WO2017104461A1 - ポリアミドイミド樹脂及び塗料 - Google Patents
ポリアミドイミド樹脂及び塗料 Download PDFInfo
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- WO2017104461A1 WO2017104461A1 PCT/JP2016/086036 JP2016086036W WO2017104461A1 WO 2017104461 A1 WO2017104461 A1 WO 2017104461A1 JP 2016086036 W JP2016086036 W JP 2016086036W WO 2017104461 A1 WO2017104461 A1 WO 2017104461A1
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- polyamide
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- cyclic amine
- imide resin
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/343—Polycarboxylic acids having at least three carboxylic acid groups
- C08G18/345—Polycarboxylic acids having at least three carboxylic acid groups having three carboxylic acid 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7685—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing two or more non-condensed aromatic rings directly linked to each other
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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
- C08G73/1003—Preparatory processes
- C08G73/1035—Preparatory processes from tetracarboxylic acids or derivatives and diisocyanates
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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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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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
- C08G73/14—Polyamide-imides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
Definitions
- Embodiments of the present invention relate to a polyamide-imide resin and a paint using the resin.
- Polyamideimide resin is widely used as a coating agent for various substrates because it is excellent in heat resistance, chemical resistance and solvent resistance. For example, it is used as a varnish for enameled wire, a heat resistant paint, and the like.
- the polyamide-imide resin is obtained by reacting a diisocyanate compound with an acid component such as a tribasic acid anhydride, and the terminal isocyanate group can be blocked with a blocking agent such as alcohol, phenol, oxime, and stabilized.
- a blocking agent such as alcohol, phenol, oxime, and stabilized.
- Patent Document 1 Also known is a polyamideimide resin in which a lactam structure is added to a terminal with a blocking agent such as ⁇ -caprolactam (Patent Document 2).
- An object of an embodiment of the present invention is to provide a polyamide-imide resin capable of forming a coating film having a high elastic modulus and a paint having high storage stability using the resin.
- One embodiment of the present invention relates to a polyamide-imide resin having an isocyanate group at a terminal, and at least a part of the isocyanate group being blocked with an ether group-containing cyclic amine.
- Another embodiment relates to a paint containing the polyamideimide resin of the above embodiment and a solvent.
- Yet another embodiment relates to a method for producing a polyamideimide resin, which comprises a step of reacting a diisocyanate compound with a tribasic acid anhydride and / or a tribasic acid halide in a solvent containing an ether group-containing cyclic amine.
- the polyamide-imide resin of this embodiment provides a coating having excellent storage stability by blocking the terminal isocyanate group with an ether group-containing cyclic amine, and a coating film having a high elastic modulus using the coating. Can be formed.
- the ether group-containing cyclic amine has an advantage that it can be used as a polymerization solvent for a polyamideimide resin and a solvent for a coating material, according to the method for producing a polyamideimide resin of this embodiment, the ether group-containing cyclic amine is A polyamide-imide resin can be synthesized using a solvent containing it, and the obtained polyamide-imide resin solution can be used as it is for a paint or the like.
- the polyamideimide resin is characterized in that at least a part of the terminal isocyanate groups are blocked with an ether group-containing cyclic amine.
- the polyamideimide resin of one embodiment is a resin obtained by reacting a diisocyanate compound with a tribasic acid anhydride or tribasic acid halide as an acid component.
- each raw material compound may be used in combination of any plural kinds.
- a polyamideimide resin containing a structural unit represented by the following general formula and having an isocyanate group at the terminal can be used.
- X represents a residue obtained by removing an acid anhydride group (or acid halide group) and a carboxyl group of an acid-base acid anhydride
- R represents a residue obtained by removing an isocyanate group of diisocyanate.
- the diisocyanate compound is not particularly limited, but 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, 3,3′-diphenylmethane diisocyanate, 3,3′-dimethoxybiphenyl-4,4′-diisocyanate, paraphenylene diisocyanate, hexa
- Examples include methylene diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, and tolylene diisocyanate. From the viewpoint of reactivity, it is preferable to use 4,4'-diphenylmethane diisocyanate.
- the polyamideimide resin according to an embodiment may partially use a diamine compound.
- the diamine compound include 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, xylylenediamine, and phenylenediamine.
- the tribasic acid anhydride is not particularly limited, but preferably includes trimellitic anhydride, and the tribasic acid halide is also not particularly limited, but tribasic acid chloride is preferable, and trimellitic anhydride chloride (anhydrous anhydride). Trimellitic acid chloride) and the like. From the viewpoint of reducing the environmental load, it is preferable to use trimellitic anhydride or the like.
