WO2021215252A1 - Resin composition for powder coating material, powder coating material, and article having coating film formed of said coating material - Google Patents

Resin composition for powder coating material, powder coating material, and article having coating film formed of said coating material Download PDF

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Publication number
WO2021215252A1
WO2021215252A1 PCT/JP2021/014843 JP2021014843W WO2021215252A1 WO 2021215252 A1 WO2021215252 A1 WO 2021215252A1 JP 2021014843 W JP2021014843 W JP 2021014843W WO 2021215252 A1 WO2021215252 A1 WO 2021215252A1
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Prior art keywords
meth
powder coating
coating material
acrylate
resin composition
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PCT/JP2021/014843
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French (fr)
Japanese (ja)
Inventor
村上　晃一
奈緒之 清家
雄一郎 柴
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Dic株式会社
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Priority to CN202180029540.0A priority Critical patent/CN115427523A/en
Priority to KR1020227033394A priority patent/KR20220143944A/en
Priority to JP2022503951A priority patent/JP7070818B2/en
Publication of WO2021215252A1 publication Critical patent/WO2021215252A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
    • 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
    • C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/24—Homopolymers or copolymers of amides or imides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/03—Powdery paints

Definitions

  • the present invention relates to a resin composition for powder coating material, a powder coating material, and an article having a coating film of the coating material.
  • powder paints are in the limelight as solvent-free paints from the viewpoint of environmental protection.
  • acrylic powder paints have excellent coating performance such as weather resistance and stain resistance, so aluminum wheels, etc. It is attracting attention for applications such as automobile parts, metal exteriors, and home appliances.
  • the powder coating material has a drawback that the smoothness of the coating film is inferior to that of the solvent type coating material.
  • the epoxy group-containing acrylic resin obtained by copolymerizing a (meth) acrylic acid alkyl ester, an epoxy group-containing acrylic monomer, and other copolymerizable vinyl-based monomers can react with an epoxy group.
  • a powder coating material containing a curing agent having a functional group has been proposed (see, for example, Patent Document 1).
  • the cured coating film obtained from this powder coating film has improved smoothness, it has a problem of insufficient thread rust resistance.
  • the problem to be solved by the present invention is a resin composition for powder coating material, a powder coating material, and a coating material of the coating material, which can obtain a cured coating material having excellent smoothness, flexibility, and thread rust resistance. To provide goods.
  • the present inventors have made an acrylic monomer having an epoxy group, an acrylic monomer having a specific structure, and other unsaturated monomers as essential raw materials.
  • the invention was completed by finding that the cured coating film obtained from the resin composition for powder coating material containing a resin is excellent in smoothness, flexibility, and thread rust resistance.
  • the acrylic monomer (a1) having an epoxy group the acrylic monomer (a2) represented by the following general formula (1), the acrylic monomer (a1) and the polypoly acrylic are used.
  • a resin composition for powder coating which contains an acrylic resin (A) containing an unsaturated monomer (a3) other than the weight (a2) as an essential raw material.
  • the present invention relates to powder coating materials and articles coated with the coating materials.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a hydrogen atom or a branched or non-branched alkyl group having 1 to 8 carbon atoms
  • R 3 has 1 carbon atom. Represents a branched or non-branched alkyl group of ⁇ 8)
  • the resin composition for powder coatings of the present invention is excellent in appearance, flexibility, and thread rust resistance, and can form a cured coating film. Therefore, it is suitably used as a coating material for coating articles such as aluminum wheels. Can be done.
  • the resin composition for powder coating of the present invention comprises an acrylic monomer (a1) having an epoxy group, an acrylic monomer (a2) represented by the following general formula (1), and the acrylic monomer (a2). It contains an acrylic resin (A) containing an unsaturated monomer (a3) other than the a1) and the acrylic monomer (a2) as an essential raw material.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a hydrogen atom or a branched or non-branched alkyl group having 1 to 8 carbon atoms
  • R 3 has 1 carbon atom. Represents a branched or non-branched alkyl group of ⁇ 8)
  • the acrylic resin (A) will be described.
  • the acrylic resin (A) has an epoxy group
  • the acrylic monomer (a1), the acrylic monomer (a2), and the unsaturated monomer (a3) are copolymerized with each other. Obtained by
  • the acrylic monomer (a1) is an acrylic monomer having an epoxy group, and is, for example, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, (meth) allyl glycidyl ether, (meth) allyl methyl glycidyl ether. , 3,4-Epoxide cyclohexylmethyl (meth) acrylate and the like, and among these, glycidyl (meth) acrylate is preferable.
  • These acrylic monomers (a1) can be used alone or in combination of two or more.
  • (meth) acrylic acid refers to one or both of methacrylic acid and acrylic acid
  • (meth) acrylate refers to one or both of methacrylate and acrylate
  • (meth) acrylate refers to one or both of methacrylate and acrylate
  • (meth) acrylate refers to one or both of methacrylate and acrylate
  • (meth) acrylate refers to one or both of methacrylate and acrylate
  • (meth) acrylate refers to one or both of methacrylate and acrylate
  • (meth) acrylate refers to one or both of methacrylate and acrylate
  • the acrylic monomer (a2) is an acrylic monomer represented by the general formula (1), and is, for example, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, and N-isopropyl (meth). ) Acrylamide, Nt-butyl (meth) acrylamide, Nt-octyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide and the like.
  • N-isopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, and N, N-diethyl (meth) acrylamide are preferable because they have an excellent balance between the flexibility of the coating film and the resistance to thread rust.
  • These acrylic monomers (a2) can be used alone or in combination of two or more.
  • the unsaturated monomer (a3) is an unsaturated monomer other than the acrylic monomers (a1) and (a2), and is, for example, (meth) acrylic acid, methyl (meth) acrylate, and ethyl (meth). ) Acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (Meta) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, cetyl (
  • EO-modified triacrylate of isocyanuric acid trimethylolpropane tri (meth) acrylate, trimethylolpropane EO-modified tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylol propanetetraacrylate, dipentaerythritol hexa (meth) acrylate , Dipentaerythritol Penta (meth) acrylate and other trifunctional or higher functional monomers, among these, styrene and / or because of the excellent balance between the flexibility of the coating film and the resistance to thread rust.
  • acrylic monomers (a3) can be used alone or in combination of two or more.
  • the amount of the acrylic monomer (a1) used is 10 to 60% by mass in the monomer component which is the raw material of the acrylic resin (A) because the appearance of the coating film and the thread rust resistance are improved. It is preferably 20 to 50% by mass, more preferably 20 to 50% by mass.
  • the amount of the acrylic monomer (a2) used is 0.1 to 30% by mass in the monomer component which is the raw material of the acrylic resin (A) because the thread rust resistance of the coating film is improved. It is preferably 0.5 to 20% by mass, more preferably 0.5 to 20% by mass.
  • the amount of the acrylic monomer (a3) used is 30 to 80% by mass in the monomer component which is the raw material of the acrylic resin (A) because the flexibility of the coating film and the thread rust resistance are improved. Is preferable, and 40 to 80% by mass is more preferable.
  • the glass transition temperature of the acrylic resin (A) is preferably 20 to 120 ° C. because the thread rust resistance of the coating film is improved. More preferably, it is 40 to 100 ° C.
  • Tg glass transition temperature to be obtained, W1: weight fraction of component 1, Tg1: glass transition temperature of homopolymer of component 1
  • the number average molecular weight of the acrylic resin (A) is preferably 1,000 to 10,000 because it is excellent in fluidity at the time of melting and thread rust resistance. More preferably, it is 2,000 to 8,000.
  • the number average molecular weight is a value converted to polystyrene based on gel permeation chromatography (hereinafter abbreviated as "GPC") measurement.
  • the method for obtaining the acrylic resin (A) can be carried out by a known polymerization method using the acrylic monomer (a1), the acrylic monomer (a2) and the unsaturated monomer (a3) as raw materials.
  • the solution radical polymerization method is preferable because it is the simplest.
  • the above solution radical polymerization method is a method in which each monomer as a raw material is dissolved in a solvent and a polymerization reaction is carried out in the presence of a polymerization initiator.
  • the solvent that can be used in this case are hydrocarbon solvents such as toluene, xylene, cyclohexane, n-hexane and octane; alcohols such as methanol, ethanol, isopropanol, n-butanol, isobutanol and sec-butanol.
  • Ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether; esters such as methyl acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, etc.
  • Solvents Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like can be mentioned. These solvents can be used alone or in combination of two or more.
  • Examples of the polymerization initiator include ketone peroxide compounds such as cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, and methylcyclohexanone peroxide; 1,1-bis (tert-butylperoxy) -3, 3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, 2,2-bis (4,5-di) tert-butylperoxycyclohexyl) propane, 2,2-bis (4,5-ditert-amylperoxycyclohexyl) propane, 2,2-bis (4,54-ditert-hexylperoxycyclohexyl) propane, 2 Peroxyketal compounds such as 2-bis (4,5-ditert-octylperoxycyclohexyl) propane, 2,2-bis (4,54-dicumyl
  • Peroxide compounds such as bis (tert-butylcyclohexyl) peroxydicarbonate; tert-butylperoxy-2-ethylhexanoate, tert-butylperoxybenzoate, 2,5-dimethyl-2,
  • Organic peroxides such as peroxyester compounds such as 5-di (benzoylperoxy) hexane, 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), etc. Azo compound of.
  • the resin composition for powder coating material of the present invention contains the acrylic resin (A), but since the physical properties of the coating film are further improved, a curing agent (B) having a functional group capable of reacting with an epoxy group. ) Is preferably contained.
