JP2003213219A - Thermosetting powder coating material and method for forming coating film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a thermosetting powder coating material which can provide a coating film having excellent film appearance, e.g. smoothness and high antifungal properties, and provide a method for forming the coating film using the powder coating material. <P>SOLUTION: An organic solvent solution or dispersion including a thermosetting resin, a curing agent and an antifungal agent as essential components for forming the coating film is spray-dried to obtain the thermosetting powder coating material having an average particle size of 5-50 μm. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermosetting powder coating containing a novel and useful antibacterial agent and a method for forming a coating film. More specifically, it is a thermosetting powder coating having an average particle size of 5 to 50 μm, which is capable of providing a coating having excellent coating appearance and high antibacterial properties. And a method for forming a coating film using the powder coating material.

[0002]

2. Description of the Related Art In recent years, powder coatings that have a low impact on the environment have been applied to a wide variety of products such as electric products such as refrigerators and microwave ovens, and home-related products such as lockers and cabinets. Alternatively, an antibacterial powder coating containing an inorganic antibacterial agent is known to be effective in suppressing the growth of bacteria on the coated surface and suppressing the generation of spots, spots, etc. on the coating film.

As a method of incorporating these organic and / or inorganic antibacterial agents into the powder coating, a method of adhering the antibacterial agent to the particle surface of the pulverized and classified powder coating or an antibacterial agent during melt kneading A method of crushing and classifying after adding is adopted.

However, according to the former method, it is difficult to uniformly attach the antibacterial agent to the particle surface of the powder coating material, and in electrostatic powder coating, the difference in electrostatic characteristics between the powder coating material and the antibacterial agent. Since the coating efficiency is different, the antibacterial agent is non-uniformly present in the coating film, so that there is a problem that sufficient antibacterial property cannot be obtained in a portion where the antibacterial agent contained in the coating film is small.

Further, the latter method has problems that the antibacterial property is lowered and the paint is discolored due to heating for a long time during melt-kneading. Further, the powder coating material formed into a coating material through a mechanical pulverization step has a drawback that the coating film appearance such as smoothness is remarkably inferior as compared with an organic solvent type coating material.

[0006]

DISCLOSURE OF THE INVENTION The inventors of the present invention have solved the above-mentioned various problems in the prior art, and obtain a thermosetting powder coating containing a highly practical antibacterial agent and a method for forming a coating film. The research was started as much as possible. The problem to be solved by the present invention is to provide a thermosetting powder coating material which is excellent in coating film appearance such as smoothness and can provide a coating film having high antibacterial properties, and a coating film forming method using the powder coating material. To provide.

[0007]

Means for Solving the Problems The present inventors have earnestly studied to solve the above-mentioned problems, and as a result, as a coating film forming component, a thermosetting resin (A) and a curing agent (B) were used. , A coating film formed by using a thermosetting powder coating obtained by spray drying an organic solvent solution containing an antibacterial agent (C) as an essential component is particularly excellent in coating appearance such as smoothness. Moreover, they have found that they also have high antibacterial properties, and have completed the present invention.

That is, the present invention, as a coating film forming component,
It is obtained by spray-drying an organic solvent solution containing a thermosetting resin (A), a curing agent (B), and an antibacterial agent (C) as essential components, and has an average particle diameter of 5 to 50 μm. The present invention provides a thermosetting powder coating material.

Further, the present invention is characterized in that the above-mentioned thermosetting powder coating material is used as a top coating material in a coating film forming method for forming a single-layer or multi-layer coating film on an object to be coated. The present invention also provides a method for forming a coating film.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The details of the present invention will be specifically described below. The thermosetting powder coating material of the present invention is obtained by spray drying an organic solvent solution or dispersion containing a thermosetting resin (A), a curing agent (B) and an antibacterial agent (C) as essential components. The average particle size is 5 to 50
It is characterized by being μm. Considering the smoothness of the thin film, the thickness is more preferably 10 to 30 μm. The above average particle diameter means a volume average median diameter, and for example, a laser diffraction particle size analyzer (SALD-2 manufactured by Shimadzu Corporation).
000).

Further, the powder coating material of the present invention is essentially spherical, and its average circularity is preferably 0.9 or more. By using a spherical powder paint, the paint fluidity and repaintability are improved. From this viewpoint, it is preferable that the particles having a circularity of 0.9 or more have a frequency of 50% or more, and more preferably 70% or more.

The circularity and the average circularity referred to here are one of the particle shape indexes representing the unevenness of the particle surface,
It is expressed as the following equation.

Circularity = (perimeter of a circle having the same area as the projected area of the particle) / (perimeter of the projected image of the particle)

Therefore, the circularity becomes 1 if the particle image is a perfect circle, and becomes smaller as the particle image deviates from the perfect circle and becomes elongated or uneven. The average circularity is calculated by dividing the sum of the circularity of each particle by the total number of particles. The shape and average circularity of the above powder coating material are determined by a flow type particle image analyzer (FPIA-
1000, manufactured by Toa Medical Electronics Co., Ltd. The shape of the powder coating material can also be confirmed by a scanning electron microscope.

Next, spray drying will be described. The powder coating material of the present invention is an organic solvent solution containing a coating film forming component (hereinafter,
Described as a powder coating material solution. ) Is obtained by spray drying. The apparatus used for spray drying may be one capable of removing the organic solvent from the sprayed powder coating material solution, for example, by contacting the sprayed powder coating material solution with a heat source gas to volatilize the organic solvent. A spray drying device or the like can be used. Since the organic solvent is volatilized, it is desirable that the device be explosion proof. Further, from the viewpoint of keeping the vapor content of the solvent in the heat source gas low, which is used for drying the sprayed powder coating material raw material solution, it is desirable to provide a solvent recovery device.

