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WO2018124006A1 - Composition pour former une couche de protection de substrat - Google Patents

Composition pour former une couche de protection de substrat Download PDF

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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
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WO
WIPO (PCT)
Prior art keywords
substrate
protective layer
resin substrate
resin
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2017/046521
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English (en)
Japanese (ja)
Inventor
江原　和也
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Nissan Chemical Corp
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Nissan Chemical Corp
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Filing date
Publication date
Application filed by Nissan Chemical Corp filed Critical Nissan Chemical Corp
Priority to JP2018559483A priority Critical patent/JP7063273B2/ja
Priority to KR1020197019440A priority patent/KR102500563B1/ko
Priority to CN201780080618.5A priority patent/CN110099974B/zh
Publication of WO2018124006A1 publication Critical patent/WO2018124006A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (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)
  • Paints Or Removers (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Encapsulation Of And Coatings For Semiconductor Or Solid State Devices (AREA)

Abstract

L'invention concerne une composition pour former une couche de protection de substrat qui, lorsqu'un substrat en résine est préparé par formation d'un substrat en résine sur un corps de base et ensuite par séparation du substrat en résine, est interposée entre le corps de base et le substrat en résine, le substrat en résine étant facile à séparer du corps de base, et fonctionnant en tant que couche de protection du substrat en résine après séparation, ladite composition pour former une couche de protection de substrat comprenant un poly(acide amique) et un solvant organique.
PCT/JP2017/046521 2016-12-27 2017-12-26 Composition pour former une couche de protection de substrat Ceased WO2018124006A1 (fr)

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CN110099974B (zh) 2022-02-25
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TWI773715B (zh) 2022-08-11
KR102500563B1 (ko) 2023-02-17
JP7063273B2 (ja) 2022-05-09
JPWO2018124006A1 (ja) 2019-10-31
CN110099974A (zh) 2019-08-06

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