  • the curing agent (B) is a curing agent having a functional group capable of reacting with an epoxy group.
  • Polyvalent carboxylic acid compounds such as brassic acid, tetradecanedicarboxylic acid, pentadecanedicarboxylic acid, hexadecanedicarboxylic acid, heptadecanedicarboxylic acid, octadecanedicarboxylic acid, eikosandicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, butanetricarboxylic acid, and many others. Examples thereof include anhydrides of valent carboxylic acids and polyvalent phenol compounds.
  • an aliphatic polyvalent carboxylic acid compound and an anhydride thereof are preferable, and dodecanedicarboxylic acid is more preferable, because a high-strength coating film can be obtained.
  • these curing agents (B) can be used alone or in combination of two or more.
  • the acrylic resin (A) and the curing agent (B) in the resin composition for powder coating of the present invention a high-strength coating film can be obtained, so that the acrylic resin (A) has
  • the equivalent ratio (A / B) of the equivalent number of epoxy groups to the equivalent number of functional groups capable of reacting with the epoxy group in the curing agent (B) is preferably 0.5 to 1.5, preferably 0.8. ⁇ 1.2 is more preferable.
  • the resin composition for powder coatings of the present invention includes organic or inorganic pigments, leveling agents, flow modifiers, light stabilizers, ultraviolet absorbers, and oxidations, as long as the effects of the present invention are not impaired.
  • Various known and commonly used additives such as inhibitors can be added.
  • a catalyst can be added for the purpose of accelerating the curing reaction during baking.
  • the resin composition for powder coating material of the present invention contains water such as silica, alkoxysilane, and a silane coupling agent within a range that does not impair the effects of the present invention.
  • Degradable silane compounds can be further included. These compounds may be used alone or in combination of two or more.
  • silane coupling agents examples include glycidyl alkoxysilane and aminoalkoxysilane. Among these, glycidyltrialkoxysilane is preferable, and glycidyltrimethoxysilane is more preferable, because a coating film having excellent thread rust resistance can be obtained.
  • the blending amount of the silane coupling agent is preferably 0.01 to 3% by mass, preferably 0.01 to 1% by mass, in the resin composition for powder coating material, because a coating film having excellent thread rust resistance can be obtained. % Is more preferable.
  • a so-called mechanical pulverization method in which various additives such as a surface conditioner are mixed, and then they are melt-kneaded and then finely pulverized and classified, can be used.
  • the powder coating material of the present invention can be applied to exteriors, household appliances, automobile supplies, motorcycle supplies, protective fences, etc., but has weather resistance, impact resistance, chipping resistance, water resistance, and thread rust resistance. It is suitable for coating metal members such as aluminum wheel alloy members because it can obtain a coating film with excellent appearance.
  • Examples of the powder coating coating method of the present invention include various known and commonly used methods such as an electrostatic powder coating method. Further, as a method of forming a cured coating film after coating the powder coating material of the present invention, it can be appropriately selected depending on the type and purpose of the base material, but it is excellent in thread rust resistance, water resistance and weather resistance. Since a coating film can be obtained, it is preferable to bake in a temperature range of 120 to 250 ° C. for 5 to 30 minutes. The coating film thickness is preferably in the range of 50 to 200 ⁇ m.
  • the epoxy equivalent and the number average molecular weight of the acrylic resin were measured by the following methods.
  • Measurement method of epoxy equivalent It was measured by the hydrochloric acid-pyridine method. To the resin, 25 ml of a hydrochloric acid-pyridine solution was added, and the mixture was heated and dissolved at 130 ° C. for 1 hour, and then titrated with a 0.1 N-potassium hydroxide alcohol solution using phenolphthalein as an indicator. The epoxy equivalent was calculated from the amount of 0.1N-potassium hydroxide alcohol solution consumed.
  • Measurement method of number average molecular weight Measured by GPC.
  • Measuring device High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation)
  • Column The following columns manufactured by Tosoh Corporation were connected in series and used.
  • TKgel G5000 (7.8 mm ID x 30 cm) x 1 "TSKgel G4000” (7.8 mm ID x 30 cm) x 1 "TSKgel G3000” (7.8 mm ID x 30 cm) x 1
  • Detector RI (Differential Refractometer) Column temperature: 40 ° C Eluent: tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection volume: 100 ⁇ L (sample concentration 4 mg / mL tetrahydrofuran solution) Standard sample: A calibration curve was prepared using the following monodisperse polystyrene.
  • NIPAM N-isopropylacrylamide
  • t-butylperoxy2-ethylhexanoate was added dropwise over 6 hours.
  • the polymerization reaction was carried out by keeping the temperature at the same temperature for 6 hours, and then the solvent was removed at 160 ° C. under a reduced pressure of 20 mmHg to obtain a number average molecular weight of 3,000, a glass transition temperature of 84 ° C., and an epoxy equivalent of 525 g / eq.
  • a solid acrylic resin (A-1) was obtained.
  • Synthesis Example 5 Synthesis of Acrylic Resin (RA-1)
  • the composition of the monomer was changed to 20 parts by mass of St, 30 parts by mass of MMA, 22 parts by mass of IBOMA, and 28 parts by mass of GMA, the number average molecular weight was 3,000 and the glass was glass.
  • a solid acrylic resin (RA-1) having a transition temperature of 94 ° C. and an epoxy equivalent of 525 g / eq was obtained.
  • Synthesis Example 6 Synthesis of Acrylic Resin (RA-2)
  • the composition of the monomer was changed to 25 parts by mass of St, 30 parts by mass of MMA, 30 parts by mass of nBMA, and 15 parts by mass of GMA, the number average molecular weight was 3,000 and the glass was glass.
  • Synthesis Example 7 Synthesis of Acrylic Resin (RA-3)
  • the composition of the monomer was changed to 15 parts by mass of St, 15 parts by mass of MMA, 42 parts by mass of nBA, and 28 parts by mass of GMA, the number average molecular weight was 3,000 and the glass was glass.
  • a solid acrylic resin (RA-3) having a transition temperature of 4 ° C. and an epoxy equivalent of 525 g / eq was obtained.
  • Tables 1 and 2 show the monomer compositions and property values of the acrylic resins (A-1) to (A-4) and (RA-1) to (RA-3) synthesized in Synthesis Examples 1 to 6 above. ..
  • Example 1 Production and evaluation of powder coating material (1)
  • DDDA dodecanedicarboxylic acid
  • benzoin 5 parts by mass of benzoin
  • a leveling agent (“Regiflow LF” manufactured by ESTRON).
  • the resin composition containing 3 parts by mass is melt-kneaded using a twin-screw kneader (“APV Kneader MP-2015 type” manufactured by Tsubako Yokohama Sales Co., Ltd.), finely pulverized, and further 200 mesh.
  • the powder coating (1) was obtained by classifying with the wire net of the above.
  • the powder coating obtained above is electrostatically powder coated on an untreated aluminum plate (A-1050P) (7 cm ⁇ 15 cm) so that the film thickness after baking is 80 to 120 ⁇ m, and then 20 at 170 ° C. Baking for minutes was performed to prepare a cured coating film for evaluation.
  • A-1050P untreated aluminum plate
  • Test 1 in which (prepared by dissolving in ion-exchanged water) was sprayed for 6 hours and test 2 in which the mixture was left to stand for 96 hours under the conditions of a temperature of 60 ° C. and a humidity of 85% were performed for a total of 5 cycles.
  • the thread rust generated from the scratches on the coated plate was visually confirmed, and the thread rust resistance was evaluated by the length of the thread rust that grew to the longest. Based on the length of the thread rust that grew to the longest, the thread rust resistance of the coating film was determined as follows. ⁇ : Maximum length of thread rust is 2.0 mm or less ⁇ : Maximum length of thread rust exceeds 2.0 mm, 3.0 mm or less ⁇ : Maximum length of thread rust exceeds 3.0 mm
  • Examples 2 to 4 Production and evaluation of powder coating materials (2) to (4)
  • the powder coating materials (2) to (4) were obtained by operating in the same manner as in Example 1 except that the acrylic resin (A-1) and DDDA blended in Example 1 were changed to the compositions shown in Table 3. It was prepared and various physical properties were evaluated.
  • Tables 3 and 4 show the compounding compositions and evaluation results of the powder coating materials (1) to (4) obtained in Examples 1 to 4 and the powder coating materials (R1) to (R3) obtained in Comparative Examples 1 to 3. Shown in.
  • the acrylic monomer (a2) represented by the general formula (1) is used as the raw material of the acrylic resin (A) which is a component of the resin composition for powder coating of the present invention.
  • the acrylic monomer (a2) represented by the general formula (1) is used as the raw material of the acrylic resin (A) which is a component of the resin composition for powder coating of the present invention.

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Abstract

Provided is a resin composition for a powder coating material, the resin composition being characterized by comprising an acrylic resin (A) which contains, as essential raw materials, an acrylic monomer (a1) having an epoxy group, an acrylic monomer (a2) represented by general formula (1), and an unsaturated monomer (a3) other than the acrylic monomer (a1) and the acrylic monomer (a2). Since a cured coating film having excellent appearance, flexibility, and filiform corrosion resistance can be obtained from said resin composition for a powder coating material, said resin composition is suitably used for a powder coating material. (In general formula (1), R1 represents a hydrogen atom or a methyl group, R2 represents a hydrogen atom or a branched or non-branched alkyl group having 1-8 carbon atoms, and R3 represents a branched or non-branched alkyl group having 1-8 carbon atoms.)