- the acid component in addition to the above-mentioned tribasic acid anhydride (or tribasic acid halide), saturated or unsaturated polybasic acids such as dicarboxylic acid and tetracarboxylic dianhydride are used, and the properties of the polyamideimide resin are impaired. It can be used in a range that does not exist. Although it does not specifically limit as dicarboxylic acid, A terephthalic acid, isophthalic acid, adipic acid, sebacic acid, etc. are mentioned.
- the tetracarboxylic dianhydride is not particularly limited, and examples thereof include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, and biphenyltetracarboxylic dianhydride. These may be used alone or in any combination of a plurality of types.
- the total amount of carboxylic acids other than tribasic acids is preferably used in the range of 0 to 30 mol% in the total carboxylic acid from the viewpoint of maintaining the properties of the polyamideimide resin.
- the polyamideimide resin has a structural unit represented by the following general formula (II).
- R 3 represents a residue excluding the isocyanate group of diisocyanate (or the amino group of diamine optionally used).
- the use ratio of diisocyanate and acid component is the molecular weight of the polyamideimide resin produced From the viewpoint of the degree of cross-linking, the diisocyanate compound (and optionally the diamine compound used) is preferably 0.8 to 1.1 mol, based on the total amount of 1.0 mol of the acid component, and preferably 0.95 to 1. The amount is more preferably 08 mol, and particularly preferably 1.0 to 1.08 mol.
- Polyamideimide resin may be modified by reacting polyhydric alcohol and isocyanate.
- polyhydric alcohol it is possible to use a dihydric alcohol such as ethylene glycol, diethylene glycol, triethylene glycol, or proylene glycol, or a polyhydric alcohol such as glycerin, trimethylolpropane, diglycerin, or triglycerin.
- the ether group-containing cyclic amine which is a blocking agent for the terminal isocyanate group is a heterocyclic amine containing an ether group, and the ether group is preferably a cyclic ether. Therefore, the ether group-containing cyclic amine is preferably a saturated heterocyclic compound having nitrogen and oxygen as heteroatoms.
- the ring is preferably a 4-membered ring to a 7-membered ring, more preferably a 5-membered ring or a 6-membered ring.
- a compound having a tetrahydro-1,4-oxazine (morpholine) ring, a tetrahydro-1,3-oxazine ring, a tetrahydro-1,2-oxazine ring, or an oxazolidine ring is preferable.
- These heterocyclic compounds may optionally have a substituent such as an alkyl group, a formyl group, and an acetyl group, and the substituent is preferably an N-hydrogen substitute.
- the elastic modulus of the coating film is not changed by blocking, but the blocking agent of this embodiment can increase the elastic modulus of the coating film by blocking.
- Preferred compounds include tetrahydro-1,4-oxazine (morpholine), 4-methylmorpholine, 4-ethylmorpholine, N-formylmorpholine, N-acetylmorpholine and the like. A plurality of these may be used in combination.
- the blocking with the blocking agent is not particularly limited, but it is blocked with 0.05 mol or more of an ether group-containing cyclic amine to sufficiently obtain the blocking effect with respect to 1 mol of the polyamideimide resin. From the viewpoint of ensuring the heat resistance and curability of the resin, it is preferably blocked with 0.15 mol or less of an ether group-containing cyclic amine.
- the conditions for synthesizing the polyamide-imide resin are various and cannot be generally specified, but the most typical method for reacting diisocyanate and tribasic acid anhydride is exemplified in, for example, JP-A-4-39323. .
- the blocking method is also not particularly limited, and the blocking agent may be reacted during the synthesis of the resin or may be reacted after the synthesis of the resin.
- an ether group-containing cyclic amine can be used as part or all of the polymerization solvent, as will be described later.
- Use of an ether group-containing cyclic amine as a polymerization solvent is preferred in that the resin can be synthesized and blocked in one step, and can also be used as a coating solvent as it is.
- the resin may be synthesized with no solvent or another polymerization solvent, and then the ether group-containing cyclic amine may be added and reacted.
- Other polymerization solvents are not particularly limited, and include N-methyl-2-pyrrolidone, N, N′-dimethylethyleneurea, N, N-dimethylacetamide or N, N-dimethylformamide, and ⁇ -butyrolactone. Two or more of these may be used in combination as appropriate.
- the number average molecular weight of the polyamide-imide resin is preferably 12,000 or more, more preferably 15,000 or more, from the viewpoint of ensuring the strength of the coating film.
- the number average molecular weight is preferably 30,000 or less, more preferably 25,000 or less in order to facilitate the formation of a paint when used as a paint or the like and to obtain a viscosity suitable for application.
