Classifications

• • 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
  • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
• • 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
  • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
  • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
• • 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
  • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
  • C08K5/3432—Six-membered rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
  • C08K5/3445—Five-membered rings

Definitions

• the present invention relates to a polyimide precursor solution.
• the polyimide molded body obtained from this polyimide precursor solution has excellent mechanical strength and high heat resistance.
• Molded products made of aromatic polyimide obtained from aromatic tetracarboxylic dianhydride and aromatic diamine are excellent in heat resistance, mechanical strength, electrical properties, solvent resistance, etc. Widely used in aircraft and aircraft fields. Since this aromatic polyimide has poor solubility, the polyamic acid that is a polyimide precursor is usually NMP (N-methyl-2-pyrrolidone), DMF (N, N-dimethylformamide), DMAc (N, N-dimethyl).
• a solution dissolved in an amide solvent such as acetamide) is applied onto the surface of the base material and then cured (imidized) at a high temperature to obtain a polyimide molded body such as a film or a belt.
• the amide solvent is used as a solvent for the polyamic acid solution, the amide solvent is released into the atmosphere during the molding of the polyimide, so there is a point that should be improved from the viewpoint of environmental compatibility.
• Patent Documents 1 to 6 propose polyimide precursor solutions obtained by dissolving a salt of a polyamic acid and a basic compound in water that does not substantially contain an organic solvent.
• Patent Documents 1 to 6 a polyimide precursor solution containing a high concentration of water has a high surface tension inherent to water, and therefore has a leveling property when applied to a substrate surface and molded. This is not sufficient, and there has been a problem that a film repelling phenomenon occurs and thickness unevenness is likely to occur. There was also a problem with storage stability.
• Patent Documents 7 and 8 are obtained by reacting a tetracarboxylic acid component and a diamine component in the presence of a strongly basic compound such as triethylamine or triethylenediamine using a solvent containing a specific alcohol as a reaction solvent.
• a polyimide precursor solution is proposed.
• an alcohol mixed with a strongly basic compound such as triethylamine or triethylenediamine is used as a polymerization solvent, it is difficult to obtain a polyimide precursor having a high polymerization degree, and there is also a problem in storage stability.
• JP-A-8-59832 JP 2002-226582 A International Publication No. 2012/8543 International Publication No. 2013/35806 International Publication No. 2013/105610 JP 2013-144750 A JP 2013-144751 A JP 2014-31445 A
• the present invention solves the above-described problems, and can produce a polyimide molded body having excellent mechanical strength, is excellent in environmental compatibility, and has good storage stability and leveling properties.
• the purpose is to provide.
• the present invention has the following purpose. 1) A polyimide precursor solution obtained by dissolving a salt of a polyamic acid and a weakly basic compound having an acid dissociation constant (pKa) of 8.5 or less and 4.5 or more in a solvent containing a polyhydric alcohol. 2) The said polyimide precursor solution whose solvent containing a polyhydric alcohol is a mixed solvent of a polyhydric alcohol and water. 3) The said polyimide precursor solution whose mixed solvent shows water content of less than 70 mass%. 4) The polyimide precursor solution using an isolated solid polyamic acid as the polyamic acid.
• pKa acid dissociation constant
• the polyimide precursor solution of the present invention does not use an amide solvent, it is excellent in environmental compatibility, has excellent storage stability and coating leveling, and uses a relatively high boiling point solvent such as a polyhydric alcohol. Therefore, process control during molding becomes easy, and a coating film having a uniform thickness can be obtained. Therefore, the polyimide precursor solution of the present invention can be suitably used as a polyimide precursor solution, and a polyimide molded body having excellent characteristics can be obtained from this solution.
