WO2016158990A1 - Composition for forming release layer, and release layer - Google Patents
Composition for forming release layer, and release layer Download PDFInfo
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- WO2016158990A1 WO2016158990A1 PCT/JP2016/060209 JP2016060209W WO2016158990A1 WO 2016158990 A1 WO2016158990 A1 WO 2016158990A1 JP 2016060209 W JP2016060209 W JP 2016060209W WO 2016158990 A1 WO2016158990 A1 WO 2016158990A1
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- WIPO (PCT)
- Prior art keywords
- release layer
- composition
- substrate
- forming
- tetracarboxylic dianhydride
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- 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
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/133305—Flexible substrates, e.g. plastics, organic film
Definitions
- the present invention relates to a release layer forming composition and 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 a laser is irradiated from the glass surface side to accompany crystallization of amorphous silicon.
- a method of peeling a plastic substrate from a glass substrate with generated hydrogen gas is disclosed.
- Patent Document 4 discloses a method for completing a liquid crystal display device by attaching a layer to be peeled (described as “transfer target layer” in Patent Document 4) to a plastic film using the techniques disclosed in Patent Documents 1 to 3. Is disclosed.
- Patent Documents 1 to 4 particularly the method disclosed in Patent Document 4, it is essential to use a substrate with high translucency, and hydrogen contained in amorphous silicon is allowed to pass through the substrate.
- hydrogen contained in amorphous silicon is allowed to pass through the substrate.
- it is necessary to irradiate a laser beam having a relatively large energy and there is a problem that the layer to be peeled is damaged.
- JP 10-125929 A Japanese Patent Laid-Open No. 10-125931 International Publication No. 2005/050754 JP-A-10-125930
- This invention is made
- the composition for peeling layer formation for forming the peeling layer which can peel without damaging the resin substrate of a flexible electronic device, and the said peeling layer are provided.
- the purpose is to provide.
- the present inventors have obtained a composition comprising a polyamic acid obtained by introducing an anchor group at either or both of the polymer chain ends, and an organic solvent.
- the present inventors have found that a release layer having an excellent adhesion to a substrate and an appropriate adhesion to a resin substrate used in a flexible electronic device and an appropriate peelability can be formed.
- a composition for forming a release layer comprising a polyamic acid obtained by introducing an anchor group into either one or both of the polymer chain ends, and an organic solvent, 2.
- a method for producing a flexible electronic device comprising a resin substrate, characterized in that a release layer of 6 is used, 8).
- the manufacturing method according to 7 is characterized in that the resin substrate is a substrate made of polyimide.
- the release layer forming composition of the present invention By using the release layer forming composition of the present invention, it is possible to obtain a release layer having excellent adhesion to the substrate, moderate adhesion to the resin substrate, and moderate release with good reproducibility. Therefore, by using the composition for forming a release layer of the present invention, in the manufacturing process of the flexible electronic device, without damaging the resin substrate formed on the substrate, the circuit provided on the substrate, and the like. The resin substrate can be separated from the substrate together with the circuit and the like. Therefore, the composition for forming a release layer of the present invention 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 release layer of the present invention contains a polyamic acid obtained by introducing an anchor group at one or both of the polymer chain ends, and an organic solvent.
- the release layer in the present invention is a layer provided immediately above a glass substrate for a predetermined purpose.
- a flexible electronic made of a substrate and a resin such as polyimide is used.
- the resin substrate can be easily peeled from the substrate.
- a release layer may be used.
- the polyamic acid used in the present invention is not particularly limited as long as it has an anchor group at the end of the polymer chain, but the polyamic acid obtained after reacting the diamine component with the tetracarboxylic dianhydride component And an amine having an anchor group or an acid anhydride having an anchor group can be obtained. That is, the polyamic acid obtained here is one in which either or both of the molecular chain ends are sealed with an anchor group-containing compound described later.
- anchor groups examples 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.
- the anchor group may be present at either one of the polymer chain ends of the polyamic acid, but it is preferable that the anchor group be present at both of the polymer chain ends. Further, between the polyamic acid obtained from the diamine component and the tetracarboxylic dianhydride component and the anchor group, an alkyl group or aryl having a carbon number of about 1 to 10 that does not significantly reduce the peelability and heat resistance. A spacer group such as a group may be present, and an ether bond, a thioether bond, an ester bond or the like may be present in these spacer groups.
- 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.
- a diamine component and an acid dianhydride component used when producing a polyamic acid from the viewpoint of improving the function as a release layer of the obtained film, a diamine component containing an aromatic diamine and an aromatic tetracarboxylic acid dicarboxylic acid are used.
- a polyamic acid obtained by reacting an acid dianhydride component containing an anhydride is preferred.
- the aromatic diamine is not particularly limited as long as it has two amino groups in the molecule and has an aromatic ring, but an aromatic diamine containing 1 to 5 benzene nuclei is preferable. Specific examples thereof include 1,4-diaminobenzene (p-phenylenediamine), 1,3-diaminobenzene (m-phenylenediamine), 1,2-diaminobenzene (o-phenylenediamine), 2,4-diamino.
- Group diamines are preferred. Specifically, p-phenylenediamine, m-phenylenediamine, 2- (3-aminophenyl) -5-aminobenzimidazole, 2- (4-aminophenyl) -5-aminobenzooxol, 4,4 ′ '-Diamino-p-terphenyl and the like are preferred.
- aromatic tetracarboxylic dianhydride is not particularly limited as long as it has two dicarboxylic anhydride sites in the molecule and has an aromatic ring, but an aromatic tetracarboxylic dianhydride contains 1 to 5 benzene nuclei.
- aromatic tetracarboxylic dianhydrides are preferred.