Description

粉体塗料用樹脂組成物、粉体塗料、該塗料の塗膜を有する物品Resin composition for powder coating material, powder coating material, article having a coating film of the coating material
　本発明は、粉体塗料用樹脂組成物、粉体塗料、該塗料の塗膜を有する物品に関する。 The present invention relates to a resin composition for powder coating material, a powder coating material, and an article having a coating film of the coating material.
　近年、大気汚染等の問題から有機溶剤に対する規制が厳しくなり、環境調和型塗料が注目されている。その中でも、粉体塗料は無溶剤型塗料として環境保護の観点から脚光を浴びており、特にアクリル系粉体塗料は耐候性、耐汚染性等の塗膜性能に優れることから、アルミホイール等の自動車部品、金属外装、家電の用途に注目されている。しかしながら、粉体塗料は溶剤型塗料と比較し、塗膜の平滑性が劣るという欠点があった。 In recent years, regulations on organic solvents have become stricter due to problems such as air pollution, and environment-friendly paints are attracting attention. Among them, powder paints are in the limelight as solvent-free paints from the viewpoint of environmental protection. In particular, acrylic powder paints have excellent coating performance such as weather resistance and stain resistance, so aluminum wheels, etc. It is attracting attention for applications such as automobile parts, metal exteriors, and home appliances. However, the powder coating material has a drawback that the smoothness of the coating film is inferior to that of the solvent type coating material.
　これに対して、（メタ）アクリル酸アルキルエステル、エポキシ基含有アクリル単量体、その他共重合可能なビニル系単量体を共重合させて得られるエポキシ基含有アクリル樹脂と、エポキシ基と反応可能な官能基を有する硬化剤とを含んでなる粉体塗料が提案されている（例えば、特許文献１参照。）。しかしながら、この粉体塗料から得られる硬化塗膜は、平滑性が改善されているものの、耐糸錆性が不十分であるという問題があった。 On the other hand, the epoxy group-containing acrylic resin obtained by copolymerizing a (meth) acrylic acid alkyl ester, an epoxy group-containing acrylic monomer, and other copolymerizable vinyl-based monomers can react with an epoxy group. A powder coating material containing a curing agent having a functional group has been proposed (see, for example, Patent Document 1). However, although the cured coating film obtained from this powder coating film has improved smoothness, it has a problem of insufficient thread rust resistance.
特開２００２－６９３６８号公報Japanese Unexamined Patent Publication No. 2002-69368
　本発明が解決しようとする課題は、平滑性、柔軟性、及び耐糸錆性に優れる硬化塗膜を得ることのできる粉体塗料用樹脂組成物、粉体塗料及び該塗料の塗膜を有する物品提供することである。 The problem to be solved by the present invention is a resin composition for powder coating material, a powder coating material, and a coating material of the coating material, which can obtain a cured coating material having excellent smoothness, flexibility, and thread rust resistance. To provide goods.
　本発明者等は、上記の課題を解決するため鋭意研究した結果、エポキシ基を有するアクリル単量体と特定構造を有するアクリル単量体と、その他の不飽和単量体を必須原料とするアクリル樹脂を含有する粉体塗料用樹脂組成物から得られる硬化塗膜が、平滑性、柔軟性、及び耐糸錆性に優れることを見出し、発明を完成させた。 As a result of diligent research to solve the above problems, the present inventors have made an acrylic monomer having an epoxy group, an acrylic monomer having a specific structure, and other unsaturated monomers as essential raw materials. The invention was completed by finding that the cured coating film obtained from the resin composition for powder coating material containing a resin is excellent in smoothness, flexibility, and thread rust resistance.
　すなわち、本発明は、エポキシ基を有するアクリル単量体（ａ１）と、下記一般式（１）で表されるアクリル単量体（ａ２）と、前記アクリル単量体（ａ１）及び前記アクリル単量体（ａ２）以外の不飽和単量体（ａ３）とを必須原料とするアクリル樹脂（Ａ）を含有することを特徴とする粉体塗料用樹脂組成物。粉体塗料及び該塗料で塗装された物品に関する。 That is, in the present invention, the acrylic monomer (a1) having an epoxy group, the acrylic monomer (a2) represented by the following general formula (1), the acrylic monomer (a1) and the polypoly acrylic are used. A resin composition for powder coating, which contains an acrylic resin (A) containing an unsaturated monomer (a3) other than the weight (a2) as an essential raw material. The present invention relates to powder coating materials and articles coated with the coating materials.
Figure JPOXMLDOC01-appb-C000002
 （一般式（１）中、Ｒ１は水素原子又はメチル基を表し、Ｒ２は水素原子、又は炭素原子数１～８の分岐又は非分岐のアルキル基を表し、Ｒ３は炭素原子数１～８の分岐又は非分岐のアルキル基を表す。）
Figure JPOXMLDOC01-appb-C000002
 (In the general formula (1), R 1 represents a hydrogen atom or a methyl group, R 2 represents a hydrogen atom or a branched or non-branched alkyl group having 1 to 8 carbon atoms, and R 3 has 1 carbon atom. Represents a branched or non-branched alkyl group of ~ 8)
　本発明の粉体塗料用樹脂組成物は、外観、柔軟性、及び耐糸錆性に優れること硬化塗膜を形成することができることから、アルミホイール等の物品を塗装する塗料に好適に用いることができる。 The resin composition for powder coatings of the present invention is excellent in appearance, flexibility, and thread rust resistance, and can form a cured coating film. Therefore, it is suitably used as a coating material for coating articles such as aluminum wheels. Can be done.
　本発明の粉体塗料用樹脂組成物は、エポキシ基を有するアクリル単量体（ａ１）と、下記一般式（１）で表されるアクリル単量体（ａ２）と、前記アクリル単量体（ａ１）及び前記アクリル単量体（ａ２）以外の不飽和単量体（ａ３）とを必須原料とするアクリル樹脂（Ａ）を含有するものである。 The resin composition for powder coating of the present invention comprises an acrylic monomer (a1) having an epoxy group, an acrylic monomer (a2) represented by the following general formula (1), and the acrylic monomer (a2). It contains an acrylic resin (A) containing an unsaturated monomer (a3) other than the a1) and the acrylic monomer (a2) as an essential raw material.
Figure JPOXMLDOC01-appb-C000003
 （一般式（１）中、Ｒ１は水素原子又はメチル基を表し、Ｒ２は水素原子、又は炭素原子数１～８の分岐又は非分岐のアルキル基を表し、Ｒ３は炭素原子数１～８の分岐又は非分岐のアルキル基を表す。）
Figure JPOXMLDOC01-appb-C000003
 (In the general formula (1), R 1 represents a hydrogen atom or a methyl group, R 2 represents a hydrogen atom or a branched or non-branched alkyl group having 1 to 8 carbon atoms, and R 3 has 1 carbon atom. Represents a branched or non-branched alkyl group of ~ 8)
　まず、前記アクリル樹脂（Ａ）について説明する。前記アクリル樹脂（Ａ）はエポキシ基を有するものであるが、前記アクリル単量体（ａ１）と、前記アクリル単量体（ａ２）と、前記不飽和単量体（ａ３）とを共重合することにより得られる。 First, the acrylic resin (A) will be described. Although the acrylic resin (A) has an epoxy group, the acrylic monomer (a1), the acrylic monomer (a2), and the unsaturated monomer (a3) are copolymerized with each other. Obtained by
　前記アクリル単量体（ａ１）は、エポキシ基を有するアクリル単量体であり、例えば、グリシジル（メタ）アクリレート、メチルグリシジル（メタ）アクリレート、（メタ）アリルグリシジルエーテル、（メタ）アリルメチルグリシジルエーテル、３，４－エポキシシクロヘキシルメチル（メタ）アクリレート等が挙げられるが、これらの中でも、グリシジル（メタ）アクリレートが好ましい。なお、これらのアクリル単量体（ａ１）は、単独で用いることも２種以上併用することもできる。 The acrylic monomer (a1) is an acrylic monomer having an epoxy group, and is, for example, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, (meth) allyl glycidyl ether, (meth) allyl methyl glycidyl ether. , 3,4-Epoxide cyclohexylmethyl (meth) acrylate and the like, and among these, glycidyl (meth) acrylate is preferable. These acrylic monomers (a1) can be used alone or in combination of two or more.
　なお、本発明において、「（メタ）アクリル酸」とは、メタクリル酸とアクリル酸の一方又は両方をいい、「（メタ）アクリレート」とは、メタクリレートとアクリレートの一方又は両方をいい、「（メタ）アクリルアミド」とは、メタクリルアミドとアクリルアミドの一方又は両方をいい、「（メタ）アクリロイル基」とは、メタクリロイル基とアクリロイル基の一方又は両方をいう。 In the present invention, "(meth) acrylic acid" refers to one or both of methacrylic acid and acrylic acid, and "(meth) acrylate" refers to one or both of methacrylate and acrylate, and "(meth) acrylate". ) Acrylamide ”refers to one or both of methacrylamide and acrylamide, and“ (meth) acryloyl group ”refers to one or both of methacrylic acid group and acryloyl group.