In the case of using the above-mentioned spray dryer for contacting the sprayed powder coating material raw material solution with the heat source gas to volatilize the organic solvent, the contact system between the powder coating material raw material solution and the heat source gas is not particularly limited. Instead, any method such as a co-current type, a counter-current type, a co-current / counter-current mixed type, which is commonly used, may be used.

Regarding the spraying method of the powder coating material solution,
Any of known and conventional types such as a rotating disk type, a two-fluid nozzle type, and a pressure nozzle type can be used. Factors for controlling the particle size during spraying include the rotation speed of the disk in the rotary disk system, the discharge speed from the nozzle in the two-fluid nozzle system, and the compression used by mixing with the raw material solution. The mixing ratio of air and the raw material solution, and the pressure nozzle type include the discharge pressure and the like, but these values may be appropriately determined according to the target particle size.

The feed rate of the raw material solution and the flow rate of the heat source gas may be appropriately determined according to the target particle size, but if the feed rate of the raw material solution and the flow rate of the heat source gas change during spray drying, Since the particle size, particle size distribution and non-volatile content of the obtained particles also change, it is desirable to keep it constant during spray drying.

Usually, the heat source gas containing particles obtained by spray drying is continuously guided to a classifying apparatus represented by a cyclone, and particles are collected and classified. In order to adjust the particle size distribution of the powder coating material of the present invention, when it is necessary to perform classification for removing coarse particles and fine particles, a commercially available general classifier can be used.

An inert gas is desirable as the heat source gas. Above all, it is preferable to use nitrogen gas in terms of cost and the like. The temperature of the heat source gas is a temperature at which the thermosetting resin and the curing agent of the powder coating material solution do not substantially cause a curing reaction, that is, the coating material of the powder coating obtained even if a partial curing reaction occurs. The temperature may be appropriately determined within a temperature range in which the performance as is not substantially impaired. The lower limit of the temperature of the heat source gas is not particularly limited, but in order to evaporate the solvent efficiently, 30 ° C or higher is preferable, and 40 ° C or higher is more preferable. Usually, the temperature of the heat source gas is 30 to 160 ° C, preferably 40 to 13 ° C.
It is appropriately determined within the range of 0 ° C.

The flow rate of the heat source gas and the supply rate of the powder coating material solution may be appropriately adjusted according to the intended particle size under the condition that the non-volatile content of the obtained particles is 99% by weight or more. . The pressure inside the apparatus is not particularly limited, and may be normal pressure, reduced pressure, or increased pressure.

The non-volatile content concentration of the powder coating material solution at the time of spray drying may be appropriately determined according to the specifications of the spray drying apparatus and the spray drying conditions.

Further, in order to evaporate the solvent more efficiently, the powder coating material raw material solution may be preheated before spray drying. At this time, the temperature for preheating is preferably 70 ° C. or lower in order to prevent gelation of the powder coating material raw material solution, and spray drying is preferably performed as soon as possible after preheating.

The powder coating thus obtained can be used as it is as a powder coating, but it may be secondarily dried by another drying method such as vacuum drying, if necessary. In that case, in order to prevent gelation of the powder coating material, it is desirable that the secondary drying be performed at a temperature of about 70 ° C. or lower.

The powder coating material solution used in the present invention is
At a temperature lower than the temperature when spraying, for example, at room temperature,
It is preferable that the thermosetting resin and the curing agent are completely dissolved in the organic solvent. When it is completely dissolved, the thermosetting resin and the curing agent are more uniformly mixed, and the appearance of the coating film, especially of the coating film, as compared with the mixing by melt kneading which is performed in the conventional manufacturing method. This is because it is possible to obtain a powder coating material with significantly improved sharpness. A solvent that does not dissolve both the thermosetting resin and the curing agent can be used as long as it does not impair the storage stability of the powder coating material raw material solution.

Next, the thermosetting resin (A) which is a coating film forming component will be described. As the thermosetting resin (A),
Any of the resins commonly used in powder coatings such as acrylic resins, polyester resins, and epoxy resins can be used, but acrylic resins and polyester resins are preferred. Further, as the thermosetting resin (A), a resin having a softening point in the range of 80 to 150 ° C. can be obtained because a powder coating having excellent storage stability during storage and a good balance of coating film appearance can be obtained. Particularly preferred.

When the thermosetting resin (A) is an acrylic resin, a known and conventional method can be applied to prepare the base acrylic resin, but a curing reactive group-containing vinyl monomer is further required. Accordingly, a method of using other copolymerizable vinyl monomers and polymerizing each of these monomers in an organic solvent is recommended because it is the simplest method. As the polymerization initiator and solvent used at that time, known and conventional ones can be used as they are.

Examples of the curing reactive group of the thermosetting resin (A) include an epoxy group, a carboxyl group, a hydroxyl group, an amide group, an amino group, an acid anhydride group, and a (block) isocyanate group. Since it is easy, at least one selected from the group consisting of epoxy groups, carboxyl groups and hydroxyl groups is desirable. Above all,
It is more preferable that at least one of the curing reactive groups is an epoxy group because of excellent storage stability and coating appearance.

To exemplify only typical vinyl monomers having a curing reactive group, first, when the curing reactive group is an epoxy group, for example, glycidyl (meth) acrylate, Various epoxy group-containing monomers such as β-methylglycidyl (meth) acrylate, glycidyl vinyl ether and allyl glycidyl ether; (2-oxo-1,3-oxolane) methyl (meth) acrylate, (2- Oxo-1,3-
Oxolane) group-containing vinyl monomers; 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4
There are various alicyclic epoxy group-containing vinyl monomers such as epoxycyclohexylethyl (meth) acrylate.

