WO2018105675A1 - Release layer production method - Google Patents
Release layer production method Download PDFInfo
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- WO2018105675A1 WO2018105675A1 PCT/JP2017/043911 JP2017043911W WO2018105675A1 WO 2018105675 A1 WO2018105675 A1 WO 2018105675A1 JP 2017043911 W JP2017043911 W JP 2017043911W WO 2018105675 A1 WO2018105675 A1 WO 2018105675A1
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- release layer
- group
- substrate
- bis
- resin substrate
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- 0 O=C(*1(*C(O2)=O)C2=O)OC1=O Chemical compound O=C(*1(*C(O2)=O)C2=O)OC1=O 0.000 description 1
Classifications
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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
- B05D3/02—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
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- 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
Definitions
- the present invention relates to a method for producing a release layer.
- Patent Documents 1, 2, and 3 an amorphous silicon thin film layer is formed on a glass substrate, a plastic substrate is formed on the thin film layer, and then laser irradiation is performed from the glass substrate side to crystallize amorphous silicon.
- a method of peeling a plastic substrate from a glass substrate 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.
- JP 10-125929 A Japanese Patent Laid-Open No. 10-125931 International Publication No. 2005/050754 JP-A-10-125930
- the present invention has been made in view of the above circumstances, and an object thereof is to provide a method for producing a release layer that can be peeled without damaging a resin substrate of a flexible electronic device.
- the inventors of the present invention made a tetracarboxylic dianhydride containing a specific tetracarboxylic dianhydride as a release layer formed on a substrate in the production of a resin substrate.
- a composition for forming a release layer containing a polyamic acid obtained by reacting a physical component and an aromatic diamine component containing a specific aromatic diamine, and an organic solvent, and forming at a firing temperature of 400 ° C. or higher.
- the inventors have found that a release layer having excellent adhesiveness with a substrate and appropriate adhesiveness with a resin substrate used as a flexible electronic device and appropriate peelability can be obtained, thereby completing the present invention.
- a tetracarboxylic dianhydride component including a tetracarboxylic dianhydride represented by the following formula (1); an aromatic diamine having at least one hydroxy group at the ortho position of at least one amino group; and at least one amino
- a polyamic acid obtained by reacting an aromatic diamine having at least one mercapto group at the ortho position of the group and a diamine component containing at least one aromatic diamine selected from aromatic diamines having a carboxy group, and organic
- a method for producing a release layer comprising a step of applying a release layer-forming composition containing a solvent to a substrate and firing at a maximum temperature of 400 ° C.
- X 1 is a tetravalent benzene ring, a tetravalent group formed by condensing two or more benzene rings, and two or more benzene rings are bonded via a single bond.
- a method for producing one or two release layers, wherein the tetracarboxylic dianhydride represented by the formula (1) includes at least one selected from the group consisting of formulas (C1) to (C12); 4).
- a method for producing a flexible electronic device comprising a resin substrate, comprising using a release layer formed by using any one of production methods 1 to 3, 5).
- a flexible electronic device comprising a step of applying a composition for forming a resin substrate on a release layer formed using any one of the manufacturing methods 1 to 3 and then firing the resin substrate at a maximum temperature of 400 ° C. or more to form a resin substrate Manufacturing method, 6).
- the production method of the release layer release layer of the present invention By adopting the production method of the release layer release layer of the present invention, a film having excellent adhesion to the substrate and appropriate adhesion to the resin substrate and appropriate release can be obtained with good reproducibility. .
- the manufacturing method of the present invention in the manufacturing process of the flexible electronic device, the resin together with the circuit or the like without damaging the resin substrate formed on the substrate or the circuit or the like provided on the substrate. The substrate can be separated from the substrate. Therefore, the manufacturing method of this invention can contribute to the simplification of the manufacturing process of a flexible electronic device provided with a resin substrate, the yield improvement, etc.
- the method for producing a release layer according to the present invention includes a tetracarboxylic dianhydride component including a tetracarboxylic dianhydride represented by the following formula (1), and at least one hydroxy at the ortho position of at least one amino group.
- a diamine component comprising at least one aromatic diamine selected from an aromatic diamine having a group, an aromatic diamine having at least one mercapto group at the ortho position of at least one amino group, and an aromatic diamine having a carboxy group;
- a composition for forming a release layer containing a polyamic acid obtained by reacting an organic solvent and an organic solvent is applied to a substrate and baked at a maximum temperature of 400 ° C. or higher.
- the release layer in the present invention is a layer provided directly on a glass substrate for a predetermined purpose, and a typical example thereof is a resin of a flexible electronic device comprising a substrate and a resin such as polyimide in a manufacturing process of the flexible electronic device. Provided between the substrate and the resin substrate in order to fix the resin substrate in a predetermined process, and after the electronic circuit or the like is formed on the resin substrate, the resin substrate can be easily separated from the substrate. The thing provided in order to do is mentioned.
- X 1 is a tetravalent benzene ring, a tetravalent group formed by condensing two or more benzene rings, and two or more benzene rings bonded via a single bond.
- Specific examples of the tetravalent group formed by condensing two or more benzene rings include a tetravalent naphthalene ring, a tetravalent anthracene ring, a tetravalent phenanthrene ring, a tetravalent tetracene ring, and the like.
- Specific examples of the tetravalent group formed by bonding two or more benzene rings through a single bond include tetravalent biphenylene, tetravalent terphenylene and the like.
- aromatic tetracarboxylic dianhydride represented by the above formula (1) examples 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, biphenyl-2,2 ′, 3,3′-tetracarboxylic dianhydride, biphenyl,2
- the aromatic tetracarboxylic dianhydride represented by the formula (1) is preferably at least one selected from the group consisting of the formulas (C1) to (C12) from the viewpoint of ensuring heat resistance. At least one selected from the group consisting of formula (C1) and formula (C9) is more preferable.
- Such a tetracarboxylic dianhydride is an aliphatic tetracarboxylic dianhydride or an aromatic tetracarboxylic dianhydride, and is preferably an aromatic tetracarboxylic dianhydride other than the above formula (1).
- the aromatic tetracarboxylic acid represented by the formula (1) is used.
- the amount of dianhydride used is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and still more preferably 95 mol% or more in the total tetracarboxylic dianhydride. . By adopting such a usage amount, a film having good peelability can be obtained with good reproducibility.
- At least one aromatic diamine selected from the aromatic diamine having a hydroxy group at the ortho position of the amino group, the aromatic diamine having a mercapto group at the ortho position of the amino group, and the aromatic diamine having a carboxy group is an aromatic diamine having at least one group selected from the group consisting of a phenolic hydroxyl group, a carboxy group, and a thiophenol group.
- diamine having a phenolic hydroxyl group, a carboxy group, and a thiophenol group, and aromatic diamines having no such group are shown below, but the present invention is not limited thereto, and these are one kind. It can use individually or in combination of 2 or more types.
