WO2016052111A1 - Corps pourvu d'un revêtement - Google Patents

Corps pourvu d'un revêtement Download PDF

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Publication number
WO2016052111A1
WO2016052111A1 PCT/JP2015/075588 JP2015075588W WO2016052111A1 WO 2016052111 A1 WO2016052111 A1 WO 2016052111A1 JP 2015075588 W JP2015075588 W JP 2015075588W WO 2016052111 A1 WO2016052111 A1 WO 2016052111A1
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WIPO (PCT)
Prior art keywords
resin
coating film
fluorine
mass
acid
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PCT/JP2015/075588
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English (en)
Japanese (ja)
Inventor
将司 北川
忠広 木口
祐 安藤
Original Assignee
大日本塗料株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by 大日本塗料株式会社 filed Critical 大日本塗料株式会社
Priority to CN201580053070.6A priority Critical patent/CN106794682B/zh
Priority to SG11201702633WA priority patent/SG11201702633WA/en
Publication of WO2016052111A1 publication Critical patent/WO2016052111A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/03—Powdery paints
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials

Definitions

  • the present invention relates to a coated body comprising a substrate and a coating film disposed on the surface of the substrate, and relates to a coated body having excellent weather resistance, wear resistance and adhesion.
  • an object of the present invention is to provide a coated body having a base material and a coating film disposed on the surface of the base material, which is excellent in weather resistance, wear resistance and adhesion.
  • these layer-separated type powder coating compositions have a composition ratio of resins constituting the fluororesin layer and the polyester resin layer formed after coating. I found a difference.
  • the layer-separated type powder coating composition described in Patent Document 2 most of the resin component constituting the fluororesin layer located on the upper side of the coating film is a fluororesin, and the polyester located on the lower side. Most of the resin components constituting the resin layer are polyester resins.
  • the layer-separated type powder coating composition described in Patent Document 3 is a resin component constituting the fluororesin layer as compared with the layer-separating type powder coating composition described in Patent Document 2.
  • the ratio of the polyester resin is high, the ratio of the fluorine resin as the resin component constituting the polyester resin layer is high, and the composition of the resin component constituting each layer is relatively close.
  • the ratio of the fluororesin constituting the fluororesin layer is not sufficiently high from the viewpoint of weather resistance and wear resistance, and there is room for improvement.
  • the present inventor specified the ratio of the fluorine resin on the coating film surface and the ratio of the fluorine resin at a position where the depth from the coating film surface corresponds to half of the film thickness. By adjusting to the range, it was found that a coated body excellent in weather resistance, abrasion resistance and adhesion was obtained, and the present invention was completed.
  • the coated body of the present invention is a coated body comprising a substrate and a coating film disposed on the surface of the substrate,
  • the coating film is formed of a coating composition containing at least a fluororesin and a resin other than the fluororesin,
  • the first fluorine concentration is 30 to 50% by mass
  • the film thickness of the coating film is T ( ⁇ m)
  • the ratio of fluorine atoms to the total mass of fluorine atoms and carbon atoms at the position of depth T / 2 ( ⁇ m) from the coating film surface is the second fluorine concentration (mass%).
  • the mass ratio (A / B) of the second fluorine concentration (A) to the first fluorine concentration (B) is 13/87 to 49/51.
  • the thickness of the coating film is 40 to 200 ⁇ m.
  • the base material is a metal base material.
  • the resin other than the fluorine resin is at least one resin selected from the group consisting of a polyester resin and an epoxy resin.
  • the coating composition is a powder coating composition.
  • the coating film has a scratch coefficient of 45 to 500.
  • the weather resistance thus, it is possible to provide a coated body excellent in wear resistance and adhesion.
  • the coated body of the present invention is a coated body comprising a substrate and a coating film disposed on the surface of the substrate, wherein the coating film includes at least a fluorine resin and a resin other than the fluorine resin.
  • the first fluorine concentration (% by mass)
  • the first fluorine concentration is 30 to 50% by mass
  • the film thickness of the coating film is T ( ⁇ m)
  • the ratio of fluorine atoms to the total mass of fluorine atoms and carbon atoms at the position of depth T / 2 ( ⁇ m) from the coating film surface is the second fluorine concentration (mass%).
  • the mass ratio (A / B) of the second fluorine concentration (A) to the first fluorine concentration (B) is 13/87 to 49/51.
  • the first fluorine concentration when the ratio of fluorine atoms to the total mass of fluorine atoms and carbon atoms on the surface of the coating film is defined as the first fluorine concentration (mass%), the first fluorine concentration is 30 to 50 mass%. It is necessary to be. If the first fluorine concentration is within the above specified range, the ratio of the fluorine resin on the coating film surface is sufficiently high, so that weather resistance and wear resistance can be improved. On the other hand, when the first fluorine concentration is less than 30% by mass, sufficient weather resistance and wear resistance cannot be obtained. In addition, although the weather resistance and the wear resistance can be improved as the first fluorine concentration is higher, the first fluorine concentration is higher than 50% by mass after satisfying the regulations on the second fluorine concentration. It is difficult to control the distribution of the fluororesin.
  • the surface of the coating film is a surface located on the side opposite to the surface where the coating film is in contact with the substrate.
