CN107151475A - A kind of powdery paints dry-mixed additive and its powdery paints of offer grain effect - Google Patents
A kind of powdery paints dry-mixed additive and its powdery paints of offer grain effect Download PDFInfo
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- CN107151475A CN107151475A CN201710461439.8A CN201710461439A CN107151475A CN 107151475 A CN107151475 A CN 107151475A CN 201710461439 A CN201710461439 A CN 201710461439A CN 107151475 A CN107151475 A CN 107151475A
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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
- C09D5/033—Powdery paints characterised by the additives
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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
- C09D5/28—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for wrinkle, crackle, orange-peel, or similar decorative effects
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
- C08K5/3447—Five-membered rings condensed with carbocyclic rings
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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
- C08L2312/00—Crosslinking
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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
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
Abstract
The invention discloses it is a kind of can as dry-mixed purposes additive, and be made up of the powdery paints with snake or moire effect that it and another bottom powder with textural characteristics are constituted.Dry-mixed additive is also in itself a kind of powdery paints constituent and has plane high glaze, is configured to one or more hydroxy polyester resins, amino resin crosslinking agent, sulfonic acid imide-type catalyst, levelling agent/degasifier and color stuffing substantially.Powdery paints with snake or moire effect is made up of above-mentioned dry-mixed additive and bottom powder, and the two is made up of the moire and snake powdery paints of the present invention dry-mixing, and the weight ratio of bottom powder and dry-mixed additive is 1：0.0001 1, preferably 1：0.01 0.1, more preferably 1：0.02‑0.05.The present invention compared with prior art, improves impact property and the stability of pattern, and the decorative effect of coating is also more preferably.
Description
Technical field
The present invention relates to powder coating technology field, more particularly to a kind of powdery paints is with dry-mixed additive and its provides line
Manage the powdery paints of effect.
Background technology
Thermosetting powder coating be a kind of solvent and volatile emissions without or few environment-friendly type coating, particularly
With VOC (Volatile Organic Compounds, VOC) discharge standard increasingly strict today, its
Meaning is very great, and the market share just increases year by year.
Thermosetting powder coating is mainly added by functional film former's resin, curing agent, levelling agent, face/filler, one or more
Plus agent (auxiliary agent), surface style agent and other performance improvement agents etc. are constituted.Preparation process is generally comprised all components together
High-speed mixer for dry mixing conjunction is placed in, then passes through the steps such as suitable extruder heat fusing mixing, tabletting, crushing and sieving.
The powdery paints being so made can be such that it sticks on ground by powder static gun, the spraying of friction rifle or fluidized bed dipping,
Typically metallic surface, is then heated or radiation curing formation film.
There is high glaze and the decorative effect of plane typically by the coating obtained by above step.But,
Some special application fields tend to use with grain decorating effect specific coatings, for example metal prized up-proof door, safety cabinet,
Hardware ＆ tools and office appliance etc..Why make such requirement, be on the one hand in order at aesthetic needs of viewing and admiring, on the other hand
Be also due to texture powdery paints generally has more preferable flaw tolerance than plane highlight type powder in itself.That is for
The coated article of large surface application is wanted, texture can cover its surface defect well to avoid spraying from failing.If without spy
Different requirement, in some special application field texture type powdery paints, especially wrinkle, moire and snakeskin line is preferred mesh
Mark.Also exactly so, demand in recent years in this respect is just growing day by day for the fact.Therefore, try to provide stable molding, be easy to system
The standby and superior above-mentioned special texture powdery paints of mechanical performance is very important.
For the powder coating material systems such as general tangerine line, mallear stria, sand streak, wrinkle, line modelled after an antique, current technology measure
It is to use various types of texture agent, such as ptfe micropowder, nylon micro mist, polypropylene, polyethylene wax, the silicone of modification
Resin, cellulose acetate-butyrate (CAB, Cellulose acetate butyrate), polyvinyl butyral resin (PVB,
Polyvinyl butyral) and based on masterbatch (Master of the liquid surfactant as active ingredient
Batch) etc., its so-called " sludge ice agent " that most typically industry is very familiar to, its preferred active component is liquid polypropylene
Acid esters levelling agent.
The preparation method of texture powdery paints is well-known.One is existing plane high glaze powder is same as, using extrusion
Machine carries out heat fusing processing, i.e., 1. a so-called step extrudes (one shot) technique；Another is exactly so-called 2. " rear addition
(post addition) " hybrid technologies.
1. the step of code type is closed including all components are placed in into high-speed mixer for dry mixing together, then uses extruder
Extrusion homogenizing.Material after extrusion is size-reduced, final powdery paints is made in sieving and packaging.But for most of texture powder
For last coating, a few typical structure often can only obtain using this technique, for example sand streak and with CAB, PVB conduct
Mallear stria of texture agent etc..
2. the preparation process of method includes：(a), the previously prepared one bottom powder for meeting performance requirement, the bottom powder can contain or not
Contain levelling agent；(b) dry-mixed additive is added into (a) component by dry-mixing.Described dry-mixing mode can be manual
Can also be mechanism, such as using the blender at a slow speed of V-structure.2. it is the existing technical scheme being most widely used,
It is advantageous that grain effect is obvious.Therefore it is also preferred as the art, and its technical advantage extended is to have sent out
Many dry-mixed additives for being adapted to such a processing mode are put on display.
It is well known that for special texture, moire, reticulate pattern, the snakeskin line that especially the present invention is defined etc., due to it
His most of powder coating material systems such as mixing of pure epoxy, epoxy/polyester, polyester/TGIC and hydroxyalkyl amide (HAA) are not too much
Easily realize, therefore traditionally using the solidification of hydroxyl polyester+amino resins (Aminoplast) crosslinking agent and special catalyst
System.This is also the preferred scheme of the art, constitutes the part of the technology of the present invention, it is adaptable to indoor or outdoor use
On the way.
Described hydroxyl polyester can be obtained easily by commercially available approach；Amino resin crosslinking agent, be typically
Glycoluril type, preferably is selected from four (methoxy) glycolurils (TMMGU, n, n are made in abbreviation ', n ", n " '-tetramethoxymethyl
Glycoluril), chemical constitution：
For example, being derived from the product Powderlink 1174 of Cytec companies of the U.S..