- Aromatic diamines having phenolic hydroxyl groups include 2,4-diaminophenol, 2,5-diaminophenol, 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, bis (3-amino-4-hydroxyphenyl) Ether, bis (4-amino-3-hydroxyphenyl) ether, bis (4-amino-3,5-dihydroxyphenyl) ether, bis (3-amino-4-hydroxyphenyl) methane, bis (4-amino-3) -Hydroxyphenyl) methane, bis (4-amino-3,5-dihydroxyphenyl) methane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis (4 -Amino-3,5-dihydroxyphenyl) sulfone, 2,2-bis ( -Amino-4-hydroxyphenyl) hex
- aromatic diamine having a carboxy group examples include 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,6-diamino-1,3-benzenedicarboxylic acid, 5-diamino-1,4-benzenedicarboxylic acid, bis (4-amino-3-carboxyphenyl) ether, bis (4-amino-3,5-dicarboxyphenyl) ether, bis (4-amino-3-carboxy) Phenyl) sulfone, bis (4-amino-3,5-dicarboxyphenyl) sulfone, 4,4′-diamino-3,3′-dicarboxybiphenyl, 4,4′-diamino-3,3′-dicarboxy -5,5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dicarboxy-5,5-
- aromatic diamines having a thiophenol group examples include 1,3-diamino-4-mercaptobenzene, 1,3-diamino-5-mercaptobenzene, 1,4-diamino-2-mercaptobenzene, bis (4-amino- 3-mercaptophenyl) ether, 2,2-bis (3-amino-4-mercaptophenyl) hexafluoropropane, and the like.
- aromatic diamines having two or more alkali-soluble groups include bis (4-amino-4-carboxy-5-hydroxyphenyl) ether and bis (4-amino-3-carboxy-5-hydroxyphenyl) methane.
- At least one aromatic diamine selected from an aromatic diamine having a hydroxy group at the ortho position of the amino group and an aromatic diamine having a carboxy group at the ortho position is preferable.
- ) To (B4) are more preferably one or more aromatic diamines.
- an aromatic diamine having a carboxy group is preferred.
- diamines can be used in addition to the above-described aromatic diamine containing an alkali-soluble group.
- a diamine may be either an aliphatic diamine or an aromatic diamine, but an aromatic diamine containing neither an ester bond nor an ether bond is preferable from the viewpoint of ensuring the strength and heat resistance of the resulting thin film.
- Examples of the other diamines include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 4,6-dimethyl-m.
- '-Methylene-bis (2,6-diisopropylaniline), bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2- Bis [4- (3-aminophenoxy) phenyl] hexafluoropropane and the like are preferable.
- the amount of the aromatic diamine having an alkali-soluble group is preferably 70 mol% or more, more preferably 80%, based on the total diamine. It is more than mol%, still more preferably more than 90 mol%, still more preferably more than 95 mol%.
- the polyamic acid contained in the composition for forming a release layer according to the present invention can be obtained by reacting the tetracarboxylic dianhydride component and the diamine component described above.
- the organic solvent used in such a reaction is not particularly limited as long as it does not adversely affect the reaction.
- Specific examples thereof include m-cresol, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2- Pyrrolidone, N-vinyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, 3-methoxy-N, N-dimethylpropylamide, 3-ethoxy-N, N-dimethylpropylamide, 3- Propoxy-N, N-dimethylpropylamide, 3-isopropoxy-N, N-dimethylpropylamide, 3-butoxy-N, N-dimethylpropylamide, 3-sec-butoxy-N, N-dimethylpropylamide, 3 -Tert-butoxy-N, N-dimethylpropylamide, ⁇ -butyrolactone and the like.
- amides represented by formula (S1), amides represented by formula (S2) and formula ( At least one selected from amides represented by S3) is preferred.
- R 1 and R 2 each independently represent an alkyl group having 1 to 10 carbon atoms.
- R 3 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
- h represents a natural number, preferably 1 to 3, more preferably 1 or 2.
- alkyl group having 1 to 10 carbon atoms examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, n- Examples include hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like. Of these, alkyl groups having 1 to 3 carbon atoms are preferable, and alkyl groups having 1 or 2 carbon atoms are more preferable.
- the reaction temperature may be appropriately set in the range from the melting point to the boiling point of the solvent used, and is usually about 0 to 100 ° C., but it prevents imidization in the solution of the resulting polyamic acid and contains a high content of polyamic acid units. In order to maintain the amount, it is preferably about 0 to 70 ° C, more preferably about 0 to 60 ° C, and still more preferably about 0 to 50 ° C.
- the reaction time depends on the reaction temperature and the reactivity of the raw material, and cannot be specified unconditionally, but is usually about 1 to 100 hours.
- a target reaction solution containing polyamic acid can be obtained.
- the weight average molecular weight of the polyamic acid thus obtained is usually about 5,000 to 500,000. From the viewpoint of improving the function of the resulting film as a release layer, preferably 6,000 to It is about 200,000, more preferably about 7,000 to 150,000.
- a weight average molecular weight is a polystyrene conversion value by a gel permeation chromatography (GPC) measurement.
- the solution obtained by diluting or concentrating the reaction solution as it is ordinarily can be used as the release layer forming composition of the present invention.
- the solvent in this case include organic solvents used in the above-described reaction.
- the solvent used for dilution is not particularly limited, and specific examples thereof include those similar to the specific examples of the reaction solvent for the reaction.
- the solvent used for dilution may be used singly or in combination of two or more.
- N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethyl-2 are used because they dissolve polyamic acid well.
- -Pyrrolidone and ⁇ -butyrolactone are preferred, and N-methyl-2-pyrrolidone is more preferred.
- ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy -2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxy A solvent having a low surface tension such as propoxy) propanol, methyl lactate, ethyl lactate, n-propyl lactate, n
- the concentration of the polyamic acid in the composition for forming a release layer of the present invention is appropriately set in consideration of the thickness of the release layer to be produced, the viscosity of the composition, etc., but is usually about 1 to 30% by mass, preferably It is about 1 to 20% by mass. By setting such a concentration, a release layer having a thickness of about 0.05 to 5 ⁇ m can be obtained with good reproducibility.
- the concentration of polyamic acid is adjusted to adjust the amount of diamine and tetracarboxylic dianhydride used as raw materials for polyamic acid, and after filtering the reaction solution, the filtrate is diluted or concentrated, and the isolated polyamic acid is used as a solvent. The amount can be adjusted by, for example, adjusting the amount when dissolved in the aqueous solution.
- the viscosity of the release layer forming composition is appropriately set in consideration of the thickness of the release layer to be produced, and the like. When it is intended, it is usually about 10 to 10,000 mPa ⁇ s, preferably about 20 to 5,000 mPa ⁇ s at 25 ° C.
- the viscosity can be measured using a commercially available liquid viscosity measurement viscometer, for example, with reference to the procedure described in JIS K7117-2 at a temperature of the composition of 25 ° C. .
- a conical plate type (cone plate type) rotational viscometer is used as the viscometer, and preferably the composition temperature is 25 ° C. using 1 ° 34 ′ ⁇ R24 as a standard cone rotor. It can be measured under the condition of ° C.
- An example of such a rotational viscometer is TVE-25L manufactured by Toki Sangyo Co., Ltd.
- composition for forming a release layer according to the present invention may contain a component such as a crosslinking agent in addition to the polyamic acid and the organic solvent, for example, in order to improve the film strength.
- a component such as a crosslinking agent in addition to the polyamic acid and the organic solvent, for example, in order to improve the film strength.
- the adhesiveness to the substrate is excellent by thermally imidizing polyamic acid by a baking method including a step of baking at a maximum temperature of 400 ° C. or higher.
- a baking method including a step of baking at a maximum temperature of 400 ° C. or higher.
- the maximum temperature at the time of firing is not particularly limited as long as it is in the range of 400 ° C. or higher and not higher than the heat resistant temperature of polyimide.
- 450 ° C. or higher is preferable, and 500 ° C. or higher is more preferable.