  • the film thickness of the coating film is T ( ⁇ m), and the ratio of fluorine atoms to the total mass of fluorine atoms and carbon atoms at a position of depth T / 2 ( ⁇ m) from the coating film surface is defined as
  • the mass ratio (A / B) of the second fluorine concentration (A) to the first fluorine concentration (B) is 13/87 to 49/51, It is preferably 25/75 to 49/51, and more preferably 30/70 to 45/55.
  • the composition ratio of the resin components in the coating film is greatly different (for example, the fluororesin layer and polyester constituting the coating film described in Patent Document 2)
  • the interface of the resin layer hardly occurs, and sufficient adhesion can be ensured.
  • the fluorine concentration is moderately contained also in the vicinity of the inner middle of the film, it has good wear resistance.
  • the region in which the ratio of fluorine atoms to the total mass of fluorine atoms and carbon atoms is 30 to 50% by mass usually varies depending on the fluorine resin and other compounding agents used. This is a region closer to the coating film surface than the position of T / 2 ( ⁇ m).
  • the composition ratio of the resin component in the coating film A greatly different region for example, the interface between the fluororesin layer and the polyester resin layer described in Patent Document 2) does not occur, and sufficient adhesion can be ensured.
  • the film thickness of the coating film is an average film thickness. For example, 10 arbitrary points of the coating film are selected, the film thickness is measured with an optical microscope or a scanning electron microscope, and the average value is calculated. It can be obtained by calculating.
  • the coating film is not a coating film obtained by coating a coating composition containing a resin other than a fluorine resin, for example, and then coating a coating composition containing a fluorine resin. Since it is a coating film obtained by coating a coating composition containing a resin and a resin other than the fluororesin, the thickness of the coating film is, for example, 40 to 200 ⁇ m.
  • the fluorine resin in the position where the ratio of fluorine atoms to the total mass of fluorine atoms and carbon atoms on the surface of the coating film (first fluorine concentration) and the depth from the coating film surface corresponds to half of the film thickness (Second fluorine concentration) can be measured using an SEM / EDS (Scanning Electron Microscope “Scanning Electron Microscope” / Energy Dispersive X-ray Spectroscope “Energy Dispersive X-ray Spectroscopy”).
  • SEM / EDS Scanning Electron Microscope “Scanning Electron Microscope” / Energy Dispersive X-ray Spectroscope “Energy Dispersive X-ray Spectroscopy”.
  • the value of the 1st fluorine concentration may change with the acceleration voltage of SEM, and the tendency is large especially when acceleration voltage is low. Therefore, it is preferable to measure by setting the SEM acceleration voltage to 10 kV to 20 kV.
  • a conductive substance for example, gold
  • the second fluorine concentration can be measured by determining the ratio of fluorine atoms and carbon atoms at a position where the depth from the coating film surface corresponds to half of the film thickness by line analysis using EDS.
  • the value of 2nd fluorine concentration may change with the acceleration voltage of SEM, and the tendency is large especially when acceleration voltage is low. Therefore, it is preferable to measure by setting the SEM acceleration voltage to 10 kV to 20 kV.
  • the cross section of the coating film is observed.
  • the coating film is mechanically cut directly, Cleave or break, and then embed it in a resin such as an epoxy resin in a state in which the coating film stands upright, and then perform processing such as grinding, polishing, etching, etc. perpendicular to the coating film with a microtome, etc.
  • a method for producing a measurement sample by applying is also known as a method for producing a measurement sample by applying.
  • the scratch coefficient of the coating film is, for example, 45 to 500.
  • the scratch coefficient of a coating film can be measured as follows. (Measuring method) It can be measured according to ASTM D968 (falling sand test method). Specifically, using a Gardner falling sand abrasion tester, a test plate was installed at an angle of 45 ° with respect to the horizontal plane, and No. 4 cinnabar (average particle size: 0.6-1. 2 mm), and the scratch coefficient is calculated from the following equation. In addition, the fall height of sand is 940 mm from the center position of a coating film.
  • V is the total amount of sand used in the sandfall test (unit: liter L)
  • T is a value obtained by subtracting the film thickness after the sandfall test from the film thickness before the sandfall test (that is, , Worn film thickness, unit: ⁇ m)]
  • the coated body of the present invention includes a base material and a coating film disposed on the surface of the base material, and the coating film includes, for example, a coating composition containing at least a fluorine resin and a resin other than the fluorine resin, preferably Is formed by applying a powder coating composition to the surface of a substrate and then melting and curing at a temperature preferably in the range of 170 to 250 ° C, more preferably in the range of 170 to 210 ° C.
  • the ratio of the fluorine resin on the coating film surface and the ratio of the fluorine resin at a position where the depth from the coating film surface corresponds to half the film thickness are adjusted to the above specific range.
  • Fluorine resin used in the coating composition is preferably a solid resin at normal temperature, and its softening point is preferably 50 to 150 ° C.
  • the fluororesin becomes a factor that brings the weather resistance and abrasion resistance to the coating film.
  • the normal temperature is a temperature in the range of 20 ° C. ⁇ 15 ° C. (5 to 35 ° C.) defined by JIS Z 8703.
  • the fluororesin preferably has a reactive site that reacts with a curing agent or the like, and preferably contains a hydroxyl group or a carboxyl group as the reactive site.
  • a fluorine resin having a hydroxyl group or a carboxyl group can be produced, for example, by copolymerizing a fluorine-containing monomer with a monomer containing a specific reactive group.
