WO2019059393A1 - Agent de durcissement pour peinture en poudre et composition de peinture en poudre comprenant cet agent de durcissement pour peinture en poudre - Google Patents

Agent de durcissement pour peinture en poudre et composition de peinture en poudre comprenant cet agent de durcissement pour peinture en poudre Download PDF

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WO2019059393A1
WO2019059393A1 PCT/JP2018/035313 JP2018035313W WO2019059393A1 WO 2019059393 A1 WO2019059393 A1 WO 2019059393A1 JP 2018035313 W JP2018035313 W JP 2018035313W WO 2019059393 A1 WO2019059393 A1 WO 2019059393A1
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compound
curing agent
powder coating
diisocyanate
group
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Japanese (ja)
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雄大 佐々木
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Nisshinbo Chemical Inc
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Nisshinbo Chemical Inc
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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
    • C08G18/08—Processes
    • C08G18/09—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture
    • 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
    • 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
    • C08G18/83—Chemically modified polymers
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C09D201/08—Carboxyl groups
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/03—Powdery paints

Definitions

  • the present invention relates to a curing agent for powder coating and a composition for powder coating containing the curing agent for powder coating.
  • Powder coatings are attracting attention as materials with low environmental impact because they do not use organic solvents and can reuse unused materials.
  • the powder coating usually requires high-temperature baking at 180 ° C. or higher, which requires a large amount of energy.
  • Patent Document 1 proposes a resin composition for powder coating using a polyester resin and a blocked isocyanate-based curing agent.
  • Patent Document 2 proposes a powder coating composition using a carboxy group-containing polyester resin and a ⁇ -hydroxyalkylamide curing agent.
  • the resin composition for powder coating described in Patent Document 1 requires a high temperature of 150 to 180 ° C. for baking, and a large amount of volatile component is generated at the time of coating film formation, which has a problem of being environmentally undesirable. .
  • the coating film using this resin composition also had the problem that mechanical physical properties were inadequate.
  • the powder coating composition described in Patent Document 2 there is a problem that the water generated at the time of curing which is characteristic of ⁇ -hydroxyalkylamide causes pinholes in the obtained coating film.
  • the present invention has been made in view of such circumstances, and is a powder coating which is excellent in storage stability, can be baked at a low temperature, and can obtain a coating film excellent in curability and adhesion. It is an object of the present invention to provide a curing agent for powder coating and a composition for powder coating comprising the curing agent for powder coating.
  • aromatic heterocyclic compound is at least one aromatic heterocyclic compound selected from the group consisting of 3,5-dimethylpyrazole, 2-methylimidazole and 1H-imidazole Hardeners for powder coatings.
  • diisocyanate compound is an aromatic diisocyanate compound.
  • the aromatic diisocyanate compound is at least one aromatic diisocyanate compound selected from the group consisting of 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate.
  • the polycarbodiimide compound derived from the diisocyanate compound has two functional groups having reactivity with the polycarbodiimide compound derived from the aromatic diisocyanate compound and the terminal isocyanate group of the polycarbodiimide compound derived from the aromatic diisocyanate compound.
  • a compound having two or more functional groups having reactivity with the terminal isocyanate group of the polycarbodiimide compound derived from the aromatic diisocyanate compound is a polyetherpolyol, a polyesterpolyol, a polycarbonatepolyol, a castor oil-based polyol and a polybutadienepolyol
  • a composition for powder coating comprising the curing agent for powder coating according to any one of the above [1] to [8] and a carboxyl group-containing resin.
  • the powder coating composition according to the above [9] wherein the carboxyl group-containing resin is a polyester resin.
  • a curing agent for powder coating which is excellent in storage stability, can be baked at low temperature, and can obtain a coating film excellent in curability and adhesion, and a curing agent for the powder coating And a powder coating composition containing the
  • the curing agent for powder coatings of the present invention comprises a modified polycarbodiimide compound obtained by modifying a polycarbodiimide compound derived from a diisocyanate compound with an aromatic heterocyclic compound having an endocyclic secondary amine nitrogen.