- the upper limit is usually about 550 ° C., preferably about 510 ° C.
- 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 as it is, and finally heating at 400 ° C. or higher.
- a method of heating at 50 to 100 ° C., heating at a temperature exceeding 100 ° C. to less than 400 ° C., and heating at 400 ° C. or higher can be mentioned.
- heating mode after heating at 50 to 150 ° C., heating at 150 to 350 ° C., then heating at 350 to 400 ° C., and finally, 400 to 510 ° C.
- a method of heating at 0 ° 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 increased stepwise and finally at 400 ° C. or higher for 30 minutes.
- a method of heating for up to 4 hours can be mentioned.
- heating is performed at 50 to 100 ° C. for 1 minute to 2 hours, heating is performed above 100 ° C. to less than 400 ° C. for 5 minutes to 2 hours, and heating is performed at 400 ° C. or higher for 30 minutes to 4 hours.
- the technique to do is mentioned.
- after heating at 50 to 150 ° C. for 1 minute to 2 hours after exceeding 150 ° C. to 350 ° C. for 5 minutes to 2 hours, then, exceeding 350 ° C. to 400 ° C. for 30 minutes.
- the release layer when the release layer is formed on the substrate, the release layer may be formed on a part of the surface of the substrate or on the entire surface.
- a release layer As an aspect of forming a release layer on a part of the surface of the substrate, an embodiment in which the release layer is formed only within a predetermined range of the substrate surface, a release layer is formed in a pattern such as a dot pattern or a line and space pattern on the entire surface of the substrate.
- substrate means what is used for manufacture of a flexible electronic device etc. by which the composition for peeling layer formation concerning this invention is applied to the surface.
- the substrate examples include glass, metal (silicon wafer, etc.), slate, etc.
- a release layer obtained using the release layer forming composition according to the present invention is sufficient. Since it has adhesiveness, glass is preferable.
- substrate surface may be comprised with the single material and may be comprised with two or more materials. As an aspect in which the substrate surface is constituted by two or more materials, a certain range of the substrate surface is constituted by a certain material, and the other surface is constituted by another material. A dot pattern is formed on the entire substrate surface. There is a mode in which a material in a pattern such as a line and space pattern is present in other materials.
- the coating method is not particularly limited.
- a cast coating method for example, a cast coating method, a spin coating method, a blade coating method, a dip coating method, a roll coating method, a bar coating method, a die coating method, an ink jet method, a printing method (a relief plate, an intaglio plate, a planographic plate). , Screen printing, etc.).
- Examples of equipment used for heating include a hot plate and an oven.
- the heating atmosphere may be under air or under an inert gas, and may be under normal pressure or under reduced pressure.
- the thickness of the release layer is usually about 0.01 to 50 ⁇ m, preferably from about 0.05 to 20 ⁇ m, more preferably about 0.05 to 5 ⁇ m from the viewpoint of productivity. To achieve the desired thickness.
- the release layer described above has excellent adhesion to a substrate, particularly a glass substrate, moderate adhesion to a resin substrate, and moderate release. Therefore, the release layer produced in 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, It can be suitably used for peeling from the substrate.
- a release layer is formed on a glass substrate by the method described above.
- a resin substrate forming solution for forming a resin substrate is applied, and this coating film is baked, so that the resin substrate fixed to the glass substrate via the release layer of the present invention is obtained.
- the firing temperature of the coating film is appropriately set according to the type of resin, etc., in the present invention, the maximum temperature during firing is preferably 400 ° C. or higher, and 450 ° C. or higher.
- the heating mode at the time of preparing the resin substrate there is a method of heating at 50 to 150 ° C., then increasing the heating temperature step by step, and finally heating at 400 ° C. or higher.
- a method of heating at 50 to 100 ° C., heating at a temperature higher than 100 ° C. to less than 400 ° C., and heating at 400 ° C. or higher can be mentioned.
- the heating mode after heating at 50 to 100 ° C., heating at over 100 ° C. to 200 ° C., and then heating at over 200 ° C. to less than 300 ° C. And heating at 400 to 450 ° C., and finally heating at 450 to 510 ° C.
- the heating mode in consideration of the firing time, after heating at 50 to 150 ° C. for 1 minute to 2 hours, the heating temperature is increased stepwise and finally at 400 ° C. or higher for 30 minutes.
- a method of heating for up to 4 hours can be mentioned.
- heating is performed at 50 to 100 ° C. for 1 minute to 2 hours, heating is performed above 100 ° C. to less than 400 ° C. for 5 minutes to 2 hours, and heating is performed at 400 ° C. or higher for 30 minutes to 4 hours.
- the technique to do is mentioned.
- the resin substrate covers the entire release layer, and the substrate is formed with an area larger than the area of the release layer.
- the resin substrate include a resin substrate made of polyimide, which is a typical resin substrate for flexible electronic devices, and examples of the resin solution for forming the resin substrate include a polyimide solution and a polyamic acid solution.
- the method for forming the resin substrate may follow a conventional method.
- a desired circuit is formed on the resin substrate fixed to the base via the release layer according to the present invention, and then, for example, the resin substrate is cut along the release layer. Is peeled from the release layer to separate the resin substrate and the substrate. At this time, a part of the substrate may be cut together with the release 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 polymer polyimide
- the release layer of the present invention has a feature of sufficiently absorbing light having a specific wavelength (for example, 308 nm) that enables application of the above LLO method, and therefore can be used as a sacrificial layer of the LLO method. Therefore, when a desired circuit is formed on a resin substrate fixed to a glass substrate through a release layer formed by using the composition according to the present invention, and then an LLO method is performed to irradiate a light beam of 308 nm. Only the release layer absorbs this light and evaporates (sublimates). Thereby, the release layer is sacrificed (acts as a sacrifice layer), and the resin substrate can be selectively peeled from the glass substrate.
- a specific wavelength for example, 308 nm
- NMP N-methylpyrrolidone
- BCS butyl cellosolve
- p-PDA p-phenylenediamine
- TPDA 4,4 "-diamino-p-terphenyl
- DBA 3,5-diaminobenzoic acid
- HAB 3, 3 '-Dihydroxybenzidine
- 6FAP 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane
- TFMB 2,2'-bis (trifluoromethyl) benzidine
- BPDA 3,3-4,4-biphenyl Tetracarboxylic dianhydride
- PMDA pyromellitic dianhydride
- PA phthalic anhydride
- CBDA 1,2,3,4-cyclobutanetetracarboxylic acid-1,2: 3,4-dianhydride
- Mw polymer weight average molecular weight
- Mw polymer weight average molecular weight
- Mw molecular weight distribution
- a GPC apparatus Shidex (registered trademark) columns KF803L and KF805L
- dimethylformamide was measured under the conditions of a flow rate of 1 ml / min and a column temperature of 50 ° C.
- Mw was made into the polystyrene conversion value.
- composition for forming release layer [Example 1-1] BCS and NMP were added to the reaction solution obtained in Synthesis Example L1, and diluted such that the polymer concentration was 5 wt% and BCS was 20 mass%, to obtain a release layer forming composition.
- Examples 1-2 to 1-5 A release layer-forming composition was obtained in the same manner as in Example 1-1 except that the reaction solutions obtained in Synthesis Examples L2 to L5 were used instead of the reaction solution obtained in Synthesis Example L1. It was.