- the number average molecular weight of the polyamide-imide resin is sampled during resin synthesis and measured using an analytical instrument such as a gel permeation chromatograph (GPC) (in the case of GPC, it is measured using a standard polystyrene calibration curve).
- GPC gel permeation chromatograph
- Polyamideimide resin can be used for various purposes.
- it is used as a binder resin for various protective and coating materials, including paints or coating agents such as heat-resistant paints and sliding part coating paints, film resins that require slipperiness, intermediate transfer belts for copying machines, etc.
- paints or coating agents such as heat-resistant paints and sliding part coating paints
- film resins that require slipperiness film resins that require slipperiness
- intermediate transfer belts for copying machines etc.
- it can be preferably used for a molded product such as an annular belt.
- the polyamideimide resin of this embodiment is blocked with a cyclic amine compound containing an ether group at the end, and this block is detached by heat.
- the reaction temperature at the time of coating film formation is preferably 250 ° C. or higher.
- the coating film is once cured at less than 250 ° C. Can be cured at 250 ° C. or higher to obtain a film with less shrinkage and excellent toughness.
- the polyamide-imide resin paint contains at least the blocked polyamide-imide resin and a solvent. This solvent is also referred to as “paint solvent”.
- the polyamide-imide resin is preferably contained in the paint in an amount of 10 to 50% by mass in order to sufficiently exert its function.
- a plurality of types of polyamide-imide resins may be used in combination, and a non-blocked polyamide-imide resin may be included in part.
- the solvent is not particularly limited as long as it dissolves or disperses the polyamideimide resin, but in one embodiment, an organic solvent is preferably used.
- Solvents that can be preferably used include, for example, polar solvents such as N-methyl-2-pyrrolidone, N, N′-dimethylformamide, 1,3-dimethylimidazolidinone, 4-morpholinecarbaldehyde, and aromatics such as xylene and toluene. Group hydrocarbons; ketones such as methyl ethyl ketone, methyl isobutyl ketone, ⁇ -butyrolactone, and ⁇ -valerolactone. These may be used in appropriate combination.
- the coating solvent preferably contains the ether group-containing cyclic amine. This is because an ether group-containing cyclic amine is added to the terminal of the polyamide-imide resin, so that a large amount of the same polarity solvent improves storage stability, and further increases crystallinity. This is because when the coating film is cured, the orientation of the polymer molecules is improved and the elastic modulus of the film is improved. From such a viewpoint, the amount of the ether group-containing cyclic amine in the coating solvent is preferably 50 to 100% by mass of the total solvent composition.
- the coating solvent is composed only of ether group-containing cyclic amine (that is, 100% by mass)
- the terminal of the polyamideimide resin and the polarity of the solvent are the same, which is most effective for improving the storage stability of the coating material and the elastic modulus of the coating film. preferable.
- the polymerization solvent used for the production of the polyamideimide resin may be used as it is, or a solvent different from the polymerization solvent may be added to adjust the viscosity appropriately. That is, in preparing the coating material, the polyamide-imide resin solution obtained by synthesizing the polyamide-imide resin can be used as it is by adding a coating solvent as required.
- the polyamide-imide resin paint can further contain a curing agent in addition to the above-mentioned polyamide-imide resin and solvent.
- a curing agent An epoxy resin (epoxy compound), a phenol resin, a melamine resin (melamine compound), an isocyanate compound etc. can be used suitably, It is preferable to use an epoxy resin (epoxy compound) especially. .
- an epoxy resin epoxy compound
- an epoxy resin epoxy compound
- a melamine resin melamine compound
- an isocyanate compound can improve the adhesiveness of a coating film more, it is preferable.
- a polyethersulfone resin, a polyimide resin, a polyamide resin, a fluororesin, or the like may be used alone or in admixture as necessary.
- the epoxy resin is not particularly limited, but triglycidyl isocyanurate, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, brominated bisphenol A type epoxy resin, biphenyl type epoxy resin, Phenol novolac type epoxy resin, cresol novolac type epoxy resin, brominated phenol novolak type epoxy resin, bisphenol A novolak type epoxy resin, naphthalene skeleton containing epoxy resin, aralkylene skeleton containing epoxy resin, biphenyl-aralkylene skeleton epoxy resin, phenol salicylaldehyde novolak Type epoxy resin, lower alkyl group substituted phenol salicylaldehyde novolac type epoxy resin, dicyclopentadiene skeleton Yes epoxy resin, glycidyl amine type epoxy resins, alicyclic epoxy resins.