  • the aromatic heterocyclic compound used for the modified polycarbodiimide compound is not particularly limited as long as it is an aromatic heterocyclic compound having an endocyclic secondary amine nitrogen.
  • the aromatic heterocyclic compound having an endocyclic secondary amine nitrogen refers to an aromatic heterocyclic compound having an amine in the heterocyclic ring.
  • the modified polycarbodiimide compound obtained by modifying the polycarbodiimide compound with an aromatic heterocyclic compound having such an endocyclic secondary amine nitrogen is for powder coatings
  • the storage stability of the composition can be improved.
  • a composition for powder coating can be prepared without reaction and gelation at the time of melt-kneading, and the dissociation initiation temperature of the aromatic heterocyclic compound having an endocyclic secondary amine nitrogen from the modified polycarbodiimide compound is If the temperature is low, the carbodiimide-modified group can be returned to a highly reactive carbodiimide group at a low temperature, so that the baking temperature can be lowered.
  • the volatile substance at the time of baking can be reduced, and the appearance of the film after baking is good without defects such as pinholes. Coating film can be obtained.
  • the aromatic heterocyclic compound having an endocyclic secondary amine nitrogen is preferably an aromatic heterocyclic compound in which the number of endocyclic nitrogens is 2 or more, more preferably substitution At least one aromatic heterocyclic compound selected from the group consisting of pyrazoles and optionally substituted imidazoles, more preferably a group consisting of 3,5-dimethylpyrazole, 2-methylimidazole and 1H-imidazole And at least one aromatic heterocyclic compound selected from
  • the aromatic heterocyclic compound having an endocyclic secondary amine nitrogen is 1H-imidazole
  • a polycarbodiimide compound derived from a diisocyanate compound having a carbodiimide group of the following formula (1) is modified with 1H-imidazole
  • the carbodiimide modified group of formula (2) is formed.
  • 1H-imidazole dissociates, it returns to the carbodiimide group of the following formula (1) having high reactivity.
  • the polycarbodiimide compound used for the said modified polycarbodiimide compound is a polycarbodiimide compound derived from a diisocyanate compound, Preferably, it is a polycarbodiimide compound derived from an aromatic diisocyanate compound.
  • the aromatic diisocyanate compound refers to an isocyanate compound in which two isocyanate groups present in the molecule are directly bonded to a carbon atom of an aromatic ring.
  • Examples of the polycarbodiimide compound derived from the diisocyanate compound include a polycarbodiimide compound derived from an aromatic diisocyanate compound and a polycarbodiimide compound derived from an aliphatic diisocyanate compound. Since the polycarbodiimide compound derived from the aromatic diisocyanate compound is superior in heat resistance to the polycarbodiimide compound derived from the aliphatic diisocyanate compound, the polycarbodiimide compound derived from the aromatic diisocyanate compound is preferable.
  • the polycarbodiimide compound derived from the diisocyanate compound has, for example, a group represented by the following general formula (3).
  • R represents a residue obtained by removing an isocyanate group from a diisocyanate compound.
  • aromatic diisocyanate compound from which the polycarbodiimide compound used for the modified polycarbodiimide compound is derived examples include 4,4′-diphenylmethane diisocyanate, 4,4′-diphenylether diisocyanate, p-phenylene diisocyanate, and m-phenylene.
  • a preferred aromatic diisocyanate compound is at least one selected from the group consisting of 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate.
  • the polycarbodiimide used in the present invention is a compound having two or more functional groups having reactivity with the polycarbodiimide compound derived from the above aromatic diisocyanate compound and the terminal isocyanate group of the polycarbodiimide compound (hereinafter referred to simply as It can be set as the copolymer with (it is also mentioned the compound which has two or more functional groups which have the reactivity with an isocyanate group).
  • Examples of the functional group possessed by the compound having two or more functional groups having reactivity with the isocyanate group include a hydroxyl group, an amino group, a carboxyl group, an acid anhydride group and the like, among which a hydroxyl group is preferable.
  • a polyol is mentioned as a compound which has two or more hydroxyl groups as a functional group which has the reactivity with an isocyanate group.
