CN106794682A - Coated-body - Google Patents

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Publication number
CN106794682A
CN106794682A CN201580053070.6A CN201580053070A CN106794682A CN 106794682 A CN106794682 A CN 106794682A CN 201580053070 A CN201580053070 A CN 201580053070A CN 106794682 A CN106794682 A CN 106794682A
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CN
China
Prior art keywords
film
acid
coated
fluororesin
coating composition
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Granted
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CN201580053070.6A
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Chinese (zh)
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CN106794682B (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

Invention problem to solve is that, there is provided weatherability, wearability and the excellent coated-body of tack.The present invention is coated-body, it is the coated-body of the film for possessing base material and configuration on the substrate surface, it is characterized in that, the film is formed by the coating composition including at least the resin beyond fluororesin and the fluororesin, when the ratio shared by fluorine atom in total quality of the fluorine atom in the film coated surface and carbon atom is set as into the 1st Funing tablet (quality %), 1st Funing tablet is 30~50 mass %, when the thickness of the film is set as into 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-body for possessing film on the substrate surface of base material and configuration, and be related to weatherability, Wearability and the excellent coated-body of tack.
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 The upper countermeasure constantly appealed for environmental pollution, at the same time from from the viewpoint of environmental protection, has carried out various limitations.Its In, organic solvent (particularly VOC VOC) is discharged into air can produce very big problem, in each field In the presence of the trend of reinforcing VOC limitations, while the direction of de- organic solvent (particularly taking off VOC) is also more active.In coating circle, make For the coating of conventional organic solvent type coatings can be replaced, it is desirable to be entirely free of VOC, it is not necessary to pump-down process, wastewater treatment And the environment-friendly coating of recyclable recycling, wherein the expectation to powder coating is constantly surging.
Under such shape Condition, the scheme of proposition is to use the polyester tree comprising the excellent fluororesin of weatherability and low cost The powder coating composition (for example, referring to patent document 1~3) of the layer divergence type of fat.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2011-12119 publications
Patent document 2：Japanese Unexamined Patent Publication 2012-41383 publications
Patent document 3：Japanese Unexamined Patent Publication 2013-76019 publications
The content of the invention
Invent problem to be solved
If but be known that using the powder coating composition of the layer divergence type as described in patent document 1~3, The weatherability aspect film that still there is room for improvement is then formed, or formation can ensure that weatherability but in wearability and tack side The face film that also there is room for improvement.
Therefore, it is an object of the invention to provide the coated-body for possessing the film of base material and configuration on the substrate surface, The weatherability of the coated-body, wearability and tack are excellent.
The means used to solve the problem
The present inventor to achieve these goals, is had made intensive studies, and as a result learns, these layer of powder of divergence type is applied Feed composition is different on the fluororesin layer that is formed and the resin ratio of components of polyester resin layer this aspect after application is constituted.
For example, for the powder coating composition of the layer divergence type described in patent document 2, constituting and being located on film It is fluororesin that the resinous principle of side fluororesin layer is most of, and the resinous principle major part for constituting the polyester resin layer positioned at downside is Polyester resin.Know the film formed for the powder coating composition of the layer divergence type as described in patent document 2, Because the composition for constituting the resinous principle of each layer differs widely, so sufficient tack cannot be obtained between each layer, sometimes Generation splitting.
On the other hand, the powder coating composition of the layer divergence type described in patent document 3, and described in patent document 2 The powder coating composition of layer divergence type compare, the ratio as the polyester resin of the resinous principle for constituting fluororesin layer is high, Ratio as the fluororesin of the resinous principle for constituting polyester resin layer is high, constitutes the ratio of components relatively phase of the resinous principle of each layer Closely.It is known however that the fluororesin ratio for constituting fluororesin layer can not be said to be foot from 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 With the proportion adjustment of the fluororesin at the position apart from the depth of film coated surface equivalent to thickness half to prescribed limit, can Weatherability, wearability and the excellent coated-body of tack are obtained, the present invention is this completes.
That is, coated-body of the invention is the coated-body of the film for possessing base material and configuration on the substrate surface, its feature It is,
The film is formed by the coating composition including at least the resin beyond fluororesin and the fluororesin,
Set when by the ratio shared by fluorine atom in total quality of the fluorine atom in the film coated surface and carbon atom During for the 1st Funing tablet (quality %), the 1st Funing tablet is 30~50 mass %,
When the thickness of the film is set as into T (μm), will be apart from the fluorine atom at film coated surface depth T/2 (μm) position 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 the 1st Funing tablet (B) is 13/87~49/51.
In the preference of coated-body of the invention, the thickness of the film is 40~200 μm.
In other preferences of coated-body of the invention, the base material is metal base.
In other preferences of coated-body of the invention, the resin beyond the fluororesin be selected from by polyester resin and At least one resin in the group of epoxy resin composition.
In other preferences of coated-body of the invention, the coating composition is powder coating composition.
In other preferences of coated-body of the invention, the cut coefficient (drawing っ か き Department numbers) of the film for 45~ 500。
Invention effect
According to the present invention, by by the ratio of fluororesin in film coated surface and in the depth apart from film coated surface equivalent to film The proportion adjustment of the fluororesin at the position of thick half can provide weatherability, wearability and tack excellent to particular range Coated-body.