- Example 2-1 Production of release layer and resin substrate [Example 2-1] Using a spin coater (conditions: about 3,000 rpm for about 30 seconds), the release layer forming composition obtained in Example 1-1 was applied to a 100 mm ⁇ 100 mm glass substrate (hereinafter the same) as a glass substrate. 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 using an oven, and the heating temperature was raised to 400 ° C. (10 ° C./min.
- the film was further heated at 400 ° C. for 30 minutes to form a release layer having a thickness of about 0.1 ⁇ m on the glass substrate to obtain a glass substrate with a release layer. During the temperature increase, the film-coated substrate was not removed from the oven but heated in the oven.
- the resin substrate forming composition S1 was applied on the release layer (resin thin film) on the glass substrate obtained above. Then, the obtained coating film was heated at 80 ° C. for 30 minutes using a hot plate, and then the atmosphere was changed to a nitrogen atmosphere using an oven, followed by heating at 140 ° C. for 30 minutes, and the heating temperature was raised to 210 ° C. (2 ° C / min, the same applies hereinafter), heated at 210 ° C for 30 minutes, heated to 300 ° C, heated to 300 ° C for 30 minutes, heated to 400 ° C, and heated to 400 ° C for 60 minutes.
- a polyimide resin substrate having a thickness of about 20 ⁇ m was formed on the release layer to obtain a glass substrate with a resin substrate / release layer.
- the film-coated substrate was not removed from the oven but heated in the oven.
- Example 2-2 A release layer and a polyimide resin substrate were formed in the same manner as in Example 2-1, except that the resin substrate formation composition S2 was used instead of the resin substrate formation composition S1. A glass substrate with a resin substrate and a release layer was obtained.
- Example 2-3 The same method as in Example 2-2, except that the release layer forming composition L2 obtained in Example 1-2 was used instead of the release layer forming composition obtained in Example 1-1. Thus, a release layer and a polyimide resin substrate were formed, and a glass substrate with a release layer and a glass substrate with a resin substrate / release layer were obtained.
- Example 2-4 The same method as in Example 2-1, except that the release layer forming composition L3 obtained in Example 1-3 was used instead of the release layer forming composition obtained in Example 1-1. Thus, a release layer and a polyimide resin substrate were formed, and a glass substrate with a release layer and a glass substrate with a resin substrate / release layer were obtained.
- Example 2-5 The same method as in Example 2-2, except that the release layer forming composition L3 obtained in Example 1-3 was used instead of the release layer forming composition obtained in Example 1-1. Thus, a release layer and a polyimide resin substrate were formed, and a glass substrate with a release layer and a glass substrate with a resin substrate / release layer were obtained.
- Example 2-6 The same method as in Example 2-1, except that the release layer forming composition L4 obtained in Example 1-4 was used instead of the release layer forming composition obtained in Example 1-1. Thus, a release layer and a polyimide resin substrate were formed, and a glass substrate with a release layer and a glass substrate with a resin substrate / release layer were obtained.
- Example 2-7 The same method as in Example 2-2, except that the release layer forming composition L4 obtained in Example 1-4 was used instead of the release layer forming composition obtained in Example 1-1. Thus, a release layer and a polyimide resin substrate were formed, and a glass substrate with a release layer and a glass substrate with a resin substrate / release layer were obtained.
- Example 2-8 Using a spin coater (conditions: about 3,000 rpm for about 30 seconds), the release layer forming composition L5 obtained in Example 1-5 was used as a glass substrate of 100 mm ⁇ 100 mm glass substrate (hereinafter the same) It was applied on top.
- the obtained coating film was heated at 100 ° C. for 2 minutes using a hot plate, and then heated at 300 ° C. for 30 minutes using an oven, and the heating temperature was raised to 400 ° C. (10 ° C./min. And then heated to 400 ° C. for 30 minutes, further heated to 500 ° C. (10 ° C./min), and heated at 500 ° C. for 10 minutes to form a release layer having a thickness of about 0.1 ⁇ m on the glass substrate.
- a glass substrate with a release layer was obtained. During the temperature increase, the film-coated substrate was not removed from the oven but heated in the oven.
- the resin substrate forming composition S2 was applied on the release layer (resin thin film) on the glass substrate obtained above. Then, the obtained coating film was heated at 80 ° C. for 30 minutes using a hot plate, and then the atmosphere was changed to a nitrogen atmosphere using an oven, followed by heating at 140 ° C. for 30 minutes, and the heating temperature was raised to 210 ° C. (2 ° C / min, the same applies hereinafter), heated at 210 ° C for 30 minutes, heated to 300 ° C, heated at 300 ° C for 30 minutes, heated to 400 ° C, heated to 400 ° C For 30 minutes, raising the heating temperature to 500 ° C. and heating at 500 ° C.
- Example 2-2 was used except that the composition for forming a release layer obtained in Comparative Examples 1-1 to 1-2 was used instead of the composition for forming a release layer obtained in Example 1-1. A release layer was formed in the same manner as described above.
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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.
1. 下記式(1)で表されるテトラカルボン酸二無水物を含むテトラカルボン酸二無水物成分と、少なくとも1つのアミノ基のオルト位に少なくとも1つのヒドロキシ基を有する芳香族ジアミン、少なくとも1つのアミノ基のオルト位に少なくとも1つのメルカプト基を有する芳香族ジアミン、及びカルボキシ基を有する芳香族ジアミンから選ばれる少なくとも1種の芳香族ジアミンを含むジアミン成分とを反応させて得られるポリアミック酸、及び有機溶媒を含む剥離層形成用組成物を基体に塗布し、最高温度400℃以上で焼成する工程を含むことを特徴とする剥離層の製造方法、
2. 前記芳香族ジアミンが、下記式(B1)~(B4)から、群から選ばれる少なくとも1種である1の剥離層の製造方法、
5. 1~3のいずれかの製造方法を用いて形成した剥離層上に、樹脂基板形成用組成物を塗布した後、最高温度400℃以上で焼成して樹脂基板を形成する工程を含むフレキシブル電子デバイスの製造方法、
6. 前記樹脂基板が、ポリイミド樹脂基板である4又は5のフレキシブル電子デバイスの製造方法
を提供する。 That is, the present invention
1. A tetracarboxylic dianhydride component including a tetracarboxylic dianhydride represented by the following formula (1); an aromatic diamine having at least one hydroxy group at the ortho position of at least one amino group; and at least one amino A polyamic acid obtained by reacting an aromatic diamine having at least one mercapto group at the ortho position of the group and a diamine component containing at least one aromatic diamine selected from aromatic diamines having a carboxy group, and organic A method for producing a release layer, comprising a step of applying a release layer-forming composition containing a solvent to a substrate and firing at a maximum temperature of 400 ° C. or higher;
2. The method for producing a release layer according to claim 1, wherein the aromatic diamine is at least one selected from the group consisting of the following formulas (B1) to (B4):
5). A flexible electronic device comprising a step of applying a composition for forming a resin substrate on a release layer formed using any one of the manufacturing methods 1 to 3 and then firing the resin substrate at a maximum temperature of 400 ° C. or more to form a resin substrate Manufacturing method,
6). The method for producing a flexible electronic device according to 4 or 5, wherein the resin substrate is a polyimide resin substrate.
