CN106118196A - Powder coating composition and manufacture method thereof - Google Patents
Powder coating composition and manufacture method thereof Download PDFInfo
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- CN106118196A CN106118196A CN201610509921.XA CN201610509921A CN106118196A CN 106118196 A CN106118196 A CN 106118196A CN 201610509921 A CN201610509921 A CN 201610509921A CN 106118196 A CN106118196 A CN 106118196A
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- coating composition
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- 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
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The present invention relates to weatherability good and the powder coating composition of layer divergence type of manufacturing expense can be reduced, more specifically, relate to a kind of powder coating composition, it contains the firming agent in hydroxyl or the polyester resin of the fluororesin of carboxyl, hydroxyl or carboxyl and the group selecting free β hydroxyalkyl amide, triglycidyl isocyanurate and isocyanate compound composition, it is possible to is formed and possesses fluorine film layer and the film of polyester film layer.
Description
The application is filing date on June 11st, 2012, and (international application no is PCT/ to Application No. 201280073908.4
JP2012/064897), the division Shen of invention entitled " powder coating composition and manufacture method thereof " application for a patent for invention
Please.
Technical field
The present invention relates to the manufacture method of powder coating composition and this powder coating composition, particularly relating to can shape
Become to possess the powder coating composition of the film of fluorine film layer and polyester film layer.It addition, this powder coating composition is the most also
It is referred to as the powder coating composition of layer divergence type.
Background technology
In recent years, the environmental problem of the earth scale such as global warming, depletion of the ozone layer, acid rain significantly increases, in the world
The countermeasure of upper appealing environmental pollution, accompanies with this, has carried out various restriction from the viewpoint of environmental conservation.Wherein, organic
The solvent (particularly VOC VOC) release in air becomes serious problems, in each industry, strengthening VOC limit
The tendency of system and dynamically also coming to life to de-organic solvent (particularly taking off VOC).In coating industry, also require that the most not
Containing VOC, need not exhaust-gas treatment and waste water process and can also recycling the coating friendly to environment instead
The coating of existing organic solvent type coatings, the expectation to powder coating is increased.
Powder coating mainly uses acrylic resin system, polyester resin system or the powder coating of epoxy resin.But,
The shortcoming that epoxy resin powder coating material has weatherability difference.
As improving the powder coating of this shortcoming, develop following powder coating: application thermal-curable acrylic resinoid
Powder coating material and the mixture of thermosetting epoxy resin powder coating material, and this mixture is heating and curing, thereby, it is possible to shape
Become the double-deck film that upper strata is acrylic resin system powder body film and lower floor is made up of epoxy resin powder body film (such as,
Referenced patent document 1～3).
On the other hand, from the viewpoint of improving weatherability, develop use weatherability than acrylic resin, polyester tree
The heat curing-type fluororesin powder coating material (such as, referenced patent document 4) of the fluororesin that fat is excellent.But, only use fluororesin
As the powder coating of resin, need the fluororesin of substantial amounts of costliness, there is the tendency of cost up.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Laid-Open Patent Publication 53-140336 publication
Patent documentation 2: Japanese Laid-Open Patent Publication 54-105135 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2001-259520 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2008-266361 publication
Summary of the invention
Invent problem to be solved
Therefore, it is an object of the invention to provide weatherability good and the powder of layer divergence type of manufacturing expense can be reduced
Body coating composition.It addition, another object of the present invention is to provide the manufacture method of this powder coating composition.
For the method solving problem
To achieve these goals, present inventor has performed further investigation, it was found that by using containing excellent weather resistance and hard
Good fluororesin, the polyester resin of low cost and the powder coating composition of specific firming agent, it is possible to low cost and saving
Operation ground forms the high-weatherability film possessing fluorine film layer and polyester film layer, thus completes the present invention.
That is, the powder coating composition of the present invention is characterised by, containing hydroxyl or the fluororesin of carboxyl, hydroxyl or
The polyester resin of carboxyl and the free beta-hydroxy alkylamide of choosing, triglycidyl isocyanurate and isocyanate compound composition
Group in firming agent, it is possible to formed possess fluorine film layer and the film of polyester film layer.
The powder coating composition of the present invention is preferably possibly together with epoxy resin.
The powder coating composition of the present invention is preferably possibly together with flitter.
In the preference of the powder coating composition of the present invention, above-mentioned polyester resin is the polyester resin of hydroxyl, and this contains
The number-average molecular weight of the polyester resin of hydroxyl is less than 5000 and weight average molecular weight is 10000～20000.
In another preference of the powder coating composition of the present invention, the melt viscosity of above-mentioned polyester resin is 3.5Pa s
(190 DEG C) below, and, based on measure start temperature be 200 DEG C and cooling rate be 10 DEG C/min under conditions of measure
Melt viscosity (Pa s) Arrhenius figure (Arrhenius plot) in, the slope in the range of 100～120 DEG C is
More than 15000.
In another preference of the powder coating composition of the present invention, above-mentioned fluororesin is the fluororesin of hydroxyl.
In another preference of the powder coating composition of the present invention, above-mentioned fluororesin (A) and above-mentioned polyester resin (B)
Mass ratio (A/B) is 50/50～10/90.
In another preference of the powder coating composition of the present invention, above-mentioned fluororesin and the dissolubility of above-mentioned polyester resin
The difference of parameter (SP value) is 0.6～0.9.
It addition, the manufacture method of the powder coating composition of the present invention is characterised by, will be containing above-mentioned fluororesin, above-mentioned
The mixture of polyester resin and above-mentioned firming agent is melting mixing at 100～160 DEG C, then, carries out after being cooled down by this mixture
Pulverize, prepare powder coating composition.
Invention effect
According to the present invention, by using fluororesin, the polyester resin of low cost excellent containing weatherability and specifically consolidating
Agent, using the teaching of the invention it is possible to provide can be with low cost and formed with saving operation and possess the high-weatherability film of fluorine film layer and polyester film layer
The powder coating composition of layer divergence type.In addition it is possible to provide the manufacture method of this powder coating composition.
Accompanying drawing explanation
Fig. 1 is the image drawn the fluorine atom being present in film cross section and obtain.
