CN106794682B - Coated-body - Google Patents

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Publication number
CN106794682B
CN106794682B CN201580053070.6A CN201580053070A CN106794682B CN 106794682 B CN106794682 B CN 106794682B CN 201580053070 A CN201580053070 A CN 201580053070A CN 106794682 B CN106794682 B CN 106794682B
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China
Prior art keywords
film
resin
coated
fluororesin
coating composition
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CN201580053070.6A
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CN106794682A (en
Inventor
北川将司
木口忠广
安藤祐
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NIPPON TORYO CO Ltd
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NIPPON TORYO CO Ltd
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    • 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

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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

Problem to be solved by the invention is, provides weatherability, wearability and the excellent coated-body of adhesion.The present invention is coated-body, it is the coated-body for having the film of base material and configuration on the substrate surface, it is characterized in that, the film including at least the coating composition of the resin other than fluororesin and the fluororesin by being formed, when the ratio shared by fluorine atom in total quality of fluorine atom and carbon atom in the film coated surface is set as the 1st Funing tablet (quality %), 1st Funing tablet is 30~50 mass %, when the film thickness of the film is set as T (μm), when fluorine atom at film coated surface depth T/2 (μm) position and the ratio in total quality of carbon atom shared by fluorine atom are set as the 2nd Funing tablet (quality %), 2nd Funing tablet (A) is 13/87~49/51 to the mass ratio (A/B) of the 1st Funing tablet (B).

Description

Coated-body
Technical field
The present invention relates to the coated-bodies for having film on the substrate surface of base material and configuration, and be related to weatherability, Wearability and the excellent coated-body of adhesion.
Background technology
In recent years, the environmental problem of the global scale such as global warming, depletion of the ozone layer, acid rain is especially concerned, international It is upper constantly to appeal that the countermeasure for environmental pollution has carried out various limitations at the same time from the viewpoint of environmental protection.Its In, organic solvent (especially volatile organic compounds VOC) is discharged into air and will produce prodigious problem, in each field In the presence of the trend for strengthening VOC limitations, while the direction of de- organic solvent (especially de- VOC) is also more active.In coating circle, make For the coating of previous organic solvent type coatings can be replaced, it is desirable that be entirely free of VOC, do not need gas exhaust treatment, wastewater treatment And the environmental-friendly coating of recyclable recycling, wherein the expectation to powder coating is constantly surging.
At such shape Condition, the scheme of proposition is using the polyester tree comprising the excellent fluororesin of weatherability and low cost The powder coating composition of the layer separation type of fat (for example, referring to Patent Documents 1 to 3).
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2011-12119 bulletins
Patent document 2：Japanese Unexamined Patent Publication 2012-41383 bulletins
Patent document 3：Japanese Unexamined Patent Publication 2013-76019 bulletins
Invention content
Problem to be solved by the invention
If but be known that the powder coating composition using layer separation type as recorded in Patent Documents 1 to 3, The film that still there is room for improvement in terms of weatherability is then formed, or is formed and can ensure that weatherability but in wearability and adhesion side The face film that also there is room for improvement.
Therefore, the purpose of the present invention is to provide the coated-body for having film on the substrate surface of base material and configuration, The weatherability of the coated-body, wearability and adhesion are excellent.
The means used to solve the problem
The present inventor to achieve the goals above, has made intensive studies, and as a result learns, the powder of these layer separation types applies Feed composition is formed by different on fluororesin layer and the resin ratio of components of polyester resin layer this aspect after constituting application.
For example, for the powder coating composition of the layer separation type recorded in patent document 2, constitutes and be located on film The resin component of side fluororesin layer is largely fluororesin, and the resin component for constituting the polyester resin layer positioned at downside is largely Polyester resin.Know and film be formed by for the powder coating composition by the layer separation type recorded in patent document 2, Since the composition for the resin component for constituting each layer differs widely, so sufficient adhesion can not be obtained between each layer, sometimes Splitting occurs.
On the other hand, the powder coating composition of the layer separation type recorded in patent document 3, recorded in patent document 2 The powder coating composition of layer separation type compare, the ratio of the polyester resin as the resin component for constituting fluororesin layer is high, The ratio of fluororesin as the resin component for constituting polyester resin layer is high, and the composition for constituting the resin component of each layer compares phase Closely.It is known however that the fluororesin ratio for constituting fluororesin layer can not be said to be foot from the viewpoint of weatherability and wearability It is enough high, also room for improvement.
Therefore, the inventors discovered that, in order to solve these technical problems, by by the ratio of the fluororesin in film coated surface Proportion adjustment with the fluororesin at the position that the depth apart from film coated surface is equivalent to film thickness half, can to prescribed limit Weatherability, wearability and the excellent coated-body of adhesion are obtained, is had thus completed the present invention.
That is, the coated-body of the present invention is the coated-body for having the film of base material and configuration on the substrate surface, feature It is,
The film by being formed including at least the coating composition of the resin other than fluororesin and the fluororesin,
It is set when by the ratio shared by fluorine atom in total quality of fluorine atom and carbon atom in the film coated surface For the 1st Funing tablet (quality %) when, the 1st Funing tablet be 30~50 mass %,
It, will be apart from the fluorine atom at film coated surface depth T/2 (μm) position when the film thickness of the film is set as T (μm) When being set as the 2nd Funing tablet (quality %) with the ratio shared by fluorine atom in total quality of carbon atom, the 2nd Funing tablet (A) is right The mass ratio (A/B) of 1st Funing tablet (B) is 13/87~49/51.
In the preference of the coated-body of the present invention, the film thickness of the film is 40~200 μm.
In other preferences of the coated-body of the present invention, the base material is metal base.
In other preferences of the coated-body of the present invention, resin other than the fluororesin be selected from by polyester resin and At least one of the group of epoxy resin composition resin.
In other preferences of the coated-body of the present invention, the coating composition is powder coating composition.
In other preferences of the coated-body of the present invention, the cut coefficient (drawing っ か き Department numbers) of the film is 45~ 500。
Invention effect
According to the present invention, by being equivalent to film by the ratio of fluororesin in film coated surface and in the depth apart from film coated surface It is excellent can to provide weatherability, wearability and adhesion to particular range for the proportion adjustment of fluororesin at the position of thick half Coated-body.
Specific implementation mode
Hereinafter, the coated-body of the present invention is described in detail.The coated-body of the present invention is to have base material and configuration at this The coated-body of film on substrate surface, which is characterized in that the film is by including at least other than fluororesin and the fluororesin The coating composition of resin is formed,
It is set when by the ratio shared by fluorine atom in total quality of fluorine atom and carbon atom in the film coated surface For the 1st Funing tablet (quality %) when, the 1st Funing tablet be 30~50 mass %,
It, will be apart from the fluorine atom at film coated surface depth T/2 (μm) position when the film thickness of the film is set as T (μm) When being set as the 2nd Funing tablet (quality %) with the ratio shared by fluorine atom in total quality of carbon atom, the 2nd Funing tablet (A) is right The mass ratio (A/B) of 1st Funing tablet (B) is 13/87~49/51.