  • polyether polyol for example, polyether polyol, polyester polyol, polycarbonate polyol, polybutadiene diol, polyolefin polyol, polyurethane polyol, polyether ester polyol, polycarbonate ester polyol, polycarbonate ether polyol, castor oil based polyol, silicone diol, polyalkylene diol, 2 , 2-dimethylol propionic acid, 2,2-dimethylol butanoic acid, N, N-bishydroxyethyl glycine, N, N-bishydroxyethyl alanine, 3,4-dihydroxybutane sulfonic acid, 3,6-dihydroxy- And 2-toluenesulfonic acid.
  • At least one selected from the group consisting of polyether polyols, polyester polyols, polycarbonate polyols, castor oil-based polyols and polybutadiene polyols is preferable.
  • a polycarbodiimide copolymer containing a constituent unit derived from a compound having two or more functional groups having reactivity with an isocyanate group with respect to 100 parts by mass of a constituent unit derived from the polycarbodiimide compound derived from the aromatic diisocyanate compound The proportion is preferably 40 to 120 parts by mass, more preferably 50 to 100 parts by mass, still more preferably 60 to 100 parts by mass, still more preferably 80 to 100 parts by mass, still more preferably 90 to 99 parts by mass .
  • the polycarbodiimide compound used for the said modified polycarbodiimide compound can be manufactured by the various method which used the diisocyanate compound as the raw material.
  • a method for producing an isocyanate-terminated polycarbodiimide by decarboxylation condensation reaction of an aromatic diisocyanate compound with carbon dioxide US Pat. No. 2,941,956, JP-B-47-33279, J. Org. Chem, 28 2069-2075 (1963), Chemical Review 1981, Vol. 81, No. 4, p619-621 etc.).
  • the decarboxylation condensation reaction of the aromatic diisocyanate compound proceeds in the presence of a carbodiimidization catalyst.
  • the carbodiimidization catalyst includes, for example, 1-phenyl-2-phospholene-1-oxide, 3-methyl-1-phenyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-oxide, 3 And 3-phospholene such as 3-phospholene isomer thereof, and the like, and among these, among these, from the viewpoint of reactivity, 3-methyl-1-phenyl-2- can be mentioned. Phosphorene-1-oxide is preferred.
  • the amount of the carbodiimidization catalyst is usually 0.1 to 3.0% by mass based on the aromatic diisocyanate compound used for the carbodiimidization.
  • the decarboxylation condensation reaction of the aromatic diisocyanate compound can be carried out without a solvent or can be carried out in a solvent.
  • a solvent which can be used alicyclic ethers such as tetrahydroxyfuran, 1,3-dioxane and dioxolane; aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; chlorobenzene, dichlorobenzene, trichlorobenzene, perchlorene, trichloroethane, Halogenated hydrocarbons such as dichloroethane; ester solvents such as ethyl acetate and butyl acetate; and ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone.
  • cyclohexanone and tetrahydroxy furan are examples of these solvent.
  • the temperature in the decarboxylation condensation reaction is not particularly limited, but is preferably 40 to 200 ° C., more preferably 50 to 130 ° C.
  • the temperature is preferably 40 ° C. to the boiling point of the solvent.
  • the concentration of the aromatic diisocyanate compound is preferably 5 to 55% by mass, more preferably 5 to 40% by mass.
  • the concentration of the aromatic diisocyanate compound is 5% by mass or more, the synthesis of the polycarbodiimide does not take too much time, and when it is 55% by mass or less, gelation during the reaction can be suppressed.
  • the solid concentration in the reaction is preferably 5 to 55% by mass, more preferably 20 to 50% by mass, of the total mass of the reaction system.
  • the compounding ratio of the compound having two or more functional groups having reactivity with an isocyanate group is preferably 40 to 100 parts by mass of the polycarbodiimide compound derived from the aromatic diisocyanate compound.
  • the amount is 120 parts by mass, more preferably 50 to 100 parts by mass, still more preferably 60 to 100 parts by mass, still more preferably 80 to 100 parts by mass, still more preferably 90 to 99 parts by mass.
  • the polycarbodiimide one having a molecular weight controlled to an appropriate degree of polymerization can be used by using a compound which reacts with the terminal isocyanate group of the polycarbodiimide such as monoisocyanate.
