CN1093155C - Novel resin-coated metallic pigment and metallic coating material containing the pigment - Google Patents
Novel resin-coated metallic pigment and metallic coating material containing the pigment Download PDFInfo
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- CN1093155C CN1093155C CN96194273A CN96194273A CN1093155C CN 1093155 C CN1093155 C CN 1093155C CN 96194273 A CN96194273 A CN 96194273A CN 96194273 A CN96194273 A CN 96194273A CN 1093155 C CN1093155 C CN 1093155C
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- resin
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- metallic pigment
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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
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/62—Metallic pigments or fillers
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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
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
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- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
The present invention provided a resin-coated metallic pigment having a resin layer formed on surface of a metallic pigment, which is excellent in weathering resistance, chemical resistance, gloss and storage stability in aqueous coating materials and permits the formation of a metallic finish. The metallic pigment is carried out by three materials such as (A), (B), (C) to cause polymerization by using (A) at least one member selected from the group consisting of radical-polymerizable unsaturated carboxylic acids, and/or, phosphoric mono-or diesters having one or two radical-polymerizable double bonds, and/or, coupling agents having a radical-polymerizable double bond, (B) at least one monomer having three or more radical-polymerizable double bonds, and (C) a polymerization initiator, adding (A) at first to treat a metallic pigment, followed by continuous and supplementary addition, little by little, of at least one of (B) and (C), and a metallic coating material obtained by using said resin-coated metallic pigment.
Description
The present invention relates to a kind of metallic pigment of new application of resin, in detail, the metallic pigment that relate to a kind of application of resin, this pigment is when using as coating pigment, metal deposit with good chemical-resistant, gloss, weathering resistance can be provided, and in water-based paint, have good storage stability.In addition, the invention still further relates to a kind of novel metal coating of forming by above-mentioned resin-coated metal pigment, coating resin and thinner, in detail, relate to a kind of coating that metal deposit with good chemical-resistant, gloss, weathering resistance is provided and has extremely good storage stability.
For a long time, metallic pigment are used to metallic paint, printing-ink, be incorporated in the plastics etc., to obtain aesthetic when paying attention to the metal sense.
Yet, adopting filming or synthetic resin that existing metallic pigment obtain, it is acidproof, alkaline-resisting etc., and chemical-resistant and water tolerance are insufficient, also have the inferior shortcoming of weathering resistance in addition.That is, after after a while, be coated with face variable color, gloss and reduce, so their use is restricted, therefore be desirable to provide a kind of chemical-resistant and weathering resistance is good and storage stability is also good metallic pigment strongly.
As the improvement scheme of this problem, proposed on the metallic pigment composition, to implement the scheme of resin coating.
Known have aluminium stuck with paste be dispersed in the organic solvent that is dissolved with the ethylene type unsaturated monomer, by with the coexistence of polymerization starter under heat, thereby the aluminium that obtains the good application of resin of chemical-resistant is stuck with paste (spy opens clear 51-11818 communique).Yet, stick with paste according to the aluminium of the application of resin of this method manufacturing and not have sufficient chemical-resistant, do not reach realistic scale.
In addition, have with aluminium stick with paste in organic solvent, disperse after, at first adsorb free-radical polymerised unsaturated carboxylic acid etc., then the motion (special fair 1-49746 communique) of the method by the polymer-coated surface that generates by monomer with free-radical polymerised pair of key more than 3.This method must be added the monomer of the application of resin of a great deal of for realizing sufficient alkali resistance, and meanwhile, not only gloss reduces, and significantly different problem of metal sense is also arranged.
In addition, the spy opens in the flat 7-3185 communique, has put down in writing by the coating siloxanes and be coated in above-mentioned siloxanes to be coated with in the application and to form the metallic pigment that three-dimensional cross-linked synthetic resins constitutes by covalent linkage.Yet these metallic pigment still can not think to have sufficient chemical-resistant.
In addition, the aluminium of above-mentioned application of resin is stuck with paste and the aluminium of uncoated resin is stuck with paste when using in aqueous medium, can react generation hydrogen and metalluster is reduced significantly with water.Therefore, when using, be necessary to take countermeasures such as emission gases as water-based paint.
Homogeneity, smoothness with raising application of resin film are purpose, the method (spy opens clear 64-40566 communique) that has the motion proposition to utilize the multipolymer of free radical polymerization monomer and oligopolymer to apply.Also there is the problem that produces a large amount of hydrogen when using in this method as water-based paint, and, because metalluster significantly reduces existing problems aspect storage stability.
The inventor etc. are for solving the problem that existing metallic pigment exist, through further investigation, found that: from free-radical polymerised unsaturated carboxylic acid, monoesters or diester with Phosphoric acid or phosphonic acid of free-radical polymerised pair of key, and have select in the coupler of free-radical polymerised pair of key at least a, to wherein adding monomer and the polymerization starter that contains free-radical polymerised pair of key more than 3 in 1 molecule continuously, perhaps have the monomer of free-radical polymerised pair of key more than 3 or in the polymerization starter any one to wherein appending continuously to add, with the resin coating being carried out on the metallic pigment surface through the multipolymer that obtains after the aforesaid operations, can achieve the goal, so finished the present invention.
That is, the present invention has following feature:
(1) metallic pigment of the application of resin that obtains by following (A), (B), (C) three kinds of raw materials, wherein (A) for from free-radical polymerised unsaturated carboxylic acid and/or have free-radical polymerised pair of key Phosphoric acid or phosphonic acid monoesters or diester and/or have select the coupler of free-radical polymerised pair of key at least a; (B) for having the monomer of free-radical polymerised pair of key more than 3; (C) be polymerization starter, at first add (A) and handle after the metallic pigment, slowly append interpolations (B) with (C) at least a, thereby at metallic surface formation polymeric resin layer.
(2) metallic pigment of the application of resin of record in above-mentioned (1), be monomer and monomeric mixture wherein, and this have the monomeric amount of free-radical polymerised pair of key more than 4 and have with respect to aforementioned that the monomeric total amount of free-radical polymerised pair of key is 10 weight %-60 weight % more than 3 with free-radical polymerised pair of key more than 4 with 3 free-radical polymerised pair of keys as the monomer with free-radical polymerised pair of key more than 3 of (B).
(3) metallic pigment of the application of resin of record in above-mentioned (1) or (2), at least a time of wherein adding above-mentioned (B) and above-mentioned (C) is more than 20% of total polymerization time.
(4) metallic pigment of the application of resin of each record in above-mentioned (1)-(3), the molecular weight that wherein has each monomeric functional group of free-radical polymerised pair of key more than 4 is more than 30, below 200.
(5) metallic pigment of the application of resin of each record in above-mentioned (1)-(4), its alkali resistance is below 2.0.
(6) contain the metallic paint of the metallic pigment of the application of resin of each record in above-mentioned (1)-(5).
(7) method for making of the metallic pigment of application of resin, it is characterized by, adopt following (A), (B), (C) three kinds of raw materials, wherein (A) for from free-radical polymerised unsaturated carboxylic acid and/or have free-radical polymerised pair of key Phosphoric acid or phosphonic acid monoesters or diester and/or have select the coupling system of free-radical polymerised pair of key at least a; (B) has the monomer of free-radical polymerised pair of key more than 3; (C) polymerization starter at first adds (A) and handles metallic pigment, afterwards, slowly append interpolations (B) with (C) at least a, thereby at metallic surface formation polymeric resin layer.