- 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-2,3,3', 4'-tetracarboxylic dianhydride,
- aromatic carboxylic dianhydrides having one or two benzene nuclei are preferred from the viewpoint of improving the function of the resulting film as a release layer.
- an aromatic tetracarboxylic dianhydride represented by any one of formulas (C1) to (C12) is preferred, and any one of formulas (C1) to (C7) and (C9) to (C11)
- the aromatic tetracarboxylic dianhydride shown is more preferred.
- the diamine component used in the present invention may contain a diamine other than an aromatic diamine, and the tetracarboxylic dianhydride component used in the present invention is Further, tetracarboxylic dianhydrides other than aromatic tetracarboxylic dianhydrides may be included.
- the amount of aromatic diamine in the diamine component is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and most preferably 100 mol%.
- the amount of aromatic tetracarboxylic dianhydride in the tetracarboxylic acid component 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%. Above, most preferably 100 mol%.
- the polyamic acid obtained is reacted with an amine having an anchor group or an acid anhydride having an anchor group.
- a polyamic acid having an anchor group at the end of the polymer chain contained in the composition for forming a release layer can be obtained.
- 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-dimethylpropyl Amides, 3-propoxy-N, N-dimethylpropylamide, 3-isopropoxy-N, N-dimethylpropylamide, 3-butoxy-N, N-dimethylpropylamide, 3-sec-butoxy-N, N-dimethyl Propylamide, 3-tert-butoxy-N, N-dimethylpropylamide, ⁇ -butyrolactone, etc. That.
- the charging ratio of the diamine component and the tetracarboxylic dianhydride component is appropriately determined in consideration of the target molecular weight and molecular weight distribution, the type of diamine and the type of tetracarboxylic dianhydride, etc.
- the ratio of the diamine component to the tetracarboxylic dianhydride component 1 is about 0.7 to 1.3, preferably about 0.8 to 1.2, and more preferably about 0.9 to 1.1.
- 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 0.05 to 0, based on the tetracarboxylic dianhydride component.
- it is about 0.1 to 0.2.
- 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. From the viewpoint of improving the function of the resulting film as a release layer, preferably 10,000 to 200,000. About 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.
- the release layer forming composition of the present invention contains an organic solvent.
- this organic solvent the same thing as the specific example of the reaction solvent of the said reaction is mentioned.
- 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 release 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 may be used singly or in combination of two or more.
- 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 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 release layer-forming composition of the present invention is appropriately set in consideration of the thickness of the release layer to be produced, etc., and in particular, a film having a thickness of about 0.05 to 5 ⁇ m can be obtained with good reproducibility. When it is intended, it is usually about 10 to 10,000 mPa ⁇ s, preferably about 20 to 5,000 mPa ⁇ s at 25 ° C.
- the viscosity can be measured using a commercially available liquid viscosity measurement viscometer, for example, with reference to the procedure described in JIS K7117-2 at a temperature of the composition of 25 ° C. .
- a conical plate type (cone plate type) rotational viscometer is used as the viscometer, and preferably the composition temperature is 25 ° C. using 1 ° 34 ′ ⁇ R24 as a standard cone rotor. It can be measured under the condition of ° C.
- An example of such a rotational viscometer is TVE-25L manufactured by Toki Sangyo Co., Ltd.
- composition for forming a release layer of the present invention may contain a crosslinking agent or the like in order to improve the film strength, for example, in addition to the polyamic acid and the organic solvent.
- the release layer When such a release layer of the present invention is formed on a substrate, the release layer may be formed on a partial surface of the substrate, or may be formed 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 of this invention is applied to the surface.
- 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 peeling layer of this invention has sufficient adhesiveness with respect to it, 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 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 release 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, and bar coating.
- Method, die coating method, ink jet method, printing method eg, relief printing, intaglio printing, planographic printing, screen printing, etc.
- the heating temperature for imidization is usually appropriately determined within the range of 50 to 550 ° C., but is preferably more than 150 ° C. to 510 ° C. By setting the heating temperature in this way, it is possible to sufficiently advance the imidization reaction while preventing the obtained film from being weakened.
- 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 heating mode in the present invention after heating at 50 to 150 ° C. for 5 minutes to 2 hours, the heating temperature is gradually increased as it is, and finally from 150 ° C. to 510 ° C. for 30 minutes to 4 hours.
- the method of heating is mentioned.
- after heating at 50 to 100 ° C. for 5 minutes to 2 hours after exceeding 100 ° C. to 375 ° C. for 5 minutes to 2 hours, and finally exceeding 375 ° C. to 450 ° C. for 30 minutes to The method of heating for 4 hours is mentioned.
- after heating at 50 to 150 ° C. for 5 minutes to 2 hours after heating at 150 ° C. to 350 ° C. for 5 minutes to 2 hours, then at 350 ° C. to 450 ° C. for 30 minutes
- a method of heating at 450 ° C. to 510 ° C. for 30 minutes to 4 hours is mentioned.
- 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 release 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 release layer described above has excellent adhesion to a substrate, particularly a glass substrate, moderate adhesion to a resin substrate, and moderate release. Therefore, the release layer of the present invention peels the resin substrate from the substrate together with the circuit formed on the resin substrate without damaging the resin substrate of the device in the manufacturing process of the flexible electronic device. Therefore, it can be suitably used.
- a release layer is formed on a glass substrate by the method described above.
- a resin solution for forming a resin substrate is applied on the release layer, and this coating film is heated to form a resin substrate fixed to the glass substrate via the release layer of the present invention.
- the substrate is formed with a larger area than the area of the release layer so as to cover the entire release layer.
