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WO1999018165A1 - Composition de resine pour revetement en poudre - Google Patents

Composition de resine pour revetement en poudre Download PDF

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Publication number
WO1999018165A1
WO1999018165A1 PCT/JP1998/004444 JP9804444W WO9918165A1 WO 1999018165 A1 WO1999018165 A1 WO 1999018165A1 JP 9804444 W JP9804444 W JP 9804444W WO 9918165 A1 WO9918165 A1 WO 9918165A1
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WO
WIPO (PCT)
Prior art keywords
component
group
resin composition
weight
powder coating
Prior art date
Application number
PCT/JP1998/004444
Other languages
English (en)
Japanese (ja)
Inventor
Toshiyuki Masuda
Hirosuke Kawabata
Katsuyuki Tanaka
Original Assignee
Kaneka Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kaneka Corporation filed Critical Kaneka Corporation
Publication of WO1999018165A1 publication Critical patent/WO1999018165A1/fr

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Classifications

    • 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
    • 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
    • C09D137/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen; Coating compositions based on derivatives of such 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
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins

Definitions

  • the present invention relates to a resin composition for a powder coating. More specifically, for example, it relates to a resin composition for powder coatings that is suitably used for automobile parts, industrial machinery, steel furniture, building interior and exterior, and household electrical appliances.
  • the present invention relates to a resin composition for a powder coating material which exhibits thermosetting properties, impact resistance, mechanical strength of a coating film, etc. and extremely excellent weather resistance. Background art
  • paints mainly containing ester resins or epoxy resins by acid-epoxy crosslinking have been used for coating automotive parts, industrial machines, steel furniture, building interiors and exteriors, and home appliances.
  • the coatings are relatively inexpensive, they have the problem of extremely poor weatherability when used outdoors:
  • Polyester resins which are often used in powder coatings, have a good balance of coating properties, but do not have sufficient weather resistance. On the other hand, acrylic resin is used to improve weather resistance. The physical property balance as polyester resin cannot be obtained. Acrylic resins tend to be harder and more brittle than polyester resins, and their mechanical properties are inferior to those of polyester resins.
  • the present invention has been made in order to solve the above problems, and an object thereof is to overcome the above-mentioned drawbacks of ester resins and epoxy resins by acid-epoxy crosslinking which have been frequently used. Not only weather resistance but also mechanical properties that could not be achieved with conventional acrylic resins. It is an object of the present invention to provide a resin composition for a powder coating for a powder coating having a new cross-linking form, which can be manufactured at a lower cost and which can be manufactured at a lower cost. Disclosure of the invention
  • the present invention provides a novel resin composition having the following constitution, whereby the above object is achieved.
  • Component (A) and Z or a component (Z) or a component (D) below which is a vinyl copolymer having both a silyl group and a glycidyl group represented by the following general formula (1) in one molecule:
  • the component (E) which is an acid is an essential component
  • the component (A) or the component (B) is a silyl group represented by the following general formula (1) as a main crosslinkable group
  • the component (B) or the following component (C) has a glass transition temperature of 40 to 100 ° C., a number average molecular weight of 2000 to 2000, and the component (A) and / or Or a resin composition for powder coatings, wherein the component (D) accounts for 20% by weight or more of the whole crosslinkable polymer.
  • Component (D) A resin composition comprising the following component (B) and the following component (C)
  • Component (B) a vinyl copolymer containing a silyl group represented by the following general formula (1)
  • R ′ is at least one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 1 to 10 carbon atoms.