本発明に係る剥離層の製造方法は、下記式(1)で表されるテトラカルボン酸二無水物を含むテトラカルボン酸二無水物成分と、少なくとも1つのアミノ基のオルト位に少なくとも1つのヒドロキシ基を有する芳香族ジアミン、少なくとも1つのアミノ基のオルト位に少なくとも1つのメルカプト基を有する芳香族ジアミン、及びカルボキシ基を有する芳香族ジアミンから選ばれる少なくとも1種の芳香族ジアミンを含むジアミン成分とを反応させて得られるポリアミック酸、及び有機溶媒を含む剥離層形成用組成物を基体に塗布し、最高温度400℃以上で焼成することを特徴とする。
本発明における剥離層とは、所定の目的でガラス基体直上に設けられる層であって、その典型例としては、フレキシブル電子デバイスの製造プロセスにおいて、基体と、ポリイミドといった樹脂からなるフレキシブル電子デバイスの樹脂基板との間に、当該樹脂基板を所定のプロセス中において固定するために設けられ、かつ、当該樹脂基板上に電子回路等の形成した後において当該樹脂基板が当該基体から容易に剥離できるようにするために設けられるものが挙げられる。 Hereinafter, the present invention will be described in more detail.
The method for producing a release layer according to the present invention includes a tetracarboxylic dianhydride component including a tetracarboxylic dianhydride represented by the following formula (1), and at least one hydroxy at the ortho position of at least one amino group. A diamine component comprising at least one aromatic diamine selected from an aromatic diamine having a group, an aromatic diamine having at least one mercapto group at the ortho position of at least one amino group, and an aromatic diamine having a carboxy group; A composition for forming a release layer containing a polyamic acid obtained by reacting an organic solvent and an organic solvent is applied to a substrate and baked at a maximum temperature of 400 ° C. or higher.
The release layer in the present invention is a layer provided directly on a glass substrate for a predetermined purpose, and a typical example thereof is a resin of a flexible electronic device comprising a substrate and a resin such as polyimide in a manufacturing process of the flexible electronic device. Provided between the substrate and the resin substrate in order to fix the resin substrate in a predetermined process, and after the electronic circuit or the like is formed on the resin substrate, the resin substrate can be easily separated from the substrate. The thing provided in order to do is mentioned.
2個以上のベンゼン環同士が縮環してなる4価の基の具体例としては、4価のナフタレン環、4価のアントラセン環、4価のフェナントレン環、4価のテトラセン環等が挙げられる。
2個以上のベンゼン環同士が単結合を介して結合してなる4価の基の具体例としては、4価のビフェニレン、4価のターフェニレン等が挙げられる。 In Formula (1), X 1 is a tetravalent benzene ring, a tetravalent group formed by condensing two or more benzene rings, and two or more benzene rings bonded via a single bond. Represents a tetravalent group selected from the following tetravalent groups.
Specific examples of the tetravalent group formed by condensing two or more benzene rings include a tetravalent naphthalene ring, a tetravalent anthracene ring, a tetravalent phenanthrene ring, a tetravalent tetracene ring, and the like. .
Specific examples of the tetravalent group formed by bonding two or more benzene rings through a single bond include tetravalent biphenylene, tetravalent terphenylene and the like.
本発明において、上記焼成時の最高温度は400℃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が、上述した基体との密着性や、樹脂基板との適度な密着性及び剥離性を向上させることを考慮すると、450℃以上が好ましく、500℃以上がより好ましい。また、その上限は通常550℃程度であるが、510℃程度が好ましい。加熱温度を上記範囲とすることで、得られる膜の脆弱化を防ぎつつ、イミド化反応や、アミノ基のオルト位にフェノール性水酸基を有するジアミンを用いた場合のベンゾオキサゾールの環化及び脱炭酸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 the composition for forming a release layer described above is applied on a substrate, the adhesiveness to the substrate is excellent by thermally imidizing polyamic acid by a baking method including a step of baking at a maximum temperature of 400 ° C. or higher. In addition, it is possible to obtain a release layer made of a polyimide film having appropriate adhesion to the resin substrate and appropriate peelability.
In the present invention, the maximum temperature at the time of firing is not particularly limited as long as it is in the range of 400 ° C. or higher and not higher than the heat resistant temperature of polyimide. In view of improving the excellent adhesion and peelability, 450 ° C. or higher is preferable, and 500 ° C. or higher is more preferable. The upper limit is usually about 550 ° C., preferably about 510 ° C. By making the heating temperature within the above range, while preventing weakening of the obtained film, imidization reaction, cyclization and decarboxylation of benzoxazole when diamine having phenolic hydroxyl group at ortho position of amino group is used It is also possible to allow the reaction to proceed sufficiently.
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400℃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~400℃未満で加熱し、400℃以上で加熱する手法が挙げられる。更に、加熱態様のより好ましい他の一例としては、50~150℃で加熱した後に、150℃超~350℃で加熱し、次いで350℃超~400℃で加熱し、最後に400℃超~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 as it is, and finally heating at 400 ° C. or higher. In particular, as a more preferable example of the heating mode, a method of heating at 50 to 100 ° C., heating at a temperature exceeding 100 ° C. to less than 400 ° C., and heating at 400 ° C. or higher can be mentioned. Furthermore, as another more preferable example of the heating mode, after heating at 50 to 150 ° C., heating at 150 to 350 ° C., then heating at 350 to 400 ° C., and finally, 400 to 510 ° C. A method of heating at 0 ° C. can be mentioned.
本発明の剥離層形成用組成物を用いて、上述の方法によって、ガラス基体上に剥離層を形成する。この剥離層の上に、樹脂基板を形成するための樹脂基板形成用溶液を塗布し、この塗膜を焼成することで、本発明の剥離層を介して、ガラス基体に固定された樹脂基板を形成する。
上記塗膜の焼成温度は、樹脂の種類等に応じて適宜設定されるものであるが、本発明では、この焼成時の最高温度を400℃以上とすることが好ましく、450℃以上とすることがより好ましく、480℃以上とすることがより一層好ましく、500℃以上とすることがさらに好ましい。樹脂基板作製の際の焼成時の最高温度をこの範囲とすることで、下地である剥離層と基体との密着性や、剥離層と樹脂基板との適度な密着性及び剥離性をより向上させることができる。
この場合も、最高温度が上記範囲となる限り、それ以下の温度で焼成する工程を含んでいてもよい。 Hereinafter, an example of a method for producing a flexible electronic device by the production method of the present invention will be described.
Using the composition for forming a release layer of the present invention, a release layer is formed on a glass substrate by the method described above. On this release layer, a resin substrate forming solution for forming a resin substrate is applied, and this coating film is baked, so that the resin substrate fixed to the glass substrate via the release layer of the present invention is obtained. Form.
Although the firing temperature of the coating film is appropriately set according to the type of resin, etc., in the present invention, the maximum temperature during firing is preferably 400 ° C. or higher, and 450 ° C. or higher. Is more preferable, and it is still more preferable to set it as 480 degreeC or more, and it is still more preferable to set it as 500 degreeC or more. By setting the maximum temperature during firing at the time of resin substrate production within this range, the adhesiveness between the release layer and the substrate as a base, and the appropriate adhesiveness and peelability between the release layer and the resin substrate are further improved. be able to.
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.