When the curing reactive group is a carboxyl group, various carboxyl group-containing monomers such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid; monomethyl fumarate; Monoethyl fumarate, monobutyl fumarate, monoisobutyl fumarate,
Monotert-butyl fumarate, monohexyl fumarate, monooctyl fumarate, mono-2-ethylhexyl fumarate, monomethyl maleate, monoethyl maleate, monobutyl maleate, monoisobutyl maleate, monotert-butyl maleate, monohexyl maleate. , Monooctyl maleate, mono 2 maleate
-Monoesters of various α, β-unsaturated dicarboxylic acids such as ethylhexyl and monohydric alcohols having 1 to 18 carbon atoms; monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, monoisobutyl itaconate, There are monoalkyl esters of itaconic acid, such as monohexyl itaconic acid, monooctyl itaconic acid and mono-2-ethylhexyl itaconic acid.

When the curing-reactive group is a hydroxyl group, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate. , 3-hydroxybutyl (meth)
Various hydroxyl group-containing (meth) acrylates such as acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate;
Addition reaction products of various (meth) acrylates and ε-caprolactone as listed above;

2-hydroxyethyl vinyl ether, 3
-Hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-
Hydroxy-2-methylpropyl vinyl ether, 5-
Various hydroxyl group-containing vinyl ethers such as hydroxypentyl vinyl ether and 6-hydroxyhexyl vinyl ether; various vinyl ethers as listed above,
addition reaction product with ε-caprolactone;

2-hydroxyethyl (meth) allyl ether, 3-hydroxypropyl (meth) allyl ether, 2-hydroxypropyl (meth) allyl ether,
4-hydroxybutyl (meth) allyl ether, 3-hydroxybutyl (meth) allyl ether, 2-hydroxy-2-methylpropyl (meth) allyl ether, 5-
Various hydroxyl group-containing allyl ethers such as hydroxypentyl (meth) allyl ether and 6-hydroxyhexyl (meth) allyl ether; addition reaction products of various allyl ethers listed above with ε-caprolactone .

Further, other copolymerizable vinyl monomers can be used, if necessary, but only representative examples of such other copolymerizable monomers are given. For example, various acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate; methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert.
Various methacrylic acid esters such as butyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate;

Various α-olefins such as ethylene, propylene and butene-1; Various halogenated olefins (halo olefins) other than fluoroolefins such as vinyl chloride and vinylidene chloride; styrene and α
Various aromatic vinyl monomers such as methylstyrene, vinyltoluene;

Dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dioctyl fumarate, dimethyl maleate, diethyl maleate, dibutyl maleate, dioctyl maleate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, dioctyl itaconate. Such as various unsaturated dicarboxylic acids with 1 to 18 carbon atoms
Diesters with monohydric alcohols;

Various amino group-containing amides such as N-dimethylaminoethyl (meth) acrylamide, N-diethylaminoethyl (meth) acrylamide, N-dimethylaminopropyl (meth) acrylamide and N-diethylaminopropyl (meth) acrylamide Unsaturated monomers; various dialkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate;

Tert-Butylaminoethyl (meth) acrylate, tert-butylaminopropyl (meth)
Various amino group-containing monomers such as acrylate, aziridinylethyl (meth) acrylate, pyrrolidinylethyl (meth) acrylate, piperidinylethyl (meth) acrylate; maleic anhydride, itaconic anhydride,
Various acid anhydride group-containing monomers such as citraconic anhydride, anhydrous (meth) acrylic acid, and tetrahydrophthalic anhydride;

Diethyl-2- (meth) acryloyloxyethyl phosphate, dibutyl-2- (meth) acryloyloxybutyl phosphate, dioctyl-2
-(Phosphorus ester group-containing monomers such as meacryloyloxyethyl phosphate and diphenyl-2- (meth) acryloyloxyethyl phosphate);
Various hydrolyzable silyl group-containing monomers such as γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane and γ- (meth) acryloyloxypropylmethyldimethoxysilane;

Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, branched (branched) aliphatic vinyl carboxylate having 9 carbon atoms. ,
Various aliphatic vinyl carboxylates such as branched aliphatic vinyl carboxylates having 10 carbon atoms, branched aliphatic vinyl carboxylates having 11 carbon atoms, and vinyl stearate;

Vinyl cyclohexanecarboxylate, vinyl methylcyclohexanecarboxylate, vinyl benzoate, p
There are various vinyl esters of carboxylic acids having a cyclic structure such as -tert-butyl vinyl benzoate.

The amount of the various curing reactive group-containing vinyl monomers as exemplified above is appropriately in the range of 10 to 70% by weight based on the total amount of vinyl monomers used. When the amount of the curing-reactive group-containing vinyl monomer used is within the above range, a coating film having excellent mechanical properties and flexibility can be obtained.

The number average molecular weight of the thermosetting acrylic resin is preferably in the range of 1,000 to 20,000, and more preferably in the range of 1,500 to 15,000. . When the number average molecular weight of the thermosetting acrylic resin is within the above range, a coating film having excellent smoothness and mechanical properties can be obtained.

The preparation method for obtaining the polyester resin used as the thermosetting resin (A) is not particularly limited, and various known and conventional methods can be used, but polyhydric alcohol and polybasic acid are condensed. It is manufactured by the method. As the curing-reactive group, a carboxyl group and / or a hydroxyl group is preferably adopted because of easy preparation.

As the polyhydric alcohol and polybasic acid that can be used as a raw material for the polyester resin used as the thermosetting resin (A), various known and commonly used compounds can be used. Use of these polyhydric alcohol and polybasic acid A polyester resin having a carboxyl group and / or a hydroxyl group can be obtained by adjusting the amount.

First of all, only representative examples of the above-mentioned polyhydric alcohols will be given. Ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol. , 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, triethylene glycol, bis-hydroxyethyl terephthalate, cyclohexanedimethanol, octanediol, diethylpropanediol, butylethylpropanediol, 2-methyl-1. , 3-propanediol, 2,2,4-trimethylpentanediol, hydrogenated bisphenol A, ethylene oxide adduct of hydrogenated bisphenol A, propylene oxide adduct of hydrogenated bisphenol A, Trimethylol ethane, trimethylol propane, glycerine, pentaerythritol, tris-hydroxyethyl isocyanurate, and the like hydroxypivalic valyl hydroxy pivalate.