In the coated-body of the present invention, when by fluorine atom institute in total quality of fluorine atom and carbon atom in film coated surface When the ratio accounted for is set as the 1st Funing tablet (quality %), it is desirable that the 1st Funing tablet is 30~50 mass %.If the 1st Funing tablet exists In above-mentioned specific range, then the ratio of the fluororesin in film coated surface is sufficiently high, therefore can improve weatherability and wearability. In contrast, if the 1st Funing tablet is less than 30 mass %, sufficient weatherability and wearability can not be obtained.In addition, though The the 1st Funing tablet the high more can improve weatherability and wearability, but under conditions of meeting the 2nd Funing tablet relevant regulations, the 1st The distribution of fluororesin in film of the Funing tablet higher than 50 mass % carries out control and is difficult.
In the present invention, the surface of film refers to being located at the face with base material contact surface opposite side of film.
It, will be apart from film coated surface depth T/2 (μ when the film thickness of film is set as T (μm) in the coated-body of the present invention M) when fluorine atom proportion is set as the 2nd Funing tablet (quality %) in total quality of the fluorine atom at position and carbon atom, It is required that the 2nd Funing tablet (A) is 13/87~49/51, preferably 25/75~49/51 to the mass ratio (A/B) of the 1st Funing tablet (B), More preferably 30/70~45/55.If mass ratio (A/B) in above-mentioned specific range, is difficult to generate resin in film The widely different region of the ratio of components of ingredient is (for example, the fluororesin layer and polyester resin of the composition film recorded in patent document 2 The interface of layer), it can also fully ensure adhesion.In addition, also include Funing tablet appropriate near the bosom of film, because This is with good wearability.
It should be noted that in the coated-body of the present invention, in total quality of fluorine atom and carbon atom shared by fluorine atom Ratio by 30~50 mass % region according to different using fluororesin and other compounding agents, but be typically Than depth T/2 (μm) position closer to the region of film coated surface.Therefore, if as apart from film coated surface depth T/2 (μm) position The 2nd Funing tablet of the fluororesin concentration index at place is set in above-mentioned specific range, then is difficult to generate resin component in film The widely different region (for example, interface of the fluororesin layer and polyester resin layer recorded in patent document 2) of ratio of components, may be used also To fully ensure adhesion.
In the present invention, the film thickness of film refers to average film thickness.Such as can by arbitrarily selected 10 points on film, Film thickness measuring is carried out using light microscope, scanning electron microscope etc., its average value is calculated and finds out.It needs to illustrate It is that in the coated-body of the present invention, film is not the coating composition application that will for example include resin other than fluororesin, later will Including film obtained from the coating composition application of fluororesin, but the painting that resin other than fluororesin and the fluororesin will be included Film obtained from feed composition application, therefore the film thickness of film is such as 40~200 μm.
In the present invention, the ratio the (the 1st in total quality of the fluorine atom in film coated surface and carbon atom shared by fluorine atom Funing tablet), and (the 2nd fluorine is dense for the ratio of fluororesin at the position of depth apart from the film coated surface half that is equivalent to film thickness Degree), SEM/EDS (Scanning Electron Microscope " scanning electron microscope "/Energy can be used Dispersive X-ray Spectroscope " energy dispersion-type X-ray spectroscope ") device and measure.
When measuring 1 Funing tablet, it can enumerate：Film coated surface first is observed with SEM first, then uses EDS into row element point Analysis, the method for measuring the ratio of fluorine atom and carbon atom.It should be noted that when observing film coated surface with SEM, due to SEM plus The reason of fast voltage, the value of the 1st Funing tablet will produce sometimes variation, especially accelerating potential it is lower in the case of the tendency compared with Greatly.It is measured it is therefore preferable that the accelerating potential of SEM is set as 10kV~20kV.It should be noted that adjoint in order to reduce SEM measure when the film coated surface caused by electron ray destruction, can before the assay in advance by the substance of electric conductivity (such as gold Deng) be vaporized on measurement sample surface.
When measuring 2 Funing tablet, first film section is observed with SEM first.Then, it is asked by using the line analysis of EDS The ratio for going out the fluorine atom and carbon atom at the position for the half that the depth apart from film coated surface is equivalent to film thickness can measure 2 Funing tablets.It should be noted that when observing film coated surface with SEM, due to the accelerating potential of SEM, the 2nd Funing tablet Value will produce sometimes variation, especially accelerating potential it is lower in the case of the tendency it is larger.It is therefore preferable that by the acceleration electricity of SEM Pressure is set as 10kV~20kV and is measured.It should be noted that when being measured with SEM to reduce caused by electron ray The substance of electric conductivity (such as gold etc.) can be vaporized on measurement sample surface by the destruction of film coated surface in advance before the assay On.
When measuring film thickness or 2 Funing tablet, film section is observed, it is however generally that, as observing film section The production method for measuring sample, can enumerate：Mechanically directly film is cut off, cut off or interrupted, then, is hung down by the film It is straight erect in the state of be embedded in the resins such as epoxy resin, later, film is vertically implemented with slicer etc. cutting, grinding, Etching etc. processing come make measure sample method.
For the coated-body of the present invention, the wearability of film as described above is high, therefore the cut coefficient of film is for example It is 45~500.It should be noted that the cut coefficient of film can measure by the following method.
(assay method)
It can be measured according to ASTM D968 (sand trail method).Specifically, passing through Gardner (Gardner) formula knockout Abrasion tester, by breadboard be arranged to horizontal plane inclination at 45 °, make No. 4 silica sand (average grain diameters：0.6~1.2mm) it falls The center of film calculates cut coefficient by following formula.It should be noted that the height of fall of sand is apart from film centre bit Set 940mm.
Cut coefficient=V/T
[in formula, V is the total amount (unit of the sand used in sand trail：Rise L), T is to subtract the film thickness before sand trail Go the value obtained by the film thickness after sand trail (that is, the film thickness of abrasion, unit：μm)]
The coated-body of the present invention has a film on the surface of the base material of base material and configuration, the film be, for example, pass through by It is painted on base material including at least the coating composition of the resin other than fluororesin and the fluororesin, preferably by powder coating composition Surface, then make at a temperature of preferably 170~250 DEG C of ranges, more preferable 170~210 DEG C of ranges its melting, solidification come shape At.It should be noted that in the coated-body of the present invention, need by the ratio of the fluororesin in film coated surface and apart from film table The depth in face is equivalent to the proportion adjustment of the fluororesin at the position of the half of film thickness to above-mentioned specific range, in order to meet this The combination of acrylic surfaces conditioning agent and wax, is mixed into aforementioned coating composition by a little regulations preferably in a manner of aftermentioned.
The fluororesin used in aforementioned coating composition is preferably the resin of solid-like at normal temperatures, and softening point is preferred It is 50~150 DEG C.In the coated-body of the present invention, fluororesin is the principal element that weatherability and wearability are brought for film.It needs It is noted that room temperature refers to, the temperature of 20 DEG C of ± 15 DEG C of (5~35 DEG C) ranges as defined in JIS Z8703.
In addition, above-mentioned fluororesin preferably has the reactive site reacted with curing agent etc., as reactive site, preferably Contain hydroxyl or carboxyl.Fluororesin with hydroxyl or carboxyl for example can be by by fluorochemical monomer and containing specific reactive The monomer of group is copolymerized to manufacture.
As above-mentioned fluorochemical monomer, can enumerate for example：Ethylene fluoride, vinylidene fluoride, trifluoro-ethylene, tetrafluoroethene, Bromo trifluoro-ethylene, chlorotrifluoroethylene, pentafluoropropene, hexafluoropropene, (complete) fluoroalkyl trifluoro vinyl ether be [(complete) fluoroalkyl Carbon number is 1~18] etc..