By the metallic pigment of the application of resin of gained of the present invention, show the chemical-resistant of the brilliance that did not in the past have, the gloss that can keep feed metal pigment to have simultaneously, and have good storage stability.
As employed metallic pigment among the present invention, comprise aluminium, copper, zinc, iron, nickel and/or their alloy, can enumerate aluminium as preferred.Its shape can be sheet, spherical, needle-like even-granular.The preferred size of metallic pigment is different according to purposes.Coating is used, the printing time spent, and median size is preferably about 1～10 μ, when being incorporated in the plastics, is preferably about about 1～200 μ, and these scopes are had no particular limits.
Free-radical polymerised unsaturated carboxylic acid as among the present invention has vinylformic acid, methacrylic acid, methylene-succinic acid, fumaric acid etc., uses wherein one or more mixture.Its usage quantity can be because of the surface-area of the kind of these metallic pigment and characteristic, particularly metallic pigment different and different, but in general, with respect to metallic pigment, be between 0.01 weight part～10 weight parts, more preferably between 0.1 weight part～5.0 weight parts.During less than 0.01 weight part, effect of the present invention, promptly chemical-resistant such as alkali resistance or acid resistance can not be brought into play well, in addition, when the monomer with free-radical polymerised pair of key more than 3 during, the polymerization system gel is arranged, can not carry out condition of stirring and take place at the metallic pigment surface aggregate.In addition, when using more than 10 weight parts, the effect of chemical-resistant etc. does not increase yet.
As the Phosphoric acid or phosphonic acid ester that has free-radical polymerised pair of key among the present invention, phosphoric acid or phosphonic monoesters or diester, concrete example is as phosphoric acid 2-methacryloxy ethyl ester, di(2-ethylhexyl)phosphate-2-methacryloxy ethyl ester, tricresyl phosphate-2-methacryloxy ethyl ester, phosphoric acid 2-acryloxy ethyl ester, di(2-ethylhexyl)phosphate-2-acryloxy ethyl ester, tricresyl phosphate-2-acryloxy ethyl ester, di(2-ethylhexyl)phosphate phenyl-2-acryloxy ethyl ester, di(2-ethylhexyl)phosphate butyl-2-methacryloxy ethyl ester, di(2-ethylhexyl)phosphate octyl group-2-acryloxy ethyl ester, phosphoric acid 2-methacryloxy propyl ester, two (2-chloroethyl) vinylphosphonate, diallyl dibutyl phosphono succinates etc. can use wherein one or more mixture.
Have in the Phosphoric acid or phosphonic acid ester of free-radical polymerised pair of key, preferred person is a phosphate monoester.Its reason can be thought because phosphate radical has 2 OH bases, therefore comparatively firm fixing of aluminum ion surface, preferred phosphate monoester is the monoesters that has methacryloxy and acryloxy, as phosphoric acid 2-methacryloxy ethyl ester, and phosphoric acid 2-acryloxy ethyl ester.
Its usage quantity can be different because of kind and characteristic, particularly its surface-area of metallic pigment, in general, with respect to these metallic pigment of 100 weight parts, is between 0.01 weight part to 30 weight part.0.1 weight part～20 weight parts more preferably.During less than 0.01 weight part, effect of the present invention, promptly chemical-resistant such as alkali resistance can not be brought into play well, uses more than 20 weight parts, can not expect that effect has increase.
The coupler that has free-radical polymerised pair of key as among the present invention has the silane type coupler, titanic acid ester type coupler, aluminium type coupler etc.
As the silane type coupler, γ-methacryloxypropyl trimethoxy silane, vinyl trichloro silane, vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three ('beta '-methoxy oxyethyl group) silane etc. are for example arranged.
As titanic acid ester type coupler isopropyl stearyl two acryloyl titanic acid ester etc. are for example arranged.
As aluminium type coupler diisopropyl acid acetyl aluminum alkoxide, zircoaluminate etc. are for example arranged.
The amount of the employed coupler that has a free-radical polymerised pair of key generally with respect to 100 weight part metallic pigment, is between 0.01 to 20 weight part according to the kind of metallic pigment and characteristic, particularly surface-area and different.More preferably between 0.1 weight part～10 weight parts.During less than 0.01 weight part, the effect of invention, promptly chemical-resistant such as alkali resistance can not be brought into play well, uses that effect can not increase yet when surpassing 20 weight parts.
When generally handling metallic pigment, handle for preventing the reaction of metallic pigment self and water, being contemplated in the inert solvent.
Because free-radical polymerised unsaturated carboxylic acid and/or have phosphoric acid, phosphonic monoesters or the diester solubleness height in inert solvent of free-radical polymerised pair of key, homodisperse with comparalive ease, so chemical-resistant is good, be difficult in water-based paint, producing the problem that storage stability descends, so preferred.
As the monomer that has free-radical polymerised pair of key more than 3 (B) among the present invention, Viscoat 295, trimethylolpropane trimethacrylate, tetramethylol methane tetraacrylate, tetra methylol propane tetraacrylate, two-trimethylolpropane tetra-acrylate, two-TriMethylolPropane(TMP), six acrylate, tetramethylol methane tetraacrylate, two-tetramethylolmethane, six acrylate etc. can be enumerated, wherein one or more mixture can be used.
The monomer that has free-radical polymerised pair of key more than 4 in the monomer that has free-radical polymerised pair of key more than 3 (B) among the present invention, preferred person is two-trimethylolpropane tetra-acrylate, tetramethylol methane tetraacrylate, two-tetramethylolmethane, six acrylate.
The usage quantity of the monomer that has free-radical polymerised pair of key more than 3 (B) among the present invention with respect to metal ingredient 100 weight parts of metallic pigment, is between 2 weight part to 50 weight parts, more preferably 3 weight parts～40 weight parts.During less than 2 weight parts, the effect of invention, promptly chemical-resistant is low, surpasses 50 weight parts, can not desired effects increase to some extent, and the fundamental characteristics of metallic paint such as brightness, gloss can reduce, and is difficult to be used for practicality.
And during as the monomer that has free-radical polymerised pair of key more than 3 (B) among the present invention, can strengthen effect of the present invention with the monomer that has a free-radical polymerised pair of key more than 4 with the monomer that has 3 free-radical polymerised pair of keys.Its ratio, with respect to the total amount of the monomer that has free-radical polymerised pair of key more than 3 (B), the monomer that has free-radical polymerised pair of key more than 4 is 10～60 weight %, more preferably 20%～50 weight %.And show the performance of chemical-resistants such as remarkable acid resistance and alkali resistance with the monomer that has free-radical polymerised pair of key more than 4.In addition, have the monomer of free-radical polymerised pair of key more than 4, be further to strengthen above-mentioned effect, preferably the molecular weight of its each functional group is 30 or more, below 200, though its reason is unclear, thinks because highly three-dimensional cross-linked caused.