On the other hand, if only typical examples of the above-mentioned polybasic acids are given, terephthalic acid,
Isophthalic acid, phthalic acid, methylterephthalic acid, trimellitic acid, pyromellitic acid or their anhydrides; succinic acid, adipic acid, azelaic acid, sebacic acid or their anhydrides; maleic acid, itaconic acid or their anhydrides Fumaric acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid or their anhydrides; cyclohexanedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and the like.

Further, as a raw material of the polyester resin, a compound having both a carboxyl group and a hydroxyl group in one molecule such as dimethanolpropionic acid and hydroxypivalate; "Cadura E10" (branched by Shell Co., Netherlands) Monoepoxy compounds such as glycidyl ester of aliphatic carboxylic acid); such as methanol, propanol, butanol, benzyl alcohol,
Various monohydric alcohols; various monohydric basic acids such as benzoic acid and p-tert-butylbenzoic acid; various fatty acids such as castor oil fatty acid, coconut oil fatty acid, soybean oil fatty acid and the like can also be used. it can.

As the polyester resin obtained by using various polyhydric alcohols, polybasic acids and other raw materials as listed above, the total of the acid value and the hydroxyl value is 10
To 250 (mgKOH / g; the same applies below),
Further, it is desirable to use those having a number average molecular weight of 500 to 10,000.

When the sum of the acid value and the hydroxyl value is within the above range, a coating film having excellent smoothness and mechanical properties can be obtained. Further, when the number average molecular weight is within the above range, not only a coating film having excellent smoothness and mechanical properties can be obtained, but also a coating having excellent storage stability can be obtained.

The structure of the polyester resin is not particularly limited as long as it is within the range of various characteristic values of the resin as described above, and may have a branched structure or a linear structure.

The epoxy resin which can be used as the thermosetting resin (A) is not particularly limited, and examples thereof include an epoxy resin such as polyglycidyl ether of bisphenol-A.

Next, the curing agent (B) will be described. As the curing agent (B) used in the present invention, a curing agent (B) that is usually used for a powder coating material is appropriately selected and used depending on the type of the curing reactive group of the base resin (B). To be done.

As the curing agent (B), when the curing-reactive group of the thermosetting resin (A) is an epoxy group, succinic acid, glutaric acid, Adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecane dicarboxylic acid, eicosane dicarboxylic acid, maleic acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, trimellitic acid, pyromellitic acid, tetrahydrophthalic acid, Hexahydrophthalic acid, cyclohexene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, or acid anhydrides thereof are available. Among them, since they are excellent in coating film physical properties and storage stability, they are aliphatic dibases. An acid is preferred, and dodecanedicarboxylic acid is particularly preferred because of its excellent coating film properties.

Further, when the curing reactive group of the thermosetting resin (A) is a carboxyl group, only representative examples of the curing agent (B) will be exemplified, and the polyglycidyl ether of bisphenol A will be described. Such as various epoxy resins; glycidyl group-containing acrylic resins, epoxy group-containing acrylic resins, polyglycidyl ethers of various polyhydric alcohols such as 1,6-hexanediol, trimethylolpropane and trimethylolethane; phthalates Acid, terephthalic acid, isophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, trimellitic acid, pyromellitic acid, polyglycidyl esters of various polycarboxylic acids; bis (3,4-epoxycyclohexyl) Various alicyclic epoxy group-containing compounds such as methyl adipate; Epoxy compound having such isocyanurate ring structure triglycidyl isocyanurate, hydroxy amides such as β- hydroxyalkyl amides.

When the curing-reactive group of the thermosetting resin (A) is a hydroxyl group, a polyblock isocyanate compound, aminoplast, etc. are particularly preferable as the curing agent (B).

As the polyblock polyisocyanate compound, only representative ones are exemplified. Various aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; xylylene diisocyanate and isophorone diisocyanate, Various cyclic aliphatic diisocyanates; organic diisocyanates such as various aromatic diisocyanates such as tolylene diisocyanate and 4,4′-diphenylmethane diisocyanate, or these organic diisocyanates, polyhydric alcohols, low molecular weight polyester resins ( polyester polyols) or caprolactam and adducts, such as water, allowed blocked with known conventional blocking agent having an active hydrogen such as oxime It is of the form to be,

Furthermore, the above-mentioned polymers of organic diisocyanates (including isocyanurate type polyisocyanate compounds) and various polyisocyanate compounds such as isocyanate biuret compounds are formed into known and commonly used blocks. Examples thereof include those obtained by blocking with an agent, so-called self-blocked polyisocyanate compounds having a uretdione bond as a structural unit, and the like.

On the other hand, examples of aminoplasts include melamine, urea, acetoguanamine, benzoguanamine,
Various amino group-containing compounds such as steroganamin and spiroguanamine, and formaldehyde, paraformaldehyde, acetaldehyde and glyoxal,
Condensates in the form obtained by reacting various aldehyde-based compound components by various conventionally known methods, or compounds in the form obtained by etherifying these condensates with alcohols, etc. is there.

Specific examples of such aminoplasts are merely representative. Hexamethoxymethylolmelamine, hexabutyletherified methylolmelamine, methylbutyl mixed etherified methylolmelamine, methyletherified methylolmelamine, n-butyletherified methylol. Melamine, isobutyl etherified methylol melamine, or their condensates; various bicyclic compounds such as hexamethoxyglycoluril, hexabutoxyglycoluril, tetramethoxymethylglycoluril; aliphatic dibasic acids and diethanolamine, etc. Various acid amides in the form of being obtained by condensation reaction with various alkanolamines; Polymerizable monomers such as butyl ether of N-methylolacrylamide Alone, or other such as obtained by copolymerizing possible Naru monomers and copolymerization reaction, and the like various polymer compounds.

