CN109385191A - A kind of scratch resistant polyester powder coating of low gloss - Google Patents
A kind of scratch resistant polyester powder coating of low gloss Download PDFInfo
- Publication number
- CN109385191A CN109385191A CN201811276549.8A CN201811276549A CN109385191A CN 109385191 A CN109385191 A CN 109385191A CN 201811276549 A CN201811276549 A CN 201811276549A CN 109385191 A CN109385191 A CN 109385191A
- Authority
- CN
- China
- Prior art keywords
- powder coating
- polyester powder
- scratch resistant
- low gloss
- phenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
- C09D5/033—Powdery paints characterised by the additives
Landscapes
- 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)
Abstract
The invention discloses a kind of scratch resistant polyester powder coatings of low gloss, are related to powder coating technology field, and the polyester powder coating contains coreaction additive, and the coreaction additive is aromatic anhydride.Polyester powder coating of the invention is using a kind of bifunctionality polyester resin containing carboxyl and hydroxyl simultaneously as film forming matter, hydroxyl thereon can be crosslinked with amino resins, carboxyl thereon can be crosslinked with the acrylic resin containing glycidyl, can obtain the polyester powder coating of low-luster；And since aromatic anhydride fusing point is lower, anhydride group can be used as co-reactant and participate in cross-linking reaction in melting process, to be further improved the scratch resistance of powdery paints, resistance to polish performance.
Description
Technical field
The present invention relates to powder coating technology field more particularly to a kind of scratch resistant polyester powder coatings of low gloss.
Background technique
Thermosetting powder coating is a kind of solvent and volatile emissions are zero or few environmental protection coating material, is especially existed
VOC (Volatile Organic Compounds, volatile organic compounds) discharge standard increasingly strict today, meaning
Very great, the market share of thermosetting powder coating just increases year by year.
In certain special field of coating, such as aluminum profile, auto parts and components, metal furniture, hardware, lamps and lanterns and other works
Industry field is required using with high outdoor durable, extremely low gloss and the resistance to powdery paints polished.To meet above-mentioned requirements, study
Personnel propose the powder coating formulation of a variety of adaptations, such as based on containing carboxyl polyester resin and based polyacrylic acid containing glycidol
Resin (GMA resin) and/or TGIC are formed as the low gloss powder coating of curing agent.Hoebeke etc. in US5436311 and
A kind of powdery paints composition of low gloss is disclosed in US5525370, uses methyl methacrylate monomer containing high concentration
The GMA resin and carboxylic polyester resin of composition have low-down gloss as main film forming matter after solidification.Separately
Outside, Muthiah and Umehara etc. also discloses that low gloss powder coating forms in US5684067 and US5491202, the former
It is that (EAA is total for addition polyethylene wax, 2-mercaptobenzothiazole zinc and ethylene-propylene acid copolymer in polyester/TGIC system
Polymers) it is used as delustering agent, minimum gloss about 10%；The latter is then to have used three kinds of polyester with dual extension-compression modulus simultaneously
Resin is solidified with the 2-2400 of same curing agent such as Cargill, it is desirable that three kinds of resins individually with curing agent solidify when its
Curing rate difference is greater than 3min/200 DEG C, and the gloss of obtained solid powder is 5-20%.
However, have the defects that on low gloss powder coating formula disclosed above it is certain, such as US5436311 and
Powdery paints prepared by 5525370, especially black formula show it is excessively poor it is resistance to polish performance, meet in application process
The friction of touch hard object is also easy to produce scratch or applying interlayer and being in contact with each other also can make coating become shinny as polishing.
Low gloss powder coating disclosed in US5684067 has used TGIC and a large amount of polyethylene wax, and TGIC is certified as one already
Kind toxic chemicals, requires stringent field to be limited many, and the wax powders such as a large amount of polyethylene waxes presence but also
It is difficult to handle and process, in addition, required " death ray (dead matte) " degree (gloss < 5% is also not achieved in its gloss
(60°)).For powdery paints disclosed in US5491202, it can satisfy in comparable degree and resistance to polish wanting for performance
It asks, but carries out the manufacture that primary extrusion is used for extinction powder using three kinds of polyester resin with different characteristics simultaneously, process item
Influence of the part to gloss is very big, and usual gloss can drift about to the direction for improving gloss, is difficult to meet the requirement of " death ray ", and cost
It is higher.
Eric Dumain etc. discloses a kind of with the excellent resistance to low gloss powder painting for polishing performance in US6310139
Material composition had both contained carboxyl using a kind of special difunctional polyester resin-this resin or had contained hydroxyl, carboxyl
For the crosslinking of GMA resin, and hydroxyl has used the closed polyisocyanate curing agent of IPDI, gloss 4%, from technical standpoint
It says, this scheme is very perfect, but special resin used is difficult to commercially obtain, and furthermore uses the closed poly- isocyanide of IPDI
Acid esters is also uneconomic as co-curing agent.Therefore develop it is a kind of it is economical, do not need to use special type polyester resin and solid
Agent and have simultaneously extremely low gloss, fabulous outdoor durable and it is resistance to polish performance powdery paints composition be highly desirable
's.