- the resin substrate include a resin substrate made of polyimide, which is a typical resin substrate for flexible electronic devices, and examples of the resin solution for forming the resin substrate include a polyimide solution and a polyamic acid solution.
- the method for forming the resin substrate may follow a conventional method.
- a desired circuit is formed on the resin substrate fixed to the base via the release layer of the present invention, and then the resin substrate is cut along the release layer, for example.
- the resin substrate and the substrate are separated by peeling from the release layer. 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 composition for forming a release layer according to the present invention has a feature of sufficiently absorbing light having a specific wavelength (for example, 308 nm) that enables application of the LLO method, and can therefore be used as a sacrificial layer for 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
- Mw weight average molecular weight
- Mw molecular weight
- 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 conversion value
- composition for forming release layer [Example 1-1] 6 g of NMP and 4 g of butyrocellosolve were added to 10 g of the reaction solution obtained in Synthesis Example L1, and the mixture was stirred at room temperature for 24 hours to obtain a release layer forming composition.
- Examples 1-2 to 1-3 A composition for forming a release layer was obtained in the same manner as in Example 1-1 except that the reaction solutions obtained in Synthesis Examples L2 to L3 were used in place of the reaction solution obtained in Synthesis Example L1, respectively. It was.
- Example 1-4 To 10 g of the reaction solution obtained in Synthesis Example L4, 9.4 g of NMP and 4.6 g of butyrocellosolve were added and stirred at room temperature for 24 hours to obtain a composition for forming a release layer.
- Comparative Example 1-1 The reaction solution obtained in Comparative Synthesis Example 1 was diluted with NMP so that the polymer concentration was 5 wt% to obtain a composition.
- Example 2-1 Formation and evaluation of release layer [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 placed on a 100 mm ⁇ 100 mm glass substrate (hereinafter the same) as a glass substrate. It was applied to. 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. And then heated at 400 ° C. for 30 minutes to form a release layer having a thickness of about 0.1 ⁇ m on the glass substrate. During the temperature increase, the film-coated substrate was not removed from the oven but heated in the oven.
- a spin coater condition: about 3,000 rpm for about 30 seconds
- Example 2-1 was used except that the release layer forming composition obtained in Examples 1-2 to 1-4 was used instead of the release layer forming composition obtained in Example 1-1.
- a release layer was formed in the same manner as described above.
- Comparative Example 2-1 A resin thin film was prepared in the same manner as in Example 2-1, except that the composition obtained in Comparative Example 1-1 was used instead of the release layer forming composition obtained in Example 1-1. Formed.
- the release layer cross-cuts (length and width 1 mm intervals, hereinafter the same) on the glass substrate with release layer obtained in Examples 2-1 to 2-4, and the resin substrate on the glass substrate with release layer and release layer -A 100 muscut was made by cross-cutting the release layer. That is, 100 crosses of 1 mm square were formed by this cross cut.
- an adhesive tape was attached to the 100 muscat portion, the tape was peeled off, and the degree of peeling was evaluated based on the following criteria (5B to 0B, B, A, AA) (Examples 3-1 to 3- 4). Further, according to the above method, a similar test was performed using the glass substrate with a resin thin film obtained in Comparative Example 2-1 (Comparative Example 3-1). The results are shown in Table 1.
- the resin substrates of Examples 3-1 to 3-4 and Comparative Example 3-1 were formed by the following method. Using a bar coater (gap: 250 ⁇ m), either the resin substrate forming composition W or X was applied on the release layer (resin thin film) on the glass substrate. The obtained coating film was heated at 80 ° C. for 10 minutes using a hot plate, and then heated at 140 ° C. for 30 minutes using an oven, and the heating temperature was raised to 210 ° C. (10 ° C./min. The same applies to the following, and the heating temperature was raised to 210 ° C. for 30 minutes, the heating temperature was raised to 300 ° C., the heating temperature was raised to 300 ° C.
- the heating temperature was raised to 400 ° C., and the heating temperature was raised to 400 ° C. for 60 minutes.
- a polyimide substrate having a thickness of about 20 ⁇ m was formed. During the temperature increase, the film-coated substrate was not removed from the oven but heated in the oven.
- the release layers of the examples are excellent in adhesion to the glass substrate and excellent in peelability from the resin substrate.
- the resin thin film of the comparative example was found to adhere to the resin layer and not peel at all when the adhesion between the glass substrate and the release layer was low or the adhesion was high.
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Abstract
Description
1. その重合体鎖末端のいずれか一方又は両方にアンカー基を導入してなるポリアミック酸と、有機溶媒とを含む剥離層形成用組成物、
2. 前記アンカー基が、シリル基又はカルボン酸基である1の剥離層形成用組成物、
3. 前記ポリアミック酸が、芳香族ジアミンを含むジアミン成分と芳香族テトラカルボン酸二無水物を含む酸二無水物成分とを反応させて得られたポリアミック酸であることを特徴とする1又は2の剥離層形成用組成物、
4. 前記芳香族ジアミンが、ベンゼン核を1~5つ含む芳香族ジアミンであることを特徴とする3の剥離層形成用組成物、
5. 前記芳香族テトラカルボン酸二無水物が、ベンゼン核を1~5つ含む芳香族テトラカルボン酸二無水物であることを特徴とする3又は4の剥離層形成用組成物、
6. 1~5のいずれかの剥離層形成用組成物を用いて形成される剥離層、
7. 6の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、
8. 前記樹脂基板が、ポリイミドからなる基板であることを特徴とする7の製造方法
を提供する。 That is, the present invention
1. A composition for forming a release layer, comprising a polyamic acid obtained by introducing an anchor group into either one or both of the polymer chain ends, and an organic solvent,
2. 1. The composition for forming a release layer, wherein the anchor group is a silyl group or a carboxylic acid group,
3. 1 or 2 peeling, wherein the polyamic acid is a polyamic acid obtained by reacting a diamine component containing an aromatic diamine and an acid dianhydride component containing an aromatic tetracarboxylic dianhydride Layer forming composition,
4). 3. The composition for forming a release layer according to 3, wherein the aromatic diamine is an aromatic diamine containing 1 to 5 benzene nuclei,
5. 3 or 4 composition for forming a release layer, wherein the aromatic tetracarboxylic dianhydride is an aromatic tetracarboxylic dianhydride containing 1 to 5 benzene nuclei,
6). A release layer formed using the release layer forming composition according to any one of 1 to 5,
7). A method for producing a flexible electronic device comprising a resin substrate, characterized in that a release layer of 6 is used,
8). The manufacturing method according to 7 is characterized in that the resin substrate is a substrate made of polyimide.