The above hexamethoxymethylol melamine is "Cymel 300, 301 or 303".
(Mitsui Cyanamid Co., Ltd.); Methylbutyl mixed etherified methylol melamine is "Cymel 23
8, 232 or 266 "(product of Mitsui Cyanamid); n-butyl etherified methylol melamine as" Super Beckamine L-164 "(product of Dainippon Ink and Chemicals, Inc.); tetramethoxymethylglycoluril as" Powder Link (POWDERL
INK) 1174 ”(product of American Cyanamid, Inc.); acid amides are“ PRIMID (PRIM)
ID) XL-552 "," Primid (PRIMI
D) QM-1260 "(manufactured by EMS), which is commercially available.

The above curing agent (B) may be used alone or in combination of two or more kinds. The mixing amount of the curing reactive group of the thermosetting resin (A) and the curing agent (B) is the equivalent of the curing reactive group of the thermosetting resin (A) to the equivalent of the curing reactive group of the curing agent (B). The ratio is preferably in the range of 2.0 to 0.5.

Next, the antibacterial agent (C) will be described. Antibacterial agents include organic antibacterial agents and inorganic antibacterial agents. To give a representative specific example of the organic antibacterial agent, for example,
Phenol, resorcin, cresol, biozole, thymol, β-naphthol and other phenolic antibacterial agents, imidazole, benzimidazole, thiabendazole and other imidazole antibacterial agents, chlorhexidine hydrochloride, chlorhexidine gluconate, chlorhexidine acetate, polyhexamethylene biguanidine hydrochloride, etc. Examples of the antibacterial agent include a biguanide antibacterial agent, an iodo antibacterial agent such as 2,3,3-triiodoallyl alcohol and diiodomethyl-p-trisulfone, and an antibacterial agent derived from a natural product such as allyl mustard oil, wasa auro, hinokitiol, and protamine.

Typical examples of the inorganic antibacterial agents include, for example, silver, copper, zinc, bismuth, or ions or complexes of these. Furthermore, inorganic antibacterial agents include zeolite, activated carbon, alumina, aluminum polyphosphate, silica gel, amorphous aluminosilicate,
Inorganic compounds such as hydroxyapatite, zirconium phosphate, titanium phosphate, potassium titanate, hydrous hydrated bismuth, hydrous zirconium oxide, and hydrotalcite are supported by an inorganic antibacterial agent.

Typical examples of inorganic compounds carrying an inorganic antibacterial agent are given below. For example, "Novalon AG-300" (manufactured by Toagosei Kagaku Co., Ltd., silver ion-supporting zirconium phosphate), " Zeomic "(manufactured by Sinanen New Ceramic Co., Ltd., zeolite supporting silver, zinc, copper ions, etc.)," Aime Top "(manufactured by Matsushita Electric Industrial Co., Ltd., silica gel supporting thiosulfato silver complex salt)," Apacider "(manufactured by Sangi, hydroxyapatite supporting silver ions) ), "A
"IS" (manufactured by Catalysts & Chemicals Industry Co., Ltd., silver ion-supporting silica or alumina) and "RAP" (manufactured by Lhasa Industry Co., Ltd., silver ion-supported aluminum polyphosphate) are mentioned. As the antibacterial agent used in the present invention, any of these known and commonly used antibacterial agents can be used.

Next, the organic solvent used in the present invention will be described. As the organic solvent, thermosetting resin (A) and /
Alternatively, a solvent capable of dissolving the curing agent (B) can be used, and one kind or two or more kinds of solvents may be used in combination, and the thermosetting resin (A) is a resin obtained by solution polymerization. Has
The solvent used in the polymerization of the thermosetting resin (A) can be used as it is as a part or all of the organic solvent.

Further, it is also preferable that the organic solvent contains a high boiling point solvent having a boiling point of 150 to 300 ° C. under normal pressure. By using a high boiling point solvent as a part of the organic solvent, it is possible to obtain a powder coating material which forms a coating film without causing coating film defects such as armpits and pinholes. The high boiling point solvent may be a single component or a mixture of a plurality of components.

As the high boiling point solvent, those having a boiling point of 150 to 250 ° C. under normal pressure are more preferably used.
Further, it is particularly preferable that the boiling point at normal pressure is +5 to + 150 ° C. with respect to the temperature when baking and curing the powder coating material of the present invention.

The amount of the high boiling point solvent used is preferably 0.005 to 2 parts, and more preferably 0.005 to 1 part, based on 100 parts of the solid content in the powder coating material solution.

If the boiling point of the high boiling point solvent at atmospheric pressure and the amount used are in the above-mentioned ranges, an appropriate amount of the high boiling point solvent remains in the powder coating material of the present invention, and cracks, pinholes, etc. at the time of baking and curing are caused. It is possible to prevent the generation of coating film defects.

Specific examples of such a high boiling point solvent include, but are not limited to, alcohols such as n-hexanol, n-octanol, 2-ethylhexanol, cyclohexanol and benzyl alcohol; ethylene glycol, propylene glycol and glycerin. Such as polyhydric alcohols;

Butyl cellosolve, hexyl cellosolve,
Ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, propylene glycol monobutyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, methyl carbitol, ethyl carbitol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether Glycol ethers such as;

Aromatic hydrocarbons such as propylbenzene, butylbenzene, pentylbenzene, diethylbenzene, dipropylbenzene, dipentylbenzene, dodecylbenzene, cyclohexylbenzene; Solvesso 1
00, Solvesso 150, Solvesso 200 (all manufactured by Exxon, USA), and mixed hydrocarbons containing aromatic hydrocarbons;