  • X is a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, a phenoxy group, a thioalkoxy group, an acyloxy group, an aminoxy group, a ketoximate group.
  • the component (A) is a vinyl monomer having a silyl group represented by the general formula (1): (a) 11 to 30 parts by weight of the component, a vinyl monomer having a glycidyl group 1 to 30 parts by weight of component (b), and copolymerizable vinyl monomer other than component (a) and component (b), which is 88 to 40 parts by weight of component (c) 2.
  • the component (A) or the component (B) comprises 3- (meth) acryloxypropyl trimethoxysilane, 3- (meth) acryloxypropyltrietoxysilane,
  • silyl group-containing vinyl monomers selected from the group consisting of 3- (meth) acryloxypropylmethyldimethoxysilane and 3- (meth) acryloxypropylmethylethoxysilane, 9.
  • the component (A) or the component (C) may be glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, or arylglycidyl ether.
  • One of the vinyl monomers containing a glycidyl group selected from the group consisting of, or any one of the above 1 to 9, characterized in that it is a copolymer of a mixture of two or more thereof The resin composition for powder coating according to the above.
  • R 2 is a linear or branched alkylene group having 1 to 20 carbon atoms.
  • the component (E) is used in an amount of 1 to 30 parts by weight based on 100 parts by weight of the component (A) and the component (Z) or 100 parts by weight of the component (D).
  • the resin composition for powder coating according to any one of the above.
  • the component (A) is usually a silyl group-containing vinyl monomer represented by the general formula (1), the component (a), and a glycidyl group-containing vinyl monomer (b) It is manufactured using component (c) which is a copolymerizable vinyl monomer other than component (a) and component (b).
  • one or more kinds of X can exist in the same molecule or different molecules of the component (A).
  • the component (A) can also be produced by introducing a silyl group or a glycidyl group into a vinyl copolymer which has no silyl group and / or glycidyl group, or a vinyl copolymer already possessed.
  • the component (a) which is a vinyl monomer containing a silyl group represented by the general formula (1) is not particularly limited as long as it has a silyl group represented by the general formula (1). 2 -CH S i ( ⁇ CH 3 ) 3,
  • CH 2 CHS i (CH 3 ) (0 CH, 2 ,
  • CH 2 CHS i (OC4H9) 3
  • CH CH S (OCcH l 3 ) 3
  • CH 2 C (CH: COO (CH 2 ) 3 S i (OCH 3 ) : i ,
  • CH 2 C (CH 3 ) COO (CH :):, S i (CH 3 ) (OCH : i ) 2 ,
  • CH 2 CHCOO (CH 2 ) :, S i (OC 2H 5) 3 ,
  • CH, C (CH COO (CH 2 ), S i (0 C 2 H.
  • CH 2 C (CH,) COO (CH 2 ), S i (0 CHCH .0 CH ;,) ,
  • CH 2 CHCH 2 OCO (ort-C 6 H COO (CH 2 ) 3 Si (OCH; where ort—C 6 H "is an orthophenylene group),
  • CH 2 CHCH 2 0 C 0 (ort-C 6 HJ COO (C H.) 3 S i (CH 3 ) (0 CH 3 ) 2 ,
  • CH 2 CH (CH 2 ) «S i (OCH ,,) 3 ,
  • CH 2 CHCH 2 0 (CH 2 ) 3 S i (O CH3) 3
  • CH 2 CHCH 2 OCO (CH 2 ) 10 S i ( ⁇ CH 3 ) 3
  • CH 2 CH (para -C 6 H,) S i ( ⁇ CH 3 ) 3 (where para—C 6 H 4 is a paraphenylene group),
  • CH 2 CH (para-C sHO S i (CH. (0 CH 3 ) 2 ,
  • CH, C (CH 3 ) (para -C 6 H 4 ) S i (0 CH 3 ) 3 ,
  • CH 2 C (CH 3 ) (para-C 6 H0 Si (CH 3 ) (alkoxysilyl group-containing monomer such as 0CHJ 2 ;
  • Silanol group-containing monomers such as 0 (CH 2 ) 3 Si (C Ha) (OH);
  • CH 2 C (CH 3 ) COO (CH,) i (OCOCH J : i and the like.
  • alkoxysilyl group-containing monomers are particularly preferred in terms of cost and stability.
  • 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloquinproline At least one selected from the group consisting of pill triethoxyquinsilane, 3- (meta) acrylic quinpropylmethyldimethoxysilane, and 3- (meta) acryloxypropyl propylmethyljetoxysilane, or Mixtures of two or more of these are mentioned.
  • “(meth) acryloxy” means “methacryloxy or acryloxy”. Note that the term “(meta)” used in the following also means the same notation.
  • One or more of these components (a) may be used in combination, and (A) at least one silyl group represented by the general formula (1) may be introduced into one molecule of the component.
  • the component (a) may be copolymerized.
  • the component (a) is preferably copolymerized in an amount of preferably 11 to 30 parts by weight in 100 parts by weight of the component (A). More preferably 11 to 27 parts by weight, particularly preferably 12 ⁇ 25 parts by weight is preferably copolymerized. If the amount of the component (a) is less than 11 parts by weight, the curing properties of the resin composition of the present invention, the mechanical strength, durability and weather resistance of the coating film are inferior. Above this, the storage stability of the resin decreases.