本発明の剥離層形成用組成物は、その重合体鎖末端のいずれか一方又は両方にアンカー基を導入してなるポリアミック酸と、有機溶媒とを含む。ここで、本発明における剥離層とは、所定の目的でガラス基体直上に設けられる層であって、その典型例としては、フレキシブル電子デバイスの製造プロセスにおいて、基体と、ポリイミドといった樹脂からなるフレキシブル電子デバイスの樹脂基板との間に当該樹脂基板を所定のプロセス中において固定するために設けられ、且つ、当該樹脂基板上に電子回路等の形成した後において当該樹脂基板が当該基体から容易に剥離できるようにするために設けられる剥離層が挙げられる。 Hereinafter, the present invention will be described in more detail.
The composition for forming a release layer of the present invention contains a polyamic acid obtained by introducing an anchor group at one or both of the polymer chain ends, and an organic solvent. Here, the release layer in the present invention is a layer provided immediately above a glass substrate for a predetermined purpose. As a typical example, in a manufacturing process of a flexible electronic device, a flexible electronic made of a substrate and a resin such as polyimide is used. Provided between the device resin substrate and 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 peeled from the substrate. For example, a release layer may be used.
また、ジアミン成分及びテトラカルボン酸二無水物成分から得られるポリアミック酸と、アンカー基との間には、炭素数1~10程度の剥離性や耐熱性を著しく低下させない炭素数のアルキル基、アリール基等のスペーサー基が存在してもよく、これらスペーサー基内には、エーテル結合、チオエーテル結合、エステル結合等が存在してもよい。 In the present invention, the anchor group may be present at either one of the polymer chain ends of the polyamic acid, but it is preferable that the anchor group be present at both of the polymer chain ends.
Further, between the polyamic acid obtained from the diamine component and the tetracarboxylic dianhydride component and the anchor group, an alkyl group or aryl having a carbon number of about 1 to 10 that does not significantly reduce the peelability and heat resistance. A spacer group such as a group may be present, and an ether bond, a thioether bond, an ester bond or the like may be present in these spacer groups.
その具体例としては、1,4-ジアミノベンゼン(p-フェニレンジアミン)、1,3-ジアミノベンゼン(m-フェニレンジアミン)、1,2-ジアミノベンゼン(o-フェニレンジアミン)、2,4-ジアミノトルエン、2,5-ジアミノトルエン、2,6-ジアミノトルエン、4,6-ジメチル-m-フェニレンジアミン、2,5-ジメチル-p-フェニレンジアミン、2,6-ジメチル-p-フェニレンジアミン、2,4,6-トリメチル-1,3-フェニレンジアミン、2,3,5,6-テトラメチル-p-フェニレンジアミン、m-キシリレンジアミン、p-キシリレンジアミン、5-トリフルオロメチルベンゼン-1,3-ジアミン、5-トリフルオロメチルベンゼン-1,2-ジアミン、3,5-ビス(トリフルオロメチル)ベンゼン-1,2-ジアミン等のベンゼン核が1つのジアミン;1,2-ナフタレンジアミン、1,3-ナフタレンジアミン、1,4-ナフタレンジアミン、1,5-ナフタレンジアミン、1,6-ナフタレンジアミン、1,7-ナフタレンジアミン、1,8-ナフタレンジアミン、2,3-ナフタレンジアミン、2,6-ナフタレンジアミン、4,4’-ビフェニルジアミン、2,2’-ビス(トリフルオロメチル)-4,4’-ジアミノビフェニル、3,3’-ジメチル-4,4’-ジアミノジフェニルメタン、3,3’-ジカルボキシ-4,4’-ジアミノジフェニルメタン、3,3’,5,5’-テトラメチル-4,4’-ジアミノジフェニルメタン、4,4’-ジアミノベンズアニリド、3,3’-ジクロロベンジジン、3,3’-ジメチルベンジジン、2,2’-ジメチルベンジジン、3,3’-ジアミノジフェニルメタン、3,4’-ジアミノジフェニルメタン、4,4’-ジアミノジフェニルメタン、2,2-ビス(3-アミノフェニル)プロパン、2,2-ビス(4-アミノフェニル)プロパン、2,2-ビス(3-アミノフェニル)-1,1,1,3,3,3-ヘキサフルオロプロパン、2,2-ビス(4-アミノフェニル)-1,1,1,3,3,3-ヘキサフルオロプロパン、3,3’-ジアミノジフェニルスルホキシド、3,4’-ジアミノジフェニルスルホキシド、4,4’-ジアミノジフェニルスルホキシド、3,3’-ビス(トリフルオロメチル)ビフェニル-4,4’-ジアミン、3,3’,5,5’-テトラフルオロビフェニル-4,4’-ジアミン、4,4’-ジアミノオクタフルオロビフェニル、2-(3-アミノフェニル)-5-アミノベンズイミダゾール、2-(4-アミノフェニル)-5-アミノベンゾオキゾール等のベンゼン核が2つのジアミン;1,5-ジアミノアントラセン、2,6-ジアミノアントラセン、9,10-ジアミノアントラセン、1,8-ジアミノフェナントレン、2,7-ジアミノフェナントレン、3,6-ジアミノフェナントレン、9,10-ジアミノフェナントレン、1,3-ビス(3-アミノフェニル)ベンゼン、1,3-ビス(4-アミノフェニル)ベンゼン、1,4-ビス(3-アミノフェニル)ベンゼン、1,4-ビス(4-アミノフェニル)ベンゼン、1,3-ビス(3-アミノフェニルスルフィド)ベンゼン、1,3-ビス(4-アミノフェニルスルフィド)ベンゼン、1,4-ビス(4-アミノフェニルスルフィド)ベンゼン、1,3-ビス(3-アミノフェニルスルホン)ベンゼン、1,3-ビス(4-アミノフェニルスルホン)ベンゼン、1,4-ビス(4-アミノフェニルスルホン)ベンゼン、1,3-ビス〔2-(4-アミノフェニル)イソプロピル〕ベンゼン、1,4-ビス〔2-(3-アミノフェニル)イソプロピル〕ベンゼン、1,4-ビス〔2-(4-アミノフェニル)イソプロピル〕ベンゼン、4,4’’-ジアミノ-p-ターフェニル、4,4’’-ジアミノ-m-ターフェニル等のベンゼン核が3つのジアミン等を挙げることができるが、これらに限定されない。これらは単独でも、2種以上を組み合わせて用いることもできる。なお、本発明において、上記芳香族ジアミンはエーテル結合及びエステル結合を含まないものを使用することが好ましい。 The aromatic diamine is not particularly limited as long as it has two amino groups in the molecule and has an aromatic ring, but an aromatic diamine containing 1 to 5 benzene nuclei is preferable.