Exxon Naphtha No. 3, Exxon naphtha No. 5, Exxon Naphtha No. 6, Exxon Solvent No. 7, Isopar G, Isopar H, Isopar L, Isopar M, Exol D40, Exol D9
0, Exol D110 (all manufactured by Exxon Inc., USA), IP Solvent 1620, IP Solvent 202
Mixed hydrocarbons containing aliphatic hydrocarbons such as 8 (manufactured by Idemitsu Petrochemical Co., Ltd.), Merbeil 20, Merbeil 30, Merbeil 40 (manufactured by Showa Shell Sekiyu Co., Ltd.), and mineral spirits;

Glycerin alkyl ether, glycerin alkyl ester; ketones such as diisobutyl ketone, methyl amyl ketone, cyclohexanone and isophorone; cyclohexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, isoamyl propionate, butyric acid alkyl ester Esters such as, stearic acid alkyl ester, benzoic acid alkyl ester, adipic acid dialkyl ester, phthalic acid dialkyl ester;

Examples include N-methylpyrrolidone, dimethylformamide, dimethylacetamide and ethylene carbonate. Among the above high boiling point solvents, the use of an aromatic solvent and / or an aliphatic solvent is preferably used because the effect of preventing the generation of coating film defects is more remarkable.

The method of adding the high boiling point solvent to the powder coating material solution is not particularly limited, but, for example, polymerization of the thermosetting resin, which is added in advance as a part of the solvent when polymerizing the thermosetting resin, is carried out. A method such as addition after completion or immediately before spray-drying the powder coating material solution is simple and recommended, and is recommended.

As the organic solvent, well-known and commonly used organic solvents can be used in addition to the above high boiling point solvents.

As typical examples of such organic solvents, methanol, ethanol, n-
Alkyl alcohols such as propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol;

Methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether,
Glycol ethers such as propylene glycol monopropyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether;

Aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; Exxon aromatic naphtha No. 2 (manufactured by Exxon, USA), such as mixed hydrocarbons containing aromatic hydrocarbons; n-pentane, n
-Aliphatic hydrocarbons such as hexane and n-octane;
Isopar C, Isopar E, Exor DSP100
/ 140, Exol D30 (all manufactured by Exxon, USA), IP Solvent 1016 (manufactured by Idemitsu Petrochemical Co., Ltd.), mixed hydrocarbons containing aliphatic hydrocarbons; cyclopentane, cyclohexane, methylcyclohexane,
Alicyclic hydrocarbons such as ethylcyclohexane;

Ethers such as tetrahydrofuran, dioxane, diisopropyl ether, di-n-butyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, acetic acid n -Butyl, isobutyl acetate, n-amyl acetate, isoamyl acetate, hexyl acetate, ethyl propionate, butyl propionate, and other esters;

From the viewpoint of improving the drying property of the paint particles during spray drying, the remaining solvent components of the organic solvent except the high boiling point solvent have a boiling point of 100 at normal pressure.
It is preferable that the solvent at a temperature of not more than 0 ° C. accounts for 65 to 100% by weight.

When the curing agent (B) is an aliphatic dibasic acid, the organic solvent contains at least one alcohol having a carbon number of 4 or less in order to increase the solubility of the curing agent, and The amount of alcohol of the number 4 or less is 4 by weight ratio with respect to the aliphatic dibasic acid contained in the powder coating raw material solution.
It is preferably double or more.

The thermosetting powder coating composition of the present invention is prepared by dissolving the above-mentioned thermosetting resin (A) and curing agent (B) in an organic solvent, and further dissolving or dispersing the above-mentioned antibacterial agent (C). It can be produced by preparing the powder coating material solution and then spray-drying the powder coating material solution. Furthermore, if necessary, other resins such as color pigments and waxes, curing catalysts, antioxidants, leveling agents, defoaming agents,
An additive such as an ultraviolet absorber may be added to the powder coating material solution and dissolved or dispersed to form a coating material.

As a method for dissolving or dispersing the antibacterial agent (C) and other additives in the powder coating material solution, a known and commonly used mixing and stirring method can be used. In addition, a plurality of colored powder coating material solutions are mixed to adjust the color, a powder coating material solution containing a colored antibacterial agent having a desired color is prepared, and spray-dried to obtain a colored antibacterial agent. You may manufacture the thermosetting powder coating material containing an agent.

Specific examples of the color pigments include, but are not limited to, aluminum flake pigment, colored aluminum flake pigment, metallic titanium flake, alumina flake, silica flake, graphite, stainless flake, plate-shaped iron oxide, and phthalocyanine. flake,
Various known and commonly used materials such as metal or metal oxide-coated mica, metal or metal oxide-coated glass flakes, copper powder, silver powder, zinc iron copper powder, titanium oxide, rouge, chrome titanium yellow, yellow iron oxide and carbon black. Inorganic pigment,

Phthalocyanine-based compounds such as phthalocyanine blue and phthalocyanine green, anthraquinone-based compounds such as induslen blue and dianthraquinonyl red, quinacridone-based compounds, azo-based compounds such as lake red, fast yellow, disazo yellow, permanent red, and nitros such as naphthol yellow. System, pigment green B, nitroso system such as naphthol green, various conventionally known organic pigments, precipitable barium sulfate, barium carbonate, flour, gypsum, alumina white, clay, silica, silica white, talc, silicic acid. Various known and conventional extender pigments such as calcium and precipitated magnesium carbonate are used.

As only other typical resins, acrylic resins, polyester resins, fluororesins, silicone resins, chlorinated polyethylene, chlorinated polypropylene, petroleum resins, epoxy resins, chlorinated resins are given. Examples include various resins such as rubber and resins other than the thermosetting resin (A) and the curing agent (B).

As the curing catalyst, known and conventional ones can be used as they are, depending on the combination of the thermosetting resin (A) and the curing agent (B).

Further, if necessary, nitrocellulose,
Various fibrin derivatives such as cellulose acetate butyrate may be used.