US5447751, Morton International, Inc, are published in nineteen ninety-five September 5, now citation conduct in full
With reference to.Disclose and use a kind of cyclamic acid (cyclamic acid) to be applied as the powder of hydroxyl polyester/glycoluril resin of catalyst
Material system, the texture of its feature is wrinkle (wrinkled finish).But it is no in recording to use dry-mixed additive.
Another granted patent US5695852, Morton International, Inc, are published on December 9th, 1997, existing
Citation is used as reference in full.Disclose and use a kind of trifluoromethanesulfonic acid diethylamine salt as catalyst, to hydroxyl polyester/glycoluril tree
A small amount of epoxide is added in fat cure system, moire (alligator) powdery paints is realized by a step expressing technique
Technical scheme.But dry-mixed additive is not also used in recording equally.
As the derivative of this two granted patents, existing developed improved technology is used respectively by US5447751
With the standard powder coating being made described in US5695852 as bottom powder, then one is added by dry-mixing into such bottom powder
Plant dry-mixed additive, such as sludge ice agent, the texture required for realizing.Specifically, into the bottom powder described in patent 5,447,751 one
As obtain is snakeskin line, and the latter is then moire.
It is well known that the substitute that may be used as above-mentioned sludge ice agent also has many kinds, such as size-reduced solid bisphenol A rings
Oxygen tree fat, CAB, PVB and aldehyde ketone resin etc..
Experience knows, using mix dry-mixed additive technology after such and originally used as US5447751 with
Technology described in US5695852 is more obvious compared to formed texture and stably；Another advantage is that can without or reduce
The epoxide used as required by US5695852, this is favourable one side as it have been found that epoxy compound in formula
Thing can greatly influence mechanical performance.But then, experience is also, it is understood that because the dry-mixed additive used is mostly for thermoplasticity
Compound or polymer, it is difficult to participate in the process of reaction in the cross-linking process of film, therefore the presence of which will be to continuous painting
The mechanical property of film produces influence, as a result causes the mechanical performance of difference, this is undesirable.Therefore effort development one kind is dry-mixed adds
Plus agent, the mechanical performance that on the one hand they can effectively provide required texture and on the other hand do not influence final film again is pole
What end needed.And then make great efforts to develop the new stable molding of a class based on such dry-mixed additive, improve current art
The texture powdery paints of defect is also extremely to need.
The content of the invention
The applicant has found the new dry-mixed additive of a class by a variety of effort and completes the present invention.It is characterized in this
The dry-mixed additive of invention is also a kind of constituent of powdery paints in itself, therefore can participate in follow-up cross-linking process and turn into
A part for cross-linked structure, so as to eliminate conventional defect, i.e., will not cause the mechanical degradation of film.
Itself it is also a kind of powdery paints it is an object of the invention to provide a kind of texture additives as dry-mixed purposes
Constituent, but show plane and high glaze if independent spraying, it is impossible to independently form texture.
It is another object of the present invention to the thermosetting for providing a kind of effective dry-mixed additive to industry and its being made up of it
Texture powdery paints.Texture is moire, reticulate pattern and snakeskin line etc. after described powder coating solidification.
The further object of the present invention is to provide a kind of thermosetting powder coating with above-mentioned texture mapping technology feature.Its structure
Bottom powder into basis can derive from any ready-made powdery paints；Again it is dry-mixed enter the present invention feature additive after its texture into
Type is more obvious and stably, has especially significantly improved mechanical performance.
A kind of dry-mixed additive of powdery paints proposed by the present invention, its raw material includes：It is hydroxy resin, amino resin crosslinked
Agent, catalyst, auxiliary agent, color stuffing.
Preferably, auxiliary agent includes levelling agent and/or degasifier.
The bottom powder composition that above-mentioned powdery paints is defined with dry-mixed additive and the present invention is based on identical cross-linking chemistry,
It is i.e. same to come from hydroxy polyester resin and amino resin crosslinking agent.Individually sprayed using dry-mixed additive, show plane and
High glaze, it is impossible to independently form texture.
Above-mentioned powdery paints is included by weight with the raw material of dry-mixed additive：50-100 parts of hydroxy resin, amino resins
1-10 parts of crosslinking agent, 0.1-1 parts of catalyst, 0.5-1.5 parts of levelling agent, 0.5-1.5 parts of degasifier, 0-50 parts of color stuffing, remaining
0-2 parts of auxiliary agent.
Above-mentioned powdery paints is included by weight with the raw material of dry-mixed additive：50-100 parts of hydroxy polyester resin, tetramethyl
1-10 parts of epoxide methyl glycoluril, N- (mesyl) -0.1-1 parts of p- tolylsulfonyl- amine, 0.5-1.5 parts of polyacrylate, peace
Cease 0.5-1.5 parts of perfume, 0-50 parts of color stuffing, 0-2 parts of remaining auxiliary agent.
Above-mentioned constituent, which must be processed into available powdery paints pattern, could constitute the dry-mixed additive of the present invention.Cause
It is essential that this extruded machine, which extrudes such procedure of processing that is homogenized, cools down, crushes and sieves,.Crushing is one particularly significant
Process, its particle size range usually require that control by 80-200 mesh sieves (Chinese Industrial Standards (CIS) sieve).It is preferred that 100-180 mesh, more excellent
Choosing for 120-140 mesh.
It has been observed that the present invention does not influence the mechanical property of coating as the dry-mixed obvious technical advantage of additive one
Such as shock resistance, this point is very unexpected.The reason for its is possible is themselves to be also a part for film-forming resin and participate in
Chemical reaction course, thus unlike other thermoplastic dry-mixed additives have damaged the continuity of film.This is very intentional
Justice.
Another special technical advantage is, general hydroxy polyester resin of the production based on the present invention+amino resin crosslinked
Also production simultaneously has the plane hard-gloss paint powder of identical cross-linking chemistry, therefore this to the producer of the texture powdery paints of chemistry
The defined dry powder additive of invention is in fact without especially preparing, and it can be derived from existing painting feed powder, and this point meaning is non-
Chang Ju great, it is possible to reduce production cycle and reduction production cost.
According to the present invention, above-mentioned formula constituent can further be optimized by adjusting the parameter of above-mentioned formula, example
Such as change color stuffing share, using and/or without using levelling agent and other auxiliary agents and/or change their consumption.It is general next
Say, texture can be increased by reducing the share of filler in formula；The outward appearance of pleasant can be carried out to pattern string by adding some colorants；
Some optional auxiliary agents influence the style of pattern by main.In principle dry-mixed line is more beneficial for using the formula for being not added with color stuffing
The formation of reason, pattern are also more preferably steady and audible, and this is desired.