Specific embodiment
Hereinafter, coated-body of the invention is described in detail.Coated-body of the invention is possess base material and configuration at this The coated-body of the film on substrate surface, it is characterised in that the film is by including at least beyond fluororesin and the fluororesin The coating composition of resin is formed,
Set when by the ratio shared by fluorine atom in total quality of the fluorine atom in the film coated surface and carbon atom During for the 1st Funing tablet (quality %), the 1st Funing tablet is 30~50 mass %,
When the thickness of the film is set as into T (μm), will be apart from the fluorine atom at film coated surface depth T/2 (μm) position 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 the 1st Funing tablet (B) is 13/87~49/51.
In coated-body of the invention, when by fluorine atom institute in total quality of the fluorine atom in film coated surface and carbon atom When the ratio for accounting for is set as the 1st Funing tablet (quality %), it is desirable to which the 1st Funing tablet is 30~50 mass %.If the 1st Funing tablet exists In above-mentioned specific scope, then the ratio of the fluororesin in film coated surface is sufficiently high, therefore can improve weatherability and wearability. On the other hand, if the 1st Funing tablet is less than 30 mass %, sufficient weatherability and wearability cannot be obtained.In addition, though 1st Funing tablet is more high more can improve weatherability and wearability, but under conditions of the 2nd Funing tablet relevant regulations are met, the 1st It is difficult that the distribution of the fluororesin in film of the Funing tablet higher than 50 mass % is controlled.
In the present invention, the surface of film refers to, positioned at the face with base material contact surface opposition side of film.
In coated-body of the invention, when the thickness of film is set as into T (μm), will be apart from film coated surface depth T/2 (μ M) when fluorine atom proportion is set as the 2nd Funing tablet (quality %) in fluorine atom at position and total quality of 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) is in above-mentioned specific scope, it is difficult to produce resin in film The widely different region of the ratio of components of composition is (for example, the fluororesin layer and polyester resin of the composition film described in patent document 2 The interface of layer), can also fully ensure tack.In addition, appropriate Funing tablet is also included near the bosom of film, because This has good wearability.
It should be noted that in coated-body of the invention, in total quality of fluorine atom and carbon atom shared by fluorine atom Ratio by the region of 30~50 mass % is according to different using fluororesin and other compounding ingredients, but 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 fluororesin concentration index at place is put in above-mentioned specific scope, is then difficult to produce resinous principle in film The widely different region (for example, interface of the fluororesin layer and polyester resin layer described in patent document 2) of ratio of components, may be used also Fully to ensure tack.
In the present invention, the thickness of film refers to average film thickness.For example 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 is obtained.Need explanation It is that in coated-body of the invention, film is not, for example by the coating composition application comprising resin beyond fluororesin, afterwards will Film obtained from coating composition application comprising fluororesin, but by the painting comprising resin beyond fluororesin and the fluororesin Film obtained from feed composition application, therefore the thickness of film is such as 40~200 μm.
In the present invention, in film coated surface the ratio the (the 1st in fluorine atom and total quality of carbon atom shared by fluorine atom Funing tablet), and the ratio of fluororesin at the position of the depth equivalent to the half of thickness of film coated surface (the 2nd fluorine is dense Degree), it is possible to use SEM/EDS (Scanning Electron Microscope " scanning electron microscope "/Energy Dispersive X-ray Spectroscope " energy dispersion-type X-ray spectroscope ") device and determine.
When determining 1 Funing tablet, can enumerate：Film coated surface first is observed with SEM first, then enters row element point with EDS Analysis, the method for determining 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 for fast voltage, the value of the 1st Funing tablet produce variation, particularly accelerating potential relatively low sometimes in the case of the tendency compared with Greatly.It is therefore preferable that the accelerating potential of SEM is set as into 10kV~20kV is measured.It should be noted that adjoint in order to reduce By the destruction of film coated surface caused by electron ray when SEM is determined, can before the assay in advance by material (such as gold of electric conductivity Deng) be deposited with measurement sample surface.
When determining 2 Funing tablet, first film section is observed with SEM first.Then, asked by using the line analysis of EDS The fluorine atom and the ratio of carbon atom gone out at the position of the depth equivalent to the half of thickness of film coated surface, can determine 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 produces variation sometimes, and the tendency is larger in the case that particularly accelerating potential is relatively low.It is therefore preferable that the acceleration of SEM is electric Pressure is set as that 10kV~20kV is measured.It should be noted that in order to reduce with SEM determine when by electron ray caused by , can be deposited with the material (such as gold etc.) of electric conductivity on measurement sample surface in advance before the assay by the destruction of film coated surface On.
When determining thickness or 2 Funing tablet, film section is observed, it is however generally that, as observing film section The preparation method for determining sample, can enumerate：Mechanically directly film is cut off, cut off or interrupted, then, is hung down by the film It is embedded in the resins such as epoxy resin in the state of straight setting, afterwards, cut with the implementation vertical to film such as slicer, ground, Etching etc. processes to make the method for determining sample.
For coated-body of the invention, the wearability of film as described above is high, thus film cut coefficient for example It is 45~500.It should be noted that the cut coefficient of film can be determined by the following method.
