forming a release layer | |
CN110050013B (en) | Method for producing release layer | |
JP6897690B2 (en) | Method of manufacturing the release layer |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 17886965 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2018559483 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20197019440 Country of ref document: KR Kind code of ref document: A |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 17886965 Country of ref document: EP Kind code of ref document: A1 |