On the other hand, the monomer containing specific reactive group refers to containing hydroxyl or carboxyl as with curing agent etc. The polymerizable monomer of aitiogenic group (reactive group).
Specifically, as the polymerizable monomer containing hydroxyl, can enumerate for example：Allyl alcohol；2- hydroxyethyl vinyls The hydroxyalkyl vinyls such as base ether, 3- hydroxypropyls vinyl ethers, 4- hydroxybutyl vinyl ethers, 4- hydroxy-cyclohexyl vinyl ethers Base ethers；2- hydroxyethyls allyl ether, 3- hydroxypropyl allyl ethers, 4- hydroxybutyls allyl ether, 4- hydroxy-cyclohexyls The hydroxy alkyls allyl ether series such as allyl ether；2- hydroxyethyls (methyl) acrylate etc. hydroxy alkyls (methyl) acrylate Class；Hydroxyacetic acid vinyl esters, hydroxy-iso-butyric acid vinyl esters, hydracrylic acid vinyl esters, hydroxybutyric acid vinyl esters, hydroxyl The esters of the hydroxyyalkyl carboxylic acids and vinyl alcohol such as vinyl valerate base ester, hydroxy-cyclohexyl vinyl esters of carboxylic acids；Hydracrylic acid, hydroxyl The carboxylic acid of base butyric acid, hydroxypentanoic acid, hydroxy-2-methyl butyric acid etc. and the esters etc. of allyl alcohol.
In addition, as the polymerizable monomer containing carboxyl, can enumerate：The monoesters class of dicarboxylic acids and allyl alcohol, (methyl) Acrylic acid, carboxyalkyl (methyl) esters of acrylic acid etc..
In addition, in the polymerization of above-mentioned fluororesin, above-mentioned fluorochemical monomer can be used and contain specific reactive group Monomer other than polymerizable monomer.As the polymerizable monomer, can enumerate：Vinyl ethers, olefines, allyl ether Class, vinyl ester, allyl esters, (methyl) esters of acrylic acid, (methyl) acrylic acid amides class, the monomer containing cyano Class, dienes etc., butenoic acid esters etc..
The specific reality of polymerizable monomer other than monomer as above-mentioned fluorochemical monomer and containing specific reactive group Example, can enumerate for example：Methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl The alkyl vinyls ethers such as vinyl ethers, chloroethyl vinyl ether；Ethylene, propylene, 1- butylene, isobutene, cyclohexene, chloroethene The olefines such as alkene, vinylidene chloride；The styrene monomers class such as styrene, α-methylstyrene；Methallyl ether, allyl The polyoxyethylenes base ethers such as base ether, butyl allyl ether, cyclohexyl allyl ether；Vinyl-acetic ester, vinyl propionate base ester, fourth Sour vinyl esters, vinyl isobutyrate base ester, vinyl valerate base ester, caproic acid vinyl esters, sad vinyl esters, versatic acid vinyl The vinyl ester of the carboxylic acids such as ester (mono- サ テ ィ ッ Network acid ビ ニ Le of バ) (preferably aliphatic acid)；Allyl propionate, acetic acid allyl The allyl esters of the carboxylic acids such as ester (preferably aliphatic acid)；(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propylene (methyl) esters of acrylic acid such as acid butyl ester, (methyl) cyclohexyl acrylate；(methyl) acrylic acid amides etc. (methyl) acrylic acid acyl Amine；The monomer class of the cyano-containings such as acrylonitrile, 2,4- dicyano -1- butylene；The dienes such as isoprene, butadiene；Butenoic acid Butenoic acids esters such as 2- hydroxy methacrylates, butenoic acid 4- hydroxybutyls etc..
The fluorine content of above-mentioned fluororesin is preferably 5~80 mass %, more preferably 10~70 mass %.In addition, above-mentioned fluorine When resin is the fluororesin containing hydroxyl, from the viewpoint of the flexibility for keeping film, the hydroxyl value of fluororesin is preferably 100mgKOH/g is hereinafter, on the other hand, from the viewpoint of assigning sufficient impact resistance to film, preferably 10mgKOH/g More than.The hydroxyl value of fluororesin is particularly preferably 30~70mgKOH/g.
In aforementioned coating composition, the content of fluororesin is preferably 20~60 mass %.
The resin other than fluororesin used in aforementioned coating composition is preferably selected from by polyester resin and epoxy At least one resin for the group that resin is formed.It should be noted that by the way that the resin other than fluororesin is applied in combination, and only make Fluororesin is used as the case where resin component to compare, the appearance and processability of film improve, and can reduce manufacturing expense. In aforementioned coating composition, the content of the resin other than fluororesin is preferably 25~64 mass %.
The polyester resin that can be used in aforementioned coating composition can make carboxylic acid composition by using well known method It is manufactured with polyol component reaction.Preferably, above-mentioned polyester resin is the resin of solid-like at normal temperatures, and softening point is preferred It is 100~150 DEG C.In addition, above-mentioned polyester resin preferably has the reactive site reacted with curing agent etc., as reactive position Point preferably comprises hydroxyl or carboxyl.
As the carboxylic acid composition that can be used in the manufacture of above-mentioned polyester resin, can enumerate for example：Phthalic acid, M-phthalic acid, terephthalic acid (TPA), naphthalenedicarboxylic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, the last of the ten Heavenly stems two Acid, 1,9- nonane dicarboxylic acids, 1,10- decane dicarboxylics, 1,12- dodecanedicarboxylic acids, 1,2- octadecane dicarboxylic acids, maleic acid, The polynary carboxylic such as fumaric acid, cyclohexane cyclohexanedimethanodibasic, hexahydrophthalic acid, tetrahydrophthalic acid, trimellitic acid, pyromellitic acid Acid, the lower alkyl esters of these polybasic carboxylic acids and its acid anhydrides and malic acid, tartaric acid, 1,2- hydroxy stearic acids, para hydroxybenzene Hydroxycarboxylic acids such as formic acid etc..
As the polyol component that can be used in the manufacture of above-mentioned polyester resin, can enumerate for example：Ethylene glycol, two Ethylene glycol, triethylene glycol, 1,2- propylene glycol, 1,3- propylene glycol, 1,3 butylene glycol, 1,4- butanediols, 1,5- pentanediols, 1,6- oneself Glycol, 1,9- nonanediols, 1,10- decanediols, neopentyl glycol, spiral shell glycol, 1,10- decanediols, 1,4 cyclohexane dimethanol, three hydroxyls Methyl ethane, trimethylolpropane, glycerine, pentaerythrite etc..
As described above, above-mentioned polyester resin as raw material and can pass through pass by using carboxylic acid composition and polyol component It is manufactured in manufacture powder coating composition usual method known to polyester resin.For example, can be appropriate by above-mentioned each raw material Combination is used with matching, and carries out esterification or ester exchange reaction at 200~280 DEG C according to conventional methods, then, under reduced pressure, Polycondensation reaction is carried out at 230~290 DEG C using catalyst, according to circumstances, then, depolymerization reaction is carried out using polyalcohol, from And manufacture polyester resin.
Above-mentioned polyester resin can be with the reactive group other than hydroxyl and carboxyl.It, can be with as the reactive site It enumerates for example：The functional groups such as amide groups, amino, itrile group, glycidyl, isocyanate group.