　前記アクリル単量体（ａ２）は、前記一般式（１）で表されるアクリル単量体であり、例えば、Ｎ－メチル(メタ)アクリルアミド、Ｎ－エチル(メタ)アクリルアミド、Ｎ－イソプロピル(メタ)アクリルアミド、Ｎ－ｔ－ブチル(メタ)アクリルアミド、Ｎ－ｔ－オクチル(メタ)アクリルアミド、Ｎ，Ｎ－ジメチル(メタ)アクリルアミド、Ｎ，Ｎ－ジエチル(メタ)アクリルアミド等が挙げられるが、これらの中でも、塗膜の柔軟性と耐糸錆性のバランスに優れることから、Ｎ－イソプロピル(メタ)アクリルアミド、Ｎ，Ｎ－ジメチル(メタ)アクリルアミド、Ｎ，Ｎ－ジエチル(メタ)アクリルアミドが好ましい。なお、これらのアクリル単量体（ａ２）は、単独で用いることも２種以上併用することもできる。 The acrylic monomer (a2) is an acrylic monomer represented by the general formula (1), and is, for example, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, and N-isopropyl (meth). ) Acrylamide, Nt-butyl (meth) acrylamide, Nt-octyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide and the like. Of these, N-isopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, and N, N-diethyl (meth) acrylamide are preferable because they have an excellent balance between the flexibility of the coating film and the resistance to thread rust. These acrylic monomers (a2) can be used alone or in combination of two or more.
　前記不飽和単量体（ａ３）は、前記アクリル単量体（ａ１）及び（ａ２）以外の不飽和単量体であり、例えば、（メタ）アクリル酸、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｓｅｃ－ブチル（メタ）アクリレート、ｎ－ペンチル（メタ）アクリレート、ｎ－ヘキシル（メタ）アクリレート、ｎ－ヘプチル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、ドデシル（メタ）アクリレート、セチル（メタ）アクリレート、ステアリル（メタ）アクリレート、ベヘニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、４－ｔｅｒｔ－ブチルシクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ベンジル（メタ）アクリレート、（メタ）アクリルアミド、（メタ）アクリロニトリル、Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、３－（メタ）アクリロイルオキシプロピルトリメトキシシラン、３－（メタ）アクリロイルオキシプロピルトリエトキシシラン、３－（メタ）アクリロイルオキシプロピルメチルジメトキシシラン、スチレン、α－メチルスチレン、ｐ－メチルスチレン、ｐ－メトキシスチレン、２－メトキシエチル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシ－ｎ－ブチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシ－ｎ－ブチル（メタ）アクリレート、３－ヒドロキシ－ｎ－ブチル（メタ）アクリレート、１，４－シクロヘキサンジメタノールモノ（メタ）アクリレート、グリセリンモノ（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート、２－（メタ）アクリロイルオキシエチル－２－ヒドロキシエチルフタレート、末端に水酸基を有するラクトン変性（メタ）アクリレート等の単官能単量体；エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、１，３－ブタンジオールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、ヒドロキシピバリン酸エステルネオペンチルグリコールジ（メタ）アクリレート、ビスフェノールＡ－ジ（メタ）アクリレート、ビスフェノールＡ－ＥＯ変性ジ（メタ）アクリレート、イソシアヌル酸ＥＯ変性ジアクリレート等の２官能単量体；イソシアヌル酸ＥＯ変性トリアクリレート、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパンＥＯ変性トリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジトリメチロールプロパンテトラアクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート等の３官能以上の単量体などが挙げられるが、これらの中でも、塗膜の柔軟性と耐糸錆性のバランスに優れることから、スチレン、及び／又はメチルメタクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、イソボルニル（メタ）アクリレート、を用いることが好ましい。なお、これらのアクリル単量体（ａ３）は、単独で用いることも２種以上併用することもできる。 The unsaturated monomer (a3) is an unsaturated monomer other than the acrylic monomers (a1) and (a2), and is, for example, (meth) acrylic acid, methyl (meth) acrylate, and ethyl (meth). ) Acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (Meta) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, cetyl (meth) ) Acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, benzyl (meth) ) Acrylate, (meth) acrylamide, (meth) acrylonitrile, N, N-dimethylaminoethyl (meth) acrylate, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3 -(Meta) acryloyloxypropylmethyldimethoxysilane, styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene, 2-methoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (Meta) acrylate, 4-hydroxy-n-butyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-n-butyl (meth) acrylate, 3-hydroxy-n-butyl (meth) acrylate, 1,4-Cyclohexanedimethanol mono (meth) acrylate, glycerin mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2, Monofunctional monomers such as- (meth) acryloyloxyethyl-2-hydroxyethylphthalate, lactone-modified (meth) acrylate having a hydroxyl group at the end; ethylene glycol di (meth) acrylate, diechi Lenglycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate , Polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di ( Bifunctional monomers such as meta) acrylate, hydroxypivalic acid ester neopentyl glycol di (meth) acrylate, bisphenol A-di (meth) acrylate, bisphenol A-EO modified di (meth) acrylate, and isocyanuric acid EO modified diacrylate. EO-modified triacrylate of isocyanuric acid, trimethylolpropane tri (meth) acrylate, trimethylolpropane EO-modified tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylol propanetetraacrylate, dipentaerythritol hexa (meth) acrylate , Dipentaerythritol Penta (meth) acrylate and other trifunctional or higher functional monomers, among these, styrene and / or because of the excellent balance between the flexibility of the coating film and the resistance to thread rust. It is preferable to use methyl methacrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and isobornyl (meth) acrylate. These acrylic monomers (a3) can be used alone or in combination of two or more.
　前記アクリル単量体（ａ１）の使用量は、塗膜の外観と耐糸錆性が向上することから、前記アクリル樹脂（Ａ）の原料である単量体成分中、１０～６０質量％が好ましく、２０～５０質量％がより好ましい。前記アクリル単量体（ａ２）の使用量は、塗膜の耐糸錆性が向上することから、前記アクリル樹脂（Ａ）の原料である単量体成分中、０．１～３０質量％が好ましく、０．５～２０質量％がより好ましい。前記アクリル単量体（ａ３）の使用量は、塗膜の柔軟性と耐糸錆性が向上することから、前記アクリル樹脂（Ａ）の原料である単量体成分中、３０～８０質量％が好ましく、４０～８０質量％がより好ましい。 The amount of the acrylic monomer (a1) used is 10 to 60% by mass in the monomer component which is the raw material of the acrylic resin (A) because the appearance of the coating film and the thread rust resistance are improved. It is preferably 20 to 50% by mass, more preferably 20 to 50% by mass. The amount of the acrylic monomer (a2) used is 0.1 to 30% by mass in the monomer component which is the raw material of the acrylic resin (A) because the thread rust resistance of the coating film is improved. It is preferably 0.5 to 20% by mass, more preferably 0.5 to 20% by mass. The amount of the acrylic monomer (a3) used is 30 to 80% by mass in the monomer component which is the raw material of the acrylic resin (A) because the flexibility of the coating film and the thread rust resistance are improved. Is preferable, and 40 to 80% by mass is more preferable.
　また、前記アクリル樹脂（Ａ）のガラス転移温度は、塗膜の耐糸錆性が向上することから、２０～１２０℃が好ましい。さらに好ましくは、４０～１００℃が好ましい。 Further, the glass transition temperature of the acrylic resin (A) is preferably 20 to 120 ° C. because the thread rust resistance of the coating film is improved. More preferably, it is 40 to 100 ° C.
　なお、本発明において、ガラス転移温度とは、
ＦＯＸの式：１／Ｔｇ＝Ｗ１／Ｔｇ１＋Ｗ２／Ｔｇ２＋・・・
（Ｔｇ：求めるべきガラス転移温度、Ｗ１：成分１の重量分率、Ｔｇ１：成分１のホモポリマーのガラス転移温度）
に従い計算により求めたものである。各成分のホモポリマーのガラス転移温度の値は、日刊工業新聞社の「粘着技術ハンドブック」またはＷｉｌｅｙ－Ｉｎｔｅｒｓｃｉｅｎｃｅの「ポリマーハンドブック（Ｐｏｌｙｍｅｒ Ｈａｎｄｂｏｏｋ）」に記載の値を採用するものとする。以下、この計算によるガラス転移温度を「設計Ｔｇ」と略称する。 In the present invention, the glass transition temperature is defined as
FOX formula: 1 / Tg = W1 / Tg1 + W2 / Tg2 + ...
(Tg: glass transition temperature to be obtained, W1: weight fraction of component 1, Tg1: glass transition temperature of homopolymer of component 1)
It was calculated according to the above. For the value of the glass transition temperature of the homopolymer of each component, the value described in the "Adhesive Technology Handbook" of Nikkan Kogyo Shimbun or the "Polymer Handbook" of Wiley-Interscience shall be adopted. Hereinafter, the glass transition temperature calculated by this calculation is abbreviated as "design Tg".
　さらに、前記アクリル樹脂（Ａ）の数平均分子量は溶融時の流動性と耐糸錆性に優れることから、１，０００～１０，０００が好ましい。さらに好ましくは２，０００～８，０００が好ましい。ここで、数平均分子量はゲル浸透クロマトグラフィー（以下、「ＧＰＣ」と略記する。）測定に基づきポリスチレン換算した値である。 Further, the number average molecular weight of the acrylic resin (A) is preferably 1,000 to 10,000 because it is excellent in fluidity at the time of melting and thread rust resistance. More preferably, it is 2,000 to 8,000. Here, the number average molecular weight is a value converted to polystyrene based on gel permeation chromatography (hereinafter abbreviated as "GPC") measurement.
　前記アクリル樹脂（Ａ）を得る方法としては、前記アクリル単量体（ａ１）、アクリル単量体（ａ２）及び不飽和単量体（ａ３）を原料として、公知の重合方法で行うことができるが、溶液ラジカル重合法が最も簡便であることから好ましい。 The method for obtaining the acrylic resin (A) can be carried out by a known polymerization method using the acrylic monomer (a1), the acrylic monomer (a2) and the unsaturated monomer (a3) as raw materials. However, the solution radical polymerization method is preferable because it is the simplest.
