WO2007132666A1 - ポリビニルアセタール粉体およびそれを用いた粉体塗料 - Google Patents
ポリビニルアセタール粉体およびそれを用いた粉体塗料 Download PDFInfo
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- WO2007132666A1 WO2007132666A1 PCT/JP2007/059082 JP2007059082W WO2007132666A1 WO 2007132666 A1 WO2007132666 A1 WO 2007132666A1 JP 2007059082 W JP2007059082 W JP 2007059082W WO 2007132666 A1 WO2007132666 A1 WO 2007132666A1
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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
- C09D129/00—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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
- C08L59/04—Copolyoxymethylenes
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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
- C09D159/00—Coating compositions based on polyacetals; Coating compositions based on derivatives of polyacetals
- C09D159/04—Copolyoxymethylenes
-
- 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
- C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; 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
- 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
- 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
- C09D5/031—Powdery paints characterised by particle size or shape
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0041—Optical brightening agents, organic pigments
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/04—Polyamides derived from alpha-amino carboxylic acids
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
Definitions
- the present invention relates to a polybulassal powder suitable for powder coatings and the like.
- the present invention also provides a powder coating containing the polyvinyl acetal powder and a pigment powder (hereinafter also referred to as a polyvinyl bi-acetal pigment-based powder coating), and the polyvinyl acetal powder and a polyamide powder.
- the present invention relates to a powder coating (hereinafter also referred to as a polybulassal polyamide-based powder coating) containing bismuth.
- powder coatings are mainly used for the purpose of protecting metal substrates from flaws and solvents.
- solvent-based paints there has been a tendency to avoid the use of solvent-based paints in order to reduce the environmental impact.
- solvent-based paints is expected to improve production speed and reduce coating costs.
- the use of powder paint is attracting attention.
- the powder coating material there is a powder coating material containing polyvinyl acetal powder.
- a powder coating material containing polyvinyl acetal powder For example, Japanese Patent Application Laid-Open No. 63-193970 discloses that 100 parts by weight of epoxy resin, which is a thermosetting resin.
- an epoxy resin powder coating containing 5 to 20 parts by weight of polybulbutyral or polybulum formal and further containing a curing agent and a filler is disclosed.
- powder coatings containing such polybulucetal generally do not always have good fluidity at the time of coating, and the impact resistance of the coating film and the thickness of the formed coating film are not necessarily good.
- the thickness uniformity (coating thickness uniformity) is not necessarily excellent.
- Powder coatings containing polyvinyl acetal powder include powder coating forms using a polybulacetal powder and a pigment powder.
- a powder coating obtained by melting and kneading rubutyral powder and a pigment and pulverizing the powder is known! /
- JP-A-10-206392 (Claims, [0011])
- JP-A 2000-281966 (Claims, [0026], [0037], [ 0039], [0062], [0097]) ⁇ .
- this powder coating is a process of melt-kneading polybutyl petital powder and pigment.
- a process for pulverizing not only the raw material before kneading but also the melt-kneaded material after kneading is necessary, and the production cost is high and the productivity is not excellent.
- it is mechanically pulverized it is not easy to obtain a desirable small particle size, and it is also difficult to obtain particles having a particle shape close to a sphere.
- a method for adjusting a powder coating material in addition to melt-kneading the above-mentioned resin powder and pigment, a method of dry blending the resin powder and the pigment is also known.
- a powder coating made by dry blending two or more kinds of powder coatings obtained by melt-kneading a resin powder and a pigment such as carbon black and pulverizing the powder coating are to be easy to color.
- Blended powder coating materials are known (for example, JP-A-7-188586 (Claims, [0007], [0010], [0014], [0015])).
- JP-A-7-188586 a melt-kneaded product (primary color powder coating material) of a resin powder and a pigment powder is dry-blended with each other! There is no disclosure about obtaining a powder coating material by dry blending, and there is no disclosure about using polyvinyl butyral powder as a resin component of the coating material.
- powder coatings obtained by dry blending a resin powder having an average particle size of 5 to 50 ⁇ m and a pigment powder having an average particle size of 0.01 to 1.0 m are also known as ones that facilitate toning.
- JP 2004-43669 (Claims, [0024], [0041], [0073], [0087], [00 88])
- Japanese Patent Application Laid-Open No. 2004-43669 butyral sallow (polybulum petital) is described only as an example, and the present inventors do not actually use the polyvinyl petital.
- the resin powder and the pigment powder cause layer separation, resulting in poor colorability.
- the fluidity of the powder coating was also insufficient.
- polyamide-based powder coatings containing polyamide powder are known as powder coatings.
- a polyamide-based powder coating containing a polyamide powder has the advantage of excellent impact resistance of a coating film (hereinafter simply referred to as “coating film”) formed on the surface of a substrate.
- coating film a coating film formed on the surface of a substrate.
- the polyamide-based powder coating generally has a defect in that the hardness of the coating film is inferior. For this reason, polyamide powder coatings are desired to have improved adhesion to the substrate and hardness of the coating film.
- the present invention has excellent fluidity during coating when applied to a powder coating, and the impact resistance and thickness uniformity of the resulting coating (coating)
- An object of the present invention is to provide a polybulassal powder that can have good film thickness uniformity. It is another object of the present invention to provide a powder coating using the polybulucetal powder. Specifically, the coating can be manufactured at low cost and has excellent colorability with a pigment.
- An object of the present invention is to provide a polyvinyl acetal pigment-based powder coating material capable of forming a film and having excellent fluidity.
- the object is to provide a paint.
- the polybulucetal powder of the present invention that has achieved the above object has an average particle size of 10 to 150 / zm and a maximum particle size of 250 / ⁇ ⁇ or less, and is compliant with JIS ⁇ 7210: 1999. It is a polybulacetal powder with a melt flow rate (MFR) force of 1 to 200 gZlO, measured according to regulations.
- MFR melt flow rate
- the polyvinyl acetal-pigment powder coating material of the present invention that has achieved the above object is a powder obtained by dry blending a poly (vinyl acetal) powder (A) and a pigment powder (B). It is a powder paint that satisfies the following conditions.
- the average particle size (AD) of the powder (A) is 10 to 150 m, and the maximum particle size is 250 ⁇ m or less.
- the average particle size (BD) of the powder (B) is 2 to 150 ⁇ m, and the maximum particle size is 250 ⁇ m or less.
- the weight ratio (B) Z (A) of the powder (B) to the powder (A) is 0.5Z100 to 50Z100.
- the polyamide-based powder coating is a powder coating obtained by dry blending the polybulassetal powder ( ⁇ ,) and the polyamide powder (C), and satisfies the following conditions.
- the polybuluacetal powder of the present invention (which is also polybuluacetal powder ( ⁇ ) and ( ⁇ ') described later) has an average particle size of 10 to 150 111 and a maximum particle size of 250 m.
