CN107151475B - A kind of powdery paints of the dry-mixed additive of powdery paints and its offer grain effect - Google Patents

A kind of powdery paints of the dry-mixed additive of powdery paints and its offer grain effect Download PDF

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CN107151475B
CN107151475B CN201710461439.8A CN201710461439A CN107151475B CN 107151475 B CN107151475 B CN 107151475B CN 201710461439 A CN201710461439 A CN 201710461439A CN 107151475 B CN107151475 B CN 107151475B
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powdery paints
snake
effect according
moire effect
functionality
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CN107151475A (en
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徐斌
童乃斌
汪厚安
李卓衡
张皓
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Anhui Huaan Imp & Exp Co Ltd
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Anhui Huaan Imp & Exp Co Ltd
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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
    • 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
    • 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
    • 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
    • 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
    • C08K3/18—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
    • 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
    • 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
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • 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
    • 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 a kind of additives that can be used as dry-mixed purposes, and are made of the powdery paints with snake or moire effect that it is constituted with another bottom powder with textural characteristics.Dry-mixed additive itself is also 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 pigments and fillers substantially.Powdery paints with snake or moire effect is made of above-mentioned dry-mixed additive and bottom powder, the two is made up of moire and snake powdery paints of the invention dry-mixing, 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.Compared with prior art, the present invention improve the stability of impact property and pattern, the decorative effect of coating is also more preferably.

Description

A kind of powdery paints of the dry-mixed additive of powdery paints and its offer grain effect
Technical field
The present invention relates to powder coating technology field more particularly to a kind of dry-mixed additive of powdery paints and its provide line Manage the powdery paints of effect.
Background technique
Thermosetting powder coating be a kind of solvent and volatile emissions without or few environment-friendly type coating, especially With VOC (Volatile Organic Compounds, volatile organic compounds) discharge standard increasingly strict today, Meaning is very great, and the market share just increases year by year.
Thermosetting powder coating mainly by functional film former's resin, curing agent, levelling agent, face/filler, one or more add Agent (auxiliary agent), surface style agent and other performance improvement agents etc. are added to constitute.Preparation process is generally comprised all components together It is placed in high-speed mixer for dry mixing conjunction, then by suitable extruder heat fusing mixing, tabletting, crushing and sieving and etc.. Powdery paints made of in this way can be such that it is adhered on ground by powder static gun, the spraying of friction rifle or fluidized bed dipping, Usually metallic surface, then heating or radiation curing form film.
There is by the obtained coating of above step the decorative effect of high glaze and plane under normal circumstances.But Some special application fields are tended to using the specific coatings with grain decorating effect, for example, metal prized up-proof door, safety cabinet, Hardware tool and office appliance etc..Why make such requirement, is on the one hand for aesthetic ornamental needs, on the other hand Being also due to texture powdery paints itself usually has better flaw tolerance than plane highlight type powder.That is for The coated article of large surface coating 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.True is also exactly in this way, demand in recent years in this respect is just growing day by day.Therefore, try to provide stable molding, be easy to make 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 Be using various types of texture agent, such as ptfe micropowder, nylon micro mist, modification polypropylene, polyethylene wax, silicone Resin, cellulose acetate-butyrate (CAB, Cellulose acetate butyrate), polyvinyl butyral (PVB, Polyvinyl butyral) and masterbatch (Master based on liquid surfactant as active ingredient Batch) etc., so-called " sludge ice agent " that most typically industry is very familiar to, preferred active constituent 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 squeezes out (one shot) technique；Another kind is exactly so-called 2. " rear addition (post addition) " hybrid technology.
1. the step of code type includes that all components are placed in high-speed mixer for dry mixing conjunction together, extruder is then used Squeeze out homogenizing.Final powdery paints is made through crushing, sieving and packaging for material after extrusion.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 use CAB, PVB as The mallear stria etc. of texture agent.
2. the preparation step of method includes: (a), previously prepared one meets the bottom powder of performance requirement, which can contain or not Contain levelling agent；(b) dry-mixed additive is added into (a) component by dry-mixing.The dry-mixing mode can be manually It is also possible to mechanism, such as the mixer at a slow speed using V-structure.2. it is the existing technical solution being most widely used, It is advantageous that grain effect is obvious.Therefore it also becomes the preferred of the art, and the technical advantage extended is to have sent out Many dry-mixed additives for being suitble to such processing method are put on display.
It is well known that for special texture, moire, reticulate pattern, the snakeskin line etc. especially of the invention defined, 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 It is easy to accomplish, therefore traditionally use the solidification of hydroxyl polyester+amino resins (Aminoplast) crosslinking agent and special catalyst System.This is also the preferred scheme of the art, constitutes a part of the technology of the present invention, suitable for indoor or outdoor use On the way.
The hydroxyl polyester can be obtained easily by commercially available approach；Amino resin crosslinking agent, typically Glycoluril type, preferably be selected from four (methoxy) glycolurils (TMMGU, n, n are made in abbreviation ', n ", n " '-tetramethoxymethyl Glycoluril), chemical structure:
For example, being derived from the product Powderlink 1174 of Cytec company, the U.S..
US5447751, Morton International, Inc are published in nineteen ninety-five September 5, now full text citation conduct With reference to.It discloses and a kind of cyclamic acid (cyclamic acid) is used to apply as hydroxyl polyester/glycoluril resin powder of catalyst Material system, the texture of feature are wrinkle (wrinkled finish).But without using dry-mixed additive in recording.