Detailed description of the invention
＜ powder coating composition ＞
The powder coating composition of the present invention contains hydroxyl or the polyester resin of the fluororesin of carboxyl, hydroxyl or carboxyl
And select the solidification in the group of free beta-hydroxy alkylamide, triglycidyl isocyanurate and isocyanate compound composition
Agent, it is possible to formed and possess fluorine film layer and the film of polyester film layer.It addition, the powder coating composition of the present invention is except using
Beyond the fluororesin that weatherability is excellent, also use cheap polyester resin, therefore, it is possible to suppress manufacturing expense and form weatherability
Excellent film.It addition, when the powder coating composition painting of the present invention is installed on base material, owing to forming two with an application
Coating film layer, therefore, it is possible to save the manufacturing process of film.It should be noted that fluorine film layer refers to be formed based on fluororesin
Film layer, polyester film layer refer to based on polyester resin formed film layer.
＜ fluororesin ＞
In the powder coating composition of the present invention, fluororesin needs at normal temperatures for the resin of solid-state, and its softening point is preferred
It it is 50～150 DEG C.Above-mentioned fluororesin forms fluorine film layer, gives weatherability to film.It should be noted that room temperature refers to JIS
Temperature in the range of 20 DEG C ± 15 DEG C (5～35 DEG C) specifying in Z 8703.
It addition, above-mentioned fluororesin needs have the reactive site reacted with firming agent etc., containing hydroxyl or carboxyl.Cause
This, above-mentioned fluororesin such as can manufacture with the monomer copolymerization containing specific reactive group by making fluorochemical monomer.
As above-mentioned fluorochemical monomer, can enumerate such as: fluorothene, vinylidene fluoride, trifluoro-ethylene, tetrafluoroethene, bromine
Trifluoro-ethylene, chlorotrifluoroethylene, pentafluoropropene, hexafluoropropene, [carbon of (entirely) fluoroalkyl is former for (entirely) fluoroalkyl trifluoro vinyl ether
Subnumber is 1～18] etc..
On the other hand, the monomer containing specific reactive group refers to containing hydroxyl or carboxyl as anti-with firming agent etc.
The polymerizable monomer of the group (reactive group) answered.
Specifically, as the polymerizable monomer of hydroxyl, can enumerate such as: 1-propenol-3；2-hydroxyethylvinyl
The hydroxyalkyl vinyl bases such as ether, 3-hydroxypropyl vinyl ethers, 4-hydroxybutyl vinyl ether, 4-hydroxy-cyclohexyl vinyl ethers
Ethers；2-hydroxyethyl allyl ether, 3-hydroxypropyl allyl ether, 4-hydroxybutyl allyl ether, 4-hydroxy-cyclohexyl alkene
The hydroxy alkyl allyl ether series such as propyl ether；(methyl) dihydroxypropyl alkyl ester classes such as (methyl) 2-Hydroxy ethyl acrylate；Hydroxyl
Vinyl acetate, hydroxy-isobutyric vinyl acetate, hydracrylic acid vinyl acetate, hydroxybutyric acid vinyl acetate, hydroxypentanoic acid vinyl acetate, hydroxyl
The hydroxyyalkyl carboxylic acids such as butylcyclohexyl vinyl carboxylates and the esters of vinyl alcohol；Hydroxyethyl allyl ester, hydroxypropyl allyl
The hydroxy alkyl pi-allyl esters etc. such as base ester, hydroxybutyl allyl ester, hydroxyisobutyl allyl ester.
It addition, as carboxylic polymerizable monomer, (methyl) acrylic acid, carboxyalkyl allyl ester etc. can be enumerated.
In these monomers containing reactive group, from the stability of resin, the viewpoint such as control of melt viscosity, preferably
The polymerizable monomer of hydroxyl.In other words, as the fluororesin of above-mentioned fluororesin, preferably hydroxyl.
It addition, in the polymerization of above-mentioned fluororesin, it is possible to use above-mentioned fluorochemical monomer and containing specific reactive group
Polymerizable monomer beyond monomer.As this polymerizable monomer, can enumerate: vinyl ethers, olefines, allyl ether series,
Vinyl ester, pi-allyl esters, (methyl) esters of acrylic acid, (methyl) acrylic acid amides class, the monomer class of cyano-containing, diene
Class etc., butenoic acid esters etc..
As the concrete example of the polymerizable monomer beyond above-mentioned fluorochemical monomer and the monomer containing specific reactive group,
Can enumerate such as: methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, IVE, cyclohexyl. vinyl
The alkyl vinyl ethers such as base ether, chloroethyl vinyl ether；Ethylene, propylene, 1-butylene, isobutene., cyclohexene, vinyl chloride, partially
The olefines such as dichloroethylene；The styrene monomer class such as styrene, α-methyl styrene；Methallyl ether, allyl ethyl
The polyoxyethylene base ethers such as ether, butyl allyl ether, cyclohexyl allyl ether；Vinyl acetate, propionate, butanoic acid ethylene
Ester, vinyl isobutyrate ester, vinyl valerate, vinyl caproate, octanoic acid vinyl acetate, vinyl neodecanoate (バ サ テ ィ ッ Network acid
PVC ニ Le) etc. the vinyl ester of carboxylic acid (preferably fatty acid)；The carboxylic acid such as allyl propionate, allyl acetate (preferably fat
Fat acid) allyl esters；(methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) propylene
(methyl) esters of acrylic acids such as acid cyclohexyl；(methyl) the acrylic acid amides classes such as (methyl) acrylic acid amides；Acrylonitrile, 2,4-bis-
The monomer class of the cyano-containings such as cyano group-1-butylene；The dienes such as isoprene, butadiene；Butenoic acid-2-hydroxy methacrylate, butenoic acid-
The butenoic acid esters etc. such as 4-hydroxybutyl.
Additionally, in the polymerization of above-mentioned fluororesin, it is also possible to use gathering of the reactive group beyond containing hydroxyl and carboxyl
Conjunction property monomer.As this reactive group, can enumerate such as: amide groups, amino, itrile group, glycidyl, NCO
Deng functional group.