　上記の溶液ラジカル重合法は、原料である各単量体を溶剤に溶解し、重合開始剤存在下で重合反応を行う方法である。この際に用いることができる溶剤としては、例えば、トルエン、キシレン、シクロヘキサン、ｎ－ヘキサン、オクタン等の炭化水素系溶剤；メタノール、エタノール、イソプロパノール、ｎ－ブタノール、イソブタノール、ｓｅｃ－ブタノール等のアルコール系溶剤、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールジメチルエーテル等のエーテル系溶剤；酢酸メチル、酢酸エチル、酢酸ｎ－ブチル、酢酸イソブチル、酢酸アミル等のエステル系溶剤；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶剤などが挙げられる。これらの溶剤は、単独で用いることも２種以上併用することもできる。 The above solution radical polymerization method is a method in which each monomer as a raw material is dissolved in a solvent and a polymerization reaction is carried out in the presence of a polymerization initiator. Examples of the solvent that can be used in this case are hydrocarbon solvents such as toluene, xylene, cyclohexane, n-hexane and octane; alcohols such as methanol, ethanol, isopropanol, n-butanol, isobutanol and sec-butanol. Ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether; esters such as methyl acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, etc. Solvents: Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like can be mentioned. These solvents can be used alone or in combination of two or more.
　前記重合開始剤としては、例えば、シクロヘキサノンパーオキサイド、３，３，５－トリメチルシクロヘキサノンパーオキサイド、メチルシクロヘキサノンパーオキサイド等のケトンパーオキサイド化合物；１，１－ビス（ｔｅｒｔ－ブチルパーオキシ）－３，３，５－トリメチルシクロヘキサン、１，１－ビス（ｔｅｒｔ－ブチルパーオキシ）シクロヘキサン、ｎ－ブチル－４，４－ビス（ｔｅｒｔ－ブチルパーオキシ）バレレート、２，２－ビス（４，４－ジｔｅｒｔ－ブチルパーオキシシクロヘキシル）プロパン、２，２－ビス（４，４－ジｔｅｒｔ－アミルパーオキシシクロヘキシル）プロパン、２，２－ビス（４，４－ジｔｅｒｔ－ヘキシルパーオキシシクロヘキシル）プロパン、２，２－ビス（４，４－ジｔｅｒｔ－オクチルパーオキシシクロヘキシル）プロパン、２，２－ビス（４，４－ジクミルパーオキシシクロヘキシル）プロパン等のパーオキシケタール化合物；クメンハイドロパーオキサイド、２，５－ジメチルヘキサン－２，５－ジハイドロパーオキサイド等のハイドロパーオキサイド類；１，３－ビス（ｔｅｒｔ－ブチルパーオキシ－ｍ－イソプロピル）ベンゼン、２，５－ジメチル－２，５－ジ（ｔｅｒｔ－ブチルパーオキシ）ヘキサン、ジイソプロピルベンゼンパーオキサイド、ｔｅｒｔ－ブチルクミルパーオキサイド等のジアルキルパーオキサイド化合物；デカノイルパーオキサイド、ラウロイルパーオキサイド、ベンゾイルパーオキサイド、２，４－ジクロロベンゾイルパーオキサイド等のジアシルパーオキサイド化合物；ビス（ｔｅｒｔ－ブチルシクロヘキシル）パーオキシジカーボネート等のパーオキシカーボネート化合物；ｔｅｒｔ－ブチルパーオキシ－２－エチルヘキサノエート、ｔｅｒｔ－ブチルパーオキシベンゾエート、２，５－ジメチル－２，５－ジ（ベンゾイルパーオキシ）ヘキサン等のパーオキシエステル化合物などの有機過酸化物と、２，２’－アゾビスイソブチロニトリル、１，１’－アゾビス（シクロヘキサン－１－カルボニトリル）等のアゾ化合物とが挙げられる。 Examples of the polymerization initiator include ketone peroxide compounds such as cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, and methylcyclohexanone peroxide; 1,1-bis (tert-butylperoxy) -3, 3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, 2,2-bis (4,5-di) tert-butylperoxycyclohexyl) propane, 2,2-bis (4,5-ditert-amylperoxycyclohexyl) propane, 2,2-bis (4,54-ditert-hexylperoxycyclohexyl) propane, 2 Peroxyketal compounds such as 2-bis (4,5-ditert-octylperoxycyclohexyl) propane, 2,2-bis (4,54-dicumylperoxycyclohexyl) propane; cumenehydroperoxide, 2, Hydroperoxides such as 5-dimethylhexane-2,5-dihydroperoxide; 1,3-bis (tert-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di ( Dialkyl peroxide compounds such as tert-butylperoxy) hexane, diisopropylbenzene peroxide, and tert-butylcumyl peroxide; diacyls such as decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, and 2,4-dichlorobenzoyl peroxide. Peroxide compounds; Peroxycarbonate compounds such as bis (tert-butylcyclohexyl) peroxydicarbonate; tert-butylperoxy-2-ethylhexanoate, tert-butylperoxybenzoate, 2,5-dimethyl-2, Organic peroxides such as peroxyester compounds such as 5-di (benzoylperoxy) hexane, 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), etc. Azo compound of.
　本発明の粉体塗料用樹脂組成物は、前記アクリル樹脂（Ａ）を含有するものであるが、塗膜物性がより向上することから、エポキシ基と反応可能な官能基を有する硬化剤（Ｂ）を含有することが好ましい。 The resin composition for powder coating material of the present invention contains the acrylic resin (A), but since the physical properties of the coating film are further improved, a curing agent (B) having a functional group capable of reacting with an epoxy group. ) Is preferably contained.
　前記硬化剤（Ｂ）は、エポキシ基と反応可能な官能基を有する硬化剤であり、例えば、スベリン酸、アゼライン酸、２，４－ジエチルグルタル酸、セバシン酸、ウンデカンジカルボン酸、ドデカンジカルボン酸、ブラシル酸、テトラデカンジカルボン酸、ペンタデカンジカルボン酸、ヘキサデカンジカルボン酸、ヘプタデカンジカルボン酸、オクタデカンジカルボン酸、エイコサンジカルボン酸、１，３－シクロヘキサンジカルボン酸、ブタントリカルボン酸等の多価カルボン酸化合物、これら多価カルボン酸の無水物、及び多価フェノール化合物などが挙げられる。これらの中でも、高強度の塗膜が得られることから、脂肪族多価カルボン酸化合物及びその無水物が好ましく、ドデカンジカルボン酸がより好ましい。また、これらの硬化剤（Ｂ）は単独で用いることも２種以上併用することもできる。 The curing agent (B) is a curing agent having a functional group capable of reacting with an epoxy group. Polyvalent carboxylic acid compounds such as brassic acid, tetradecanedicarboxylic acid, pentadecanedicarboxylic acid, hexadecanedicarboxylic acid, heptadecanedicarboxylic acid, octadecanedicarboxylic acid, eikosandicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, butanetricarboxylic acid, and many others. Examples thereof include anhydrides of valent carboxylic acids and polyvalent phenol compounds. Among these, an aliphatic polyvalent carboxylic acid compound and an anhydride thereof are preferable, and dodecanedicarboxylic acid is more preferable, because a high-strength coating film can be obtained. Further, these curing agents (B) can be used alone or in combination of two or more.
　本発明の粉体塗料用樹脂組成物における前記アクリル樹脂（Ａ）と前記硬化剤（Ｂ）との配合量としては、高強度の塗膜が得られることから、前記アクリル樹脂（Ａ）中のエポキシ基の当量数と、前記硬化剤（Ｂ）中のエポキシ基と反応可能な官能基の当量数との当量比（Ａ／Ｂ）が、０．５～１．５が好ましく、０．８～１．２がより好ましい。 As the blending amount of the acrylic resin (A) and the curing agent (B) in the resin composition for powder coating of the present invention, a high-strength coating film can be obtained, so that the acrylic resin (A) has The equivalent ratio (A / B) of the equivalent number of epoxy groups to the equivalent number of functional groups capable of reacting with the epoxy group in the curing agent (B) is preferably 0.5 to 1.5, preferably 0.8. ~ 1.2 is more preferable.
　本発明の粉体塗料用樹脂組成物には、本発明の効果を損なわない範囲内で、有機系ないしは無機系の顔料をはじめ、レベリング剤、流動調整剤、光安定剤、紫外線吸収剤、酸化防止剤等の公知慣用の種々の添加剤を添加することができる。また、焼き付け時の硬化反応を促進する目的で、触媒を添加することもできる。 The resin composition for powder coatings of the present invention includes organic or inorganic pigments, leveling agents, flow modifiers, light stabilizers, ultraviolet absorbers, and oxidations, as long as the effects of the present invention are not impaired. Various known and commonly used additives such as inhibitors can be added. In addition, a catalyst can be added for the purpose of accelerating the curing reaction during baking.
本発明の粉体塗料用樹脂組成物には、塗膜の耐糸錆性を向上させるために、本発明の効果を損なわない範囲内で、シリカ及びアルコキシシラン、シランカップリング剤のような加水分解可能なシラン化合物をさらに含むことができる。なお、これらの化合物は、単独で用いることも、２種以上併用することもできる。 In order to improve the thread rust resistance of the coating film, the resin composition for powder coating material of the present invention contains water such as silica, alkoxysilane, and a silane coupling agent within a range that does not impair the effects of the present invention. Degradable silane compounds can be further included. These compounds may be used alone or in combination of two or more.
