CN1910243A - Colored brilliant pigment - Google Patents

Abstract

A colored bright pigment, characterized in that it comprises a scaly glass and, formed on the surface thereof, a silica-based coating film containing an organic pigment. It is preferred that a titanium oxide is coated on the surface of the above scaly glass, or, that a metal is coated on the surface of the above scaly glass and further the above silica-based coating film is coated. The above colored bright pigment is compounded in a paint, a resin composition, an ink, a cosmetic and the like, and can provide a color which exhibits high feeling of transparency and brightness, and also exhibits high saturation and clearness and accuracy.

Description

Colored brilliant pigment

Technical field

The present invention relates to a kind of colored brilliant pigment that shows high-clarity and lightness.Further, the present invention relates to a kind of colored brilliant pigment with metalluster and interference color.Further, coating material, resin combination, printing ink or the makeup of the present invention about containing described colored brilliant pigment.

Background technology

About brilliant pigment, the squamous sheet glass of previously known flakey aluminium powder, graphite platy shaped particle, squamous sheet glass, silver-coating and be coated with for example mica platy shaped particle of titanium dioxide or ferric oxide of metal oxide.

Because these colored brilliant pigment characteristics showed are light and glittering giving out light on their reflecting surfaces, so they can be used for coating material, printing ink, resin combination, makeup etc.When this brilliant pigment is used for coating material, printing ink or resin combination,, so can gives the surface of coated product, print product or layered product respectively and have the different outward appearances of good ornamental uniqueness because these pigment combine with the tone of substrate.

In addition, about having the brilliant pigment of metalluster, wherein known aluminium powder is arranged, by grinding the product that obtained by the paper tinsel shape resin of metallic cover and the mica powder of metallic cover.Because these brilliant pigments have metalluster, can produce strong lightness by them, thereby obtain good outward appearance pattern.

Therefore, brilliant pigment is at the coating material that is used to apply automobile, motorcycle, OA (office automation) equipment, mobile telephone, household electrical appliance; The printing ink that is used for various PRN devices or writing material, and the makeup aspect has very wide application.

Significantly, the flakey basis material table that coats with titanium dioxide or ferric oxide reveals various interference color, depends on the thickness (referring to, for example, JP 10-101957-A) of coat.But, being difficult to produce the transparent tone that produces by this class interference color colour developing, colour developing wherein is different from the colour developing that takes place in the pigment dyestuff photoabsorption.

Therefore, JP 7-133211-A discloses a kind of colored cosmetic pigment, and it obtains by coat the metal oxide gel that contains pigment on the surface of the inorganic base with smooth surface.In addition, JP 2001-152049-A discloses a kind of tinting pigment, and it coats with the metal oxide gel that uses mineral dye.

On the other hand, although the powder that is coated with metal-powder or is coated with metal can show high lightness, because it is an Achromatic color, thereby its pattern (design) is poor.Therefore, in order to obtain Chromatic color, adopted wherein tinting pigment and powder are carried out the blended method, this powder is by metal-powder or metallic cover.But, also there is a problem, promptly owing to belong to powder or do not have the color that handsel belongs to the powder of coating with no handsel and be highlighted, thereby be difficult to obtain transparent tone.

Therefore, JP 6-92546-B discloses a kind of colorize method, and it comprises by the resin-coating method pigment is adhered on the single aluminum slice.

Summary of the invention

The problem to be solved in the present invention

Because disclosed technology relates to cosmetic pigment among the above-mentioned JP 7-133211-A, the therefore actual here inorganic substance that use can be mica.But the micaceous appearance color is almost white in many cases, even therefore also can't obtain transparent tone after mica is contained the metal oxide gel coating of pigment.

In addition, in the disclosed technology of JP 7-133211-A, be difficult to obtain the sufficient adhesive capacity of pigment, cause to obtain transparent tone.In addition, even can increase the adhesive capacity of pigment, but the problem that exists is the pigment separate easily, and step more complicated and trouble.

Thereby the object of the invention provides a kind of brilliant pigment that shows high-clarity and lightness and high chroma and transparent tone.Another object of the present invention provides coating material, resin combination, printing ink and the makeup that use this brilliant pigment.

The method of dealing with problems

Broad research by the inventor, the result shows, found a kind of transparent color that shows high-clarity and lightness, and, can obtain high chroma by being coated on the surface that the base mateiral of choosing the squamous sheet glass with coat wantonly is gone up on the surface with the silica-based coat film that contains pigment.The present inventor has finished the present invention by furtheing investigate.