- the melt flow rate measured in accordance with the provisions of JIS K7210: 1999 is 1 to 200 gZ
- the polybulacetal composing the polybulacetal powder of the present invention is usually a bisulfate.
- the above bull alcohol polymer can be obtained by a conventionally known method, that is, by polymerizing a bull ester monomer and saponifying the obtained polymer.
- a method for polymerizing vinyl ester monomers conventionally known methods such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization can be applied.
- the polymerization initiator an azo initiator, a peroxide initiator, a redox initiator or the like is appropriately selected according to the polymerization method.
- the saponification reaction can be applied by alcoholysis or hydrolysis using a conventionally known alkali catalyst or acid catalyst. Among them, the method using methanol as a solvent and caustic soda (NaOH) as a catalyst is most preferable because it is simple. .
- butyl ester monomer examples include formate butyl, vinyl acetate, propionate butyl, butyrate butyl, isobutyrate butyl, pivalate butyl, versatic acid butyl, strength. Forces such as butyrate pronate, butyral prillate, laurate, palmitate, stearate, oleate and benzoate are preferred, especially acetate.
- a vinyl alcohol polymer obtained by saponifying a polymer obtained by polymerizing a vinyl ester monomer has a different content of each unit depending on the degree of saponification. It contains bull ester units corresponding to bull ester monomers.
- the butyl alcohol polymer obtained by the above production method includes a butyl alcohol unit and an acetyl acetate unit.
- the vinyl ester monomer when polymerized, it can be copolymerized with other monomers within the range without impairing the gist of the present invention.
- examples of other monomers include ethylene, propylene, n-butene, ⁇ -olefins such as isobutylene, acrylic acid and its salts, methyl acrylate, ethyl acrylate, ⁇ -propyl acrylate, and i-propyl acrylate.
- the polybutacetal can be obtained by acetalizing a butyl alcohol polymer.
- the acetal cake can be obtained by applying a conventionally known method.
- a vinyl alcohol polymer and an aldehyde may be mixed in the presence of an acid catalyst.
- the acid catalyst used in the acetalization is not particularly limited, and any of organic acids and inorganic acids can be used. Examples thereof include acetic acid, paratoluenesulfonic acid, nitric acid, sulfuric acid, and hydrochloric acid. Of these, hydrochloric acid, sulfuric acid, and nitric acid are more generally used, and hydrochloric acid is particularly preferably used.
- polybulucetal acetalized with an aldehyde having 2 to 6 carbon atoms examples include acetoaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-hexyl aldehyde, 2-ethylbutyraldehyde, and the like. Two or more kinds may be used in combination. Of these, aldehydes having 4 to 6 carbon atoms, particularly n-butyl aldehyde, are preferably used. In the case of a powder paint containing 2 to 6 carbon atoms, particularly polyamide resin, it is possible to suitably obtain a powder paint intended for the present invention by using an aldehyde having 4 to 6 carbon atoms. it can.
- the degree of acetalization of the polybulucetal used in the present invention is preferably 40 to 85 mol%, and more preferably 50 to 85 mol%. When the degree of acetalization is within this range, a powder coating that is excellent in fluidity during coating, coating coloration, and adhesion to a substrate, and that can provide a uniform coating thickness. can get.
- the content of poly Bulle ⁇ Se tar Bulle ester units from 0.1 to 30 mole 0/0 the content of 10 to 50 mole 0 Bulle alcohol units Must be 0 Is preferred. In this case, it is possible to obtain a powder coating material that can form a coating film that is excellent in adhesion to the substrate and superior in impact resistance and hardness.
- the values of the degree of acetalization, the content of the bull ester unit, and the content of the bull alcohol unit are the ratios to all the bull monomer units constituting the polyblucetal.
- the polyvinyl acetal used in the present invention may contain a functional group such as a carboxyl group, a primary hydroxyl group, an epoxy group, an amino group, or an isocyanate group in the molecule.
- the method for introducing the functional group into the molecule is not particularly limited. For example, (1) a carboxyl group or primary hydroxyl group such as (meth) acrylic acid or hydroxyethyl (meth) acrylate is added.
- Examples include a method of acetalizing a group-containing butyl alcohol polymer, and (3) a method of acetalizing a vinyl alcohol polymer with an aldehyde compound having a carboxyl group, such as darioxylic acid.
- the polybulacetal powder of the present invention has an average particle size (AD) of 10 to 150 ⁇ m and a maximum particle size of 250 ⁇ m or less. By satisfying this condition, the polybulacetal powder can impart excellent colorability to the coating film.
- the average particle size is preferably 130 m or less and optimally 100 m or less.
- the lower limit is preferably 20 ⁇ m or more.
- the average particle diameter of the polyvinyl acetal powder can be determined by measurement by laser diffraction method.
- the apparatus that can be used for the measurement include a particle size distribution measuring apparatus SALD2200 manufactured by Shimadzu Corporation. Is mentioned.
- SALD2200 particle size distribution measuring apparatus manufactured by Shimadzu Corporation. Is mentioned.
- the maximum particle size can also be determined by the end point value of the particle size distribution obtained by the same measurement.
- the polyvinyl acetal powder may be composed of single particles, or may be composed of aggregated particles of primary particles. It is preferable that the polyvinyl acetal powder also has an aggregate particle force of primary particles. In this case, the average particle diameter (AD) and the maximum particle diameter of the polyvinyl acetal powder are those of the aggregate particles. ! Uh. [0026] When the polyburacetal powder is also configured to have an aggregate particle force of primary particles, the primary particles have an average particle size of 5 ⁇ m or less and a maximum particle size of 10 ⁇ m or less. It is preferable.
- the primary particles are the first particles produced in the acetal reaction of poly (bull alcohol).
- the average particle size of primary particles can be determined from, for example, three photographs (three) of powders taken at a magnification of 1000 using a scanning electron microscope (SEM). It can be obtained by measuring the particle size (more than 50 points per photo) and calculating the average value.
- the primary particle size may be the major axis of the primary particle, and the maximum primary particle size may be the maximum primary particle size that can also determine SEM photographic power.
- the polyvinyl acetal powder satisfies the specific primary particle size and aggregate particle size, excellent adhesion to the substrate and high hardness can be imparted, and further the coating film can be imparted. Excellent colorability and uniform coating thickness can be imparted.
- the polybuluacetal powder of the present invention has an MFR of 1 to 200 gZlO.
- the MFR is preferably 5 to 150 gZlO min, optimally 10 to 120 gZlO min.
- the MFR is less than lg ZlO, the coloration of the coating film is insufficient, the adhesion to the substrate is lowered, and the uniformity of the coating film thickness may be insufficient. If it exceeds 200gZlO, the coloration and impact resistance of the paint film will decrease, and the fluidity of the melted paint will increase, resulting in insufficient uniformity of the paint film, and the paint will drip. May occur.