  • the vinyl monomer containing a glycidyl group as the component (b) is not particularly limited, and includes, for example, glycidyl (meth) acrylate, 2-methyldaricidyl (meth) acrylate, and arylglycidyl ether.
  • glycidyl (meth) acrylate 2-methyldaricidyl (meth) acrylate
  • arylglycidyl ether arylglycidyl ether.
  • One type selected from the group or a mixture of two or more types thereof can be mentioned.
  • component (b) may be used in combination, and preferably 100 to 30 parts by weight of component (A) obtained by using these monomers is used in an amount of 1 to 30 parts by weight. It is polymerized. More preferably, 2 to 26 parts by weight, particularly preferably 5 to 25 parts by weight, is copolymerized. If the amount of component (b) copolymerized is less than 1 part by weight, the mechanical properties of the coating film will be poor, and if it exceeds 30 parts by weight, the smoothness will be reduced.
  • the other copolymerizable vinyl monomer as the component (c) is not particularly limited, and examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate.
  • Vinyl monomers such as methacrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, and hexyl (meth) acrylate; styrene, ⁇ -methylstyrene , Chlorostyrene, 4-hydroxystyrene, vinyl toluene, and other aromatic hydrocarbon-based monomers; acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, and dianhydride Polymerizable carbon-carbon double bonds such as ⁇ , / 3-ethylenically unsaturated carboxylic acids such as crotonic acid, fumaric acid, and citraconic acid, styrenesulfonate, and vinyl
  • Macromolecules containing a tacrylyl group (above, manufactured by Toa Gosei Chemical Co., Ltd.); other vinyls such as vinyl methyl ether, vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene, and vinylimidazole. And the like.
  • the component (II) has a silyl group represented by the general formula (1) as a main crosslinkable group.
  • the number of silyl groups is preferably 50% or more, more preferably 70% or more, and more preferably 80% or more, based on the total number of crosslinkable groups. Is particularly preferred.
  • the method for producing the component (II) known polymerization methods such as bulk polymerization, suspension polymerization, and solution polymerization can be used.However, from the viewpoint of ease of synthesis, radical initiation such as a peroxide azo compound is particularly preferred. Solution polymerization using an agent is preferred.
  • Polymerization solvents used in the solution polymerization include hydrocarbons (toluene, xylene, ⁇ -hexane, cyclohexane, etc.), acetates (ethyl acetate, butyl acetate, etc.), alcohols (methanol, ethanol, isopropanol, ⁇ -butanol, etc., ethers (eg, ethyl ethyl solvent, butyl ether, cellosolve acetate), ketones (methyl ethyl ketone, ethyl acetate, ethyl acetate, diacetone alcohol, methyl isobutyl ketone) And non-reactive solvents such as acetone, etc.).
  • hydrocarbons toluene, xylene, ⁇ -hexane, cyclohexane, etc.
  • acetates ethyl acetate, butyl acetate, etc.
  • the initiator used for the solution polymerization is not particularly limited, but may be benzo peroxide.
  • Organic peroxides such as tert-butyl peroxide, 2,2'-azobisisobutyronitrile and 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile).
  • Radical initiators such as azo compounds such as 2,2'-azobis (2-cyclopropylpropionitrile) and 2,2'-azobis (2-methylbutyronitrile) are preferred.
  • a predetermined amount of the above-mentioned monomers, an initiator, a chain transfer agent, and the like are added to a polymerization solvent, polymerization is performed, and the solvent is removed under reduced pressure to obtain the component (A). Is obtained.
  • the number average molecular weight of the component (A) is from 2000 to 2000, preferably from 300 to 10000.
  • the molecular weight is less than 2000, it is difficult for the coating film to exhibit sufficient mechanical properties, and when it is more than 2000, there is a problem that the smoothness of the coating film is poor.
  • the glass transition temperature of the component (A) is from 40 to 100 ° C, preferably from 50 to 80 ° C.
  • the temperature is lower than 400 ° C, the storage stability of the powder coating material is poor.
  • the temperature is higher than 100 ° C, the smoothness of the coating film is poor.
  • the component (B) can be produced by copolymerizing the component (a) and the component (c).