  • fluorine-containing monomer examples include vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, bromotrifluoroethylene, chlorotrifluoroethylene, pentafluoropropylene, hexafluoropropylene, and (per) fluoroalkyltrifluoro.
  • a monomer containing a specific reactive group is a polymerizable monomer containing a hydroxyl group or a carboxyl group as a group (reactive group) that reacts with a curing agent or the like.
  • examples of the hydroxyl group-containing polymerizable monomer include allyl alcohol; hydroxyalkyl vinyl ethers such as 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxycyclohexyl vinyl ether; 2-hydroxy Hydroxyalkyl allyl ethers such as ethyl allyl ether, 3-hydroxypropyl allyl ether, 4-hydroxybutyl allyl ether, 4-hydroxycyclohexyl allyl ether; hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate; Vinyl hydroxyacetate, vinyl hydroxyisobutyrate, vinyl hydroxypropionate, vinyl hydroxybutyrate, vinyl hydroxyvalerate, Esters of hydroxyalkyl carboxylic acids such as vinyl droxycyclohexylcarboxylate and vinyl alcohol; esters of hydroxy acids such as hydroxypropanoic acid, hydroxybutanoi
  • examples of the carboxyl group-containing polymerizable monomer include monoesters of dicarboxylic acid and allyl alcohol, (meth) acrylic acid, carboxyalkyl (meth) acrylates, and the like.
  • a polymerizable monomer other than the fluorine-containing monomer and a monomer containing a specific reactive group may be used.
  • Such polymerizable monomers include vinyl ethers, olefins, allyl ethers, vinyl esters, allyl esters, (meth) acrylic acid esters, (meth) acrylic acid amides, cyano group-containing monomers, dienes, etc. And crotonic acid esters.
  • polymerizable monomer other than the fluorine-containing monomer and the monomer containing a specific reactive group include, for example, alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, and chloroethyl vinyl ether.
  • alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, and chloroethyl vinyl ether.
  • Olefins such as ethylene, propylene, 1-butene, isobutylene, cyclohexene, vinyl chloride and vinylidene chloride; styrene monomers such as styrene and ⁇ -methylstyrene; methyl allyl ether, ethyl allyl ether, butyl allyl ether, cyclohexyl allyl Alkyl allyl ethers such as ether; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinyl hexanoate, octa Vinyl esters of carboxylic acids (preferably fatty acids) such as vinyl acid and vinyl versatate; allyl esters of carboxylic acids (preferably fatty acids) such as allyl propionate and allyl acetate; methyl (meth) acrylate, (meta ) (Meth) acrylic esters such as ethyl acrylate, buty
  • the fluorine resin preferably has a fluorine content of 5 to 80% by mass, more preferably 10 to 70% by mass.
  • the hydroxyl value of the fluorine resin is preferably 100 mgKOH / g or less from the viewpoint of maintaining the flexibility of the coating film. From the viewpoint of imparting impact properties, it is preferably 10 mgKOH / g or more.
  • the hydroxyl value of the fluororesin is preferably 30 to 70 mgKOH / g.
  • the fluorine resin content is preferably 20 to 60% by mass.
  • the resin other than the fluororesin used in the coating composition is preferably at least one resin selected from the group consisting of polyester resins and epoxy resins.
  • a resin other than the fluorine resin in combination, the appearance and workability of the coating film can be improved and the manufacturing cost can be reduced as compared with the case where only the fluorine resin is used as the resin component.
  • the content of the resin other than the fluorine resin is preferably 25 to 64% by mass.
  • the polyester resin that can be used in the coating composition can be produced by reacting a carboxylic acid component and a polyhydric alcohol component by a known method.
  • the polyester resin is preferably a solid resin at normal temperature, and its softening point is preferably 100 to 150 ° C.
  • the said polyester resin has a reactive site
  • carboxylic acid components that can be used in the production of the polyester resin include phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,2-octadecanedicarboxylic acid, maleic acid, fumaric acid, cyclohexanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid Polycarboxylic acids such as trimellitic acid and pyromellitic acid, lower alkyl esters of these polycarboxylic acids and acid anhydrides thereof, and malic acid, tartaric acid, 1,2-hydroxystearic acid, paraoxybenzoic acid, etc
  • polyhydric alcohol component examples include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4 -Butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, spiroglycol, 1,10-decanediol, 1,4- Examples include cyclohexanedimethanol, trimethylolethane, trimethylolpropane, glycerin, pentaerythritol and the like.
  • the polyester resin can be produced by an ordinary method known for producing a polyester resin for a coating composition using a carboxylic acid component and a polyhydric alcohol component as raw materials.
  • the above-mentioned raw materials are used in appropriate combinations and mixing ratios, subjected to esterification or transesterification at 200 to 280 ° C. according to a conventional method, and then subjected to polycondensation reaction at 230 to 290 ° C. using a catalyst under reduced pressure.
  • a polyester resin can be produced by performing a depolymerization reaction with a polyhydric alcohol.
  • the polyester resin may have a reactive group other than a hydroxyl group and a carboxyl group.
  • reactive sites include functional groups such as amide groups, amino groups, nitrile groups, glycidyl groups, and isocyanate groups.
  • the polyester resin is preferably a hydroxyl group-containing polyester resin from the viewpoint of cross-linking reaction and control of coating film properties. From the viewpoint of controlling the melt viscosity, the polyester resin preferably has a number average molecular weight of 5,000 or less and a weight average molecular weight of 10,000 to 20,000.