• the polyimide precursor in the present invention is an aromatic polyimide precursor and is a homopolymer or copolymer of polyamic acid having a structural unit represented by the general formula (1).
• the polyimide obtained from this polyimide precursor is preferably a non-thermoplastic polyimide, and its glass transition temperature is preferably 250 ° C. or higher.
• R represents a tetravalent aromatic residue containing at least one carbon 6-membered ring, and each of the tetravalent divalent groups forms a pair, and each pair of divalent groups is adjacent to the carbon 6-membered ring. Provided by carbon atoms.
• R ′ represents a divalent aromatic residue having 1 to 4 carbon 6-membered rings.
• the polyamic acid can be obtained by reacting a tetracarboxylic acid component with a diamine component.
• the tetracarboxylic acid component is a tetracarboxylic acid having an aromatic ring (tetracarboxylic acid, dianhydride or esterified product thereof), specifically, for example, pyromellitic acid, 3, 3 ′, 4 , 4′-biphenyltetracarboxylic acids, 2,3,3 ′, 4′-biphenyltetracarboxylic acids, 2,2 ′, 3,3′-biphenyltetracarboxylic acids, 4,4′-oxydiphthalic acids, 3,3 ', 4,4'-benzophenonetetracarboxylic acids, 3,3', 4,4'-diphenylsulfonetetracarboxylic acids, p-terphenyltetracarboxylic acids, m-terphenyltetracarboxylic acids, etc., and mixtures thereof Can be mentioned.
• pyromellitic acid 3, 3 ′, 4 , 4′-
• pyromellitic acids 3,3 ′, 4,4′-biphenyltetracarboxylic acids, 3,3 ′, 4,4′-benzophenone tetracarboxylic acids, 4,4′-oxydiphthalic acids, and their Mixtures are preferred.
• the diamine component is an aromatic diamine.
• p-phenylenediamine p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, and mixtures thereof are preferred.
• an isolated solid polyamic acid as the polyamic acid.
• the use of an isolated solid polyamic acid means that a solid polyamic acid polymerized in advance in another system is used in the production of the polyimide precursor solution of the present invention.
• the solid polyamic acid for example, polyamic acid powder obtained by suspension polymerization of a tetracarboxylic acid component and a diamine component can be preferably used.
• the polyamic acid obtained by the suspension polymerization method can be obtained, for example, by a method described in Japanese Patent Nos. 2951484 and 3386856.
• the tetracarboxylic acid component and the diamine component can be obtained by reacting in a poor solvent that does not dissolve the polyamic acid.
• the reaction temperature is preferably ⁇ 20 to 60 ° C., particularly preferably 0 to 30 ° C.
• the reaction product polyamic acid is not dissolved in the poor solvent but is suspended in the solvent.
• the solvent can be removed to obtain a powdery polyamic acid.
• the poor solvent means a solvent having a polyamic acid solubility of less than 1 g at 25 ° C. with respect to 100 g of the solvent.
• solvents such as ethers and ketones can be used.
• THF tetrahydrofuran
• acetone acetone
• mixtures thereof are preferably used.
• a solid polyamic acid having a high polymerization degree can be obtained, and a polyimide precursor solution having a high polymerization degree can be obtained using this.
• the content of the poor solvent in the obtained powdery polyamic acid is preferably less than 1% by mass with respect to the total mass of the powder.
• the polyimide precursor solution of the present invention has a polyamic acid and acid dissociation constant (pKa) of 8.5 or less, 4.5 or more, preferably 8.5 or less, 5.5 or more, more preferably 8.5 or less, A salt composed of 7.0 or more weakly basic compound is used as a polyimide precursor.
• the pKa of the basic compound is one of the indexes for quantitatively expressing the strength of the base, and is the value of the acid dissociation constant of the conjugate acid of the base. That is, it is represented by the negative common logarithm of the equilibrium constant (Ka) of the dissociation reaction in which protons are released from the acid, and is obtained by performing acid-base titration at a measurement temperature of 25 ° C.