Therefore provide a kind of scratch resistance of economy, the resistance to powder painting for polishing performance, extremely low gloss, fabulous outdoor durable
Material is and its needs.
Summary of the invention
Technical problems based on background technology, the invention proposes a kind of scratch resistant polyester powders of low gloss to apply
Material, using a kind of bifunctionality polyester resin containing carboxyl and hydroxyl simultaneously as film forming matter, with amino resins and containing shrink
Glyceryl acrylic resin is as curing agent, and powdery paints obtained is with compared with low gloss, fabulous outdoor durable
With excellent flow leveling, and aromatic anhydride participates in cross-linking reaction as co-reactant, is further improved the anti-of powdery paints
It scratches, resistance to polish performance.
The scratch resistant polyester powder coating of a kind of low gloss proposed by the present invention, it is described anti-altogether containing coreaction additive
Answering additive is aromatic anhydride.
Preferably, the coreaction additive is cyclic aromatic acid anhydrides or/and chain aromatic anhydride.
Preferably, the structural formula of the cyclic aromatic acid anhydrides is as follows:
Wherein, R1 is selected from the straight chained alkyl of H or C1-C5 or the branched alkyl of C1-C5；Preferably, the cyclic aromatic
Fusing point≤135 DEG C of acid anhydrides.
Preferably, the structural formula of the chain aromatic anhydride is as follows:
Wherein, R2For phenyl or alkyl-substituted phenyl, R3For phenyl or alkyl-substituted phenyl, it is preferable that the alkyl replaces
Phenyl is that contraposition substituent methyl phenyl, ortho position substitution aminomethyl phenyl, contraposition replace ethylphenyl, ortho position substitution ethylphenyl, right
Position substituted propyl phenyl, ortho position substitution propyl phenyl, contraposition replace isopropyl phenyl, any in ortho position substitution isopropyl phenyl
One kind, preferably R2For phenyl, R3For phenyl；Preferably, fusing point≤90 DEG C of the chain aromatic anhydride.
Preferably, additive amount of the coreaction additive in coating is 0.5-10wt%；It is preferred that 0.7-1.5wt%.
Preferably, the raw material of the polyester powder coating is by weight percentage, comprising: at the same it is double containing carboxyl and hydroxyl
Degree of functionality polyester resin 40-60%, amino resins 2-6%, acrylic resin 14-23%, aromatic acid containing glycidyl
Acid anhydride 0.5-10%, catalyst 0.2-1%, auxiliary agent and/or colorant 0-40%；Preferably, raw material by weight percentage, wraps
Include: at the same bifunctionality polyester resin 40-50% containing carboxyl and hydroxyl, amino resins 2-4%, containing the propylene of glycidyl
Acid resin 15-20%, aromatic anhydride 0.7-1.5%, catalyst 0.3-0.6%, auxiliary agent and/or colorant 28-36%.
Preferably, the weight average molecular weight of bifunctionality polyester resin described while containing carboxyl and hydroxyl is 1000-
40000, preferably 1500-10000, are more highly preferred to 3000-6000；Glass transition temperature be 40-80 DEG C, preferably 45-65 DEG C, more
It is preferred 50-65 DEG C；Acid value is 10-100mgKOH/g, preferably 20-80mgKOH/g, is more highly preferred to 25-40mgKOH/g；Hydroxyl value
For 10-100mgKOH/g, preferably 20-80mgKOH/g, it is more highly preferred to 25-40mgKOH/g.
Herein, while the bifunctionality polyester resin containing carboxyl and hydroxyl is the tree as made of polyacid and polyol condensating
Rouge, polyacid can be terephthalic acid (TPA), M-phthalic acid, Isosorbide-5-Nitrae-cyclohexyldicarboxylic acids, adipic acid, maleic acid, succinic acid, inclined benzene
One of tricarboxylic acid is a variety of, and polyalcohol can be ethylene glycol, diethylene glycol (DEG), propylene glycol, hexylene glycol, neopentyl glycol, cyclohexyl two
One of methanol, trimethylolpropane are a variety of.The resin for meeting above-mentioned condition can be obtained by commercially available approach, such as be pacified
The trade mark SJ4229 product of Hui Shenjian new material limited liability company, acid value 30-36mgKOH/g, hydroxyl value 15-
30mgKOH/g, Tg >=63.0 DEG C, the trade mark YC3030 product of Anhui Yongchang new material Co., Ltd, acid value 27-
36mgKOH/g, hydroxyl value 25-30mgKOH/g, Tg >=63.0 DEG C.