That is to say, the present invention relates to:

(1) a kind of colored brilliant pigment, it comprises the surface form slection of taking up an official post and becomes the silica-based coat film that the squamous glass flake base mateiral of coat, the surface of wherein said base mateiral are contained pigment to coat,

(2) colored brilliant pigment of above-mentioned (1), wherein said pigment are mineral dye or pigment dyestuff,

(3) colored brilliant pigment of above-mentioned (1) or (2), wherein the mean particle size of pigment is 10nm～1 μ m,

(4) each colored brilliant pigment in above-mentioned (1)～(3), wherein base mateiral is that the squamous glass flake that forms the coating rete is gone up on its surface,

(5) colored brilliant pigment of above-mentioned (4) wherein applies rete and is made up of at least a metal, and described metal is selected from gold and silver, platinum, palladium, titanium, cobalt and nickel, and/or its alloy,

(6) colored brilliant pigment of above-mentioned (4) wherein applies rete and is made up of at least a metal oxide, and described metal oxide is selected from titanium oxide, ferric oxide and zirconium white,

(7) each colored brilliant pigment in above-mentioned (1)～(6), wherein silica-based coating film is the matrix that only comprises silica basically,

(8) a kind of coating material comprises in above-mentioned (1)～(7) each colored brilliant pigment,

(9) a kind of resin combination comprises in above-mentioned (1)～(7) each colored brilliant pigment,

(10) a kind of printing ink, comprise in above-mentioned (1)～(7) each colored brilliant pigment and

(11) a kind of makeup comprise in above-mentioned (1)～(7) each colored brilliant pigment.

The invention effect

Colored brilliant pigment of the present invention coats with the silica-based coat film that comprises the squamous glass flake that contains pigment.Be different from mica, because the squamous glass flake is transparent, and has smooth surface, therefore the pigment of being made up of this base mateiral shows high transparency and lightness.In addition, because the colour developing of pigment of the present invention is not fully based on interference color, and be based on pigment, so the present invention can obtain to have the transparent color of high chroma.

Therefore, shade can realize that this is unknown in the prior art by these colored brilliant pigments are applied in coating material or the resin composition.For example, the surface is normally observed from Small angle in many cases in the surface that constitutes curved surface.Even in this case, use the coating material of colored brilliant pigment of the present invention or the transparent tone of resin combination can not be damaged, thereby colored brilliant pigment of the present invention is preferred.

In addition, when using the squamous glass flake that coated by metal oxide (particularly titanium oxide) as base mateiral, can obtain such brilliant pigment, wherein the color of pigment (particularly pigment dyestuff) is different with the squamous glass flake that shows interference color.In this case, when observing from different perspectives, all can obtain the so-called effect (flip-flop) of tonal variation, thereby can provide different tones for product.

Brief Description Of Drawings

Fig. 1 has shown the cross sectional representation of an embodiment of colored brilliant pigment of the present invention.

The explanation of mark

1: colored brilliant pigment

21: the squamous glass flake

22: coat

31: silica-based coat film

32: pigment

Implement best mode of the present invention

Colored brilliant pigment of the present invention is characterised in that the optional squamous glass flake base mateiral with coating layer in surface coats with the silica-based coat film that contains pigment.

(base mateiral)

As base mateiral of the present invention, the preferred squamous glass flake that uses with height smooth surface and high-clarity.Applying rete can be formed on the surface of these squamous glass flakes.Because when the squamous glass flake is used metallic cover, obtain metalluster, the therefore preferred squamous glass flake that uses this metallic cover.The example of metal is at least a following metal that is selected from: gold and silver, platinum, palladium, titanium, cobalt and nickel and/or its alloy.And, owing to when the squamous glass flake coats with metal oxide (especially titanium oxide), show interference color, the therefore preferred squamous glass flake that uses this coating.Metal oxide is preferably at least a to be selected from following metal oxide: titanium oxide, ferric oxide and zirconium white, wherein, titanium oxide is more preferred.

Squamous glass flake used among the present invention can be by the preparation of " blowing " method." blowing " method comprises the steps: the melting cullet material; When with gas such as air etc. when blow nozzle blows out, take out the glass of thawing continuously from rounded slot, wherein said nozzle is installed in the inboard of rounded slot; Expanding, it forms balloon-like when melting glass, stretches then; With thin glass crushing, thereby form the squamous glass flake.

During as melt molding, the surface of gained squamous glass flake remains with the flame polished surface with slickness.Described squamous glass flake is because of its smooth surface reflected light well.Preferably these squamous glass flakes are added in coating material or the resin combination, because can obtain high lightness.As the squamous glass flake, for example, (RCF-015 REF-015) can be from Nippon Sheet Glass Co. for RCF-160, REF-160, and Ltd. is commercial to be obtained for MICROGLAS (registered trademark) R-GLASFLAKE (registered trademark) R-series.

Method with metallic cover squamous glass flake is not particularly limited, and can be any in the currently known methods.

As with metallic cover and show the squamous glass flake of brightness, METASHINE (registered trademark) RPS series, MC5480PS for example, MC5230PS, MC5150PS, MC5090PS, MC5030PS, MC2080PS, ME2040PS, ME2025PS, MC5480NS, MC5230NS, MC5150NS, MC5090NS, MC5030NS, MC5480NB, MC5230NB, MC5150NB, MC5090NB, MC5030NB, MC1040NB and MC1020NB can be from Nippon Sheet Glass Co., and Ltd. is commercial to be obtained.