  • the component (a) is preferably copolymerized in 100 parts by weight of the component (B), preferably in an amount of 1 to 30 parts by weight. More preferably 3 to 25 parts by weight, particularly preferably 5 to 2 parts by weight 5 parts by weight are preferably copolymerized. If the amount of the component (a) is less than 1 part by weight, the curing properties of the resin composition of the present invention, the mechanical strength, durability and weather resistance of the coating film are poor, and the amount exceeds 30 parts by weight. And the storage stability of the resin decreases
  • component (A) may be used in combination, and the component (A) may be copolymerized so that at least one silyl group is introduced into one molecule of the component (B). I just need.
  • component (B) can be produced by introducing a silyl group into the vinyl copolymer having no or already having a silyl group.
  • the component (B) may be a silyl group represented by the general formula (1) alone as a crosslinkable functional group, but when both a silyl group and a glycidyl group are used, a vinyl-based monomer containing a glycidyl group is used.
  • One or a mixture of two or more of the component (b) may be used, and preferably 1 to 50 parts by weight of the above component (B) is copolymerized in 100 parts by weight. More preferably, the copolymer is copolymerized in an amount of 3 to 40 parts by weight, particularly preferably 5 to 30 parts by weight.
  • the component (C) can be produced by copolymerizing the component (b) and the component (c). Furthermore, when the silyl group represented by the general formula (1) is used, the component (a) may be copolymerized.
  • the component (b) is preferably copolymerized in an amount of preferably 1 to 50 parts by weight in 100 parts by weight of the component (C). It is more preferable that the copolymerization is more preferably 3 to 40 parts by weight, particularly preferably 5 to 30 parts by weight.
  • the amount of the component (b) is less than 1 part by weight, the curing properties of the resin composition of the present invention and the mechanical strength of the coating film are poor.
  • the amount exceeds 50 parts by weight the storage stability of the resin is increased. And smoothness are reduced.
  • component (b) may be used in combination, and the component (b) is preferably used in such a manner that at least two glycidyl groups are preferably introduced into one molecule of the component (C). What is necessary is just to polymerize.
  • the component (C) can also be produced by introducing the glycidyl group into a vinyl copolymer having no or already having the glycidyl group.
  • the component (C) may be prepared by using one or a mixture of two or more types of the component (a). And preferably 100 to 30 parts by weight of the component (C). Partially copolymerized. More preferably, 2 to 26 parts by weight, particularly preferably 5 to 25 parts by weight, is copolymerized.
  • the number average molecular weight of the component (B) or the component (C) is from 2000 to 2000, preferably from 3000 to 10000.
  • the glass transition temperature of the component (B) or the component (C) is from 40 to 100 ° C, preferably from 50 to 80 ° C.
  • the temperature is lower than 40 ° C., the storage stability of the powder coating material is poor.
  • the temperature is higher than 10 ° C., the smoothness of the coating film is poor.
  • the method for producing the component (B) or the component (C) known polymerization methods such as bulk polymerization, suspension polymerization, and solution polymerization can be used as in the case of the component (A).
  • Solution polymerization using a radical initiator such as a peroxide azo compound is preferred from the viewpoint of easiness.
  • component (A) and the Z or (D) component form a siloxane bond by the action of moisture and can be crosslinked and cured.
  • other cross-linkable and curable polymers including homopolymers and copolymers, and cross-linkable groups including silyl groups, epoxy groups, and hydroxyl groups
  • epoxy resins, polyester resins, and acrylyl Resins, silicone resins and the like may be used in combination.
  • component (A) and / or component (D) may be used for the entire cross-linkable curable polymer (including component (A) and Z or (D)). It is preferable to use 20% by weight or more, preferably 30% by weight, more preferably 50% by weight, and particularly preferably 80% by weight or more.
  • the aliphatic dibasic acid as the component (E) is not particularly limited, but is preferably a compound represented by the general formula (2), and various kinds of compounds having different carbon numbers of R 2 may be used in combination. Can also. R 2 is a linear or branched alkylene group having 1 to 20 carbon atoms, preferably has 4 to 18 carbon atoms, and is preferably linear.
