WO2013039029A1 - ポリイミド樹脂、これを用いた樹脂組成物および積層フィルム - Google Patents
ポリイミド樹脂、これを用いた樹脂組成物および積層フィルム Download PDFInfo
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- WO2013039029A1 WO2013039029A1 PCT/JP2012/073025 JP2012073025W WO2013039029A1 WO 2013039029 A1 WO2013039029 A1 WO 2013039029A1 JP 2012073025 W JP2012073025 W JP 2012073025W WO 2013039029 A1 WO2013039029 A1 WO 2013039029A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- 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
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
- C08G77/455—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences containing polyamide, polyesteramide or polyimide sequences
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives 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 C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2379/00—Other polymers having nitrogen, with or without oxygen or carbon only, in the main chain
- B32B2379/08—Polyimides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/202—LCD, i.e. liquid crystal displays
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2479/00—Presence of polyamine or polyimide
- C09J2479/08—Presence of polyamine or polyimide polyimide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/14—Layer or component removable to expose adhesive
- Y10T428/1476—Release layer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2839—Web or sheet containing structurally defined element or component and having an adhesive outermost layer with release or antistick coating
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2852—Adhesive compositions
- Y10T428/2896—Adhesive compositions including nitrogen containing condensation polymer [e.g., polyurethane, polyisocyanate, etc.]
Definitions
- the present invention relates to a heat-resistant adhesive. More specifically, the present invention relates to a heat-resistant pressure-sensitive adhesive that does not generate volatile matter due to decomposition of the pressure-sensitive adhesive even in a high-temperature environment, has excellent pressure-sensitive adhesive properties, and can be used as a process material when manufacturing electronic devices.
- Rubber adhesives such as natural rubber and styrene-butadiene rubber have generally been used as adhesives, but high heat resistance is required for process materials when manufacturing electronic devices.
- Acrylic resins and silicone resins have been used.
- Acrylic resins also have high transparency, so they are often used in optical materials for flat displays such as liquid crystal displays (see, for example, Patent Document 1), but they are long at temperatures of 200 ° C. or higher and even 250 ° C. or higher. When left for a long time, the acrylic resin itself is decomposed to generate volatile components, so that the heat resistance is insufficient. Silicone resins have a wide operating temperature range from low temperature to high temperature, and show higher heat resistance than acrylic resins (see, for example, Patent Document 2), but are left for a long time at temperatures of 250 ° C. or higher, or even 300 ° C. or higher. In such a case, volatile components are generated by decomposition or the like. In addition, since the silicone-based pressure-sensitive adhesive contains a low molecular weight silicone component, there is a problem that these adversely affect electronic components.
- Examples of the resin having heat resistance of 250 ° C. or higher include polyimide resin.
- a polyimide resin for use as an adhesive for example, a siloxane-based polyimide resin copolymerized with a siloxane-based diamine has been proposed for the purpose of suppressing gas generated during curing and exhibiting excellent adhesiveness.
- Patent Document 3 a polysiloxane polyimide resin having a glass transition temperature of 100 ° C. to 150 ° C. by copolymerizing a siloxane component with a siloxane component is used. It has been proposed (see, for example, Patent Document 4).
- the object of the present invention is to provide a polyimide resin having good adhesiveness at room temperature without generating volatile components due to decomposition even at a high temperature of 250 ° C. or higher, and an adhesive resin and an adhesive resin using the same It is to provide a laminated film.
- the present invention has at least an acid dianhydride residue and a diamine residue, has a glass transition temperature of 30 ° C. or lower, and the residue of the polysiloxane diamine represented by the general formula (1) as the diamine residue. It is a polyimide resin characterized by including a group.
- n is a natural number, and the average value calculated from the average molecular weight of the polysiloxane diamine is in the range of 5-30.
- R 1 and R 2 may be the same or different and each represents an alkylene group having 1 to 30 carbon atoms or a phenylene group.
- R 3 to R 6 may be the same or different and each represents an alkyl group having 1 to 30 carbon atoms, a phenyl group or a phenoxy group.
- a highly heat-resistant polyimide resin that exhibits good adhesiveness at room temperature and does not generate volatile components due to decomposition even at a high temperature of 250 ° C. or higher, and an adhesive resin and an adhesive resin laminate using the polyimide resin A film can be provided.
- the polyimide resin of the present invention can be used as an adhesive layer laminated film or an adhesive layer laminated substrate by being laminated on a heat resistant insulating film, a glass substrate or the like.