　好適なシランカップリング剤の例としては、グリシジルアルコキシシランおよびアミノアルコキシシランなどが挙げられる。これらの中でも、耐糸錆性に優れる塗膜が得られることからグリシジルトリアルコキシシランが好ましく、グリシジルトリメトキシシランがより好ましい。 Examples of suitable silane coupling agents include glycidyl alkoxysilane and aminoalkoxysilane. Among these, glycidyltrialkoxysilane is preferable, and glycidyltrimethoxysilane is more preferable, because a coating film having excellent thread rust resistance can be obtained.
前記シランカップリング剤の配合量としては、耐糸錆性に優れる塗膜が得られることから、粉体塗料用樹脂組成物中、０．０１～３質量％が好ましく、０．０１～１質量％がより好ましい。 The blending amount of the silane coupling agent is preferably 0.01 to 3% by mass, preferably 0.01 to 1% by mass, in the resin composition for powder coating material, because a coating film having excellent thread rust resistance can be obtained. % Is more preferable.
　本発明の粉体塗料の調製方法としては、公知慣用の種々の方法を利用することができるが、例えば、前記アクリル樹脂（Ａ）と、前記硬化剤（Ｂ）と、必要に応じて、顔料、表面調整剤等の種々の添加剤とを混合し、次いで、それらを溶融混練したのちに、微粉砕、分級するという、いわゆる機械粉砕方式などを利用することができる。 As a method for preparing the powder coating material of the present invention, various known and commonly used methods can be used. For example, the acrylic resin (A), the curing agent (B), and, if necessary, pigments. , A so-called mechanical pulverization method in which various additives such as a surface conditioner are mixed, and then they are melt-kneaded and then finely pulverized and classified, can be used.
　本発明の粉体塗料は、エクステリア、家電用品、自動車用品、二輪車用品、防護柵等に塗装することが可能であるが、耐候性、耐衝撃性、耐チッピング性、耐水性、耐糸錆性等に優れる高外観の塗膜が得られることから、アルミホイール合金部材等の金属部材への塗装に適している。 The powder coating material of the present invention can be applied to exteriors, household appliances, automobile supplies, motorcycle supplies, protective fences, etc., but has weather resistance, impact resistance, chipping resistance, water resistance, and thread rust resistance. It is suitable for coating metal members such as aluminum wheel alloy members because it can obtain a coating film with excellent appearance.
　本発明の粉体塗料の塗装方法としては、静電粉体塗装法等の公知慣用の種々の方法が挙げられる。また、本発明の粉体塗料を塗装後、硬化塗膜とする方法としては、基材の種類や目的に応じて適宜選択することができるが、耐糸錆性、耐水性及び耐候性に優れる塗膜が得られることから、１２０～２５０℃の温度範囲で、５～３０分間の範囲で焼き付けることが好ましい。また、塗装膜厚は、５０～２００μｍの範囲が好ましい。 Examples of the powder coating coating method of the present invention include various known and commonly used methods such as an electrostatic powder coating method. Further, as a method of forming a cured coating film after coating the powder coating material of the present invention, it can be appropriately selected depending on the type and purpose of the base material, but it is excellent in thread rust resistance, water resistance and weather resistance. Since a coating film can be obtained, it is preferable to bake in a temperature range of 120 to 250 ° C. for 5 to 30 minutes. The coating film thickness is preferably in the range of 50 to 200 μm.
　以下に本発明を具体的な実施例を挙げてより詳細に説明する。なお、アクリル樹脂のエポキシ当量及び数平均分子量は、下記の方法で測定したものである。
［エポキシ当量の測定方法］
塩酸－ピリジン法により測定した。樹脂に、塩酸－ピリジン溶液２５ｍｌを加え、１３０℃で１時間、加熱溶解した後、フェノールフタレインを指示薬として０．１Ｎ－水酸化カリウムアルコール溶液で滴定した。消費した０．１Ｎ－水酸化カリウムアルコール溶液の量によってエポキシ当量を算出した。 Hereinafter, the present invention will be described in more detail with reference to specific examples. The epoxy equivalent and the number average molecular weight of the acrylic resin were measured by the following methods.
[Measuring method of epoxy equivalent]
It was measured by the hydrochloric acid-pyridine method. To the resin, 25 ml of a hydrochloric acid-pyridine solution was added, and the mixture was heated and dissolved at 130 ° C. for 1 hour, and then titrated with a 0.1 N-potassium hydroxide alcohol solution using phenolphthalein as an indicator. The epoxy equivalent was calculated from the amount of 0.1N-potassium hydroxide alcohol solution consumed.
［数平均分子量の測定方法］
ＧＰＣにより測定した。
測定装置：高速ＧＰＣ装置（東ソー株式会社製「ＨＬＣ－８２２０ＧＰＣ」）
カラム：東ソー株式会社製の下記のカラムを直列に接続して使用した。
　「ＴＳＫｇｅｌ　Ｇ５０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
　「ＴＳＫｇｅｌ　Ｇ４０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
　「ＴＳＫｇｅｌ　Ｇ３０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
　「ＴＳＫｇｅｌ　Ｇ２０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
検出器：ＲＩ（示差屈折計）
カラム温度：４０℃
溶離液：テトラヒドロフラン（ＴＨＦ）
流速：１．０ｍＬ／分
注入量：１００μＬ（試料濃度４ｍｇ／ｍＬのテトラヒドロフラン溶液）
標準試料：下記の単分散ポリスチレンを用いて検量線を作成した。 [Measurement method of number average molecular weight]
Measured by GPC.
Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series and used.
"TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 This "TSKgel G2000" (7.8 mm ID x 30 cm) x 1 Detector: RI (Differential Refractometer)
Column temperature: 40 ° C
Eluent: tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection volume: 100 μL (sample concentration 4 mg / mL tetrahydrofuran solution)
Standard sample: A calibration curve was prepared using the following monodisperse polystyrene.
（単分散ポリスチレン）
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－５００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－１０００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－２５００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－５０００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－１」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－２」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－４」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－２０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－４０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－８０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－１２８」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－２８８」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－５５０」 (Unidispersed polystyrene)
"TSKgel Standard Polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation
（合成例１：アクリル樹脂（Ａ－１）の合成）
　攪拌機、温度計、コンデンサー及び窒素ガス導入口を備えた反応容器に、キシレン６７質量部を仕込んで、窒素雰囲気下に１３５℃まで昇温した。そこへ、スチレン（以下、「Ｓｔ」と略記する。）２５質量部、メチルメタクリレート（以下、「ＭＭＡ」と略記する。）４５質量部、グリシジルメタクリレート（以下、「ＧＭＡ」と略
記する。）２８質量部、Ｎ－イソプロピルアクリルアミド（以下、「ＮＩＰＡＭ」と略記する。）２質量部およびｔ－ブチルパーオキシ２－エチルヘキサノエート６．０質量部からなる混合物を６時間に亘って滴下し、滴下終了後も同温度に６時間保持して重合反応を行い、しかる後１６０℃で２０ｍｍＨｇの減圧下に溶剤をのぞき、数平均分子量３，０００、ガラス転移温度８４℃、エポキシ当量５２５ｇ／ｅｑなる固形のアクリル樹脂（Ａ－１）を得た。 (Synthesis Example 1: Synthesis of Acrylic Resin (A-1))
67 parts by mass of xylene was charged in a reaction vessel equipped with a stirrer, a thermometer, a condenser and a nitrogen gas inlet, and the temperature was raised to 135 ° C. under a nitrogen atmosphere. There, 25 parts by mass of styrene (hereinafter abbreviated as "St"), 45 parts by mass of methyl methacrylate (hereinafter abbreviated as "MMA"), and glycidyl methacrylate (hereinafter abbreviated as "GMA") 28. A mixture consisting of 2 parts by mass, 2 parts by mass of N-isopropylacrylamide (hereinafter abbreviated as "NIPAM") and 6.0 parts by mass of t-butylperoxy2-ethylhexanoate was added dropwise over 6 hours. After the completion of the dropping, the polymerization reaction was carried out by keeping the temperature at the same temperature for 6 hours, and then the solvent was removed at 160 ° C. under a reduced pressure of 20 mmHg to obtain a number average molecular weight of 3,000, a glass transition temperature of 84 ° C., and an epoxy equivalent of 525 g / eq. A solid acrylic resin (A-1) was obtained.
（合成例２：アクリル樹脂（Ａ－２）の合成）
単量体の組成を、Ｓｔ　２０質量部、ＭＭＡ　２５質量部、ｎ－ブチルアクリレート（以下、「ｎＢＡ」と略記する。）１７質量部、イソボルニルメタクリレート（以下、「ＩＢＯＭＡ」と略記する。）５質量部、ＧＭＡ　２８質量部、Ｎ－イソプロピルメタクリルアミド（以下、「ＮＩＰＭＡＡ」と略記する。）５質量部に変更した以外は合成例１と同様に操作することにより、数平均分子量２，８００、ガラス転移温度５１℃、エポキシ当量５２５ｇ／ｅｑなる固形のアクリル樹脂（Ａ－２）を得た。 (Synthesis Example 2: Synthesis of Acrylic Resin (A-2))
The composition of the monomer is abbreviated as St 20 parts by mass, MMA 25 parts by mass, n-butyl acrylate (hereinafter abbreviated as “nBA”) 17 parts by mass, and isobornyl methacrylate (hereinafter abbreviated as “IBOMA”). ) Number average molecular weight 2, A solid acrylic resin (A-2) having an epoxy equivalent of 525 g / eq at 800 and a glass transition temperature of 51 ° C. was obtained.