  • the component (E) includes, for example, adipic acid, sebacic acid, azelaic acid, dodecanoic acid, and the like. Sebacic acid and dodecanoic acid are preferable in terms of balance of physical properties such as storage stability and mechanical strength. preferable.
  • the aliphatic dibasic acid of the component (E) is preferably used in an amount of 1 to 30 parts by weight, more preferably 2 to 30 parts by weight, per 100 parts by weight of the component (A) and / or the component (D). To 25 parts by weight, particularly preferably 3 to 20 parts by weight.
  • the amount of the component (E) is less than 1 part by weight, the curability and mechanical properties of the coating film are insufficient.
  • the amount is more than 30 parts by weight, the storage stability and the smoothness are low. Decrease.
  • the ratio of the number of glycidyl groups in the component (A) and / or the component (D) to the number of carboxyl groups in the aliphatic dibasic acid in the component (E) is 1: 3 to 3 : 1. It is preferable, but the range of 1: 2 to 2: 1 is more preferable.
  • the aliphatic dibasic acid can serve as a catalyst for hydrolysis and condensation of the silyl group represented by the general formula (1), so that the crosslinking of the silyl group represented by the general formula (1) (1) Epoxy crosslinking occurs at the same time, but a curing catalyst can be added to promote crosslinking of silyl groups more smoothly.
  • any curing catalyst can be used without particular limitation as long as it promotes the hydrolysis reaction of the silyl group represented by the general formula (1) and can promptly cause a condensation reaction.
  • examples thereof include a mixture or a reaction product with a nitrogen-containing compound, phosphoric acid or phosphoric acid esters, and an organometallic compound.
  • the curing catalyst include, for example, organic sulfonic acid compounds such as dodecylbenzenesulfonic acid, para-toluenesulfonic acid, 1-naphthalenesulfonic acid, and 2-naphthalenesulfonic acid; the organic sulfonic acid compound and a nitrogen-containing compound ( For example, 1-amino-12-propanol, monoethanolamine, diethanolamine, 2- (methylamino) ethanol, 2-dimethylethanolamine, 2-amino-2-methyl-11-propanol, diisopropanol Mixtures or reactants with amines, 3-aminopropanol, 2-methylamino-2-methylpropanol, morpholine, oxazolidine, 4,4-dimethyloxazolidine, 3,4,4-trimethyloxazolidine, etc.); phosphorus Acid, monomethyl phosphite, monoethyl phos E over door, mono-butyl phosphat
  • Amines such as hexylamine, di-2-ethylhexylamine, N, N-dimethyldodecylamine, DABC ⁇ , DBU, morpholine, diisopropanoylamine; these amines and acidic phosphorus Reaction products with acid esters; Alkali compounds such as sodium hydroxide and hydroxylating hydroxide; benzyl triethylammonium chloride or bromide, tetraprammonium chloride Or quaternary ammonium salts such as bromide, and phosphonium salts; divalent tin compounds such as tin octylate and tin stearate, dibutyltin dioctarate, dibutyltin dilaurate, dibutyltin diacetate, and dibutyltin Diacetyl acetate, dibutyltin bistriethoxyquin silicate, dibut
  • organic titanate compounds and organic zirconium compounds are preferred from the viewpoint of curability during baking.
  • the amount of these curing catalysts used is 100 parts by weight of component (A) and component Z or (D).
  • the amount is preferably from 0.01 to 15 parts by weight, more preferably from 0.1 to 10 parts by weight, based on parts by weight.
  • the amount is less than 0.01 part by weight, there is no effect of promoting the crosslinking of the silyl group, and when the amount is more than 15 parts by weight, problems such as lack of storage stability and deterioration of the appearance of the coating film occur.
  • the resin composition for powder coatings may contain, if necessary, resins such as polyester, epoxy and acryl, inorganic pigments such as titanium dioxide, carbon black, iron oxide and chromium oxide, and phthalocyanine and quinacdrine resins.
  • resins such as polyester, epoxy and acryl
  • inorganic pigments such as titanium dioxide, carbon black, iron oxide and chromium oxide
  • phthalocyanine and quinacdrine resins additives
  • Additives such as organic pigments, coloring aids, spreading agents, defoamers, ultraviolet absorbers, antistatic agents, and antiblocking agents can be added.