NMP:N-メチルピロリドン
BCS:ブチルセロソルブ
p-PDA:p-フェニレンジアミン
TPDA:4,4”-ジアミノ-p-ターフェニル
DBA:3,5-ジアミノ安息香酸
HAB:3,3’-ジヒドロキシベンジシン
6FAP:2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン
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
PA:フタル酸無水物
CBDA:1,2,3,4-シクロブタンテトラカルボン酸-1,2:3,4-二無水物 [1] Abbreviations of compounds NMP: N-methylpyrrolidone BCS: butyl cellosolve p-PDA: p-phenylenediamine TPDA: 4,4 "-diamino-p-terphenyl DBA: 3,5-diaminobenzoic acid HAB: 3, 3 '-Dihydroxybenzidine 6FAP: 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane TFMB: 2,2'-bis (trifluoromethyl) benzidine BPDA: 3,3-4,4-biphenyl Tetracarboxylic dianhydride PMDA: pyromellitic dianhydride PA: phthalic anhydride CBDA: 1,2,3,4-cyclobutanetetracarboxylic acid-1,2: 3,4-dianhydride
ポリマーの重量平均分子量(以下Mwと略す)と分子量分布は、日本分光(株)製GPC装置(Shodex(登録商標)カラムKF803LおよびKF805L)を用い溶出溶媒としてジメチルホルムアミドを流量1ml/分、カラム温度50℃の条件で測定した。なお、Mwはポリスチレン換算値とした。 [2] Measurement of weight average molecular weight and molecular weight distribution The polymer weight average molecular weight (hereinafter abbreviated as Mw) and molecular weight distribution were measured using a GPC apparatus (Shodex (registered trademark) columns KF803L and KF805L) manufactured by JASCO Corporation. As a measurement, dimethylformamide was measured under the conditions of a flow rate of 1 ml / min and a column temperature of 50 ° C. In addition, Mw was made into the polystyrene conversion 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剥離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 substrate formation composition or the peeling layer formation composition was prepared by diluting a reaction liquid as mentioned later.
p-PDA20.261g(0.1875モル)とTPDA12.206g(0.0469モル)をNMP617.4gに溶解し、15℃に冷却後、PMDA50.112g(0.2298モル)を添加し、窒素雰囲気下、50℃で48時間反応させた。得られたポリマーのMwは82,100、分子量分布は2.7であった。 <Synthesis Example S1 Synthesis of Polyamic Acid (S1) for Film>
20.261 g (0.1875 mol) of p-PDA and 12.206 g (0.0469 mol) of TPDA are dissolved in 617.4 g of NMP, cooled to 15 ° C., and then 50.112 g (0.2298 mol) of PMDA is added, and a nitrogen atmosphere The reaction was allowed to proceed at 50 ° C. for 48 hours. Mw of the obtained polymer was 82,100, and molecular weight distribution was 2.7.
p-PDA3.176g(0.0294モル)をNMP88.2gに溶解し、BPDA8.624g(0.0293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 S2 Synthesis of Polyamic Acid (S2) for Film>
3.176 g (0.0294 mol) of p-PDA was dissolved in 88.2 g of NMP, and 8.624 g (0.0293 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.
p-PDA1.413g(0.0131モル)とDBA0.221g(0.0015モル)をNMP35.2gに溶解し、PMDA3.166g(0.0145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64,400、分子量分布2.9であった。 <Synthesis Example L1 Synthesis of polyamic acid (L1)>
p-PDA (1.413 g, 0.0131 mol) and DBA (0.221 g, 0.0015 mol) were dissolved in NMP (35.2 g), PMDA (3.166 g, 0.0145 mol) was added, and then, at 23 ° C. under a nitrogen atmosphere. The reaction was performed for 24 hours. Mw of the obtained polymer was 64,400 and molecular weight distribution was 2.9.
p-PDA1.070g(0.0099モル)とDBA0.645g(0.0042モル)をNMP35.2gに溶解し、PMDA3.084g(0.0141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57,700、分子量分布2.9であった。 <Synthesis Example L2 Synthesis of polyamic acid (L2)>
After dissolving 1.070 g (0.0099 mol) of p-PDA and 0.645 g (0.0042 mol) of DBA in 35.2 g of NMP and adding 3.084 g (0.0141 mol) of PMDA, the reaction was performed at 23 ° C. under a nitrogen atmosphere. The reaction was performed for 24 hours. Mw of the obtained polymer was 57,700 and molecular weight distribution was 2.9.
p-PDA1.404g(0.0124モル)とHAB0.312g(0.0014モル)をNMP35.2gに溶解し、PMDA3.084g(0.0141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32,900、分子量分布2.5であった。 <Synthesis Example L3 Synthesis of polyamic acid (L3)>
p-PDA (1.404 g, 0.0124 mol) and HAB (0.312 g, 0.0014 mol) were dissolved in NMP (35.2 g), PMDA (3.084 g, 0.0141 mol) was added, and the mixture was added at 23 ° C. under a nitrogen atmosphere. The reaction was performed for 24 hours. The obtained polymer had Mw of 32,900 and a molecular weight distribution of 2.5.
p-PDA1.025g(0.0095モル)とHAB0.879g(0.0041モル)をNMP35.2gに溶解し、PMDA2.896g(0.0133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22,000、分子量分布2.0であった。 <Synthesis Example L4 Synthesis of polyamic acid (L4)>
1.025 g (0.0095 mol) of p-PDA and 0.879 g (0.0041 mol) of HAB were dissolved in 35.2 g of NMP, and 2.896 g (0.0133 mol) of PMDA was added, and then at 23 ° C. under a nitrogen atmosphere. The reaction was performed for 24 hours. Mw of the obtained polymer was 22,000 and molecular weight distribution was 2.0.
p-PDA1.5206g(0.0141モル)と6FAP0.105g(0.0029モル)をNMP35.2gに溶解し、PMDA3.004g(0.0138モル)を添加した後、窒素雰囲気下、23℃で22時間反応させた。その後、更にPA0.170g(0.0012モル)を添加した後、窒素雰囲気下、23℃で22時間反応させた。得られたポリマーのMwは22,100、分子量分布1.9であった。 <Synthesis Example L5 Synthesis of polyamic acid (L5)>
After dissolving 1.5206 g (0.0141 mol) of p-PDA and 0.105 g (0.0029 mol) of 6FAP in 35.2 g of NMP, and adding 3.004 g (0.0138 mol) of PMDA at 23 ° C. in a nitrogen atmosphere. The reaction was carried out for 22 hours. Thereafter, 0.170 g (0.0012 mol) of PA was further added, followed by reaction at 23 ° C. for 22 hours in a nitrogen atmosphere. Mw of the obtained polymer was 22,100 and molecular weight distribution was 1.9.
p-PDA1.29g(0.0011モル)をNMP43.2gに溶解し、BPDA3.509g(0.0012モル)を添加した後、窒素雰囲気下、23℃で24時間反応させた。得られたポリマーのMwは34,000、分子量分布2.0であった。 <Comparative Synthesis Example B1 Synthesis of Polyamic Acid (B1)>
1.29 g (0.0011 mol) of p-PDA was dissolved in 43.2 g of NMP, and 3.509 g (0.0012 mol) of BPDA was added, followed by reaction at 23 ° C. for 24 hours in a nitrogen atmosphere. Mw of the obtained polymer was 34,000 and molecular weight distribution 2.0.
TFMB2.86g(0.0089モル)をNMP35.2gに溶解し、CBDA1.944g(0.0099モル)を加え、窒素雰囲気下、23℃で24時間反応させた。得られたポリマーのMwは69,200、分子量分布2.2であった。得られた溶液は、PGMEに可溶であった。 <Comparative Synthesis Example B2 Synthesis of Polyamic Acid (B2)>
2.86 g (0.0089 mol) of TFMB was dissolved in 35.2 g of NMP, 1.944 g (0.0099 mol) of CBDA was added, and the mixture was reacted at 23 ° C. for 24 hours in a nitrogen atmosphere. Mw of the obtained polymer was 69,200 and molecular weight distribution 2.2. The resulting solution was soluble in PGME.