- MFR is 190 based on JIS K7210: 1999. C, measured under a load of 2160g
- the MFR of the polybulacetal powder can be mainly controlled by the degree of polymerization and the degree of acetalization of the polyvinyl rubetal composing the polybulacetal powder.
- the MFR of the polyvinyl acetal powder can be controlled by the polymerization degree of the butyl alcohol polymer used as the raw material of the polybuacetal, and as the polymerization degree increases, the polyvinyl acetal powder The MFR can be reduced.
- the degree of polymerization is usually 150 to 2000, preferably 200 to 1500.
- the polybulassetal powder having such a specific primary particle size and aggregate particle size and having the above-mentioned MFR can be obtained, for example, by the following method.
- an aqueous solution of a vinyl alcohol polymer ⁇ concentration 3 to 15% by weight; Weight of alcohol polymer) Z (Weight of vinyl alcohol polymer aqueous solution) X Calculated by 100 ⁇ is adjusted to 80-100 ° C, and the temperature is gradually decreased over 10-60 minutes. When the temperature drops to -10-30 ° C, aldehyde and catalyst are added. Continue the reaction for 30 to 300 minutes while keeping the temperature constant. Furthermore, the temperature is raised to 30 to 200 ° C, and the temperature is raised to 30 to 80 ° C. Next, after washing with water and neutralization treatment, the desired polyvinyl acetal powder is obtained by drying.
- aggregate particles having a maximum particle size exceeding 250 m are hardly generated, but when aggregate particles exceeding the maximum particle size of 250 / zm are generated, they may be removed by a filter, a sieve or the like.
- the water content of the polyvinyl acetal powder is preferably 2.5% by weight or less because surface smoothness after coating can be improved.
- Examples of the method for reducing the water content to 2.5% by weight or less include a method of removing water to a specified amount or less by drying after washing with water or a mixed solution of water Z alcohol after acetalization. Can be mentioned.
- a more preferable water content is 2.0% by weight or less.
- the residual amount of aldehyde used for the acetalization in the polybuluacetal powder is 150 ppm (weight ppm, the same shall apply hereinafter) or less, so that the powder paint of the present invention can be obtained more suitably.
- the ability to do is also preferable.
- Examples of the method for reducing the residual aldehyde amount to 150 ppm or less include a method of purifying polybulucetal by washing with water or a mixed solution of water Z alcohol to remove the aldehyde to a specified amount or less.
- the content of residual aldehyde is more preferably 120 ppm or less, and further preferably 10 ppm or less.
- the polybulacetal powder can be suitably used for a powder coating material.
- the fluidity of the powder during coating is good, and the resulting coating film has good impact resistance and thickness uniformity (coating thickness uniformity).
- Specific examples applied to the powder coating material include polyblucacetal pigment-based powder coating material and polybulucaltal polyamide-based powder coating material, which will be described below.
- the polybuluacetal pigment-based powder coating of the present invention comprises:
- Powder coating made by dry blending polyvinylacetal powder (A) and pigment powder (B)
- the powder coating material satisfies the following conditions.
- the average particle size (AD) of the powder (A) is 10 to 150 m, and the maximum particle size is 250 ⁇ m or less.
- the average particle size (BD) of the powder (B) is 2 to 150 ⁇ m, and the maximum particle size is 250 ⁇ m or less.
- the weight ratio (B) Z (A) of the powder (B) to the powder (A) is 0.5Z100 to 50Z100.
- the polyvinyl acetal pigment-based powder coating can be produced simply by dry blending a polybule acetal with a pigment, so that it is excellent in productivity and can be produced at low cost. Furthermore, since polybulassal is excellent in transparency, it is possible to form a coating film having excellent colorability.
- excellent colorability means that there is no or very little coloring unevenness, and does not mean whether the pigment is uniformly dispersed in the coating film.
- the polybulucetal-pigment-based powder coating is excellent in fluidity of the powder coating because the resin powder and the pigment powder do not cause layer separation.
- polyvinylacetal is excellent in adhesion to the base material, it can provide excellent adhesiveness to the base material without any pretreatment with a primer or the like, and has a high hardness. It is also possible to form a coating film having
- pigment powder ( ⁇ ) to be dry-blended with the polyvinyl acetal powder ( ⁇ ) examples include, for example, titanium oxide, iron oxide, brown rice, carbon black, phthalocyanine green, phthalocyanine blue, and diazo yellow. , Quinacridone, aluminum metal, pearl pigment
- mice Mica, light diffusing agent (glass beads, silicone, polymethylmetatalylate, etc.), barium sulfate, barium carbonate, calcium carbonate, magnesium carbonate, clay, talc and other pigment powders.
- a seed powder is used.
- titanium oxide, iron oxide, red pepper, carbon black, phthalocyanine green, phthalocyanine blue, diazo yellow, quinacridone, aluminum metal, pearl pigment, and mica power at least one powder selected More preferably, at least one powder selected from iron oxide, carbon black, and pearl pigment power is used.
- Conditions (1) and (2) are conditions relating to the polyvinyl acetal powder (A) and are as described above.
- the condition (3) that is, the average particle diameter (BD) of the pigment powder (B) is 2 to 150. / ⁇ ⁇ and a maximum particle size of 25 O / zm or less.
- the average particle size is preferably 130 ⁇ m or less, and optimally 100 ⁇ m or less.
- the lower limit of the average particle size is preferably 5 m or more, and optimally 10 m or more.
- the average particle size and the maximum particle size of the pigment powder (B) can be determined by the same method as the average particle size and the maximum particle size of the polyvinyl acetal powder described above.
- condition (4) that is, the average particle diameter of the powder (A) expressed in units of l AD-BD lm.
- the absolute value of the difference in the average particle diameter of the powder (B)) ⁇ 100.
- the condition of 5 that is, the weight ratio) 7 (eight) of the polybulacetal powder (A) and the pigment powder (B) satisfies 0.5ZlOO to 50ZlOO.
- the preferred weight ratio ( ⁇ ) ⁇ ( ⁇ ) is 1 ⁇ 100 ⁇ 50 ⁇ 100, and it is more preferable [1/100 ⁇ 30/100] / 1 00.
- a poly (b) acetal pigment-based powder coating of the present invention in combination with a polyamide-based resin powder (C) (hereinafter also simply referred to as powder (C)). is there.
- Examples of the polyamide-based resin include nylon 6, nylon 6, 6, nylon 6-6, 6 copolymer, nylon-9, nylon-6, 10, nylon 11, nylon 12, and the like. Two or more types are used. Among them, nylon-11 and nylon —12 is more preferred.
- polyamide-based resin powders in combination, a high impact resistance can be imparted to the coating film, and furthermore, a powder coating excellent in fluidity and powder-off properties can be obtained.
- “powder-off” is an evaluation item corresponding to the amount of extra paint adhering to the surface of the base material when the powder paint is applied to the surface of the substrate, and is determined visually.