  • the number average molecular weight and the weight average molecular weight can be determined using polystyrene as a standard substance by gel permeation chromatography (GPC).
  • the hydroxyl value of the polyester resin is preferably 20 to 100 mgKOH / g, more preferably 30 to 80 mgKOH / g.
  • the acid value of the polyester resin is preferably 20 to 80 mgKOH / g, and more preferably 30 to 80 mgKOH / g.
  • the content of the polyester resin in the coating composition is preferably 25 to 64% by mass, and more preferably 25 to 63% by mass.
  • the epoxy resin that can be used in the coating composition is preferably a resin that is solid at room temperature, and its softening point is preferably 50 to 150 ° C.
  • an epoxy resin By using an epoxy resin, the adhesion to the substrate can be improved. It does not specifically limit as said epoxy resin, The epoxy resin conventionally used in the epoxy resin-type coating composition can be used.
  • the epoxy resin for example, bisphenol A type diglycidyl ether resin, bisphenol F type diglycidyl ether resin, aminoglycidyl ether resin, bisphenol AD type diglycidyl ether resin, bisphenol Z type diglycidyl ether resin, O -Cresol novolac epoxy resin, phenol novolac epoxy resin, biphenol glycidyl ether resin, cyclopentadiene skeleton epoxy resin, naphthalene skeleton epoxy resin, GMA acrylic resin, etc., and other substituents other than epoxy groups of these resins are replaced with other substituents Examples thereof include resins obtained by a modification reaction using a carboxyl group-terminated polybutadiene-acrylonitrile (CTBN) or a modification reaction such as esterification.
  • CTBN carboxyl group-terminated polybutadiene-acrylonitrile
  • the epoxy resin preferably has an epoxy equivalent of 300 to 1200, particularly preferably 400 to 1000.
  • the content of the epoxy resin in the coating composition is preferably 0.3 to 5% by mass.
  • the coating composition preferably contains an acrylic surface conditioner and a wax.
  • an acrylic surface conditioner and wax may be blended separately in the raw material of the coating composition, or a mixture obtained by previously mixing the acrylic surface conditioner and the wax in the raw material of the coating composition. You may mix in.
  • the acrylic surface conditioner that can be used in the coating composition is a compounding agent that contributes to the surface adjustment of the coating film, it has a property of melting at the temperature at which the coating film is formed. Therefore, the softening point of the acrylic surface conditioner is preferably 75 to 100 ° C.
  • the softening point of the acrylic surface conditioner can be measured by a ring and ball softening point test method based on JIS K 2207 (2006). JIS K 2207 (2006) is originally a standard for petroleum asphalt, but can also be applied to the measurement of the softening point of acrylic surface conditioners.
  • the acrylic surface conditioner is a dibasic acid ester having a polymerizable unsaturated double bond (component X), at least one selected from an acrylic acid alkyl ester and a methacrylic acid alkyl ester (component Y), and optionally Is preferably a copolymer obtained by copolymerizing at least one of acrylic acid and methacrylic acid.
  • component X polymerizable unsaturated double bond
  • component Y methacrylic acid alkyl ester
  • the dibasic acid ester include maleic acid diesters such as maleic acid diethyl ester, maleic acid monoesters, fumaric acid diesters such as diethyl fumarate, and fumaric acid monoesters.
  • the alkyl acrylate include normal butyl acrylate.
  • alkyl methacrylate include normal butyl methacrylate.
  • the acrylic surface conditioner is, for example, a copolymer of the component X and the component Y as described above, and thus is a component different from the core-shell type acrylic resin particles described later.
  • the content of the acrylic surface conditioner in the coating composition is preferably 0.5 to 6% by mass.
  • the wax that can be used in the coating composition is preferably a wax having a melting point of 40 ° C. or higher, and the melting point of the wax is more preferably 50 ° C. to 100 ° C.
  • the melting point of the wax can be measured by a visual method described in JIS K 0064 (1992).
  • Specific examples of the wax include castor oil, amide compounds, polyolefins such as polyethylene and polypropylene, acrylic compounds such as ethylene-vinyl acetate copolymer and ethylene-acrylic acid copolymer. These waxes may be used alone or in combination of two or more.
  • the content of the wax in the coating composition is preferably 0.3 to 10% by mass.
  • the mass ratio (w / s) of the wax (w) to the acrylic surface conditioner (s) is preferably 0.06 to 20.
  • the coating composition preferably contains a curing agent.
  • the curing agent is not particularly limited as long as it reacts with a fluororesin or a resin other than the fluororesin to form a cross-linked bond, but from ⁇ -hydroxyalkylamide, triglycidyl isocyanurate and an isocyanate compound.
  • ⁇ -Hydroxyalkylamides can be suitably used when the resin component has a carboxyl group, and those having two or more functional groups per molecule can be used for low-temperature curability and coating films obtained by coating. Particularly preferred from the viewpoint of water resistance.
  • ⁇ -hydroxyalkylamide include N, N-di ( ⁇ -hydroxyethyl) acetamide, bis ( ⁇ -hydroxyethyl) adipamide, bis ( ⁇ -hydroxypropyl) adipamide, bis [N, N-di ( ⁇ -hydroxy). Ethyl)] adipamide and bis [N, N-di ( ⁇ -hydroxypropyl)] adipamide are particularly preferred.