  • a compound which reacts with the terminal isocyanate group of the polycarbodiimide such as monoisocyanate.
  • the monoisocyanate for sealing the end of the polycarbodiimide and controlling the polymerization degree in this way for example, phenyl isocyanate, p- and m-tolyl isocyanate, p-isopropylphenyl isocyanate and the like can be used. In particular, phenyl isocyanate is suitably used.
  • methanol having a hydroxyl group, isopropyl alcohol, phenol, polyethylene glycol monomethyl ether, etc .; butylamine having an amino group, diethylamine etc .; propionone having a carboxy group Compounds having an acid, benzoic acid, etc. and an acid anhydride, etc. can be used.
  • the modified polycarbodiimide compound is obtained by modifying a polycarbodiimide compound with an aromatic heterocyclic compound having an endocyclic secondary amine nitrogen.
  • modification of the polycarbodiimide compound with an aromatic heterocyclic compound having an endocyclic secondary amine nitrogen can be carried out without a solvent, for example, the polycarbodiimide compound is mixed with an organic solvent, and the endocyclic secondary amine is mixed there.
  • the compound can also be synthesized by adding an aromatic heterocyclic compound having nitrogen to an equivalent amount within the following range with respect to a carbodiimide group, and stirring and reacting.
  • the amount of addition of the aromatic heterocyclic compound having an endocyclic secondary amine nitrogen is preferably 1 to 2 equivalents with respect to 1 equivalent of the carbodiimide group, and the amount of excess aromatic heterocyclic compound is small, and at the time of heat treatment amine More preferably, it is 1 to 1.2 equivalents in view of the fact that
  • the reaction temperature for modification of the polycarbodiimide compound with the aromatic heterocyclic compound having an endocyclic secondary amine nitrogen is preferably from room temperature (about 25 ° C.) to 120 ° C. in view of reaction rate and side reaction during modification. is there.
  • the modification of the polycarbodiimide compound with the aromatic heterocyclic compound having an endocyclic secondary amine nitrogen is preferably carried out with stirring, and the reaction time varies depending on the temperature, but is preferably about 0.1 to 10 hours.
  • the content of the modified polycarbodiimide compound contained in the curing agent for powder coatings of the present invention is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass. is there.
  • the curing agent for powder coatings of the present invention may, if necessary, other conventional curing agents, such as aliphatic or aromatic amines, as long as the effects of the present invention are not impaired
  • an acid anhydride, phenol, dihydrazide, dicyandiamide, acid group-containing polyester, blocked isocyanate, dibasic acid and the like may be used in combination.
  • the curing agent for powder coatings of the present invention can cure a resin composition that undergoes a crosslinking reaction with a carbodiimide group.
  • resin compositions include, for example, carboxyl group-containing resins having a carboxyl group in the molecule.
  • Preferable carboxyl group-containing resins include, for example, polyester resins, polyurethane resins, polyamide resins, acrylic resins, vinyl acetate resins, polyolefin resins, polyimide resins, and the like, from the easiness of crosslinking reaction with carbodiimide group.
  • composition for powder coating contains the above-mentioned curing agent for powder coating and a carboxyl group-containing resin. As a result, the storage stability of the powder coating composition is improved, baking can be performed at a low temperature, and a coating film excellent in curability and adhesion can be obtained.
  • the curing agent for powder coatings used for the composition for powder coatings of the present invention is as described in the section of "Hardener for powder coatings" described above.
  • the content of the curing agent for powder coating in the composition for powder coating of the present invention is, for example, 0.5 to 1.5 equivalents, preferably 0 based on the functional group equivalent of the carboxyl group-containing resin described later. .8-1.2 equivalents.
  • the total content of the curing agent for powder coating and the carboxyl group-containing resin in the composition for powder coating is preferably 60% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more More preferably, it is 95 mass% or more, for example, 100 mass%.
  • polyester resin As a carboxyl group-containing resin used for the composition for powder coating of this invention, a polyester resin, a polyurethane resin, a polyamide resin, an acrylic resin, vinyl acetate resin, polyolefin resin, a polyimide resin etc. are mentioned, for example. Among them, polyester resins, polyurethane resins, and acrylic resins are preferable from the viewpoint of weather resistance, and polyester resins are more preferably used.