- the polyimide resin of the present invention has a glass transition temperature of 30 ° C. or lower, preferably 20 ° C. or lower.
- the glass transition temperature is 30 ° C. or lower, good adhesiveness is exhibited when a substrate serving as an adherend is pressure-bonded to an adhesive layer film formed using the polyimide resin of the present invention.
- the lower limit of the glass transition temperature is not particularly limited, but is preferably ⁇ 30 ° C. or higher, more preferably ⁇ 20 ° C. or higher.
- the glass transition temperature is ⁇ 30 ° C. or higher, it has an appropriate tackiness and, for example, can be easily peeled off after a protective film that has been subjected to a mold release treatment is laminated.
- adheresiveness means that the base material has an adhesive strength that does not peel off naturally when the adhesive layer film is pressure-bonded to the base material at a room temperature of 20 ° C. to 30 ° C. Specifically, it indicates that when the base material to be adhered is peeled off at a peeling angle of 90 degrees and 50 mm / min, it has an adhesive force of 1 g / cm or more.
- the polyimide resin of the present invention exhibits high heat resistance.
- the heat resistance in the present invention is defined by the decomposition start temperature at which volatile matter is generated by decomposition or the like.
- the preferable decomposition start temperature is 250 ° C. or higher, more preferably 300 ° C. or higher.
- the decomposition start temperature of the present invention can be measured using a thermogravimetric analyzer (TGA). The measurement method will be specifically described. A predetermined amount of polyimide resin is charged into TGA and held at 60 ° C. for 30 minutes to remove moisture absorbed by the polyimide resin. Next, the temperature is raised to 500 ° C. at 5 ° C./min. The temperature at which weight reduction starts from the obtained weight reduction curve was taken as the decomposition start temperature.
- TGA thermogravimetric analyzer
- the polyimide resin of the present invention has at least an acid dianhydride residue and a diamine residue.
- the diamine residue includes a polysiloxane diamine residue represented by the general formula (1).
- n is a natural number, and the average value calculated from the average molecular weight of the polysiloxane diamine is in the range of 5-30.
- R 1 and R 2 may be the same or different and each represents an alkylene group having 1 to 30 carbon atoms or a phenylene group.
- R 3 to R 6 may be the same or different and each represents an alkyl group having 1 to 30 carbon atoms, a phenyl group or a phenoxy group.
- Preferred examples of the alkyl group having 1 to 30 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group.
- the average molecular weight of the polysiloxane diamine can be determined by calculating the amino group equivalent by neutralizing titration of the amino group of the polysiloxane diamine and doubling the amino group equivalent. For example, a predetermined amount of polysiloxane diamine used as a sample is collected and placed in a beaker, and this is dissolved in a predetermined amount of a 1: 1 mixed solution of isopropyl alcohol (hereinafter referred to as IPA) and toluene, and this solution is stirred. The 0.1N hydrochloric acid aqueous solution was dropped while the amino group equivalent was calculated from the amount of the 0.1N hydrochloric acid aqueous solution dropped when the neutralization point was reached. A value obtained by doubling this amino group equivalent is the average molecular weight.
- IPA isopropyl alcohol
- the molecular weight is calculated from the chemical structural formula, and the relation between the numerical value of n and the molecular weight is obtained as a relational expression of a linear function. Can do.
- the average molecular weight can be obtained by applying the average molecular weight to this relational expression.
- n in the present invention represents an average value.
- n is in the range of 5-30, preferably in the range of 7-25.
- the glass transition temperature of the polyimide resin can be adjusted to 30 ° C. or lower. Further, gelation does not occur during polymerization of the polyimide resin.
- polysiloxane diamine represented by the general formula (1) examples include ⁇ , ⁇ -bis (3-aminopropyl) polydimethylsiloxane, ⁇ , ⁇ -bis (3-aminopropyl) polydiethylsiloxane, ⁇ , ⁇ , ⁇ -bis (3-aminopropyl) polydipropylsiloxane, ⁇ , ⁇ -bis (3-aminopropyl) polydibutylsiloxane, ⁇ , ⁇ -bis (3-aminopropyl) polydiphenoxysiloxane, ⁇ , ⁇ -bis (2 -Aminoethyl) polydimethylsiloxane, ⁇ , ⁇ -bis (2-aminoethyl) polydiphenoxysiloxane, ⁇ , ⁇ -bis (4-aminobutyl) polydimethylsiloxane, ⁇ , ⁇ -bis (4-aminobutyl) polydi
- the polyimide resin of the present invention preferably contains 60 mol% or more of the residue of the polysiloxane diamine represented by the general formula (1) in all diamine residues, more preferably 70 mol% or more, and 75 It is more preferably at least mol%, particularly preferably at least 80 mol%. Moreover, although there is no restriction
- the glass transition temperature of the polyimide resin can be reduced to 30 ° C. or less, and good adhesiveness at room temperature is exhibited. be able to.