Another granted patent US5695852, Morton International, Inc are published on December 9th, 1997, existing Full text citation is as reference.Disclose use a kind of trifluoromethanesulfonic acid diethylamine salt as catalyst, to hydroxyl polyester/glycoluril tree A small amount of epoxide is added in rouge curing system, and moire (alligator) powdery paints is realized by a step extrusion process Technical solution.But equally also without using dry-mixed additive in recording.
As the derivative of this two granted patents, existing developed improved technology is used respectively by US5447751 With manufactured standard powder coating described in US5695852 as bottom powder, then pass through dry-mixing addition one into such bottom powder The dry-mixed additive of kind, such as sludge ice agent, texture required for realizing.Specifically, into 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 may be used as the substitute of above-mentioned sludge ice agent, there are many more kinds, such as the solid bisphenol A ring through crushing Oxygen resin, CAB, PVB and aldehyde ketone resin etc..
Experience knows, using mix dry-mixed additive technology after such and originally use such as US5447751 and Technology described in US5695852 is more obvious and stable compared to texture is formed by；Another advantage is that can not have to or reduce The epoxide used as required by US5695852, this is favourable one side as it have been found that formula in epoxy compound Object can greatly influence mechanical performance.But then, experience is also, it is understood that since the dry-mixed additive used is mostly for thermoplasticity Compound or polymer are difficult to participate in the process of reaction in the cross-linking process of film, therefore their presence will be applied to continuous The mechanical property of film has an impact, and as a result leads to the mechanical performance of difference, this is undesirable.Therefore make great efforts to develop a kind of dry-mixed add Add agent, it is pole that on the one hand on the other hand they, which can effectively provide required texture and not influence the mechanical performance of final film, What end needed.And then makes great efforts to develop a kind of novel stable molding based on such dry-mixed additive, improves current art The texture powdery paints of defect is also extremely to need.
Summary of the invention
The applicant completes the present invention by a kind of novel dry-mixed additive of various effort discovery.Its main feature is that this The dry-mixed additive of invention itself is also a kind of constituent of powdery paints, therefore can participate in subsequent cross-linking process and become A part of cross-linked structure not will lead to the mechanical degradation of film to eliminate previous defect.
The object of the present invention is to provide a kind of texture additives as dry-mixed purposes, itself are also a kind of powdery paints Constituent, but plane and high glaze are shown if independent spraying, texture can not be independently formed.
It is another object of the present invention to provide a kind of effectively dry-mixed additive and its thermosetting property being made of it to industry Texture powdery paints.Texture is moire, reticulate pattern and snakeskin line etc. after the 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 Any ready-made powdery paints can be derived from the bottom powder on basis；Again it is dry-mixed enter feature additive of the invention after its texture at Type is more obvious and stablizes, and has especially significantly improved mechanical performance.
A kind of dry-mixed additive of powdery paints proposed by the present invention, raw material includes: hydroxy resin, amino resin crosslinked Agent, catalyst, auxiliary agent, pigments and fillers.
Preferably, auxiliary agent includes levelling agent and/or degasifier.
The bottom powder composition that the dry-mixed additive of above-mentioned powdery paints and the present invention are defined is based on identical cross-linking chemistry, I.e. with derived from hydroxy polyester resin and amino resin crosslinking agent.Individually sprayed using dry-mixed additive, show plane and High glaze cannot independently form texture.
The raw material of the dry-mixed additive of above-mentioned powdery paints includes: 50-100 parts of hydroxy resin by weight, 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 pigments and fillers, remaining 0-2 parts of auxiliary agent.
The raw material of the dry-mixed additive of above-mentioned powdery paints includes: 50-100 parts of hydroxy polyester resin by weight, tetramethyl 1-10 parts of oxygroup methyl glycoluril, N- (mesyl) -0.1-1 parts of p- tolylsulfonyl- amine, 0.5-1.5 parts of polyacrylate, peace 0.5-1.5 parts of perfume of breath, 0-50 parts of pigments and fillers, 0-2 parts of remaining auxiliary agent.
Above-mentioned constituent, which must be processed into available powdery paints pattern, could constitute dry-mixed additive of the invention.Cause This is homogenized through extruder extrusion, is cooling, crushing and such procedure of processing of being sieved is essential.Crushing is one particularly significant Process, particle size range usually requires that control by 80-200 mesh (Chinese Industrial Standards (CIS) sieve).It is preferred that 100-180 mesh, more excellent Choosing is 120-140 mesh.
It has been observed that the present invention does not influence the mechanical property of coating as dry-mixed additive one apparent technical advantage Such as shock resistance, this point is very unexpected.It is the possible reason is themselves being also a part of film-forming resin and participating in Chemical reaction course, because having damaged the continuity of film rather than other thermoplastic dry-mixed additives.This is very intentionally Justice.
Another special technical advantage is, general production is based on hydroxy polyester resin of the invention+amino resin crosslinked The producer of the texture powdery paints of chemistry also produces the plane hard-gloss paint powder with identical cross-linking chemistry, therefore this simultaneously It invents defined dry powder additive to be in fact not necessarily to especially prepare, 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 composition object can be advanced optimized by adjusting the parameter of above-mentioned formula, example Such as change pigments and fillers share, using and/or without using levelling agent and other auxiliary agents and/or the dosage for changing them.It is general next It says, the share for reducing filler in formula can increase texture；The appearance of pleasant can be carried out to pattern string by adding certain colorants； Certain optional auxiliary agents will mainly influence the style of pattern.Dry-mixed line is more advantageous to using the formula that pigments and fillers are not added in principle The formation of reason, pattern are also more preferably steady and audible, 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 generate 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 guarantee to generate effective chemical crosslinking, the degree of functionality of the polyester resin of hydroxyl degree of functionality is greater 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 of the invention preferred.