Preferably, hydroxy resin is the polyester resin of hydroxyl degree of functionality and/or poly- (methyl) third of hydroxyl degree of functionality
Olefin(e) acid resin.These resins can produce chemical crosslinking with glycoluril type amino resin crosslinking agent in the presence of a catalyst, specifically such as
Under：
Preferably, the number-average molecular weight of the polyester resin of hydroxyl degree of functionality is 1000-40000, preferably 1500-
10000。
Preferably, to ensure to produce effective chemical crosslinking, the degree of functionality of the polyester resin of hydroxyl degree of functionality is more than 2,
Preferably 2.2-3.5.It is generally believed that high functionality is beneficial to being sufficiently formed for texture, and low degree of functionality is more likely to be formed
The surface of smooth gloss, therefore the resin with high functionality is the preferred of the present invention.
Preferably, the hydroxyl value of the polyester resin of hydroxyl degree of functionality is 10-100mgKOH/g, preferably 20-80mgKOH/
G, more preferably 25-50mgKOH/g.
Preferably, the glass transition temperature Tg of the polyester resin of hydroxyl degree of functionality is 40-80 DEG C, preferably 45-65
DEG C, more preferably 50-65 DEG C.
The polyester resin of above-mentioned hydroxyl degree of functionality is generally formed by corresponding polyacid and polyol condensating.It is described polynary
The example of acid has terephthalic acid (TPA), M-phthalic acid, Isosorbide-5-Nitrae-cyclohexyldicarboxylic acids, adipic acid, maleic acid, butanedioic acid and inclined benzene three
Formic acid etc.；The example of the polyalcohol have ethylene glycol, diethylene glycol (DEG), propane diols, hexylene glycol, neopentyl glycol, cyclohexane dimethanol and
Trimethylolpropane etc..
These resins can be obtained by commercially available approach, for example：
More specifically, may browse through：www.cytec.com；Www.dsmcoatingresins.com and
The description as described in polyester resin (polyester resin) in www.nanfangresin.com, now citation is used as reference in full.
This is known for the person skilled of the art.
Meanwhile, poly- (methyl) acrylic resin can also as film-forming resin, they can individually or with above-mentioned hydroxyl
The polyester resin of degree of functionality is combined as a part for film-forming resin.
Chemically, poly- (methyl) acrylic resin can be obtained by polymerization, and its preparation method is without particular limitation, as long as
The requirement that the present invention is limited can be met.Traditionally, the copolymerization process often used includes polymerisation in bulk, free based sols and gathered
Conjunction, emulsion polymerization and suspension polymerisation etc., wherein free radical solution polymerization is preferred.Correlation of such technology to the art
It is known for technical staff.
According to the present invention, described poly- (methyl) acrylic resin is hydroxyl degree of functionality.Can be following by selecting
Structures alone introduces hydroxy functional group into composition：
Wherein：R1For H or C1-C4Alkyl, preferably H or C1-C2Alkyl, more preferably methyl；R2For methylol
Or ethoxy, preferably methylol.
These monomers, can individually, can also combine be added in the composition of copolymer.According to the present invention, its
Consumption is the 1-60wt%, more preferably preferably 5-50wt%, 10-30wt% of poly- (methyl) acrylic resin gross weight.
According to the present invention, described poly- (methyl) acrylic resin is also possible that (methyl) acrylate, is specifically (first
Base) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) third
Olefin(e) acid N-butyl, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (first
Base) 2-ethyl hexyl acrylate, (methyl) dodecylacrylate and (methyl) benzyl acrylate etc..
In addition, being also possible that other vinyl monomers, such as styrene or methylbenzene second in the comonomer of the present invention
Alkene.According to the present invention, its consumption is the 10-70%, preferably 35-50% of poly- (methyl) acrylic resin gross weight.
Also need to add initiator in the polymerization process of poly- (methyl) acrylic resin, cited includes the isobutyl of azo two
Nitrile (AIBN), dibenzoyl peroxide (BPO), TBHP and cumyl peroxide etc., wherein with BPO and peroxide
It is preferred to change diisopropylbenzene (DIPB).
Preferably, the number-average molecular weight of poly- (methyl) acrylic resin of hydroxyl degree of functionality is 1000-20000, preferably
For 2000-10000, more preferably 2000-5000.
Preferably, the hydroxyl value of poly- (methyl) acrylic resin of hydroxyl degree of functionality is 10-100mgKOH/g, is preferably
20-80mgKOH/g, more preferably 25-50mgKOH/g.
Preferably, the glass transition temperature Tg of poly- (methyl) acrylic resin of hydroxyl degree of functionality is 30-110 DEG C,
Preferably 45-70 DEG C.
Preferably, the glycoluril resin that it is melamine/formaldehyde resin, alkoxylate that amino resin crosslinking agent, which is, especially
HMMM and tetramethoxymethylglycoluril；Preferably tetramethoxymethylglycoluril, because it is in room temperature shape
It is solid under state, is particularly suitable for use in the purposes of powdery paints.
Above-mentioned crosslinking agent easily can be bought by the approach of business, such as purchased from Cytec companies of the U.S.
Powderlink 1174, its main technical characteristic is as follows：
In addition, such crosslinking agent can also be available from Taiyuan, Shanxi Ke Yuan Chemical Co., Ltd.s, these lead to this technology
It is known for the person skilled in domain.
According to the present invention, the weight ratio of amino resin crosslinking agent and hydroxy resin is 4-20：100, preferably 5-7：100,
Depend primarily on the hydroxyl value of resin.
Preferably, catalyst is organic sulfonic acid and/or sulfonyl imide compounds, it is possible to provide bright and clean surface.
Preferably, organic sulfonic acid and/or the sulfonyl imide compounds shared percentage by weight in powdery paints of the present invention
For 0.05-3%, more preferably preferably 0.1-1%, 0.2-0.5%.
It is preferred that, catalyst be p-methyl benzenesulfonic acid, dinonylnaphthalene sulfonic acid, DBSA, two benzenesulfonimides and/
Or N- (mesyl)-p- tolylsulfonyl- amine, preferably N- (mesyl)-p- tolylsulfonyl- amine.
A kind of powdery paints for providing snake or moire effect that the present invention is also proposed, its raw material includes：Above-mentioned powder
The dry-mixed additive of coating, and bottom powder.