- epoxy resins can be used alone or in admixture of two or more.
- the epoxy resin may be added alone and allowed to react with the polyamide-imide resin, but may be added together with a curing agent or curing accelerator of the epoxy resin so that an unreacted product of the epoxy resin does not remain after curing. .
- the melamine compound is not particularly limited, and examples thereof include a methylol group-containing compound obtained by reacting melamine with formaldehyde, paraformaldehyde or the like.
- the methylol group is preferably etherified with an alcohol having 1 to 6 carbon atoms.
- isocyanate compound examples include polyisocyanate of hexamethylene diisocyanate such as duranate, polyisocyanate synthesized from 4,4′-diphenylmethane diisocyanate, and the like.
- the mass average molecular weight of these polyisocyanates is preferably 500 to 9000, more preferably 1000 to 5000.
- Each compounding amount of the epoxy resin, isocyanate compound, and melamine compound added to the coating is 100 parts by mass of the polyamideimide resin, while ensuring the adhesion improvement effect by blending them, respectively. From the viewpoint of sufficiently exhibiting the characteristics, or in order not to cause phase separation while sufficiently curing the polyamideimide resin, it is preferably 1 to 40 parts by mass, and more preferably 5 to 15 parts by mass. .
- Other resins may be mixed with the polyamideimide resin to form a polymer alloy.
- the method for polymer alloying is not particularly limited, and a general mixing method such as a lab stirrer can be used. However, since there is a possibility of gelation depending on the time and temperature when mixing, it is preferable to complete the mixing within 2 hours at a temperature of 35 ° C. or lower.
- the polyamide-imide resin paint may further contain other optional components.
- a coating material such as a pigment, a filler, an antifoamer, antiseptic
- the surfactant is not particularly limited, but the components for forming the coating film are uniformly mixed and do not separate until the coating film is dried (no separation occurs), and many after baking. Those in which no residue remains are preferred.
- the content of the surfactant is not particularly limited, but is preferably 0.01% by mass or more in the coating material and 0.5% by mass or more in order to maintain a uniform mixed state. More preferred. On the other hand, the content of the surfactant is preferably 10% by mass or less in the paint so that a large amount of carbon remains during baking of the coating film and does not adversely affect the film forming property. It is more preferable that
- the paint preferably contains a filler as necessary in order to improve the water resistance of the coating film.
- the type of filler can be selected according to the application of the coating film in consideration of its water resistance, chemical resistance, etc., and is preferably one that does not dissolve in water.
- the filler includes metal powder, metal oxide (aluminum oxide, zinc oxide, tin oxide, titanium oxide, etc.), glass beads, glass flakes, glass particles, ceramics, silicon carbide, silicon oxide, fluoride. Calcium, carbon black, graphite, mica, barium sulfate and the like can be mentioned. These may be used alone or in combination of two or more.
- the coating method of the paint is not particularly limited, and known coating methods such as dipping coating, spray coating, and brush coating can be employed. It is preferable to dilute to an appropriate concentration by appropriately adjusting the amount of solvent according to the coating method.
- the coating film is formed by drying (preliminary drying) and curing (firing).
- the conditions for drying and curing are not particularly limited, and are preferably set as appropriate according to the heat resistance characteristics of the substrate to be used. In order to ensure the adhesion and toughness of the coating film, it is preferable to perform heating at 250 ° C. or higher.
- a method for producing a polyamideimide resin of the present embodiment is a step of reacting a diisocyanate compound with a tribasic acid anhydride and / or a tribasic acid halide in a solvent containing an ether group-containing cyclic amine. It is characterized by including.
- the raw material compound to be used is as described in the section of the polyamideimide resin.
- the ether group-containing cyclic amine that is the polymerization solvent is also as described above.
- resin synthesis and isocyanate group blocking can be performed in one step.
- the ether group-containing cyclic amine is suitable as a solution polymerization solvent and a coating solvent for the polyamideimide resin, the obtained polymerization solution can be used as it is for a coating or the like.
- the content of the ether group-containing cyclic amine in the polymerization solvent is preferably 50% by mass or more. In that case, the resin solution after polymerization can be preferably used as it is as a paint.
- 3-alkyl-2-oxazolidinone may be used alone, or may be used by mixing with other polar solvents.
- the polymerization solvent that can be used in combination include N-methyl-2-pyrrolidone, N, N′-dimethylethyleneurea, N, N-dimethylacetamide or N, N-dimethylformamide, and ⁇ -butyrolactone. Two or more species may be used in appropriate combination.
- the reaction temperature is not particularly limited, and may be set as appropriate according to the boiling point of the polymerization solvent to be used.