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 usually 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, succinic acid and inclined benzene three Formic acid etc.；The example of the polyalcohol have ethylene glycol, diethylene glycol (DEG), propylene glycol, hexylene glycol, neopentyl glycol, cyclohexane dimethanol and Trimethylolpropane etc..
These resins can be obtained by commercially available approach, such as:
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 full text citation is as reference. This is well known for the related technical personnel of the art.
Meanwhile poly- (methyl) acrylic resin can also be used as film-forming resin, they can individually or with above-mentioned hydroxyl The polyester resin of degree of functionality is combined as a part of film-forming resin.
Chemically, poly- (methyl) acrylic resin can be obtained by polymerization, and preparation method is without particular limitation, as long as It is able to satisfy the requirement that the present invention limits.Traditionally, the copolymerization process being often used includes that bulk polymerization, free based sols are poly- Conjunction, emulsion polymerization and suspension polymerisation etc., wherein free radical solution polymerization is preferred.Correlation of such technology to the art It is well known for technical staff.
According to the present invention, poly- (methyl) acrylic resin is hydroxyl degree of functionality.It 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 and also combine be added in the composition of copolymer.According to the present invention, Dosage is the 1-60wt%, preferably 5-50wt%, more preferably 10-30wt% of poly- (methyl) acrylic resin total weight.
According to the present invention, poly- (methyl) acrylic resin is also possible that (methyl) acrylate, 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 in comonomer of the invention, such as styrene or methylbenzene second Alkene.According to the present invention, dosage is the 10-70%, preferably 35-50% of poly- (methyl) acrylic resin total weight.
Also need to be added initiator in the polymerization process of poly- (methyl) acrylic resin, cited includes two isobutyl of azo Nitrile (AIBN), dibenzoyl peroxide (BPO), tert-butyl hydroperoxide and cumyl peroxide etc., wherein with BPO and peroxide It is preferred for changing 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, 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 melamine/formaldehyde resin, alkoxylated glycoluril resin, especially Hexamethoxymethyl melamine and tetramethoxymethylglycoluril；Preferably tetramethoxymethylglycoluril, because it is in room temperature shape It is solid, the purposes especially suitable for powdery paints under state.
Above-mentioned crosslinking agent can easily be bought by the approach of business, such as purchased from Cytec company, the U.S. Powderlink 1174, main technical characteristic are as follows:
In addition, such crosslinking agent is also possible to purchased from Taiyuan, Shanxi Ke Yuan Chemical Co., Ltd., these lead this technology It is well known for the related technical personnel in domain.
According to the present invention, the weight ratio of amino resin crosslinking agent and hydroxy resin be 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 weight percent in powdery paints of the present invention For 0.05-3%, preferably 0.1-1%, more preferably 0.2-0.5%.
Preferably, catalyst be p-methyl benzenesulfonic acid, dinonylnaphthalene sulfonic acid, dodecyl benzene sulfonic acid, two benzenesulfonimides and/ Or N- (mesyl)-p- tolylsulfonyl- amine, preferably N- (mesyl)-p- tolylsulfonyl- amine.
A kind of powdery paints that can provide snake or moire effect that the present invention also proposes, raw material include: above-mentioned powder Coating dry-mixed additive and bottom powder.
Preferably, bottom powder is 1:0.0001-1 with the weight ratio of dry-mixed additive with above-mentioned powdery paints, 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 closed sulfonic acid type catalysis of amine Agent, auxiliary agent, pigments and fillers.
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 is typically characterised by: if without using dry-mixed additive, individually also may be implemented after solidification wrinkle with Any one of either shallow moire, therefore itself be also a kind of texture type powdery paints, but be formed by stable stability pole Difference, rejection rate is excessively high for plant produced.
Such powdery paints constituent is well known for the related technical personnel of the art.Such as by above Those of disclosed by listed US5447751 and US5695852, now full text citation is as reference.The present invention is to such system There is no particular limitation for bottom powder, as long as not influencing implementation of the invention.But it is right as appropriate bottom powder Content disclosed by US5447751 and US5695852 does the improvement of a little parts and derivative is also to allow.
The raw material of above-mentioned bottom powder includes: 50-100 parts of hydroxy resin by weight, 1-10 parts of amino resin crosslinking agent, ammonia or 0.1-1 parts of amine closed sulfonic acid type catalyst, 0.5-1.5 parts of levelling agent, 0.5-1.5 parts of degasifier, 0-50 parts of pigments and fillers, remaining 0-2 parts of auxiliary agent.
The raw material of above-mentioned bottom powder includes: 50-100 parts of hydroxy resin by weight, and 1-5 parts of solid epoxy, amino tree 1-10 parts of rouge crosslinking agent, 0.1-1 parts of ammonia or amine closed sulfonic acid type catalyst, 0.5-1.5 parts of levelling agent, degasifier 0.5-1.5 Part, 0-50 parts of pigments and fillers, 0-2 parts of remaining auxiliary agent.