(assay method)
Can be determined according to ASTM D968 (sand trail method).Specifically, by Gardner (Gardner) formula knockout Abrasion tester, breadboard is arranged to, with the horizontal 45 ° of inclinations, to make No. 4 silica sand (average grain diameters：0.6~1.2mm) fall The center of film, cut coefficient is calculated by following formula.It should be noted that the height of fall of sand is apart from film centre bit Put 940mm.
Cut coefficient=V/T
[in formula, V is the total amount (unit of sand used in sand trail：Rise L), T is to subtract the thickness before sand trail Value (that is, the thickness of abrasion, unit obtained by the thickness gone after sand trail：μm)]
Coated-body of the invention possesses the film of base material and configuration on the surface of the base material, and the film is, for example, by inciting somebody to action Coating composition including at least the resin beyond fluororesin and the fluororesin, powder coating composition is preferably painted on base material Surface, then make at a temperature of preferably 170~250 DEG C scopes, more preferably 170~210 DEG C scopes its melting, solidification come shape Into.It should be noted that, it is necessary to by the ratio of the fluororesin in film coated surface and apart from film table in coated-body of the invention The depth in face equivalent to the fluororesin at the position of the half of thickness proportion adjustment to above-mentioned specific scope, in order to meet this , be mixed into aforementioned coating composition for the combination of acrylic surfaces conditioning agent and wax in mode described later preferably by a little regulations.
The fluororesin used in aforementioned coating composition is preferably at normal temperatures the resin of solid-like, and its softening point is preferred It is 50~150 DEG C.In coated-body of the invention, fluororesin is the principal element that weatherability and wearability are brought for film.Need It is noted that normal temperature refers to, 20 DEG C of temperature of ± 15 DEG C of (5~35 DEG C) scopes of JIS Z8703 regulations.
In addition, above-mentioned fluororesin preferably has the reactive site with the reaction such as curing agent, as reactive site, preferably Contain hydroxyl or carboxyl.Fluororesin with hydroxyl or carboxyl for example can be by by fluorochemical monomer and containing specific reactivity The monomer copolymerization of group is manufactured.
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 alkyl allyl ether series such as allyl ether；2- hydroxyethyls (methyl) acrylate etc. hydroxy alkyl (methyl) acrylate Class；Hydroxyacetic acid vinyl esters, hydroxy-iso-butyric acid vinyl esters, hydracrylic acid vinyl esters, hydroxybutyric acid vinyl esters, hydroxyl The hydroxyyalkyl carboxylic acids such as vinyl valerate base ester, hydroxy-cyclohexyl vinyl esters of carboxylic acids and the esters of vinyl alcohol；Hydracrylic acid, hydroxyl The carboxylic acid of base butyric acid, hydroxypentanoic acid, hydroxy-2-methyl butyric acid etc. and the esters of allyl alcohol etc..
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, it is possible to use above-mentioned fluorochemical monomer and contain specific reactive group Monomer beyond polymerizable monomer.As the polymerizable monomer, can enumerate：Vinyl ethers, olefines, allyl ether Class, vinyl ester, pi-allyl esters, (methyl) esters of acrylic acid, (methyl) acrylic acid amides class, the monomer containing cyano group Class, dienes etc., butenoic acid esters etc..
The specific reality of the polymerizable monomer beyond the 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, IVE, cyclohexyl The alkyl vinyl ethers such as vinyl ethers, chloroethyl vinyl ether；Ethene, propylene, 1- butylene, isobutene, cyclohexene, chloroethene The olefines such as alkene, vinylidene chloride；The styrene monomer class such as styrene, AMS；Methallyl ether, allyl The polyoxyethylene 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 (preferably aliphatic acid) such as ester (the サ テ ィ ッ Network acid PVC ニ Le of バ mono-)；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 acids 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 acid esters such as 2- hydroxy methacrylates, butenoic acid 4- hydroxybutyls etc..
The Oil repellent 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 from the viewpoint of the flexibility for keeping film, the hydroxyl value of fluororesin is preferably Below 100mgKOH/g, on the other hand, from from the viewpoint of sufficient impact resistance is assigned 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 beyond fluororesin used in aforementioned coating composition is preferably selected from by polyester resin and epoxy At least one resin of the group that resin is constituted.It should be noted that by the resin being applied in combination beyond fluororesin, and only make Compared as the situation of resinous principle with fluororesin, the outward appearance and processability of film are improved, and can reduce manufacturing expense. In aforementioned coating composition, the content of the resin beyond fluororesin is preferably 25~64 mass %.
The polyester resin that can be used in aforementioned coating composition can make carboxylic acid composition by using known method Manufactured with polyol component reaction.Preferably, above-mentioned polyester resin is the resin of solid-like at normal temperatures, and its softening point is preferred It is 100~150 DEG C.In addition, above-mentioned polyester resin preferably has the reactive site with the reaction such as curing agent, 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, butanedioic 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, PMA 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- propane diols, 1,3- propane diols, 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 can be by using carboxylic acid composition and polyol component as raw material and by closing Manufactured with usual method known to polyester resin in manufacture powder coating composition.For example, can be appropriate by above-mentioned each raw material Combination, is used with matching, and is esterified 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 have the reactive group beyond hydroxyl and carboxyl.As the reactive site, can be with Enumerate for example：The functional groups such as amide groups, amino, itrile group, glycidyl, NCO.