The method that coats the squamous glass flake with metal oxide is not particularly limited, and currently known methods such as sputtering method, sol-gel method, CVD method and LPD method all can be used.When the granular base material coats with metal oxide as the squamous glass flake, preferably use the LPD method, wherein metal oxide from the metal salt precipitate to the surface on.And in order to show interference color, the metal oxide with high diffraction efficiency is preferred.For example, in the situation of titanium oxide, use the intermediate processing of neutralization reaction optimal, for example wherein the rutile form of titanium dioxide can directly be deposited in the lip-deep method of squamous glass flake.More particularly, as open in JP 2001-31421-A by inventor of the present invention, it is included in 55～85 ℃ and pH value and is no more than at 1.3 o'clock, precipitates the method for the titanium dioxide of rutile crystal form from titaniferous solution.

As the squamous glass flake that coats and show interference color with metal oxide, for example, METASHINE (registered trademark) RRC series, MC5090RS for example, MC5090RY, MC5090RR, MC5090RB, MC5090RG, MC1080RS, MC1080RY, MC1080RR, MC1080RB, MC1080RG, MC1040RS, MC1040RY, MC1040RR, MC1040RB, MC1040RG, MC1020RS, MC1020RY, MC1020RR, MC1020RB, MC1020RG, MC5090FG, MC5090FR, MC5090FB and MC5090FC can be from Nippon Sheet Glass Co., and Ltd. is commercial to be obtained.

The present invention becomes the mean particle size and the mean thickness of the squamous glass flake of coat film to be not particularly limited to the form slection of taking up an official post of its surface, although they according to using order difference.Usually, mean particle size is preferably 1～500 μ m, and mean thickness is preferably 0.1～10 μ m.If granularity is excessive, the fragmentation when brilliant pigment being added in coating material or the resin combination of squamous glass flake.Especially, under the situation that the squamous glass flake coats with titanium oxide, because the exposure of cross section makes the basic component that is included in wherein to ooze out.

In addition on the one hand, when undersized, the plane random orientation of brilliant pigment in coating material or the resin combination, the reflected light that has weakened and sent from single particulate, thus cause the luminance loss.

When brilliant pigment is used for printing ink, preferred less granularity, and the mean particle size that can form the squamous glass flake of coat on the surface is preferably 1～40 μ m, and mean thickness is preferably 0.5～3 μ m.

In order to give or to improve chemical resistant properties, especially for the alkali resistance of squamous glass flake of the present invention, wherein can form coat film in its surface, coating such as the upper space can oxidized zirconium, aluminum oxide, zinc oxide.Having zirconic coating is finished by currently known methods such as liquid phase deposition.

(pigment)

The used pigment of the present invention can be any pigment dyestuff or mineral dye.Although the present invention is not particularly limited the size of used pigment, mean particle size is preferably 10nm～1 μ m.When mean particle size during less than 10nm, the weather resistance of the pigment extreme difference that becomes.On the other hand, when mean particle size surpassed 1 μ m, it is big that the opacifying power of pigment becomes, and causes the luminance loss.Therefore, tone dies down, if coat film is very thin, loses the surface flatness of coat film so.

The content of pigment preferably is no more than 30% (quality), is more preferably less than 10% (quality), most preferably is 0.1～3.0% (quality), with respect to the quality of base mateiral (optional squamous glass flake with coat film).

Kind to mineral dye is not particularly limited, and still, preferably uses following pigment.The pigment title is represented according to Color Index Generic Name (hereinafter being abbreviated as C.I.GN.).

Promptly, these pigment comprise red iron oxide (C.I.GN. Pigment red 101), iron black (C.I.GN. Pigment black 11), titan yellow (C.I.GN. Pigment Yellow 73 157, yellow 53, brown 24), zinc-iron brown (C.I.GN. Pigment Yellow 73 119, brown 33), cobalt titanate green (C.I.GN. Pigment green 50), cobalt green (C.I.GN. Pigment green 26), cobalt blue (C.I.GN. Pigment blue 28), copper iron oxide black (C.I.GN. Pigment black 26), zinc sulphide (C.I.GN. Pigment white 7), barium sulfate (C.I.GN. Pigment white 21), mazarine (C.I.GN. Pigment blue 29), lime carbonate (C.I.GN. Pigment white 18), violet cobalt (C.I.GN. pigment violet rowland 14), Yellow iron oxides (C.I.GN. Pigment Yellow 73 42, yellow 43), carbon black (C.I.GN. Pigment black 7), blue-greenish colour (ferrocyan) (C.I.GN. pigment blue 27), or the like.

Although the kind to pigment dyestuff is not particularly limited, it exemplarily is phthalocyanine pigment, insoluble azo colour, azo lake pigment, anthraquinone pigment, quinacridone pigment, two  piperazine pigment, diketopyrrolo-pyrrole pigment, anthracene pyridine pigment, anthanthrene ketone pigment, indanthrone pigment, flavanthrone pigment, purple cyclic ketones (perinone) pigment, perillene (perilene) pigment, thioindigo color, etc.

In C.I.GN, when being applied to automobile when needing weathering resistance, preferably use pigment dyestuff such as pigment green 36, Pigment red 179, pigment Blue 15, etc.