From the viewpoint of control cross-linking reaction, Physical properties of coating film, above-mentioned polyester resin is preferably the polyester tree containing hydroxyl Fat.In addition, from the viewpoint of controlling melt viscosity, above-mentioned polyester resin preferably its number-average molecular weight is 5000 or less and weight is equal Molecular weight is 10000~20000.Herein, number-average molecular weight and weight average molecular weight can by gel permeation chromatography (GPC) with Polystyrene is found out as standard substance.
In the case where above-mentioned polyester resin is polyester resin containing hydroxyl, the hydroxyl value of polyester resin is preferably 20~ 100mgKOH/g, more preferably 30~80mgKOH/g.In addition, the acid value of above-mentioned polyester resin is preferably 20~80mgKOH/g, More preferably 30~80mgKOH/g.
When aforementioned coating composition includes polyester resin, the content of the polyester resin in aforementioned coating composition is preferably 25~64 mass %, more preferably 25~63 mass %.
The epoxy resin that can be used in aforementioned coating composition is preferably the resin of solid-like, softening at normal temperatures Preferably 50~150 DEG C of point.By using epoxy resin, the adaptation with base material can be improved.As above-mentioned epoxy resin, do not have There is special restriction, the epoxy resin used in epoxy resin coating composition all the time can be used.
Above-mentioned epoxy resin can specifically include for example：In addition to bisphenol A-type 2-glycidyl ether resin, bisphenol-f type two contract Water glycerine ether resin, aminoglycidyl ether resin, bisphenol-A D type 2-glycidyls ether resin, bisphenol Z type 2-glycidyl Ether resin, o-cresol phenolic resin varnish, phenol novolac epoxy resins, xenol ethylene oxidic ester ether resin, ring Further include by the ring of these resins except cyclopentadiene skeleton epoxy resin, naphthalene skeleton epoxy resin, GMA acrylic resins etc. Substituent group other than oxygroup is substituted for the resin after other substituent groups, such as：By with carboxyl terminal Polybutadiene-acrylonitrile (CTBN) it is modified the resin etc. obtained by the modified-reaction of reaction, esterification etc..It should be noted that the epoxy of epoxy resin is worked as Amount preferably 300~1200, particularly preferably 400~1000.
When aforementioned coating composition includes epoxy resin, the content of the epoxy resin in aforementioned coating composition is preferably 0.3~5 mass %.
Aforementioned coating composition preferably comprises acrylic surfaces conditioning agent and wax.Though not knowing detailed mechanism, lead to It is to make coating composition to cross and mix acrylic surfaces conditioning agent and wax, the effect shown in aforementioned coating composition Surface tension reduces and fluororesin is made to be easier to concentrate on the effect in film coated surface, and is melted after can preventing application The effect that the viscosity of coating composition becomes larger when melting, therefore can be easily by the ratio and distance of the fluororesin in film coated surface The depth of film coated surface is equivalent in the proportion adjustment to above-mentioned specific range of the fluororesin at the position of the half of film thickness.It needs It is noted that acrylic surfaces conditioning agent and wax can respectively be mixed into the raw material of coating composition, it can also be by third Olefin(e) acid class surface conditioner and wax are pre-mixed obtained mixture and mix into the raw material of coating composition.
The acrylic surfaces conditioning agent that can be used in aforementioned coating composition contributes to film coated surface adjusting Compounding agent, therefore with the property dissolved at the temperature at which film is formed.Therefore, above-mentioned acrylic surfaces conditioning agent is soft Change preferably 75~100 DEG C of point.It should be noted that in the present invention, the softening point of acrylic surfaces conditioning agent can root It is measured according to based on the global formula softening point test method of JIS K2207 (2006).JIS K 2207 (2006) were oil drip originally Green relevant Regulations lattice, but it is readily applicable to the softening point measurement of acrylic surfaces conditioning agent.
Above-mentioned acrylic surfaces conditioning agent be preferably make to have the dibasic acid ester (ingredient X) of polymerism unsaturated double-bond, At least one (ingredient Y) selected from alkyl acrylate and alkyl methacrylate, and it is optional, be selected from acrylic acid and first Copolymer obtained from least one of base acrylic acid is copolymerized.Herein, it as above-mentioned dibasic acid ester, can enumerate for example： Dimethyl esters, the fumaric monoalkylesters such as the maleic acid diesters such as maleic acid diethyl ester, maleic acid monoester, fumaric acid diethyl ester Deng.As alkyl acrylate, can enumerate for example：N-butylacrylate etc..As alkyl methacrylate, such as can To enumerate n-butyl methacrylate etc..
It should be noted that above-mentioned acrylic surfaces conditioning agent is, for example, the copolymerization such as above-mentioned ingredient X and ingredient Y Object, therefore it is different ingredient with core shell acrylic resin particle as be described hereinafter.
When aforementioned coating composition includes acrylic surfaces conditioning agent, the acrylic compounds table in aforementioned coating composition The content of face conditioning agent is preferably 0.5~6 mass %.
The wax that can be used in aforementioned coating composition is preferably the wax that fusing point is 40 DEG C or more, and the fusing point of the wax is more excellent It is selected as 50 DEG C~100 DEG C.It should be noted that in the present invention, the fusing point of wax can be remembered by JIS K 0064 (1992) The visual method of load measures.As the concrete example of the wax, can enumerate：Castor oil, amide compound, polyethylene, polypropylene Etc. acrylic compounds such as polyolefins, ethylene vinyl acetate, ethylene-acrylic acid copolymer etc..These waxes It can be used alone, be also applied in combination two or more.
When aforementioned coating composition includes wax, the content of the wax in aforementioned coating composition is preferably 0.3~10 matter Measure %.In addition, in aforementioned coating composition, wax (w) is excellent relative to the mass ratio (w/s) of acrylic surfaces conditioning agent (s) It is selected as 0.06~20.
Aforementioned coating composition preferably comprises curing agent.As curing agent, if it is with other than fluororesin, the fluororesin Resin reaction forms the substance of cross-bond, then there is no particular limitation, is preferably selected from by beta-hydroxyalkylamides, isocyanide urine Curing agent in the group of sour three-glycidyl ester and isocyanate compound composition.It should be noted that when above-mentioned coating combines When object includes curing agent, the content of the curing agent in aforementioned coating composition is preferably 2~25 mass %.
Beta-hydroxyalkylamides can be preferably used for the case where resin component is with carboxyl, from curability at low temperatures, application From the perspective of the water resistance of obtained film, particularly preferred each intramolecular has the beta-hydroxy alkyl of 2 or more functional groups Amide.As beta-hydroxyalkylamides, particularly preferred N, N- bis- (beta-hydroxy ethyl) acetamide, bis- (beta-hydroxy ethyl) adipyls Diamines, bis- (beta-hydroxy propyl) adipamides, bis- [N, N- bis- (beta-hydroxy ethyl)] adipamides, bis- [(β-hydroxyl of N, N- bis- Base propyl)] adipamide.Beta-hydroxyalkylamides are worked as relative to the preferred hydroxy amide base of carboxyl in resin for 0.5~1.5 Amount.
Isocyanuric acid three-glycidyl ester can be preferably used for the case where resin component is with carboxyl.As isocyanuric acid Three-glycidyl ester can be enumerated for example as trade name：Araldite (registered trademark) PT 710, Araldite (registrars Mark) PT 810, Araldite (registered trademark) PT 910, (all Huntsman is public by Araldite (registered trademark) PT 912 Department's manufacture) etc..Isocyanuric acid three-glycidyl ester is 0.5~1.5 equivalent relative to the preferred glycidyl of carboxyl in resin.