- the powder coating material has good powder fall-off property
- the amount of the above-mentioned extra paint is small, or the extra paint is not adhered, so that the coating unevenness of the paint does not easily occur.
- the powdering property decreases, the amount of the extra paint increases, and uneven application of the paint tends to occur.
- the polyamide-based resin powder (C) preferably has an average particle size (CD) of 10 to 150 / ⁇ m and a maximum particle size of 250 / z m or less.
- the average particle diameter of the polyamide-based resin powder is preferably 130 ⁇ m or less, and more preferably 100 ⁇ m or less.
- the lower limit is preferably 20 m or more.
- the polyamide-based resin powder can be formed into a desired particle size by, for example, pulverizing polyamide resin.
- the average particle size and the maximum particle size of the polyamide-based resin powder (C) can be obtained by the same method as the average particle size and the maximum particle size of the polyvinyl acetal powder described above.
- the weight ratio (A) Z (C) of the polyvinyl acetal powder (A) and the polyamide resin powder (C) is 20Z100 ⁇ : LOOZ5 is preferred.
- the weight ratio (A) / (C) is more preferably 50/100 to 100/5, still more preferably 50ZlOO to 100ZlO.
- the powder coating material of the present invention preferably has a configuration in which the powder component ( ⁇ ) is the main component, or the powder ( ⁇ ) and the powder (C) are the main components, as the resin component. .
- the total of the powder ( ⁇ ) and the powder (C) is preferably 80% by weight or more. 90% by weight or more is more preferable. 100% by weight is more preferable.
- the powder ( ⁇ ) and the powder (C) are melt-kneaded and then pulverized to obtain the powder ( ⁇ ) and the powder.
- a composite powder with the body (C) you can dry blend with polyvinylacetal powder ( ⁇ )! /.
- the inorganic fine particles (D) may also be blended, or polybulassal powder ( This is a preferred embodiment because it further improves the fluidity of the powder coating material comprising A) and the pigment powder (B), further improves the adhesion to the substrate, and further improves the hardness.
- the inorganic fine particles (D) are distinguished from pigments, and examples thereof include silica and acid aluminum.
- the inorganic particles (D) preferably have an average particle size of 1 ⁇ m or less.
- the average particle diameter of the inorganic particles (D) is more preferably 0.5 m or less, and further preferably 0.1 ⁇ m or less.
- the inorganic particles can be pulverized to a desired particle size.
- the average particle size and the maximum particle size of the inorganic fine particles (D) can be determined by the same method as the average particle size and the maximum particle size of the polyvinyl acetal powder.
- the inorganic fine particles (D) are 0.0001 to 100 parts by weight of the powder (A) or 100 parts by weight of the powder (A) and the powder (C) when the powder (C) is used. 5 parts by weight is preferably blended, more preferably 0.0001 to 2 parts by weight, even more preferably 0.001 to 2 parts by weight, and most preferably 0.001 to 1 part by weight.
- the powder coating of the present invention may contain a curing agent such as isocyanate compound, epoxy compound, hydroxyalkylamide, amino compound, aliphatic dibasic acid, or acid anhydride.
- a curing agent such as isocyanate compound, epoxy compound, hydroxyalkylamide, amino compound, aliphatic dibasic acid, or acid anhydride.
- the amount of curing agent used is usually 20 parts by weight or less per 100 parts by weight of powder (A) or 100 parts by weight of powder (A) and powder (C) when powder (C) is used.
- the amount is preferably 15 parts by weight or less, more preferably 10 parts by weight or less.
- the epoxy compound is not particularly limited as long as it is a compound containing an epoxy group!
- triglycidyl isocyanurate is used.
- Hydroxyalkylamides include, for example, carboxylic acids and candy or carboxylic acid esters. And ⁇ -hydroxyalkylamine in the presence of alkoxide such as sodium or potassium.
- carboxylic acid and carboxylic acid ester include succinic acid, adipic acid, glutaric acid, dimethyl succinate, ethyl succinate, dimethyl adipate, and the like.
- j8-hydroxyalkylamine include N-methylethanolamine, diethanolamine, and N-methylpropanolamine.
- Examples of the commercially available hydroxyalkylamide include “Primid” series manufactured by EMS-PRIMID.
- the amino compound is not particularly limited as long as it is an amino group-containing compound, and examples thereof include urea, melamine, and urea resin.
- the aliphatic dibasic acid is not particularly limited, but dodecanedioic acid is generally used.
- the acid anhydride is not particularly limited, but trimellitic anhydride and pyromellitic anhydride are generally used.
- the polyvinyl acetal pigment-based powder coating of the present invention can be obtained by dry blending the polyvinyl acetal powder (A), the pigment powder (B), and other components added as necessary.
- the dry blending method include a method in which both are uniformly mixed, for example, a method using a drive render, a Henschel mixer, a ball mill, or the like.
- the polybulassal polyamide-based powder coating of the present invention is
- the adhesion to the substrate can be improved, and for example, the substrate surface without pretreatment of the substrate surface with a primer or the like can be performed.
- a coating film that adheres well to the surface can be formed.
- a coating film having high impact resistance and hardness can be formed on the substrate surface.
- the composition of the powder (C ') is not particularly limited as long as it is a polyamide powder.
- various nylon powders specifically, nylon 6, nylon 66, nylon 6 and nylon 66, Copolymer, nylon 9, nylon 610, nylon 11, nylon 12, etc. may be used. These may be used alone or in combination of two or more.
- the powder (C ') must be nylon 11 powder or nylon 12 powder because it can form a powder coating that excels in adhesion to the substrate and in the hardness and impact resistance of the coating film. Is preferred.
- the particle size of the powder (C ') is not particularly limited, but the average particle size is preferably 150 m or less, and the maximum particle size is preferably 250 m or less.
- the average particle size of the powder (C ′) is preferably 130 m or less, more preferably 100 m or less.
- the average particle size and the maximum particle size of the powder (C ′) may be obtained by the same method as the average particle size and the maximum particle size of the polyvinyl acetal powder described above.
- the powder (C ') may be formed, for example, by pulverizing a polyamide resin, and the average particle size can be controlled by appropriately selecting a pulverization method.
- the maximum particle size of the powder (C ′) can be controlled by a method such as fractionation using a filter or a sieve, as in the case of the above-described polybulacetal powder.
- Conditions (I) and (II) are conditions relating to the polyvinyl acetal powder ( ⁇ ′) and are as described above.
- the weight ratio is preferably in the range of 50ZlOO to 100Z5, more preferably in the range of 50ZlOO to 100ZlO. If the mixing ratio ( ⁇ ,) ⁇ (C ') is greater than 100Z5, the impact resistance of the coating film may be reduced.
- the weight ratio is preferably in the range of 50ZlOO to 100Z5, more preferably in the range of 50ZlOO to 100ZlO.