Preferably, the amino resins is one of melamine resin, alkoxylated glycoluril resin or more
Kind, preferably hexamethoxymethyl melamine or tetramethoxymethylglycoluril or combinations thereof.
Preferably, the epoxide equivalent of the acrylic resin containing glycidyl is less than 1000, and preferably smaller than 750, more
It is preferably less than 550；Glass transition temperature is 30-110 DEG C, preferably 45-70 DEG C；Number-average molecular weight is 1000-20000, excellent
2000-10000 is selected, 2000-5000 is more highly preferred to.
Herein, the preparation of the acrylic resin containing glycidyl is will to contain epoxy based monomers to be added to acrylic ester copolymer
In monomer made from copolymerization, the structural formula containing epoxy based monomers is as follows:
Wherein, containing R in epoxy based monomers1、R2Selected from H, methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, uncle
Any one in butyl, preferably R1For H or methyl, more preferably methyl, preferably R2For H；Preferably, the acrylic acid is total
Polycondensation monomer includes methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl, first
Base n-propyl, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-BMA, third
Olefin(e) acid isobutyl ester, Isobutyl methacrylate, tert-butyl acrylate, Tert-butyl Methacrylate, 2-EHA, first
Base 2-EHA, 2-ethyl hexyl acrylate, 2-Propenoic acid, 2-methyl-, octyl ester, dodecylacrylate, methacrylic acid 12
At least one of Arrcostab, benzyl acrylate, benzyl methacrylate；Preferably, the acrylate co-monomers
In further include vinyl monomer, optimal ethylene base class monomer is one or both of styrene or methyl styrene；It is preferred that
Ground, with the total weight containing epoxy based monomers and acrylate co-monomers, wherein the weight percent containing epoxy based monomers is
15-70%, the weight percent of acrylic comonomers are 30-85%；Preferably, the weight percent containing epoxy monomer is
25-50%, the weight percent of acrylic comonomers are 50-75%.
Herein, the preparation method of glycidyl acrylic resin is required without special, using the prior art.
Usually used copolymerization process includes bulk polymerization, dissociate the methods of radical solution polymerization, emulsion polymerization and suspension polymerisation, wherein with
Free radical solution polymerization process is more preferred；It also needs that initiator is added in polymerization process, the initiator includes but not only limits
In one of azodiisobutyronitrile, dibenzoyl peroxide, tert-butyl hydroperoxide and cumyl peroxide etc., wherein with
Dibenzoyl peroxide, cumyl peroxide are preferred.
The acrylic resin containing glycidyl for meeting above-mentioned condition can be obtained by commercially available approach, such as U.S.
The AHA7550 of Isocryl EP550 of Estron company, 560 and 570 and AHA International, 7570 and 7700
Deng.
Herein, catalyst is acidic catalyst；Sulfonic acid can be closed for organic sulfonic acid strong acid, imines sulphonyl type catalyst, amine
One of or it is a variety of.
Wherein, the organic sulfonic acid strong acid includes p-methyl benzenesulfonic acid, dinonylnaphthalene sulfonic acid, one in dodecyl benzene sulfonic acid
Kind is a variety of；The imines sulphonyl type catalyst includes two benzenesulfonimides, N- (mesyl)-p- tolylsulfonyl- amine；Institute
Stating amine closing sulfonic acid is that ammonia or amine component are obtained with sulfonic acid component reaction, wherein ammonia or amine component include methyl amine, dimethyl
Amine, Trimethylamine, ethamine, propylamine, di-n-propylamine, butylamine, triethylamine, dibutylamine, benzyl amine, ethanol amine, dimethyl ethanol
Amine, N, one of N- diethyl ethylene diamine, diisopropanolamine (DIPA) or a variety of；Sulfonic acid component includes p-methyl benzenesulfonic acid, o- nitrobenzene
Sulfonic acid, m- nitrobenzene-sulfonic acid, p- nitrobenzene-sulfonic acid, nitrobenzene -2,4- disulfonic acid, 2- nitrotoleune base -3- sulfonic acid, ortho position sulphur
One of yl benzoic acid, sulfosalicylic acid, sulfosalicylic phthalate, 2,4- dinitrobenzene sulfonic acid, 3,5- dinitrobenzene sulfonic acid
Or it is a variety of；It is preferred that p-methyl benzenesulfonic acid, o- nitrobenzene-sulfonic acid, m- nitrobenzene-sulfonic acid, p- nitrobenzene-sulfonic acid, nitrobenzene -2,4- two
One of sulfonic acid, ortho position sulfosalicylic acid, sulfosalicylic acid are a variety of.