In the scope of not damaging effect of the present invention, also can use the monomer that has the two keys of 1 to 2 polymerizability in 1 molecule.For example, methyl acrylic ester, vinyl cyanide, crotononitrile, vinyl-acetic ester, propionate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylates, 1 such as esters of acrylic acids such as vinylbenzene, alpha-methyl styrene, methyl acrylate, methyl methacrylate, 3-butylene glycol dimethacrylate, neopentylglycol diacrylate, 1,6 hexanediol diacrylate, Vinylstyrene etc.Can use wherein a kind or more than one miscellany.Its usage quantity is between 0.1 weight part to 10 weight part with respect to 100 weight part metallic pigment.Usage quantity surpasses 10 weight parts, and the effect of invention promptly, is used the metallic pigment of the application of resin of gained, and when making metal deposit, characteristic reduces, and the heat-resistant stability of metallic pigment also reduces, and is difficult to be used for practicality.The metallic pigment of application of resin of the present invention obtain by the following method: at first untreated metallic pigment are scattered in the organic solvent, heat in the limit afterwards, stir on the limit, the limit adds (A) handles the metallic pigment surface, (A) for from free-radical polymerised unsaturated carboxylic acid, the phosphoric acid that has free-radical polymerised pair of key, phosphonic list or diester and have select the coupler of free-radical polymerised pair of key at least a; Slowly add continuously on one side then (B) and (C) at least a, wherein (B) for having the monomer of free-radical polymerised pair of key more than 3, wherein (C) on one side carry out polymerization for polymerization starter, thereby at the surperficial formation of metallic pigment resin layer.
After at first untreated metallic pigment being disperseed in organic solvent, heat and stir simultaneously, add (A) simultaneously when handling, though be not particularly limited, the weight concentration of the metallic pigment in organic solvent is preferably 1～30%.During less than 1%, though but homodisperse, the quantity of solvent of handling is excessive, and so removal process effort thereafter is bad.Surpass 30%, it is inhomogeneous that the dispersion of metallic pigment becomes easily, neither be preferred.In addition, this handles preferred temperature is 40 ℃～150 ℃, and time range is 5 minutes～10 hours.When being lower than 40 ℃, need expending time in addition and temperature be risen to the polymerization temperature of (B), when being higher than 150 ℃, must think better of the easy ignition issues of organic solvent steam, not preferred.In addition, if treatment time less than 5 minutes, then the diffusion of (A) becomes insufficient easily, and as surpassing 10 hours, then effect can not increase, and only can expend time in, so not preferred.
Gently add continuously on one side then (B): have the monomer of free-radical polymerised pair of key more than 3 with (C): at least a in the polymerization starter, carry out polymerization on one side, make metallic pigment surface formation resin layer.Among the present invention, append continuously adding (B) with (C) at least a be important.Specifically, can slowly add simultaneously (B) with (C), or add (C) earlier, slowly add then (B), or add (B) earlier, slowly add then (C), any way all can.Among the present invention, can think by append continuously adding (B) with (C) in at least aly carry out polymerization, can form three-dimensional highly cross-linked resin layer in the metallic surface.Polymerization temperature is not particularly limited, is preferably 60 ℃～150 ℃,, be desirably under the inert atmospheres such as nitrogen, helium and carry out for improving polymerization efficiency.In addition, when adding continuously, preferably with (B), (C) with dilutions such as organic solvents after, adopt the dosing pump reinforced with certain speed, the reinforced time is promptly appended the interpolation time, is preferably more than 20% of polymerization time.Polymerization time is not particularly limited, and is 2 hours～10 hours scope.At this, polymerization time is meant from (B) and (C) is present in the reaction system simultaneously and begins, is less than 1% o'clock time to the unreacted reactant of (B).20% o'clock of reinforced deficiency of time polymerization time, the effect of adding is little, not preferred continuously.In addition, for reducing the reaction times, the preferably reinforced time is below 90% of polymerization time, for further shortening the reaction times, boosts productivity, and expectation is below 70%.
The metallic pigment of gained application of resin of the present invention are compared with the metallic pigment before the processing, its specific surface area increases to some extent, but compare with the metallic pigment of the prepared application of resin of existing method, it is characterized in that the specific surface area increasing degree reduces significantly, oil number also reduces.Its reason, consideration are because the resin layer that forms in the metallic surface is more even, and have formed the three-dimensional cross-linked of height, adopt the characteristics such as showing good chemical-resistant, gloss, weathering resistance of filming of the metallic pigment of application of resin of the present invention.
Among the present invention, the organic solvent that uses during polymerization can be aliphatic hydrocarbons such as hexane, heptane, pentane, mineral turpentine, aromatic hydrocarbonss such as benzene,toluene,xylene, solvent naphtha, ethers such as tetrahydrofuran (THF), diethyl ether, ester classes such as ethyl acetate, butylacetate.
The polymerization starter that the present invention is used, be general known free radical generating agent, benzoyl peroxide, lauroyl peroxide, two-peroxides such as (4-tert-butylcyclohexyl) peroxycarbonates are arranged, and 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo is two-2, azo-compounds such as 4-methyl pentane nitrile.Its usage quantity is not particularly limited in the present invention, has the monomer of free-radical polymerised pair of key more than 3 with respect to 100 weight parts, is 0.1 weight part～50 weight parts.
The metallic pigment of application of resin of the present invention are when being used for coating, and it is filmed and shows extremely good alkali resistance characteristic.This is considered to even alkali is invaded the inside of filming, also be difficult to arrive the reason on metallic pigment surface owing in the metallic pigment surface applied three-dimensional cross-linked resin layer is highly arranged, and as shown in the embodiment of the present invention, alkali-proof value is 0.01～2.0.
Metallic paint of the present invention can be used as solvent based coating or water-based paint etc. and uses, and mainly contains 3 kinds of basal component, i.e. the metallic pigment of (a) coating resin, (b) application of resin and (c) thinner.
Coating resin as solvent based coating, can use the existing used coating resin of metallic paint arbitrarily, for example acrylic resin, Synolac, oil-free alkyd resin, vinyl chloride resin, urethane resin, melmac, unsaturated polyester resin, urea resin, cellulose-type resin, Resins, epoxy, fluoro-resin etc., they can be used alone or as a mixture.
The preferable amount of the metallic pigment of the application of resin of using in the solvent based coating with respect to 100 weight part coating resins, is preferably 0.1 weight part～100 weight parts, more preferably 1 weight part～50 weight parts.During metallic pigment less than 0.1 weight part of this application of resin, as the metalluster deficiency of metallic paint necessity, use when surpassing 100 weight parts, the metallic pigment amount in the coating is too much, and the application operability is poor, and the quality of filming is not good yet, can not be practical.
Thinner as solvent based coating, aromatics such as toluene, dimethylbenzene are arranged, fatty compoundss such as hexane, heptane, octane, alcohols such as ethanol, butanols, ester such as ethyl acetate, butylacetate class, ketones such as butanone, muriates such as trichloroethane, cellosolve classes such as ethylene glycol monoethyl ether, these thinners can separately or mix more than 2 kinds and use.Its composition should be considered to determine after the solvability to coating resin, film formation characteristic, the application operability etc.
Can in solvent based coating, add additives such as the general pigment that uses of coating industry, dyestuff, wetting agent, dispersion agent, the agent of anti-segregation, levelling agent, antiseize paste, anti-peeling agent, anti-peptizing agent, defoamer.
Pigment of the present invention also can be used for water-based paint with resin by using water-based paint, and this water-based paint can be water soluble resin or water-dispersed resin with resin, and they can use separately or use with the miscellany form.Its kind can have nothing in common with each other because of purpose, purposes, has no particular limits, and water-based paint resins such as acrylic type, vinylformic acid-melamine type, polyester type, polyurethane-type are generally arranged, and wherein vinylformic acid-melamine type is the most frequently used.