- the powder ( ⁇ ') and the powder (C) are the main components of the resin component contained in the powder paint. More specifically, the total of the ratio of the powder ( ⁇ ′) and the ratio of the powder (C ′) in the resin component contained in the powder coating is preferably 80% by weight or more, 90% More preferred is 100% by weight.
- the polybulucetal-polyamide-based powder coating of the present invention may contain materials other than powder ( ⁇ ,) and powder (C,).
- the content of the particles (D') is such that the powder ( ⁇ ') and the powder (C' ) Is usually in the range of 0.0001 to 5 parts by weight, and the range of 0.0001 to 2 parts by weight is in the range of 0.001 to 1 part by weight. More preferred.
- the kind of particles (D ′) and the average particle diameter are the same as those of the inorganic particles (D).
- the polybroacetal polyamide-based powder coating power of the present invention an isocyanate compound, an epoxy compound, a hydroxyalkylamide, an amino compound, an aliphatic dibasic acid, an acid anhydride, and the like. May further be included.
- the solvent resistance of the coating film can be improved.
- Specific examples of these curing agents are the same as described above.
- the content is usually 20 parts by weight or less and 15 parts by weight with respect to 100 parts by weight in total of the powder ( ⁇ ′) and the powder (C ′). 10 parts by weight or less are more preferable.
- each of the materials included in the polybulacetal-polyamide-based powder coating of the present invention is, for example, after each material is individually formed, What is necessary is just to dry-blend according to a predetermined mixing ratio.
- the dry blending method include a method in which both are uniformly mixed, for example, a method using a drive render, a Henschel mixer, a ball mill, or the like.
- the angle of repose of the polybulacetal polyamide-based powder coating of the present invention is usually less than 55 °, preferably less than 53 °, and more preferably less than 50 °. Angle of repose is 55 ° or more If this happens, it may be difficult to control the fluidity during painting, and the smoothness of the coating film may be lost.
- the angle of repose can be evaluated using a so-called powder tester.
- the powder coating containing the polybulassal powder of the present invention is various powder coatings.
- the powder coating method include a fluidized immersion method, an electrostatic coating method, and a thermal spraying method.
- the coating temperature condition varies depending on the coating method and the MFR of the polyvinyl acetal used, but is preferably about 100 to 300 ° C.
- Examples of the base material to be coated with the powder coating material containing the polybulacetal powder of the present invention include metals such as steel pipes and steel plates, ceramics, ceramics, glass, plastics, and the like.
- the powder coating containing the polyvinyl acetal powder of the present invention is suitable for coating a steel pipe, and further, a cart composed of a steel pipe coated with the powder coating (eg, a shopping cart, a force rack).
- a cart composed of a steel pipe coated with the powder coating (eg, a shopping cart, a force rack).
- the appearance of carts, carts, airport carts, etc., especially shopping carts, will be good.
- the surface of the substrate is degreased, phosphated, or plated as necessary to improve the adhesion to the substrate or the corrosion resistance and appearance of the coating film.
- Primer treatment such as treatment or epoxy resin may be performed.
- the coating film can also have a multilayer structure by applying a powder coating material containing the polyvinyl acetal powder of the present invention onto a base material typified by a metal.
- the method of multi-layering is not particularly limited.
- the method of applying the powder coating a plurality of times, the application of the powder coating and another powder coating in a predetermined pattern for example, alternately
- a method of performing the coating multiple times, a mixture of the powder coating material and another powder coating material is applied, and due to the difference in affinity between the two, phase separation is performed at the time of melting on the substrate surface, so that a single coating is performed.
- a method of forming a multilayered resin layer can be used.
- the method of applying the powder coating material a plurality of times is more preferable because it is not necessary to consider the affinity between the resin.
- the powder ( ⁇ ) is dried at 105 ° C for 3 hours using a dryer, and the formula ⁇ (weight of powder (A) before drying)-(weight of powder (A) after drying) ⁇ Z ⁇ drying Calculated from the weight of the previous powder (A) ⁇ X 100 (%).
- the particle size of the largest primary particle observed from the SEM photograph was measured. ⁇ Average particle diameter of polyvinylacetal powder (aggregate particles), pigment powder, polyamide-based resin powder, inorganic particles ⁇
- the particle size distribution was measured with a SALD2200 particle size distribution analyzer manufactured by Shimadzu Corporation.
- the value of the end point of the particle size distribution measured by the particle size distribution measuring device SALD2200 manufactured by Shimadzu Corporation was taken as the maximum particle size.
- the angle of repose of the powder coating samples prepared in Examples and Comparative Examples was determined by the following method.
- each powder coating sample was measured with 500 g.
- the fluidity of each powder coating in the coating chamber was evaluated by visually observing the state of the upper surface of the powder coating blown up by air from the perforated plate. The evaluation criteria are shown below.
- the state of the coating film formed on the surface of the base material was confirmed by visual observation, and the powder fallen property of each powder coating was evaluated. The evaluation criteria are shown below.
- the colorability of the coating film applied to the substrate was visually evaluated according to the following criteria.
- the thickness of the coating film formed on the substrate surface was measured for each powder paint at 5 points, and the average value d
- the ratio of 2 (d2Zdl) was determined as a percentage (%).
- the substrate on which the coating film of each powder coating sample was formed was left on the floor surface so that the coating film would be on top, and an iron ball with a weight of 2 kg was allowed to fall freely from the height of 2 m vertically above it. Collided. The state of the coating film after the collision was visually observed to evaluate the impact resistance of the coating film. The evaluation criteria are shown below.
- the adhesion of the coating film formed on the substrate surface was measured according to JIS K 5600-5-6: 1999 (General test method for coating materials-Part 5: Mechanical properties of coating film-Section 6: Adhesion: Cross-cut method) ) And classified according to the classification of test results described in the JIS standard (Class 0 represents the best adhesion, and Class 5 represents the least adhesive state).
- the hardness of the coating film formed on the surface of the base material is determined according to JIS K 5600-5-4: 1999 (Paint general test method Part 5: Mechanical properties of the coating film Section 4: Gravity hardness: Pencil method) Evaluation was made based on regulations. The coating hardness decreases in the order of H, HB, and B.
- Pigment powder ⁇ Mercury's “Iriodin (registered trademark) 100 Silver Pearl” (pearl pigment) (average particle size 35 ⁇ m, particle size exceeding 250 m) No particles) ⁇ 5 g was mixed with a drive renderer to obtain the powder coating of the present invention.
- the surface of a 0.8 mm thick x 50 mm x 100 mm stainless steel plate was washed with a detergent and degreased, and thoroughly washed with ion-exchanged water to obtain a substrate.
- the above-mentioned powder coating material was applied to the base material by a fluid immersion method. In the fluid immersion, air is blown into a cylindrical coating chamber (fluid chamber) (height 50 cm, diameter 30 cm) through a perforated plate to flow the powder coating, and the stainless steel plate base material in the fluidized bed. The paint was suspended.