- the reaction is preferably performed at a temperature of 100 to 180 ° C.
- the polymerization reaction is preferably performed in an atmosphere such as nitrogen in order to reduce the influence of moisture in the air.
- the reaction of the acid component and the diisocyanate component can be performed, for example, by the following procedure.
- (1) A method in which an acid component and a diisocyanate component are used at a time and reacted to synthesize a polyamideimide resin.
- (2) After reacting an acid component with an excess amount of a diisocyanate component to synthesize an amide-imide oligomer having an isocyanate group at the terminal, an acid component is added to react with the terminal isocyanate group to obtain a polyamide-imide resin. How to synthesize.
- the diisocyanate component After reacting the excess amount of the acid component with the diisocyanate component to synthesize an amide-imide oligomer having an acid or acid anhydride group at the terminal, the diisocyanate component is added to form the terminal acid or acid anhydride group.
- Example 1 250.3 g (1.00 mol) of 4,4′-diphenylmethane diisocyanate, 192.1 g (1.00 mol) of trimellitic anhydride, and 660 g of 4-methylmorpholine were equipped with a thermometer, a stirrer, and a condenser. The mixture was charged in a 2 liter flask, heated to 110 ° C. with stirring in a dried nitrogen stream, reacted for about 4 hours, further held for 6 hours at 160 ° C., and a number average molecular weight of 19,000. A blocked polyamideimide resin solution (solid content concentration: about 40% by mass) was obtained.
- the number average molecular weight of the polyamideimide resin was measured under the following conditions.
- GPC model Hitachi L6000 Detector: Hitachi L4000 type UV Wavelength: 270nm
- Data processor ATT 8
- Solvent: DMF / THF 1/1 (liter) + phosphoric acid 0.06M + lithium bromide 0.06M
- Injection volume 5 ⁇ l Pressure: 49 kgf / cm 2 (4.8 ⁇ 10 6 Pa)
- Flow rate 1.0 ml / min
- Example 4 254 g (1.02 mol) of 4,4'-diphenylmethane diisocyanate, 192.1 g (1.0 mol) of trimellitic anhydride, and 660 g of N-formylmorpholine were equipped with a thermometer, a stirrer, and a condenser. The mixture was charged into a 2 liter flask, heated to 110 ° C. with stirring in a dry nitrogen stream, reacted for about 4 hours, further maintained at 160 ° C. for 4 hours, and a number average molecular weight of 23,000. A blocked polyamideimide resin solution was obtained. It was confirmed by NMR measurement that the obtained polyamideimide resin was blocked with 0.06 mol of N-formylmorpholine with respect to 1 mol of the resin.
- ⁇ Adhesion> The resin solutions obtained in the above examples and comparative examples were applied to a substrate (aluminum plate JIS H 4000, thickness 1 mm, unpolished), and then baked at 270 ° C. for 30 minutes to obtain a coating film plate having a thickness of about 20 ⁇ m.
- the initial adhesion was measured.
- the adhesion was measured according to the old JIS K 5400 (%, cross-cut residual rate). That is, using a cutter knife on the test surface, cuts of 1 ⁇ 1 mm square grids were made to form 100 grids.
- Mending tape # 810 manufactured by 3M Co., Ltd.
- the peel test was performed 5 times, and the number of cells was counted each time.
