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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