- the flow immersion conditions are shown below. • Preheating of the substrate: temperature 300 ° C, time 15 minutes
- Example 1 MFRl lgZlO content, butyral was used in the same manner as in Example 1 except that PVA-2 (polybulal alcohol) (polymerization degree 600, saponification degree 98 mol%) was used instead of PVA-1. degree 75 mole 0/0, the content 2 mol 0/0 acetic acid Bulle units, poly Bulle butyral content of 20 mole 0/0 Bulle alcohol units (PVB 2) were prepared, resulting PVB 2 was used in the same manner as in Example 1 to prepare a polyvinyl propylal pigment-based powder coating material. Powder coating was performed in the same manner as in Example 1 except that the powder coating material prepared above was used instead of the powder coating material used in Example 1. Table 1 shows the evaluation results of the coating film obtained. The moisture content of PVB 2 was 0.8% and the butyraldehyde content was lOOppm.
- Example 1 MFR 1.6 gZlO was used in the same manner as in Example 1 except that PVA-3 (polybulal alcohol) (polymerization degree 1000, saponification degree 98 mol%) was used instead of PVA-1.
- PVA-3 polybulal alcohol
- PVB 3 polymerization degree 78 mol%
- content of 2 mol% of acetic acid Bulle units, Bulle alcohol units of the content of 20 mole 0/0 of poly Bulle butyral the (PVB 3) were prepared, resulting PVB 3 was used in the same manner as in Example 1 to prepare a polybutylar-pigment-based powder coating material.
- Powder coating was performed in the same manner as in Example 1 except that the powder coating material prepared above was used instead of the powder coating material used in Example 1. Table 1 shows the evaluation results of the coating film obtained.
- the moisture content of PV B-3 was 0.9% and the butyraldehyde content was lOOppm.
- Example 1 In Example 1, except that PVA-4 (polybulal alcohol) (polymerization degree 200, saponification degree 98 mol%) was used instead of PVA-1, it was MFR150gZlO content and butyralization. degree 78 mole 0/0, the content 2 mol 0/0 acetic acid Bulle units, Bulle content of 20 mol of alcohol unit 0/0 of poly Bulle butyral (PVB 4) were prepared, resulting PVB 4 a Using, in the same manner as in Example 1, a polyvinyl petital pigment-based powder coating was prepared. . Powder coating was performed in the same manner as in Example 1 except that the powder coating material prepared above was used instead of the powder coating material used in Example 1. Table 1 shows the evaluation results of the coating film obtained. The moisture content of PVB 4 was 0.7% and the butyraldehyde content was 90 ppm.
- Example 1 In Example 1, except that 20 g of pigment was used instead of 5 g of pigment, a polyvinyl butyral pigment-based powder coating material was prepared and powder-coated in the same manner as in Example 1. Table 1 shows the evaluation results of the coatings obtained.
- Example 1 instead of the pigment “Iriodin (registered trademark) 100 Silver PearlJ, pigment ⁇ “ Toka Black # 7100F ”(carbon black) manufactured by Tokai Carbon Co., Ltd., average particle size 42 m, particle size 250 m Except for using no excess particles ⁇ , a polyvinyl-butyra pigmented powder coating was prepared and powder-coated in the same manner as in Example 1. Table 1 shows the evaluation results of the coatings obtained.
- Example 1 instead of the pigment “Iriodin (registered trademark) 100 Silver PearlJ, the pigment ⁇ Moritashita Valve Industrial Co., Ltd.“ Valve MR270EJ (acid ferric iron), average particle size 20 ⁇ m, A polyvinyl butyrate one-loud pigment-based powder coating material was prepared and powder-coated in the same manner as in Example 1 except that no particles with a particle diameter exceeding 250 m were used. The results are shown in Table 1.
- Example 8 (using inorganic powder)
- Example 1 In Example 1, except that 0.1 part by weight of silica (“Aerosil R972” manufactured by Nippon Aerosil Co., Ltd .; average particle diameter of 16 nm) was combined with 100 parts by weight of polyvinyl butyral powder in the powder coating. In the same manner as in Example 1, a polybutylar-pigment-based powder was prepared and coated with powder. Table 1 shows the evaluation results of the coating film obtained.
- Example 1 In Example 1, except that PVA-5 (polybulal alcohol) (polymerization degree 150, saponification degree 98 mol%) was used instead of PVA-1, MFR300gZlO content was obtained in the same manner as in Example 1. Bed butyral degree 68 mole 0/0, the content 2 mol 0/0 acetic acid Bulle units, Bulle alcohol units Thus, polybutyral (PVB-5) having a content of 20 mol% was obtained. A polyvinyl butyral pigment-based powder coating material was prepared and powder-coated in the same manner as in Example 1 except that PVB-5 was used instead of PVB-1 used in Example 1. Table 1 shows the evaluation results of the coating film obtained.
- PVA-5 polybulal alcohol
- saponification degree 98 mol% MFR300gZlO content was obtained in the same manner as in Example 1. Bed butyral degree 68 mole 0/0, the content 2 mol 0/0 acetic acid Bulle units, Bulle alcohol units
- PVB-5 poly
- Example 1 In Example 1, except that PVA-6 (polybulal alcohol) (polymerization degree 1700, saponification degree 98 mol%) was used instead of PVA-1, the same as in Example 1, MFRO. 5 gZlO content, butyral Polybutyral (PVB-6) having a degree of conversion of 68 mol%, a content of 2 mol% of acetic acid units and a content of 20 mol% of units of butyl alcohol was obtained.
- PVB-6 polyvinyl butyral pigment-based powder coating was prepared and powder-coated in the same manner as in Example 1 except that PVB-6 was used instead of PVB-1 used in Example 1. Table 1 shows the evaluation results of the coating film obtained.
- Example 1 instead of “5 g of pigment with respect to 100 g of polybutyral powder”, “55 g of pigment with respect to 100 g of polyvinylbutyral powder shown in Table 1” was used. In the same manner as in 1, a polybutylar pigment-based powder coating was prepared and powder coating was performed. Table 1 shows the evaluation results of the coating film obtained.
- Example 1 instead of “5 g of pigment with respect to 100 g of polybutyral powder”, “0.2 g of pigment with respect to 100 g of polyvinylpropylar powder shown in Table 1” was used. In the same manner as in Example 1, a polybutypetital pigment-based powder coating was prepared and powder coating was performed. Table 1 shows the evaluation results of the coating film obtained.
- Comparative Example 7 (average particle diameter of pigment powder, I AD—BD 00 or more)
- Example 1 a polyvinyl-butyra pigment pigment system was used in the same manner as in Example 1 except that the pigment “Iriodin (registered trademark) 100 Silver PearlJ” was used instead of the pigment (carbon black, average particle size 200 m). A powder coating was prepared and powder coating was performed, and the evaluation results of the coating film obtained are shown in Table 1.