- a residue of the polysiloxane diamine and an aromatic diamine residue is 1 to 40 mol%, preferably 2 to 30 mol%, based on the total diamine residues.
- an aromatic diamine represented by the general formula (2) is preferably used.
- the aromatic diamine represented by the general formula (2) it is preferable because properties such as adhesiveness and heat resistance can be achieved at a higher level.
- X represents a group selected from O, SO 2 , CO, CH 2 , C (CH 3 ) 2 and C (CF 3 ) 2 .
- R 7 to R 14 may be the same or different and are a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a hydroxyl group, a halogen, a carboxyl group, a sulfone group, a nitro group, and a cyano group.
- aromatic diamine examples include p-phenylenediamine, m-phenylenediamine, 2,5-diaminotoluene, 2,4-diaminotoluene, 3,5-diaminobenzoic acid, 2,6-diaminobenzoic acid, 2 -Methoxy-1,4-phenylenediamine, 4,4'-diaminobenzanilide, 3,4'-diaminobenzanilide, 3,3'-diaminobenzanilide, 3,3'-dimethyl-4,4'-diamino Benzanilide, 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (3-aminophenyl) fluorene, 9,9-bis (3-methyl-4-aminophenyl) fluorene, 9,9- Bis (3,5-dimethyl-4-aminophenyl) fluorene, 9,9-bis (3-methoxy-4-a
- aromatic diamines having a highly flexible structure are preferable. Specifically, 1,3-bis (3-aminophenoxy) benzene, 3,3′-diaminodiphenylsulfone, 3,3 '-Diaminodiphenyl ether and 3,3'-diaminobenzophenone are preferred, and 1,3-bis (3-aminophenoxy) benzene and 3,3'-diaminodiphenylsulfone are particularly preferred.
- the polyimide resin of the present invention preferably contains an aromatic tetracarboxylic dianhydride residue as an acid dianhydride residue.
- aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2′dimethyl-3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 5,5′dimethyl-3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic Acid dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2,3,3 ′, 4 ′ -Diphenyl
- a tetracarboxylic dianhydride having an aliphatic ring can be contained to such an extent that the heat resistance of the polyimide resin is not impaired.
- Specific examples of the tetracarboxylic dianhydride having an aliphatic ring include 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2 1,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,5-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-bicyclohexene tetracarboxylic dianhydride, 2,4,5-cyclohexanetetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- C] furan
- the molecular weight of the polyimide resin of the present invention can be adjusted by making the tetracarboxylic acid component or diamine component used in the synthesis equimolar, or by making either excessive. Either the tetracarboxylic acid component or the diamine component can be excessive, and the polymer chain terminal can be sealed with a terminal blocking agent such as an acid component or an amine component.
- a dicarboxylic acid or an anhydride thereof is preferably used as the terminal blocking agent for the acid component, and a monoamine is preferably used as the terminal blocking agent for the amine component.
- the acid equivalent of the tetracarboxylic acid component including the end-capping agent of the acid component or the amine component and the amine equivalent of the diamine component are equimolar.
- dicarboxylic acid such as benzoic acid, phthalic anhydride, tetrachlorophthalic anhydride, aniline or its anhydride, monoamine is terminated. You may add as a sealing agent.
- the molar ratio of the tetracarboxylic acid component / diamine component of the polyimide resin can be adjusted as appropriate so that the viscosity of the resin solution is in a range that can be easily used for coating or the like.
- the molar ratio of the tetracarboxylic acid component / diamine component is generally adjusted within the range of 100 to 95/100.
- the molar ratio should be adjusted within the range where the adhesive strength does not decrease. Is preferred.
- the method for synthesizing the polyimide resin of the present invention is not particularly limited.
- polyamic acid which is a precursor of the polyimide resin of the present invention
- tetracarboxylic dianhydride and diamine are stirred in an organic solvent at 0 to 100 ° C. for 1 to 100 hours to form a polyamic acid resin solution.