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
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Abstract
Description
本発明の実施形態は、高弾性率の塗膜を形成可能なポリアミドイミド樹脂と、該樹脂を用いた貯蔵安定性の高い塗料を提供することを課題とする。
本発明の一実施形態は、末端にイソシアネート基を有し、該イソシアネート基の少なくとも一部が、エーテル基含有環状アミンでブロックされた、ポリアミドイミド樹脂に関する。
1.ポリアミドイミド樹脂
ポリアミドイミド樹脂は、末端のイソシアネート基の少なくとも一部が、エーテル基含有環状アミンでブロックされていることを特徴とする。
一実施形態のポリアミドイミド樹脂は、ジイソシアネート化合物と、酸成分としての三塩基酸無水物又は三塩基酸ハライドとを反応させて得られる樹脂である。ここで、各原料化合物は、各々、任意に複数種を組み合わせて使用してもよい。
ジカルボン酸としては、特に限定されないが、テレフタル酸、イソフタル酸、アジピン酸、及びセバシン酸等が挙げられる。テトラカルボン酸二無水物としては、特に限定されないが、ピロメリット酸二無水物、ベンゾフェノンテトラカルボン酸二無水物、及びビフェニルテトラカルボン酸二無水物等が挙げられる。これらは、単独で用いられるほか、複数種を任意の組み合わせで使用してもよい。
三塩基酸以外のカルボン酸(ジカルボン酸とテトラカルボン酸)の総量は、ポリアミドイミド樹脂の特性を保つ観点から、全カルボン酸中に0~30モル%の範囲で使用されるのが好ましい。
環は、4員環~7員環であることが好ましく、5員環又は6員環であることがより好ましい。
より詳細には、テトラヒドロ-1,4-オキサジン(モルホリン)環、テトラヒドロ-1,3-オキサジン環、テトラヒドロ-1,2-オキサジン環、又はオキサゾリジン環を有する化合物であることが好ましい。これらの複素環化合物は、アルキル基、ホルミル基、アセチル基等の置換基を任意に有していても良く、置換基は、N原子の水素の置換体であることが好ましい。
従来のブロック剤では、ブロッキングにより塗膜の弾性率に変化を与えないが、本実施形態のブロック剤は、ブロッキングにより塗膜の弾性率を高めることができる。
ブロック剤を樹脂の合成中に反応させるときは、後述するとおり、エーテル基含有環状アミンを重合溶媒の一部又は全部として用いることができる。重合溶媒としてエーテル基含有環状アミンを用いることにより、樹脂の合成とブロック化を一段階で行うことができ、かつ、塗料の溶媒としてもそのまま使用することができる点で好ましい。
ポリアミドイミド樹脂塗料は、上記ブロック化されたポリアミドイミド樹脂と、溶媒とを少なくとも含む。この溶媒を、「塗料溶媒」とも記す。
ポリアミドイミド樹脂は、その機能を十分に発揮させるために、塗料中に10~50質量%含まれることが好ましい。複数種のポリアミドイミド樹脂を組み合わせて使用してもよく、ブロック化されていないポリアミドイミド樹脂を一部に含んでいてもよい。
溶媒は、ポリアミドイミド樹脂を溶解又は分散させるものであれば、特に限定はされないが、一実施形態においては有機溶媒を用いることが好ましい。
好ましく使用できる溶媒としては、例えば、N-メチル-2-ピロリドン、N,N′-ジメチルホルムアミド、1,3-ジメチルイミダゾリジノン、4-モルホリンカルボアルデヒド等の極性溶媒;キシレン、トルエン等の芳香族炭化水素;メチルエチルケトン、メチルイソブチルケトン、γ-ブチロラクトン、δ-バレロラクトン等のケトン類などが挙げられる。これらを適宜組み合わせて使用してもよい。
こうした観点から、塗料溶媒中のエーテル基含有環状アミンの量は、全溶媒組成の50~100質量%であることが好ましい。塗料溶媒がエーテル基含有環状アミンのみからなる(つまり100質量%)と、ポリアミドイミド樹脂末端と溶媒の極性が同じになるため、塗料の貯蔵安定性と塗膜の弾性率向上のためには最も好ましい。
ポリアミドイミド樹脂塗料は、上記のポリアミドイミド樹脂と溶媒に加え、さらに硬化剤を含むことができる。硬化剤としては、特に限定されないが、エポキシ樹脂(エポキシ化合物)、フェノール樹脂、メラミン樹脂(メラミン化合物)、イソシアネート化合物などを適宜用いることができ、なかでもエポキシ樹脂(エポキシ化合物)を用いることが好ましい。エポキシ樹脂を配合することにより、ポリアミドイミド樹脂の熱的、機械的、電気的特性をより向上させることができる。また、エポキシ樹脂(エポキシ化合物)、メラミン樹脂(メラミン化合物)、及びイソシアネート化合物は、塗膜の密着性をより向上させることができるために好ましい。
硬化剤とは別に、必要に応じて、ポリエーテルスルホン樹脂、ポリイミド樹脂、ポリアミド樹脂、又はフッ素樹脂等を、単独で、又は混合して用いてもよい。