（合成例３：アクリル樹脂（Ａ－３）の合成）
単量体の組成を、Ｓｔ　１０質量部、ＭＭＡ　３０質量部、ｎ－ブチルメタクリレート（以下、「ｎＢＭＡ」と略記する。）１３質量部、ＧＭＡ　４５質量部、Ｎ－ｔ－オクチルアクリルアミド（以下、「ＮＯＡＡ」と略記する。）２質量部に変更した以外は合成例１と同様に操作することにより、数平均分子量３，０００、ガラス転移温度６０℃、エポキシ当量３４０ｇ／ｅｑなる固形のアクリル樹脂（Ａ－３）を得た。 (Synthesis Example 3: Synthesis of Acrylic Resin (A-3))
The composition of the monomer is St 10 parts by mass, MMA 30 parts by mass, n-butyl methacrylate (hereinafter abbreviated as "nBMA") 13 parts by mass, GMA 45 parts by mass, Nt-octylacrylamide (hereinafter, abbreviated as "nBMA"). It is abbreviated as "NOAA".) By operating in the same manner as in Synthesis Example 1 except that it was changed to 2 parts by mass, a solid acrylic resin having a number average molecular weight of 3,000, a glass transition temperature of 60 ° C., and an epoxy equivalent of 340 g / eq. (A-3) was obtained.
（合成例４：アクリル樹脂（Ａ－４）の合成）
　攪拌機、温度計、コンデンサー及び窒素ガス導入口を備えた反応容器に、キシレン６７質量部を仕込んで、窒素雰囲気下に１３５℃まで昇温した。そこへ、Ｓｔ　３０質量部、ＭＭＡ　２０質量部、ＧＭＡ　２０質量部、ｎＢＭＡ　２０質量部、Ｎ，Ｎ－ジメチルアクリルアミド（以下、「ＤＭＡＡ」と略記する。）１０質量部およびｔ－ブチルパーオキシ２－エチルヘキサノエート４．０質量部からなる混合物を６時間に亘って滴下し、滴下終了後も同温度に６時間保持して重合反応を行い、さらに、３－グリシドキシプロピルトリメトキシシランを０．５質量部加え、３０分攪拌混合した。しかる後、１６０℃で２０ｍｍＨｇの減圧下に溶剤をのぞき、数平均分子量５，０００、ガラス転移温度７２℃、エポキシ当量７５０ｇ／ｅｑなる固形のアクリル樹脂（Ａ－４）を得た。 (Synthesis Example 4: Synthesis of Acrylic Resin (A-4))
67 parts by mass of xylene was charged in a reaction vessel equipped with a stirrer, a thermometer, a condenser and a nitrogen gas inlet, and the temperature was raised to 135 ° C. under a nitrogen atmosphere. There, St 30 parts by mass, MMA 20 parts by mass, GMA 20 parts by mass, nBMA 20 parts by mass, N, N-dimethylacrylamide (hereinafter abbreviated as "DMAA") 10 parts by mass and t-butyl peroxy 2 A mixture consisting of 4.0 parts by mass of -ethylhexanoate was added dropwise over 6 hours, and after the addition was completed, the mixture was kept at the same temperature for 6 hours to carry out a polymerization reaction, and further, 3-glycidoxypropyltrimethoxysilane was added. Was added by 0.5 parts by mass, and the mixture was stirred and mixed for 30 minutes. Then, the solvent was removed at 160 ° C. under a reduced pressure of 20 mmHg to obtain a solid acrylic resin (A-4) having a number average molecular weight of 5,000, a glass transition temperature of 72 ° C., and an epoxy equivalent of 750 g / eq.
（合成例５：アクリル樹脂（ＲＡ－１）の合成）
単量体の組成を、Ｓｔ　２０質量部、ＭＭＡ　３０質量部、ＩＢＯＭＡ　２２質量部、ＧＭＡ　２８質量部に変更した以外は合成例１と同様に操作することにより、数平均分子量３，０００、ガラス転移温度９４℃、エポキシ当量５２５ｇ／ｅｑなる固形のアクリル樹脂（ＲＡ－１）を得た。 (Synthesis Example 5: Synthesis of Acrylic Resin (RA-1))
By operating in the same manner as in Synthesis Example 1 except that the composition of the monomer was changed to 20 parts by mass of St, 30 parts by mass of MMA, 22 parts by mass of IBOMA, and 28 parts by mass of GMA, the number average molecular weight was 3,000 and the glass was glass. A solid acrylic resin (RA-1) having a transition temperature of 94 ° C. and an epoxy equivalent of 525 g / eq was obtained.
（合成例６：アクリル樹脂（ＲＡ－２）の合成）
単量体の組成を、Ｓｔ　２５質量部、ＭＭＡ　３０質量部、ｎＢＭＡ　３０質量部、ＧＭＡ　１５質量部に変更した以外は合成例１と同様に操作することにより、数平均分子量３，０００、ガラス転移温度６５℃、エポキシ当量９００ｇ／ｅｑなる固形のアクリル樹脂（ＲＡ－２）を得た。 (Synthesis Example 6: Synthesis of Acrylic Resin (RA-2))
By operating in the same manner as in Synthesis Example 1 except that the composition of the monomer was changed to 25 parts by mass of St, 30 parts by mass of MMA, 30 parts by mass of nBMA, and 15 parts by mass of GMA, the number average molecular weight was 3,000 and the glass was glass. A solid acrylic resin (RA-2) having a transition temperature of 65 ° C. and an epoxy equivalent of 900 g / eq was obtained.
（合成例７：アクリル樹脂（ＲＡ－３）の合成）
単量体の組成を、Ｓｔ　１５質量部、ＭＭＡ　１５質量部、ｎＢＡ　４２質量部、ＧＭＡ　２８質量部に変更した以外は合成例１と同様に操作することにより、数平均分子量３，０００、ガラス転移温度４℃、エポキシ当量５２５ｇ／ｅｑなる固形のアクリル樹脂（ＲＡ－３）を得た。 (Synthesis Example 7: Synthesis of Acrylic Resin (RA-3))
By operating in the same manner as in Synthesis Example 1 except that the composition of the monomer was changed to 15 parts by mass of St, 15 parts by mass of MMA, 42 parts by mass of nBA, and 28 parts by mass of GMA, the number average molecular weight was 3,000 and the glass was glass. A solid acrylic resin (RA-3) having a transition temperature of 4 ° C. and an epoxy equivalent of 525 g / eq was obtained.
　上記の合成例１～６で合成したアクリル樹脂（Ａ－１）～（Ａ－４）及び（ＲＡ－１）～（ＲＡ－３）の単量体組成及び性状値を表１及び２に示す。
Figure JPOXMLDOC01-appb-I000004
Tables 1 and 2 show the monomer compositions and property values of the acrylic resins (A-1) to (A-4) and (RA-1) to (RA-3) synthesized in Synthesis Examples 1 to 6 above. ..
Figure JPOXMLDOC01-appb-I000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
（実施例１：粉体塗料（１）の製造及び評価）
　合成例１で得られたアクリル樹脂（Ａ－１）８４質量部、ドデカンジカルボン酸（以下、「ＤＤＤＡ」と略記する。）１６質量部、ベンゾイン５質量部及びレベリング剤（ＥＳＴＲＯＮ製「レジフローＬＦ」）３質量部を配合した樹脂組成物を、二軸混練機（ツバコー横浜販売株式会社製「ＡＰＶ・ニーダーＭＰ－２０１５型」）を使用して溶融混練した後、微粉砕し、さらに、２００メッシュの金網で分級し、粉体塗料（１）を得た。 (Example 1: Production and evaluation of powder coating material (1))
84 parts by mass of the acrylic resin (A-1) obtained in Synthesis Example 1, 16 parts by mass of dodecanedicarboxylic acid (hereinafter abbreviated as "DDDA"), 5 parts by mass of benzoin, and a leveling agent ("Regiflow LF" manufactured by ESTRON). ) The resin composition containing 3 parts by mass is melt-kneaded using a twin-screw kneader (“APV Kneader MP-2015 type” manufactured by Tsubako Yokohama Sales Co., Ltd.), finely pulverized, and further 200 mesh. The powder coating (1) was obtained by classifying with the wire net of the above.
［評価用硬化塗膜の作製］
　上記で得られた粉体塗料を未処理アルミ板（Ａ－１０５０Ｐ）（７ｃｍ×１５ｃｍ）に、焼き付け後の膜厚が８０～１２０μｍとなるように静電粉体塗装した後、１７０℃で２０分間焼き付けを行い、評価用硬化塗膜を作製した。 [Preparation of cured coating film for evaluation]
The powder coating obtained above is electrostatically powder coated on an untreated aluminum plate (A-1050P) (7 cm × 15 cm) so that the film thickness after baking is 80 to 120 μm, and then 20 at 170 ° C. Baking for minutes was performed to prepare a cured coating film for evaluation.
［平滑性試験］
ＰＣＩ（パウダーコーティングインスティチュート）による粉体塗膜の平滑性目視判定用標準板を用いて判定した。標準板は、１～１０の１０枚あり、数字が大きくなるに従い、平滑性が良好となる。作成した粉体塗膜の平滑性がどの標準板に相当するかを目視で判定した。判定した結果をもとに、平滑性を以下のように判定した。
〇：平滑性が８以上
△：平滑性が６～７
×：平滑性が５以下 [Smoothness test]
Judgment was made using a standard plate for visually determining the smoothness of the powder coating film by PCI (Powder Coating Institute). There are 10 standard plates from 1 to 10, and the larger the number, the better the smoothness. It was visually determined which standard plate the smoothness of the prepared powder coating film corresponded to. Based on the judgment result, the smoothness was judged as follows.