Isocyanate compound can be preferred for the case where resin component contains hydroxyl, more preferably blocked isocyanate Compound.Preferably, isocyanate compound solid-like at normal temperatures.Isocyanate compound relative to the hydroxyl in resin, Isocyanate group is preferably 0.05~1.5 equivalent, more preferably 0.8~1.2 equivalent.
It should be noted that above-mentioned block isocyanate compound for example can be by making aliphatic, aromatic series or fragrance Aliphatic diisocyanate is reacted with the low molecular compound of active hydrogen to be obtained polyisocyanate and is reacted with block agent And (マ ス キ Application グ) is sheltered to manufacture, therefore manufacture is also easy.It should be noted that as above-mentioned diisocyanate, It can enumerate：Toluylene diisocya-nate, 4,4 '-diphenylmethane isocyanates, benzene dimethylene diisocyanate, six Methylene diisocyanate, 4,4 '-di-2-ethylhexylphosphine oxides (cyclohexyl isocyanate), methylcyclohexane diisocyanate, bis- (isocyanic acids Root closes methyl) hexamethylene, isophorone diisocyanate, dimer acid diisocyanate, lysine diisocyanate etc., as The low molecular compound of above-mentioned active hydrogen, can enumerate：Water, ethylene glycol, propylene glycol, trimethylolpropane, glycerine, sorb Alcohol, ethylenediamine, ethanol amine, diethanol amine, hexamethylene diamine etc. and chlorinated isocyanurates, uretdione (ウ レ チ ジ オ Application), the low molecular weight polyester containing hydroxyl, polycaprolactone etc..In addition, the concrete example as block agent, can enumerate：Methanol, The lactams such as the phenols such as the alcohols such as ethyl alcohol, benzyl alcohol, phenol, cresols, caprolactam, butyrolactam, cyclohexanone, oxime, first and second The oximes such as ketoxime.For example, the concrete example as blocked isocyanate, can enumerate：Block is carried out using epsilon-caprolactams and is obtained The isophorone diisocyanate (the Vestagon B1530 of Ying Chuan companies manufacture, the Crelan UI of Beyer Co., Ltd's manufacture) arrived Deng.
Aforementioned coating composition can include core shell acrylic resin particle.By using core shell acrylic tree Fat granule, can improve the processability of film under the premise of not reducing weatherability.
For above-mentioned core shell acrylic resin particle, it is preferable that the ratio that will be measured by nitrogen adsorption methods The value of surface area substitutes into formula：D=6/ (α × S) (in formula, D：Average primary particle diameter (μm), α：Density (g/cm3)、S：Specific surface Product (m2/ g)) calculated by average primary particle diameter be 0.1~0.5 μm, and with laser diffraction/scattering formula particle size distribution measuring dress The average aggregate particle size for setting measurement is 5~50 μm.
Above-mentioned core shell acrylic resin particle preferably has in particle surface selected from by carbonyl, hydroxyl and glycidol Base composition group in functional group it is at least one kind of.
It is 20 DEG C or less that above-mentioned core shell acrylic resin particle, which preferably has the glass transition temperature comprising stratum nucleare, Be the polymer phase of rubber-like at room temperature and glassy polymeric at room temperature that the glass transition temperature of shell is 50 DEG C or more The heterogeneous structure of object phase.Core shell acrylic resin particle for example can be by that will form the 1st of the polymer phase of rubber-like Polymerizable monomer carries out emulsification and suspension polymerisation, and it is 20 DEG C of rubber like polymer particle below to form glass transition temperature Paragraph 1 react and it is subsequent in the presence of above-mentioned rubber like polymer particle, will be formed glass transition temperature be 50 DEG C with On the polymerizable monomer of glassy polymers phase carry out the 2nd section of free radical polymerization reaction to obtain.Herein, in order to by function Group is directed into the particle surface of above-mentioned core shell acrylic resin particle, constitutes the free-radical polymerised list of glassy polymers Body preferably has the functional group at least one kind of group for selecting free carboxyl group, hydroxyl and glycidyl composition.
The rubber-like polymer for constituting stratum nucleare is, for example, the unsaturation list that can be used in the synthesis of rubber-like polymer The polymer of body.The glass transition temperature of rubber-like polymer is preferably 20 DEG C hereinafter, being more preferably -30~-10 DEG C of model It encloses.Herein, it as the concrete example of unsaturated monomer, can enumerate for example：(methyl) methyl acrylate, (methyl) acrylic acid second Ester, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) 2-ethylhexyl acrylate, (methyl) acrylic acid moon Osmanthus ester etc. (methyl) alkyl acrylate；The vinyl esters such as vinyl-acetic ester；Vinyl chloride, vinyl fluoride, vinylidene chloride, inclined two The vinyl halides such as vinyl fluoride or vinylidene halide；The nitrogenous unsaturated monomers such as (methyl) acrylonitrile, (methyl) acrylamide； The aromatic compounds such as styrene, α-methylstyrene, vinyltoluene；(methyl) dihydroxypropyl ethyl ester, methylol (first Base) unsaturated monomer containing hydroxyl such as acrylamide；The unsaturated carboxylic acids such as (methyl) acrylic acid；Butadiene, isoprene etc. Diene-based monomer etc..These unsaturated monomers may be used alone, can also be used in combination two or more.As rubbery polymeric The typical example of object can be enumerated：Poly- (methyl) acrylic rubber, polybutadiene rubber, polyisoprene rubber, polychlorostyrene second Alkene, SBR styrene butadiene rubbers, s-B-S rubber, styrene-isoprene-styrene rubber, benzene second Alkene-butene rubber, styrene-ethylene rubber and ethylene-propylene rubber etc..Among those, particularly preferred poly- (methyl) propylene Acid esters rubber, polybutadiene rubber, polyisoprene rubber and SBR styrene butadiene rubbers.
It is 50 DEG C or more, preferably to reach 80 that the glassy polymers for constituting shell, which is, for example, with glass transition temperature, The polymer of the mode of~100 DEG C of ranges and the free radical polymerization monomer after being adjusted.Herein, as free-radical polymerised Monomer can use general vinyl monomer etc., can enumerate：Above-mentioned unsaturated monomer etc..As with above-mentioned official The vinyl monomer that can be rolled into a ball, can enumerate for example：(methyl) acrylic acid 2- hydroxyethyls ester, (methyl) acrylic acid 2- hydroxypropyls The carbon number 2 of the acrylic or methacrylic acids such as ester, (methyl) acrylic acid 3- hydroxy-propyl esters, (methyl) dihydroxypropyl butyl ester ~8 hydroxyalkyl acrylate；The unsaturations such as the polyether polyol such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol and (methyl) acrylic acid The monoesters of carboxylic acid；The polyether polyol such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol and (methyl) acrylic acid 2- hydroxyethyl esters etc. The monoether of unsaturated monomer containing hydroxyl；Alpha, beta-unsaturated carboxylic acid and Cardura E10 (Shell Chemical Co's manufacture) or α- The addition product of mono-epoxy compounds as olefin epoxide；(methyl) glycidyl acrylate and acetic acid, propionic acid, to uncle The addition product of monoacid as butylbenzoic acid, fatty acid；As maleic anhydride or itaconic anhydride not containing acid anhydrides The monoesters compound or diester compound of the glycols such as saturated compounds and ethylene glycol, 1,6-HD, neopentyl glycol；Hydroxyethyl second Such hydroxyalkyl vinyl ether class as alkene ether, (methyl) acrylic acid 3- chlorine-2-hydroxyls propyl diester include containing for chlorine There are the monomer, allyl alcohol, the unsaturated monomer etc. containing epoxy group of hydroxyl.These free radical polymerization monomers can individually make With can also be applied in combination two or more.