The amine closing sulfonic acid or imines sulphonyl type catalyst for meeting above-mentioned condition can also be obtained by commercially available approach, such as
The Escat 320 of Estron, Sythron'sThe AHA6319 of X-320, MTSI of 32-18A, Allnex, AHA,
AHA6328。
Auxiliary agent of the invention includes one of levelling agent, plasticizer, stabilizer, degasifier, filler or a variety of.
The invention also provides a kind of aromatic anhydrides to be used for the scratch resistant polyester powder coating of above-mentioned low gloss.
The preparation method of the above-mentioned scratch resistant polyester powder coating of low gloss: by all raw materials be placed in high-speed mixer into
Row dry-mixing, is then transferred in extruder, obtains after heat fusing mixing, tabletting, crushing, sieving.Wherein, it crushed
80-200 mesh, preferably 100-180 mesh, are more highly preferred to 140-180 mesh.
The construction method of the above-mentioned scratch resistant polyester powder coating of low gloss: can be sprayed by powder static gun, friction rifle,
The methods of fluidized bed dipping, heat fusing sintering are adhered to it on grounds such as metal, and then heating or radiation curing form film.
The utility model has the advantages that the powdery paints is to use the present invention provides a kind of low gloss scratch resistant polyester powder coating
Contain the bifunctionality polyester resin of carboxyl and hydroxyl as film forming matter, with amino resins and containing the acrylic acid of glycidyl
Resin is as curing agent, and under the effect of the catalyst, amino resins is handed over the hydroxylic moiety on bifunctionality polyester resin
Connection, the acrylic resin containing glycidyl are crosslinked with the carboxy moiety on bifunctionality polyester resin, instead due to two kinds
The reaction speed answered is different, to generate good extinction effect, obtains the polyester powder coating of low-luster.The present invention also public affairs
A kind of additive aromatic anhydride is opened, is added in above-mentioned polyester powder coating, since its fusing point is lower, in melting process
Middle anhydride group can be used as co-reactant and participate in cross-linking reaction, to be further improved the scratch resistance of powdery paints, resistance to polish
Performance.
Specific embodiment
In the following, technical solution of the present invention is described in detail by specific embodiment.
Embodiment 1
The present invention proposes a kind of scratch resistant polyester powder coating of low gloss, and raw material is by weight percentage, comprising: same
When bifunctionality polyester resin 60% containing carboxyl and hydroxyl, amino resins 6%, containing the acrylic resin of glycidyl
23%, aromatic anhydride 10%, catalyst 1%.
Wherein, the aromatic anhydride is 3- methyl phthalic anhydride.
Wherein, while the weight average molecular weight of the bifunctionality polyester resin containing carboxyl and hydroxyl is 1000, glass transition
Temperature Tg is 40 DEG C, acid value 27-35mgKOH/g, hydroxyl value 25-32mgKOH/g.
Wherein, amino resins is tetramethoxymethylglycoluril.
Wherein, for the epoxide equivalent of the acrylic resin containing glycidyl less than 1000, glass transition temperature is 30 DEG C,
Number-average molecular weight is 1000.
Wherein, catalyst is organic sulfonic acid strong acid.
The preparation method of the above-mentioned scratch resistant polyester powder coating of low gloss: by all raw materials be placed in high-speed mixer into
Row dry-mixing, is then transferred in extruder, obtains after heat fusing mixing, tabletting, crushing, sieving.
The construction method of the above-mentioned scratch resistant polyester powder coating of low gloss: can be sprayed by powder static gun, friction rifle,
The methods of fluidized bed dipping, heat fusing sintering are adhered to it on grounds such as metal, and then heating or radiation curing form film.
Embodiment 2
The present invention proposes a kind of scratch resistant polyester powder coating of low gloss, and raw material is by weight percentage, comprising: same
When bifunctionality polyester resin 40% containing carboxyl and hydroxyl, amino resins 2%, containing the acrylic resin of glycidyl
14%, aromatic anhydride 3.8%, catalyst 0.2%, auxiliary agent 38%, colorant 2%.
Wherein, the aromatic anhydride is 4- t-butyl phthalic anhydride.
Wherein, while the bifunctionality polyester resin containing carboxyl and hydroxyl is the tree as made of polyacid and polyol condensating
Rouge, the weight average molecular weight of the resin are 40000, and glass transition temperature is 80 DEG C, acid value 25-30mgKOH/g, and hydroxyl value is
20-26mgKOH/g。
Wherein, amino resins is tetramethoxymethylglycoluril.
Wherein, the acrylic resin containing glycidyl is will to contain epoxy based monomers to be added in acrylate co-monomers
Made from copolymerization, the epoxide equivalent of the resin is less than 750, and glass transition temperature is 110 DEG C, number-average molecular weight 20000.
Wherein, catalyst is imines sulphonyl type catalyst.
Wherein, auxiliary agent includes levelling agent, plasticizer, filler.
Wherein, colorant is organic pigment phthalocyanine blue.