  • the ⁇ -hydroxyalkylamide preferably has a hydroxylamide group of 0.5 to 1.5 equivalents relative to the carboxyl group in the resin.
  • Triglycidyl isocyanurate can be suitably used when the resin component has a carboxyl group.
  • the triglycidyl isocyanurate include Araldite (registered trademark) PT 710, Araldite (registered trademark) PT 810, Araldite (registered trademark) PT 910, Araldite (registered trademark) PT 912 (all manufactured by Huntsman).
  • Etc. The triglycidyl isocyanurate preferably has 0.5 to 1.5 equivalents of glycidyl group based on the carboxyl group in the resin.
  • the isocyanate compound can be suitably used when the resin component has a hydroxyl group, and is more preferably a blocked isocyanate compound.
  • the isocyanate compound is preferably solid at room temperature.
  • the isocyanate group is preferably from 0.05 to 1.5 equivalents, particularly preferably from 0.8 to 1.2 equivalents, based on the hydroxyl groups in the resin.
  • the blocked isocyanate compound may be masked by reacting, for example, a polyisocyanate obtained by reacting an aliphatic, aromatic or araliphatic diisocyanate with a low molecular weight compound having active hydrogen with a blocking agent. Therefore, manufacturing is also easy.
  • the diisocyanate include tolylene diisocyanate, 4,4′-diphenylmethane isocyanate, xylylene diisocyanate, hexamethylene diisocyanate, 4,4′-methylene bis (cyclohexyl isocyanate), methylcyclohexane diisocyanate, bis (isocyanatomethyl) cyclohexane, isophorone.
  • Diisocyanate, dimer acid diisocyanate, lysine diisocyanate, etc. can be mentioned.
  • the low molecular weight compound having active hydrogen include water, ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, ethylenediamine, ethanolamine, diethanolamine, hexamethylenediamine.
  • Etc., isocyanurate, uretidione, hydroxyl group Low molecular weight polyesters having, polycaprolactone and the like.
  • the blocking agent include alcohols such as methanol, ethanol and benzyl alcohol, phenols such as phenol and crezone, lactams such as caprolactam and butyrolactam, and oximes such as cyclohexanone, oxime and methyl ethyl ketoxime.
  • specific examples of the blocked isocyanate include isophorone diisocyanate blocked with ⁇ -caprolactam (Evonik Vestagon B1530, Bayer Cleran UI), and the like.
  • the coating composition may contain core-shell type acrylic resin particles.
  • core-shell type acrylic resin particles By using the core-shell type acrylic resin particles, the processability of the coating film can be improved without lowering the weather resistance.
  • the core-shell type acrylic resin particles preferably have at least one functional group selected from the group consisting of a carbonyl group, a hydroxyl group and a glycidyl group on the particle surface.
  • the core-shell type acrylic resin particles are a multiphase comprising a rubbery polymer phase at room temperature where the glass transition temperature of the core layer is 20 ° C. or less and a glassy polymer phase at room temperature where the glass transition temperature of the shell layer is 50 ° C. or more. It preferably has a structure.
  • the core-shell type acrylic resin particles include, for example, a first polymer monomer that forms a rubber-like polymer phase by emulsion and suspension polymerization to form rubber-like polymer particles having a glass transition temperature of 20 ° C. or less.
  • the radical polymerizable monomer constituting the glassy polymer is a functional group selected from the group consisting of a carboxyl group, a hydroxyl group and a glycidyl group. It preferably has at least one group.
  • the rubbery polymer constituting the core layer is, for example, a polymer of an unsaturated monomer that can be used for the synthesis of a rubbery polymer.
  • the glass transition temperature of the rubbery polymer is preferably 20 ° C. or less, and more preferably in the range of ⁇ 30 to ⁇ 10 ° C.
  • the unsaturated monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl ( Alkyl (meth) acrylates such as meth) acrylate: Vinyl esters such as vinyl acetate: Vinyl halides such as vinyl chloride, vinyl fluoride, vinylidene chloride, vinylidene fluoride or vinylidene halides: (meth) acrylonitrile, (meth) acrylamide, etc.
  • Nitrogen-containing unsaturated monomer Aromatic compounds such as styrene, ⁇ -methylstyrene and vinyltoluene: Hydroxyl-containing unsaturated monomers such as hydroxyethyl (meth) acrylate and methylol (meth) acrylamide: (meth) acrylic acid
  • Hydroxyl-containing unsaturated monomers such as hydroxyethyl (meth) acrylate and methylol (meth) acrylamide
  • Unsaturated carboxylic acids such as: Dienes, and diene monomers such as isoprene and the like. These unsaturated monomers may be used independently and may be used in combination of 2 or more type.
  • Typical examples of rubber-like polymers are poly (meth) acrylate rubber, polybutadiene rubber, polyisoprene rubber, polyvinyl chloride, styrene-butadiene rubber, styrene-butadiene-styrene rubber, styrene-isoprene-styrene rubber, styrene- Examples include butylene rubber, styrene-ethylene rubber, and ethylene-propylene rubber. Among these, poly (meth) acrylate rubber, polybutadiene rubber, polyisoprene rubber, and styrene-butadiene rubber are particularly preferable.
  • the glassy polymer constituting the shell layer is, for example, a polymer of a radical polymerizable monomer adjusted to have a glass transition temperature of 50 ° C. or higher, preferably 80 to 100 ° C.