When organic pigment was used for makeup, at first exemplary was red pigment, comprises FD; C red No.2, FD ﹠amp; C Red No.3, FD ﹠amp; C Red No.102, FD ﹠amp; C RedNo.104, FD ﹠amp; C Red No.105, FD ﹠amp; C Red No.106, FD ﹠amp; C RedNo.201, FD ﹠amp; C Red No.202, FD ﹠amp; C Red No.203, FD ﹠amp; C RedNo.204, FD ﹠amp; C Red No.205, FD ﹠amp; C Red No.206, FD ﹠amp; C RedNo.207, FD ﹠amp; C Red No.208, FD ﹠amp; C Red No.213, FD ﹠amp; C RedNo.214, FD ﹠amp; C Red No.215, FD ﹠amp; C Red No.218, FD ﹠amp; C RedNo.219, FD ﹠amp; C Red No.220, FD ﹠amp; C Red No.221, FD ﹠amp; C RedNo.223, FD ﹠amp; C Red No.225, FD ﹠amp; C Red No.226, FD ﹠amp; C RedNo.227, FD ﹠amp; C Red No.228, FD ﹠amp; C Red No.230 (1), FD ﹠amp; C RedNo.230 (2), FD ﹠amp; C Red No.231, FD ﹠amp; C Red No.232, FD ﹠amp; C RedNo.405, etc.

In addition, as yellow ultramarine, exemplary have a FD ﹠amp; C Yellow No.4, FD ﹠amp; CYellow No.5, FD ﹠amp; C Yellow No.201, FD ﹠amp; C Yellow No.202-1, FD ﹠amp; C Yellow No.202-2, FD ﹠amp; C Yellow No.203, FD ﹠amp; C YellowNo.204, FD ﹠amp; C Yellow No.205, FD ﹠amp; C Yellow No.401, FD ﹠amp; CYellow No.402, FD ﹠amp; C Yellow No.403, FD ﹠amp; C Yellow No.404, FD ﹠amp; C Yellow No.405, FD ﹠amp; C Yellow No.406, FD ﹠amp; C YellowNo.407.

As veridian, exemplary have a FD ﹠amp; C Green No.3, FD ﹠amp; C GreenNo.201, FD ﹠amp; C Green No.202, FD ﹠amp; C Green No.204, FD ﹠amp; CGreen No.205, FD ﹠amp; C Green No.401, FD ﹠amp; C Green No.402, etc.

In addition, as blue pigments, exemplary have a FD ﹠amp; C Blue No.1, FD ﹠amp; CBlue No.2, FD ﹠amp; C Blue No.201, FD ﹠amp; C Blue No.202, FD ﹠amp; CBlue No.203, FD ﹠amp; C Blue No.204, FD ﹠amp; C Blue No.205, FD ﹠amp; CBlue No.403, FD ﹠amp; C Blue No.404, and as orange pigments, exemplary have a FD ﹠amp; C Orange No.201, FD ﹠amp; C Orange No.203, FD ﹠amp; C OrangeNo.204, FD ﹠amp; C Orange No.205, FD ﹠amp; C Orange No.206, FD ﹠amp; COrange No.207, FD ﹠amp; C Orange No.401, FD ﹠amp; C Orange No.402, FD ﹠amp; C Orange No.403.Except these pigment, further illustration has FD ﹠amp; C BrownNo.201, FD ﹠amp; C Purple No.201, FD ﹠amp; C Purple No.401 and FD ﹠amp; CBlack No.401.

When the squamous glass flake that coats with titanium oxide shows interference color, the interference color of squamous glass flake are not particularly limited with combining of pigment color.If make interference color near the color (especially pigment dyestuff) of pigment, then can increase the degree of depth of color, make to form preferred colors.

When the squamous glass flake that shows interference color is used as the coat film of the silica-based coat film coating that is not contained pigment, it is a bit different that interference color seem, and because light scatter seems also to be opaque and white, when especially observing coated surperficial with Small angle.

But, when the squamous glass flake that shows interference color coats with the silica-based coat film that contains pigment, and during subsequently as coat film,, not only do not observe different interference colors, and do not observe White-opalescent even observe the surface that is coated with Small angle.Even when any angle was observed, the tone of this coating was stable, therefore can obtain the shade of color.

By using and the different interference color of pigment color (especially pigment dyestuff), can obtain so-called effect, that is, and the color differences of the different demonstrations of angle according to the observation.In only using the brilliant pigment effect of interference color, the variation of tone and optical wavelength is similar, can realize freely changing of color in effect simultaneously, and wherein interference color and pigment color differ from one another, for example blue and yellow, perhaps red and green.

(silica-based coat film)

Pigment is included in the silica-based coat film, and is coated on the surface of base mateiral (that is, can form the squamous glass flake of coat in its surface).Silica-based coat film is easy to be applied on the surface of granulous squamous glass flake, for example passes through sol-gel method.In addition, silica-based coat film can be used as preferably that wherein pigment will be with dispersed matrix with which.

Silica-based coat film can comprise silica as main component, and its matrix can only be made up of silica basically.As the composition beyond the silica, titanium or zirconium can be included in wherein, to regulate refractive index or to give alkali resistance.