From 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 from the viewpoint of control melt viscosity, above-mentioned polyester resin preferably its number-average molecular weight is less than 5000 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 obtained as standard substance.
In the case where above-mentioned polyester resin is the polyester resin containing hydroxyl, the hydroxyl value of polyester resin is preferably 20~ 100mgKOH/g, more preferably 30~80mgKOH/g.In addition, the acid number 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 at normal temperatures, its softening Point is preferably 50~150 DEG C.By using epoxy resin, the adaptation with base material can be improved.As above-mentioned epoxy resin, do not have There is special restriction, it is possible to use the epoxy resin used in epoxy resin coating composition all the time.
Above-mentioned epoxy resin can specifically be included for example：Except 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 Outside cyclopentadiene skeleton epoxy resin, naphthalene skeleton epoxy resin, GMA acrylic resins etc., also including by the ring of these resins Substitution base beyond epoxide is substituted for the resin after other substitution bases, for example：By using carboxyl terminal Polybutadiene-acrylonitrile (CTBN) resin being modified obtained by the modified-reaction of reaction, esterification etc. etc..It should be noted that the epoxy of epoxy resin is worked as Amount is 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 Mixing acrylic surfaces conditioning agent and the wax in aforementioned coating composition is crossed, the effect for showing is to make coating composition Surface tension is reduced and fluororesin is easier to concentrate on the effect in film coated surface, and is melted after can preventing application The viscosity of coating composition becomes big effect when melting, therefore can easily by the ratio and distance of the fluororesin in film coated surface The depth of film coated surface is equivalent in proportion adjustment to the above-mentioned specific scope of the fluororesin at the position of the half of thickness.Need It is noted that acrylic surfaces conditioning agent and wax can mix into the raw material of coating composition respectively, it is also possible to by third Mixture obtained by olefin(e) acid class surface conditioner and wax are pre-mixed mixes 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 regulation Compounding ingredient, therefore with the property dissolved at a temperature of when film is formed.Therefore, aforesaid propylene acids surface conditioner is soft Change point and be preferably 75~100 DEG C.It should be noted that in the present invention, the softening point of acrylic surfaces conditioning agent can be with root Determined according to based on the global formula softening point test method of JIS K2207 (2006).JIS K 2207 (2006) were oil drips originally Blue or green related Regulations lattice, but it is also possible to suitable for the softening point measurement of acrylic surfaces conditioning agent.
Aforesaid propylene acids surface conditioner is preferably, make the dibasic acid ester (component X) with polymerism unsaturated double-bond, Selected from least one (the composition Y) of alkyl acrylate and alkyl methacrylate, and optionally, selected from acrylic acid and first Base it is acrylic acid at least one carry out copolymer obtained from copolymerization.Herein, as above-mentioned dibasic acid ester, can enumerate for example： Dimethyl ester, the fumaric monoalkylesters such as the maleic acid diesters such as maleic acid diethyl ester, maleic mono-ester, fumaric acid diethyl ester Deng.As alkyl acrylate, can enumerate for example：N-butylacrylate etc..As alkyl methacrylate, for example may be used To enumerate n-butyl methacrylate etc..
It should be noted that aforesaid propylene acids surface conditioner is, for example, the copolymerization of component X described above and composition Y Thing, therefore be different compositions from 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 preferably fusing point that can be used in aforementioned coating composition is more than 40 DEG C of wax, and the fusing point of the wax is more excellent Elect 50 DEG C~100 DEG C as.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 is determined.As the concrete example of the wax, can enumerate：Castor oil, amide compound, polyethylene, polypropylene Deng acrylic compounds such as TPO, ethylene vinyl acetate, ethylene-acrylic acid copolymer etc..These waxes 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 Amount %.In addition, in aforementioned coating composition, wax (w) is excellent relative to the mass ratio (w/s) of acrylic surfaces conditioning agent (s) Elect 0.06~20 as.
Aforementioned coating composition preferably comprises curing agent.As curing agent, if with fluororesin, the fluororesin beyond Resin reaction, forms the material of cross-bond, then there is no particular limitation, is preferably selected from being urinated by beta-hydroxyalkylamides, isocyanide Curing agent in the group of sour three-glycidyl ester and isocyanate compound composition.It should be noted that when above-mentioned coating combination When thing 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 resinous principle has a case that carboxyl, from curability at low temperatures, application From the viewpoint of the water resistance of the film for obtaining, particularly preferred each intramolecular has more than the 2 beta-hydroxy alkyl of functional group Acid amides.As beta-hydroxyalkylamides, particularly preferred N, N- bis- (beta-hydroxy ethyl) acetamide, double (beta-hydroxy ethyl) adipyls Diamines, double (beta-hydroxy propyl group) adipamides, double [N, N- bis- (beta-hydroxy ethyl)] adipamides, double [(β-hydroxyl of N, N- bis- Base propyl group)] adipamide.Beta-hydroxyalkylamides relative to the preferred hydroxy amide base of carboxyl in resin be 0.5~1.5 work as Amount.