- the composition of the polyimide resin becomes soluble in an organic solvent, after the polyamic acid is polymerized, the temperature is raised to 120 to 300 ° C. and stirred for 1 to 100 hours to convert it to polyimide to obtain a polyimide resin solution.
- toluene, o-xylene, m-xylene, p-xylene, or the like may be added to the reaction solution, and water generated in the imidization reaction may be removed by azeotropy with these solvents.
- Solvents for synthesizing polyimide or a polyamic acid that is a polyimide precursor include, for example, amide polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, and ⁇ - Lactone polar solvents such as propiolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -caprolactone, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, ethyl cellosolve acetate, Examples thereof include methyl carbitol, ethyl carbitol, diethylene glycol dimethyl ether (diglyme), and ethyl lactate. These may be used alone or in combination of two or more.
- the concentration of the polyimide resin solution or the polyamic acid resin solution is usually preferably 10 to 80% by
- polyamic acid resin solution In the case of a polyamic acid resin solution, it is applied to a substrate such as a film or glass and dried to form a coating film, followed by heat treatment to convert it into polyimide.
- a substrate such as a film or glass
- the conversion from polyimide precursor to polyimide requires a temperature of 240 ° C. or higher, but by including an imidization catalyst in the polyamic acid resin composition, imidization at a lower temperature and in a shorter time becomes possible. .
- the imidization catalyst include pyridine, trimethylpyridine, ⁇ -picoline, quinoline, isoquinoline, imidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-phenylimidazole, 2,6-lutidine, triethylamine, m -Hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, p-hydroxyphenylacetic acid, 4-hydroxyphenylpropionic acid, p-phenolsulfonic acid, p-aminophenol, p-aminobenzoic acid, and the like. It is not limited.
- the imidization catalyst is preferably 3 parts by weight or more, and more preferably 5 parts by weight or more with respect to 100 parts by weight of the polyamic acid solid content. By containing 3 parts by weight or more of the imidization catalyst, imidization can be completed even by a lower temperature heat treatment. Further, it is preferably 10 parts by weight or less, more preferably 8 parts by weight or less. By setting the content of the imidization catalyst to 10 parts by weight or less, the amount of the imidization catalyst remaining in the polyimide resin layer after the heat treatment can be minimized, and generation of volatile matter can be suppressed.
- the resin composition of the present invention is mainly used as an adhesive resin composition.
- the resin composition contains at least the polyimide resin of the present invention.
- other resins and fillers can be added as long as the effects of the present invention are not impaired.
- Other resins include heat-resistant polymer resins such as acrylic resins, acrylonitrile resins, butadiene resins, urethane resins, polyester resins, polyamide resins, polyamideimide resins, epoxy resins, and phenol resins.
- the filler include organic or inorganic fine particles and filler. Specific examples of the fine particles and filler include silica, alumina, titanium oxide, quartz powder, magnesium carbonate, potassium carbonate, barium sulfate, mica and talc.
- surfactants silane coupling agents, and compounds with reactive functional groups such as crosslinking groups in the molecule are added for the purpose of improving properties such as adhesiveness, heat resistance, coating properties, and storage stability. May be.
- the reactive functional group include an epoxy group, an isocyanate group, a vinyl group, and an acetyl group, and a compound having two or more of these functional groups in one molecule is preferable.
- the resin composition of the present invention has a glass transition temperature of 30 ° C. or lower, preferably 20 ° C. or lower.
- the glass transition temperature is 30 ° C. or lower, good adhesiveness is exhibited when a substrate serving as an adherend is pressure-bonded to an adhesive layer film formed using the resin composition of the present invention.
- the lower limit of the glass transition temperature is not particularly limited, but is preferably ⁇ 30 ° C. or higher, more preferably ⁇ 20 ° C. or higher.
- the glass transition temperature is ⁇ 30 ° C. or higher, it has an appropriate tackiness and, for example, can be easily peeled off after a protective film that has been subjected to a mold release treatment is laminated.
- the resin composition of the present invention exhibits high heat resistance and has a decomposition start temperature of 250 ° C. or higher, preferably 300 ° C. or higher.
- the laminated film of the present invention can be used mainly as an adhesive laminated film, and can be obtained by laminating the resin composition of the present invention on one side or both sides of a heat-resistant insulating film.
- the laminated film of the present invention can also be used as an adhesive film as it is.