Specifically, as the polymerizable monomer containing amino, amino alkyl vinyl ethers, aminoalkyl alkene can be enumerated
Propyl group ethers, as the polymerizable monomer of amide-containing, can enumerate (methyl) acrylamide, N-methyl (methyl) acrylamide
Deng, as the polymerizable monomer of nitrile group-containing, (methyl) acrylonitrile etc. can be enumerated, as the polymerism list containing glycidyl
Body, can enumerate glycidyl allyl ether, (methyl) glycidyl acrylate etc., as the polymerization containing NCO
Property monomer, can enumerate vinyl isocyanate, acrylic acid isocyanatoethyl methacrylate etc..
The Oil repellent of above-mentioned fluororesin is preferably 5～80 mass %, more preferably 10～70 mass %.The fluorine of fluororesin contains
When amount is more than 5 mass %, it is possible to give sufficient weatherability to the film obtained by the powder coating composition of the present invention, this
Outward, when the Oil repellent of fluororesin is below 80 mass %, additionally it is possible to give sufficient chemical-resistant to this film.On it addition,
When stating the fluororesin that fluororesin is hydroxyl, from the viewpoint of the flexibility keeping film, the hydroxyl value of fluororesin is preferably
Below 100mgKOH/g, on the other hand, from the viewpoint of giving sufficient resistance to impact to film, preferably 10mgKOH/g
Above.The hydroxyl value of fluororesin is particularly preferably 30～70mgKOH/g.
＜ polyester resin ＞
In the powder coating composition of the present invention, polyester resin can utilize public affairs by making carboxylic acid composition with polyol component
The method reaction known manufactures, and needs have the reactive site reacted with firming agent etc., accordingly, it would be desirable to be containing hydroxyl or carboxylic
Base, being the resin of solid-state at normal temperatures, its softening point is preferably 100～150 DEG C.Above-mentioned polyester resin forms polyester film layer,
Constitute a part for film.Thus, compared with the film being only made up of fluorine film layer, the outward appearance of film and processability are improved, and
And manufacturing expense can be cut down.
As the carboxylic acid composition that can use in the manufacture of above-mentioned polyester resin, can enumerate such as: phthalic acid,
M-phthalic acid, p-phthalic acid, naphthalenedicarboxylic acid, succinic acid, 1,3-propanedicarboxylic acid, adipic acid, 1,5-pentanedicarboxylic acid., suberic acid, Azelaic Acid, the last of the ten Heavenly stems two
Acid, 1,9-nonane dicarboxylic acid, 1,10-decane dicarboxylic, 1,12-dodecanedicarboxylic acid, 1,2-octadecane dicarboxylic acid, maleic acid,
The polynary carboxylics such as fumaric acid, cyclohexane cyclohexanedimethanodibasic, hexahydrophthalic acid, tetrahydrophthalic acid, trimellitic acid, PMA
Acid, the lower alkyl esters of these polybasic carboxylic acids and anhydride thereof and malic acid, tartaric acid, 1,2-hydroxy stearic acid, para hydroxybenzene
The hydroxy carboxylic acid etc. such as formic acid.
As the polyol component that can use in the manufacture of above-mentioned polyester resin, can enumerate such as: ethylene glycol, two
Ethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3 butylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-are own
Glycol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, the spiroglycol, 1,10-decanediol, 1,4 cyclohexane dimethanol, three
Hydroxymethyl ethane, trimethylolpropane, glycerol, tetramethylolmethane etc..
As it has been described above, above-mentioned polyester resin can be by using carboxylic acid composition and polyol component as raw material and by closing
Manufacture in the known usual method manufacturing powder coating composition polyester resin.For example, it is possible to above-mentioned each raw material is fitted
Work as combination, use with proportioning, carry out according to conventional methods being esterified or ester exchange reaction at 200～280 DEG C, then, in decompression
Under, use catalyst to carry out polycondensation reaction at 230～290 DEG C, according to circumstances, then, utilize polyhydric alcohol to carry out depolymerization reaction,
Thus manufacture polyester resin.
Above-mentioned polyester resin can have the reactive group beyond hydroxyl and carboxyl.As this reactive site, permissible
Enumerate the functional groups such as such as amide groups, amino, itrile group, glycidyl, NCO.
From the viewpoint of controlling cross-linking reaction, Physical properties of coating film, above-mentioned polyester resin is preferably the polyester resin of hydroxyl.
It addition, from the viewpoint of controlling melt viscosity, preferably its number-average molecular weight is less than 5000 to above-mentioned polyester resin and weight average divides
Son amount is 10000～20000.Here, number-average molecular weight and weight average molecular weight can pass through gel permeation chromatography (GPC) with poly-
Styrene is obtained as standard substance.
In the case of the polyester resin that above-mentioned polyester resin is hydroxyl, the hydroxyl value of polyester resin be preferably 20～
100mgKOH/g, more preferably 30～80mgKOH/g.When the hydroxyl value of polyester resin is less than 20mgKOH/g, it is difficult to obtain film
Sufficiently mechanical properties, solvent resistance, on the other hand, during more than 100mgKOH/g, need to meet the firming agent of the amount of this hydroxyl value
(such as, isocyanate compound), expense increases.It addition, the acid number of above-mentioned polyester resin is preferably 20～80mgKOH/g, more
It is preferably 30～80mgKOH/g.When the acid number of polyester resin is less than 20mgKOH/g, it is difficult to obtain the sufficiently machinery thing of film
Property, solvent resistance, on the other hand, during more than 100mgKOH/g, need to meet firming agent (such as, the β-hydroxyl alkane of the amount of this acid number
Base amide and triglycidyl isocyanurate), expense increases.
The melt viscosity of above-mentioned polyester resin is preferably 3.5Pa s (190 DEG C) below.The melted of above-mentioned polyester resin is glued
When degree is more than 3.5Pa s (190 DEG C), it is difficult to occur the layer of film to separate.It addition, above-mentioned polyester resin is being opened based in mensuration
Beginning temperature be 200 DEG C and cooling rate be 10 DEG C/min under conditions of the Arrhenius figure of melt viscosity (Pa s) that measures
In, the slope in the range of 100～120 DEG C is preferably more than 15000.It should be noted that in the mensuration of melt viscosity, use テ
The flow graphs such as the flow graph ARES that ィ エ イ イ Application ス ツルメン ト company manufactures, measure and start temperature and cooling rate
Condition in addition is the parallel-plate of diameter 40mm, band gap width 1.0mm, frequency 9.42rad/s, strain 1.0%.It addition, by institute
The measurement result of the melt viscosity obtained be depicted as transverse axis be the 1/T reciprocal of temperature T (K), the longitudinal axis be melt viscosity V (Pa s)
The figure of logarithm lnV, make Arrhenius figure, thus, it is possible to obtain the slope of 100～120 DEG C of interior straight lines.This straight line
When slope is more than 15000, the layer of film separates and is easily formed, and the most preferably, more preferably this slope is 16000～20000.