  • any additive can be blended within the range that does not inhibit the effects of the present invention.
  • a pigment, a filler, a leveling agent, surfactant, a dispersing agent, a plasticizer, an ultraviolet absorber, antioxidant etc. can be mentioned, for example.
  • composition for powder coating of the present invention a method of dry blending the curing agent for powder coating and the carboxyl group-containing resin, the curing agent for powder coating, and the carboxyl group-containing resin And the like, and then cooled and then crushed.
  • composition for powder coating of the present invention is applied to an object to be coated by a known coating method such as electrostatic coating method, fluid immersion method, spraying method, etc., it is heated to cause a crosslinking reaction, so-called baking Thus, a coating film can be formed.
  • a known coating method such as electrostatic coating method, fluid immersion method, spraying method, etc.
  • the baking temperature usually requires a high temperature of 180 ° C. or more, but can preferably be 150 ° C. or less, more preferably 140 ° C. or less by using the powder coating composition of the present invention.
  • the baking time may be, for example, in the range of 5 minutes to 2 hours, although it depends on the baking temperature, the coating thickness of the composition for powder coating, and the like.
  • Synthesis Example 2 Synthesis of Modified Polycarbodiimide Compound (b)
  • the modified poly of Synthesis Example 2 was prepared in the same manner as in Synthesis Example 1 except that 39.9 parts by mass of 1H-imidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., Cuazole SIZ) was used as the aromatic heterocyclic compound.
  • the carbodiimide compound (b) was obtained.
  • Synthesis Example 3 Synthesis of Modified Polycarbodiimide Compound (c) Modification of Synthesis Example 3 in the same manner as in Synthesis Example 1 except that 56.3 parts by mass of 3,5-dimethylpyrazole (DMP, manufactured by Nippon Finechem Co., Ltd.) was used as the aromatic heterocyclic compound in Synthesis Example 1. The polycarbodiimide compound (c) was obtained.
  • DMP 3,5-dimethylpyrazole
  • Synthesis Example 4 Synthesis of Modified Polycarbodiimide Compound (d) In Synthesis Example 1, 57.8 parts by mass of the compounded amount of polycarbonate diol, 27.4 parts by mass of the compounded amount of phenyl isocyanate, and 1.3 parts by mass of 3-methyl-1-phenyl-2-phospholene-1-oxide.
  • a modified polycarbodiimide compound (d) of Synthesis Example 4 was obtained in the same manner as in Synthesis Example 1 except that the amount was changed to 3 parts by mass and the carbodiimidization reaction time was 5 hours.
  • Synthesis Example 5 Synthesis of Modified Polycarbodiimide Compound (e) A modified polycarbodiimide compound of Synthesis Example 5 (Synthesis Example 1) except that in Synthesis Example 1, the polyol was changed to 97.9 parts by mass of polyester polyol (Polylite OD-X-2171 manufactured by DIC Corporation) got e).
  • Synthesis Example 6 Synthesis of Modified Polycarbodiimide Compound (f) In Synthesis Example 1, 96.4 parts by mass of tolylene diisocyanate as a diisocyanate compound was added to diphenylmethane diisocyanate (manufactured by Tosoh Corp., Millionate (registered trademark) MT, 4,4′-diphenylmethane diisocyanate) in polycarbonate diol A modified polycarbodiimide compound (f) of Synthesis Example 6 was obtained in the same manner as in Synthesis Example 1 except that the blending amount of 2-methylimidazole was changed to 33.5 parts by mass, and the carbodiimidization reaction time was changed to 5 hours. .
  • Synthesis Example 7 Synthesis of Modified Polycarbodiimide Compound (g) A modified polycarbodiimide compound of Synthesis Example 7 was prepared in the same manner as in Synthesis Example 1 except that 59.3 parts by mass of diisopropylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of the aromatic heterocyclic compound in Synthesis Example 1. g) got.