The metallic pigment consumption of used application of resin in the water-based paint with respect to 100 weight part coating resins, is 0.1 weight part～100 weight parts.Be preferably 1 weight part～50 weight parts especially.During metallic pigment less than 0.1 weight part of this application of resin, as the metalluster deficiency of metallic paint necessity, use when surpassing 100 weight parts, the metallic pigment amount in the coating is too much, and the application operability is poor, and the quality of filming is not good yet, can not be practical.
In addition, belong to normally used various additives in this field, as dispersion agent, thickening material, anti-drip agent, mould inhibitor, UV light absorber, film coalescence aid, tensio-active agent, other organic solvents, water etc., as long as its kind and quantity without detriment to effect of the present invention, can be added arbitrarily.
The metallic paint of indication of the present invention desolventizes outside type coating, the water-based paint, also can be other coating commonly used, for example powder coating etc.
Below, enumerating embodiments of the invention, the present invention is not subjected to the restriction of these embodiment.In addition, test method that present embodiment adopted and measuring method are as described below.
(1) estimates the making of using coated plate
Use the aluminium of application of resin to stick with paste, estimate the metallic paint that alkali resistance is used by the preparation of coating formula shown in the table 1.
Table 1 coating formula (weight part)
| The aluminium of application of resin is stuck with paste (being scaled nonvolatile component) | 9 |
| Thinner * 1 | 40 |
| Acrylic resin * 2 | 100 |
| Nitrocellulose resin solution * 3 | 50 |
* 1 butylacetate (30 parts), toluene (45 parts), Virahol (20 parts),
The miscellany of ethyl cellosolve (5 parts)
* 2 ACRYDIC A-166 (non-volatility composition: 45%) (big
Japanese ink chemistry (strain) is made, normal dry type acrylic resin)
* 3 with LIG 1/2 (non-volatility composition: 70%)
(Asahi Chemical Industry's industry (strain) is made, industrial soluble cotton) is with rare
The non-volatility composition of releasing agent * 1 preparation accounts for 16% solution
The thinner that the above table of the viscosity of this coating is remembered is adjusted to 13 seconds (FC#4,20 ℃), is sprayed on the ABS resin plate, and being coated with and being filled to thickness is 10 μ.In 50 ℃ of dryings 30 minutes, make to estimate and use coated plate afterwards.
(2) alkali-proof mensuration
Lower part of above-mentioned coated plate be impregnated in the beaker that the 2.5N NaOH aqueous solution is housed, placed 24 hours down for 20 ℃.With after coated plate washing, the drying, by the condition d (8-d method) of JIS-Z-8722 (1982) partly and do not flood the part colour examining, obtain aberration Δ E after the test by the 6.3.2 of JIS-Z-8730 (1980) to dipping.
(3) gloss retention
Measure the 60 degree gloss (input angle, reflection angle are 60 degree) of above-mentioned coated plate with glossmeter.60 of the aluminium paste that is untreated is spent gloss as G, and the 60 degree gloss that application of resin aluminium is stuck with paste are tried to achieve gloss retention R as G ' according to following formula.
R＝(G′/G)×100
(4) oil number
The aluminium of application of resin is stuck with paste in 105 ℃ of heat treated 3 hours, makes sample, measures with dibutyl phthalate by the B method (scraping the skill in using a kitchen knife in cookery) of JIS K 6221-1982.
(5) specific surface area
Remove the solvent that aluminium is stuck with paste by the acetone displacement, it is Powdered that sample is become, and measures the specific surface area of the sample that becomes powder in BET1 point type specific surface area (Tianjin, island FLOW SORB2300).
Embodiment 1
Add 75 gram aluminium in the four-necked bottle that volume is 1 liter and stick with paste (Asahi Chemical Industry Co., Ltd makes MG-51, metal ingredient ratio 67%) and 300 gram mineral turpentine, logical nitrogen stirs down, with interior temperature rise to 80 ℃.Add 0.375 gram vinylformic acid then, continue to stir 30 minutes down at 80 ℃.Afterwards, with 2.5 gram trimethylolpropane trimethacrylates and 1.0 gram two-trimethylolpropane tetra-acrylate (each molecule of functional group amount 116.5) and 0.35 gram 2,2 '-azo two-2, the 4-methyl pentane nitrile is dissolved in the 19 gram mineral turpentine, with the speed of about 0.13 gram/minute this solution is added reaction system with pump of constant delivery type, added in 3 hours.Then temperature in the system is remained 80 ℃, make polymerization time amount to 6 hours.At this moment, sampling, with the unreacted amount of the trimethylolpropane trimethacrylate in the gas Chromatographic Determination filtrate, the reacting more than 99.5% of add-on.With the muddy reacting liquid filtering, the aluminium that obtains application of resin was stuck with paste after polymerization finished.The non-volatility component content (according to JIS-K-5910) that this aluminium is stuck with paste is 65.0 weight %.With respect to aluminum metal composition 100 weight parts, the amount of application of resin is 8.3 weight parts.The result can infer thus, vinylformic acid, trimethylolpropane trimethacrylate, two-trimethylolpropane tetra-acrylate, 2,2 '-azo is two-2, the 4-methyl pentane nitrile existing more than 98% attached on the aluminium surface.
Embodiment 2
Except that embodiment 1 used trimethylolpropane trimethacrylate and two-trimethylolpropane tetra-acrylate replaced with the 3.5 gram trimethylolpropane trimethacrylates, stick with paste with the aluminium that legal system gets application of resin by embodiment 1.
Embodiment 3
Add 75 gram aluminium in the four-necked bottle that volume is 1 liter and stick with paste (Asahi Chemical Industry Co., Ltd makes MG-51, metal ingredient ratio 67%) and 300 gram mineral turpentine, logical nitrogen stirs down, with interior temperature rise to 60 ℃.Add 0.375 gram vinylformic acid then, continue to stir 30 minutes down at 60 ℃.Afterwards, 6.4 gram Viscoat 295s and 1.6 gram two-tetramethylolmethane, six acrylate (each molecule of functional group amount 96.3) are scattered in the reaction system.Then with 0.8 gram 2,2 '-azo is two-2, the 4-methyl pentane nitrile is dissolved in the 19 gram mineral turpentine, with the speed of about 0.08 gram/minute this solution is added reaction system with pump of constant delivery type, adds in 4 hours.Temperature in the system is remained 60 ℃, make polymerization time amount to 7 hours.Polymerization finishes after-filtration muddy reaction solution, and the aluminium that obtains application of resin is stuck with paste.The non-volatility component content (according to JIS-K-5910) that this aluminium is stuck with paste is 60.0 weight %.With respect to 100 weight part aluminum metal compositions, the amount of application of resin is 18.2 weight parts.The result can infer thus, vinylformic acid, Viscoat 295, two-tetramethylolmethane, six acrylate, 2,2 '-azo is two-2, the 4-methyl pentane nitrile existing more than 99% attached on the aluminium surface.