＜ epoxy resin ＞
The powder coating composition of the present invention, in order to improve the adaptation with base material, preferably possibly together with epoxy resin.
In the powder coating composition of the present invention, epoxy resin needs the resin for being solid-state at normal temperatures, its softening point
It is preferably 50～150 DEG C.As above-mentioned epoxy resin, it is not particularly limited, it is possible to use be coated with at epoxy resin powder body in the past
The epoxy resin used in the manufacture of feed composition.
As above-mentioned epoxy resin, specifically, can enumerate such as: bisphenol A-type diglycidyl ether resin, bis-phenol
F type diglycidyl ether resin, aminoglycidyl ether resin, bisphenol-A D type diglycidyl ether resin, bisphenol Z type
Diglycidyl ether resin, o-cresol phenolic resin varnish, phenol novolac epoxy resins, biphenyl glycidyl
Ether resin, the epoxy resin of cyclopentadienyl skeleton, the epoxy resin of naphthalene skeleton, GMA acrylic resin etc. and by these set
Substituent group beyond the epoxy radicals of fat is substituted by the resin of other substituent groups, such as by using carboxyl terminal polybutadiene-the third
The resin etc. that the transformation reactions such as the modified-reaction of alkene nitrile (CTBN), esterification obtain.It addition, the epoxide equivalent of epoxy resin is preferably
300～1200, particularly preferably 400～1000.
＜ firming agent ＞
In the powder coating composition of the present invention, firming agent needs for selecting free beta-hydroxy alkylamide, isocyanuric acid three to contract
Firming agent in the group of water glyceride and isocyanate compound composition, it is possible to hydroxyl or the fluororesin of carboxyl, hydroxyl
Or the polyester resin of carboxyl and epoxy resin react and form cross-bond.
＜ ＜ beta-hydroxy alkylamide ＞ ＞
In the case of the resin used in the powder coating composition of the present invention has carboxyl, β-hydroxyalkyl is preferably used
Amide is as firming agent.As beta-hydroxy alkylamide, the viewpoint of the resistance to water of the film obtained from curability at low temperatures, application goes out
Sending out, particularly preferred each intramolecular has the beta-hydroxy alkylamide of more than 2 functional groups.As beta-hydroxy alkylamide, the most excellent
Select N, N-bis-(beta-hydroxy ethyl) acetamide, double (beta-hydroxy ethyl) adipamide, double (beta-hydroxy propyl group) adipamide,
Double [N, N-bis-(beta-hydroxy ethyl)] adipamide, double [N, N-bis-(beta-hydroxy propyl group)] adipamide.β-hydroxyalkyl acyl
Amine is 0.5～1.5 equivalents relative to the preferred hydroxy amide base of the carboxyl in resin.
＜ ＜ triglycidyl isocyanurate ＞ ＞
In the case of the resin used in the powder coating composition of the present invention has carboxyl, isocyanuric acid is preferably used
Three-glycidyl ester (TGIC) is as firming agent.As triglycidyl isocyanurate, can enumerate such as with trade name:
Araldite (registered trade mark) PT 710, Araldite (registered trade mark) PT 810, Araldite (registered trade mark) PT 910,
Araldite (registered trade mark) PT 912 (all Ha ンツマン company manufacture) etc..
＜ ＜ isocyanate compound ＞ ＞
It addition, from the viewpoint of the Physical properties of coating film such as hardness of film, hydrolytic resistance, in the powder coating composition of the present invention
Isocyanate compound can also be coordinated as firming agent, but be block isocyanate compound the most further.Above-mentioned different
Cyanate esters is the isocyanate compound of solid the most at normal temperatures.
It addition, above-mentioned block isocyanate compound such as can be by making aliphatic, aromatic series or aromatic-aliphatic
The low molecular compound of diisocyanate and active hydrogen reacts and obtains polyisocyanate and react with block agent and cover
Covering and manufacture, it is the easiest therefore to manufacture.It addition, as above-mentioned diisocyanate, can enumerate: toluene di-isocyanate(TDI), 4,4 '-
(cyclohexyl is different for diphenylmethane isocyanate, XDI, hexamethylene diisocyanate, 4,4 '-di-2-ethylhexylphosphine oxide
Cyanate), methylcyclohexane diisocyanate, double (isocyanatomethyl) hexamethylene, isophorone diisocyanate, dimer
Acid diisocyanate, lysinediisocyanate etc., as the low molecular compound of above-mentioned active hydrogen, can enumerate: water,
Ethylene glycol, propylene glycol, trimethylolpropane, glycerol, sorbitol, ethylenediamine, ethanolamine, diethanolamine, hexamethylene diamine etc., Yi Jiyi
Cyanurate, uretdione, low molecular weight polyester containing hydroxyl, polycaprolactone etc..It addition, as the tool of block agent
Style, can enumerate: acyl in the phenols such as the alcohols such as methanol, ethanol, benzyl alcohol, phenol, cresol, caprolactam, butyrolactam etc.
The oximes such as amine, Ketohexamethylene, oxime, methyl ethyl ketoxime.Such as, as the concrete example of blocked isocyanate, can enumerate: utilize ε-oneself
Isophorone diisocyanate that lactams carries out block and obtains (the ベ ス タ go Application B1530 that エ ボ ニ ッ Network company manufactures,
バ イ エ Le company manufacture Network レ ラ Application UI) etc..