  • tolylene diisocyanate
  • polycarbodiimide compound (1) was not modified by the aromatic heterocyclic compound.
  • Example 1 100 parts by mass of a saturated polyester resin for powder coating (Nippon Yupika Co., Ltd., Iupicoat GV-230), 45.0 parts by mass of the modified polycarbodiimide compound (a) obtained in Synthesis Example 1 as a curing agent After melt-kneading with Toyo Seiki Co., Ltd. product at 100 ° C. for 5 minutes, it was crushed with a table-top crusher (Osaka Chemical Co., Ltd. product WONDER BLENDER) to obtain a composition for powder coating .
  • a saturated polyester resin for powder coating Nippon Yupika Co., Ltd., Iupicoat GV-230
  • a modified polycarbodiimide compound (a) obtained in Synthesis Example 1 as a curing agent After melt-kneading with Toyo Seiki Co., Ltd. product at 100 ° C. for 5 minutes, it was crushed with a table-top crusher (Osaka Chemical Co., Ltd. product WONDER BLENDER)
  • Example 2 A powder coating composition of Example 2 was obtained in the same manner as in Example 1 except that the modifying agent was changed to 43.7 parts by mass of the modified polycarbodiimide compound (b) obtained in Synthesis Example 2 as a curing agent. Obtained.
  • Example 3 A powder coating composition of Example 3 was obtained in the same manner as in Example 1 except that the modifying agent was changed to 46.4 parts by mass of the modified polycarbodiimide compound (c) obtained in Synthesis Example 3 as a curing agent. Obtained.
  • Example 4 A powder coating composition of Example 4 is obtained in the same manner as in Example 1 except that the modifying agent is changed to 35.3 parts by mass of the modified polycarbodiimide compound (d) obtained in Synthesis Example 4 as a curing agent. Obtained.
  • Example 5 A powder coating composition of Example 5 is obtained in the same manner as in Example 1 except that the modifying agent is changed to 45.3 parts by mass of the modified polycarbodiimide compound (e) obtained in Synthesis Example 5 as a curing agent. Obtained.
  • Example 6 The powder coating composition of Example 6 is obtained in the same manner as in Example 1 except that the modifying agent is changed to 52.5 parts by mass of the modified polycarbodiimide compound (f) obtained in Synthesis Example 6 as a curing agent. Obtained.
  • Comparative Example 1 A powder coating composition of Comparative Example 1 was obtained in the same manner as in Example 1 except that the polycarbodiimide compound (g) obtained in Synthesis Example 7 was changed to 37.0 parts by mass as a curing agent in Example 1.
  • the polycarbodiimide compound (g) obtained in Synthesis Example 7 was changed to 37.0 parts by mass as a curing agent in Example 1.
  • Comparative example 2 A powder coating composition of Comparative Example 1 is obtained in the same manner as in Example 2 except that the curing agent is changed to 37.0 parts by mass of the polycarbodiimide compound (1) obtained in Synthesis Example 8 in Example 1. The
  • Comparative example 3 A powder coating composition of Comparative Example 3 was obtained in the same manner as in Example 1 except that 32.9 parts by mass of the blocked isocyanate compound (manufactured by Evonik, VESTAGON B1530) was used as the curing agent. .
  • Comparative example 4 100 parts by mass of a saturated polyester resin for powder coating (Nippon YUPICA CO., LTD., UPICA COAT GV-230) was used as it is as a resin for powder coating.
  • Example 1 is the same as Example 1 except that the curing agent is changed to 7.9 parts by mass of N, N, N ', N'-tetrakis (2-hydroxyethyl) adipoamide (manufactured by Tokyo Chemical Industry Co., Ltd.). The composition for powder coating of Comparative Example 5 was obtained.
  • composition for powder coating materials of the comparative example 2 gelatinized during melt-kneading for 5 minutes on 100 degreeC conditions.
  • the results are shown in Table 2.
  • a blank indicates that there is no blending, and (-) indicates that it has not been implemented.
  • the powder coating compositions of Examples 1 to 6 are excellent in storage stability, can be baked at low temperature (150 ° C. or less), have a good appearance after baking, and have excellent curability and adhesion. It was found that an excellent coating film was obtained.