Preferably, bottom powder is 1 with the weight ratio of dry-mixed additive with above-mentioned powdery paints：0.0001-1, preferably 1：
0.01-0.1, more preferably 1：0.02-0.05.
Preferably, the raw material of bottom powder includes：Hydroxy resin, amino resin crosslinking agent, ammonia or the sulfonic acid type catalysis of amine closing
Agent, auxiliary agent, color stuffing.
Preferably, auxiliary agent includes levelling agent and/or degasifier.
According to the present invention, as the bottom powder of powder coating material system of the present invention by hydroxyl polyester, amino resin crosslinking agent and spy
Different catalyst etc. is constituted, and it is typically characterised by：If without using dry-mixed additive, its can also individually realize after solidification wrinkle and
Any one of either shallow moire, therefore itself be also a class texture type powdery paints, but the stable stability pole formed
Difference, percent defective is too high for plant produced.
Such powdery paints constituent is known for the person skilled of the art.For example by above
Those disclosed by listed US5447751 and US5695852, now citation is used as reference in full.The present invention is to such system
There is no particular limitation for bottom powder, as long as not influenceing the implementation of the present invention.But it is right as appropriate bottom powder
It is also what is allowed that content disclosed by US5447751 and US5695852, which does the improvement of a little parts and derivative,.
The raw material of above-mentioned bottom powder includes by weight：50-100 parts of hydroxy resin, 1-10 parts of amino resin crosslinking agent, ammonia or
0.1-1 parts of the sulfonic acid type catalyst of amine closing, 0.5-1.5 parts of levelling agent, 0.5-1.5 parts of degasifier, 0-50 parts of color stuffing, remaining
0-2 parts of auxiliary agent.
The raw material of above-mentioned bottom powder includes by weight：50-100 parts of hydroxy resin, 1-5 parts of solid epoxy, amino tree
0.1-1 parts of the sulfonic acid type catalyst of 1-10 parts of fat crosslinking agent, ammonia or amine closing, 0.5-1.5 parts of levelling agent, degasifier 0.5-1.5
Part, 0-50 parts of color stuffing, 0-2 parts of remaining auxiliary agent.
The raw material of above-mentioned bottom powder includes by weight：50-100 parts of hydroxy polyester resin, 1-5 parts of solid epoxy, four
1-10 parts of methoxymethyl glycoluril, amine 0.1-1 parts of sulfonic acid of closing, 0.5-1.5 parts of polyacrylate, 0.5-1.5 parts of styrax, face
0-50 parts of filler, 0-2 parts of remaining auxiliary agent.
According to the present invention, separately made powdery paints is stilled need as bottom powder.It is characterized in that experience extruder is extruded in advance
Procedure of processing as homogenizing, cooling, crushing and sieving etc..The particle size range of crushing usually requires that control by 80-200 mesh
Sieve (Chinese Industrial Standards (CIS) sieve).It is preferred that 100-180 mesh, more preferably 120-140 mesh.
According to the present invention, above-mentioned bottom powder formula constituent can obtain further excellent by adjusting the parameter of above-mentioned formula
Change, such as changing color stuffing share, using and/or without using levelling agent and other auxiliary agents and/or changing their consumption.
In addition, the bottom powder powdery paints of the present invention can also arbitrarily add colouring agent, be usually one or more
Pigment or dyestuff.May also be further containing one or more performance aids, such as levelling agent, plasticizer, stabilizer are such as
Prevent stabilizer, degasifier such as styrax, one or more fillers that UV degrades.The example of pigment has inorganic TiO2, oxygen
Change iron oxide red and yellow, chromium pigment and carbon black；Organically include phthalocyanine blue, azo, anthraquinone, thioindigo, benzanthrone, triphen dioxane and quinoline
A word used for translation (two) ketone pigment, reducing dye, Lai Keshi acid, alkali and mordant dye.Dyestuff can be replaced by pigment.
Preferably, hydroxy resin is the polyester resin of hydroxyl degree of functionality and/or poly- (methyl) third of hydroxyl degree of functionality
Olefin(e) acid resin, with the polyester resin and poly- (methyl) of hydroxyl degree of functionality in above-mentioned dry-mixed additive on hydroxyl degree of functionality
The explanation of acrylic resin.
Preferably, the number-average molecular weight of the polyester resin of hydroxyl degree of functionality is 1000-40000, preferably 1500-
10000。
Preferably, the degree of functionality of the polyester resin of hydroxyl degree of functionality is more than 2, preferably 2.2-3.5.
Preferably, the hydroxyl value of the polyester resin of hydroxyl degree of functionality is 10-100mgKOH/g, preferably 20-80mgKOH/
G, more preferably 25-50mgKOH/g.
Preferably, the glass transition temperature Tg of the polyester resin of hydroxyl degree of functionality is 40-80 DEG C, preferably 45-65
DEG C, more preferably 50-65 DEG C.
Preferably, the number-average molecular weight of poly- (methyl) acrylic resin of hydroxyl degree of functionality is 1000-20000, preferably
For 2000-10000, more preferably 2000-5000.
Preferably, the hydroxyl value of poly- (methyl) acrylic resin of hydroxyl degree of functionality is 10-100mgKOH/g, is preferably
20-80mgKOH/g, more preferably 25-50mgKOH/g.
Preferably, the glass transition temperature Tg of poly- (methyl) acrylic resin of hydroxyl degree of functionality is 30-110 DEG C,
Preferably 45-70 DEG C.
Preferably, amino resin crosslinking agent be glycoluril type amino resins, with above-mentioned dry-mixed additive on amino resins
The explanation of crosslinking agent；Preferably tetramethoxymethylglycoluril.
Preferably, ammonia or the sulfonic acid type catalyst of amine closing is by ammonia or the amine salt formed with sulfonic acid reaction, it is possible to provide
Texture；The structure of amine is：RxNH3-x, wherein R is C1-4Alkyl, 0 ＜ x≤3.
Preferably, ammonia or the sulfonic acid type catalyst of amine the closing shared percentage by weight in powdery paints of the present invention are
0.05-3%, preferably 0.1-1%, more preferably 0.2-0.5%.