Isocyanuric acid three-glycidyl ester can be preferably used for resinous principle has a case that carboxyl.As isocyanuric acid Three-glycidyl ester, can enumerate for example as trade name：Araldite (registration mark) PT 710, Araldite (registrars Mark) (all Huntsman are public for PT 810, Araldite (registration mark) PT 910, Araldite (registration mark) 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 situation that resinous principle contains hydroxyl, more preferably blocked isocyanate Compound.Preferably, isocyanate compound solid-like at normal temperatures.Isocyanate compound relative to the hydroxyl in resin, NCO 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 reacts with the low molecular compound of active hydrogen and obtains PIC and reacted with block agent And sheltered (マ ス キ Application グ) and manufacture, therefore manufacture also easy.It should be noted that as above-mentioned diisocyanate, Can enumerate：Toluylene diisocya-nate, 4,4 '-diphenylmethane isocyanate, XDI, six Methylene diisocyanate, 4,4 '-di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate), methylcyclohexane diisocyanate, double (isocyanic acids Root closes methyl) hexamethylene, IPDI, dimer acid diisocyanate, LDI etc., as The low molecular compound of above-mentioned active hydrogen, can enumerate：Water, ethylene glycol, propane diols, trimethylolpropane, glycerine, sorb Alcohol, ethylenediamine, monoethanolamine, 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, as the concrete example of block agent, can enumerate：Methyl alcohol, The lactams such as the phenols such as the alcohols such as ethanol, phenmethylol, phenol, cresols, caprolactam, butyrolactam, cyclohexanone, oxime, first and second The oximes such as ketoxime.For example, as the concrete example of blocked isocyanate, can enumerate：Block is carried out using epsilon-caprolactams and obtain The IPDI (the Vestagon B1530 of Ying Chuan companies manufacture, the Crelan UI of Beyer Co., Ltd's manufacture) for arriving 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 weatherability is not reduced.
For above-mentioned core shell acrylic resin particle, it is preferable that the ratio that will be determined 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 putting measure is 5~50 μm.
Above-mentioned core shell acrylic resin particle preferably has selected from by carbonyl, hydroxyl and glycidol in particle surface At least a kind of functional group in the group of base composition.
It is less than 20 DEG C that above-mentioned core shell acrylic resin particle preferably has the glass transition temperature comprising stratum nucleare Be at room temperature the polymer phase of rubber-like and the glass transition temperature of shell is more than 50 DEG C of glassy polymeric at room temperature The heterogeneous structure of thing phase.Core shell acrylic resin particle for example can be by the 1st of the polymer phase by rubber-like is formed the Polymerizable monomer is emulsified and suspension polymerisation, forms the rubber like polymer particle that glass transition temperature is less than 20 DEG C 1st section of reaction, and follow-up in the presence of above-mentioned rubber like polymer particle, will be formed glass transition temperature for 50 DEG C with On the polymerizable monomer of glassy polymers phase the 2nd section of radical polymerization reaction is carried out 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 a kind group for selecting free carboxyl group, hydroxyl and glycidyl to constitute.
Constitute the unsaturation list that the rubber-like polymer of stratum nucleare can for example, be used in the synthesis of rubber-like polymer The polymer of body.The glass transition temperature of rubber-like polymer is preferably less than 20 DEG C, more preferably -30~-10 DEG C of model Enclose.Herein, 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 month Osmanthus ester etc. (methyl) alkyl acrylate；The vinyl esters such as vinyl-acetic ester；Vinyl chloride, PVF, vinylidene chloride, inclined two The vinyl halides such as PVF or vinylidene halide；The nitrogenous unsaturated monomers such as (methyl) acrylonitrile, (methyl) acrylamide； The aromatic compounds such as styrene, AMS, 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 thing, can enumerate：Poly- (methyl) ACM, polybutadiene rubber, polyisoprene rubber, polychlorostyrene second Alkene, SBR styrene butadiene rubberses, s-B-S rubber, SIS, 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 rubberses.
Constitute shell glassy polymers be, for example, with glass transition temperature be more than 50 DEG C, preferably to reach 80 The polymer of~100 DEG C of modes of scope and the free radical polymerization monomer after being adjusted.Herein, as free-radical polymerised Monomer, it is possible to 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 methacrylics such as ester, (methyl) acrylic acid 3- hydroxy-propyl esters, (methyl) dihydroxypropyl butyl ester acid ~8 hydroxyalkyl acrylate；The unsaturation such as the PPGs such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol and (methyl) acrylic acid The monoesters of carboxylic acid；The PPGs such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol and (methyl) acrylic acid 2- hydroxyethyl esters etc. The monoether of the 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 containing acid anhydrides not The monoesters compound or diester compound of the glycols such as saturated compounds and ethylene glycol, 1,6-HD, neopentyl glycol；Hydroxyethyl second Hydroxyalkyl vinyl ether class, (methyl) acrylic acid 3- chlorine-2-hydroxyls propyl diester as alkene ether are such to include containing for chlorine There are monomer, allyl alcohol, the unsaturated monomer containing epoxy radicals of hydroxyl etc..These free radical polymerization monomers can individually make With, it is also possible to it is applied in combination two or more.
Above-mentioned core shell acrylic resin particle can be by known method all the time, such as：Pre-existing Added under conditions of rubber-like polymer emulsion free radical polymerization monomer and free-radical polymerised initiator emulsion polymerization, Suspension polymerization etc. is obtained.