Above-mentioned core shell acrylic resin particle can by well known method all the time, such as：Pre-existing Added under conditions of rubber-like polymer lotion free radical polymerization monomer and free-radical polymerised initiator emulsion polymerization, Suspension polymerization etc. obtains.
It is hud typed in aforementioned coating composition when aforementioned coating composition includes core shell acrylic resin particle The content of acrylic resin particle is preferably 0.1~5 mass %.
Aforementioned coating composition can also contain bright pigments.It should be noted that when using bright pigments, Ke Yiti High alkali resistance.There is also squamaceous bright pigments in bright pigments.As bright pigments, can enumerate for example：Aluminium powder pigment, Nickel powder pigment, bronze, silver powder, bronze powder, copper powder, stainless steel powder pigment, mica (mica) pigment, graphite pigment, glass flake Pigment, the glass powder for having carried out metal coating, the mica powder for having carried out metal coating, the molding powder and squama for having carried out metal coating Flake ferric oxide pigment etc..
Above-mentioned coating composition other than containing bright pigments, can also contain usually used pigment, such as Color pigment, extender pigment etc..As coloring pigment, can enumerate for example：Titanium oxide, yellow iron oxide, titan yellow, colcother, zinc barium In vain, the inorganic pigments such as antimony oxide, it is Hansa yellow 5G, permanent yellow FGL, phthalocyanine blue, indanthrene blue RS, permanent bordeaux F5RK, strong Organic pigments such as brilliant scarlet G G etc..On the other hand, it as extender pigment, can enumerate for example：Barium sulfate, barium carbonate, calcium carbonate, Clay, silicon dioxide powder, diatomite, talcum, basic magnesium carbonate, alumina white etc..In addition, needing to have in the base material that should want application In the case of having rust-preventing characteristic, aforementioned coating composition can contain rust resisting pigment.As rust resisting pigment, can enumerate for example：Contracting Alloy/calcium orthophosphate, aluminum phosphate, condensation of aluminum phosphate, trbasic zinc phosphate, aluminium phosphite, zinc phosphite, Arizona bacilli, zinc molybdate, calcium molybdate, molybdenum Sour manganese etc..These pigment may be used alone, can also be used in combination two or more.
When aforementioned coating composition includes pigment, in aforementioned coating composition total content of pigment be preferably 0.2~ 35 mass %.
In addition, in aforementioned coating composition, the plasticizer as general additive for coatings can be mixed as needed, is consolidated Change accelerating agent, crosslinking promotes catalyst, ultra-violet absorber, light stabilizer, antioxidant, fluidity regulator, anti-sagging agent With antifoaming agent etc..
The manufacturing method of aforementioned coating composition can be enumerated for example：The tree other than above-mentioned fluororesin, fluororesin will be included The mixture of fat, acrylic surfaces conditioning agent and wax melting mixing at 100~160 DEG C, then, after which is cooled down It crushes, the method for preparing powder coating composition.Can preferably will include tree other than above-mentioned fluororesin, fluororesin After the mixture of fat, acrylic surfaces conditioning agent and wax carries out dry type mixing using Henschel mixer etc., total kneading is used The melting mixing at 120~140 DEG C such as machine is classified using the woven wire etc. of 180 mesh (96 μm), is obtained after cooling, crushing To powder coating composition.
As the coating process of aforementioned coating composition, can enumerate for example：Corona charging formula electrostatic powder body coating, friction Band electric-type electrostatic powder body coating, slipper dip formula powder body coating, electrostatic flowing impregnated powder body coating and electric field cloud formula (Electricity circle Network ラ ウ De formula) powder body coating etc..It, can be preferably in 160~250 DEG C of ranges, more preferably in 170~220 DEG C of ranges after application At a temperature of, make coating composition melting, cure to form film.
Constituting the base material of the coated-body of the present invention can enumerate for example：The metal bases such as steel, zinc, aluminium, copper and tin, but It is that bottom layer treatment preferably is carried out to metallic substrate surface in order to improve the adhesion to film.It should be noted that base material root According to its purposes there are variously-shaped, can enumerate such as plate.The film for constituting the coated-body of the present invention is typically incorporated in base On one surface of material.
The concrete example of coated-body as the present invention, can enumerate：The transport machine of automobile, electric car, aircraft etc. and its The industrial machineries material such as component, bridge and its component, steel tower and its component, building component, waterproof material piece, slot, pipe, building are outer Sight, door, window element, monument, hall Deng Jian Building components, the central partition of road, guardrail, sound proof panel, makrolon system The road components such as light-transmitting plate, semaphore, communicating machine and its component, family's electrical article, Electrical and Electronic component etc..
Embodiment
Hereinafter, by enumerating embodiment, the present invention will be described in more detail, but the present invention is not by following implementation Any restrictions of example.
<The Production Example of acrylic surfaces conditioning agent>
(acrylic surfaces conditioning agent A)
300 mass of butyl acetate is added in the polyplant for having reflux cooler, thermometer, blender and dropwise adding tank Part, in a nitrogen environment, dropwise addition solution A as shown below is added dropwise 3 hours at 110 DEG C.Tertiary pentyl is added after completion of dropwise addition Peroxy -5 mass parts of 2 ethyl hexanoic acid ester is kept for 2 hours at 110 DEG C.Temperature is promoted to 130 DEG C later, under reduced pressure Butyl acetate is distilled off, acrylic surfaces conditioning agent A is obtained.Acrylic surfaces are measured by gel permeation chromatography The polystyrene of conditioning agent A changes number average molecular weight.As a result it is 3500.In addition, according to based on JIS K's 2207 (2006) Global formula softening point test method measures the softening point of acrylic surfaces conditioning agent A, and result is 83 DEG C.
Solution A is added dropwise：Including 324 mass parts of n-butylacrylate, 65 mass parts of acrylic acid, maleic acid diethyl ester 28 The solution of mass parts, t-amyl peroxy -200 mass parts of 15 mass parts of 2 ethyl hexanoic acid ester and butyl acetate.
(acrylic surfaces conditioning agent B)
Other than solution B is added dropwise shown in following and replaces that solution A is added dropwise, with acrylic surfaces conditioning agent A's The same mode of Production Example obtains acrylic surfaces conditioning agent B.Acrylic surfaces tune is measured by gel permeation chromatography The polystyrene of section agent B changes number average molecular weight, result 4100.In addition, the ring by being based on JIS K 2207 (2006) Ball-type softening point test method measures the softening point of acrylic surfaces conditioning agent B, and result is 92 DEG C.
Solution B is added dropwise：Including 324 mass parts of n-butylacrylate, 65 mass parts of acrylic acid, fumaric acid diethyl ester 28 The solution of mass parts, t-amyl peroxy -200 mass parts of 15 mass parts of 2 ethyl hexanoic acid ester and butyl acetate.
(acrylic surfaces conditioning agent C)
Other than solution C is added dropwise shown in following and replaces that solution A is added dropwise, with acrylic surfaces conditioning agent A's The same mode of Production Example obtains acrylic surfaces conditioning agent C.Acrylic surfaces tune is measured by gel permeation chromatography The polystyrene of section agent C changes number average molecular weight, result 2900.In addition, the ring by being based on JIS K 2207 (2006) Ball-type softening point test method measures the softening point of acrylic surfaces conditioning agent C, and result is 78 DEG C.