In the powder coating composition of the present invention, the softening point of isocyanate compound is preferably 10～120 DEG C, the most excellent
Elect 40～100 DEG C as.When softening point is less than 10 DEG C, there is solidification or formed granular in powder coating composition under normal temperature environment
Block, the most preferred.On the other hand, when softening point is more than 120 DEG C, powder coating composition is manufactured by melting mixing
Time, it is difficult to make isocyanate compound be uniformly dispersed in this powder coating composition, damage obtained film sometimes
Slickness, coating strength, the performance such as moisture-proof.Above-mentioned isocyanate compound is relative to the preferred Carbimide. of the hydroxyl in resin
Ester group is 0.05～1.5 equivalents, particularly preferably 0.8～1.2 equivalents.When this NCO is less than 0.05 equivalent, powder body is coated with
The curing degree of feed composition is not enough, and the film performance such as adaptation, hardness of film, chemical-resistant may reduce.It addition, this is different
When cyanic acid ester group is more than 1.5 equivalent, film may become fragile, and thermostability, chemical-resistant, moisture-proof etc. are likely to be deteriorated.
Additionally, blocked isocyanate is costly, therefore, when using the blocked isocyanate of excess, expense increases.
＜ flitter ＞
The powder coating composition of the present invention can be possibly together with flitter.Flitter there is also lepidiod flash of light
Pigment.As flitter, can enumerate such as: aluminium powder pigment, nikel powder pigment, bronze, argentum powder, bronze powder, copper powder, rustless steel
Powder pigment, pigments, mica, graphite pigment, glass flake pigments, carry out the glass dust of metal coated, carried out metal coated
Mica powder, the molding powder having carried out metal coated and flakey iron oxide pigment etc..In the powder coating composition of the present invention
The content of flitter is preferably 0.1～30 mass %, more preferably 0.5～20 mass %.The content of this flitter is less than
During 0.1 mass %, it is difficult to the light sense of film, on the other hand, during more than 30 mass %, the layer separation property possible deviation of film,
And with flitter exposing in film coated surface, chemical-resistant and the moisture-proof etc. of film may be made to be deteriorated.Additionally,
Costly, when using the flitter of excess, expense increases flitter.
＜ coloring pigment, extender pigment and rust resisting pigment ＞
The powder coating composition of the present invention is in addition to containing flitter, it is also possible to containing normally used pigment,
Such as coloring pigment, extender pigment etc..As coloring pigment, can enumerate such as: titanium oxide, yellow iron oxide, titan yellow, ferrum
The inorganic pigments such as pellet, Griffith's zinc white., stibium oxide, hansa yellow 5G, durable yellow FGL, phthalocyanine blue, indanthrene blue RS, durable red F5RK,
The organic pigments etc. such as bright fast scarlet G.On the other hand, as extender pigment, can enumerate such as: barium sulfate, brium carbonate, carbonic acid
Calcium, clay, silicon dioxide powder, kieselguhr, Talcum, alkaline magnesium carbonate, alumina white etc..It addition, need at the base material that should want application
In the case of rust-preventing characteristic to be had, the powder coating composition of the present invention can contain rust resisting pigment.As rust resisting pigment, permissible
Enumerate such as: condensed phosphoric acid calcium, aluminum phosphate, condensation of aluminum phosphate, zinc phosphate, aluminium phosphite, zinc phosphite, Arizona bacilli, molybdic acid
Zinc, calcium molybdate, manganese molybdate etc..These pigment may be used alone, can also be used in combination two or more.
＜ other additives ＞
It addition, in the powder coating composition of the present invention, can coordinate as required as general additive for coatings
Plasticizer, curing accelerator, crosslinking promote catalyst, surface conditioner, UV absorbent, light stabilizer, antioxidant, stream
Dynamic property regulator, anti-sagging agent and defoamer etc..
＜ fluororesin and the mass ratio ＞ of polyester resin
In the powder coating composition of the present invention, from the viewpoint of weatherability and low cost, fluororesin (A) and polyester tree
The mass ratio (A/B) of fat (B) is preferably 50/50～10/90.The ratio that fluororesin is shared in fluororesin with the total of polyester resin
When example is more than 50 mass %, the usage amount of expensive fluororesin increases, and therefore cost up, on the other hand, fluororesin is in fluorine tree
When ratio shared in the total of fat and polyester resin is less than 10 mass %, sometimes can not get sufficient weatherability.
＜ fluororesin and solubility parameter ＞ of polyester resin
In the powder coating composition of the present invention, fluororesin is preferably with the difference of the solubility parameter (SP value) of polyester resin
0.6～0.9.When the difference of the SP value of fluororesin and polyester resin is less than 0.6, when melting, being solidified to form film, fluororesin with
Polyester resin is the most compatible, it is difficult to occurring upper strata, the such layer of lower floor to separate, on the other hand, the difference of this SP value is more than 0.9
Time, although can separate by genetic horizon, but worry between upper strata and lower floor, to produce splitting.It addition, as the dissolving of resin
The SP value of degree parameter calculates in the following manner.Resin is dissolved in oxolane (THF), prepares 10 mass % solution, divide and take
This solution a certain amount of, is set to V by this volume (ml)THF.It addition, drip respectively in the solution point taken hexane (Hexane) and
Ion exchange water (Water) titrates.The dripping quantity (ml) that the moment of nebulousurine occurs is set to VHexaneAnd VWater。
Obtained value is substituted in following formula (1) and (2), calculates SPnAnd SPh.Then, by obtained SPnAnd SPhSubstitution formula
(3), in, SP value is obtained.
SPn=(SPTHF×VTHF+SPHexane×VHexane)/(VTHF+VHexane)…(1)
SPh=(SPTHF×VTHF+SPWater×VWater)/(VTHF+VWater)…(2)
SP=10^ ((logSPn+logSPh)/2)…(3)
(wherein, SPTHF=9.1, SPHexane=7.3, SPWater=23.4)
＜ solidifies ＞
When making above-mentioned polyester resin react with above-mentioned firming agent, from opening under conditions of programming rate is 10 DEG C/min
The temperature difference beginning to melt to start solidification is preferably more than 50 DEG C, more preferably 80～100 DEG C.Said temperature difference is less than 50 DEG C
Time, the powder coating composition of the present invention when forming film, the mobility of this powder coating composition is easily reduced, film
Clarities etc. reduce sometimes.Need explanation time, melted start the mixture that temperature (DEG C) is polyester resin and firming agent
Elastic modelling quantity starts temperature when reducing, and solidification starts the elastic modelling quantity that temperature (DEG C) is this mixture and starts temperature when raising
Degree.Therefore, when measuring said temperature difference, need the change measuring polyester resin with the elastic modelling quantity of the mixture of firming agent.