Regarding the coating method, the base material to be coated is coated by various known and commonly used methods such as electrostatic spraying method or triboelectric charging coating method, fluidized dipping, etc. About 120 ~ 250 ℃
It suffices to carry out baking at the temperature of, and in this way a powder coated product can be obtained.

The thermosetting powder coating material of the present invention can be preferably used as a topcoat coating material in a coating film forming method for forming a single-layer or multi-layer coating film on an object to be coated.

Here, the article to be coated refers to a base material to which the coating material is applied, and more specifically, it is an unpainted metal material such as an unpainted steel plate or an untreated or chemically treated aluminum base material. Examples include base materials used for road vehicles such as automobile bodies and motorcycle bodies, base materials used for automobile parts such as aluminum wheels, and base materials used for beverage cans. Also included are base materials used for road vehicles such as automobile bodies that have been subjected to electrodeposition coating. Furthermore, base materials used for home appliances, vending machines, steel furniture, etc., such as electrogalvanized steel sheets, hot-dip galvanized steel sheets, roof tiles; glasses; or various inorganic building materials; gates or fences Examples include various building materials, such as a class; various building interior and exterior materials, such as an aluminum sash.

These base materials may be processed into a shape according to the end use, or may be in a form to which a PCM (pre-coat metal) coating method is applied, that is, a roughly flat plate-like base material. However, after the coating film is formed by the method of the present invention, it may be bent into a predetermined shape according to the purpose, and further, it may be completely post-processed such as coil coating. It may be a substrate used in the coating system provided.

As described above, the thermosetting powder coating material of the present invention is applied to various kinds of substrates to be coated by the conventional method, and then baked according to the conventional method. By allowing it to dry,
It is possible to give a powder coated article having excellent appearance and antibacterial properties.

[0097]

EXAMPLES Next, the present invention will be described more specifically by reference examples, examples and comparative examples, but it goes without saying that the present invention is not limited to these examples.
In the following, all "parts" mean "parts by weight" unless otherwise specified.

Example 1 (Preparation example of thermosetting powder coating composition (X-1) containing antibacterial agent according to the present invention) Finedic A-254 (Dainippon Ink and Chemicals Incorporated glycidyl group-containing solid acrylic resin epoxy equivalent 5)
00) 84 parts, dodecanedioic acid (Ube Industries, aliphatic dibasic acid) 16 parts, benzoin 0.5 part, modaflow (Monsanto company leveling agent) 1 part methyl ethyl ketone 1
It was dissolved by heating in 00 parts, 50 parts of isobutanol, and 0.5 parts of Solvesso 100 (Exxon). Then, 0.5 part of biosol as an antibacterial agent was mixed and dispersed in the above resin solution with a mixer.

This organic solvent solution was spray-dried using an explosion-proof vertical descending cocurrent spray dryer equipped with a solvent recovery device, using a rotating disk system as the spray system. The rotation speed of the disk was 15,000 rpm, nitrogen gas was used as the heat source gas, and the raw material solution and the heat source gas were brought into contact with each other in a vertically descending cocurrent manner. The gas temperature was set to 120 ° C. Feed rate of powder coating material solution preheated to 60 ° C 0.5kg / hr
The powder coating composition (X-1) was obtained by spraying into a spray drying apparatus with the above method and collecting particles of the powder coating material dried in the apparatus with a cyclone. The average particle size of the particles was 25 μm, and the average circularity was 0.92.

Example 2 (Preparation example of thermosetting powder coating composition (X-2) containing antibacterial agent according to the present invention) The antibacterial agent used in Example 1 was Novalon AG-300 (manufactured by Toagosei Kagaku Co., Ltd.) 0.5. A powder coating material (X-2) was prepared in the same manner as in Example 1 except that the parts were changed. Average particle size is 26 μm
The average circularity was 0.91.

Example 3 (Preparation Example of Thermosetting Powder Coating (X-3) Containing Antibacterial Agent According to the Present Invention) Finedic M-8034 (Dainippon Ink and Chemicals Incorporated Hydroxyl group-containing solid polyester resin, hydroxyl value 30)
87 parts, Vestagon B-1530 (manufactured by Degussa, blocked isocyanate compound) 13 parts, benzoin 0.5
Parts, 1 part of Modaflow (a leveling agent manufactured by Monsanto) were dissolved in 150 parts of methyl ethyl ketone and 0.5 parts of Solvesso 150 (Exxon) by heating. Then, as an antibacterial agent, Novalon AG-300 (manufactured by Toagosei Kagaku) 1.0
Parts were mixed and dispersed in the above resin solution with a mixer. This organic solvent solution was spray dried in the same manner as in Example 1. A powder coating material (X-3) was obtained by collecting particles of the powder coating material dried in the apparatus with a cyclone. The average particle size of the particles was 30 μm, and the average circularity was 0.95.

Example 4 (Preparation example of thermosetting powder coating material (X-4) containing antibacterial agent according to the present invention) Finedick M-8961 (Dainippon Ink and Chemicals Incorporated carboxylic acid group-containing solid polyester resin acid value) Three
3) 95 parts, Primid XL552 (manufactured by EMS, hydroxyalkylamide) 5 parts, benzoin 0.5 part, modaflow (Monsanto leveling agent) 1 part, methyl ethyl ketone 150 parts, Solvesso 100 (Exxon)
It melt | dissolved in 0.5 part by heating. Then, Taipaek CR-9
30 parts of 0 (acid value titanium manufactured by Ishihara Sangyo Co., Ltd.) and 1.0 part of diiodomethyl-p-trisulfone as an antibacterial agent were mixed and dispersed in the above resin solution with a mixer. This organic solvent solution was spray dried in the same manner as in Example 1. By collecting particles of the powder coating dried in the device with a cyclone,
A powder coating (X-4) was obtained. Average particle size is 40 μm
The average circularity was 0.95.