Solution C is added dropwise：Including 324 mass parts of n-butylacrylate, 47 mass parts of maleic acid diethyl ester, fumaric acid two The solution of 46 mass parts of ethyl ester, t-amyl peroxy -200 mass parts of 15 mass parts of 2 ethyl hexanoic acid ester and acetic acid butyl ester.
<The making example of powder coating composition>
It is formulated according to shown in table 1, raw material is put into super mixer and is mixed 1 minute.Then by obtained mixing The twin shaft kneading machine (Toshiba manufactures) that object is adjusted to 120 DEG C with temperature is kneaded, by the chill roll cold rolling of the mixture of discharge, it It uses sprayer of hammer crusher (pinmill) to crush afterwards, is classified using the net of 180 mesh, obtains embodiment 1~11 and comparative example 1~3 Powder coating composition (50% volume average particle size：32μm).
<The making example of coated-body>
Breadboard (coated-body) is made with the powder coating composition of embodiment 1~11 and comparative example 1~3.Specifically, The chromic acid of plate thickness 1.5mm, chromic acid salt treatment aluminium sheet are hung vertically, with corona charging formula daubing machine of electrostatic powder (ASAHI SUNAC Company manufactures PG-1 types) electrostatic spraying makes its film thickness reach 60 μm under -60kV voltages, using electric furnace at 190 DEG C × 20 minutes Condition be sintered, then direct cooled to room temperature, to make breadboard.
<<Evaluation>>
Various measurement and evaluation test are carried out to obtained breadboard, the results are shown in table 1.
<The assay method of film thickness>
Breadboard is stood vertically in the transparent cup of embedding with specimen holder, flows into epoxy resin " Epocure thereto (manufacture of Buehler companies) host agent+curing agent ", makes epoxy resin be fully cured, obtains by the breadboard of epoxy resin embedding. With grinder " EcoMet 3000+AutoMet2000 (Buehler companies manufacture) " on the pouncing paper and moccasin of #320, #600 Metadi, Master Prep (manufacture of Buehler companies) are injected, to being ground by the breadboard of epoxy resin embedding, is obtained Film section.SEM (SU-70 of new and high technology Co., Ltd. of Hitach manufacture) is used to obtained film section, with accelerating potential 1kv, 900 times of multiple measure film thickness at 10, find out its average value.
<The assay method of the mass ratio of fluorine atom and carbon atom>
As mensuration machine, SEM uses the SU-70 that new and high technology Co., Ltd. of Hitach manufactures, EDS to use Oxford Instruments The INCA X-Sight (Model 7969) of (Oxford Instruments) Co., Ltd manufacture.In EDS, select cobalt as The element quantitatively optimized carries out condition setting.The parameter of device is Livetime 100 seconds at this time, processing time (Process Time) 5, spectral range (Spectrum range 0-20kev), port number (Number of channels) 1K.
(assay method of the 1st Funing tablet)
1st Funing tablet is the ratio (matter shared by fluorine atom in total quality of fluorine atom and carbon atom in film coated surface Measure %).First, breadboard is cut into about 1cm × 1cm, it, will in order to reduce the destruction of the film coated surface caused by electron ray Gold is vaporized on the sample of this cutting, and the adhesive tape of the sample electric conductivity after gold vapor deposition is fixed on SEM observation platforms, so SEM observations are carried out with accelerating potential 15kv, 500 times of multiple afterwards.Then, arbitrary to select 245 μ m, 185 μm of areas using EDS Film coated surface, the Elemental redistribution for carrying out the film coated surface measures, measures the ratio of carbon atom and fluorine atom, and find out fluorine atom With the ratio shared by fluorine atom in total quality of carbon atom.Later, change the position for carrying out Elemental redistribution measurement, to film table Fluorine atom in face (245 185 μm of μ m) and the ratio in total quality of carbon atom shared by fluorine atom carry out 9 measurement.It will The average value of 10 measurement results is as the 1st Funing tablet.
(assay method of the 2nd Funing tablet)
2nd Funing tablet is the fluorine atom and carbon atom at the position for the half that the depth apart from film coated surface is equivalent to film thickness Total quality in ratio (quality %) shared by fluorine atom.First, in order to reduce the film coated surface caused by electron ray Gold is vaporized on the breadboard by epoxy resin embedding used in film thickness measuring by damage, is steamed the gold with the adhesive tape of electric conductivity Sample after plating is fixed on SEM observation platforms, and SEM observations are carried out with accelerating potential 15kv, 900 times of multiple.Then, in distance The depth of film coated surface is equivalent at the position of the half of film thickness, is chosen at random parallel with film coated surface and 135 μm of length Line, the Elemental redistribution that the line is carried out with EDS measures (line analysis), measures the ratio of carbon atom and fluorine atom, and finds out fluorine atom With the ratio shared by fluorine atom in total quality of carbon atom.Later, change the position for carrying out Elemental redistribution measurement, painting of adjusting the distance The depth of film surface is equivalent in total quality of the fluorine atom at the position of the half of film thickness and carbon atom shared by fluorine atom Ratio carries out 9 measurement.Using the average value of 10 measurement results as the 2nd Funing tablet.
<Wearability>
It is measured according to ASTM D968 (sand trail method).Specifically, using Gardner's formula falling sand abrasion test Breadboard is disposed relative to horizontal plane inclination at 45 ° by machine, falls No. 4 silica sands in the center of film, and asked by following formula Go out cut coefficient.It should be noted that the height of fall of sand is the center 940mm apart from film.
Cut coefficient=V/T
[in formula, V is the total amount (unit of sand used in sand trail：Rise L), T is subtracted for the film thickness before sand trail and is fallen Value obtained from film thickness after sand test is (that is, the film thickness of abrasion, unit：μm)]
It should be noted that according to the cut coefficient of calculating, according to following evaluation criteria, wearability is evaluated.
◎ cut coefficients are 100 or more
Zero cut coefficient is 45 less than 100
△ cut coefficients are 40 less than 45
× cut coefficient is less than 40
<Weatherability>
For using breadboard (application obtained from the powder coating composition of embodiment 1~11 and comparative example 1~3 Body), using the promotion weathering tester according to JIS B7753 (sunlight atmospheric exposure test mode), carry out weatherability evaluation.It needs It is noted that test period is set as 3000 hours.With gloss meter, (micro-TRI-gross BYK companies manufacture：Enter anti- 60 ° of firing angle) the preceding 60 ° of bright luster values with after experiment in 3000 hours of experiment are measured, find out 60 ° of minute surfaces after experiment in 3000 hours Change rate of the gloss value relative to 60 ° of bright luster values before experiment carries out weatherability evaluation according to following evaluation criteria.
◎ change rates are 90% or more
Zero change rate is 70% less than 90%
△ change rates are 50% less than 70%
× change rate is less than 50%
<Adhesion>
According to JIS K5600-5-6 (cross-section method), the film of breadboard is cut into 100 pieces of go trellis shapes with the intervals 1mm, Disbonded test is carried out with adhesive tape, and finds out the residual rate after disbonded test, according to following evaluation criteria, evaluates adhesion.