Embodiment 4
Add 75 gram aluminium in the four-necked bottle that volume is 1 liter and stick with paste (Asahi Chemical Industry Co., Ltd makes MG-51, metal ingredient ratio 67%) and 300 gram mineral turpentine, logical nitrogen stirs down, with interior temperature rise to 70 ℃.Add 0.4 gram vinylformic acid then, continue to stir 30 minutes down at 80 ℃.Afterwards, with 0.5 gram 1,6-hexanediyl ester, 3.0 gram trimethylolpropane trimethacrylates, 1.5 gram tetramethylol methane tetraacrylates (each molecule of functional group amount 88) and 0.5 gram azobis isobutyronitrile are dissolved in the 38 gram mineral turpentine, with the speed of about 0.24 gram/minute this solution is added reaction system with pump of constant delivery type, added in 3 hours.Temperature in the system is remained 80 ℃, make polymerization time amount to 6 hours.Polymerization finishes after-filtration muddy reaction solution, and the aluminium that obtains application of resin is stuck with paste.The non-volatility component content (according to JIS-K-5910) that this aluminium is stuck with paste is 62.0 weight %.With respect to 100 weight part aluminum metal compositions, the amount of application of resin is 11.6 weight parts.The result can infer thus, vinylformic acid, 1,6 hexanediol diacrylate, Viscoat 295, tetramethylol methane tetraacrylate and 2,2 '-azobis isobutyronitrile existing more than 98% attached on the aluminium surface.
Embodiment 5
The quantitative change that removes the trimethylolpropane trimethacrylate that embodiment 1 is used is 1.0 grams, and the quantitative change of two-trimethylolpropane tetra-acrylate is outside 2.5 grams, sticks with paste with the aluminium that legal system gets application of resin by embodiment 1.The non-volatility component content (according to JIS-K-5910) that this aluminium is stuck with paste is 60.0%.
Embodiment 6
The quantitative change that removes used trimethylolpropane trimethacrylate is 2.5 grams, the quantitative change of two-trimethylolpropane tetra-acrylate is 1.0 grams, and with 0.35 gram 2,2 '-azo two-2, the 4-methyl pentane nitrile be dissolved in solution that 19 grams obtain in the mineral turpentine with pump of constant delivery type with the speed of about 0.32 gram/minute outside adding within 1.2 hours, stick with paste with the aluminium that legal system gets application of resin by embodiment 1.The non-volatility component content (according to JIS-K-5910) that this aluminium is stuck with paste is 65.0%.
Embodiment 7
Add 150 gram aluminium in the four-necked bottle that volume is 2 liters and stick with paste (Asahi Chemical Industry Co., Ltd makes MG-51, metal ingredient ratio 67%) and 2-propyl alcohol 600 grams, logical nitrogen stirs down, with interior temperature rise to 70 ℃.Add vinyltrimethoxy silane 7 grams and Purified Water 7 grams then, stirred 5 hours.Afterwards, filter the muddy reaction solution, carefully wash with mineral turpentine.The aluminium that obtains is thus stuck with paste 75 grams add in the four-necked bottle of 1 liter of volume with 300 gram mineral turpentine, logical nitrogen stirs down, with interior temperature rise to 80 ℃.Afterwards, with 2.5 gram trimethylolpropane trimethacrylates, 1.0 gram two-trimethylolpropane tetra-acrylate and 0.35 gram 2,2 '-azo two-2, the 4-methyl pentane nitrile is dissolved in the 19 gram mineral turpentine, with the speed of about 0.13 gram/minute this solution is added reaction system with pump of constant delivery type, added in 3 hours.Temperature in the system is remained 80 ℃, make polymerization time amount to 6 hours.Polymerization finishes after-filtration muddy reaction solution, and the aluminium that obtains application of resin is stuck with paste.The non-volatility component content (according to JIS-K-5910) that this aluminium is stuck with paste is 65.0 weight %.With respect to 100 weight part aluminum metal compositions, the amount of application of resin is 8.3 weight parts.The result can infer thus, vinyltrimethoxy silane, trimethylolpropane trimethacrylate, two-trimethylolpropane tetra-acrylate, 2,2 '-azo is two-2, the 4-methyl pentane nitrile existing more than 98% attached on the aluminium surface.
Embodiment 8
Remove with vinylformic acid replace with acid phosphoric acid 2-methacryloxy ethyl ester (big eight chemical companies make, MR-200) outside, stick with paste with the aluminium that legal system gets application of resin by embodiment 1.The non-volatility component content (according to JIS-K-5910) that this aluminium is stuck with paste is 65.0 weight %.The result can infer thus, acid phosphoric acid 2-methacryloxy ethyl ester, trimethylolpropane trimethacrylate, two-trimethylolpropane tetra-acrylate, 2,2 '-azo is two-2, the 4-methyl pentane nitrile existing more than 98% attached on the aluminium surface.Comparative example 1
Except not carrying out appending continuously the operation of interpolation, but outside monomer (B), polymerization starter added together, stick with paste with the aluminium that legal system gets application of resin by embodiment 1 by charge pump.Comparative example 2
Add operation except carrying out appending continuously, but outside monomer (B), polymerization starter added together, stick with paste with the aluminium that legal system gets application of resin by embodiment 2 by charge pump.Comparative example 3
Except 2.5 gram trimethylolpropane trimethacrylates, 1.0 gram two-trimethylolpropane tetra-acrylate and 0.35 are restrained 2,2 '-azo two-2, the 4-methyl pentane nitrile is dissolved in the 19 gram mineral turpentine, add with the speed of pump of constant delivery type with about 0.76 gram/minute, 0.5 outside hour adding, stick with paste with the aluminium that legal system gets application of resin by embodiment 1.The non-volatility component content (according to JIS-K-5910) that this aluminium is stuck with paste is 60.0%.Comparative example 4
Except the miscellany that vinylformic acid replaced with 0.88 gram vinyltrimethoxy silane, 0.06 gram phosphoric acid, 0.06 gram water and 1.00 gram 2-butanols, trimethylolpropane trimethacrylate and two-trimethylolpropane tetra-acrylate replaced with 3.5 restrain trimethylolpropane trimethacrylates, trimethylolpropane trimethacrylate is dissolved in the solution that obtains in the 19 gram mineral turpentine to add by the speed of pump of constant delivery type with about 0.78 gram/minute, 0.5 outside hour adding, stick with paste with the aluminium that legal system gets application of resin by embodiment 1.The non-volatility component content (according to JIS-K-5910) that this aluminium is stuck with paste is 60.0%.Comparative example 5
Remove and do not carry out appending continuously the operation of interpolation, but trimethylolpropane trimethacrylate is dissolved in outside the disposable adding of the solution that obtains in the mineral turpentine, stick with paste with the aluminium that legal system gets application of resin by comparative example 4 by pump of constant delivery type.The non-volatility component content (according to JIS-K-5910) that this aluminium is stuck with paste is 60.0%.
The performance that embodiment 1～8, comparative example 1～5 gained aluminium are stuck with paste is as shown in table 2.
In the table 2, the cooperation ratio of polyfunctional monomer is illustrated in the shared ratio (weight ratio) of monomer that has free-radical polymerised pair of key more than 4 in the monomer total amount that has free-radical polymerised pair of key more than 3.