• Typical examples of weakly basic compounds having a pKa of 8.5 or less and 4.5 or more include nitrogen-containing heterocyclic compounds.
• pyridine derivatives such as pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 4-ethyl-2-methylimidazole Imidazole derivatives such as 1-methyl-4-ethylimidazole, quinoline derivatives such as quinoline and isoquinoline, and the like.
• 1,2-dimethylimidazole and 2-ethyl-4-methylimidazole are preferably used.
• the maximum value be the pKa value of the basic compound.
• the blending amount of the weakly basic compound with respect to the polyamic acid is preferably 1 to 4 mol, more preferably 1.5 to 3 mol, relative to 1 mol of the polyamic acid constituent unit. Two or more weakly basic compounds may be blended, and in that case, the total blending amount thereof may be within the above range.
• the polyimide precursor solution of the present invention can be obtained by adding a solvent containing a weak basic compound and a polyhydric alcohol to the polyamic acid and dissolving it.
• the polyhydric alcohol refers to an organic compound having two or more alcoholic hydroxyl groups in one molecule.
• polyhydric alcohol examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5 -Pentanediol, 2-butene-1,4-diol, 2-methyl-2,4-pentanediol, glycerin, 2-ethyl-2-hydroxymethyl-1,3-propanediol, 1,2,6-hexane
• examples include triol, diethylene glycol, dipropylene glycol, triethylene glycol, and tetraethylene glycol. Of these, ethylene glycol and diethylene glycol are preferably used.
• a solvent composed only of polyhydric alcohol can be used, or a mixed solvent of polyhydric alcohol and water can be used.
• polyhydric alcohols may be used alone or in combination.
• a mixed solvent of polyhydric alcohol and water is preferably used.
• the water content in the mixed solvent of polyhydric alcohol and water is preferably less than 70% by mass with respect to the total mass of the solvent, from the viewpoint of storage stability, coating leveling properties and film strength, and is 60% by mass. More preferably, it is less than.
• the solvent containing the polyhydric alcohol preferably does not contain a solvent other than the polyhydric alcohol and water.
• the content of the amide solvent is less than 2% by mass with respect to the total mass of the solvent from the viewpoint of environmental compatibility. It is preferable that it is less than 1% by mass.
• the amide solvent is an organic solvent having an amide bond in which a hydrogen atom may be substituted with an alkyl group.
• N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N— Examples include dimethylacetamide.
• the concentration of the polyimide precursor is preferably 0.1 to 60% by mass, more preferably 1 to 40% by mass, and still more preferably 10 to 30% by mass.
• the concentration of the polyimide precursor is calculated as a ratio of the total mass of the polyamic acid and the weak basic compound to the total mass of the polyimide precursor solution.
• the intrinsic viscosity [ ⁇ ] of the polyimide precursor is preferably 0.7 or more, more preferably 1.0 or more, and further preferably 1.2 or more.
• [ ⁇ ] is a value directly related to the molecular weight of the polymer, and is measured in a N, N-dimethylacetamide solvent at a polyimide precursor concentration of 0.5 mass% and 25 ° C.
• the polyimide precursor solution of the present invention can also be obtained by directly reacting a tetracarboxylic acid component and a diamine component in a solvent containing a polyhydric alcohol in which a weakly basic compound coexists.
• a tetracarboxylic acid component which is a monomer
• the polyimide precursor solution contains a polyhydric alcohol or water, the molecular weight of the polyamic acid may decrease due to long-term storage. Therefore, it is preferable to use a powdered polyamic acid as a solution immediately before polyimide molding. Further, the obtained polyamic acid solution preferably has a storage temperature of 10 ° C. or lower, more preferably 0 ° C. or lower.
• the polyimide precursor solution of the present invention can be processed into a film or belt by a usual method, or a film can be formed.
• a polyimide precursor solution is obtained by casting a solution of a polyimide precursor to a desired thickness on a substrate such as a glass plate by a film applicator, removing the solvent, and then imidizing by heating. .