In the mensuration of elastic modelling quantity, use the rheology such as the flow graph ARES that テ ィ エ イ イ Application ス ツルメン ト company manufactures
Instrument, the condition beyond programming rate is the parallel-plate of diameter 40mm, band gap width 1.0mm, frequency 9.42rad/s, strain
1.0%, temperature range 80～200 DEG C.
It addition, start temperature TR in the temperature (DEG C) that above-mentioned fluororesin and above-mentioned firming agent are started reaction as solidification
(A) temperature (DEG C), using above-mentioned polyester resin and above-mentioned firming agent starting to react, as when solidifying beginning temperature TR (B), solidifies
Start temperature TR (A) and solidify temperature difference TR (the B)-TR (A) starting temperature TR (B) preferably more than 15 DEG C, more preferably 20
More than DEG C.When temperature difference TR (B)-TR (A) is less than 20 DEG C, the powder coating composition of the present invention forms layer during film and separate
Property reduces sometimes.
Manufacture method ＞ of ＜ powder coating composition
The manufacture method of the powder coating composition of the present invention is the method preparing above-mentioned powder coating composition, in detail
For, it is characterised in that mix melted at 100～160 DEG C for the above-mentioned mixture containing fluororesin, polyester resin and firming agent
Refining, then, pulverizes after being cooled down by this mixture, prepares powder coating composition.Can preferably by above-mentioned containing fluorine tree
After the mixture of fat, polyester resin and firming agent utilizes Henschel mixer etc. to carry out dry type mixing, use kneader etc. 120
～melting mixing at 140 DEG C, after cooling down, pulverizing, use the golden net etc. of 180 mesh (96 μm) to carry out classification, obtain powder coating group
Compound.
＜ film ＞
The powder coating composition of the present invention is coated with by usual way and installs to such as to comprise window frame for building, for building
On the surface of the base material of the steel such as the carbon steel of the aluminium alloy of plate etc., railway bridge, road bridge, gas tank, Oil Tank, steel tower etc., connect
, in the range of preferably 170～250 DEG C, at a temperature in the range of more preferably 170～210 DEG C, make its melted, solidification, thus shape
Become film.Here, the fluororesin of the powder coating composition of the present invention with polyester resin is incompatible and genetic horizon separates, therefore,
Can be formed and possess fluorine film layer and the film of polyester film layer.By fluororesin and the segregation of polyester resin, lower layer side is (i.e.,
Side near substrate surface) it is polyester film layer, upper layer side (that is, away from the side of substrate surface) is fluorine film layer.It addition,
In the case of using epoxy resin in the powder coating composition of the present invention, epoxy resin is positioned at lower layer side.It addition, additive
It is oriented in the upper layer side of film.
Embodiment
Hereinafter, by embodiment and comparative example, the present invention is illustrated in more detail.
The making ＞ of ＜ polyester resin A
Using the neopentyl glycol 2652g of the alcohol composition as polyester resin, as carboxylic acid composition M-phthalic acid 3966g,
Put into as tetra-n-butyl titanate esters 4.7g of catalysts and possess agitating device, heater, thermometer, fractionating device
With in the stainless steel reaction vessel of nitrogen ingress pipe, in a nitrogen atmosphere while stirring, carry out at 250 DEG C 16 hours
Polycondensation reaction, terminates reaction, obtains polyester resin A when reaching predetermined hydroxyl value.
The making ＞ of ＜ polyester resin B
Using the neopentyl glycol 2496g of the alcohol composition as polyester resin, as carboxylic acid composition M-phthalic acid 4233g,
Put into as tetra-n-butyl titanate esters 4.7g of catalysts and possess agitating device, heater, thermometer, fractionating device
With in the stainless steel reaction vessel of nitrogen ingress pipe, in a nitrogen atmosphere while stirring, carry out at 250 DEG C 16 hours
Polycondensation reaction, terminates reaction, obtains polyester resin B when reaching predetermined acid number.
The making of ＜ powder coating composition and evaluation ＞
According to the formula shown in table 1～3, raw material is mixed, melting mixing at 130 DEG C, by obtained mixture cooling
After pulverize, prepare powder coating composition.
The evaluation ＞ of ＜ powder coating composition
Above-mentioned powder coating composition is carried out various evaluation test.Show the result in table 4～6.
The making ＞ of ＜ bread board
First, in order to carry out the evaluation test of powder coating composition, make bread board.First, by the chromium of thickness of slab 1.5mm
Acid chromate processes aluminium sheet and vertically hangs, and (rising sun サ Na ッ Network company manufactures to use corona charging formula daubing machine of electrostatic powder
PG-1 type), on this aluminium sheet, carry out electrostatic spraying with the voltage of-60kV and make thickness be 60 μm, then, utilize electric furnace 190
DEG C × calcine under conditions of 20 minutes, directly let cool to reaching room temperature, make bread board.
60 ° of mirror surface luster ＞ of ＜
According to JIS K 5600-4-7, use Grossmeters (the miniature TRI Grossmeters (micro-that BYK company manufactures
TRI-gross): enter angle of reflection 60 °) it is measured.
State ＞ of ＜ film
Visually confirm the state of the film coated surface after bread board making.
◎ ... without exception
Zero ... Fructus Citri grandis shape surface
△ ... rough surface
× ... there is foreign body
＜ layer separation property ＞
The film of bread board is cut, utilizes microscope (キ エ Application ス company) that this film cross section is seen
Examine, evaluate whether be separated into the upper and lower inside film.It addition, utilize scanning electron microscope (Hitachi's high-tech company system
The ultrahigh resolution analysis scanning electronic microscope SU-70 made) this film cross section is observed, confirm fluorine by elementary analysis
The element (fluororesin) distribution in film cross section.The fluorine atom being present in film cross section of embodiment 8 will be drawn and
The image obtained is shown in Figure 1.Closeer part in figure is fluorine element (fluororesin) how part, it is known that locally lie in (partially
) in upper strata.
Layer separation property (microscope observation)
Zero ... two separate completely occurs.
△ ... the two separate of local occurs.I.e., although there occurs two separate, but with the fluorine of two separate completely
Thickness is compared, and there is the thickness part less than 1/2.