Reference Example 1 (Powder coating for base coat (T-
Preparation of 1)) In Example 1, the antibacterial agent was not added, and Alpaste 12
A powder coating containing 10 parts of 00M (a non-leafing type aluminum pigment manufactured by Toyo Aluminum Co., Ltd.) was prepared. The average particle size was 26 μm and the average circularity was 0.91.

Comparative Reference Example 1 (Preparation of Powder Coating (Z-1) by Melt-Kneading Antibacterial Agent for Comparison) Finedic A-254 (Dainippon Ink and Chemicals Incorporated Solid Acrylic Resin Containing Glycidyl Group Epoxy Equivalent 5)
00) 84 parts, dodecanedioic acid (Ube Industries, aliphatic dibasic acid) 16 parts, benzoin 0.5 part, modaflow (Monsanto company leveling agent) 1 part and Novalon AG-300 (Toagosei Kagaku Kagaku) as an antibacterial agent. (Manufactured by the company) 0.5 part is mixed with a Henschel mixer, and Busus Conider PR46 type 1
The mixture was melt-kneaded with a shaft kneader at 100 ° C. for 100 revolutions, cooled, pulverized, and classified with a 200-mesh wire net to obtain a powder coating (Z-1). The average particle size was 45 μm and the average circularity was 0.82.

Comparative Reference Example 2 (Preparation of Powder Coating (Z-2) Dry-blended with Antibacterial Agent for Comparison) 100 parts of the powder coating prepared without adding the antibacterial agent in Example 1 was used as an antibacterial agent. 0.5 part of biosol was dry blended for 2 minutes with a Henschel mixer to prepare a powder coating (Z-2).

Powder coatings (X-1) obtained in Examples
(X-4) and comparative reference powder coatings (Z-1) to (Z-
2) is coated on a 0.8 mm thick polished steel plate treated with zinc phosphate with an electrostatic spray coating machine for powder coating, and then baked at 180 ° C. for 20 minutes to give a cured coating film. Various test plates formed were obtained. The evaluation and judgment results of these coating films are summarized in Table 1.

On the surface of the test plate, a suspension of Escherichia coli, which is known as a bacterium that affects the human body, was dropped, and a film was adhered thereto and stored at 35 ° C. for 24 hours. The surviving bacteria on the coated article were washed out with (Muller Hilton medium). This wash solution was used as a test solution and cultured at 37 ° C. for 2 days by a pour plate culture method using a culture medium for measuring the number of bacteria to measure the number of viable cells in the wash solution. In addition, antibacterial property is CFU / mL
The evaluation was made by the change in the number of viable bacteria represented by (colony forming unit per 1 mL of the washing solution). The results of these evaluations are summarized in Table 2.

Then, the powder coating material (T
-1) was used as a base coat paint and baked at 180 ° C. for 20 minutes, and then as the top coat paint, the powder paints (X-1) to (X-3) obtained in Examples and the powder paint for comparison reference (Z- A multilayer coating film was formed by curing 1) to (Z-2) at 180 ° C. for 20 minutes. The evaluation and judgment results of these coating films are summarized in Table 3. In addition, the results of evaluation and determination of antibacterial properties of these coating films are summarized in Table 4.

[0109]

[Table 1]

[0110]

[Table 2]

[0111]

[Table 3]

[0112]

[Table 4]

<< Procedures for Evaluation of Physical Properties of Coating Film and Antibacterial Property >> Film Thickness: Measured with an electromagnetic film thickness meter. Smoothness: Five-level evaluation and judgment were carried out by visual judgment. Evaluation "5"; Evaluation of very smooth and smooth coated surface "4"; Evaluation of small rounds "3"; Evaluation of large rounds "2"; Evaluation of large rounds and many fine dust skin When observed: Evaluation “1”; when there is a large round, the fine dust skin is remarkable, and the appearance of the coating film is significantly impaired.

Coating gloss: Measured by the specular gloss of JIS-K5400. Antibacterial property: Change in viable cell count expressed in CFU / mL (colony forming unit per 1 mL of wash)

[0115]

As has been made clear by the detailed description above,
It is an object of the present invention that the thermosetting powder coating material and the multilayer coating film according to the present invention have, in particular, an excellent appearance and a high antibacterial property as compared with the case of the comparative example. Expression of various effects is recognized.

Front page continuation (51) Int.Cl. ⁷ identification code FI theme code (reference) C09D 7/12 C09D 7/12 163/00 163/00 F term (reference) 4D075 AE03 CA45 CA48 CB04 DA06 DB02 DB05 DB07 DB13 DB14 DC01 DC10 DC18 DC38 EA02 EA19 EB08 EB13 EB16 EB19 EB20 EB22 EB32. HA416 HA446 HA466 JA39 JA64 JB18 JB20 JB32 JC12 JC38 JC43 KA02 KA03 KA06 MA02 MA07 MA09 MA10 NA05 PA06 PA19

Claims (5)

[Claims] 1. An organic solvent solution or dispersion containing a thermosetting resin (A), a curing agent (B), and an antibacterial agent (C) as essential components as a film-forming component is obtained by spray drying. A thermosetting powder coating material having an average particle diameter of 5 to 50 μm. 2. The average circularity of the thermosetting powder coating material is 0.9.
The thermosetting powder coating material according to claim 1, which is as described above. 3. The thermosetting resin (A) has a curing-reactive group,
3. At least one selected from the group consisting of epoxy group, carboxyl group and hydroxyl group.
The thermosetting powder coating material described in 1. 4. The thermosetting resin (A) according to claim 1, wherein at least one curing reactive group is an epoxy group, and the curing agent (B) is an aliphatic dibasic acid. Thermosetting powder coating. 5. A method for forming a single-layer or multi-layer coating film on an article to be coated, wherein the thermosetting powder coating composition according to claim 1 is used as a top coat. A method for forming a coating film, which is used as a paint.