The preparation method of the above-mentioned scratch resistant polyester powder coating of low gloss: by all raw materials be placed in high-speed mixer into
Row dry-mixing, is then transferred in extruder, obtains after heat fusing mixing, tabletting, crushing, sieving.
The construction method of the above-mentioned scratch resistant polyester powder coating of low gloss: can be sprayed by powder static gun, friction rifle,
The methods of fluidized bed dipping, heat fusing sintering are adhered to it on grounds such as metal, and then heating or radiation curing form film.
Embodiment 3
The present invention proposes a kind of scratch resistant polyester powder coating of low gloss, and raw material is by weight percentage, comprising: same
When bifunctionality polyester resin 40% containing carboxyl and hydroxyl, amino resins 2%, containing the acrylic resin of glycidyl
20%, aromatic anhydride 1.5%, catalyst 0.5%, auxiliary agent 36%.
Wherein, the aromatic anhydride is 4- methyl phthalic anhydride.
Wherein, while the bifunctionality polyester resin containing carboxyl and hydroxyl is the tree as made of polyacid and polyol condensating
Rouge, the weight average molecular weight of the resin are 2000, and glass transition temperature is 45 DEG C, acid value 20-26mgKOH/g, hydroxyl value 22-
27mgKOH/g。
Wherein, amino resins is tetramethoxymethylglycoluril.
Wherein, the acrylic resin containing glycidyl is will to contain epoxy based monomers to be added in acrylate co-monomers
Made from copolymerization, the epoxide equivalent of the resin is less than 550, and glass transition temperature is 45 DEG C, number-average molecular weight 2000.
Wherein, catalyst is that amine closes sulfonic acid.
Wherein, auxiliary agent includes levelling agent, plasticizer, degasifier, filler.
The preparation method of the above-mentioned scratch resistant polyester powder coating of low gloss: by all raw materials be placed in high-speed mixer into
Row dry-mixing, is then transferred in extruder, obtains after heat fusing mixing, tabletting, crushing, sieving.
The construction method of the above-mentioned scratch resistant polyester powder coating of low gloss: can be sprayed by powder static gun, friction rifle,
The methods of fluidized bed dipping, heat fusing sintering are adhered to it on grounds such as metal, and then heating or radiation curing form film.
Embodiment 4
The present invention proposes a kind of scratch resistant polyester powder coating of low gloss, and raw material is by weight percentage, comprising: same
When bifunctionality polyester resin 50% containing carboxyl and hydroxyl, amino resins 4%, containing the acrylic resin of glycidyl
15%, aromatic anhydride 0.7%, catalyst 0.3%, auxiliary agent 29.5%, colorant 0.5%.
Wherein, the aromatic anhydride is paratolunitrile acid anhydride.
Wherein, while the weight average molecular weight of the bifunctionality polyester resin containing carboxyl and hydroxyl is 10000, glass transition
Temperature is 65 DEG C, acid value 35-40mgKOH/g, hydroxyl value 30-36mgKOH/g.
Wherein, amino resins is tetramethoxymethylglycoluril.
Wherein, for the epoxide equivalent of the acrylic resin containing glycidyl less than 550, glass transition temperature is 70 DEG C；
Number-average molecular weight is 15000.
Wherein, catalyst is that amine closes sulfonic acid.
Auxiliary agent of the invention includes levelling agent, plasticizer, stabilizer, degasifier, filler.
The preparation method of the above-mentioned scratch resistant polyester powder coating of low gloss: by all raw materials be placed in high-speed mixer into
Row dry-mixing, is then transferred in extruder, obtains after heat fusing mixing, tabletting, crushing, sieving.
The construction method of the above-mentioned scratch resistant polyester powder coating of low gloss: can be sprayed by powder static gun, friction rifle,
The methods of fluidized bed dipping, heat fusing sintering are adhered to it on grounds such as metal, and then heating or radiation curing form film.
Embodiment 5
The present invention proposes a kind of scratch resistant polyester powder coating of low gloss, and raw material is by weight percentage, comprising: same
When bifunctionality polyester resin 48% containing carboxyl and hydroxyl, amino resins 3.5%, containing the acrylic resin of glycidyl
16.8%, aromatic anhydride 1.2%, catalyst 0.5%, auxiliary agent 29%, colorant 1%；Wherein, while containing carboxyl and hydroxyl
Bifunctionality polyester resin is the YC3030 product in Anhui Yongchang, and amino resins is tetramethoxymethylglycoluril, contains glycidol
The acrylic resin of base is the Isocryl EP550 of Estron company, and aromatic anhydride is phthalic anhydride, and catalyst is
The X-320 of Allnex.
The preparation method of the above-mentioned scratch resistant polyester powder coating of low gloss: by all raw materials be placed in high-speed mixer into
Row dry-mixing, is then transferred in extruder, obtains after heat fusing mixing, tabletting, crushing, sieving.