× ... polyester resin is exposed to upper surface.
Layer separation property (elementary analysis)
Zero ... fluorine element locally lies in upper strata.
△ ... fluorine element locally lies in upper strata, but fluorine element exists in lower floor.
× ... fluorine element is present in whole film.
＜ adaptation ＞
According to JIS K 5600-5-6 (cross-section method), film is cut into the chessboard trellis of 100 pieces that are spaced 1mm, passes through
Paste the adhesive tape after adhesive tape and peel off the stripping evaluating whether to produce film.It addition, about the record in table, denominator represents
Being cut into tessellated piece of number (100), molecule represents that adhesive tape remains in the block number of the film in bread board after peeling off.
＜ resistance to weight falling property ＞
According to JIS K5600-5-3 (Du Pont's formula), in order to the repellence of height of fall 50cm being evaluated for film,
Using center of impact is the weight of 1/2 inch of φ and 500g, observes the rupturing of film, peels off.
＜ boiling water resistance ＞
By bread board dipping 24 hours in ion exchange water (95 ± 5 DEG C), after water-cooled, it is dried, by according to JIS K
The method of 5600-5-6 (cross-section method) evaluates the adaptation of film.It addition, about the record in table, denominator represents and is cut into chessboard
The block number (100) of trellis, molecule represents that adhesive tape remains in the block number of the film in bread board after peeling off.
＜ resistance to mortar ＞
Coating ash paste in the film coated surface of bread board, 50 DEG C, stand 24 hours under the high humidity environment of 95RH%, from
Peel off ash lumps in bread board, use ion exchange water to wash, then, the state of visual valuation film.
＜ resistance to nitric acid ＞
In order to be loaded on the glass cap of 70 mass % aqueous solution of nitric acid, by bread board lid to this vial, make
The film coated surface of bread board is exposed in steam 60 minutes, then, uses ion exchange water to wash, then, utilizes aberration
Meter (CR-300 that ミ ノ Le タ company manufactures) measures dried film coated surface relative to the film coated surface before being exposed to steam
Aberration Δ E.
The resistance to salt acidic ＞ of ＜
The film coated surface of bread board drips 10 10 mass % aqueous hydrochloric acid solutions, covers dial conduct thereon
Lid, after 15 minutes, uses ion exchange water to wash, then, and the state of the dried film of visual valuation.
＜ moisture-proof ＞
By bread board 50 DEG C, place 3000 hours under the high humidity environment of 95RH%, use ion exchange water to wash,
Then, let cool, after drying, the state of visual valuation film.
＜ salt water resistance sprayability ＞
Bread board is placed 3000 hours in bread board under the salt spray environment of 35 DEG C, uses ion exchange water to carry out
Washing, then, lets cool, after drying, the state of visual valuation film.
＜ promotes weatherability ＞
Use the promotion weathering tester according to JIS B 7753 (sunshine weather meter mode), by test period
It is set as 3000 hours, 60 ° of bright luster value conservation rates before test is set as 100%, utilizes gloss meter (miniature TRI light
Pool degree meter, BYK company manufactures: enter angle of reflection 60 °) 60 ° of bright luster value conservation rates after determination test, it addition, utilize aberration
(ミ ノ Le タ company manufactures meter: CR-300) the aberration Δ E before and after determination test.
[table 3]
[table 6]
Hereinafter, the raw material described in table 1～3 is illustrated.
Fluororesin
Asahi Glass Co., Ltd manufactures, trade name: Le ミ Off ロ Application LF710F (fluororesin of hydroxyl), solubility parameter
(SP value) 9.16
Polyester resin A
The polyester resin of hydroxyl, hydroxyl value 45mgKOH/g, number-average molecular weight 3200, weight average molecular weight 13200, dissolubility
Parameter (SP value) 9.99, melt viscosity 3.1Pa s (190 DEG C), is being 200 DEG C and cooling rate based on starting temperature in mensuration
Oblique in the range of 100～120 DEG C in the Arrhenius figure of the melt viscosity (Pa s) measured under conditions of being 10 DEG C/min
Rate is 18425
Polyester resin B
Carboxylic polyester resin, acid number 48mgKOH/g, number-average molecular weight 3900, weight average molecular weight 12300, dissolubility
Parameter (SP value) 9.84, melt viscosity 2.5Pa s (190 DEG C), is being 200 DEG C and cooling rate based on starting temperature in mensuration
Oblique in the range of 100～120 DEG C in the Arrhenius figure of the melt viscosity (Pa s) measured under conditions of being 10 DEG C/min
Rate is 15346
Acrylic resin A
The ARUFON UH-2170 that East Asia synthesis Zhu Shihui company manufactures, the acrylic resin of hydroxyl, the equal molecule of number
Amount 4600, weight average molecular weight 14000, solubility parameter (SP value) 9.19, melt viscosity 4.3Pa s (190 DEG C), based on
Measure start temperature be 200 DEG C and cooling rate be 10 DEG C/min under conditions of the A Lunni of melt viscosity (Pa s) that measures
In Wu Situ, the slope in the range of 100～120 DEG C is 12739
Acrylic resin B
The ARUFON UC-3920 that East Asia synthesis Zhu Shihui company manufactures, carboxylic acrylic resin, the equal molecule of number
Amount 5800, weight average molecular weight 15500, solubility parameter 9.32, melt viscosity 4.8Pa s (190 DEG C), is opening based in mensuration
Beginning temperature be 200 DEG C and cooling rate be 10 DEG C/min under conditions of the Arrhenius figure of melt viscosity (Pa s) that measures
In slope in the range of 100～120 DEG C be 10498
Flitter
Aluminum scale powder, aluminum company of Japan manufactures, trade name: PCF7620A
Coloring pigment
Titanium oxide, E.I.Du Pont Company manufactures, trade name: TI-PURE R-960
Epoxy resin
Toto Kasei KK manufactures, trade name: エ Port ト ト DT-112
Epsilon-caprolactams blocked isocyanate
Isocyanate compound, エ ボ ニ ッ Network デ グ サ company manufactures, trade name: ベ ス タ go Application B1530
Beta-hydroxy alkylamide
エ system ス グ リ ルテック company manufactures, trade name: PRIMID XL-552
Triglycidyl isocyanurate
Ha ンツマン company manufactures, trade name: ARALDITE PT-810
Surface conditioner
BYK-Chemie company manufactures, trade name: BYK-360P
From starting to melt to start the temperature difference of solidification under conditions of programming rate is 10 DEG C/min
In the polyester resin A reaction with epsilon-caprolactams blocked isocyanate (isocyanate compound), in the speed that heats up
Melted beginning temperature (softening point) under conditions of degree is 10 DEG C/min is 95 DEG C, and it is 183 DEG C that solidification starts temperature.