Specific examples thereof include 1,4-diaminobenzene (p-phenylenediamine), 1,3-diaminobenzene (m-phenylenediamine), 1,2-diaminobenzene (o-phenylenediamine), 2,4-diamino. Toluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 4,6-dimethyl-m-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2 , 4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 5-trifluoromethylbenzene-1 , 3-diamine, 5-trifluoromethylbenzene-1,2-diamine, 3,5-bis (trifluoromethyl A diamine having one benzene nucleus such as benzene-1,2-diamine; 1,2-naphthalenediamine, 1,3-naphthalenediamine, 1,4-naphthalenediamine, 1,5-naphthalenediamine, 1,6-naphthalenediamine 1,7-naphthalenediamine, 1,8-naphthalenediamine, 2,3-naphthalenediamine, 2,6-naphthalenediamine, 4,4′-biphenyldiamine, 2,2′-bis (trifluoromethyl) -4 , 4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetramethyl -4,4'-diaminodiphenylmethane, 4,4'-diaminobenzanilide, 3,3'-dichlorobenzidine, 3,3'-dimethylbenz 2,2'-dimethylbenzidine, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 2,2-bis (3-aminophenyl) propane, 2,2 -Bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-aminophenyl)- 1,1,1,3,3,3-hexafluoropropane, 3,3′-diaminodiphenyl sulfoxide, 3,4′-diaminodiphenyl sulfoxide, 4,4′-diaminodiphenyl sulfoxide, 3,3′-bis ( Trifluoromethyl) biphenyl-4,4′-diamine, 3,3 ′, 5,5′-tetrafluorobiphenyl-4,4′-diamine, 4,4′-diaminoocta Benzene nuclei having two diamines such as luorobiphenyl, 2- (3-aminophenyl) -5-aminobenzimidazole, 2- (4-aminophenyl) -5-aminobenzoxazole; 1,5-diaminoanthracene, 2,6-diaminoanthracene, 9,10-diaminoanthracene, 1,8-diaminophenanthrene, 2,7-diaminophenanthrene, 3,6-diaminophenanthrene, 9,10-diaminophenanthrene, 1,3-bis (3- Aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (3-aminophenyl) benzene, 1,4-bis (4-aminophenyl) benzene, 1,3-bis ( 3-aminophenylsulfide) benzene, 1,3-bis (4-aminophenylsulfide) benze 1,4-bis (4-aminophenylsulfide) benzene, 1,3-bis (3-aminophenylsulfone) benzene, 1,3-bis (4-aminophenylsulfone) benzene, 1,4-bis (4 -Aminophenylsulfone) benzene, 1,3-bis [2- (4-aminophenyl) isopropyl] benzene, 1,4-bis [2- (3-aminophenyl) isopropyl] benzene, 1,4-bis [2 -(4-Aminophenyl) isopropyl] benzene, 4,4 ″ -diamino-p-terphenyl, 4,4 ″ -diamino-m-terphenyl and the like, and benzene nuclei having three diamines can be mentioned. However, it is not limited to these. These can be used alone or in combination of two or more. In the present invention, the aromatic diamine preferably does not contain an ether bond or an ester bond.
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溶液を塗布し、この塗膜を加熱することで、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。この際、剥離層を全て覆うようにして、剥離層の面積と比較して大きい面積で、基板を形成する。樹脂基板としては、フレキシブル電子デバイスの樹脂基板として代表的なポリイミドからなる樹脂基板が挙げられ、それを形成するための樹脂溶液としては、ポリイミド溶液やポリアミック酸溶液が挙げられる。当該樹脂基板の形成方法は、常法に従えばよい。 Hereinafter, an example of the manufacturing method of the flexible electronic device using the peeling layer of this invention is demonstrated.