The raw material of above-mentioned bottom powder includes: 50-100 parts of hydroxy polyester resin by weight, and 1-5 parts of solid epoxy, four 1-10 parts of methoxymethyl glycoluril, sulfonic acid 0.1-1 parts of amine 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, as bottom powder, there is still a need for separately made powdery paints.It is characterized in that experience extruder squeezes out 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 It sieves (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 composition object can obtain further excellent by adjusting the parameter of above-mentioned formula Change, such as changes pigments and fillers share, using and/or without using levelling agent and other auxiliary agents and/or the dosage for changing them etc..
In addition to this, colorant can also be arbitrarily added in the bottom powder powdery paints of the present invention, usually one or more Pigments or dyes.One or more performance aids may also further be contained, such as levelling agent, plasticizer, stabilizer are such as Stabilizer, the degasifier such as styrax, one or more fillers for preventing UV from degrading.The example of pigment has inorganic TiO2, oxygen Change iron oxide red and yellow, chromium pigment and carbon black；It 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 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 poly- (methyl) in above-mentioned dry-mixed additive about the polyester resin of hydroxyl degree of functionality and 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 greater 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, 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, in above-mentioned dry-mixed additive about amino resins The explanation of crosslinking agent；Preferably tetramethoxymethylglycoluril.
Preferably, ammonia or the closed sulfonic acid type catalyst of amine are to be reacted to be formed by salt with sulfonic acid by ammonia or amine, it is possible to provide Texture；The structure of amine are as follows: RxNH3-x, wherein R is C1-4Alkyl, 0 x≤3 <.
Preferably, ammonia or the closed sulfonic acid type catalyst of the amine shared weight percent 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, ethanol amine, dimethylethanolamine, N, N- diethyl ethylene diamine 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 acid, 3,5- dinitrobenzene sulfonic acid and/or cyclamic acid, preferably p-methyl benzenesulfonic acid, o-nitrobenzene sulfonic acid, 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 further include: epoxy resin.
According to the present invention, solid epoxy can also exist in the composition of powdery paints of the present invention, although its dosage Seldom.If using epoxy resin in the formula composition of bottom powder, it will pass through the secondary hydroxyl and glycoluril curing agent hair in composition Raw effect, therefore it is also configured to a part of film-forming resin of the present invention.
According to the present invention, the epoxy resin can be optional bisphenol A-type, bisphenol-f type, bisphenol S type, EPN type (line Property novolac epoxy resin), ECN type (o-cresol linear phenolic epoxy resin), three oxybenzene methylmethane types, four phenolic group ethane types and its His heterocyclic type and their modified version product；It according to the present invention, is also suitable by the product containing halogen of cited epoxy resin It closes, they can usually provide better 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 Rouge, more preferably 1-9 type bisphenol A type epoxy resin solid product, yet more preferably 2-7 type bisphenol A type epoxy resin solid produce Product, particularly preferably 3-4 type bisphenol A type epoxy resin solid product.
Preferably, epoxy resin shared weight percent in powdery paints of the present invention is 0.01-1%, preferably 0.1- 0.5%, preferred 0.2-0.4%.
Although required texture may be implemented using above-mentioned solid epoxy according to the present invention, effect is same Fairly limited, texture is less than normal or insufficient, furthermore also has the mechanical performance of difference, therefore is not that the present invention is especially desired to 's.
Preferably, the raw material of powdery paints further include: acetyl butyryl base cellulose (CAB), polyvinyl butyral (PVB) And/or aldehyde ketone resin.
According to the present invention, it needs to add dry-mixed additive into bottom powder of the invention.
Dry-mixed additive is added into bottom powder to realize that desired texture mapping technology is well-known in the industry.Industry Existing multiple types alternative additive, such as CAB, PVB, aldehyde ketone resin and sludge ice agent etc., wherein should it is most wide be to float Flower agent.Certain solid bisphenol A epoxy resins and aldehyde ketone resin through crushing are also particularly suitable for purposes of the invention, therefore they It is a kind of effective dry-mixed additive.
CAB is thermoplastic resin, and molecular formula can be expressed as:
[C6H7O2(OCOCH3)x(OCOC3H7)y(OH)3-x-y]n
No. CAS: 9004-36-8
Ideal chemical structural formula are as follows:
Wherein: R is
Industrial most important CAB supplier is U.S. Eastman Kodak Company, it possesses family's acetyl group (acetyl) product different with bytyry (butyryl) content.
Three kinds of typical products can be used as the purposes of powdery paints texture agent, and main technical characteristic summary see the table below:
US5321063, Nippon Oil and Fats are published on June 14th, 1994, and now full text citation is as reference. Another granted patent US5498663, Nippon Oil and Fats, is published on March 12nd, 1996, and now also full text is cited As reference.It discloses and uses epoxy containing above-mentioned CAB and/or epoxy/polyester mixed powder coating as dry-mixed additive Realize the technical solution of desired texture, but acquired texture is mallear stria, is not the texture type of the invention defined, because This is also not belonging to technology scope of the invention.
Another kind can be used as dry-mixed additive and use PVB resin.PVB can pass through polyvinyl alcohol (PVA) and butyraldehyde It is condensed in acid condition, No. CAS: 63148-65-2.
Since aldol condensation always not can be carried out completely, in being formed by resin structure 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, these resins lead this technology It is well known for the related technical personnel in domain.Such as be commercially available from Kuraray (Kuraray) company B20H and 30T or 60H etc., preferably is selected from B20H and 30T.But using the resulting texture of such resin is shallow flat mallear stria, is not institute of the present invention The texture type defined, therefore equally also it is not belonging to technology scope of the invention.