Solidification starts temperature difference TR (B) of temperature TR (A) and solidification beginning temperature TR (B)
Fluororesin and epsilon-caprolactams blocked isocyanate (isocyanate compound) start the solidification of reaction and start temperature
TR (A) is 167 DEG C, and polyester resin A and epsilon-caprolactams blocked isocyanate (isocyanate compound) start the solidification of reaction
Starting temperature TR (B) is 182 DEG C, and temperature difference TR (B)-TR (A) is 15 DEG C.
Claims (6)
1. a powder coating composition, it contains hydroxyl or the polyester resin of the fluororesin of carboxyl, hydroxyl or carboxyl, consolidates
Agent and the flitter of 0.1～30 mass %, it is possible to formed and possess fluorine film layer and the film of polyester film layer,
Described firming agent is epsilon-caprolactams blocked isocyanate,
Described flitter is selected from aluminium powder pigment, nikel powder pigment, bronze, argentum powder, bronze powder, copper powder, stainless steel powder pigment, enters
Gone metal coated glass dust, carried out the mica powder of metal coated, the molding powder having carried out metal coated and flakey oxygen
Change at least one in ferrum pigment,
The hydroxyl value of described fluororesin is 30～70mgKOH/g, and the hydroxyl value of described polyester resin is 30～80mgKOH/g, or,
The acid number of described polyester resin is 30～80mgKOH/g.
2. powder coating composition as claimed in claim 1, it is characterised in that possibly together with epoxy resin.
3. powder coating composition as claimed in claim 1, it is characterised in that the melt viscosity of described polyester resin is
3.5Pa s (190 DEG C) below, and, based on to start temperature be 200 DEG C and bar that cooling rate is 10 DEG C/min measuring
In the Arrhenius figure of the melt viscosity (Pa s) measured under part, the slope in the range of 100～120 DEG C is more than 15000.
4. powder coating composition as claimed in claim 1, it is characterised in that described fluororesin (A) and described polyester resin
(B) mass ratio (A/B) is 50/50～10/90.
5. powder coating composition as claimed in claim 1, it is characterised in that described fluororesin is molten with described polyester resin
The difference of solution degree parameter (SP value) is 0.6～0.9.
6. the method for the powder coating composition according to any one of a manufacturing claims 1～5, it is characterised in that will contain
There is mixture melting mixing at 100～160 DEG C of described fluororesin, described polyester resin and described firming agent, then, should
Pulverize after mixture cooling, prepare powder coating composition.
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| PCT/JP2012/064897 WO2013186832A1 (en) | 2012-06-11 | 2012-06-11 | Powder coating material composition and method for producing same |
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| CN110591514A (en) * | 2018-06-12 | 2019-12-20 | Ａｇｃ株式会社 | Powder coating material and method for producing powder coating material |
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| CN103937382A (en) * | 2014-03-21 | 2014-07-23 | 安徽蓝柯复合材料有限公司 | Coil coating and preparation method thereof |
| CN107429103B (en) * | 2015-03-02 | 2019-12-24 | Ａｇｃ株式会社 | Powder coating material, coated article, and method for producing coated article |
| CN105273581B (en) * | 2015-11-06 | 2017-12-22 | 广州擎天材料科技有限公司 | A kind of high IR rapid curing coil powdery paints and preparation method thereof |
| CN105400317A (en) * | 2015-11-27 | 2016-03-16 | 安徽锦洋氟化学有限公司 | Wet-heat resistant fluorocarbon powder coating |
| CN105400395A (en) * | 2015-11-27 | 2016-03-16 | 安徽锦洋氟化学有限公司 | High-performance PVDF fluorocarbon powder coating |
| WO2017110924A1 (en) * | 2015-12-25 | 2017-06-29 | 旭硝子株式会社 | Powder coating, method for producing powder coating, and coated article |
| EP3401374B1 (en) * | 2016-01-04 | 2020-09-02 | AGC Inc. | Powder coating material, method for producing powder coating material, and coated article |
| BR112019004399A2 (en) | 2016-09-18 | 2019-05-28 | Akzo Nobel Coatings Int Bv | hybrid polyester and fluorocarbon powder coating composition and substrate coating method |
| CN106883694B (en) * | 2017-03-31 | 2021-06-22 | 中山市凯德美氟碳新材料有限公司 | Fluorocarbon powder coating for corrosion prevention of industrial equipment and preparation method thereof |
| JP6298198B1 (en) * | 2017-05-26 | 2018-03-20 | 関西ペイント株式会社 | Powder coating composition |
| CN107254239B (en) * | 2017-06-07 | 2019-05-14 | 扬州彩虹粉末涂料有限公司 | A kind of composite modified fluorine carbon polyester powdery paints and preparation method thereof |
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| WO2011048965A1 (en) * | 2009-10-22 | 2011-04-28 | ダイキン工業株式会社 | Method for producing coated article, and coated article |
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| JP2012041383A (en) * | 2010-08-12 | 2012-03-01 | Dainippon Toryo Co Ltd | Layer separation type matte powder coating composition |
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| CN107011774A (en) * | 2017-04-10 | 2017-08-04 | 立邦涂料（天津）有限公司 | A kind of high rigidity powder paint compositions and its production and use |
| CN110591514A (en) * | 2018-06-12 | 2019-12-20 | Ａｇｃ株式会社 | Powder coating material and method for producing powder coating material |
| CN110591514B (en) * | 2018-06-12 | 2022-02-22 | Ａｇｃ株式会社 | Powder coating material and method for producing powder coating material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104520395A (en) | 2015-04-15 |
| WO2013186832A1 (en) | 2013-12-19 |
| JPWO2013186832A1 (en) | 2016-02-01 |
| SG11201408188VA (en) | 2015-02-27 |
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