エポキシ樹脂は単独で添加してポリアミドイミド樹脂と反応させてもよいが、硬化後にエポキシ樹脂の未反応物が残留しにくいように、エポキシ樹脂の硬化剤又は硬化促進剤等と共に添加してもよい。
充填材の種類は、その耐水性や耐薬品性等を考慮し、塗膜の用途に応じて選択することができ、水に溶解しないものであることが好ましい。具体的には、充填材としては、金属粉、金属酸化物(酸化アルミ、酸化亜鉛、酸化スズ、酸化チタン等)、ガラスビーズ、ガラスフレーク、ガラス粒子、セラミックス、炭化珪素、酸化珪素、弗化カルシウム、カーボンブラック、グラフアイト、マイカ、及び硫酸バリウム等を挙げることができる。これらは、各々が単独で用いられるほか、複数種を組み合わせて使用してもよい。
本実施形態のポリアミドイミド樹脂の製造方法は、ジイソシアネート化合物と、三塩基酸無水物及び/又は三塩基酸ハライドとを、エーテル基含有環状アミンを含む溶媒中で反応させる工程を含むことを特徴とする。
使用する原料化合物については、上記ポリアミドイミド樹脂の項において説明したとおりである。
重合溶媒中のエーテル基含有環状アミンの含有量は、50質量%以上であることが好ましい。その場合には、重合後の樹脂溶液を、そのまま塗料として好ましく使用することもできる。
重合反応は、空気中の水分の影響を低減するため、窒素等の雰囲気下で行うことが好ましい。
(1)酸成分、及びジイソシアネート成分を一度に使用し、反応させてポリアミドイミド樹脂を合成する方法。
(2)酸成分と、ジイソシアネート成分の過剰量とを反応させて、末端にイソシアネート基を有するアミドイミドオリゴマーを合成した後、酸成分を追加して末端のイソシアネート基と反応させてポリアミドイミド樹脂を合成する方法。
(3)酸成分の過剰量と、ジイソシアネート成分を反応させて、末端に酸又は酸無水物基を有するアミドイミドオリゴマーを合成した後、ジイソシアネート成分を追加して末端の酸又は酸無水物基と反応させてポリアミドイミド樹脂を合成する方法。
4,4′-ジフェニルメタンジイソシアネート250.3g(1.00モル)、無水トリメリット酸192.1g(1.00モル)、及び4-メチルモルホリン660gを、温度計、攪拌機、及び冷却管を備えた2リットルのフラスコに仕込み、乾燥させた窒素気流中で撹拌しながら110℃に昇温して約4時間反応させ、さらに160℃に保持して6時間反応させて、数平均分子量19,000のブロック化ポリアミドイミド樹脂溶液(固形分濃度:約40質量%)を得た。得られたポリアミドイミド樹脂は、NMR測定により、樹脂1モルに対し、0.02モルの4-メチルモルホリンでブロックされていることを確認した。
NMRの測定は、Bruker社製1H-NMR装置を用い、以下の条件で行った。
基準物質:テトラメチルシラン、0ppm
溶媒:ジメチルスルホキシド-d6
周波数:400MHz
温度:23℃±3℃
また、各合成樹脂は、アセトンを用いて再沈殿させたものを試料とした。
GPC機種:日立 L6000
検出器:日立 L4000型UV
波長:270nm
データ処理機:ATT 8
カラム:Gelpack GL-S300MDT-5×2
カラムサイズ:8mmφ×300mm
溶媒:DMF/THF=1/1(リットル)+リン酸0.06M+臭化リチウム0.06M
試料濃度:5mg/1ml
注入量:5μl
圧力:49kgf/cm2(4.8×106Pa)
流量:1.0ml/min
4,4′-ジフェニルメタンジイソシアネート125.2g(0.5モル)、3,3′-ジメチル-4,4′-ジイソシアナトビフェニル132.2g(0.5モル)、無水トリメリット酸192.1g(1.0モル)、及び4-メチルモルホリン904gを、温度計、攪拌機、及び冷却管を備えた2リットルのフラスコに仕込み、乾燥させた窒素気流中で撹拌しながら110℃に昇温して約4時間反応させ、さらに160℃に保持して6時間反応させて、数平均分子量20,000のブロック化ポリアミドイミド樹脂溶液を得た。得られたポリアミドイミド樹脂は、NMR測定により、樹脂1モルに対し、0.11モルの4-メチルモルホリンでブロックされていることを確認した。
4,4′-ジフェニルメタンジイソシアネート125.2g(0.5モル)、3,3′-ジメチル-4,4′-ジイソシアナトビフェニル158.6g(0.6モル)、無水トリメリット酸192.1g(1.0モル)、及びN-ホルミルモルホリン904gを、温度計、攪拌機、及び冷却管を備えた2リットルのフラスコに仕込み、乾燥させた窒素気流中で撹拌しながら温度を110℃に昇温して約4時間反応させ、さらに160℃に保持して2時間反応させて、数平均分子量15,600のブロック化ポリアミドイミド樹脂溶液を得た。得られたポリアミドイミド樹脂は、NMR測定により、樹脂1モルに対し、0.15モルのN-ホルミルモルホリンでブロックされていることを確認した。