The construction method of the above-mentioned scratch resistant polyester powder coating of low gloss: can be sprayed by powder static gun, friction rifle,
The methods of fluidized bed dipping, heat fusing sintering are adhered to it on grounds such as metal, and then heating or radiation curing form film.
Embodiment 6
The present invention proposes a kind of scratch resistant polyester powder coating of low gloss, and raw material is by by weight, comprising: contains simultaneously
250 parts of bifunctionality polyester resin SJ4229 (Anhui mind sword), the amino resins tetramethoxymethylglycoluril of carboxyl and hydroxyl
13.5 parts of AHA1209 (Anhui Huaan), 90 parts of acrylic resin AHA7570 (Anhui Huaan), benzoic acid containing glycidyl
5 parts of acid anhydride, 2 parts of catalyst AHA6328 (Anhui Huaan), 5 parts of levelling agent AHA1088P (Anhui Huaan), styrax AHA4100 (peace
Emblem Huaan) 5 parts, 175 parts of native sulfate of barium W44 (Guizhou Hua Jia), 3 parts of carbon black.
The preparation method of the above-mentioned scratch resistant polyester powder coating of low gloss: each raw material is placed in hand mix in polybag
3-5 minutes, twin-screw test melting homogenizing, tabletting, cooling, stone roller in extruder (model: SLJ-30A, Yantai east brightness) is added
Wear into fine powder, sieving by 180 mesh to get.
Embodiment 7
Compared with Example 1, difference is only that the additive amount of benzoyl oxide is 11 parts, the acrylic acid tree containing glycidyl
108 parts of rouge AHA7570 (Anhui Huaan), remaining is all the same.
Embodiment 8
Compared with Example 1, difference is only that the additive amount of benzoyl oxide is 17 parts, the acrylic acid tree containing glycidyl
126 parts of rouge AHA7570 (Anhui Huaan), remaining is all the same.
Embodiment 9
The present invention proposes a kind of scratch resistant polyester powder coating of low gloss, and raw material is by by weight, comprising: contains carboxyl
Bifunctionality polyester resin with hydroxyl while the bifunctionality polyester resin SJ4229 (Anhui mind sword) 250 containing carboxyl and hydroxyl
Part, 13.5 parts of amino resins tetramethoxymethylglycoluril AHA1209 (Anhui Huaan), the acrylic resin containing glycidyl
90 parts of AHA7570 (Anhui Huaan), 5 parts of phthalic anhydride, 2 parts of catalyst AHA6328 (Anhui Huaan), (Anhui levelling agent AHA1088P
Huaan) 5 parts, 5 parts of styrax AHA4100 (Anhui Huaan), 175 parts of native sulfate of barium W44 (Guizhou Hua Jia), 3 parts of carbon black.
The preparation method of the above-mentioned scratch resistant polyester powder coating of low gloss: each raw material is placed in hand mix in polybag
3-5 minutes, twin-screw test melting homogenizing, tabletting, cooling, stone roller in extruder (model: SLJ-30A, Yantai east brightness) is added
Wear into fine powder, sieving by 180 mesh to get.
Embodiment 10
Compared with Example 1, difference is only that the additive amount of phthalic anhydride is 11 parts, the acrylic resin containing glycidyl
The additive amount of AHA7570 (Anhui Huaan) is 119 parts, remaining is all the same.
Embodiment 11
Compared with Example 1, difference is only that the additive amount of phthalic anhydride is 11 parts of acrylic resins containing glycidyl
The additive amount of AHA7570 (Anhui Huaan) is 143 parts, remaining is all the same.
Comparative example 1
Compared with Example 1, difference, which is only that, does not add benzoyl oxide, the acrylic resin containing glycidyl
The additive amount of AHA7570 (Anhui Huaan) is 75 parts, remaining is all the same.
The performance of polyester powder coating obtained in the embodiment of the present invention is measured.
One, pilot project:
The preparation of sample: by polyester obtained/GMA powder coating electrostatic spraying on degreasing cold-rolled steel sheet, 200 DEG C/15
Minute solidification, is then tested by following test method, test result is shown in Table 1.
1. coating thickness
With magnetic thickness measuring instrument, (QNix4500 of Automation Dr.Nix GmbH company, thickness measuring instrument Germany is straight
It connects and measures.
2. appearance
Detect by an unaided eye: surfacing no significant defect is denoted as zero, has light defects to be denoted as △, has obvious shortcoming to be calculated as
×。
3. gloss
It is carried out by GB/T1743-89 standard, 60 ° of reflectivity, using Micro-gloss60 ° 4442 of German BYK company
Directly measure.
4. impact strength
It carries out by GB/T1732-88 standard, is carried out with hammer impact resistance analyzer.Wherein 50Kgcm is just recoiling by being designated as
50+, square impact is by being designated as 50, and so on.