Further, certain aldehyde ketone resins are suitable as dry-mixed additive of the invention and provide desired texture.Ketone Urea formaldehyde is a kind of polymer 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, contain carbonyl 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 certain compounds containing primary/secondary hydroxyl and resin are suitable as dry-mixed addition of the invention Agent.
Ketone resin is well-known in coating and ink industry, and such resin is commercially available from Shandong sage horse biology Science and Technology Ltd..More specifically, may browse through: www.smabio.com description as described in AK ketone resin, now full text is cited As reference.
Suitable aldehyde ketone resin is not particularly limited, as long as they meet the requirements.In general, it selects according to the present invention It selects low molecular weight, there is suitable softening point, such as 50-150 DEG C, preferably 80-120 DEG C of product is preferred.It such as is typically ketone Urea formaldehyde AK120 and urea formaldehyde HS-A81, preferably HS-A81.
Preferably, aldehyde ketone resin shared weight percent in powdery paints of the present invention is 0.01-1%, preferably 0.1- 0.5%, preferred 0.2-0.4%.
Although texture of the presently claimed invention may be implemented using above-mentioned aldehyde ketone resin, effect is fairly limited, Texture is less than normal or insufficient, furthermore also has the mechanical performance of difference.The application of even now can regard a part of the 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 is adsorbed on the joint product in solid propenoic acid resin.It is also possible to epoxy/polyester mixed type powder Joint product of the last coating as the aforesaid liquid levelling agent of adsorbent material.It preferably can be "+5% propylene of 95% brightener Acid butyl ester liquid levelling agent " it is compound.
According to the present invention, this kind of sludge ice agent can be easily obtained from the market by commercially available approach.It is a kind of preferred Product be Mount Huang Hui Jiu dusty material Co., Ltd WHCC.
Preferably, sludge ice agent shared weight percent 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, effect may be implemented using above-mentioned sludge ice agent according to the present invention Same fairly limited, texture is less than normal.It furthermore with the mechanical performance of relative mistake, therefore is not that the present invention is especially desired to yet 's.
The present invention is cooperated using above-mentioned dry-mixed dose and above-mentioned bottom powder, and film is made to be presented snake or moire, clean mark, It is of moderate size, and stable molding, rejection rate is low, while mechanical performance is very outstanding
Detailed description of the invention
Fig. 1 is the film of present invention gained typical crepe pattern.
Fig. 2 is the film of the typical moire pattern of present invention gained.
Fig. 3 is the film of the typical big snake pattern of present invention gained.
Fig. 4 is the film of the typical snakeskin line pattern of present invention gained.
Specific embodiment
In the following, technical solution of the present invention is described in detail by specific embodiment.
Embodiment 1 prepares basic bottom powder 1-1, is denoted as D1-1 (wrinkle, black)
It is by weight that 300 parts of hydroxy polyester resin YE-2080,19 parts of tetramethoxymethylglycolurils, 1.5 parts of amine are closed 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 test extruder and melt homogenizing, tabletting, cooling and are milled into Fine powder, sieving obtain basic bottom powder (D1-1) by 140 mesh.
Embodiment 2 prepares basic bottom powder 1-2, is denoted 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 Tetramethoxymethylglycoluril, the closed Catalyzed by p-Toluenesulfonic Acid agent AHA6319 of 3.0 parts of amine, 6 parts of polyacrylate flow agents AHA1088P, 75 parts of TiO2With 1.5 parts of styrax mixing 3-5min, it is then added in twin-screw test extruder and melts Change, tabletting, cooling 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 denoted 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 Curing agent tetramethoxymethylglycoluril, the closed Catalyzed by p-Toluenesulfonic Acid agent AHA6319 of 2.0 parts of amine, 6 parts of polyacrylate levellings 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 test and use Homogenizing is melted in extruder, tabletting, cooling and is milled into fine powder, and sieving obtains basic bottom powder (D1-3) by 140 mesh.
Embodiment 4 prepares dry powder additive 1-1, is denoted 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 test extruder Middle melting homogenizing, tabletting, cooling and is milled into fine powder, and sieving obtains dry-mixed additive (A1-1) by 160 mesh.
It verifies 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 levelling, gloss 97.8%, square impact 50Kgcm.
Embodiment 5 prepares powdery paints 1-1, is denoted as a 1-1
It is uniformly mixed to the dry-mixed additive (A1-1) that 2g is added in the basis 100g bottom powder (D1-1) and obtains powdery paints (example 1-1)。
Electrostatic spraying is on degreasing cold-rolled steel sheet, 200 DEG C/15min solidification.Then it is tested by following test method, Concrete outcome is as shown in the table.
Embodiment 6 prepares powdery paints 2-1, is denoted as a 2-1
Operate it is same as Example 6, wherein basic bottom powder is (D1-2).Its specific mixed proportion and test result is as follows Shown in table.
Embodiment 7 prepares powdery paints 3-1, is denoted as a 3-1
Operate it is same as Example 6, wherein basic bottom powder is (D1-3).Its specific mixed proportion and test result is as follows Shown in table.
Embodiment 8 prepares powdery paints 3-2, is denoted as a 3-2
Operate it is same as Example 6, wherein basic bottom powder is (D1-3).Its specific mixed proportion and test result is as follows Shown in table.
Embodiment 9 prepares powdery paints 3-3, is denoted as a 3-3
Operate it is same as Example 6, wherein basic bottom powder is (D1-3).Its specific mixed proportion and test result is as follows Shown in table.