- a heat-resistant insulating film is peeled and it can also be used as an adhesive transfer film which transfers an adhesive layer to a glass substrate etc.
- Examples of the heat-resistant insulating film of the present invention include films made of aromatic polyimide resins, polyphenylene sulfide resins, aromatic polyamide resins, polyamideimide resins, aromatic polyester resins, etc., and aromatic polyimide resins
- a polyimide film consisting of Specific products of polyimide film include “Kapton” (registered trademark) manufactured by Toray DuPont Co., Ltd., “Upilex” (registered trademark) manufactured by Ube Industries, Ltd., and “Apical” (registered trademark) manufactured by Kaneka Corporation. ) And the like.
- the thickness of the heat-resistant insulating film is not particularly limited, but is preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, and further preferably 10 ⁇ m or more from the viewpoint of strength as a support. Further, from the viewpoint of flexibility, it is preferably 150 ⁇ m or less, more preferably 75 ⁇ m or less, and further preferably 50 ⁇ m or less.
- the resin composition coating method examples include a bar coater, a roll coater, a knife coater, a comma coater, a reverse coater, a doctor blade float coater, a gravure coater, and a slit die coater.
- the organic solvent in the resin composition is removed by heat treatment to perform imidization.
- the heat treatment temperature is 100 to 300 ° C, preferably 150 to 250 ° C.
- the heat treatment time is usually appropriately selected from 20 seconds to 30 minutes, and may be continuous or intermittent.
- the resin composition may be applied and dried on each side, or may be applied and dried on both sides simultaneously. If necessary, a release-treated film may be laminated on the coated resin composition surface.
- the thickness of the resin composition to be laminated can be appropriately selected, but is 0.1 ⁇ m to 500 ⁇ m, preferably 1 ⁇ m to 100 ⁇ m, and more preferably 2 ⁇ m to 50 ⁇ m.
- one or both surfaces of the heat-resistant insulating film may be subjected to an adhesive improvement treatment depending on the purpose.
- an adhesive improvement treatment a discharge treatment such as a normal pressure plasma treatment, a corona discharge treatment, a low temperature plasma treatment or the like is preferable.
- ⁇ Presses, roll laminators, etc. can be used to crimp other substrates to the adhesive tape.
- the pressure may be applied by applying a temperature, but it is 100 ° C. or lower, preferably 80 ° C. or lower.
- the pressure bonding is most preferably performed at a room temperature of 20 to 30 ° C.
- the pressure bonding may be performed in air or in nitrogen. Preferably in vacuum.
- a release treatment may be applied to one side or both sides of the heat-resistant insulating film depending on the purpose.
- the mold release treatment those treated by applying a silicone resin, a fluorine resin or the like are preferable.
- the resin composition layer of the laminated film is laminated and pressure-bonded to a base material such as a glass substrate.
- a press, a roll laminator, or the like can be used for the pressure bonding.
- the temperature at this time is 20 ° C. or higher and 200 ° C. or lower, preferably 180 ° C. or lower.
- the pressure bonding may be performed in air or in nitrogen. Preferably in vacuum.
- the heat-resistant insulating film is peeled off and then pressure-bonded using a press, a roll laminator or the like.
- the pressure may be applied by applying a temperature, but it is 100 ° C. or lower, preferably 80 ° C. or lower.
- the pressure bonding is most preferably performed at a room temperature of 20 to 30 ° C.
- the pressure bonding may be performed in air or in nitrogen. Preferably in vacuum.
- the resin composition may be directly applied to a glass substrate and dried.
- the coating method include spin coater, screen printing, gravure coater, slit die coater, and bar coater.
- the temperature at which weight loss starts was read from the obtained weight loss curve, and this temperature was taken as the thermal decomposition start temperature.
- Production Example 1 Polymerization of polyamic acid resin solution
- APPS2 86 g (0.1 mol), 44DAE 80.1 g (0.4 mol) together with DMAc 1285 g
- 155.1 g (0.5 mol) of ODPA was added and reacted at room temperature for 1 hour and then at 60 ° C. for 5 hours to obtain a 20 wt% polyamic acid resin solution (PA1). .
- Production Examples 2 to 11 Polymerization of polyamic acid resin solution
- PA2 to PA11 A 30% by weight polyamic acid resin solution (PA2 to PA11) was obtained in the same manner as in Production Example 1 except that the types and amounts of acid dianhydride and diamine were changed as shown in Table 1.