Table 2 aluminium is stuck with paste performance
| The cooperation ratio % of polyfunctional monomer * 1 | Reinforced time * 2 (%) | Oil number (gram/gram) | Storage stability * 3 in the water-based paint | Alkali resistance Δ E (8-d method) | Gloss retention (%) | |
| Embodiment 1 | 29 | 50 | 1.42 | ○ | 0.7 | 91 |
| Embodiment 2 | 0 | 50 | 1.61 | ○ | 1.7 | 90 |
| Embodiment 3 | 20 | 57 | 1.56 | ○ | 0.2 | 90 |
| Embodiment 4 | 33 | 50 | 1.45 | ○ | 0.3 | 90 |
| Embodiment 5 | 71 | 50 | 1.70 | ○ | 2.0 | 89 |
| Embodiment 6 | 29 | 20 | 1.60 | ○ | 1.0 | 90 |
| Embodiment 7 | 29 | 50 | 1.31 | ○ | 0.2 | 92 |
| Embodiment 8 | 29 | 50 | 1.41 | ○ | 0.6 | 90 |
| Comparative example 1 | 29 | 0 | 1.82 | × | 2.5 | 88 |
| Comparative example 2 | 0 | 0 | 1.90 | × | 3.0 | 85 |
| Comparative example 3 | 29 | 8 | 1.84 | × | 2.3 | 88 |
| Comparative example 4 | 0 | 7 | 1.44 | ○ | 15.0 | 88 |
| Comparative example 5 | 0 | 0 | 1.44 | ○ | 17.0 | 88 |
* 1 monomer that has a free-radical polymerised pair of key more than 4
* the reinforced time of 2 compositions (B) and/or composition (C) accounts for the per-cent of polymerization time
* the storage stability in 3 water-based paints
Zero: 10 milliliters of gas generating capacities/below the gram
*: 10 milliliters of gas generating capacities/more than the gram
Embodiment 9
Use the aluminium paste of the application of resin of embodiment 1 gained to stick with paste (MG-51: Asahi Chemical Industry Co., Ltd makes) and fluoro-resin with the aluminium paste of the application of resin of comparative example 2 gained, the aluminium of uncoated plastic resin treatment, make after the coating according to the coating formula of table 3, (on 1 * 70 * 150mm), making thickness is 30 μ to be coated on aluminium sheet with the gas blowout finishing.100 ℃ were descended dry 30 minutes then, made the metal deposit of fluororesin-type.
Table 3 coating formula (weight part)
| LUM IFURON LF 200 *1 | 100 |
| Aluminium is stuck with paste (in non-volatility composition 100%) | 10.2 |
| DURANATE TPA-100 *2 | 7.8 |
| Thinner *3 | 150 |
| Add up to | 268.0 |
* 1 ... Asahi Glass (strain) is made
* 2 ... Asahi Chemical Industry's industry (strain) is made
* 3 ... toluene/dimethylbenzene/ethyl acetate and butyl acetate
Weight ratio=30/20/20/30
This metal deposit is carried out the spot test of chemical-resistant under 20 ℃, implemented 10 days, estimate the variable color degree of filming then.In addition, carry out 3000 hours exposure test in same filming with weather at sunshine (sunshinew etherom eter, SW O M).Chemical-resistant is tested used medicine and is respectively 10% hydrochloric acid, 10%NaOH, the 10% vitriolic aqueous solution.Its result is as shown in table 4.
The variable color degree evaluation that table 4 is filmed
| The kind that aluminium is stuck with paste | The variable color degree of filming | |||
| 10% hydrochloric acid spot test | The 10%NaOH spot test | 10% sulfuric acid spot test | Weather meter test at sunshine | |
| The aluminium of the application of resin of embodiment 1 is stuck with paste | ○ | ○ | ○ | ○ |
| The aluminium of the application of resin of comparative example 2 is stuck with paste | △ | △ | ○ | △ |
| MG-51 (untreated aluminium paste) | × | × | × | △ |
Zero: no variable color
△: little have a variable color
*: obviously variable color
As seen from the above table, the not variation fully of in the chemical-resistant test, filming of filming that the aluminium of the application of resin of the employing embodiment of the invention 1 is stuck with paste.And in the test that weather carries out in sunshine, what the aluminium of the application of resin of the employing embodiment of the invention 1 was stuck with paste films, and its appearance of film is also almost distinguished and misknowed variation, shown good weathering resistance.
Embodiment 10
Press the coating formula of table 5, use vinylidene fluoride type fluoro-resin to make after the resin type coating, coat on the aluminium sheet with bar-shaped coating machine, making thickness is 30 μ, 240 ℃ of dryings 5 minutes, makes and films then.Carry out chemical-resistant spot test similarly to Example 9.As a result, what the aluminium of the application of resin of employing embodiment 1 was stuck with paste films, identical with embodiment 9, has demonstrated extremely good chemical-resistant.
Table 5 coating formula (weight part)
| Paraloid B-44 *1 | 15.2 |
| Aluminium is stuck with paste (in non-volatility composition 100%) | 9.2 |
| Thinner *2 | 120 |
| NEOFLON VDF VP-850 *3 | 45.6 |
| Add up to | 190.0 |
* 1 ... Rohm and Haas company makes
* 2 ... isophorone/dimethyl phthalate/toluene/isobutyl acetate/acetate
The weight ratio of ethyl ester=45/24/15/8/8
* 3 ... Daikin Industries company produces
Embodiment 11
The aluminium of the application of resin of embodiment 1 gained stuck with paste to stick with paste according to the coating formula of table 6 with the aluminium of the application of resin of comparative example 2 gained make after the coating, be coated on the ABS resin plate with the gas blowout finishing in the same manner with embodiment 10, making thickness is 30 μ.Drying was measured the 60 degree gloss of filming after 24 hours under the room temperature then, and the coating film gloss that the result adopts the aluminium of the application of resin of embodiment 1 gained to stick with paste as can be seen is 65% high value, and the coating film gloss of the aluminium paste of the application of resin of employing comparative example 2 gained is 53%.
Table 6 coating formula (weight part)
| ACRYDIC A -801 *1 | 100 |
| Aluminium is stuck with paste (in non-volatility composition 100%) | 5 |
| DURANATE TPA -100 | 16.2 |
| Thinner *2 | 120 |
| Catalyzer (two lauric acid dibutylesters) | 1.0 |
| Add up to | 242.2 |
* 1 ... big Japanese ink chemistry (strain) is made
* 2 ... ethyl acetate and butyl acetate/toluene/dimethylbenzene/methoxyacetic acid propyl ester
Weight ratio=20/30/30/15/5
Embodiment 12
The aluminium of the application of resin of embodiment 1～8, comparative example 1～5 gained stuck with paste make water-based paint, estimate its storage stability by table 7 proportioning.Above-mentioned coating 100 is restrained in the Erlenmeyer flask that joins 200 milliliters respectively, seal with the plug of being with volume pipette, the aerogenesis state of 50 ℃ of following placements after 24 hours is shown in preceding table 2.The aluminium of the application of resin of embodiment 1 gained stuck with paste make water-based paint by table 7 proportioning, be coated on the aluminium sheet with the gas blowout finishing, making thickness is 30 μ.170 ℃ of following dryings were made and are filmed after 20 minutes then, obtained having filming of good metal sense.