Embodiment 10 prepares powdery paints 3-4, is denoted as a 3-4
Operate it is same as Example 6, wherein basic bottom powder is (D1-3).Its specific mixed proportion and test result is as follows Shown in table.
Comparative example 3-0 prepares powdery paints 3-0, is denoted as a 3-0
Operate it is same as Example 6, wherein basic bottom powder is (D1-3).Its specific mixed proportion and test result is as follows Shown in table.
As seen from the above table: can steadily be realized using the dry-mixed additive of present invention gained and desired obtain texture, machine Tool performance will not decline.In general, with the raising of dry-mixed additive amount, texture can change to small direction.And conduct Comparison, comparative example 3-0, which is used, is similar to example disclosed in US5447751, and as a result moire is very small, and lines occurs not Continuous broken end, mechanical performance cannot also receive completely.
Comparative example 4-1
It is mixed to 0.5g sludge ice agent WHCC (Mount Huang Hui Jiu dusty material Co., Ltd) is added in the basis 100g bottom powder (D1-1) It closes and uniformly obtains comparative example 4-1.
Electrostatic spraying is on degreasing cold-rolled steel sheet, 200 DEG C/15min solidification.Then it is tested by test method as above, Concrete outcome is as shown in the table.
Comparative example 4-2
Operation is identical as 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
It is mixed to 0.5g aldehyde ketone resin HS-A81 (Changsha Chang Tai Industrial Co., Ltd.) is added in the basis 100g bottom powder (D1-1) It closes and uniformly obtains comparative example 5-1.
Electrostatic spraying is on degreasing cold-rolled steel sheet, 200 DEG C/15min solidification.Then it is tested by test method as above, Concrete outcome is as shown in the table.
Comparative example 5-2
Operation is identical as 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 becomes relatively glossy and stablizes after sludge ice agent WHCC is added into basic bottom powder D1-1, figure Case can not obtain desired snakeskin line there is no significantly changing；In comparative example 4-2, add into basic bottom powder D1-3 Add 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 moire is even reduced into the wrinkle of standard, this is unexpected.
Sample of the present invention measures as follows:
1. coating thickness
It is straight with magnetic thickness measuring instrument (QNix4500 of degree analyzer Germany Automation Dr.Nix GmbH company) 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, is denoted as zero, 5 < △ E < 10 Between indicate general, be denoted as △, the expression of △ E > 10 is poor, be calculated as ×.
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 (60)

1. a kind of powdery paints that can provide snake or moire effect, which is characterized in that its raw material includes: powdery paints with dry-mixed Additive and bottom powder；
The powdery paints is composed of the following components with its raw material of dry-mixed additive: hydroxy resin, amino resin crosslinking agent, catalysis Agent, auxiliary agent, pigments and fillers；The hydroxy resin is the polyester resin of hydroxyl degree of functionality and/or the poly- (first of hydroxyl degree of functionality Base) acrylic resin；The catalyst is p-methyl benzenesulfonic acid, dinonylnaphthalene sulfonic acid, dodecyl benzene sulfonic acid, two benzenesulfonimides And/or N- (mesyl)-p- tolylsulfonyl- amine；The raw material of the bottom powder include: hydroxy resin, amino resin crosslinking agent, Ammonia or the closed sulfonic acid type catalyst of amine, auxiliary agent, pigments and fillers.
2. can provide the powdery paints of snake or moire effect according to claim 1, which is characterized in that the powdery paints Number-average molecular weight with the polyester resin of hydroxyl degree of functionality in dry-mixed additive is 1000-40000.
3. can provide the powdery paints of snake or moire effect according to claim 1, which is characterized in that the powdery paints Number-average molecular weight with the polyester resin of hydroxyl degree of functionality in dry-mixed additive is 1500-10000.
4. can provide the powdery paints of snake or moire effect according to claim 1, which is characterized in that the powdery paints It is greater than 2 with the degree of functionality of the polyester resin of hydroxyl degree of functionality in dry-mixed additive.
5. can provide the powdery paints of snake or moire effect according to claim 1, which is characterized in that the powdery paints Degree of functionality with the polyester resin of hydroxyl degree of functionality in dry-mixed additive is 2.2-3.5.
6. can provide the powdery paints of snake or moire effect according to claim 1, which is characterized in that the powdery paints Hydroxyl value with the polyester resin of hydroxyl degree of functionality in dry-mixed additive is 10-100mgKOH/g.
7. can provide the powdery paints of snake or moire effect according to claim 1, which is characterized in that the powdery paints Hydroxyl value with the polyester resin of hydroxyl degree of functionality in dry-mixed additive is 20-80mgKOH/g.
8. can provide the powdery paints of snake or moire effect according to claim 1, which is characterized in that the powdery paints Hydroxyl value with the polyester resin of hydroxyl degree of functionality in dry-mixed additive is 25-50mgKOH/g.
9. can provide the powdery paints of snake or moire effect according to claim 1, which is characterized in that the powdery paints Glass transition temperature Tg with the polyester resin of hydroxyl degree of functionality in dry-mixed additive is 40-80 DEG C.
10. can provide the powdery paints of snake or moire effect according to claim 1, which is characterized in that the powder applies Material is 45-65 DEG C with the glass transition temperature Tg of the polyester resin of hydroxyl degree of functionality in dry-mixed additive.
11. can provide the powdery paints of snake or moire effect according to claim 1, which is characterized in that the powder applies Material is 50-65 DEG C with the glass transition temperature Tg of the polyester resin of hydroxyl degree of functionality in dry-mixed additive.