  • a radical polymerizable monomer a general vinyl monomer or the like can be used, and examples thereof include the above-described unsaturated monomer.
  • the vinyl monomer having the functional group include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, etc.
  • esters acrylic acid or methacrylic acid hydroxyalkyl having 2 to 8 carbon atoms Esters; monoesters of polyether polyols such as polyethylene glycol, polypropylene glycol, polybutylene glycol, and unsaturated carboxylic acids such as (meth) acrylic acid; polyether polyols such as polyethylene glycol, polypropylene glycol, polybutylene glycol; Hide Monoethers with hydroxyl-containing unsaturated monomers such as xylethyl (meth) acrylate; adducts of ⁇ , ⁇ -unsaturated carboxylic acids with monoepoxy compounds such as Cardura E10 (manufactured by Shell Chemical) and ⁇ -olefin epoxides Adducts of glycidyl (meth) acrylate with monobasic acids such as acetic acid, propionic acid, pt-butylbenzoic acid and fatty acids; acid anhydride group-containing unsaturated compounds such as male
  • the core-shell type acrylic resin particles are obtained by a conventionally known method, for example, an emulsion polymerization method or a suspension polymerization method in which a radical polymerizable monomer and a radical polymerizable initiator are added in the presence of a rubbery polymer emulsion in advance. Obtainable.
  • the content of the core-shell type acrylic resin particles in the coating composition is preferably 0.1 to 5% by mass.
  • the coating composition may further contain a bright pigment.
  • a bright pigment when a luster pigment is used, alkali resistance can be improved.
  • Bright pigments include, for example, aluminum powder pigment, nickel powder pigment, gold powder, silver powder, bronze powder, copper powder, stainless steel powder pigment, mica pigment, graphite pigment, glass flake pigment, metal-coated glass powder, metal coating Mica powder, metal-coated plastic powder, and scaly iron oxide pigment.
  • the coating composition may contain a commonly used pigment such as a colored pigment or an extender pigment in addition to the bright pigment.
  • a commonly used pigment such as a colored pigment or an extender pigment in addition to the bright pigment.
  • the color pigment include inorganic pigments such as titanium oxide, yellow iron oxide, titanium yellow, bengara, lithopone and antimony oxide, Hansa Yellow 5G, Permanent Yellow FGL, Phthalocyanine Blue, Indanthrene Blue RS, Permanent Red F5RK, And organic pigments such as Brilliant First Scarlet G.
  • examples of extender pigments include barium sulfate, barium carbonate, calcium carbonate, clay, silica powder, diatomaceous earth, talc, basic magnesium carbonate, and alumina white.
  • the said coating composition may contain a rust prevention pigment, when the rust prevention property is required for the base material which should be painted.
  • rust preventive pigments include condensed calcium phosphate, aluminum phosphate, condensed aluminum phosphate, zinc phosphate, aluminum phosphite, zinc phosphite, calcium phosphite, zinc molybdate, calcium molybdate, and manganese molybdate. Can be mentioned. These pigments may be used alone or in combination of two or more.
  • the total content of the pigment in the coating composition is preferably 0.2 to 35% by mass.
  • plasticizers as additives for general coatings, plasticizers, curing accelerators, crosslinking accelerators, ultraviolet absorbers, light stabilizers, antioxidants, fluidity modifiers, anti-sagging agents and antifoaming agents You may mix
  • the method for producing the coating composition includes, for example, melting and kneading a mixture containing the fluororesin, a resin other than the fluororesin, an acrylic surface conditioner and a wax at 100 to 160 ° C., and then cooling and pulverizing the mixture. And a method for preparing a powder coating composition.
  • a mixture containing the above fluororesin, a resin other than fluororesin, an acrylic surface conditioner and wax is dry blended with a Henschel mixer or the like, and then melt-kneaded at 120 to 140 ° C. using a co-kneader or the like, and cooled.
  • the powder coating composition can be obtained by classification using a 180 mesh (96 ⁇ m) wire mesh or the like.
  • the coating method of the coating composition examples include corona charging electrostatic powder coating, friction charging electrostatic powder coating, fluidized immersion powder coating, electrostatic fluidized immersion powder coating, and electric field cloud powder. Examples include body painting.
  • the coating composition can be formed by melting and curing the coating composition at a temperature of preferably 160 to 250 ° C., more preferably 170 to 220 ° C.
  • Examples of the substrate constituting the coated body of the present invention include metal substrates such as steel, zinc, aluminum, copper, and tin. In order to improve adhesion to the coating film, the surface of the metal substrate is used. Those subjected to ground treatment are preferred.
  • the base material has various shapes depending on its use, and examples thereof include a plate shape. However, the coating film constituting the coated body of the present invention is usually formed on one surface of the base material. ing.
  • coated body of the present invention include automobiles, trains, aircraft and other transportation equipment and members thereof, bridges and members thereof, steel towers and members thereof, civil engineering members, waterproof sheets, tanks, pipes and other industrial equipment, Building exteriors, doors, window gates, monuments, building components such as poles, road median strips, guardrails, sound barriers, polycarbonate translucent plates, traffic lights and other road components, communication equipment and components, home appliances, electricity And electronic components.