合成例S1及びS2で得られた反応液を、それぞれ、そのまま樹脂基板形成用組成物として用いた。 [4] Preparation of Resin Substrate Forming Composition The reaction solutions obtained in Synthesis Examples S1 and S2 were used as they were as the 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、剥離層形成用組成物を得た。 [5] Preparation of composition for forming release layer [Example 1-1]
BCS and NMP were added to the reaction solution obtained in Synthesis Example L1, and diluted such that the polymer concentration was 5 wt% and BCS was 20 mass%, to obtain a release layer forming composition.
合成例L1で得られた反応液の代わりに、それぞれ合成例L2~L5で得られた反応液を用いた以外は、実施例1-1と同様の方法で、剥離層形成用組成物を得た。 [Examples 1-2 to 1-5]
A release layer-forming composition was obtained in the same manner as in Example 1-1 except that the reaction solutions obtained in Synthesis Examples L2 to L5 were used instead of the reaction solution obtained in Synthesis Example L1. It was.
合成例L1で得られた反応液の代わりに、それぞれ比較合成例B1とB2で得られた反応液を用いた以外は、実施例1-1と同様の方法で、剥離層形成用組成物を得た。 [Comparative Examples 1-1 to 1-2]
In the same manner as in Example 1-1, except that the reaction solutions obtained in Comparative Synthesis Examples B1 and B2 were used in place of the reaction solution obtained in Synthesis Example L1, the release layer forming composition was prepared. Obtained.
[実施例2-1]
スピンコーター(条件:回転数3,000rpmで約30秒)を用いて、実施例1-1で得られた剥離層形成用組成物を、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分間加熱し、加熱温度を400℃まで昇温(10℃/分)し、さらに400℃で30分間加熱し、ガラス基板上に厚さ約0.1μmの剥離層を形成し、剥離層付きガラス基板を得た。なお、昇温の間、膜付き基板をオーブンから取り出すことはせず、オーブン内で加熱した。 [6] Production of release layer and resin substrate [Example 2-1]
Using a spin coater (conditions: about 3,000 rpm for about 30 seconds), the release layer forming composition obtained in Example 1-1 was applied to a 100 mm × 100 mm glass substrate (hereinafter the same) as a glass substrate. 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 using an oven, and the heating temperature was raised to 400 ° C. (10 ° C./min. The film was further heated at 400 ° C. for 30 minutes to form a release layer having a thickness of about 0.1 μm on the glass substrate to obtain a glass substrate with a release layer. During the temperature increase, the film-coated substrate was not removed from the oven but heated in the oven.
樹脂基板形成用組成物S1の代わりに樹脂基板形成用組成物S2を用いた以外は、実施例2-1と同様の方法で、剥離層及びポリイミド樹脂基板を形成し、剥離層付きガラス基板及び樹脂基板・剥離層付きガラス基板を得た。 [Example 2-2]
A release layer and a polyimide resin substrate were formed in the same manner as in Example 2-1, except that the resin substrate formation composition S2 was used instead of the resin substrate formation composition S1. A glass substrate with a resin substrate and a release layer was obtained.
実施例1-1で得られた剥離層形成用組成物の代わりに、実施例1-2で得られた剥離層形成用組成物L2を用いた以外は、実施例2-2と同様の方法で、剥離層及びポリイミド樹脂基板を形成し、剥離層付きガラス基板及び樹脂基板・剥離層付きガラス基板を得た。 [Example 2-3]
The same method as in Example 2-2, except that the release layer forming composition L2 obtained in Example 1-2 was used instead of the release layer forming composition obtained in Example 1-1. Thus, a release layer and a polyimide resin substrate were formed, and a glass substrate with a release layer and a glass substrate with a resin substrate / release layer were obtained.
実施例1-1で得られた剥離層形成用組成物の代わりに、実施例1-3で得られた剥離層形成用組成物L3を用いた以外は、実施例2-1と同様の方法で、剥離層及びポリイミド樹脂基板を形成し、剥離層付きガラス基板及び樹脂基板・剥離層付きガラス基板を得た。 [Example 2-4]
The same method as in Example 2-1, except that the release layer forming composition L3 obtained in Example 1-3 was used instead of the release layer forming composition obtained in Example 1-1. Thus, a release layer and a polyimide resin substrate were formed, and a glass substrate with a release layer and a glass substrate with a resin substrate / release layer were obtained.
実施例1-1で得られた剥離層形成用組成物の代わりに、実施例1-3で得られた剥離層形成用組成物L3を用いた以外は、実施例2-2と同様の方法で、剥離層及びポリイミド樹脂基板を形成し、剥離層付きガラス基板及び樹脂基板・剥離層付きガラス基板を得た。 [Example 2-5]
The same method as in Example 2-2, except that the release layer forming composition L3 obtained in Example 1-3 was used instead of the release layer forming composition obtained in Example 1-1. Thus, a release layer and a polyimide resin substrate were formed, and a glass substrate with a release layer and a glass substrate with a resin substrate / release layer were obtained.
実施例1-1で得られた剥離層形成用組成物の代わりに、実施例1-4で得られた剥離層形成用組成物L4を用いた以外は、実施例2-1と同様の方法で、剥離層及びポリイミド樹脂基板を形成し、剥離層付きガラス基板及び樹脂基板・剥離層付きガラス基板を得た。 [Example 2-6]
The same method as in Example 2-1, except that the release layer forming composition L4 obtained in Example 1-4 was used instead of the release layer forming composition obtained in Example 1-1. Thus, a release layer and a polyimide resin substrate were formed, and a glass substrate with a release layer and a glass substrate with a resin substrate / release layer were obtained.
実施例1-1で得られた剥離層形成用組成物の代わりに、実施例1-4で得られた剥離層形成用組成物L4を用いた以外は、実施例2-2と同様の方法で、剥離層及びポリイミド樹脂基板を形成し、剥離層付きガラス基板及び樹脂基板・剥離層付きガラス基板を得た。 [Example 2-7]
The same method as in Example 2-2, except that the release layer forming composition L4 obtained in Example 1-4 was used instead of the release layer forming composition obtained in Example 1-1. Thus, a release layer and a polyimide resin substrate were formed, and a glass substrate with a release layer and a glass substrate with a resin substrate / release layer were obtained.
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1-5で得られた剥離層形成用組成物L5を、ガラス基体としての100mm×100mmガラス基板(以下同様)の上に塗布した。
そして、得られた塗膜を、ホットプレートを用いて100℃で2分間加熱し、その後、オーブンを用いて、300℃で30分間加熱し、加熱温度を400℃まで昇温(10℃/分)し、400℃で30分間加熱し、さらに、500℃まで昇温(10℃/分)し、500℃で10分間加熱し、ガラス基板上に厚さ約0.1μmの剥離層を形成し、剥離層付きガラス基板を得た。なお、昇温の間、膜付き基板をオーブンから取り出すことはせず、オーブン内で加熱した。 [Example 2-8]
Using a spin coater (conditions: about 3,000 rpm for about 30 seconds), the release layer forming composition L5 obtained in Example 1-5 was used as a glass substrate of 100 mm × 100 mm glass substrate (hereinafter the same) It was applied on top.