- Example 1-8 instead of polybulubutyral powder lOOg, nylon powder coating (Agrima's “T Gris7452j; Nylon-11) (average) Other than using 130g powder (Examples 13 and 16 are 150g) containing 30g (Examples 13 and 16 are 50g) ”Particle size 120 ⁇ m, no particles exceeding 250 ⁇ m) In the same manner as in 1-8, a polybulutyllar-pigment-based powder was prepared and powder-coated. Table 2 shows the evaluation results of the coating film obtained.
- Comparative Examples 1 to 3 instead of 100 g of polybutyl butyral powder, a nylon powder coating (“T Gris7452j; Nylon 11” manufactured by Arkema) (average particle size) Same as Comparative Examples 1 to 3 except that 130g powder (Comparative Example 10 is 103g) containing 30g (Comparative Example 10 is 3g) "was used. In the same manner, a polybutylar pigment-based powder was prepared, and powder coating was performed. Table 2 shows the evaluation results of the coating film obtained.
- Comparative Example 4 instead of 100 g of polybulupetital powder, nylon powder coating (“T Gris7452” manufactured by Arkema; Nylon-11) (average particle size 120 m, particle size over 250 ⁇ m) Polyburbutira as in Comparative Example 4 except that 100g was used. A one-loud pigment-based powder was prepared and powder-coated. Table 2 shows the evaluation results of the coating film obtained.
- Polybulutyl powder (A-1) lOOg prepared in Example 1 and nylon 11 powder as polyamide powder (B) (Archema, “T Gris7452”: average particle size 120 ⁇ m, particle size 30 g) was mixed, and the polyvinyl butyral-polyamide powder coating material of Example 17 was obtained. Using the obtained powder coating material, coating was performed on a base material having a stainless steel plate force in the same manner as in Example 1. Table 3 shows the evaluation results of the obtained coating film.
- poly Bulle alcohol PVA-2: polymerization degree 600, saponification degree 98 mol 0/0 powder except for using in the same manner as in Example 1, polyvinyl butyral (PVB 2 ') Got the body.
- the moisture content of PVB-2 was 0.8% and the residual amount of butyraldehyde was lOOppm.
- the obtained PVB-2 ′ powder was sieved in the same manner as in Example 1 to remove the powder having a particle size of 250 / zm or more, and polyvinyl butyral powder (A-2) )
- the MFR of the obtained powder (A-2) was l lg / 10 min.
- the average particle size of the primary particles in the powder (A-2) was 3.2 m, and the average particle size of the powder (A-2) was 60 ⁇ m.
- Example 18 a powder coating material of Example 18 was obtained in the same manner as Example 17 except that powder (A-2) prepared above was used instead of powder (A-1). . Using the obtained powder coating material, a substrate having a stainless plate strength was applied in the same manner as in Example 1. Table 3 shows the evaluation results of the obtained coating film.
- polybulal alcohol PVA-3: polymerization degree 1000, saponification degree 98
- mole 0/0 was prepared in the same manner as in Example 1 to obtain a powder of a polyvinyl butyral (PVB 3 ').
- the moisture content of PVB-3 was 0.9% and the residual amount of butyraldehyde was lOOppm.
- the obtained PVB-3 ′ powder was sieved in the same manner as in Example 1 to remove the powder having a particle size of 250 / zm or more, and polyvinyl butyral powder (A-3) )
- the MFR of the obtained powder (A-3) was 1.6 gZlO.
- the average particle size of primary particles in powder (A-3) was 3 ⁇ m, and the average particle size of powder (A-3) was 80 ⁇ m.
- Example 19 a powder coating material of Example 19 was obtained in the same manner as Example 17 except that powder (A-3) prepared above was used instead of powder (A-1). . Using the obtained powder coating material, a substrate having a stainless plate strength was applied in the same manner as in Example 1. Table 3 shows the evaluation results of the obtained coating film.
- PVB-4 ' polyvinyl butyral powder was prepared in the same manner as in Example 1 except that polybulal alcohol (PVA-4: polymerization degree 200, saponification degree 98 mol%) was used instead of PVA-1. Obtained. PVB-4 'butyral degree 78 mol 0/0, PVB-4' acetate bi in - content of Le unit 2 mol%, the content of Bulle alcohol units was 20 mol%. The moisture content of PVB-4 was 0.7% and the residual butyraldehyde content was 90 ppm.
- the obtained PVB-4 ′ powder was sieved in the same manner as in Example 1 to remove the powder having a particle diameter of 250 m or more, and polyvinyl butyral powder (A-4) Got.
- the MFR of the obtained powder (A-4) was 150 gZlO.
- the average particle size of the primary particles in the powder (A-4) was 3 ⁇ m, and the average particle size of the powder (A-4) was 80 ⁇ m.
- Example 20 a powder coating material of Example 20 was obtained in the same manner as Example 17 except that powder (A-4) prepared above was used instead of powder (A-1). . Using the obtained powder coating material, a substrate having a stainless plate strength was applied in the same manner as in Example 1. Table 3 shows the evaluation results of the obtained coating film.
- Example 21 When preparing a powder coating, the weight of nylon 11 powder mixed with powder (A-1) is 50 g. A powder coating material of Example 21 was obtained in the same manner as Example 17 except that. Using the obtained powder coating, the same procedure as in Example 1 was performed on a base material having a stainless plate strength. Table 3 shows the evaluation results of the coating film obtained.
- Silica particles (Aerosil R972 manufactured by Nippon Aerosil Co., Ltd., average particle diameter: 16 nm) with respect to a total of 100 parts by weight of the powder (A-1) and nylon 11 powder (B) when preparing the powder coating
- a powder coating material of Example 22 was obtained in the same manner as in Example 17, except that 0.1 part by weight of the powder was further added.
- coating was performed on a base material such as a stainless steel plate in the same manner as in Example 1.
- Table 3 shows the evaluation results of the obtained coating film.
- poly Bulle alcohol PVA-7: degree of polymerization 150, degree of saponification of 98 mol 0/0 powder except for using in the same manner as in Example 1, polyvinyl butyral (PVB 7 ') Got the body.
- the obtained PVB-7 'powder was sieved in the same manner as in Example 1 to remove the powder having a particle diameter of 250 m or more, and polyvinyl butyral powder (A-7) Got.
- the MFR of the obtained powder (A-7) was 300 gZlO.
- the average particle size of primary particles in powder (A-7) was 7 ⁇ m, and the average particle size of powder (A-7) was 70 ⁇ m.
- Example 12 a powder coating material of Comparative Example 12 was obtained in the same manner as in Example 17 except that the above prepared powder (A-7) was used instead of powder (A-1). .
- a substrate having a stainless plate strength was applied in the same manner as in Example 1.
- Table 3 shows the evaluation results of the obtained coating film.