Preferably, amine is methyl amine, dimethyl amine, Trimethylamine, ethamine, propylamine, di-n-propylamine, butylamine, triethylamine, two
Butylamine, benzyl amine, monoethanolamine, dimethylethanolamine, N, N- diethyl ethylene diamines and/or diisopropanolamine (DIPA), preferably diethyl
Amine and/or N, N- diethyl ethylene diamine.
Preferably, sulfonic acid is p-methyl benzenesulfonic acid, o-nitrobenzene sulfonic acid, m-nitrobenzene sulfonic acid, p-nitrophenyl sulfonic acid, nitro
Benzene -2,4- disulfonic acid, 2- nitrotoleune base -3- sulfonic acid, ortho position sulfosalicylic acid, sulfosalicylic acid, sulfosalicylic phthalate, 2,
4- dinitrobenzene sulfonic acids, 3,5- dinitrobenzene sulfonic acids and/or cyclamic acid, preferably p-methyl benzenesulfonic acid, o-nitrobenzene sulfonic acid, a nitre
Base benzene sulfonic acid, p-nitrophenyl sulfonic acid, nitrobenzene -2,4- disulfonic acid, ortho position sulfosalicylic acid, sulfosalicylic acid and/or cyclamic acid,
More preferably p-methyl benzenesulfonic acid and/or cyclamic acid.
Preferably, the raw material of bottom powder also includes：Epoxy resin.
According to the present invention, solid epoxy can also be present in the composition of powdery paints of the present invention, although its consumption
Seldom.If using epoxy resin in the formula composition of bottom powder, it will be sent out by the secondary hydroxyl in composition and glycoluril curing agent
Raw effect, therefore it is also configured to a part for film-forming resin of the present invention.
According to the present invention, described epoxy resin can be optional bisphenol A-type, bisphenol-f type, bisphenol S type, EPN type (lines
Property novolac epoxy resin), ECN types (orthoresol linear phenolic epoxy resin), three oxybenzene methylmethane types, four phenolic group ethane types and its
His heterocyclic type and their modified version product；It is also suitable by the product containing halogen of cited epoxy resin according to the present invention
Close, they can generally provide more preferable heat-resisting and electrical insulation capability.
Preferably, epoxy resin is bisphenol A type epoxy resin or bisphenol f type epoxy resin, preferably bisphenol type epoxy tree
Fat, more preferably 1-9 types bisphenol A type epoxy resin solid product, yet more preferably 2-7 types bisphenol A type epoxy resin solid are produced
Product, particularly preferably 3-4 types bisphenol A type epoxy resin solid product.
Preferably, epoxy resin shared percentage by weight in powdery paints of the present invention is 0.01-1%, preferably 0.1-
0.5%, preferred 0.2-0.4%.
Although can realize required texture using above-mentioned solid epoxy according to the present invention, its effect is same
Fairly limited, texture is less than normal or insufficient, the mechanical performance also in addition with difference, therefore is not that the present invention is especially desired to
's.
Preferably, the raw material of powdery paints also includes：Acetyl butyryl base cellulose (CAB), polyvinyl butyral resin (PVB)
And/or aldehyde ketone resin.
According to the present invention, it is necessary to add dry-mixed additive into the bottom powder of the present invention.
Dry-mixed additive is added into bottom powder to realize that desired texture mapping technology in the industry is well-known.Industry
The existing alternative additive of polytype, such as CAB, PVB, aldehyde ketone resin and sludge ice agent, wherein should it is most wide be floating
Flower agent.Some size-reduced solid bisphenol A epoxy resins and aldehyde ketone resin are also particularly suitable for the purposes of the present invention, therefore they
It is a kind of effective dry-mixed additive.
CAB is thermoplastic resin, and its molecular formula can be expressed as：
[C6H7O2(OCOCH3)x(OCOC3H7)y(OH)3-x-y]n
No. CAS：9004-36-8
Preferably chemical structural formula is：
Wherein：R is
Industrial most important CAB suppliers are U.S.'s Eastman Kodak Companies, and it possesses family's acetyl group
(acetyl) product different with bytyry (butyryl) content.
Three kinds of typical products can as powdery paints texture agent purposes, its main technical characteristic, which is summarized, see the table below：
US5321063, Nippon Oil and Fats, are published on June 14th, 1994, and now citation is used as reference in full.
Another granted patent US5498663, Nippon Oil and Fats, is published on March 12nd, 1996, is now also cited in full
It is used as reference.Disclose and use epoxy and/or epoxy/polyester mixed powder coating containing above-mentioned CAB as dry-mixed additive
The technical scheme of desired texture is realized, but resulting texture is mallear stria, is not the texture type of the invention defined, because
This is also not belonging to the technology category of the present invention.
It is another to use PVB resin as dry-mixed additive.PVB can pass through polyvinyl alcohol (PVA) and butyraldehyde
Condensation is formed in acid condition, its No. CAS：63148-65-2.
Because aldol condensation can not always be carried out completely, thus in the resin structure formed by remaining it is a certain amount of-
OH.Hydroxy radical content number depend on degree of acetylation, primitive rule is that its higher remaining-OH number of degree of acetylation is just cured
Few, vice versa.
Be suitable as the dry-mixed additive use of powdery paints is its low molecular weight product, and these resins are led to this technology
It is known for the person skilled in domain.B20H and 30T for example commercially available from Kuraray (Kuraray) company or
60H etc., preferably is selected from B20H and 30T.But use the texture obtained by such resin to be shallow flat mallear stria, it is not institute of the present invention
The texture type defined, therefore equally also it is not belonging to the technology category of the present invention.
Further, some aldehyde ketone resins are suitable as the desired texture of dry-mixed additive offer of the present invention.Ketone
Urea formaldehyde is the polymer that a class is obtained by ketone and/or aldehyde through polycondensation reaction, also referred to as ketone resin or polyketone resin.It is changed
Learning structure can be described as：
In general, carbonyl is contained in non-modified aldehyde ketone resin molecular structure, end group is hydroxyl, in coating, ink
There is widely purposes with other field.
We have found that, some compounds containing primary/secondary hydroxyl and resin are suitable as dry-mixed addition of the invention
Agent.
Ketone resin is it is well known that such resin is biological commercially available from the holy horse in Shandong in coating and ink industry
Science and Technology Ltd..More specifically, may browse through：Www.smabio.com descriptions as described in AK ketone resins, are now cited in full
It is used as reference.