12. can provide the powdery paints of snake or moire effect according to claim 1, which is characterized in that the powder applies The number-average molecular weight for expecting poly- (methyl) acrylic resin of hydroxyl degree of functionality in dry-mixed additive is 1000-20000.
13. can provide the powdery paints of snake or moire effect according to claim 1, which is characterized in that the powder applies The number-average molecular weight for expecting poly- (methyl) acrylic resin of hydroxyl degree of functionality in dry-mixed additive is 2000-10000.
14. can provide the powdery paints of snake or moire effect according to claim 1, which is characterized in that the powder applies The number-average molecular weight for expecting poly- (methyl) acrylic resin of hydroxyl degree of functionality in dry-mixed additive is 2000-5000.
15. can provide the powdery paints of snake or moire effect according to claim 1, which is characterized in that the powder applies The hydroxyl value for expecting poly- (methyl) acrylic resin of hydroxyl degree of functionality in dry-mixed additive is 10-100mgKOH/g.
16. can provide the powdery paints of snake or moire effect according to claim 1, which is characterized in that the powder applies The hydroxyl value for expecting poly- (methyl) acrylic resin of hydroxyl degree of functionality in dry-mixed additive is 20-80mgKOH/g.
17. can provide the powdery paints of snake or moire effect according to claim 1, which is characterized in that the powder applies The hydroxyl value for expecting poly- (methyl) acrylic resin of hydroxyl degree of functionality in dry-mixed additive is 25-50mgKOH/g.
18. can provide the powdery paints of snake or moire effect according to claim 1, which is characterized in that the powder applies Expect that the glass transition temperature Tg of poly- (methyl) acrylic resin of hydroxyl degree of functionality in dry-mixed additive is 30-110 DEG C.
19. can provide the powdery paints of snake or moire effect according to claim 1, which is characterized in that the powder applies Expect that the glass transition temperature Tg of poly- (methyl) acrylic resin of hydroxyl degree of functionality in dry-mixed additive is 45-70 DEG C.
20. can provide the powdery paints of snake or moire effect according to claim 1, which is characterized in that the powder applies Material is glycoluril type amino resins with amino resin crosslinking agent in dry-mixed additive.
21. can provide the powdery paints of snake or moire effect according to claim 1, which is characterized in that the powder applies Material is tetramethoxymethylglycoluril with amino resin crosslinking agent in dry-mixed additive.
22. can provide the powdery paints of snake or moire effect according to claim 1, which is characterized in that the powder applies Material includes levelling agent and/or degasifier with auxiliary agent in dry-mixed additive.
23. can provide the powdery paints of snake or moire effect according to claim 1, which is characterized in that Di Fenyu powder Coating is 1:0.0001-1 with the weight ratio of dry-mixed additive.
24. can provide the powdery paints of snake or moire effect according to claim 1, which is characterized in that Di Fenyu powder Coating is 1:0.01-0.1 with the weight ratio of dry-mixed additive.
25. can provide the powdery paints of snake or moire effect according to claim 1, which is characterized in that Di Fenyu powder Coating is 1:0.02-0.05 with the weight ratio of dry-mixed additive.
26. can provide the powdery paints of snake or moire effect according to claim 1, which is characterized in that in the bottom powder Hydroxy resin is the polyester resin of hydroxyl degree of functionality and/or poly- (methyl) acrylic resin of hydroxyl degree of functionality.
27. can provide the powdery paints of snake or moire effect according to claim 26, which is characterized in that in the bottom powder The number-average molecular weight of the polyester resin of hydroxyl degree of functionality is 1000-40000.
28. can provide the powdery paints of snake or moire effect according to claim 26, which is characterized in that in the bottom powder The number-average molecular weight of the polyester resin of hydroxyl degree of functionality is 1500-10000.
29. can provide the powdery paints of snake or moire effect according to claim 26, which is characterized in that in the bottom powder The degree of functionality of the polyester resin of hydroxyl degree of functionality is greater than 2.
30. can provide the powdery paints of snake or moire effect according to claim 26, which is characterized in that in the bottom powder The degree of functionality of the polyester resin of hydroxyl degree of functionality is 2.2-3.5.
31. can provide the powdery paints of snake or moire effect according to claim 26, which is characterized in that in the bottom powder The hydroxyl value of the polyester resin of hydroxyl degree of functionality is 10-100mgKOH/g.
32. can provide the powdery paints of snake or moire effect according to claim 26, which is characterized in that in the bottom powder The hydroxyl value of the polyester resin of hydroxyl degree of functionality is 20-80mgKOH/g.
33. can provide the powdery paints of snake or moire effect according to claim 26, which is characterized in that in the bottom powder The hydroxyl value of the polyester resin of hydroxyl degree of functionality is 25-50mgKOH/g.
34. can provide the powdery paints of snake or moire effect according to claim 26, which is characterized in that in the bottom powder The glass transition temperature Tg of the polyester resin of hydroxyl degree of functionality is 40-80 DEG C.
35. can provide the powdery paints of snake or moire effect according to claim 26, which is characterized in that in the bottom powder The glass transition temperature Tg of the polyester resin of hydroxyl degree of functionality is 45-65 DEG C.
36. can provide the powdery paints of snake or moire effect according to claim 26, which is characterized in that in the bottom powder The glass transition temperature Tg of the polyester resin of hydroxyl degree of functionality is 50-65 DEG C.