The obtained coating film was heated at 100 ° C. for 2 minutes using a hot plate, and then heated at 300 ° C. for 30 minutes using an oven, and the heating temperature was raised to 400 ° C. (10 ° C./min. And then heated to 400 ° C. for 30 minutes, further heated to 500 ° C. (10 ° C./min), and heated at 500 ° C. for 10 minutes to form a release layer having a thickness of about 0.1 μm on the glass substrate. A glass substrate with a release layer was obtained. During the temperature increase, the film-coated substrate was not removed from the oven but heated in the oven.
実施例1-1で得られた剥離層形成用組成物の代わりに、それぞれ比較例1-1~1-2で得られた剥離層形成用組成物を用いた以外は、実施例2-2と同様の方法で、剥離層を形成した。 [Comparative Examples 2-1 and 2-2]
Example 2-2 was used except that the composition for forming a release layer obtained in Comparative Examples 1-1 to 1-2 was used instead of the composition for forming a release layer obtained in Example 1-1. A release layer was formed in the same manner as described above.
上記実施例2-1~2-8及び比較例2-1~2-2で得られた剥離層付きガラス基板について、剥離層とガラス基板との剥離性を、下記手法にて確認した。なお、下記の試験は、同一のガラス基板で行った。 [7] Evaluation of peelability For the glass substrates with release layers obtained in Examples 2-1 to 2-8 and Comparative Examples 2-1 to 2-2, the peelability between the release layer and the glass substrate is as follows. It was confirmed by the method. In addition, the following test was done with the same glass substrate.
実施例2-1~2-8及び比較例2-1~2-2で得られた剥離層付きガラス基板上の剥離層をクロスカット(縦横1mm間隔、以下同様)し、100マスカットを行った。すなわち、このクロスカットにより、1mm四方のマス目を100個形成した。
そして、この100マスカット部分に粘着テープを貼り付けて、そのテープを剥がし、以下の基準(5B~0B,B,A,AA)に基づき、剥離性を評価した。結果を表1に示す。
<判定基準>
5B:0%剥離(剥離なし)
4B:5%未満の剥離
3B:5~15%未満の剥離
2B:15~35%未満の剥離
1B:35~65%未満の剥離
0B:65%~80%未満の剥離
B:80%~95%未満の剥離
A:95%~100%未満の剥離
AA:100%剥離(すべて剥離) <Cross-cut test peelability evaluation of resin thin film>
The release layers on the glass substrates with release layers obtained in Examples 2-1 to 2-8 and Comparative Examples 2-1 to 2-2 were cross-cut (1 mm in length and width, the same applies hereinafter), and 100 mass cuts were performed. . That is, 100 crosses of 1 mm square were formed by this cross cut.
Then, an adhesive tape was affixed to the 100 muscat portion, the tape was peeled off, and peelability was evaluated based on the following criteria (5B to 0B, B, A, AA). The results are shown in Table 1.
<Criteria>
5B: 0% peeling (no peeling)
4B: Less than 5% peeling 3B: Less than 5-15% peeling 2B: 15-35% peeling 1B: 35-65% peeling 0B: 65% -80% peeling B: 80% -95 % Peeling A: 95% to less than 100% peeling AA: 100% peeling (all peeling)
実施例2-1~2-8及び比較例2-1~2-2で得られた樹脂基板・剥離層付きガラス基板の樹脂基板を、カッターを用いて25mm幅の短冊状にカットした。そして、カットした樹脂基板の先端にセロハンテープを貼り付け、これを試験片とした。この試験片を、(株)アトニック製プッシュプルテスターを用いて剥離角度が90°となるように剥離試験を行い、下記の基準に基づいて剥離性を評価した。結果を表1に示す。
<判定基準>
5B:0%剥離(剥離なし)
4B:5%未満の剥離
3B:5~15%未満の剥離
2B:15~35%未満の剥離
1B:35~65%未満の剥離
0B:65%~80%未満の剥離
B:80%~95%未満の剥離
A:95%~100%未満の剥離
AA:100%剥離(すべて剥離) <Evaluation of peelability of resin substrate>
The resin substrates of the resin substrates / glass substrates with release layers obtained in Examples 2-1 to 2-8 and Comparative Examples 2-1 to 2-2 were cut into strips having a width of 25 mm using a cutter. And the cellophane tape was affixed on the front-end | tip 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 90 °, and peelability was evaluated based on the following criteria. The results are shown in Table 1.
<Criteria>
5B: 0% peeling (no peeling)
4B: Less than 5% peeling 3B: Less than 5-15% peeling 2B: 15-35% peeling 1B: 35-65% peeling 0B: 65% -80% peeling B: 80% -95 % Peeling A: 95% to less than 100% peeling AA: 100% peeling (all peeling)
Claims (6)
- 下記式(1)で表されるテトラカルボン酸二無水物を含むテトラカルボン酸二無水物成分と、少なくとも1つのアミノ基のオルト位に少なくとも1つのヒドロキシ基を有する芳香族ジアミン、少なくとも1つのアミノ基のオルト位に少なくとも1つのメルカプト基を有する芳香族ジアミン、及びカルボキシ基を有する芳香族ジアミンから選ばれる少なくとも1種の芳香族ジアミンを含むジアミン成分とを反応させて得られるポリアミック酸、及び有機溶媒を含む剥離層形成用組成物を基体に塗布し、最高温度400℃以上で焼成する工程を含むことを特徴とする剥離層の製造方法。
- 前記式(1)で表されるテトラカルボン酸二無水物が、式(C1)~(C12)からなる群から選ばれる少なくとも1種を含む請求項1又は2記載の剥離層の製造方法。
- 請求項1~3のいずれか1項記載の製造方法を用いて形成される剥離層を用いることを特徴とする、樹脂基板を備えるフレキシブル電子デバイスの製造方法。 A method for producing a flexible electronic device comprising a resin substrate, comprising using a release layer formed using the production method according to any one of claims 1 to 3.
- 請求項1~3のいずれか1項記載の製造方法を用いて形成した剥離層上に、樹脂基板形成用組成物を塗布した後、最高温度400℃以上で焼成して樹脂基板を形成する工程を含むフレキシブル電子デバイスの製造方法。 A step of forming a resin substrate by applying a composition for forming a resin substrate on a release layer formed by using the manufacturing method according to any one of claims 1 to 3 and then baking at a maximum temperature of 400 ° C or higher. A method for manufacturing a flexible electronic device.
- 前記樹脂基板が、ポリイミド樹脂基板である請求項4又は5記載のフレキシブル電子デバイスの製造方法。 The method for manufacturing a flexible electronic device according to claim 4, wherein the resin substrate is a polyimide resin substrate.
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JP7230398B2 (en) | 2018-09-26 | 2023-03-01 | 東レ株式会社 | SACRIFIC LAYER RESIN COMPOSITION AND METHOD FOR MANUFACTURING SEMICONDUCTOR ELECTRONIC PARTS |
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KR20190094198A (en) | 2019-08-12 |
TW201831621A (en) | 2018-09-01 |
CN110050013A (en) | 2019-07-23 |
KR102439479B1 (en) | 2022-09-05 |
JP7088023B2 (en) | 2022-06-21 |
JPWO2018105675A1 (en) | 2019-10-24 |
CN110050013B (en) | 2022-11-29 |
TWI823840B (en) | 2023-12-01 |
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