Suitable aldehyde ketone resin is not particularly limited, as long as they meet the requirements.In general, according to present invention choosing
Select low molecule amount, with suitable softening point, such as 50-150 DEG C, preferably 80-120 DEG C of product is preferred.For example it is typically ketone
Urea formaldehyde AK120 and urea formaldehyde HS-A81, preferably HS-A81.
Preferably, aldehyde ketone resin shared percentage by weight in powdery paints of the present invention is 0.01-1%, preferably 0.1-
0.5%, preferred 0.2-0.4%.
Although can realize texture of the presently claimed invention using above-mentioned aldehyde ketone resin, its effect is fairly limited,
Texture is less than normal or insufficient, the mechanical performance also in addition with difference.The application of even now can regard the part of the present invention as, but
The present invention is not especially desired to.
So-called sludge ice agent is well-known in the industry.It can be acrylic resin (being commonly called as brightener) and/or
Polyether-type liquid levelling agent adsorbs the joint product in solid propenoic acid resin.Can also use epoxy/polyester mixed type powder
Last coating as the aforesaid liquid levelling agent of sorbing material joint product.It is preferred that can be " the propylene of 95% brightener+5%
Acid butyl ester liquid levelling agent " it is compound.
According to the present invention, this kind of sludge ice agent can be easily commercially available by commercially available approach.It is a kind of preferred
Product be Mount Huang Hui Jiu dusty materials Co., Ltd WHCC.
Preferably, sludge ice agent shared percentage by weight in powdery paints of the present invention is 0.01-1%, preferably 0.1-
0.5%, preferred 0.2-0.4%.
Although required texture and stable molding, its effect can be realized using above-mentioned sludge ice agent according to the present invention
Same fairly limited, texture is less than normal.In addition also there is the mechanical performance of relative mistake, therefore be not that the present invention is especially desired to
's.
The present invention is coordinated using above-mentioned dry-mixed dose and above-mentioned bottom powder, makes film presentation snake or moire, clean mark,
It is of moderate size, and stable molding, percent defective is low, while mechanical performance is very outstanding
Brief description of the drawings
The film of Fig. 1 typical crepe patterns obtained by the present invention.
The film of Fig. 2 typical moire patterns obtained by the present invention.
The film of Fig. 3 typical big snake patterns obtained by the present invention.
The film of Fig. 4 typical snakeskin line patterns obtained by the present invention.
Embodiment
Below, technical scheme is described in detail by specific embodiment.
Embodiment 1 prepares basic bottom powder 1-1, is designated as D1-1 (wrinkle, black)
300 parts of hydroxy polyester resin YE-2080,19 parts of tetramethoxymethylglycolurils, 1.5 parts of amine are closed by weight
Catalyzed by p-Toluenesulfonic Acid agent AHA6319,6 parts of polyacrylate flow agent AHA1088P, 170 parts of barium sulfate, 1.5 parts of styraxes and
3.0 parts of carbon black mixing 3-5min, are then added in twin-screw experiment extruder and melt homogenizing, tabletting, cool down and be milled into
Fine powder, sieving obtains basic bottom powder (D1-1) by 140 mesh.
Embodiment 2 prepares basic bottom powder 1-2, is designated as D1-2 (moire, white)
By weight by 300 parts of hydroxy polyester resin YE-2080,15 parts of solid bisphenol A type epoxy resin KD213,19 parts
Catalyzed by p-Toluenesulfonic Acid agent AHA6319,6 parts of polyacrylate flow agents that tetramethoxymethylglycoluril, 3.0 parts of amine are closed
AHA1088P, 75 parts of TiO2With 1.5 parts of styrax mixing 3-5min, it is then added in twin-screw experiment extruder and melts
Change, tabletting, cool down and be milled into fine powder, sieving obtains basic bottom powder (D1-2) by 140 mesh.
Embodiment 3 prepares basic bottom powder 1-3, is designated as D1-3 (moire, black)
By weight by 300 parts of hydroxy polyester resin YE-2080,10 parts of solid bisphenol A type epoxy resin KD213,19 parts
Catalyzed by p-Toluenesulfonic Acid agent AHA6319,6 parts of polyacrylate levellings that curing agent tetramethoxymethylglycoluril, 2.0 parts of amine are closed
Agent AHA1088P, 30 parts of barium sulfate, 3.0 parts of carbon blacks and 1.5 parts of styrax mixing 3-5min, are then added to twin-screw experiment use
Homogenizing is melted in extruder, tabletting, cools down and is milled into fine powder, sieving obtains basic bottom powder (D1-3) by 140 mesh.
Embodiment 4 prepares dry powder additive 1-1, is designated as A1-1 (high optical plane)
By weight by 300 parts of hydroxy polyester resin P550,19 parts of tetramethoxymethylglycolurils, 1.5 parts of N- (methylsulfonyls
Base)-p- tolylsulfonyl- amine RD1218,6 parts of polyacrylate flow agent AHA1088P, 100 parts of TiO2, 75 parts of barium sulfate,
1.5 parts of styraxes and 1.0 parts of surface property modifying agent WH999 mixing 3-5min, are then added to twin-screw experiment extruder
Middle melting homogenizing, tabletting, cools down and is milled into fine powder, sieving obtains dry-mixed additive (A1-1) by 160 mesh.
Verify as a comparison, by (A1-1) electrostatic spraying of dry-mixed additive on degreasing cold-rolled steel sheet, 200 DEG C/15min is solid
Change.Show the surface of smooth high glaze, 6 grades of PCI levellings, gloss 97.8%, square impact 50Kgcm.
Embodiment 5 prepares powdery paints 1-1, is designated as a 1-1
Into 100g basic bottom powder (D1-1), addition 2g dry-mixed additive (A1-1) is well mixed obtains powdery paints (example
1-1)。
Electrostatic spraying is on degreasing cold-rolled steel sheet, 200 DEG C/15min solidifications.Then tested by following test method,
Concrete outcome is as shown in the table.
Embodiment 6 prepares powdery paints 2-1, is designated as a 2-1
Operation is same as Example 6, wherein basic bottom powder is (D1-2).Its specific mixed proportion and test result are as follows
Shown in table.
Embodiment 7 prepares powdery paints 3-1, is designated as a 3-1
Operation is same as Example 6, wherein basic bottom powder is (D1-3).Its specific mixed proportion and test result are as follows
Shown in table.
Embodiment 8 prepares powdery paints 3-2, is designated as a 3-2
Operation is same as Example 6, wherein basic bottom powder is (D1-3).Its specific mixed proportion and test result are as follows
Shown in table.