  • the mixing ratio of these additives can be appropriately selected according to the required characteristics, and they can be mixed and used.
  • the powder coating is produced by, for example, melting and kneading the resin composition for powder coating of the present invention containing the above additives as necessary using a melt kneader such as a heating roll or a whisker. After cooling, it is prepared by grinding. Alternatively, a curing catalyst, a pigment, an additive, and the like are added to a solution after polymerization of the component (A) and / or the component (D), and the mixture is mixed to obtain a resin composition for a powder coating according to the present invention. Drying methods can also be used. The powder coating obtained in this manner is applied to a substrate by a known method such as electrostatic coating or fluid immersion coating.
  • the thickness of the coating film can be appropriately selected as required, and is usually from 20 to 200 m, preferably from 40 to 150 m. If it is less than 20 / m, it tends to cause unevenness in the coating film, and if it is more than 200 / m, there is a problem that the coating film tends to have irregularities.
  • the resulting coating material can be cured sufficiently by baking at a temperature of usually about 150 to 200 ° C for 5 minutes to 1 hour, and has properties such as weather resistance and acid resistance. Excellent cured product (coating) can be formed. When the temperature is lower than 150 ° C or shorter than 5 minutes, the coating is not sufficiently cured, and when the temperature is higher than 200 ° C or longer than 1 hour, the workability is deteriorated. In addition, there is a problem in that costs such as energy and utility costs rise.
  • composition of the present invention is used, for example, for building interiors and exteriors such as aluminum siding fins, road materials such as guardrails, and home appliances such as air conditioners and refrigerators.
  • the measurement was performed by gel permeation chromatography (GPC). Using a 600 type GPC system manufactured by Waters, the port form was used as the mobile phase, and the flow rate was 1 mL-Zmin. Column temperature was measured at 40 ° C. The number average molecular weight was calculated using polystyrene as a standard sample.
  • GPC gel permeation chromatography
  • the appearance of the coating film was visually evaluated.
  • the appearance of the coating film after irradiation for 3 hours with a sunshine weather meter was visually evaluated.
  • the evaluation was made by the cross-cut tape method according to JIS K540.
  • ⁇ Increase in gel fraction within 5%, ⁇ : 5 to 10%, ⁇ : 10 to 5%, X: 20% or more
  • a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet tube, and a dropping funnel was charged with 50 parts of toluene, and heated to 110 ° C while introducing nitrogen gas.
  • a monomer mixture containing the copolymer component (indicated by a part) was dropped at a constant rate over 5 hours from a dropping funnel. After the addition of the mixture was completed, a mixture of 0.5 part of 2,2′-azobisisobutyronitrile and 10 parts of toluene was added dropwise at a constant speed over 1 hour. After dripping, 1
  • TSMA is 3-methacryloxypropyltrimethoxysilane
  • TESMA is 3-methacryloxyquinpropyltriethoxysilane
  • MMA is methylmethacrylate
  • BA butylacrylate
  • ST is styrene.
  • GMA indicates glycidyl methacrylate
  • HEMA indicates 2-hydroxyshethyl methacrylate
  • AIBN indicates 2,2'-azobisisobutyronitrile.
  • T i 0 2 is Ishihara Sangyo Co., Ltd. dioxide Ji Yun (trade name: Tipaque CR 0), Modaflow shows the US Monsanto Co. of leveling-ring agents.)
  • ⁇ i 0 2 is Ishihara Sangyo Co., Ltd. of titanium dioxide (trade name: Thailand base one click CR 9 0), Modafu opening one shows the US Monsanto Co. of leveling agent.)
  • Comparative Examples 1-3 According to Table 4, powder coatings ( ⁇ - 21) to ( ⁇ - 23) were produced in the same manner as in the examples. Table 4 shows the results of evaluation of the performance of the coating film obtained by coating in the same manner as in the examples.
  • T i 0 2 is Ishihara Sangyo Co., Ltd. of titanium dioxide (trade name: TIPAQUE CR 9 0), block I cios ⁇ Natick door is Plock of I-Soviet Holon of Daicel Huls Co., Ltd. Diisocyanate (trade name: VES TAGON B1065), Modaflow refers to a repelling agent manufactured by Monsanto Co., USA.) Industrial applicability
  • a powder coating having a novel cross-linking form that has excellent weather resistance, acid resistance, appearance, adhesion, and mechanical strength, clears environmental problems, and can be manufactured at low cost. It is possible to provide.