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 Alkali resistance high.The bright pigments of flakey are there is also 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 dust for having carried out metal coating, the molding powder and squama that have carried out the metal mica powder being coated with, carried out metal coating Flake ferric oxide pigment etc..
Above-mentioned coating composition can also contain usually used pigment in addition to containing bright pigments, for example 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 pigment 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, 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, having the base material of application should be wanted to need 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, can as needed mix the plasticizer as general additive for coatings, consolidate Change accelerator, crosslinking and promote catalyst, ultra-violet absorber, light stabilizer, antioxidant, fluidity regulator, anti-sagging agent With defoamer etc..
The manufacture method of aforementioned coating composition can be enumerated for example：By comprising the tree beyond above-mentioned fluororesin, fluororesin The mixture of fat, acrylic surfaces conditioning agent and wax melting mixing at 100~160 DEG C, then, after the mixture is cooled down Crushed, the method for preparing powder coating composition.Can preferably by comprising the tree beyond above-mentioned fluororesin, fluororesin After the mixture of fat, acrylic surfaces conditioning agent and wax carries out dry type mixing using Henschel mixer etc., common kneading is used The melting mixing at 120~140 DEG C such as machine, cooling, crush after, be classified using the woven wire etc. of 180 mesh (96 μm), obtain 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..After application, it may be preferred in 160~250 DEG C of scopes, more preferably in 170~220 DEG C of scopes At a temperature of, melt coating composition, solidify to form film.
The base material for constituting coated-body of the invention can be enumerated for example：The metal bases such as steel, zinc, aluminium, copper and tin, but It is that, in order to improve the tack to film, its preferred pair metallic substrate surface carries out bottom layer treatment.It should be noted that base material root Exist according to its purposes variously-shaped, such as tabular etc. can be enumerated.The film for constituting coated-body of the invention is typically incorporated in base On the surface of of material.
As the concrete example of coated-body of the invention, can enumerate：The transport machine of automobile, electric car, aircraft etc. and its The industrial machinery material such as component, bridge and its component, steel tower and its component, building component, waterproof material piece, groove, pipe, building are outer Sight, door, window element, monument, hall Deng Jian Building component, the central partition of road, guardrail, sound proof panel, makrolon system The road components such as light-passing board, semaphore, communicating machine and its component, family's electrical article, Electrical and Electronic part etc..
Embodiment
Hereinafter, by enumerating embodiment, the present invention will be described in more detail, but the present invention is not implemented by following Any limitation of example.
<The Production Example of acrylic surfaces conditioning agent>
(acrylic surfaces conditioning agent A)
The mass of butyl acetate 300 is added in the polyplant for possessing reflux cooler, thermometer, agitator 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-the mass parts of 2 ethyl hexanoic acid ester 5, is kept for 2 hours at 110 DEG C.Temperature is promoted to 130 DEG C afterwards, under reduced pressure Butyl acetate is distilled off, acrylic surfaces conditioning agent A is obtained.Acrylic surfaces are determined by gel permeation chromatography The polystyrene conversion number mean molecule quantity of conditioning agent A.Result is 3500.In addition, according to based on JIS K's 2207 (2006) Global formula softening point test method determines the softening point of acrylic surfaces conditioning agent A, is as a result 83 DEG C.
Solution A is added dropwise：Comprising the mass parts of n-butylacrylate 324, the mass parts of acrylic acid 65, maleic acid diethyl ester 28 The solution of mass parts, t-amyl peroxy-mass parts of 2 ethyl hexanoic acid ester 15 and the mass parts of butyl acetate 200.
(acrylic surfaces conditioning agent B)
In addition to being replaced solution A is added dropwise with following shown dropwise addition solution Bs, with acrylic surfaces conditioning agent A's The same mode of Production Example, obtains acrylic surfaces conditioning agent B.Acrylic surfaces are determined by gel permeation chromatography to adjust The polystyrene conversion number mean molecule quantity of section agent B, is as a result 4100.In addition, by the ring based on JIS K 2207 (2006) Ball softening point test method determines the softening point of acrylic surfaces conditioning agent B, is as a result 92 DEG C.
Solution B is added dropwise：Comprising the mass parts of n-butylacrylate 324, the mass parts of acrylic acid 65, fumaric acid diethyl ester 28 The solution of mass parts, t-amyl peroxy-mass parts of 2 ethyl hexanoic acid ester 15 and the mass parts of butyl acetate 200.
(acrylic surfaces conditioning agent C)
In addition to being replaced solution A is added dropwise with following shown dropwise addition solution Cs, with acrylic surfaces conditioning agent A's The same mode of Production Example, obtains acrylic surfaces conditioning agent C.Acrylic surfaces are determined by gel permeation chromatography to adjust The polystyrene conversion number mean molecule quantity of section agent C, is as a result 2900.In addition, by the ring based on JIS K 2207 (2006) Ball softening point test method determines the softening point of acrylic surfaces conditioning agent C, is as a result 78 DEG C.
Solution C is added dropwise：Comprising the mass parts of n-butylacrylate 324, the mass parts of maleic acid diethyl ester 47, fumaric acid two The solution of the mass parts of ethyl ester 46, t-amyl peroxy-mass parts of 2 ethyl hexanoic acid ester 15 and the mass parts of acetic acid butyl ester 200.