Embodiment 9 prepares powdery paints 3-3, is designated as a 3-3
Operation is same as Example 6, wherein basic bottom powder is (D1-3).Its specific mixed proportion and test result are as follows
Shown in table.
Embodiment 10 prepares powdery paints 3-4, is designated as a 3-4
Operation is same as Example 6, wherein basic bottom powder is (D1-3).Its specific mixed proportion and test result are as follows
Shown in table.
Comparative example 3-0 prepares powdery paints 3-0, is designated as a 3-0
Operation is same as Example 6, wherein basic bottom powder is (D1-3).Its specific mixed proportion and test result are as follows
Shown in table.
As seen from the above table：Using dry-mixed additive obtained by the present invention can stably realize it is desired obtain texture, its machine
Tool performance will not decline.In general, with the raising of dry-mixed additive amount, texture can change to small direction.And conduct
Contrast, its comparative example 3-0 uses the example being similar to disclosed in US5447751, and as a result moire is very small, and lines occurs not
Continuous broken end, its mechanical performance can not also receive completely.
Comparative example 4-1
0.5g sludge ice agents WHCC (Mount Huang Hui Jiu dusty materials Co., Ltd) is added into the basic bottom powder (D1-1) of 100g to mix
Conjunction uniformly obtains comparative example 4-1.
Electrostatic spraying is on degreasing cold-rolled steel sheet, 200 DEG C/15min solidifications.Then tested by as above test method,
Concrete outcome is as shown in the table.
Comparative example 4-2
Operation is identical with comparative example 4-1, wherein basic bottom powder is changed to (D1-3).Concrete outcome is as shown in the table.
Comparative example 5-1
0.5g aldehyde ketone resins HS-A81 (Changsha Chang Tai Industrial Co., Ltd.s) is added into the basic bottom powder (D1-1) of 100g to mix
Conjunction uniformly obtains comparative example 5-1.
Electrostatic spraying is on degreasing cold-rolled steel sheet, 200 DEG C/15min solidifications.Then tested by as above test method,
Concrete outcome is as shown in the table.
Comparative example 5-2
Operation is identical with comparative example 5-1, wherein basic bottom powder is changed to (D1-3).Concrete outcome is as shown in the table.
In comparative example 4-1, pattern after sludge ice agent WHCC is added into basic bottom powder D1-1 becomes relatively glossy and stably, figure
Obvious change does not occur for case, can not obtain desired snakeskin line；In comparative example 4-2, add into basic bottom powder D1-3
Plus sludge ice agent WHCC, what is obtained is very tiny moire；And in comparative example 5-1 and 5-2, by adding aldehyde ketone resin HS-
A81, can change the textured pattern of original formulation, and its moire is even reduced into the wrinkle of standard, and this is unexpected.
Sample of the present invention is determined as follows：
1. coating thickness
It is straight with magnetic thickness measuring instrument (QNix4500 of Automation Dr.Nix GmbH companies of degree analyzer Germany)
Connect and measure.
2. outward appearance
Detect by an unaided eye：Surfacing no significant defect is designated as zero, has light defects to be designated as △, has open defect to be calculated as
×。
3. gloss
Carried out by GB/T1743-89 standards, 60 ° of reflectivity, using Micro-gloss60 ° 4442 of German BYK companies
Directly measure.
4. impact strength
Carry out, carried out with hammer impact resistance analyzer by GB/T1732-88 standards.Wherein 50Kgcm just recoils are by being designated as
50+, square impact is by being designated as 50, and the rest may be inferred.
5. levelling
Detect by an unaided eye progress PCI classifications, wherein 10 be best, 0 is worst.
6. adhesive force
Carried out by GB/T9286-1998 standards, 6 grades of partition of the level, 0 is best, and 5 is worst.
7. aberration
Directly measured, represented with △ E with BGD-551 types color difference meter.△ E ＜ 5 expression well, is designated as zero, 5 ＜ △ E ＜ 10
Between represent general, be designated as △, △ E ＞ 10 expression is poor, be calculated as ×.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.
Claims (10)
1. the dry-mixed additive of a kind of powdery paints, it is characterised in that its raw material includes：Hydroxy resin, amino resin crosslinking agent,
Catalyst, auxiliary agent, color stuffing.
2. the dry-mixed additive of powdery paints according to claim 1, it is characterised in that hydroxy resin is hydroxyl degree of functionality
Polyester resin and/or hydroxyl degree of functionality poly- (methyl) acrylic resin；
Preferably, the number-average molecular weight of the polyester resin of hydroxyl degree of functionality is 1000-40000, preferably 1500-10000；It is excellent
Selection of land, the degree of functionality of the polyester resin of hydroxyl degree of functionality is more than 2, preferably 2.2-3.5；Preferably, hydroxyl degree of functionality
The hydroxyl value of polyester resin is 10-100mgKOH/g, more preferably preferably 20-80mgKOH/g, 25-50mgKOH/g；Preferably,
The glass transition temperature Tg of the polyester resin of hydroxyl degree of functionality is 40-80 DEG C, more preferably preferably 45-65 DEG C, 50-65
℃；
Preferably, the number-average molecular weight of poly- (methyl) acrylic resin of hydroxyl degree of functionality is 1000-20000, is preferably
2000-10000, more preferably 2000-5000；Preferably, the hydroxyl value of poly- (methyl) acrylic resin of hydroxyl degree of functionality is
10-100mgKOH/g, preferably 20-80mgKOH/g, more preferably 25-50mgKOH/g；Preferably, hydroxyl degree of functionality is poly-
The glass transition temperature Tg of (methyl) acrylic resin is 30-110 DEG C, preferably 45-70 DEG C；
Preferably, amino resin crosslinking agent is glycoluril type amino resins, preferably tetramethoxymethylglycoluril.
3. the dry-mixed additive of powdery paints according to claim 1 or claim 2, it is characterised in that catalyst be organic sulfonic acid and/
Or sulfonyl imide compounds；It is preferred that, catalyst is p-methyl benzenesulfonic acid, dinonylnaphthalene sulfonic acid, DBSA, hexichol
Sulfimide and/or N- (mesyl)-p- tolylsulfonyl- amine, preferably N- (mesyl)-p- tolylsulfonyl- amine；
Preferably, auxiliary agent includes levelling agent and/or degasifier.