The silica-based coat film preferred thickness that comprises pigment is 50nm～1 μ m.When thickness was not more than 50nm, it can not contain the pigment of capacity, and tone shoals or the pigment that wherein comprises is easy to separate.

In addition on the one hand, when thickness surpasses 1 μ m, thereby tone deepens and loses lightness, and the layer that perhaps contains pigment is easy to separate.In addition, the cost of product uprises.

(production method that contains the silica-based coat film of pigment)

The production method that contains the silica-based coat film of pigment can be finished as follows: base mateiral is dispersed in the coating solution that contains organic metallic compound (containing the silicone ingredients that hydrolysis/condensation can take place) and pigment, then described organometallic compound is hydrolyzed/polycondensation, makes the surface of base mateiral be coated by silica-based coat film.In addition, organometallic compound can only be made up of silicoorganic compound.For the organometallic compound except that silicoorganic compound, it comprises for example organic titanic compound, organic zirconate and organo-aluminium compound.

The example of the silicoorganic compound that comprise in the coating solution is tetraalkoxysilane (as tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes etc.) and methyl trialkoxysilane (as methyltrimethoxy silane, Union carbide A-162, methyl tripropoxy silane, methyl three butoxy silanes, etc.).

In these silicoorganic compound, preferred use low-molecular-weight relatively compound, for example, have 3 or the tetraalkoxysilane of the alkoxyl group of carbon atom still less, because such tetraalkoxysilane can form better coating.In addition, in the polymkeric substance of these tetraalkoxysilanes, preferably use mean polymerisation degree to be no more than 5 polymkeric substance.

Coating solution comprises the silicoorganic compound of 0.5～20 quality % and the pigment of 0.1～5 quality %.Coating solution also comprises the water that is used for hydrolysis reaction.For example, the blending ratio (mol ratio) as the alkoxide silicon of silicoorganic compound and water be preferably 1: 25～100.By changing the component proportions of silicoorganic compound and pigment, can adjust the ratio of silica and pigment in the final coating.

Coating solution can further comprise solvent.The example of solvent comprises organic solvent such as hydrocarbon (for example hexane, toluene, hexanaphthene etc.); Halohydrocarbon (as methylene dichloride, tetracol phenixin, trieline etc.); Ketone (as acetone, methylethylketone etc.); Nitrogenous compound (as diethylamine etc.); Alcohol; Ester (as ethyl acetate etc.).In these solvents, preferably use alcoholic solvent, for example comprise methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, butanols and amylalcohol.In these alcohol, the example of the preferred alcohol that uses is to have 3 or the linear saturated monohydroxy alcohol of carbon atom still less, as methyl alcohol, and ethanol, 1-propyl alcohol and 2-propyl alcohol are because their velocity of evaporation at normal temperatures are fast.

Coating solution also comprises catalyzer.The type of catalyzer is basic catalyst preferably, ammonium hydroxide for example, ammoniacal liquor, sodium hydroxide etc.The pH of coating solution is generally 10～14.

As the catalyzer that is used for sol-gel method, use an acidic catalyst usually, example hydrochloric acid, hydrofluoric acid, nitric acid, acetic acid etc.But squamous glass flake of the present invention is similar with being used for, and when silica-based coat film is applied to the particulate state base mateiral, assembles mutually between particle, therefore preferably uses basic catalyst in this law is bright.

Base mateiral (promptly can form the squamous glass flake of coat film in its surface) is distributed in the coating solution with 1～60 quality %, and dispersion liquid was placed 1～15 hour, thus silicoorganic compound hydrolysis and polycondensation.As a result, produced the silica-based coat film that contains dispersed color, wherein having formed thickness on the whole surface of base mateiral is the coating of 50nm～1 μ m.Then, washed product is filtered and drying.Drying was preferably carried out 3～5 hours under room temperature to 200 ℃.

(purposes)

Because colored brilliant pigment security of the present invention and stability are high, and show pearliness and interfere iris, so it may be used on various uses, resin combination for example, printing ink, coating material, makeup etc.

For example, resin combination is applied to cosmetics containers, food product containers, wall coverings, floor overcover, home appliances, annex, stationery, toy, bathtub, bathhouse article, footwear, sporting goods, toiletry etc.

Printing ink is used and is comprised the packing parcel, wrapping paper, and wallpaper, clothes, decorative sheet, textiles, various films, label, etc.

Coating material can be used for the exterior coating of automobile, motorcycle or bike; Material of construction; Ceramic tile; Furniture; Household supplies; Container; Office appliance; Sporting goods; Deng.

Cosmetic applications comprises face cosmetic, the color make-up makeup, and cosmetic hair, etc.In these makeup, colored brilliant pigment especially preferably is used in end powder as in basis end powder and the flour, perhaps be used in the color make-up as eye shadow, and brush makeup, nail varnish, eyeliner, mascara, lipstick, colored powder, etc.Here the form for makeup does not have particular restriction, and the example of this class form comprises powder, cake, and pen, rod, ointment, liquid, emulsion, frost, etc.