<The making example of powder coating composition>
Formula according to table 1, raw material is put into super mixer and is mixed 1 minute.Then by resulting mixing Thing is adjusted to 120 DEG C of twin shaft kneading machine (Toshiba manufactures) mixing with temperature, and the mixture that will be discharged is cold rolling with chill roll, it Crushed with sprayer of hammer crusher (pinmill) afterwards, be classified using the net of 180 mesh, obtain 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 thickness of slab 1.5mm, chromic acid salt treatment aluminium sheet are vertically hung, with corona charging formula daubing machine of electrostatic powder (ASAHI SUNAC Company manufacture PG-1 types) electrostatic spraying makes its thickness reach 60 μm under -60kV voltages, using electric furnace at 190 DEG C × 20 minutes Condition be sintered, room temperature is then directly naturally cooled to, so as to make breadboard.
<<Evaluate>>
Breadboard to obtaining carries out various measure and evaluation test, the results are shown in table 1.
<The assay method of thickness>
Breadboard is stood vertically in the transparent cup of embedding with specimen holder, epoxy resin " Epocure is flowed into thereto (manufacture of Buehler companies) host+curing agent ", is fully cured epoxy resin, 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 Injection Metadi, Master Prep (manufacture of Buehler companies), to being ground by the breadboard of epoxy resin embedding, obtains Film section.To the film section that obtains using SEM (SU-70 that new and high technology Co., Ltd. of Hitach is manufactured), with accelerating potential 1kv, 900 times of multiple determine thickness at 10, obtain its average value.
<The assay method of the mass ratio of fluorine atom and carbon atom>
Used as the SU-70 that mensuration machine, SEM are manufactured using new and high technology Co., Ltd. of Hitach, EDS uses Oxford Instruments The INCA X-Sight (Model 7969) of (Oxford Instruments) Co., Ltd manufacture.In EDS, cobalt conduct is selected The quantitative element for optimizing, carries out condition setting.Now the parameter of device is Livetime 100 seconds, process time (Process Time) 5, spectral range (Spectrum range 0-20kev), port number (Number of channels) 1K.
(assay method of the 1st Funing tablet)
Ratio (matter of 1st Funing tablet shared by fluorine atom in the fluorine atom and total quality of carbon atom in film coated surface Amount %).First, breadboard is cut into about 1cm × 1cm, in order to reduce by the destruction of film coated surface caused by electron ray, will Be fixed on the adhesive tape of the sample electric conductivity after gold evaporation on SEM observation platforms on the sample that this cuts by gold evaporation, so SEM observations are carried out with accelerating potential 15kv, 500 times of multiple afterwards.Then, using EDS, any selection 245 μ m, 185 μm of areas Film coated surface, the Elemental redistribution for carrying out the film coated surface determines, and determines the ratio of carbon atom and fluorine atom, and obtain fluorine atom With the ratio shared by fluorine atom in total quality of carbon atom.Afterwards, changing carries out the position of Elemental redistribution measure, 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 measure.Will The average value of the measurement result of 10 times is used 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 of the depth equivalent to the half of thickness of film coated surface Total quality in ratio (quality %) shared by fluorine atom.First, in order to reduce by film coated surface caused by electron ray Damage, by gold evaporation on the breadboard by epoxy resin embedding used by film thickness measuring, 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 At position of the depth of film coated surface equivalent to the half of thickness, choose at random parallel with film coated surface and 135 μm of length Line, the Elemental redistribution that the line is carried out with EDS determines (line analysis), determines the ratio of carbon atom and fluorine atom, and obtains fluorine atom With the ratio shared by fluorine atom in total quality of carbon atom.Afterwards, changing carries out the position of Elemental redistribution measure, painting of adjusting the distance The depth on film surface is equivalent to shared by fluorine atom in the fluorine atom and total quality of carbon atom at the position of the half of thickness Ratio carries out 9 measure.Using the average value of the measurement result of 10 times as the 2nd Funing tablet.
<Wearability>
It is measured according to ASTM D968 (sand trail method).Specifically, Gardner's formula falling sand abrasion test is used Machine, horizontal plane inclination at 45 ° is disposed relative to by breadboard, 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, the total amount (unit of the sand that V is used by sand trail：Rise L), T is that the thickness before sand trail subtracts It is worth (that is, the thickness of abrasion, unit obtained from thickness after sand test：μm)]
It should be noted that according to the cut coefficient for calculating, according to following metewands, evaluating wearability.
◎ cuts coefficient is more than 100
Zero cut coefficient is 45 less than 100
△ cuts coefficient is 40 less than 45
× cut coefficient is less than 40
<Weatherability>
For breadboard (application obtained from the powder coating composition using 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.Need It is noted that test period is set as into 3000 hours.With gloss meter, (micro-TRI-gross BYK companies manufacture：Enter anti- 60 ° of firing angle) 60 ° of bright luster values before determination test and after experiment in 3000 hours, obtain 60 ° of minute surfaces after experiment in 3000 hours Gloss number relative to experiment before 60 ° of rates of change of bright luster value, according to following metewands, carry out weatherability evaluation.