- PVB-8 ' polyvinyl butyral powder was prepared in the same manner as in Example 1 except that polybulal alcohol (PVA-8: polymerization degree 1700, saponification degree 98 mol%) was used instead of PVA-1. Obtained. PVB 8 'butyral degree of 68 mol 0/0, PVB-8' acetate bi in - content of Le unit 2 mol%, the content of Bulle alcohol units was 30 mol%.
- the obtained PVB-8 ′ powder was sieved in the same manner as in Example 1 to obtain a particle size of 250
- the powder of m or more was removed to obtain polyvinyl butyral powder (A-8).
- the MFR of the obtained powder (A-8) was 0.5 gZlO.
- the average particle size of the primary particles in the powder (A-8) was 2.8 m, and the average particle size of the powder (A-8) was 75 ⁇ m.
- Example 13 a powder coating material of Comparative Example 13 was obtained in the same manner as in Example 17 except that the powder (A-8) prepared above was used instead of the powder (A-1). .
- a substrate having a stainless plate strength was applied in the same manner as in Example 1.
- Table 3 shows the evaluation results of the obtained coating film.
- a powder paint of Comparative Example 14 was obtained in the same manner as in Comparative Example 12 except that the weight of the nylon 11 powder mixed with the powder (A-7) was 3 g when producing the powder paint.
- a substrate made of a stainless steel plate was coated in the same manner as in Example 1. Table 3 shows the evaluation results of the coatings obtained.
- Example 15 The powder coating material that only the nylon 11 powder used in Example 17 had strength was designated as Comparative Example 15. Using the obtained powder coating material, a coating made of a stainless steel plate was applied in the same manner as in Example 1. Table 3 shows the evaluation results of the obtained coating film.
- a powder paint of Comparative Example 16 was obtained in the same manner as in Example 17, except that 20 g of powder (A-l) and 150 g of nylon 11 powder were mixed when the powder paint was produced. Using the obtained powder coating material, coating was performed on a substrate having a stainless plate strength in the same manner as in Example 1. Table 3 shows the evaluation results of the coatings obtained.
- the polybulacetal powder of the present invention is suitable for powder coating applications.
- the powder coating containing the polyvinyl acetal powder of the present invention can be used for a wide range of applications, and is particularly suitable for coating on steel pipes.
- the final product of powder coatings is for carts such as shopping carts, rafters, carts, airport carts, water pipes, metal baskets, chemical tanks, overcoats for home appliances, automobile parts, etc. It can be used suitably. On the other hand, it can be suitably used for molding methods using a resin powder such as rotational molding and compression molding.
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Abstract
Description
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Priority Applications (4)
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CN2007800178746A CN101448876B (zh) | 2006-05-15 | 2007-04-26 | 聚乙烯醇缩醛粉体以及使用该粉体的粉体涂料 |
KR1020087030452A KR101106945B1 (ko) | 2006-05-15 | 2007-04-26 | 폴리비닐아세탈 분체 및 이를 사용한 분체 도료 |
EP20070742517 EP2022813B1 (en) | 2006-05-15 | 2007-04-26 | Polyvinyl acetal powder coating material |
US12/298,965 US7968639B2 (en) | 2006-05-15 | 2007-04-26 | Polyvinyl acetal powder and powder coating material using the same |
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JP2006135363A JP4865403B2 (ja) | 2006-05-15 | 2006-05-15 | ポリビニルアセタール系粉体塗料 |
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US (1) | US7968639B2 (ja) |
EP (1) | EP2022813B1 (ja) |
JP (1) | JP4865403B2 (ja) |
KR (2) | KR101106945B1 (ja) |
CN (1) | CN101448876B (ja) |
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WO2012023518A1 (ja) * | 2010-08-19 | 2012-02-23 | 株式会社クラレ | ポリビニルアセタール系粉体塗料 |
JP2012158705A (ja) * | 2011-02-02 | 2012-08-23 | Nippon Telegr & Teleph Corp <Ntt> | 粉体塗料 |
JP2014095078A (ja) * | 2012-11-07 | 2014-05-22 | Kuraray Europe Gmbh | 選択された粘度を有するポリビニルアセタールの製造方法 |
TWI453262B (zh) * | 2008-01-16 | 2014-09-21 | Kuraray Co | Polyvinyl acetal powder coating |
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JP5036404B2 (ja) * | 2007-05-29 | 2012-09-26 | 株式会社クラレ | 樹脂組成物および粉体塗料 |
JP5036403B2 (ja) * | 2007-05-29 | 2012-09-26 | 株式会社クラレ | ポリビニルアセタール系熱硬化性樹脂組成物および粉体塗料 |
DE102009047589B4 (de) | 2009-12-07 | 2014-01-16 | Kuraray Europe Gmbh | Verfahren zur Beschichtung von Substraten mit antimikrobiellen Beschichtungsmassen auf Basis von Polyvinylacetalen |
US9051476B2 (en) * | 2010-12-30 | 2015-06-09 | Ticona Llc | Powder containing a polyoxymethylene polymer for coating metallic substrates |
JP2013023598A (ja) * | 2011-07-21 | 2013-02-04 | Kuraray Co Ltd | アクリル系熱可塑性樹脂組成物 |
JP5667536B2 (ja) * | 2011-07-29 | 2015-02-12 | 株式会社クラレ | アクリル系熱可塑性樹脂組成物 |
CN105062253A (zh) * | 2015-09-07 | 2015-11-18 | 王璐 | 一种铝合金型材用涂料 |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI453262B (zh) * | 2008-01-16 | 2014-09-21 | Kuraray Co | Polyvinyl acetal powder coating |
WO2012023518A1 (ja) * | 2010-08-19 | 2012-02-23 | 株式会社クラレ | ポリビニルアセタール系粉体塗料 |
JP2012158705A (ja) * | 2011-02-02 | 2012-08-23 | Nippon Telegr & Teleph Corp <Ntt> | 粉体塗料 |
JP2014095078A (ja) * | 2012-11-07 | 2014-05-22 | Kuraray Europe Gmbh | 選択された粘度を有するポリビニルアセタールの製造方法 |
Also Published As
Publication number | Publication date |
---|---|
JP4865403B2 (ja) | 2012-02-01 |
CN101448876B (zh) | 2012-08-08 |
EP2022813A1 (en) | 2009-02-11 |
US20090311547A1 (en) | 2009-12-17 |
CN101448876A (zh) | 2009-06-03 |
US7968639B2 (en) | 2011-06-28 |
KR20090025237A (ko) | 2009-03-10 |
KR101066810B1 (ko) | 2011-09-22 |
KR20110074635A (ko) | 2011-06-30 |
JP2007302847A (ja) | 2007-11-22 |
KR101106945B1 (ko) | 2012-01-20 |
EP2022813A4 (en) | 2011-11-02 |
TW200804431A (en) | 2008-01-16 |
EP2022813B1 (en) | 2013-07-24 |
TWI406873B (zh) | 2013-09-01 |
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