For other application, colored brilliant pigment is applied to watercolor, greasepaint, and corium, leatheroid, textile printing, button, lacquer, ceramic outside surface, etc.

Hereinafter, by the mode of embodiment the present invention is carried out specific explanations, wherein routine 1-1 to 1-3 is to use the embodiment of mineral dye, and embodiment 2-1 to 2-4 is to use pigment dyestuff

Embodiment.

Embodiment 1-1

With tetraethoxysilane (15ml), ethanol (300ml) and pure water (60ml) mix.Add the solution (0.8g) that contains inorganic pigment microparticles (mean particle size is about 70nm) in mixture, the cobalt blue of 40 quality % (C.I.GN. Pigment blue 28) is mixed and made into coating solution with mixture.

Then, the glass flake (30g) (Ltd. produces for MEG020PS, Nippon SheetGlass Co.) that silver is coated is added in the above-mentioned coating solution, stirs and blend mixture in agitator.The glass flake mean particle size that silver coats is 20 μ m, and mean thickness is 0.7 μ m, and shows metalluster.Then, be that 25% ammonium hydroxide aqueous solution (14ml) is added in the coating solution with concentration, the mixture that obtains stirs also and mixed 2～3 hours, thereby the dehydration property polycondensation takes place.By this reaction, the silica coat film that comprises mineral dye is deposited on the surface of glass flake in the coating solution equably.Subsequently, filter and cleaning reaction solution, repeat this program repeatedly, drying heated 2 hours down at 180 ℃ at last, thereby obtained with the silica coat (thickness: the 100nm) brilliant pigment of Bao Fuing that contains mineral dye.Brilliant pigment shows the blueness with metalluster.

Fig. 1 represents the exemplary horizontal interface of the brilliant pigment that so obtains.Colored brilliant pigment 1 of the present invention is characterised in that coat 22 is formed on the base mateiral squamous glass flake 21, and the coat in this example is made up of metal, i.e. the layer that coats of silver, in addition 32 be pigment, that is, in this example, be mineral dye, i.e. cobalt blue.Base mateiral is coated by silica-based coat film 31, and described coat film contains the pigment of dispersed.

Embodiment 1-2

Adopt the mode similar to embodiment 1-1, (carbon black: (cobalt blue: particulate C.I.GN. Pigment blue 28) obtains brilliant pigment to the mineral dye that uses among fine particle replacement embodiment 1-1 C.I.GN. Pigment black 7) except using mineral dye.That is,, obtained the brilliant pigment that coats with the silica coat film (100nm is thick) that contains mineral dye by this process.This brilliant pigment shows the black with metalluster.

Embodiment 1-3

With tetraethoxysilane (4ml), ethanol (75ml) and pure water (15ml) mix.Add the solution (0.75g) that contains inorganic pigment microparticles (the about 100nm of mean particle size) in mixture, the cobalt blue of 10 quality % (C.I.GN. Pigment blue 28) mixes mixture with the preparation coating solution.

Then, the squamous glass flake (30g) (MC5090NS, by NipponSheet Glass Co., Ltd. produces) that nickel is coated is added in the above-mentioned coating solution, stirs and blend mixture in agitator.The glass flake mean particle size that nickel coats is 90 μ m, mean thickness 5.0 μ m, and present metalluster.Then, be that 25% ammonium hydroxide aqueous solution (0.9ml) is added in the coating solution with concentration, the mixture that obtains mixed 2～3 hours, so that the dehydration property polycondensation to take place.By this reaction, the silica coat film that contains mineral dye is deposited on the surface of squamous glass flake in the coating solution equably.Subsequently, filter and cleaning reaction solution, repeat this process repeatedly, drying heated 2 hours down at 180 ℃ at last, thereby obtained with the silica coat film (thickness: the 100nm) brilliant pigment of Bao Fuing that contains mineral dye.Brilliant pigment shows the black with metalluster.

Comparative Examples 1-1

The brilliant pigment that the squamous glass flake that coats with silver among the embodiment 1-1 coats as the silica-based coating that is not contained pigment.

Comparative Examples 1-2

By the mode similar, except the aluminium powder that uses commercial purchase comes the squamous glass flake that silver coats among the alternative embodiment 1-1 to embodiment 1-1.

(evaluation of brilliant pigment)

Take by weighing each 1g of brilliant pigment that obtains among embodiment 1-1 to 1-3 and the Comparative Examples 1-1 to 1-2 respectively, (Acryl Autoclear Super, by Nippon Paint Co., Ltd. produces) mixes with acrylic resin (49g is in amount of solid).Fully stir the mixture with the coating agitator, to obtain coating solution.With applicator mixing solutions is coated to the recording paper that is used for determining the coating opacifying power, and recording paper is placed at normal temperatures with thorough drying, thus the preparation coat film.

The pattern of coat film is estimated by the sensory testing of 5 people panel of experts.The sensory testing carries out under the sunlight by day, the brightness of evaluate color and transparency.The comprehensive assessment of 5 people panel of experts is summarized as follows.

About embodiment 1-1

The brightness that coat film is strong owing to metalluster demonstrates, and in film, observe transparent mazarine.Pattern does not disappear, even coated pattern do not take place when surperficial yet and disappear because observe from Small angle.