〇: Smoothness is 8 or more Δ: Smoothness is 6 to 7
X: Smoothness is 5 or less
［エリクセン試験］
上記で得られた評価用塗膜の塗膜面をエリクセン試験機（「ＥＲＩＣＨＳＥＮＧＭＢＨ＆ＣＯ．Ｍｏｄｅｌ ２００」）で押し出し試験を行い、ワレが発生したときの押し出した長さを測定した。押し出し長さをもとに、塗膜の柔軟性を以下のように判定した。
〇：押し出し長さが７．０ｍｍを超える
△：押し出し長さが５．０～７．０ｍｍ
×：押し出し長さが５．０ｍｍ未満 [Eriksen test]
The coating film surface of the evaluation coating film obtained above was subjected to an extrusion test with an Eriksen testing machine (“ERICHSENGMBH & CO. Model 200”), and the extruded length when cracks occurred was measured. Based on the extrusion length, the flexibility of the coating film was determined as follows.
〇: Extruded length exceeds 7.0 mm Δ: Extruded length is 5.0 to 7.0 mm
X: Extruded length is less than 5.0 mm
［耐糸錆性の評価］
　上記で得られた評価用硬化塗膜にカッターナイフで基材の素地に達するように１３ｃｍの直線の傷を２本入れ、ＣＡＳＳ試験機にて次の試験を行った。温度５０℃、噴霧液量１．２～１．８ｃｃ／ｈ、噴霧圧力０．１ＭＰａの条件下、塩水（塩化銅（ＩＩ）水和物２．６g、氷酢酸１０ｃｃ、並塩５００ｇを１０Ｌのイオン交換水に溶解し調製）を６時間噴霧する試験１と、温度６０℃、湿度８５％の条件下９６時間放置する試験２とを１サイクルとして、合計５サイクル行った。ＣＡＳＳ試験終了後、塗装板の傷から生じた糸錆を目視にて確認し、最長に成長した糸錆の長さにより耐糸錆性を評価した。最長に成長した糸錆の長さをもとに、塗膜の耐糸錆性を以下のように判定した。
〇：糸錆の最長長さが２．０ｍｍ以下
△：糸錆の最長長さが２．０ｍｍを超え、３．０ｍｍ以下
×：糸錆の最長長さが３．０ｍｍを超える [Evaluation of thread rust resistance]
Two 13 cm straight scratches were made on the cured coating film for evaluation obtained above with a cutter knife so as to reach the base material of the base material, and the following test was performed with a CASS tester. Under the conditions of a temperature of 50 ° C., a spray liquid volume of 1.2 to 1.8 cc / h, and a spray pressure of 0.1 MPa, 10 L of salt water (2.6 g of copper (II) chloride hydrate, 10 cc of glacial acetic acid, and 500 g of normal salt). Test 1 in which (prepared by dissolving in ion-exchanged water) was sprayed for 6 hours and test 2 in which the mixture was left to stand for 96 hours under the conditions of a temperature of 60 ° C. and a humidity of 85% were performed for a total of 5 cycles. After the CASS test was completed, the thread rust generated from the scratches on the coated plate was visually confirmed, and the thread rust resistance was evaluated by the length of the thread rust that grew to the longest. Based on the length of the thread rust that grew to the longest, the thread rust resistance of the coating film was determined as follows.
〇: Maximum length of thread rust is 2.0 mm or less Δ: Maximum length of thread rust exceeds 2.0 mm, 3.0 mm or less ×: Maximum length of thread rust exceeds 3.0 mm
（実施例２～４：粉体塗料（２）～（４）の製造及び評価）
　実施例１で配合したアクリル樹脂（Ａ－１）及びＤＤＤＡを、表３に示す組成に変更した以外は、実施例１と同様に操作することにより、粉体塗料（２）～（４）を調製し、各種物性を評価した。 (Examples 2 to 4: Production and evaluation of powder coating materials (2) to (4))
The powder coating materials (2) to (4) were obtained by operating in the same manner as in Example 1 except that the acrylic resin (A-1) and DDDA blended in Example 1 were changed to the compositions shown in Table 3. It was prepared and various physical properties were evaluated.
（比較例１～３：粉体塗料（Ｒ１）～（Ｒ３）の製造及び評価）
　実施例１で配合したアクリル樹脂（Ａ－１）及びＤＤＤＡを、表４に示す通りに変更した以外は、実施例１と同様に操作することにより、粉体塗料（Ｒ１）～（Ｒ３）を調製し、各種物性を評価した。 (Comparative Examples 1 to 3: Production and Evaluation of Powder Paints (R1) to (R3))
The powder coating materials (R1) to (R3) were obtained by operating in the same manner as in Example 1 except that the acrylic resin (A-1) and DDDA blended in Example 1 were changed as shown in Table 4. It was prepared and various physical properties were evaluated.
　上記の実施例１～４で得た粉体塗料（１）～（４）及び比較例１～３で得た粉体塗料（Ｒ１）～（Ｒ３）の配合組成及び評価結果を表３及び４に示す。 Tables 3 and 4 show the compounding compositions and evaluation results of the powder coating materials (1) to (4) obtained in Examples 1 to 4 and the powder coating materials (R1) to (R3) obtained in Comparative Examples 1 to 3. Shown in.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
　実施例１～４の本発明の粉体塗料用樹脂組成物から得られる硬化塗膜は、平滑性、柔軟性、及び耐糸錆性に優れることが確認された。 It was confirmed that the cured coating films obtained from the resin compositions for powder coatings of the present invention of Examples 1 to 4 were excellent in smoothness, flexibility, and thread rust resistance.
　一方、比較例１～３は、本発明の粉体塗料用樹脂組成物の成分であるアクリル樹脂（Ａ）の原料として、一般式（１）で表されるアクリル単量体（ａ２）を用いない例であるが、良好な塗膜の平滑性、柔軟性及び耐糸錆性を全て満たすものは得られなかった。 On the other hand, in Comparative Examples 1 to 3, the acrylic monomer (a2) represented by the general formula (1) is used as the raw material of the acrylic resin (A) which is a component of the resin composition for powder coating of the present invention. Although this is not the case, it was not possible to obtain a coating material that satisfies all of the good smoothness, flexibility, and thread rust resistance of the coating film.

Claims (6)

  1. 　エポキシ基を有するアクリル単量体（ａ１）と、下記一般式（１）で表されるアクリル単量体（ａ２）と、前記アクリル単量体（ａ１）及び前記アクリル単量体（ａ２）以外の不飽和単量体（ａ３）とを必須原料とするアクリル樹脂（Ａ）を含有することを特徴とする粉体塗料用樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
     （一般式（１）中、Ｒ１は水素原子又はメチル基を表し、Ｒ２は水素原子、又は炭素原子数１～８の分岐又は非分岐のアルキル基を表し、Ｒ３は炭素原子数１～８の分岐又は非分岐のアルキル基を表す。）     Other than the acrylic monomer (a1) having an epoxy group, the acrylic monomer (a2) represented by the following general formula (1), the acrylic monomer (a1) and the acrylic monomer (a2). A resin composition for powder coating, which contains an acrylic resin (A) containing the unsaturated monomer (a3) of the above as an essential raw material.
    Figure JPOXMLDOC01-appb-C000001
     (In the general formula (1), R 1 represents a hydrogen atom or a methyl group, R 2 represents a hydrogen atom or a branched or non-branched alkyl group having 1 to 8 carbon atoms, and R 3 has 1 carbon atom. Represents a branched or non-branched alkyl group of ~ 8)
  2. 　前記アクリル樹脂（Ａ）の原料である単量体成分中の前記アクリル単量体（ａ１）が１０～６０質量％であり、前記アクリル単量体（ａ２）が０．１～３０質量％であり、前記アクリル単量体（ａ３）が３０～８０質量％である請求項１記載の粉体塗料用樹脂組成物。 The acrylic monomer (a1) in the monomer component which is the raw material of the acrylic resin (A) is 10 to 60% by mass, and the acrylic monomer (a2) is 0.1 to 30% by mass. The resin composition for powder coating according to claim 1, wherein the acrylic monomer (a3) is 30 to 80% by mass.
  3. 　さらに、エポキシ基と反応可能な官能基を有する硬化剤（Ｂ）とを含有する請求項１又は２記載の粉体塗料用樹脂組成物。 The resin composition for powder coating material according to claim 1 or 2, further containing a curing agent (B) having a functional group capable of reacting with an epoxy group.
  4. 　前記硬化剤（Ｂ）が、脂肪族多価カルボン酸及び／又はその無水物である請求項３記載の粉体塗料用樹脂組成物。 The resin composition for powder coating material according to claim 3, wherein the curing agent (B) is an aliphatic polyvalent carboxylic acid and / or an anhydride thereof.
  5. 　請求項１～４いずれか１項記載の粉体塗料用樹脂組成物から得られる粉体塗料。 A powder coating material obtained from the resin composition for powder coating material according to any one of claims 1 to 4.
  6. 　請求項５記載の粉体塗料の塗膜を有する物品。 An article having a coating film of the powder coating according to claim 5.
PCT/JP2021/014843 2020-04-24 2021-04-08 Resin composition for powder coating material, powder coating material, and article having coating film formed of said coating material WO2021215252A1 (en)

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