- Example 1 A polyamic acid resin solution (PA3) obtained in Production Example 3 is dried on a 0.7 mm-thick alkali-free glass substrate (manufactured by Corning) with a spin coater so that the thickness after drying and imidization becomes 10 ⁇ m. After adjusting and rotating, it heat-processed for 10 minutes at 120 degreeC, and after drying, it heat-processed for 10 minutes at 250 degreeC, and imidized completely, and obtained the polyimide resin laminated glass substrate.
- PA3 polyamic acid resin solution obtained in Production Example 3 is dried on a 0.7 mm-thick alkali-free glass substrate (manufactured by Corning) with a spin coater so that the thickness after drying and imidization becomes 10 ⁇ m. After adjusting and rotating, it heat-processed for 10 minutes at 120 degreeC, and after drying, it heat-processed for 10 minutes at 250 degreeC, and imidized completely, and obtained the polyimide resin laminated glass substrate.
- Examples 2-4 Except for changing the polyamic acid resin solution as shown in Table 3, the same operation as in Example 1 was performed to obtain a polyimide film laminated glass substrate.
- Comparative Examples 1 and 2 Except for changing the polyamic acid resin solution as shown in Table 3, the same operation as in Example 1 was performed to obtain a polyimide film laminated glass substrate.
- Table 3 summarizes the adhesive strength of the obtained polyimide film laminated glass substrate, the glass transition temperature of the polyimide resin, and the thermal decomposition start temperature.
- the glass transition temperature of the polyimide resin was 30 ° C. or less, and good adhesiveness was exhibited. Moreover, decomposition start temperature was 300 degreeC or more, and showed high heat resistance. In the comparative example, since the glass transition temperature was higher than 30, the adhesiveness was not expressed.
- Table 3 summarizes the adhesive strength of the obtained polyimide film laminated glass substrate, the glass transition temperature of the polyimide resin, and the thermal decomposition start temperature.
- n in the general formula (1) is 5 to 30, the glass transition temperature of the polyimide resin was 30 ° C. or less, and good adhesiveness was exhibited. Moreover, decomposition start temperature was 300 degreeC or more, and showed high heat resistance. In the comparative example, when n is less than 5, the glass transition temperature is high and does not exhibit tackiness, and when it exceeds 30, the polyamic acid resin solution is gelled.
- Table 5 summarizes the adhesive strength of the obtained polyimide film laminated glass substrate, the glass transition temperature of the polyimide resin, and the thermal decomposition start temperature.
- Example 13 A heat-resistant resin solution (PA-4) obtained in Production Example 4 was dried on a polyimide film (“Kapton” 300H manufactured by Toray DuPont Co., Ltd.) having a thickness of 100 ⁇ m and a width of 250 mm, which had been subjected to a release treatment with a silicone resin. After coating with a comma coater so that the film thickness after imidization was 15 ⁇ m, heat treatment was performed at 120 ° C. for 1 minute and then at 250 ° C. for 1 minute to obtain a polyimide resin laminated film having a polyimide resin layer on one side.
- a polyimide film (“Kapton” 300H manufactured by Toray DuPont Co., Ltd.) having a thickness of 100 ⁇ m and a width of 250 mm, which had been subjected to a release treatment with a silicone resin. After coating with a comma coater so that the film thickness after imidization was 15 ⁇ m, heat treatment was performed at 120 ° C. for
- a polyimide film (“Kapton” 150EN manufactured by Saitoray DuPont Co., Ltd.) is superimposed on the polyimide resin laminated glass substrate created by the above method, and the polyimide film is pressure-bonded using a hand roll at room temperature of 25 ° C. A glass substrate was obtained. The adhesive force of the obtained polyimide film laminated glass substrate was 11 g / cm.
- a highly heat-resistant polyimide resin that exhibits good adhesiveness at room temperature and does not generate volatile components due to decomposition even at a high temperature of 250 ° C. or higher, and an adhesive resin and an adhesive resin laminate using the polyimide resin A film can be provided.