5. levelling
It detects by an unaided eye and carries out PCI classification, wherein 10 is best, 0 is worst.
6. adhesive force
It is carried out by GB/T9286-1998 standard, 6 grades of partition of the level, 0 is best, and 5 is worst.
7. color difference
It is directly measured with BGD-551 type color difference meter, is indicated with △ E.The expression of △ E < 5 well, be denoted as zero, > 5- < 10 it
Between indicate general, be denoted as △, the expression of > 10 is poor, be calculated as ×.
8. hardness
It carries out, is tested with BGD-506 type trolley type pencil hardometer, hardness is divided by GB/T 9286-2007 standard
19 grades such as 9H-H, HB, B-9B, wherein 9H is most hard, and 9B is most soft.
9. scratch resistance
It selects 4H pencil to be tested with BGD-506 type trolley type pencil hardometer, observation classification visually is carried out to scratch,
6 grades of partition of the level, wherein 0 is best, 5 be worst.
10. resistance to polish
It is rubbed with common A4 paper to specimen surface, observation classification, partition of the level 6 visually is carried out to the space of a whole page after friction
A grade, wherein 0 is best, 5 be worst.
Two, test result
The performance test results of 1 polyester powder coating of table
From table 1 it follows that the addition of aromatic anhydride can effectively improve hardness, the scratch resistance of film coated surface with
And it is resistance to polish characteristic, but will appear negative effect instead when its adding too much.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of scratch resistant polyester powder coating of low gloss, which is characterized in that containing coreaction additive, the coreaction adds
Adding object is aromatic anhydride.
2. the scratch resistant polyester powder coating of low gloss according to claim 1, which is characterized in that the coreaction addition
Object is cyclic aromatic acid anhydrides or/and chain aromatic anhydride.
3. the scratch resistant polyester powder coating of low gloss according to claim 2, which is characterized in that the cyclic aromatic
The structural formula of acid anhydrides is as follows:
Wherein, R1 is selected from the straight chained alkyl of H or C1-C5 or the branched alkyl of C1-C5；Preferably, the cyclic aromatic acid anhydrides
Fusing point≤135 DEG C.
4. the scratch resistant additive of improvement polyester powder coating gloss according to claim 2, which is characterized in that the chain
The structural formula of shape aromatic anhydride is as follows:
Wherein, R2For phenyl or alkyl-substituted phenyl, R3For phenyl or alkyl-substituted phenyl, it is preferable that the alkyl-substituted phenyl
Ethylphenyl, ortho position substitution ethylphenyl, contraposition is replaced to take for contraposition substituent methyl phenyl, ortho position substitution aminomethyl phenyl, contraposition
For any one in propyl phenyl, ortho position substitution propyl phenyl, contraposition substitution isopropyl phenyl, ortho position substitution isopropyl phenyl
Kind, preferably R2For phenyl, R3For phenyl；Preferably, fusing point≤90 DEG C of the chain aromatic anhydride.
5. the scratch resistant polyester powder coating of low gloss according to claim 1-4, which is characterized in that described total
Reacting additive amount of the additive in coating is 0.5-10wt%；It is preferred that 0.7-1.5wt%.
6. the scratch resistant polyester powder coating of low gloss according to claim 1-5, which is characterized in that described poly-
The raw material of ester powdery paints is by weight percentage, comprising: while the bifunctionality polyester resin 40- containing carboxyl and hydroxyl
60%, amino resins 2-6%, the acrylic resin 14-23% containing glycidyl, aromatic anhydride 0.5-10%, catalyst
0.2-1%, auxiliary agent and/or colorant 0-40%；Preferably, raw material is by weight percentage, comprising: while containing carboxyl and hydroxyl
Bifunctionality polyester resin 40-50%, amino resins 2-4%, acrylic resin 15-20%, the virtue containing glycidyl of base
Fragrant race's acid anhydrides 0.7-1.5%, catalyst 0.3-0.6%, auxiliary agent and/or colorant 28-36%.
7. the scratch resistant polyester powder coating of low gloss according to claim 6, which is characterized in that it is described and meanwhile contain carboxyl
Weight average molecular weight with the bifunctionality polyester resin of hydroxyl is 1000-40000, and preferably 1500-10000 is more highly preferred to 3000-
6000；Glass transition temperature is 40-80 DEG C, preferably 45-65 DEG C, is more highly preferred to 50-65 DEG C；Acid value is 10-100mgKOH/g,
It is preferred that 20-80mgKOH/g, is more highly preferred to 25-40mgKOH/g；Hydroxyl value is 10-100mgKOH/g, preferably 20-80mgKOH/g, more
For preferred 25-40mgKOH/g.