  • the composition for powder coating of Comparative Example 1 using a polycarbodiimide compound not modified with an aromatic heterocyclic compound as a curing agent was capable of baking at a low temperature, but the appearance after baking was poor Met.
  • Comparative Example 3 using a blocked isocyanate compound conventionally used as a curing agent for powder coatings Comparative Example 4 using only a powder coating resin, conventionally used as a curing agent for powder coatings
  • Comparative Example 5 using N, N, N ', N'-tetrakis (2-hydroxyethyl) adipamide the baking temperature is insufficient at 150.degree. C. or less, and the curability and adhesion of the coating film are sufficient. It was not a thing.
  • Comparative Example 5 when baked at 180 ° C. good solvent resistance was exhibited, but pinholes derived from a small amount of water generated by the curing reaction were generated, and appearance defects of the coating film after baking were generated. did.

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

L'invention concerne un agent de durcissement destiné à une peinture en poudre et comprenant un composé de polycarbodiimide modifié qui est obtenu par modification d'un composé de polycarbodiimide dérivé d'un composé diisocyanate, cette modification étant effectuée à l'aide d'un composé hétérocyclique aromatique comprenant un azote d'amine secondaire endocyclique.
PCT/JP2018/035313 2017-09-25 2018-09-25 Agent de durcissement pour peinture en poudre et composition de peinture en poudre comprenant cet agent de durcissement pour peinture en poudre Ceased WO2019059393A1 (fr)

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JP2017183827 2017-09-25
JP2017-183827 2017-09-25

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2021059835A1 (fr) * 2019-09-25 2021-04-01
JP2023151759A (ja) * 2022-04-01 2023-10-16 関西ペイント株式会社 粉体塗料

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09157588A (ja) * 1995-10-04 1997-06-17 Nisshinbo Ind Inc ウレタン系塗料用硬化剤及びポリエステル／ウレタン系塗料
JPH1135850A (ja) * 1997-05-19 1999-02-09 Nisshinbo Ind Inc 粉体塗料用硬化剤、該硬化剤を含む粉体塗料組成物及び粉体塗装
JP2004027035A (ja) * 2002-06-26 2004-01-29 Nisshinbo Ind Inc ディスクパッド用粉体塗料組成物及びそれによって塗装されたディスクパッド
JP2007138080A (ja) * 2005-11-21 2007-06-07 Nisshinbo Ind Inc 変性ポリカルボジイミド組成物及び変性ポリカルボジイミド
WO2016163284A1 (fr) * 2015-04-06 2016-10-13 日清紡ケミカル株式会社 Composé polycarbodiimide modifié, agent de durcissement, et composition de résine thermodurcissable

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09157588A (ja) * 1995-10-04 1997-06-17 Nisshinbo Ind Inc ウレタン系塗料用硬化剤及びポリエステル／ウレタン系塗料
JPH1135850A (ja) * 1997-05-19 1999-02-09 Nisshinbo Ind Inc 粉体塗料用硬化剤、該硬化剤を含む粉体塗料組成物及び粉体塗装
JP2004027035A (ja) * 2002-06-26 2004-01-29 Nisshinbo Ind Inc ディスクパッド用粉体塗料組成物及びそれによって塗装されたディスクパッド
JP2007138080A (ja) * 2005-11-21 2007-06-07 Nisshinbo Ind Inc 変性ポリカルボジイミド組成物及び変性ポリカルボジイミド
WO2016163284A1 (fr) * 2015-04-06 2016-10-13 日清紡ケミカル株式会社 Composé polycarbodiimide modifié, agent de durcissement, et composition de résine thermodurcissable

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2021059835A1 (fr) * 2019-09-25 2021-04-01
WO2021059835A1 (fr) * 2019-09-25 2021-04-01 日清紡ケミカル株式会社 Composé polycarbodiimide modifié possédant un groupe hydrophile
JP2023151759A (ja) * 2022-04-01 2023-10-16 関西ペイント株式会社 粉体塗料
JP7836217B2 (ja) 2022-04-01 2026-03-26 関西ペイント株式会社 粉体塗料

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