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Abstract
Description
下記製造例1~18に記載のポリアミド酸樹脂溶液(PA1~PA18)を厚さ18μmの電解銅箔の光沢面に厚さ20μmになるようにバーコーターで塗布後、80℃で10分、150℃で10分乾燥し、さらに窒素雰囲気下250℃で10分加熱処理を行って、ポリイミドに変換し、ポリイミド積層銅箔を得た。次に得られたポリイミド積層銅箔の銅箔を塩化第2鉄溶液で全面エッチングし、ポリイミドの単膜を得た。
上記で得られたポリイミドの単膜約15mgをアルミ製標準容器に詰め、熱重量分析装置 TGA-50(島津製作所(株)製)を用いて測定した。測定条件は、60℃で30分保持した後、昇温速度5℃/分で500℃まで昇温した。
各実施例および比較例で得られたポリイミドフィルム積層ガラス基板上のポリイミドフィルムを10mm幅に切り目を入れ、10mm幅のポリイミドフィルムを TOYO BOLDWIN社製”テンシロン”UTM-4-100にて引っ張り速度50mm/分、90゜剥離で測定した。
試料となるポリシロキサン系ジアミン5gをビーカーに採取し、ここに、IPA:トルエンが1:1の混合溶液を50mL入れ溶解した。次に、京都電子工業(株)製の電位差自動測定装置AT-610を用い、0.1N塩酸水溶液を撹拌しながら滴下し、中和点となる滴下量を求めた。得られた0.1N塩酸水溶液の滴下量から下式(3)を用いて平均分子量を算出した。
2×〔10×36.5×(滴下量(g))〕/5=平均分子量 (3)
次に、用いたポリシロキサン系ジアミンがn=1であった場合およびn=10であった場合の分子量を化学構造式から計算し、nの数値と分子量の関係を一次関数の関係式として求めた。この関係式に上記平均分子量をあてはめ、nの平均値を求めた。
BPDA:3,3’,4,4’-ビフェニルテトラカルボン酸二無水物
ODPA:3,3’,4,4’-ジフェニルエーテルテトラカルボン酸二無水物
BTDA:3,3’,4,4’-ベンゾフェノンテトラカルボン酸二無水物
SiDA:1,1,3,3-テトラメチル-1,3-ビス(3-アミノプロピル)ジシロキサン(分子量:248、式(1)においてn=1)
APPS1:α,ω-ビス(3-アミノプロピル)ポリジメチルシロキサン(平均分子量:400、式(1)においてn=3)
APPS2:α,ω-ビス(3-アミノプロピル)ポリジメチルシロキサン(平均分子量:860、式(1)においてn=9)
APPS3:α,ω-ビス(3-アミノプロピル)ポリジメチルシロキサン(平均分子量:1600、式(1)においてn=19)
APPS4:α,ω-ビス(3-アミノプロピル)ポリジメチルシロキサン(平均分子量:3000、式(1)においてn=37)
APPS5:α,ω-ビス(3-アミノプロピル)ポリジメチルシロキサン(平均分子量:4400、式(1)においてn=57)
44DAE:4,4’-ジアミノジフェニルエーテル
APB:1,3-ビス(3-アミノフェノキシ)ベンゼン
33DDS:3,3’-ジアミノジフェニルスルホン
PDA:p-フェニレンジアミン
m-TB:2,2’-ジメチル-4,4’-ジアミノビフェニル
TPE-R:1,4-ビス(3-アミノフェノキシ)ベンゼン
DMAc:N,N-ジメチルアセトアミド 。
温度計、乾燥窒素導入口、温水・冷却水による加熱・冷却装置、および、攪拌装置を付した反応釜に、APPS2 86g(0.1mol)、44DAE 80.1g(0.4mol)をDMAc 1285gと共に仕込み、溶解させた後、ODPA 155.1g(0.5mol)を添加し、室温で1時間、続いて60℃で5時間反応させて、20重量%のポリアミド酸樹脂溶液(PA1)を得た。
酸二無水物、ジアミンの種類と仕込量を表1のように変えた以外は製造例1と同様の操作を行い、30重量%のポリアミド酸樹脂溶液(PA2~PA11)を得た。
酸二無水物、ジアミンの種類と仕込量を表2のように変えた以外は製造例1と同様の操作を行い、30重量%のポリアミド酸樹脂溶液(PA12~PA18)を得た。
厚さ0.7mmの無アルカリガラス基板(コーニング社製)上に、製造例3で得られたポリアミド酸樹脂溶液(PA3)を、乾燥、イミド化後の厚みが10μmになるようにスピンコーターで回転数を調整して塗布し、120℃で10分熱処理して乾燥した後、250℃で10分熱処理して完全にイミド化を行い、ポリイミド樹脂積層ガラス基板を得た。
ポリアミド酸樹脂溶液を表3のごとく変えた以外は、実施例1と同様の操作を行い、ポリイミドフィルム積層ガラス基板を得た。
ポリアミド酸樹脂溶液を表3のごとく変えた以外は、実施例1と同様の操作を行い、ポリイミドフィルム積層ガラス基板を得た。
ポリアミド酸樹脂溶液をPA-9に変えた以外は、実施例1と同様の操作を行い、ポリイミドフィルム積層ガラス基板を得た。