4. a kind of powdery paints that snake or moire effect are provided, it is characterised in that its raw material includes：Such as claim 1-3
The dry-mixed additive of any one powdery paints, and bottom powder.
5. the powdery paints of snake or moire effect can be provided according to claim 4, it is characterised in that bottom powder and such as right
It is required that any one of 1-3 powdery paints is 1 with the weight ratio of dry-mixed additive：0.0001-1, preferably 1：0.01-0.1, more
Preferably 1：0.02-0.05.
6. the powdery paints of snake or moire effect can be provided according to claim 4 or 5, it is characterised in that the original of bottom powder
Material includes：Hydroxy resin, amino resin crosslinking agent, ammonia or amine closing sulfonic acid type catalyst, auxiliary agent, color stuffing.
7. the powdery paints of snake or moire effect can be provided according to claim 6, it is characterised in that hydroxy resin be containing
The polyester resin of hydroxy functionality and/or poly- (methyl) acrylic resin of hydroxyl degree of functionality；
Preferably, the number-average molecular weight of the polyester resin of hydroxyl degree of functionality is 1000-40000, preferably 1500-10000；It is excellent
Selection of land, the degree of functionality of the polyester resin of hydroxyl degree of functionality is more than 2, preferably 2.2-3.5；Preferably, hydroxyl degree of functionality
The hydroxyl value of polyester resin is 10-100mgKOH/g, more preferably preferably 20-80mgKOH/g, 25-50mgKOH/g；Preferably,
The glass transition temperature Tg of the polyester resin of hydroxyl degree of functionality is 40-80 DEG C, more preferably preferably 45-65 DEG C, 50-65
℃；
Preferably, the number-average molecular weight of poly- (methyl) acrylic resin of hydroxyl degree of functionality is 1000-20000, is preferably
2000-10000, more preferably 2000-5000；Preferably, the hydroxyl value of poly- (methyl) acrylic resin of hydroxyl degree of functionality is
10-100mgKOH/g, preferably 20-80mgKOH/g, more preferably 25-50mgKOH/g；Preferably, hydroxyl degree of functionality is poly-
The glass transition temperature Tg of (methyl) acrylic resin is 30-110 DEG C, preferably 45-70 DEG C；
Preferably, amino resin crosslinking agent is glycoluril type amino resins, preferably tetramethoxymethylglycoluril.
8. the powdery paints of snake or moire effect can be provided according to claim 6 or 7, it is characterised in that ammonia or amine envelope
The sulfonic acid type catalyst closed is by ammonia or the amine salt formed with sulfonic acid reaction；The structure of amine is：RxNH3-x, wherein R is C1-4's
Alkyl, 0 ＜ x≤3；
Preferably, amine is methyl amine, dimethyl amine, Trimethylamine, ethamine, propylamine, di-n-propylamine, butylamine, triethylamine, dibutyl
Amine, benzyl amine, monoethanolamine, dimethylethanolamine, N, N- diethyl ethylene diamines and/or diisopropanolamine (DIPA), preferably diethylamine and/
Or N, N- diethyl ethylene diamine；
Preferably, sulfonic acid be p-methyl benzenesulfonic acid, o-nitrobenzene sulfonic acid, m-nitrobenzene sulfonic acid, p-nitrophenyl sulfonic acid, nitrobenzene -2,
4- disulfonic acid, 2- nitrotoleune base -3- sulfonic acid, ortho position sulfosalicylic acid, sulfosalicylic acid, sulfosalicylic phthalate, 2,4- bis-
Nitrobenzene-sulfonic acid, 3,5- dinitrobenzene sulfonic acids and/or cyclamic acid, preferably p-methyl benzenesulfonic acid, o-nitrobenzene sulfonic acid, m-nitro
Sulfonic acid, p-nitrophenyl sulfonic acid, nitrobenzene -2,4- disulfonic acid, ortho position sulfosalicylic acid, sulfosalicylic acid and/or cyclamic acid, it is more excellent
Elect p-methyl benzenesulfonic acid and/or cyclamic acid as；
Preferably, auxiliary agent includes levelling agent and/or degasifier.
9. the powdery paints of snake or moire effect can be provided according to claim any one of 6-8, it is characterised in that bottom powder
Raw material also include：Epoxy resin；
Preferably, epoxy resin is bisphenol A type epoxy resin or bisphenol f type epoxy resin, preferably bisphenol A type epoxy resin,
More preferably 1-9 types bisphenol A type epoxy resin solid product, yet more preferably 2-7 types bisphenol A type epoxy resin solid product,
Particularly preferably 3-4 types bisphenol A type epoxy resin solid product.
10. the powdery paints of snake or moire effect can be provided according to claim any one of 4-9, it is characterised in that powder
The raw material of last coating also includes：Acetyl butyryl base cellulose, polyvinyl butyral resin and/or aldehyde ketone resin.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111154305A (en) * | 2019-12-24 | 2020-05-15 | 广东合邦新型粉末涂料科技股份有限公司 | Base powder and external texture agent wrinkle powder and preparation and spraying method thereof |
| CN112745709A (en) * | 2020-01-13 | 2021-05-04 | 万辉(广州)高新材料有限公司 | Art powder coating with snakeskin effect and preparation method thereof |
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| CN1079763A (en) * | 1992-04-10 | 1993-12-22 | 莫顿国际股份有限公司 | Form the powder coating of wrinkle surface layer |
| US5573828A (en) * | 1994-03-08 | 1996-11-12 | Morton International, Inc. | Wrinkle finish powder coating |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1079763A (en) * | 1992-04-10 | 1993-12-22 | 莫顿国际股份有限公司 | Form the powder coating of wrinkle surface layer |
| US5573828A (en) * | 1994-03-08 | 1996-11-12 | Morton International, Inc. | Wrinkle finish powder coating |
| CN106519924A (en) * | 2016-10-28 | 2017-03-22 | 福建万安实业集团有限公司 | Turtle shell appearance imitated type powder paint |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111154305A (en) * | 2019-12-24 | 2020-05-15 | 广东合邦新型粉末涂料科技股份有限公司 | Base powder and external texture agent wrinkle powder and preparation and spraying method thereof |
| CN112745709A (en) * | 2020-01-13 | 2021-05-04 | 万辉(广州)高新材料有限公司 | Art powder coating with snakeskin effect and preparation method thereof |
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| CN107151475B (en) | 2019-09-13 |
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