Table 7 coating formula (weight part)
| The metal ingredient of the metallic pigment of application of resin | 2821 |
| Water soluble acrylic resin's (heating nubbin=50%) *1 | 370 |
| Water-soluble melamine resin (heating nubbin=50%) *2 | 100 |
| Pure water | 491 |
| Add up to | 3782 |
* 1 ... ALM ATEXWA-911 (chemistry (strain) manufacturing is pressed in Mitsui east)
The middle dimethylethanolamine that adds is adjusted pH to 9.5
* 2 ... CYMEL 350 (Mitsui CYTEC (strain) manufacturing)
Embodiment 13
The aluminium of measuring the application of resin of embodiment 1 gained is stuck with paste, the aluminium of the application of resin of comparative example 2 gained is stuck with paste, the aluminium of uncoated plastic resin treatment is stuck with paste (MG-51: specific surface area Asahi Chemical Industry Co., Ltd's manufacturing).Its result is as shown in table 8.The specific surface area that the aluminium of the application of resin of embodiment 1 gained is stuck with paste is 1.9 times that uncoated plastic resin treatment aluminium is stuck with paste, the specific surface area that the aluminium of the application of resin of comparative example 2 gained is stuck with paste is 3.0 times that the aluminium of uncoated plastic resin treatment is stuck with paste, thus the result as can be seen the aluminium of the application of resin of embodiment 1 gained muddled what apply is highly three-dimensional cross-linked resin.
Table 8 specific surface area
Embodiment 14
Replace with outside the MH-8801 (Asahi Chemical Industry Co., Ltd makes, metal ingredient content 65%) except that embodiment 1 used aluminium is stuck with paste, stick with paste by the aluminium that embodiment 1 makes application of resin with method.Measure the aluminium of the application of resin of gained and stick with paste alkali resistance, aberration Δ E=0.3 has shown good alkali resistance.Comparative example 6
Change into outside the MH-8801 (Asahi Chemical Industry Co., Ltd makes, metal ingredient content 65%) except that comparative example 2 used aluminium are stuck with paste, stick with paste by the aluminium that comparative example 2 is made application of resin with method.Measure the aluminium of the application of resin of gained and stick with paste alkali resistance, aberration Δ E=3.1.
Embodiment 15
The aluminium of measuring the application of resin of embodiment 14 gained is stuck with paste, the aluminium of the application of resin of comparative example 6 gained is stuck with paste, the aluminium of uncoated plastic resin treatment is stuck with paste (MH-8801: specific surface area Asahi Chemical Industry Co., Ltd's manufacturing).Its result is as shown in table 9.The specific surface area that the aluminium of the application of resin of embodiment 14 gained is stuck with paste is 1.5 times that uncoated plastic resin treatment aluminium is stuck with paste, the specific surface area that the aluminium of the application of resin of comparative example 6 gained is stuck with paste is 3.0 times that aluminium that uncoated is handled is stuck with paste, thus the result as can be seen the aluminium of the application of resin of embodiment 13 gained muddled what apply is highly three-dimensional cross-linked resin.
Table 9 specific surface area
| Comparative example 6 | 28.5 | 3.0 |
| MH-8801 | 9.5 | - |
The metallic pigment of application of resin of the present invention be the resin of high crosslink density owing to what apply, so chemical-resistant, weathering resistance and storage stability are good.And specific surface area is little, and oil number is little, can be being suppressed to bottom line because the gloss that application of resin causes reduces.
Because above-mentioned reason, the metallic pigment of application of resin of the present invention are suitable for use in metallic paint, printing-ink, are admixed to the purposes in the plastics.
In addition,, therefore be applicable to the parts such as car body, collision bumper, side mirror of life requirement, the extraneous adornment of buildingss such as veneer, roof, wall, and field such as household electrical appliances because metallic paint of the present invention has good weathering resistance.
Claims (9)
1, a kind of metallic pigment of application of resin, it is characterized in that, use following (A), (B), (C) three kinds of raw materials, wherein (A) is from free-radical polymerised unsaturated carboxylic acid, and/or have the monoesters or a diester of the Phosphoric acid or phosphonic acid of free-radical polymerised pair of key, and/or have select in the coupler of free-radical polymerised pair of key at least a, (B) for having the monomer of free-radical polymerised pair of key more than 3, (C) be polymerization starter, at first adding (A) handles after the metallic pigment, with (B) with (C) at least aly slowly append adding, form the polymeric resin layer in the metallic surface
Wherein, the consumption of the free-radical polymerised unsaturated carboxylic acid (A) is 0.01～10 weight part with respect to 100 weight part metallic pigment, having the monoesters of Phosphoric acid or phosphonic acid of free-radical polymerised pair of key or the consumption of diester is 0.01～30 weight part with respect to 100 weight part metallic pigment, the consumption that has the coupler of free-radical polymerised pair of key is 0.01～30 weight part with respect to 100 weight part metallic pigment, and the consumption that has the coupler of free-radical polymerised pair of key is 0.01～20 weight part with respect to 100 weight part metallic pigment; (B) consumption is 2～50 weight parts with respect to metal ingredient 100 weight parts of metallic pigment; (C) consumption is 0.1～50 weight part with respect to the monomer that 100 weight parts have free-radical polymerised pair of key more than 3.
2, according to the metallic pigment of the application of resin of claim 1 record, it is characterized in that, as the monomer that has free-radical polymerised pair of key more than 3 of (B) is the monomer and the monomeric miscellany that has free-radical polymerised pair of key more than 4 that has 3 free-radical polymerised pair of keys, has wherein that the monomeric weight ratio of free-radical polymerised pair of key is 10～60% more than 4.
3, according to the metallic pigment of the application of resin of claim 1 record, it is characterized in that, (B) with (C) at least a joining day of appending be more than 20% of polymerization time.
4, according to the metallic pigment of the application of resin of claim 2 record, it is characterized in that, (B) with (C) at least a joining day of appending be more than 20% of polymerization time.
According to the metallic pigment of the application of resin of claim 1 record, it is characterized in that 5, the molecular weight that has monomeric each functional group of free-radical polymerised pair of key more than 4 is more than 30 below 200.
According to the metallic pigment of the application of resin of claim 2 record, it is characterized in that 6, the molecular weight that has monomeric each functional group of free-radical polymerised pair of key more than 4 is more than 30 below 200.
According to the metallic pigment of the application of resin of claim 3 record, it is characterized in that 7, the molecular weight that has monomeric each functional group of free-radical polymerised pair of key more than 4 is more than 30 below 200.
According to the metallic pigment of the application of resin of claim 4 record, it is characterized in that 8, the molecular weight that has monomeric each functional group of free-radical polymerised pair of key more than 4 is more than 30 below 200.