ポリアミド酸樹脂溶液を表4のごとく変えた以外は、実施例1と同様の操作を行い、ポリイミドフィルム積層ガラス基板を得た。
ポリアミド酸樹脂溶液(PA-10、PA-11)が重合中にゲル化したため、粘着力、ガラス転移温度、分解改組温度の測定は不可能であった。
ポリアミド酸樹脂溶液を表5のごとく変えた以外は、実施例1と同様の操作を行い、ポリイミドフィルム積層ガラス基板を得た。
シリコーン樹脂で離型処理した厚み100μm、幅250mmのポリイミドフィルム(“カプトン”300H 東レ・デュポン(株)製)に、製造例4で得られた耐熱性樹脂溶液(PA-4)を、乾燥、イミド化後の膜厚が15μmになるようにコンマコーターで塗工後、120℃で1分、続いて250℃で1分熱処理し、片面にポリイミド樹脂層を有するポリイミド樹脂積層フィルムを得た。次に、ポリイミド樹脂層上にシリコーン樹脂で離型処理した厚み38μm、幅250mmのPETフィルムを25℃でラミネートし、保護フィルム付きポリイミド樹脂積層フィルムを得た。
Claims (11)
- ジアミン残基として、一般式(1)で表されるポリシロキサン系ジアミンの残基を全ジアミン残基中60モル%以上含む請求項1記載のポリイミド樹脂。
- ジアミン残基として、さらに芳香族ジアミンの残基を全ジアミン残基中1~40モル%含む請求項1または2記載のポリイミド樹脂。
- 前記一般式(2)で表される芳香族ジアミンが、1,3-ビス(3-アミノフェノキシ)ベンゼンまたは3,3’-ジアミノジフェニルスルホンであることを特徴とする請求項4記載のポリイミド樹脂。
- 酸二無水物残基が芳香族テトラカルボン酸二無水物の残基である請求項1~5のいずれかに記載のポリイミド樹脂。
- 少なくとも請求項1~6のいずれかに記載のポリイミド樹脂を含む樹脂組成物。
- ガラス転移温度が30℃以下である請求項7記載の樹脂組成物。
- 耐熱性絶縁フィルムの少なくとも片面に、請求項7または8記載の樹脂組成物を積層した積層フィルム。
- 樹脂組成物を積層する耐熱性絶縁フィルムの表面が、離型処理されている請求項9記載の積層フィルム。
- 請求項9または10記載の積層フィルムにおいて、積層した樹脂組成物表面に、離型処理されたフィルムをさらに積層した積層フィルム。
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EP12832347.4A EP2735580A4 (en) | 2011-09-12 | 2012-09-10 | POLYIMIDE RESIN, RESIN COMPOSITION, AND LAMINATED FILM USING THE SAME |
KR20147000228A KR20140068846A (ko) | 2011-09-12 | 2012-09-10 | 폴리이미드 수지, 이것을 사용한 수지 조성물 및 적층 필름 |
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WO2016021646A1 (ja) * | 2014-08-08 | 2016-02-11 | 東レ株式会社 | 仮貼り用接着剤、接着剤層、ウエハ加工体およびこれを用いた半導体装置の製造方法、リワーク溶剤、ポリイミド共重合体、ポリイミド混合樹脂、ならびに樹脂組成物 |
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- 2012-09-10 US US14/344,227 patent/US20150017370A1/en not_active Abandoned
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Also Published As
Publication number | Publication date |
---|---|
JPWO2013039029A1 (ja) | 2015-03-26 |
KR20140068846A (ko) | 2014-06-09 |
TW201317276A (zh) | 2013-05-01 |
CN103748141B (zh) | 2016-04-20 |
JP6090161B2 (ja) | 2017-03-08 |
MY171368A (en) | 2019-10-10 |
CN103748141A (zh) | 2014-04-23 |
TWI579318B (zh) | 2017-04-21 |
US20150017370A1 (en) | 2015-01-15 |
EP2735580A4 (en) | 2015-02-25 |
EP2735580A1 (en) | 2014-05-28 |
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