About embodiment 1-2

The brightness that coat film is strong owing to metalluster shows, and in film, observe transparent aterrimus.Pattern does not disappear, even because observe the coated White-opalescent that yet do not occur when surperficial from Small angle.

About embodiment 1-3

The brightness that coat film is strong owing to metalluster demonstrates, and in film, observe transparent aterrimus.Pattern does not disappear, even because observe the coated White-opalescent that yet do not occur when surperficial as Small angle.

About Comparative Examples 1-1

Observe the light tone that has metalluster.When Small angle is observed, observe transparent color, White-opalescent does not appear.

About Comparative Examples 1-2

Compare with embodiment 1-1 or embodiment 1-3,, observe low-light level and white scattering although observe light tone with metalluster.Coated when surperficial when observing from Small angle, the White-opalescent degree is higher.

Result according to top embodiment and Comparative Examples research draws to draw a conclusion.

Comparison shows that between embodiment 1-1 and Comparative Examples 1-1 contains the silica coat film of mineral dye by coating, and the original brightness that metalluster produces does not disappear, and can keep shade.

In addition, comparison shows that between embodiment 1-1 and Comparative Examples 1-1 when the aluminium that uses silver to coat during as the base mateiral of brilliant pigment, observed low-light level and white scattering.Especially, coated when surperficial when observing from Small angle, White-opalescent degree grow causes the tone of non-constant.

Embodiment 2-1

With tetraethoxysilane (15ml), ethanol (300ml) and pure water (60ml) mix.In mixture, add and contain 10 quality % pigment dyestuffs (the C.I.GN. pigment Blue 15: the 3) solution (3.0g) of particulate (mean particle size is about 100nm), blend mixture is to prepare coating solution.

Then, the squamous glass flake (30g) (MC1020RB, by Nippon Sheet Glass Co., Ltd. produces) that titanium dioxide is coated is added in the above-mentioned coating solution, stirs and blend mixture in agitator.The mean particle size of squamous glass flake is 20 μ m, and mean thickness is 1.3 μ m, and shows the sapphirine interference color.Then, be that 25% ammonium hydroxide aqueous solution (14ml) is added in the coating solution with concentration, the mixture that obtains mixed 2～3 hours, so that the dehydration property polycondensation to take place.By this reaction, the silica coat film that contains organic pigment is deposited on the surface of squamous glass flake in the coating solution equably.Subsequently, filter and cleaning reaction solution, this process repeats repeatedly, and drying heated 2 hours at 180 ℃ at last, thereby obtains being contained the silica coat film (thickness: the 100nm) brilliant pigment of Bao Fuing of organic pigment.Brilliant pigment demonstrates blueness.

Identical among the schematic horizontal interface of gained brilliant pigment and above-mentioned Fig. 1, wherein coat 22 is a titanium dioxide, and pigment 32 is pigment dyestuffs.

Embodiment 2-2

By the mode similar to embodiment 2-1, except squamous glass flake (MC1020RY:Nippon Sheet Glass Co. with the coated by titanium dioxide of the yellow interference color of represent light, Ltd. produce) be used for replacing the squamous glass flake of the coated by titanium dioxide among the embodiment 2-1, preparation brilliant pigment.

Embodiment 2-3

By the mode similar to embodiment 2-1, except the mean particle size with the silver coating is that 80 μ m, mean thickness are the squamous glass flake that 1.3 μ m and the squamous glass flake that shows metalluster (MC2080PS:Nippon Sheet Glass) are used for replacing coated by titanium dioxide among the embodiment 2-1, the preparation brilliant pigment.Thereby, obtained the brilliant pigment that coats with the silica coat film (thickness is 100nm) that contains organic pigment.Brilliant pigment shows the blueness that has metalluster.

Embodiment 2-4

With tetraethoxysilane (4ml), ethanol (75ml) and pure water (15ml) mix.(the C.I.GN. pigment Blue 15: the 3) solution (0.75g) of particulate (mean particle size is about 100nm), blend mixture is with the preparation coating solution for the pigment dyestuff of adding 10 quality % in mixture.

Then, the squamous glass flake (30g) that nickel is coated (MC5090NS, by NipponSheet Glass Co., Ltd. produces) is added in the above-mentioned coating solution.In agitator, mixture is stirred and mixing.The mean particle size of squamous glass flake is 90 μ m, and mean thickness is 5.0 μ m, and shows the color with metalluster.Then, be that 25% ammonium hydroxide aqueous solution (0.9ml) is added in the coating solution with concentration, the mixture that obtains was mixed 2～3 hours, so that the dehydration property polycondensation to take place.By this reaction, the silica coat film that contains organic pigment is deposited on the surface of glass flake in the coating solution equably.Subsequently, filter and cleaning reaction solution, this program repeats repeatedly, and drying heated 2 hours at 180 ℃ at last, thereby obtains being contained the brilliant pigment of silica coat film (thickness 100nm) coating of organic pigment.Brilliant pigment shows the blueness with metalluster.