37. can provide the powdery paints of snake or moire effect according to claim 26, which is characterized in that in the bottom powder The number-average molecular weight of poly- (methyl) acrylic resin of hydroxyl degree of functionality is 1000-20000.
38. can provide the powdery paints of snake or moire effect according to claim 26, which is characterized in that in the bottom powder The number-average molecular weight of poly- (methyl) acrylic resin of hydroxyl degree of functionality is 2000-10000.
39. can provide the powdery paints of snake or moire effect according to claim 26, which is characterized in that in the bottom powder The number-average molecular weight of poly- (methyl) acrylic resin of hydroxyl degree of functionality is 2000-5000.
40. can provide the powdery paints of snake or moire effect according to claim 26, which is characterized in that in the bottom powder The hydroxyl value of poly- (methyl) acrylic resin of hydroxyl degree of functionality is 10-100mgKOH/g.
41. can provide the powdery paints of snake or moire effect according to claim 26, which is characterized in that in the bottom powder The hydroxyl value of poly- (methyl) acrylic resin of hydroxyl degree of functionality is 20-80mgKOH/g.
42. can provide the powdery paints of snake or moire effect according to claim 26, which is characterized in that in the bottom powder The hydroxyl value of poly- (methyl) acrylic resin of hydroxyl degree of functionality is 25-50mgKOH/g.
43. can provide the powdery paints of snake or moire effect according to claim 26, which is characterized in that in the bottom powder The glass transition temperature Tg of poly- (methyl) acrylic resin of hydroxyl degree of functionality is 30-110 DEG C.
44. can provide the powdery paints of snake or moire effect according to claim 26, which is characterized in that in the bottom powder The glass transition temperature Tg of poly- (methyl) acrylic resin of hydroxyl degree of functionality is 45-70 DEG C.
45. can provide the powdery paints of snake or moire effect according to claim 1, which is characterized in that in the bottom powder Amino resin crosslinking agent is glycoluril type amino resins.
46. can provide the powdery paints of snake or moire effect according to claim 1, which is characterized in that in the bottom powder Amino resin crosslinking agent is tetramethoxymethylglycoluril.
47. can provide the powdery paints of snake or moire effect according to claim 1, which is characterized in that in the bottom powder Ammonia or the closed sulfonic acid type catalyst of amine are to be reacted to be formed by salt with sulfonic acid by ammonia or amine；The structure of amine are as follows: RxNH3-x, wherein R is C1-4Alkyl, 0 x≤3 <.
48. can provide the powdery paints of snake or moire effect according to claim 47, which is characterized in that in the bottom powder Amine be methyl amine, dimethyl amine, Trimethylamine, ethamine, propylamine, di-n-propylamine, butylamine, triethylamine, dibutylamine, benzyl amine, Ethanol amine, dimethylethanolamine, N, N- diethyl ethylene diamine and/or diisopropanolamine (DIPA).
49. can provide the powdery paints of snake or moire effect according to claim 47, which is characterized in that in the bottom powder Amine is diethylamine and/or N, N- diethyl ethylene diamine.
50. can provide the powdery paints of snake or moire effect according to claim 47, which is characterized in that in the bottom powder Sulfonic acid is 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- dinitrobenzene sulfonic acid, 3,5- dinitrobenzene sulfonic acid and/or cyclamic acid.
51. can provide the powdery paints of snake or moire effect according to claim 47, which is characterized in that in the bottom powder Sulfonic acid is p-methyl benzenesulfonic acid, o-nitrobenzene sulfonic acid, m-nitrobenzene sulfonic acid, p-nitrophenyl sulfonic acid, nitrobenzene -2,4- disulfonic acid, neighbour Position sulfosalicylic acid, sulfosalicylic acid and/or cyclamic acid.
52. can provide the powdery paints of snake or moire effect according to claim 47, which is characterized in that sulfonic acid is to first Benzene sulfonic acid and/or cyclamic acid.
53. can provide the powdery paints of snake or moire effect according to claim 1, which is characterized in that in the bottom powder Auxiliary agent includes levelling agent and/or degasifier.
54. can provide the powdery paints of snake or moire effect according to claim 1, which is characterized in that the raw material of bottom powder Further include: epoxy resin.
55. can provide the powdery paints of snake or moire effect according to claim 54, which is characterized in that in the bottom powder Epoxy resin is bisphenol A type epoxy resin or bisphenol f type epoxy resin.
56. can provide the powdery paints of snake or moire effect according to claim 54, which is characterized in that in the bottom powder Epoxy resin is bisphenol A type epoxy resin.
57. can provide the powdery paints of snake or moire effect according to claim 54, which is characterized in that in the bottom powder Epoxy resin is 1-9 type bisphenol A type epoxy resin solid product.
58. can provide the powdery paints of snake or moire effect according to claim 54, which is characterized in that in the bottom powder Epoxy resin is 2-7 type bisphenol A type epoxy resin solid product.
59. can provide the powdery paints of snake or moire effect according to claim 54, which is characterized in that in the bottom powder Epoxy resin is 3-4 type bisphenol A type epoxy resin solid product.
60. can provide the powdery paints of snake or moire effect described in -59 any one according to claim 1, which is characterized in that powder The raw material of last coating further include: acetyl butyryl base cellulose, polyvinyl butyral and/or aldehyde ketone resin.
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CN111154305B (en) * 2019-12-24 2022-06-24 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

Citations (3)

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Publication number Priority date Publication date Assignee Title
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

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Publication number Priority date Publication date Assignee Title
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

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