9, the metallic paint that contains the metallic pigment of the application of resin of each record in the claim 1 to 8.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP131828/95 | 1995-05-30 | ||
| JP13182895 | 1995-05-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1185798A CN1185798A (en) | 1998-06-24 |
| CN1093155C true CN1093155C (en) | 2002-10-23 |
Family
ID=15067057
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96194273A Expired - Lifetime CN1093155C (en) | 1995-05-30 | 1996-05-29 | Novel resin-coated metallic pigment and metallic coating material containing the pigment |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP3903325B2 (en) |
| KR (1) | KR100327274B1 (en) |
| CN (1) | CN1093155C (en) |
| MY (1) | MY121596A (en) |
| TW (1) | TW425419B (en) |
| WO (1) | WO1996038506A1 (en) |
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| US7837777B2 (en) | 2004-03-24 | 2010-11-23 | Toyo Aluminium Kabushiki Kaisha | Metallic pigment composition and UV metallic ink composition or UV metallic coating composition using the same |
| CN1898340B (en) * | 2003-12-23 | 2011-06-22 | 埃卡特有限公司 | Metal pigments comprising a cross-linkable binding agent coating, coating composition, method for the production of coated metal pigments and use thereof |
| CN109415576A (en) * | 2016-09-06 | 2019-03-01 | Dic株式会社 | Resin-coated inorganic or metallic pigments |
| US11186722B2 (en) | 2016-09-06 | 2021-11-30 | Dic Corporation | Resin coated inorganic or metallic pigment |
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| JP2000044835A (en) * | 1998-07-27 | 2000-02-15 | Asahi Chem Ind Co Ltd | Resin-coated metallic pigment and metallic coating material produced by using the pigment |
| JP2001115061A (en) * | 1999-10-14 | 2001-04-24 | Showa Aluminum Powder Kk | Metal pigment and its production |
| JP2001139887A (en) * | 1999-11-11 | 2001-05-22 | Asahi Kasei Metals Kk | Metallic powder coating composition |
| JP2003020413A (en) * | 2001-07-10 | 2003-01-24 | Cemedine Co Ltd | Highly designable composition |
| JP2004307409A (en) * | 2003-04-08 | 2004-11-04 | Fuji Kasei Kk | Pigment for cosmetic and cosmetic containing the same |
| CN1774482B (en) * | 2003-07-18 | 2010-04-28 | 东洋铝株式会社 | Flake pigment, coating material and powder coating composition each containing the same, and surface-treating agent for flaky particle for use therein |
| US7223476B2 (en) | 2004-06-14 | 2007-05-29 | Ppg Industries Ohio, Inc. | Composite flakes and methods for making and using the same |
| JP5352939B2 (en) * | 2004-09-28 | 2013-11-27 | セイコーエプソン株式会社 | Encapsulated inorganic fine particles and production method thereof, coating composition containing encapsulated inorganic fine particles and coating method thereof, and printing composition containing encapsulated inorganic fine particles and printing method thereof |
| JP4942294B2 (en) * | 2004-12-16 | 2012-05-30 | 東洋アルミニウム株式会社 | Metallic pigment and paint containing the same |
| FR2879613B1 (en) * | 2004-12-22 | 2007-01-26 | Toyal Europ Sa Sa | COMPOSITION OF METAL PIGMENTS |
| EP1953195B1 (en) | 2005-10-13 | 2017-12-13 | Toyo Aluminium Kabushiki Kaisha | Coated metal pigment, method for production of the pigment, and coating composition comprising the pigment |
| JP4611176B2 (en) | 2005-10-31 | 2011-01-12 | 東洋アルミニウム株式会社 | Method for producing resin-coated metal pigment |
| JP4921923B2 (en) * | 2006-10-25 | 2012-04-25 | テクノポリマー株式会社 | Resin composition for extrusion molding, molded product and laminated product |
| JP5153160B2 (en) * | 2007-02-16 | 2013-02-27 | 旭化成ケミカルズ株式会社 | Metal pigment composition |
| JP2010254934A (en) * | 2009-04-28 | 2010-11-11 | Tokai Rika Co Ltd | Metallic coating and metallic ink, metallic coated film, as well as producing method of them |
| EP2479224B1 (en) | 2009-09-18 | 2017-02-22 | Asahi Kasei Kabushiki Kaisha | Resin-coated metal pigment, and process for producing same |
| KR101471737B1 (en) | 2010-06-08 | 2014-12-10 | 아사히 가세이 케미칼즈 가부시키가이샤 | Metallic pigment composition |
| JP2015505716A (en) * | 2011-11-15 | 2015-02-26 | アプセト ゲーエムベーハー アンド ツェーオー．カーゲー | Polymer modified substrate, its manufacture and its use |
| US9499696B2 (en) | 2012-09-14 | 2016-11-22 | Toyo Aluminum Kabushiki Kaisha | Colored metallic pigment and method for producing the same |
| JP2014088508A (en) * | 2012-10-30 | 2014-05-15 | Asahi Kasei Chemicals Corp | Resin-coated metallic pigment and coating composition |
| JP6020103B2 (en) * | 2012-12-06 | 2016-11-02 | セイコーエプソン株式会社 | UV-curable ink jet composition and recorded matter |
| JP6766154B2 (en) * | 2016-09-06 | 2020-10-07 | Dic株式会社 | Resin coated aluminum pigment |
| EP3921374A2 (en) | 2019-02-05 | 2021-12-15 | Silberline Limited | New product |
| KR20230001525A (en) * | 2021-06-28 | 2023-01-04 | 아사히 가세이 가부시키가이샤 | Packaging body of metallic pigment composition |
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| US4750940A (en) * | 1985-09-07 | 1988-06-14 | Asahi Kasei Metals Limited | Novel resin-coated metallic pigment and a process for producing the same |
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| JPS59224102A (en) * | 1983-06-03 | 1984-12-17 | Ricoh Co Ltd | Surface treating method of magnetic powder |
| JPS62253668A (en) * | 1985-09-07 | 1987-11-05 | Asahi Kasei Metals Kk | Novel resin-coated metallic pigment and its production |
| JPH0692546B2 (en) * | 1988-06-16 | 1994-11-16 | 昭和アルミパウダー株式会社 | Colored metallic pigment and method for producing the same |
| JP2535432B2 (en) * | 1990-05-16 | 1996-09-18 | 旭化成メタルズ株式会社 | Aluminum pigment composition for low temperature curable one-pack paint |
-
1996
- 1996-05-29 KR KR1019970707377A patent/KR100327274B1/en active IP Right Grant
- 1996-05-29 TW TW085106386A patent/TW425419B/en not_active IP Right Cessation
- 1996-05-29 JP JP53636896A patent/JP3903325B2/en not_active Expired - Lifetime
- 1996-05-29 CN CN96194273A patent/CN1093155C/en not_active Expired - Lifetime
- 1996-05-29 WO PCT/JP1996/001450 patent/WO1996038506A1/en not_active Application Discontinuation
- 1996-05-30 MY MYPI96002096A patent/MY121596A/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4750940A (en) * | 1985-09-07 | 1988-06-14 | Asahi Kasei Metals Limited | Novel resin-coated metallic pigment and a process for producing the same |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1898340B (en) * | 2003-12-23 | 2011-06-22 | 埃卡特有限公司 | Metal pigments comprising a cross-linkable binding agent coating, coating composition, method for the production of coated metal pigments and use thereof |
| US7837777B2 (en) | 2004-03-24 | 2010-11-23 | Toyo Aluminium Kabushiki Kaisha | Metallic pigment composition and UV metallic ink composition or UV metallic coating composition using the same |
| CN1930251B (en) * | 2004-03-24 | 2011-08-17 | 东洋铝株式会社 | Metallic pigment composition, and UV-metallic ink composition or UV-metallic coating composition using the same |
| CN109415576A (en) * | 2016-09-06 | 2019-03-01 | Dic株式会社 | Resin-coated inorganic or metallic pigments |
| US11186722B2 (en) | 2016-09-06 | 2021-11-30 | Dic Corporation | Resin coated inorganic or metallic pigment |
| CN109415576B (en) * | 2016-09-06 | 2022-02-25 | Dic株式会社 | Resin-coated inorganic or metallic pigment |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100327274B1 (en) | 2002-09-27 |
| CN1185798A (en) | 1998-06-24 |
| MY121596A (en) | 2006-02-28 |
| WO1996038506A1 (en) | 1996-12-05 |
| TW425419B (en) | 2001-03-11 |
| JP3903325B2 (en) | 2007-04-11 |
| KR19990007854A (en) | 1999-01-25 |
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| EXPY | Termination of patent right or utility model |