8. the scratch resistant polyester powder coating of the described in any item low gloss of according to claim 6 or 7, which is characterized in that described
Amino resins is one of melamine resin, alkoxylated glycoluril resin or a variety of, preferably hexa methoxy first
Base melamine or tetramethoxymethylglycoluril or combinations thereof.
9. according to the scratch resistant polyester powder coating of the described in any item low gloss of claim 6-8, which is characterized in that described to contain
The epoxide equivalent of the acrylic resin of glycidyl is less than 1000, and preferably smaller than 750, it is more highly preferred to less than 550；Vitrifying turns
Changing temperature is 30-110 DEG C, preferably 45-70 DEG C；Number-average molecular weight is 1000-20000, preferably 2000-10000, is more highly preferred to
2000-5000。
10. a kind of application of aromatic anhydride in polyester powder coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811276549.8A CN109385191A (en) | 2018-10-30 | 2018-10-30 | A kind of scratch resistant polyester powder coating of low gloss |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811276549.8A CN109385191A (en) | 2018-10-30 | 2018-10-30 | A kind of scratch resistant polyester powder coating of low gloss |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109385191A true CN109385191A (en) | 2019-02-26 |
Family
ID=65427175
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811276549.8A Withdrawn CN109385191A (en) | 2018-10-30 | 2018-10-30 | A kind of scratch resistant polyester powder coating of low gloss |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109385191A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112708332A (en) * | 2020-12-29 | 2021-04-27 | 老虎表面技术新材料（苏州）有限公司 | Weather-resistant high-temperature-resistant powder coating composition |
| WO2022143404A1 (en) * | 2020-12-29 | 2022-07-07 | 老虎表面技术新材料（苏州）有限公司 | Extinction ultralow-temperature curing powder coating composition and coating layer thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6310139B1 (en) * | 1999-08-31 | 2001-10-30 | Reichhold, Inc. | Burnish resistant powder coating compositions |
| CN103509437A (en) * | 2013-09-04 | 2014-01-15 | 安徽东方金河精密机械制造有限公司 | Indoor decorative metal powder paint |
-
2018
- 2018-10-30 CN CN201811276549.8A patent/CN109385191A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6310139B1 (en) * | 1999-08-31 | 2001-10-30 | Reichhold, Inc. | Burnish resistant powder coating compositions |
| CN103509437A (en) * | 2013-09-04 | 2014-01-15 | 安徽东方金河精密机械制造有限公司 | Indoor decorative metal powder paint |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112708332A (en) * | 2020-12-29 | 2021-04-27 | 老虎表面技术新材料（苏州）有限公司 | Weather-resistant high-temperature-resistant powder coating composition |
| WO2022143404A1 (en) * | 2020-12-29 | 2022-07-07 | 老虎表面技术新材料（苏州）有限公司 | Extinction ultralow-temperature curing powder coating composition and coating layer thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO1996034063A1 (en) | Coating composition, process for preparing the composition, and process for preparing dispersion of inorganic oxide sol | |
| CN109486373A (en) | A kind of weather resistant low brightness pool powdery paints | |
| JPH07224146A (en) | Curable resin composition, coating composition and method for forming film | |
| JP4836542B2 (en) | Paint composition | |
| CN109385191A (en) | A kind of scratch resistant polyester powder coating of low gloss | |
| KR101638407B1 (en) | Acryl-based semi-matt powder coating composition with high transparency | |
| CN109401573A (en) | A kind of polyester/GMA powdery paints | |
| CN112409868B (en) | Powder coating with ice flower texture effect | |
| US3753935A (en) | Nonyellowing acrylic enamel containing an acid phosphate catalyst | |
| JP7011556B2 (en) | Coating composition and method for forming a multi-layer coating film | |
| JP2013221131A (en) | Pigment dispersing resin | |
| JP2533117B2 (en) | Resin composition for paint | |
| CN111763443B (en) | Powder coating matting agent and application thereof in matting powder coating | |
| US20240218203A1 (en) | Hydroxyalkylamide- based coating compositions | |
| RU2676633C1 (en) | Agent for pigmented coating and produced therefrom coatings | |
| CN107151475A (en) | A kind of powdery paints dry-mixed additive and its powdery paints of offer grain effect | |
| KR101719667B1 (en) | Low density putty composition for repairing vehicles | |
| JPH0978010A (en) | Thermosetting powder coating composition | |
| JPH0479391B2 (en) | ||
| JP2533121B2 (en) | Resin composition for paint | |
| JP2003026989A (en) | Thermosetting powder coating composition | |
| KR100805653B1 (en) | Low Aqueous Non-Aqueous Dispersion-Acrylic Urethane Coating Composition | |
| JP2009286887A (en) | Glossy electrodeposition coating composition excellent in low staining properties | |
| JPH07113102B2 (en) | Resin composition for water-based paint | |
| JPS644831B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20190226 |