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. A resin solution for forming a resin substrate is applied on the release layer, and this coating film is heated to form a resin substrate fixed to the glass substrate via the release layer of the present invention. At this time, the substrate is formed with a larger area than the area of the release layer so as to cover the entire release layer. Examples of 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.
[1]化合物の略語
p-PDA:p-フェニレンジアミン
DATP:4,4’’-ジアミノ-p-ターフェニル
TFMB:2,2’―ビス(トリフルオロメチル)ベンジジン
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
PMDA:ピロメリット酸二無水物
BPDA:3,3’,4,4’-ビフェニルテトラカルボン酸二無水物
LS-3280:4-アミノフェノキシジメチルビニルシラン
LS-3150:3-アミノプロピルトリエトキシシラン
TMA:トリメリット酸無水物
IHPA:イソフタルアルデヒド
NMP:N-メチル-2-ピロリドン EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to these Examples.
[1] Abbreviations of compounds p-PDA: p-phenylenediamine DATP: 4,4 ″ -diamino-p-terphenyl TFMB: 2,2′-bis (trifluoromethyl) benzidine 6FAP: 2,2-bis ( 3-amino-4-hydroxyphenyl) hexafluoropropane PMDA: pyromellitic dianhydride BPDA: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride LS-3280: 4-aminophenoxydimethylvinylsilane LS -3150: 3-aminopropyltriethoxysilane TMA: trimellitic anhydride IHPA: isophthalaldehyde NMP: N-methyl-2-pyrrolidone
ポリマーの重量平均分子量(以下Mwと略す)及び分子量分布の測定は、日本分光株式会社製GPC装置(カラム:Shodex製 OHpak SB803-HQ、及びOHpak SB804-HQ;溶離液:ジメチルホルムアミド/LiBr・H2O(29.6mM)/H3PO4(29.6mM)/THF(0.1wt%);流量:1.0mL/分;カラム温度:40℃;Mw:標準ポリスチレン換算値)を用いて行った。 [2] Measurement of weight average molecular weight and molecular weight distribution The weight average molecular weight (hereinafter abbreviated as Mw) and molecular weight distribution of a polymer are measured by a GPC apparatus manufactured by JASCO Corporation (column: OHpak SB803-HQ manufactured by Shodex and OHpak SB804- HQ; 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 conversion value).
<合成例F1 ポリアミック酸(F1)の合成>
p-PDA 20.261g(187mmol)とDATP 12.206g(47mmol)をNMP 617.4gに溶解させた。得られた溶液を15℃に冷却し、そこへPMDA 50.112g(230mmol)を加え、窒素雰囲気下、50℃まで昇温し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。 [3] Synthesis of Polymer <Synthesis Example F1 Synthesis of polyamic acid (F1)>
20.261 g (187 mmol) of p-PDA and 12.206 g (47 mmol) of DATP were dissolved in 617.4 g of NMP. The obtained solution was cooled to 15 ° C., 50.112 g (230 mmol) of PMDA was added thereto, and the temperature was raised to 50 ° C. in a nitrogen atmosphere and reacted for 48 hours. Mw of the obtained polymer was 82,100, and molecular weight distribution was 2.7.
p-PDA 3.218g(30mmol)をNMP 88.2gに溶解させた。得られた溶液にBPDA 8.581g(29mmol)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107,300、分子量分布4.6であった。 <Synthesis Example F2 Synthesis of polyamic acid (F2)>
3.218 g (30 mmol) of p-PDA was dissolved in 88.2 g of NMP. To the obtained solution, 8.581 g (29 mmol) of BPDA was added and reacted at 23 ° C. for 24 hours under a nitrogen atmosphere. Mw of the obtained polymer was 107,300, and the molecular weight distribution was 4.6.
p-PDA 2.66g(24.6mmol)とTFMB 0.18g(0.6mmol)をNMP 90gに溶解させた。得られた溶液に、PMDA 6.09g(27.9mmol)を加え、窒素雰囲気下、23℃で24時間反応させた後、LS-3280 1.08g(5.6mmol)を加えて更に24時間反応させてポリアミック酸の両端にシリル基を導入した。得られたポリマーのMwは62,700、分子量分布2.7であった。 <Synthesis Example L1 Synthesis of polyamic acid (L1)>
2.66 g (24.6 mmol) of p-PDA and 0.18 g (0.6 mmol) of TFMB were dissolved in 90 g of NMP. PMDA 6.09 g (27.9 mmol) was added to the resulting solution and reacted at 23 ° C. for 24 hours under a nitrogen atmosphere, followed by addition of LS-3280 1.08 g (5.6 mmol) and further reaction for 24 hours. Thus, silyl groups were introduced at both ends of the polyamic acid. Mw of the obtained polymer was 62,700 and molecular weight distribution was 2.7.
p-PDA 2.96g(27.3mmol)とTFMB 0.19g(0.6mmol)をNMP 90gに溶解させた。得られた溶液に、PMDA 6.34g(29.1mmol)を加え、窒素雰囲気下、23℃で24時間反応させた後、LS-3150 0.52g(2.3mmol)を加えて更に24時間反応させてポリアミック酸の両端にシリル基を導入した。得られたポリマーのMwは51,100、分子量分布2.8であった。 <Synthesis Example L2 Synthesis of polyamic acid (L2)>
2.96 g (27.3 mmol) of p-PDA and 0.19 g (0.6 mmol) of TFMB were dissolved in 90 g of NMP. PMDA 6.34 g (29.1 mmol) was added to the obtained solution and reacted at 23 ° C. for 24 hours under a nitrogen atmosphere, and then LS-3150 0.52 g (2.3 mmol) was added and reacted for another 24 hours. Thus, silyl groups were introduced at both ends of the polyamic acid. Mw of the obtained polymer was 51,100 and molecular weight distribution was 2.8.