○：100/100 (sum of the cut portion after experiment before quantity/experiment of remaining cut portion)
△：85/100~99/100
×：84/100 or less
Table 1
It should be noted that the detailed content of raw material recorded in table 1 is as follows.
(Asahi Glass Co., Ltd manufactures (* 1) fluororesin, trade name：Lumiflon LF710F, the fluorine tree containing hydroxyl Fat)
(Daicel-Cytec Co., Ltd. manufactures (* 2) polyester resin, trade name：Acrylic Coat 4642-3)
(Toto Kasei KK manufactures (* 3) epoxy resin, trade name：Epotote DT-112)
(* 4) curing agent (epsilon-caprolactams blocked isocyanate, Evonik Degussa Corp.'s manufacture, trade name：Vestagon B1530)
(* 5) silica-based surface conditioner (manufacture of Bi Ke chemical companies, trade name：BYK360P)
(* 6) using the acrylic surfaces conditioning agent A obtained in the Production Example of above-mentioned acrylic surfaces conditioning agent ~C.
(* 7) wax (castor oil, 80 DEG C of fusing point, the manufacture of her rattan liquefaction company, trade name：Castor-oil plant solidified oil)
(* 8) using crosslinking resin particles prepared by the following method.
(* 9) using the core shell acrylic resin particle prepared by the following method.
(preparation example of crosslinking resin particles)
The preparation example of crosslinking resin particles shown in table 1 is illustrated below.Use homo-mixer (Mizuho works Industry Co., Ltd. manufactures, desktop high-speed uniform mixer LR), with rotating speed 12000rpm, oil phase as shown below is dispersed in In water phase as shown below.Dispersion liquid is directed into the polymer reactor for having blender, heating device and thermometer, 60 It is persistently stirred at DEG C 6 hours, carries out suspension polymerisation.The suspension is filtered under diminished pressure, obtained reaction product is washed with water, Dry, crushing obtains crosslinking resin particles of 6.8 μm of volume average particle size.
Oil phase
80 mass parts of butyl acrylate cores
20 mass parts of dimethacrylate tetradecane diols ester
0.3 mass parts of benzoyl peroxide
Water phase
400 mass parts of deionized water
8 mass parts of polyvinyl alcohol (saponification degree 85%)
0.07 mass parts of lauryl sodium sulfate
(preparation example of core shell acrylic resin particle)
The preparation example of core shell acrylic resin particle shown in table 1 is illustrated below.
The polyvinyl alcohol water solution 300g of deionized water 1500g and 5 volume % are added in the aggregation container of 5L capacity, makes It is stirred with 4500rpm with homo-mixer (AS ONE Co., Ltd. manufactures), while being added at one time and make the positive fourth of acrylic acid (polymerization is drawn by base ester 576g, diacrylate 1,4- butanediol esters 12g, allyl methacrylate 12g and lauroyl peroxide 6g Send out agent) dissolving obtained from monomer mixed solution, carry out 1 hour decentralized processing, obtain monomer dispersion liquid.Then, hold in the polymerization Blender and reflux condenser are installed on device, stirred in stream of nitrogen gas, while being warming up to 70 DEG C.It is stirred at 70 DEG C, simultaneously React within 2 hours.At this moment, it is sampled from the suspension of obtained polymer particle, the polymerization for measuring monomer turns Rate, result 94%.Then the suspension of obtained polymer particle is cooled to 60 DEG C.The suspension is stirred with 4500rpm Liquid, while the monomer emulsion for the 2nd section of reaction as shown below is continuously added in 15 minutes.It (is reacted for the 2nd section Monomer emulsion is by by methyl methacrylate 352g, ethyl acrylate 40g, methacrylic acid 2- hydroxyethyl esters 10g, two Methacrylic acid glycol ester 8g, 2,2 '-azodiisobutyronitrile 4g, 1 mass % sodium dodecyl sulfate aqueous solution 100g, go Ionized water 100g is mixed and is prepared.)
Polymerization starts, and at the time of observing fever, is warming up to 80 DEG C, carries out 3 hours slaking reactions.The suspension that will be obtained Liquid is dehydrated with centrifugal separator after being cooled to room temperature and is cleaned, and air-drying for one day night is carried out at 60 DEG C, is obtained hud typed Acrylic resin particle.
It is measured according to the DSC of core shell acrylic resin particle, the glass transition of rubber-like polymer phase (stratum nucleare) Temperature is -20 DEG C, and the glass transition temperature of glassy polymers phase (shell) is 83 DEG C.By by with specific surface area/micropore The average primary particle diameter that the specific surface area that distribution measurement device ASAP 2020 (Shimadzu Corporation's system) is measured is calculated It it is 0.1 μm, by laser diffraction/scattering formula particle size distribution analyzer Partica LA-950V2, (hole field makes institute's strain formula meeting Society's system) the average aggregate particle size that is measured is 6 μm.

Claims (12)

1. coated-body is the coated-body for having the film of base material and configuration on the substrate surface, which is characterized in that
The film is by the coating including at least resin, acrylic surfaces conditioning agent and wax other than fluororesin, the fluororesin Composition is formed,
When the ratio shared by fluorine atom in total quality of fluorine atom and carbon atom in the film coated surface is set as the 1st When Funing tablet (quality %), the 1st Funing tablet is 30~50 mass %,
It, will be apart from the fluorine atom and carbon at film coated surface depth T/2 (μm) position when the film thickness of the film is set as T (μm) When ratio in total quality of atom shared by fluorine atom is set as the 2nd Funing tablet (quality %), the 2nd Funing tablet (A) is to the 1st fluorine The mass ratio (A/B) of concentration (B) is 13/87~49/51.
2. coated-body as described in claim 1, which is characterized in that the film thickness of the film is 40~200 μm.
3. coated-body as claimed in claim 1 or 2, which is characterized in that the base material is metal base.
4. coated-body as claimed in claim 1 or 2, which is characterized in that the resin other than the fluororesin is selected from by polyester At least one of the group of resin and epoxy resin composition resin.
5. coated-body as claimed in claim 1 or 2, which is characterized in that the coating composition is powder coating composition.
6. coated-body as claimed in claim 1 or 2, which is characterized in that the cut coefficient of the film is 45~500.
7. coated-body as claimed in claim 1 or 2, which is characterized in that the base material is metal base, other than the fluororesin Resin be selected from least one of the group being made of polyester resin and epoxy resin resin.
8. coated-body as claimed in claim 1 or 2, which is characterized in that the base material is metal base, the coating composition For powder coating composition.
9. coated-body as claimed in claim 1 or 2, which is characterized in that the base material is metal base, other than the fluororesin Resin be selected from least one of the group being made of polyester resin and epoxy resin resin, the coating composition is powder Coating composition.
10. coated-body as claimed in claim 1 or 2, which is characterized in that the base material is metal base, and the film is drawn Trace coefficient is 45~500.
11. coated-body as claimed in claim 1 or 2, which is characterized in that the base material be metal base, the fluororesin with Outer resin is selected from least one of the group being made of polyester resin and epoxy resin resin, the cut coefficient of the film It is 45~500.
12. coated-body as claimed in claim 1 or 2, which is characterized in that the base material be metal base, the fluororesin with Outer resin is selected from least one of the group being made of polyester resin and epoxy resin resin, and the coating composition is powder The cut coefficient of body coating composition, the film is 45~500.
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CN109971317A (en) 2017-12-27 2019-07-05 Ａｇｃ株式会社 The manufacturing method of powder coating
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CN106794682A (en) 2017-05-31

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