  • Acrylic surface conditioner A In a polymerization apparatus equipped with a reflux condenser, a thermometer, a stirrer, and a dropping tank, 300 parts by mass of butyl acetate was added, and a dropping solution A shown below was dropped at 110 ° C. over about 3 hours under a nitrogen atmosphere. After completion of the dropwise addition, 5 parts by mass of t-amylperoxy-2-ethylhexanoate was added and kept at 110 ° C. for 2 hours. Thereafter, the temperature was raised to 130 ° C., and butyl acetate was distilled off under reduced pressure to obtain an acrylic surface conditioning agent A.
  • An acrylic surface conditioning agent B was obtained in the same manner as in the production example of the acrylic surface conditioning agent A, except that the dropping solution B shown below was used instead of the dropping solution A.
  • the number average molecular weight in terms of polystyrene of the acrylic surface conditioning agent B was measured by gel permeation chromatography, it was 4100.
  • Dropping solution B a solution comprising 324 parts by weight of normal butyl acrylate, 65 parts by weight of acrylic acid, 28 parts by weight of fumaric acid diethyl ester, 15 parts by weight of t-amylperoxy-2-ethylhexanoate, and 200 parts by weight of butyl acetate .
  • An acrylic surface conditioning agent C was obtained in the same manner as in the production example of the acrylic surface conditioning agent A, except that the following dropping solution C was used instead of the dropping solution A. It was 2900 when the polystyrene conversion number average molecular weight of the acrylic surface conditioning agent C was measured by gel permeation chromatography. Moreover, it was 78 degreeC when the softening point of the acrylic type surface conditioning agent C was measured by the ring and ball type softening point test method based on JISK2207 (2006).
  • Drop solution C From 324 parts by weight of normal butyl acrylate, 47 parts by weight of maleic acid diethyl ester, 46 parts by weight of fumaric acid diethyl ester, 15 parts by weight of t-amylperoxy-2-ethylhexanoate, and 200 parts by weight of butyl acetate Solution.
  • ⁇ Preparation example of powder coating composition> In accordance with the formulation shown in Table 1, the raw materials were put into a high speed mixer and mixed for 1 minute. Next, the obtained mixture is kneaded using a biaxial kneader (manufactured by Toshiba) whose temperature is adjusted to 120 ° C., the discharged kneaded material is cold-rolled with a cooling roll, and then pulverized using a pin mill.
  • the powder coating compositions of Examples 1 to 11 and Comparative Examples 1 to 3 (50% volume average particle size: 32 ⁇ m) were obtained.
  • Test plates were prepared using the powder coating compositions of Examples 1 to 11 and Comparative Examples 1 to 3. Specifically, a chromic acid chromate-treated aluminum plate having a thickness of 1.5 mm is suspended in the vertical direction, and a voltage of ⁇ 60 kV using a corona-charged electrostatic powder coating machine (PG-1 type manufactured by Asahi Sunac Corporation). The film was electrostatically coated to a film thickness of 60 ⁇ m, baked in an electric furnace at 190 ° C. for 20 minutes, and allowed to cool to room temperature as it was to prepare a test plate.
  • PG-1 type corona-charged electrostatic powder coating machine
  • the first fluorine concentration is the ratio (mass%) of fluorine atoms to the total mass of fluorine atoms and carbon atoms on the coating film surface.
  • the test plate was cut out to about 1 cm ⁇ 1 cm, and in order to reduce damage to the coating film surface by the electron beam, gold was vapor-deposited on the cut-out sample, and the gold-deposited sample was fixed to the SEM observation stand with conductive tape. Thereafter, SEM observation was performed at an acceleration voltage of 15 kv and a magnification of 500 times.
  • the coating surface having an area of 245 ⁇ m ⁇ 185 ⁇ m is arbitrarily selected by EDS, elemental mapping measurement is performed on the coating surface, the ratio of carbon atoms to fluorine atoms is measured, and the total of fluorine atoms and carbon atoms is measured. The proportion of fluorine atoms in the mass was determined.
  • the second fluorine concentration is a ratio (mass%) of fluorine atoms in the total mass of fluorine atoms and carbon atoms at a position where the depth from the coating film surface corresponds to half of the film thickness.
  • gold was vapor-deposited on a test plate embedded in an epoxy resin used for film thickness measurement in order to reduce damage to the coating film surface by an electron beam, and this gold-deposited sample was conducted to an SEM observation stand. After fixing with the adhesive tape, SEM observation was performed at an acceleration voltage of 15 kv and a magnification of 900 times.
  • a line parallel to the coating film surface and having a length of 135 ⁇ m is arbitrarily selected, and element mapping measurement of the line by EDS (line Analysis), the ratio of carbon atoms to fluorine atoms was measured, and the ratio of fluorine atoms to the total mass of fluorine atoms and carbon atoms was determined. Then, the place where element mapping measurement was performed was changed, and the ratio of fluorine atoms in the total mass of fluorine atoms and carbon atoms at a position where the depth from the coating film surface corresponds to half of the film thickness was measured nine times. The average value of 10 measurement results was defined as the second fluorine concentration.