• the solution is applied onto the target substrate, dried and heated, the substrate can be coated with polyimide.
• the polyimide precursor solution of the present invention is, for example, a known material such as a pigment, conductive carbon black and metal particles, a lithium secondary battery active material, an abrasive, a dielectric, a lubricant, and the like.
• the filler can be blended.
• other polymers and solvents such as ethers, monohydric alcohols, ketones, esters, halogenated hydrocarbons, hydrocarbons and the like can be added as long as the effects of the present invention are not impaired.
• Films and coatings produced from the polyimide precursor solution of the present invention include, for example, various electrical insulating films (heat-resistant insulating tape, heat-resistant adhesive tape, high-density magnetic recording base, capacitor, FPC, etc.), intermediate transfer belts for copying machines , Fixing belts for copying machines, electrodes for lithium secondary batteries, sliding members filled with fluororesin or graphite, structural members reinforced with glass fibers or carbon fibers, various spacers (insulating spacers for power transistors, magnetic head spacers, Power relay spacers, transformer spacers, etc.), wire / cable insulation coatings, enamel coating materials (solar cells, low temperature storage tanks, space insulation, integrated circuits, slot liners, etc.), ultrafiltration membranes, gas separation membranes, etc. It is suitably used for production.
• various electrical insulating films heat-resistant insulating tape, heat-resistant adhesive tape, high-density magnetic recording base, capacitor, FPC, etc.
• intermediate transfer belts for copying machines Fixing belts
• polyamic acid powder A was obtained from pyromellitic dianhydride (PMDA) and 4,4′-oxydianiline (ODA). That is, 21.9 g of PMDA was dissolved in 500 ml of THF and kept at 0 ° C. To this, 500 ml of THF solution of 20.0 g of ODA was gradually added and reacted at 0 ° C. for 2 hours to obtain a suspension containing polyamic acid. A polyamic acid was isolated from the suspension to obtain a polyamic acid powder. [ ⁇ ] of the polyamic acid at this time was 1.50. This is designated as polyamic acid powder A.
• PMDA pyromellitic dianhydride
• ODA 4,4′-oxydianiline
• a polyamic acid powder is formed from 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) and 4,4′-oxydianiline (ODA). Obtained. That is, 2.96 g of BPDA was suspended in 50 ml of THF and kept at 0 ° C. A solution prepared by dissolving 2.00 g of ODA in 50 ml of THF was gradually added thereto and reacted at 0 ° C. for 2 hours to obtain a suspension of polyamic acid. A polyamic acid was isolated from the suspension to obtain a polyamic acid powder. [ ⁇ ] of the polyamic acid at this time was 2.19. This is designated as polyamic acid powder B.
• BPDA 4,4′-biphenyltetracarboxylic dianhydride
• ODA 4,4′-oxydianiline
• a polyamic acid powder was obtained from 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) and p-phenylenediamine (PDA). Specifically, 8.06 g of BPDA was suspended in 60 ml of acetone and kept at room temperature (20 ° C.). A solution obtained by dissolving 2.91 g of PDA in 129 ml of acetone was gradually added thereto and reacted at room temperature for 1 hour to obtain a polyamic acid suspension. A polyamic acid was isolated from the suspension to obtain a polyamic acid powder. [ ⁇ ] of the polyamic acid at this time was 1.85. This is designated as polyamic acid powder C.
• BPDA 4,4′-biphenyltetracarboxylic dianhydride
• PDA p-phenylenediamine
• ⁇ Storage stability> When the intrinsic viscosity of the polyamic acid after the polyimide precursor solution is allowed to stand at 25 ° C. for 100 hours is measured and the rate of change is less than 10%, the storage stability is “good” and the rate of change is 10% or more. In some cases, the storage stability was determined to be “bad”.
• the polyimide precursor solution was applied on a glass plate as a base material using a film applicator, and the coating film was applied at 50 ° C. for 10 minutes, 80 ° C. for 30 minutes, 120 ° C. for 30 minutes, 200 ° C. under a nitrogen gas atmosphere.
• Heat treatment was performed at 20 ° C. for 20 minutes, 300 ° C. for 20 minutes, and then 350 ° C. for 10 minutes to form a polyimide film coating having a thickness of about 20 ⁇ m.