p-PDA 3.06(28.3mmol)をNMP 90gに溶解させた。得られた溶液に、PMDA 6.42g(29.4mmol)を加え、窒素雰囲気下、23℃で24時間反応させた後、LS-3150 0.52g(2.4mmol)を加えて更に24時間反応させてポリアミック酸の両端にシリル基を導入した。得られたポリマーのMwは47,800、分子量分布2.8であった。 <Synthesis Example L3 Synthesis of polyamic acid (L3)>
p-PDA 3.06 (28.3 mmol) was dissolved in 90 g of NMP. PMDA 6.42 g (29.4 mmol) was added to the resulting solution and reacted at 23 ° C. for 24 hours under a nitrogen atmosphere, and then LS-3150 0.52 g (2.4 mmol) was added and reacted for another 24 hours. Thus, silyl groups were introduced at both ends of the polyamic acid. Mw of the obtained polymer was 47,800 and molecular weight distribution was 2.8.
p-PDA 0.78g(7.2mmol)をNMP 17.6gに溶解させた。得られた溶液に、PMDA 1.51g(6.9mmol)を加え、窒素雰囲気下、23℃で24時間反応させた後、TMA 0.11g(0.3mmol)を加えて更に24時間反応させてポリアミック酸の両端にカルボン酸基を導入した。得られたポリマーのMwは48,000、分子量分布3.1であった。 <Synthesis Example L4 Synthesis of polyamic acid (L4)>
0.78 g (7.2 mmol) of p-PDA was dissolved in 17.6 g of NMP. To the obtained solution, 1.51 g (6.9 mmol) of PMDA was added and reacted at 23 ° C. for 24 hours under a nitrogen atmosphere, and then 0.11 g (0.3 mmol) of TMA was added and reacted for another 24 hours. Carboxylic acid groups were introduced at both ends of the polyamic acid. The obtained polymer had Mw of 48,000 and a molecular weight distribution of 3.1.
6FAP 3.18g(0.059モル)をNMP70gに溶解させた。得られた溶液にIHPA 7.92g(0.060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107,300、分子量分布4.6であった。 <Comparative Synthesis Example 1 Synthesis of Polybenzoxazole Precursor (B1)>
3.18 g (0.059 mol) of 6FAP was dissolved in 70 g of NMP. To the resulting solution, 7.92 g (0.060 mol) of IHPA was added and reacted at 23 ° C. for 24 hours under a nitrogen atmosphere. Mw of the obtained polymer was 107,300, and the molecular weight distribution was 4.6.
合成例F1,F2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W,Xとして用いた。 [4] Preparation of Resin Substrate Forming Composition The reaction solutions obtained in Synthesis Examples F1 and F2 were used as resin substrate forming compositions W and X, respectively.
[実施例1-1]
合成例L1で得られた反応液10gに、NMP6gとブチロセロソルブ4g添加し、室温で24時間撹拌し、剥離層形成用組成物を得た。 [5] Preparation of composition for forming release layer [Example 1-1]
6 g of NMP and 4 g of butyrocellosolve were added to 10 g of the reaction solution obtained in Synthesis Example L1, and the mixture was stirred at room temperature for 24 hours 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~L3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 1-3]
A composition for forming a release layer was obtained in the same manner as in Example 1-1 except that the reaction solutions obtained in Synthesis Examples L2 to L3 were used in place of the reaction solution obtained in Synthesis Example L1, respectively. It was.
合成例L4で得られた反応液10gに、NMP9.4gとブチロセロソルブ4.6g添加し、室温で24時間撹拌し、剥離層形成用組成物を得た。 [Example 1-4]
To 10 g of the reaction solution obtained in Synthesis Example L4, 9.4 g of NMP and 4.6 g of butyrocellosolve were added and stirred at room temperature for 24 hours to obtain a composition for forming a release layer.
比較合成例1で得られた反応液を、ポリマー濃度が5wt%となるようにNMPで希釈して、組成物を得た。 [Comparative Example 1-1]
The reaction solution obtained in Comparative Synthesis Example 1 was diluted with NMP so that the polymer concentration was 5 wt% to obtain a composition.
[実施例2-1]
スピンコータ(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、更に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] Formation and evaluation of release layer [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 placed on a 100 mm × 100 mm glass substrate (hereinafter the same) as a glass substrate. It was applied to.
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. And then heated at 400 ° C. for 30 minutes to form a release layer having a thickness of about 0.1 μm on the glass substrate. 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、それぞれ実施例1-2~1-4で得られた剥離層形成用組成物を用いた以外は、実施例2-1と同様の方法で、剥離層を形成した。 [Examples 2-2 to 2-4]
Example 2-1 was used except that the release layer forming composition obtained in Examples 1-2 to 1-4 was used instead of the release layer forming composition obtained in Example 1-1. A release layer was formed in the same manner as described above.
実施例1-1で得られた剥離層形成用組成物の代わりに、比較例1-1で得られた組成物を用いた以外は、実施例2-1と同様の方法で、樹脂薄膜を形成した。 [Comparative Example 2-1]
A resin thin film was prepared in the same manner as in Example 2-1, except that the composition obtained in Comparative Example 1-1 was used instead of the release layer forming composition obtained in Example 1-1. Formed.