  • Scratch coefficient V / T [In the formula, V is the total amount of sand used in the sandfall test (unit: liter L), and T is a value obtained by subtracting the film thickness after the sandfall test from the film thickness before the sandfall test (that is, , Worn film thickness, unit: ⁇ m)]
  • the wear resistance was evaluated according to the following evaluation criteria. ⁇ ⁇ ⁇ ⁇ Scratch coefficient is 100 or more ⁇ ⁇ ⁇ Scratch coefficient is 45 or more and less than 100 ⁇ ⁇ ⁇ Scratch coefficient is 40 or more and less than 45 ⁇ ⁇ ⁇ ⁇ Scratch coefficient is less than 40
  • ⁇ Weather resistance> Accelerated weathering tester based on JIS B7753 (Sunshine weatherometer method) for test plates (coating bodies) obtained using the powder coating compositions of Examples 1 to 11 and Comparative Examples 1 to 3 Was used to evaluate the weather resistance.
  • the test time was 3000 hours.
  • the 60 ° specular gloss value before the test and after the 3000 hour test was measured with a gloss meter (manufactured by micro-TRI-gross BYK: incident reflection angle 60 °), and the 60 ° specular gloss value before the test after the 3000 hour test.
  • the change rate of the specular gloss value was determined, and the weather resistance was evaluated according to the following evaluation criteria.
  • ⁇ ⁇ ⁇ Change rate is 90% or more ⁇ ⁇ ⁇ ⁇ Change rate is 70% or more and less than 90% ⁇ ⁇ ⁇ ⁇ Change rate is 50% or more and less than 70% ⁇ ⁇ ⁇ ⁇ Change rate is less than 50%
  • ⁇ Adhesiveness> In accordance with JIS K5600-5-6 (cross-cut method), the coating on the test plate was cut into a grid of 100 squares at 1 mm intervals, a peel test was performed using an adhesive tape, and the residual rate after the peel test The adhesion was evaluated according to the following evaluation criteria. ⁇ : 100/100 (number of cut parts remaining after the test / total number of cut parts before the test) ⁇ : 85/100 to 99/100 X: 84/100 or less
  • a stirrer and a reflux condenser were attached to the polymerization vessel, and the temperature was raised to 70 ° C. while stirring under a nitrogen stream. The reaction was carried out for 2 hours while stirring at 70 ° C. At this time, sampling was performed from the obtained suspension of polymer particles, and the polymerization conversion rate of the monomer was measured and found to be 94%. The resulting polymer particle suspension was then cooled to 60 ° C. While stirring this suspension at 4500 rpm, a monomer emulsion for the second stage reaction shown below was continuously added over 15 minutes.
  • the monomer emulsion for the second stage reaction was 352 g of methyl methacrylate, 40 g of ethyl acrylate, 10 g of 2-hydroxyethyl methacrylate, 8 g of ethylene glycol dimethacrylate, 4 g of 2,2′-azobisisobutyronitrile, 1 mass. % 100% sodium dodecyl sulfonate aqueous solution and 100 g of deionized water were mixed to prepare.
  • the temperature was raised to 80 ° C., and an aging reaction was performed for 3 hours.
  • the obtained suspension was cooled to room temperature, dehydrated and washed using a centrifuge, and further air-dried at 60 ° C. overnight to obtain core-shell type acrylic resin particles.
  • the glass transition temperature of the rubber-like polymer phase (core layer) was ⁇ 20 ° C.
  • the glass transition temperature of the glass-like polymer phase (shell layer) was 83 ° C.
  • Specific primary surface area / pore distribution measuring device Asap 2020 (manufactured by Shimadzu Corporation) has an average primary particle size calculated from specific surface area measurement of 0.1 ⁇ m, and a laser diffraction / scattering particle size distribution measuring device Partica.
  • the average secondary particle diameter measured by LA-950V2 manufactured by Horiba, Ltd. was 6 ⁇ m.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

La présente invention aborde le problème de production d'un corps pourvu d'un revêtement qui présente une excellente résistance aux intempéries, à l'usure et une excellente capacité d'adhérence. La présente invention concerne un corps pourvu d'un revêtement qui comprend une base et un film de revêtement qui est disposé sur la surface de la base, et qui est caractérisé en ce que : le film de revêtement est formé à partir d'une composition de matériau de revêtement qui contient au moins une résine fluorée et une résine autre que la résine fluorée; si le taux d'atomes de fluor dans la masse totale d'atomes de fluor et d'atomes de carbone dans la surface du film de revêtement est défini comme une première concentration de fluor (% en masse), la première concentration de fluor est de 30 à 50 % en masse; et si l'épaisseur du film de revêtement est définie comme T (µm) et le taux d'atomes de fluor dans la masse totale d'atomes de fluor et d'atomes de carbone à une profondeur de T/2 (μm) à partir de la surface du film de revêtement est défini comme une seconde concentration de fluor (% en masse), le rapport massique de la seconde concentration de fluor (A) à la première concentration de fluor (B), à savoir A/B est de 13/87 à 49/51.
PCT/JP2015/075588 2014-09-30 2015-09-09 Corps pourvu d'un revêtement WO2016052111A1 (fr)

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JP6868181B2 (ja) * 2016-12-26 2021-05-12 富士フイルムビジネスイノベーション株式会社 粉体塗料
JP6298198B1 (ja) * 2017-05-26 2018-03-20 関西ペイント株式会社 粉体塗料組成物
US11015080B2 (en) * 2019-08-15 2021-05-25 Ppg Industries Ohio, Inc. Powder coating compositions and coatings formed therefrom
KR102416188B1 (ko) * 2021-02-18 2022-07-05 한국세라믹기술원 선도유지 패키징용 항균성 세라믹 하이브리드 필름 및 이의 제조방법

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