Comparative Examples 2-1

The squamous glass flake of coated by titanium dioxide among the embodiment 2-1 is used as the brilliant pigment that is not coated by the silica coat film.

Comparative Examples 2-2

By the mode similar to embodiment 2-1, (Iriodin 221, Merck ﹠amp except the mica sheet with the coated by titanium dioxide that shows blue interference; Co., Inc. produces, and granularity is 5～25 μ m) replace the squamous glass flake of coated by titanium dioxide, preparation brilliant pigment.

Comparative Examples 2-3

By the mode similar to embodiment 2-3, the aluminium powder of buying except commerce is used for replacing the squamous glass flake that silver coats among the embodiment 2-3, the preparation brilliant pigment.

(evaluation of brilliant pigment)

Take by weighing each 1g of brilliant pigment of gained among embodiment 2-1 to 2-4 and the Comparative Examples 2-1 to 2-3 respectively, with acrylic resin (49g, solid weight) (Ltd. produces for Acryl Autoclear Super, NipponPaint Co.).Use the coating agitator fully to stir the mixture that obtains, with the preparation coating material.With applicator mixing solutions is coated to the recording paper that is used for determining the coating opacifying power, and recording paper is placed at normal temperatures with thorough drying, thus the preparation coat film.

The pattern of coat film is estimated by the sensory testing of 5 people panel of experts.The sensory testing carries out under the sunlight by day, the brightness of evaluate color and transparency.The comprehensive assessment of 5 people panel of experts is summarized as follows.

About embodiment 2-1

In coat film, observe transparent mazarine with strong brightness.Pattern does not disappear, even because coated when surperficial when observing from Small angle, the variation of White-opalescent and interference color do not occur yet.

About embodiment 2-2

When coated surperficial of right-angle view, observe very strong brightness and yellow interference color.Coated when surperficial when observing from Small angle, observe transparent color, and White-opalescent do not occur.

About embodiment 2-3

Obtain having the transparent mazarine of strong brightness owing to metalluster.In addition, in addition coated when surperficial when observing from Small angle, and pattern does not disappear, because White-opalescent do not occur.

About embodiment 2-4

Obtain having the transparent mazarine of strong brightness owing to metalluster.In addition, in addition coated when surperficial when observing from Small angle, and pattern does not disappear, because White-opalescent do not occur.

About Comparative Examples 2-1

When coated surperficial of right-angle view, observe blue interference.Coated when surperficial when observing from Small angle, color becomes reddish blueness, and owing to White-opalescent occurred, its transparency disappears.

About Comparative Examples 2-2

The change of color is identical with embodiment 2-2.Even when coated surperficial of right-angle view, observe low-light level and white scattering.In addition, coated when surperficial when observing from Small angle, White-opalescent is stronger.

About Comparative Examples 2-3

Although pigment shows the brightness that produces because of metalluster, its brightness is compared low with embodiment 2-3 or embodiment 2-4, and observes the white light scattering.In addition, coated when surperficial when observing from Small angle, the formation degree of fault (cloudiness) is stronger.

By studying the result of top embodiment and Comparative Examples, carry out following explanation.

From the relatively discovery between embodiment 2-1 and Comparative Examples 2-1, can contain the silica coat film of organic pigment by application, even coated when surperficial, also can keep not having shade muddy and the interference color variation when observing from Small angle.

From the relatively discovery between embodiment 2-2 and Comparative Examples 2-2,, observe low lightness and white scattering when the mica that uses coated by titanium dioxide during as the base mateiral of brilliant pigment.Especially, coated when surperficial when observing from Small angle, White-opalescent degree grow causes the tone of non-constant.

Commercial Application

Coloring pigment of the present invention can be applied to various fields as coating material, resin combination Thing, printing ink, cosmetics, artificial marble, coated paper, etc.

Claims (11)

1. colored brilliant pigment comprises the surface form slection of taking up an official post and becomes the squamous glass flake base mateiral of coat, and the silica-based coat film that the surface of wherein said base mateiral is contained pigment coats.

2. the colored brilliant pigment of claim 1, wherein said pigment is mineral dye or pigment dyestuff.

3. claim 1 or 2 colored brilliant pigment, the mean particle size of wherein said pigment is 10nm～1 μ m.

4. each colored brilliant pigment in the claim 1～3, wherein said base mateiral are to form the squamous glass flake that applies rete in its surface.

5. the colored brilliant pigment of claim 4, wherein said coating rete is made up of at least a metal, and it is selected from gold and silver, platinum, palladium, titanium, cobalt and nickel, and/or its alloy.

6. the colored brilliant pigment of claim 4, wherein said coating rete is made up of at least a metal oxide, and it is selected from titanium oxide, ferric oxide and zirconium white.

7. each colored brilliant pigment in the claim 1～6, wherein said silica-based coat film is the matrix that only comprises silica basically.

8. coating material comprises in the claim 1～7 each colored brilliant pigment.

9. resin combination comprises in the claim 1～7 each colored brilliant pigment.

10. printing ink comprises in the claim 1～7 each colored brilliant pigment.

11. makeup comprise in the claim 1～7 each colored brilliant pigment.

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