4,4′-ジフェニルメタンジイソシアネート257.5g(1.02モル)、無水トリメリット酸192.1g(1.0モル)、及びN-ホルミルモルホリン660gを、温度計、攪拌機、及び冷却管を備えた2リットルのフラスコに仕込み、乾燥させた窒素気流中で撹拌しながら110℃に昇温して約4時間反応させ、さらに160℃に保持して4時間反応させて、数平均分子量23,000のブロック化ポリアミドイミド樹脂溶液を得た。得られたポリアミドイミド樹脂は、NMR測定により、樹脂1モルに対し、0.06モルのN-ホルミルモルホリンでブロックされていることを確認した。
4,4′-ジフェニルメタンジイソシアネート250.3g(1.0モル)、無水トリメリット酸192.1g(1.0モル)、及びN-メチル-2-ピロリドン660gを、温度計、攪拌機、及び冷却管を備えた2リットルのフラスコに仕込み、乾燥させた窒素気流中で撹拌しながら140℃に昇温して約6時間反応させ、数平均分子量22,000のポリアミドイミド樹脂溶液を得た。
上記実施例及び比較例で得られた樹脂溶液を、基材(アルミニウム板JIS H 4000、厚み1mm、未研摩)に塗布した後、270℃で30分間焼付けて、膜厚約20μmの塗膜板を作製し、初期の密着性を測定した。
密着性は、旧JIS K 5400に準じて測定した(%、クロスカット残率)。すなわち、試験面にカッターナイフを用いて、1×1mm四方の碁盤目の切り傷を入れ、100個の碁盤目を形成した。碁盤目部分にメンディングテープ#810(スリーエム(株)製)を強く圧着させ、テープをゆっくりと引き剥がした後、碁盤目の状態を観察し、100マス中の残マス数を%で示した。剥離試験は5回行って、各回毎にマス目数を数えた。
得られた樹脂溶液を40℃で6ヶ月間放置し、貯蔵の前後で粘度を測定して、粘度変化率を調べた。粘度は、JIS C 2103 に準拠して、B型回転粘度計を用い、25℃、ローター4号、回転数12rpmで測定した。
ガラス板上に上記各樹脂溶液を塗布し、270℃で30分加熱硬化した後、剥離して、膜厚約20μm、幅10mm、長さ60mmの塗膜を作製した。
引張試験機は、(株)島津製作所製「オートグラフAGS-5kNG」を用い、チャック間長さ20mm、引張速度5mm/分の条件で引張試験を行って、引張強度、弾性率、及び伸び率を求めた。
以上の結果を、表1に示す。密着性は、5回の試験で得られた平均値を示す。
既に述べられたもの以外に、本発明の新規かつ有利な特徴から外れることなく、上記の実施形態に様々な修正や変更を加えてもよいことに注意すべきである。したがって、そのような全ての修正や変更は、添付の請求の範囲に含まれることが意図されている。
Claims (7)
- 末端にイソシアネート基を有し、該イソシアネート基の少なくとも一部が、エーテル基含有環状アミンでブロックされた、ポリアミドイミド樹脂。
- 前記ポリアミドイミド樹脂1モルに対し、0.05~0.15モルのエーテル基含有環状アミンでブロックされた、請求項1記載のポリアミドイミド樹脂。
- 数平均分子量が12,000~30,000である、請求項1又は2記載のポリアミドイミド樹脂。
- 請求項1~3のいずれか一項記載のポリアミドイミド樹脂、及び溶媒を含有する塗料。
- 前記溶媒中のエーテル基含有環状アミンの含有量が50質量%以上である、請求項4記載の塗料。
- ジイソシアネート化合物と、三塩基酸無水物及び/又は三塩基酸ハライドとを、エーテル基含有環状アミンを含む溶媒中で反応させる工程を含む、ポリアミドイミド樹脂の製造方法。
- 前記溶媒中のエーテル基含有環状アミンの含有量が50質量%以上である、請求項6記載のポリアミドイミド樹脂の製造方法。
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GB2578446A (en) * | 2018-10-26 | 2020-05-13 | Mahle Int Gmbh | Bearing material, bearing and method |
GB2578446B (en) * | 2018-10-26 | 2021-04-21 | Mahle Int Gmbh | Bearing material, bearing and method |
US11739278B2 (en) | 2018-10-26 | 2023-08-29 | Mahle International Gmbh | Bearing material, bearing and method for its manufacture |
Also Published As
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US20180320022A1 (en) | 2018-11-08 |
US11214709B2 (en) | 2022-01-04 |
JPWO2017104461A1 (ja) | 2018-09-27 |
JP6822416B2 (ja) | 2021-01-27 |
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