[実施例3-1~3-4,比較例3-1]
以下の方法により、表1に示した剥離層と樹脂基板の組み合わせとなるよう基板を作製し、剥離性の評価をした。
実施例2-1~2-4で得られた剥離層とガラス基板の剥離性及び当該剥離層(樹脂薄膜)と樹脂基板の剥離性を確認した。なお、樹脂基板としては、ポリイミドからなる樹脂基板を用いた。
まず、実施例2-1~2-4で得られた剥離層付きガラス基板上の剥離層のクロスカット(縦横1mm間隔、以下同様)、並びに、樹脂基板・剥離層付きガラス基板上の樹脂基板・剥離層のクロスカットを行うことにより、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張り付けて、そのテープを剥がし、以下の基準(5B~0B,B,A,AA)に基づき、剥離の程度を評価した(実施例3-1~3-4)。また、上記手法に準じて、比較例2-1で得られた樹脂薄膜付きガラス基板を用いて、同様の試験を行った(比較例3-1)。結果を表1に示す。 [7] Evaluation of peelability [Examples 3-1 to 3-4, Comparative example 3-1]
By the following method, the board | substrate was produced so that it might become a combination of the peeling layer shown in Table 1, and the resin substrate, and peelability was evaluated.
The peelability of the release layer and glass substrate obtained in Examples 2-1 to 2-4 and the peelability of the release layer (resin thin film) and the resin substrate were confirmed. As the resin substrate, a resin substrate made of polyimide was used.
First, the release layer cross-cuts (length and width 1 mm intervals, hereinafter the same) on the glass substrate with release layer obtained in Examples 2-1 to 2-4, and the resin substrate on the glass substrate with release layer and release layer -A 100 muscut was made by cross-cutting the release layer. That is, 100 crosses of 1 mm square were formed by this cross cut.
Then, an adhesive tape was attached to the 100 muscat portion, the tape was peeled off, and the degree of peeling was evaluated based on the following criteria (5B to 0B, B, A, AA) (Examples 3-1 to 3- 4). Further, according to the above method, a similar test was performed using the glass substrate with a resin thin film obtained in Comparative Example 2-1 (Comparative Example 3-1). The results are shown in Table 1.
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) 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)
バーコーター(ギャップ:250μm)を用いて、ガラス基板上の剥離層(樹脂薄膜)の上に樹脂基板形成用組成物W又はXのいずれかを塗布した。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、140℃で30分間加熱し、加熱温度を210℃まで昇温(10℃/分、以下同様)し、210℃で30分間、加熱温度を300℃まで昇温し、300℃で30分間、加熱温度を400℃まで昇温し、400℃で60分間加熱し、剥離層上に厚さ約20μmのポリイミド基板を形成した。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。 The resin substrates of Examples 3-1 to 3-4 and Comparative Example 3-1 were formed by the following method.
Using a bar coater (gap: 250 μm), either the resin substrate forming composition W or X was applied on the release layer (resin thin film) on the glass substrate. The obtained coating film was heated at 80 ° C. for 10 minutes using a hot plate, and then heated at 140 ° C. for 30 minutes using an oven, and the heating temperature was raised to 210 ° C. (10 ° C./min. The same applies to the following, and the heating temperature was raised to 210 ° C. for 30 minutes, the heating temperature was raised to 300 ° C., the heating temperature was raised to 300 ° C. for 30 minutes, the heating temperature was raised to 400 ° C., and the heating temperature was raised to 400 ° C. for 60 minutes. A polyimide substrate having a thickness of about 20 μm was formed. During the temperature increase, the film-coated substrate was not removed from the oven but heated in the oven.
Claims (8)
- その重合体鎖末端のいずれか一方又は両方にアンカー基を導入してなるポリアミック酸と、有機溶媒とを含む剥離層形成用組成物。 A composition for forming a release layer comprising a polyamic acid obtained by introducing an anchor group at one or both of the polymer chain ends, and an organic solvent.
- 前記アンカー基が、シリル基又はカルボン酸基である請求項1記載の剥離層形成用組成物。 The composition for forming a release layer according to claim 1, wherein the anchor group is a silyl group or a carboxylic acid group.
- 前記ポリアミック酸が、芳香族ジアミンを含むジアミン成分と芳香族テトラカルボン酸二無水物を含む酸二無水物成分とを反応させて得られたポリアミック酸であることを特徴とする請求項1又は2記載の剥離層形成用組成物。 The polyamic acid is a polyamic acid obtained by reacting a diamine component containing an aromatic diamine and an acid dianhydride component containing an aromatic tetracarboxylic dianhydride. The composition for peeling layer formation of description.
- 前記芳香族ジアミンが、ベンゼン核を1~5つ含む芳香族ジアミンであることを特徴とする請求項3記載の剥離層形成用組成物。 The composition for forming a release layer according to claim 3, wherein the aromatic diamine is an aromatic diamine containing 1 to 5 benzene nuclei.
- 前記芳香族テトラカルボン酸二無水物が、ベンゼン核を1~5つ含む芳香族テトラカルボン酸二無水物であることを特徴とする請求項3又は4記載の剥離層形成用組成物。 The composition for forming a release layer according to claim 3 or 4, wherein the aromatic tetracarboxylic dianhydride is an aromatic tetracarboxylic dianhydride containing 1 to 5 benzene nuclei.
- 請求項1~5のいずれか1項記載の剥離層形成用組成物を用いて形成される剥離層。 A release layer formed using the release layer forming composition according to any one of claims 1 to 5.
- 請求項6記載の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, wherein the release layer according to claim 6 is used.
- 前記樹脂基板が、ポリイミドからなる基板であることを特徴とする請求項7に記載の製造方法。 The manufacturing method according to claim 7, wherein the resin substrate is a substrate made of polyimide.
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