• the thickness of arbitrary nine places was measured. When the fluctuation range of the thickness was less than ⁇ 10% with respect to the average value, the leveling property was judged as “good”, and when the fluctuation range was ⁇ 10% or more, the leveling property was judged as “bad”.
• Example 1 25 A mixture of polyamic acid powder A and 1,2-dimethylimidazole (pKa 7.7) (1,2-dimethylimidazole is used in an amount of 2.5 moles per mole of the polyamic acid constituent unit)
• a polyimide precursor solution A-1 having a concentration of 15% by mass as a polyimide precursor was obtained by dissolving in ethylene glycol at 0 ° C. Table 1 shows the results of characterization of this precursor solution.
• Example 2 25 A mixture of polyamic acid powder B and 1,2-dimethylimidazole (pKa 7.7) (1,2-dimethylimidazole is used in an amount of 2.5 moles per mole of polyamic acid constituent unit)
• a polyimide precursor solution B-1 having a concentration of 15% by mass as a polyimide precursor was obtained by dissolving in ethylene glycol at 0 ° C. Table 1 shows the results of characterization of this precursor solution.
• Example 3 A polyimide precursor solution B-2 was obtained in the same manner as in Example 2 except that 2-ethyl-4-methylimidazole (pKa 8.3) was used as the basic compound. Table 1 shows the results of characterization of this precursor solution.
• Example 4 A polyimide precursor solution A-2 was obtained in the same manner as in Example 1 except that diethylene glycol was used as the solvent. Table 1 shows the results of characterization of this precursor solution.
• Example 5 A polyimide precursor solution B-3 was obtained in the same manner as in Example 2 except that diethylene glycol was used as the solvent. Table 1 shows the results of characterization of this precursor solution.
• a polyimide precursor solution A-5 was obtained in the same manner as in Example 1 except that triethylamine (pKa 11.8), which is a strongly basic compound, was used as the basic compound. Table 1 shows the results of characterization of these precursor solutions.
• a polyimide precursor solution A-6 was obtained in the same manner as in Example 1 except that triethylenediamine (pKa 8.8), which is a strongly basic compound, was used as the basic compound. Table 1 shows the results of characterization of these precursor solutions.
• a polyimide precursor solution B-8 was obtained in the same manner as in Example 2 except that the solvent was water. Table 1 shows the results of characterization of these precursor solutions.
• a polyimide precursor solution B-9 was obtained in the same manner as in Example 2, except that the solvent was water and the basic compound was triethylamine (pKa 11.8), which is a strongly basic compound. Table 1 shows the results of characterization of these precursor solutions.
• the polyimide precursor solution of the present invention is excellent in storage stability and leveling properties. Furthermore, it can be seen that the polyimide film obtained from this polyimide precursor solution has excellent mechanical strength. In addition, since no amide solvent is used, it is excellent in environmental compatibility.
• the polyimide precursor solution of the present invention can be suitably used for the production of an electric insulating film such as FPC, a belt for a copying machine, an electrode for a lithium secondary battery, an electric wire / cable insulating coating, and a film separation.
• an electric insulating film such as FPC
• a belt for a copying machine an electrode for a lithium secondary battery
• an electric wire / cable insulating coating an electric wire / cable insulating coating

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
• Processes Of Treating Macromolecular Substances (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=51933555

Family Applications (1)

Country Status (5)

Cited By (3)

Citations (6)

Family Cites Families (2)

• 2014
  • 2014-05-19 WO PCT/JP2014/063215 patent/WO2014189002A1/ja active Application Filing
  • 2014-05-19 CN CN201480028910.9A patent/CN105229083B/zh active Active
  • 2014-05-19 JP JP2015518234A patent/JP6433890B2/ja active Active
  • 2014-05-19 KR KR1020157032267A patent/KR20160012132A/ko not_active Application Discontinuation
  • 2014-05-20 TW TW103117592A patent/TWI642695B/zh not_active IP Right Cessation

Patent Citations (6)

Also Published As

Similar Documents

Legal Events