◎ rates of change are more than 90%
Zero rate of change is 70% less than 90%
△ rates of change are 50% less than 70%
× rate of change is less than 50%
<Tack>
According to JIS K5600-5-6 (cross-section method), the film of breadboard is cut into 100 pieces of go trellis shapes with 1mm intervals, Disbonded test is carried out with adhesive tape, and obtains the residual rate after disbonded test, according to following metewands, evaluate tack.
○：100/100 (sum of the cut portion before the quantity/experiment of the cut portion remained after experiment)
△：85/100~99/100
×：Less than 84/100
Table 1
It should be noted that the detailed content of raw material described 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) the acrylic surfaces conditioning agent A obtained in the Production Example of above-mentioned acrylic surfaces conditioning agent is used ~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) crosslinking resin particles prepared by following method is used.
(* 9) the core shell acrylic resin particle prepared by following method is used.
(preparation example of crosslinking resin particles)
The preparation example to crosslinking resin particles shown in table 1 is illustrated below.Use homo-mixer (Mizuho works Industry Co., Ltd. manufactures, desktop high-speed uniform blender 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 possessing agitator, heater and thermometer, 60 Persistently stirred at DEG C 6 hours, carry out suspension polymerisation.The suspension filtration under diminished pressure, the reaction product that will be obtained are cleaned with water, Dry, crush, obtain crosslinking resin particles of 6.8 μm of volume average particle size.
Oil phase
The mass parts of butyl acrylate cores 80
The mass parts of dimethacrylate tetradecane diols ester 20
The mass parts of benzoyl peroxide 0.3
Water phase
The mass parts of deionized water 400
The mass parts of polyvinyl alcohol (saponification degree 85%) 8
The mass parts of lauryl sodium sulfate 0.07
(preparation example of core shell acrylic resin particle)
The preparation example to the 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 % is added in the aggregation container of 5L capacity, is made It is stirred with 4500rpm with homo-mixer (AS ONE Co., Ltd. manufactures), while disposable addition makes the positive fourth of acrylic acid Base ester 576g, diacrylate 1,4- butanediol esters 12g, ALMA 12g and lauroyl peroxide 6g (draw by polymerization Hair agent) monomer mixed solution obtained from dissolving, 1 hour decentralized processing is carried out, obtain monomer dispersion liquid.Then, hold in the polymerization Agitator and reflux condenser are installed on device, are stirred in stream of nitrogen gas, while being warming up to 70 DEG C.Stirred at 70 DEG C, while React within 2 hours.At this moment, it is sampled from the suspension of the polymer particle for obtaining, the polymerization for determining monomer turns Rate, is as a result 94%.The suspension of the polymer particle that will then obtain is cooled to 60 DEG C.The suspension is stirred with 4500rpm Liquid, while continuously adding as shown below for the 2nd section of monomer emulsion of reaction in 15 minutes.(for the 2nd section reaction 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, the sodium dodecyl sulfate aqueous solution 100g of 1 mass %, go Ionized water 100g is mixed and is prepared.)
Polymerization starts, and when heating is observed, is warming up to 80 DEG C, carries out 3 hours slaking reactions.The suspension that will be obtained Liquid is dehydrated cleaning after being cooled to room temperature with centrifugal separator, and air-drying for one day night is carried out at 60 DEG C, obtains hud typed Acrylic resin particle.
DSC according to core shell acrylic resin particle is determined, 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 determined is calculated It it is 0.1 μm, by laser diffraction/scattering formula particle size distribution analyzer Partica LA-950V2, (hole makes institute's strain formula meeting Society's system) the average aggregate particle size that is determined is 6 μm.

Claims (6)

1. coated-body, it is the coated-body of the film for possessing base material and configuration on the substrate surface, it is characterised in that
The film is formed by the coating composition including at least the resin beyond fluororesin and the fluororesin,
When the ratio shared by fluorine atom in total quality of the fluorine atom in the film coated surface and carbon atom is set as into the 1st During Funing tablet (quality %), the 1st Funing tablet is 30~50 mass %,
When the thickness of the film is set as into T (μm), will be apart from the fluorine atom and carbon at film coated surface depth T/2 (μm) position 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 claimed in claim 1, it is characterised in that the thickness of the film is 40~200 μm.
3. coated-body as claimed in claim 1 or 2, it is characterised in that the base material is metal base.
4. the coated-body as described in any one of claims 1 to 3, it is characterised in that the resin beyond the fluororesin is choosing At least one resin in the group of free polyester resin and epoxy resin composition.
5. the coated-body as described in any one of Claims 1 to 4, it is characterised in that the coating composition is powder coating Composition.
6. the coated-body as described in any one of Claims 1 to 5, it is characterised in that the cut coefficient of the film is 45~ 500。
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JP6298198B1 (en) * 2017-05-26 2018-03-20 関西ペイント株式会社 Powder coating composition
CN109971317A (en) 2017-12-27 2019-07-05 Ａｇｃ株式会社 The manufacturing method of powder coating
US11015080B2 (en) * 2019-08-15 2021-05-25 Ppg Industries Ohio, Inc. Powder coating compositions and coatings formed therefrom
KR102416188B1 (en) * 2021-02-18 2022-07-05 한국세라믹기술원 Antimicrobial ceramic hybrid film for Keep-freshness packaging and its manufacturing method

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