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Abstract

L'invention se rapporte à une composition de résine pour revêtement en poudre comportant un copolymère de vinyle (A) portant à la fois un groupe silyle et un groupe glycidyle dans la molécule et/ou à une composition de résine (D) comportant un copolymère de vinyle (B) portant un groupe silyle spécifique et un copolymère de vinyle (C) portant un groupe glycidyle, et un diacide aliphatique en tant que composants principaux. Le composant (A) ou (B) contient le groupe silyle spécifique en tant que groupe de réticulation principal, le composant (A), (B) ou (C) possède une température de transition vitreuse comprise entre 40 °C et 100 °C et un poids moléculaire moyen en nombre compris entre 2000 et 20000, et le composant (A) et/ou (D) constitue au moins 20 % de la quantité totale des polymères réticulables. La composition de résine décrite ci-dessus ne présente pas les inconvénients des résines d'esters ou des résines époxy classiques du type à réticulation acide-époxy, et elle permet d'obtenir une matière pour revêtement en poudre ayant un nouveau type de réticulation. Cette matière peut donner un film de revêtement présentant non seulement une excellente résistance aux intempéries mais également des caractéristiques mécaniques qu'il est impossible d'obtenir avec les résines acryliques fabriquées conformément à l'art antérieur de la technique; le revêtement obtenu ne présente aucun danger pour l'environnement et peut être fabriqué à faible coût.
PCT/JP1998/004444 1997-10-02 1998-10-01 Composition de resine pour revetement en poudre WO1999018165A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP26943697 1997-10-02
JP9/269436 1997-10-02
JP2472298 1998-02-05
JP10/24722 1998-02-05

Publications (1)

Publication Number Publication Date
WO1999018165A1 true WO1999018165A1 (fr) 1999-04-15

Family

ID=26362293

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1998/004444 WO1999018165A1 (fr) 1997-10-02 1998-10-01 Composition de resine pour revetement en poudre

Country Status (1)

Country Link
WO (1) WO1999018165A1 (fr)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07509014A (ja) * 1992-07-14 1995-10-05 ゼネカ・リミテッド 粉体塗料組成物

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07509014A (ja) * 1992-07-14 1995-10-05 ゼネカ・リミテッド 粉体塗料組成物

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