CN101415783A - Flaky particle and brightening pigment, and cosmetic preparation, coating composition, resin composition, and ink composition each containing these - Google Patents
Flaky particle and brightening pigment, and cosmetic preparation, coating composition, resin composition, and ink composition each containing these Download PDFInfo
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- CN101415783A CN101415783A CN 200780012034 CN200780012034A CN101415783A CN 101415783 A CN101415783 A CN 101415783A CN 200780012034 CN200780012034 CN 200780012034 CN 200780012034 A CN200780012034 A CN 200780012034A CN 101415783 A CN101415783 A CN 101415783A
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Abstract
The invention provides flaky particles having a particle size distribution in which when the particle diameter corresponding to a cumulative volume of 10% from the small-particle-diameter side is expressed by D10 and the particle diameter corresponding to a cumulative volume of 90% from the small-particle-diameter side is expressed by D90, then the value of D90/D10 is 2.0-3.0 and D10 is 4.7-25 [mu]m, and the maximum particle diameter is 90 [mu]m or smaller. Also provided is a brightening pigment which comprises flaky particles and, formed on at least part of the surface of the flaky particles, at least one member selected between a metal layer and a metal oxide layer and has a particle size distribution in which when the particle diameter corresponding to a cumulative volume of 10% from the small-particle-diameter side is expressed by D10 and the particle diameter corresponding to a cumulative volume of 90% from the small-particle-diameter side is expressed by D90, then the value of D90/D10 is 2.0-3.0 and D10 is 4.7-25 mu m, and the maximum particle diameter is 90 mu m or smaller.
Description
Technical field
The present invention relates to a kind of lamelliform particle and bright pigment and at least a cosmetic material, coating composition, resin combination and the ink composite that contain in them.
Technical background
Always, as show nacreous bright pigment (below, be sometimes referred to as pearlescent pigment.), have metal oxides such as utilizing titanium oxide and ferric oxide cover lamelliform particles such as mica, synthetic mica, talcum, flake glass, laminar silica or laminar pearl white the surface and material.In addition, useful these metal oxide multilayer cover sheet shape particle surfaces are proposed and material.(for example :) with reference to " her rattan " pigment dictionary ", first edition, Co., Ltd. of levying department editor towards storehouse bookstore, on September 25th, 2000, p.239-241 ".
In addition, as the bright pigment that shows metalluster (below, be sometimes referred to as metalluster pigment), have lamelliform particles such as metal cover sheet shape glass, mica or synthetic mica such as utilizing silver, gold or nickel the surface and material (for example: open clear 62-175045 communique and the spy opens flat 4-2636 communique) with reference to Japan is real.
In addition, as metalluster pigment not only use aforesaid utilize metal and metal oxide cover sheet shape particle and material, and can use the lamelliform particle that constitutes by metals such as aluminium or copper (for example :) separately with reference to " her rattan " pigment dictionary ", first edition, Co., Ltd. of levying the editor of department towards storehouse bookstore, on September 25th, 2000, p.232-234 ".In addition, also can use guanin and laminar pearl white etc. as pearlescent pigment (for example :) sometimes separately with reference to " her rattan " pigment dictionary ", first edition, Co., Ltd. of levying department editor towards storehouse bookstore, on September 25th, 2000, p.239-241 ".
Utilized aforesaid lamelliform particle bright pigment (below, abbreviate pigment sometimes as.) by utilizing its even surface reflection ray, demonstrate good light sense.
And, propose to have by the granularity of regulating bright pigment to obtain the light sense and can not cause the bright based coating composition (for example :) of filter stoppage when applying repeatedly with reference to TOHKEMY 2002-155240 communique.
But the width of the size-grade distribution of the lamelliform particle that uses in the present bright pigment is wide and comprise many micro mists and meal.And, much less use the pigment of lamelliform particle separately, utilizing the pigment of metal level and metal oxide layer cover sheet shape particle exactly, the width of its size-grade distribution is also wide.
For example, use wide (containing multiparticulates and the meal) lamelliform particle of the width of size-grade distribution as base material, make pearlescent pigment by using the contour refractive index substance of titanium oxide to cover this base material, in the case, descend, do not have problems such as particle sense owing to containing many micro mists so having produced bright sense in appearance.In addition, owing to comprise many meal, therefore exist as inferior problem: filter stoppage when for example filtering the coating composition that contains this pearlescent pigment, do not use in the filming that this coating composition coating forms pigment fitly directed and part is outstanding, excessive pigment is considered to the foreign matter in the coating.
In addition, even carry out granularity adjusting as the bright pigment that proposes in the TOHKEMY 2002-155240 communique, also be difficult to realize having concurrently the bright pigment of following excellent properties: can realize the bright pigment that solves these problems fully, i.e. light sense fully, particle sense; And can suppress the obstruction of strainer more reliably and be taken as foreign matter to discern.
Summary of the invention
Therefore, one purpose of the present invention is, a kind of lamelliform particle is provided, and it is being used under the situation of pigment, can realize high particle sense and light sense, and can suppress the obstruction of strainer and be taken as the generation that foreign matter such as discerns at problem.In addition, another object of the present invention is to, a kind of bright pigment is provided, it can realize high particle sense and light sense, and can suppress the obstruction of strainer and be taken as the generation that foreign matter such as discerns at problem.In addition, a further object of the present invention is, a kind of cosmetic material, coating composition, resin combination and ink composite that contains these lamelliform particles and bright pigment is provided.
In the size-grade distribution of lamelliform particle of the present invention, volume that will a little side begins by particle diameter be accumulated as 10% o'clock pairing particle diameter be set at D10, will a little side begins by particle diameter volume be accumulated as 90% o'clock pairing particle diameter and be set under the situation of D90, the value of D90/D10 is 2.0～3.0, D10 is 4.7 μ m～25 μ m, and maximum particle diameter is below the 90 μ m.
Need to prove that so-called lamelliform particle for example is meant in this specification sheets: thickness for example is about 2～100 flakey particle in scope, the length-to-diameter ratio (median size/mean thickness) of 0.1 μ m～8.0 μ m.In addition, the particle diameter of so-called lamelliform particle is meant the scattering of light equivalent diameter when utilizing the laser diffraction and scattering method to measure lamelliform particle.So-called scattering of light equivalent diameter, according to for example " up-to-date powder physical property figure says (third edition) " (distribution on June 30th, 2004, publisher: storehouse Tian Feng, the distribution unit: the limited エ ヌ ジ of commercial firm-テ イ-), be defined as showing the scattering pattern that approaches most by the particle light scattering pattern of measuring gained, and have the diameter of the ball of the specific refractory power identical with this particle.
In addition, so-called size-grade distribution is in the population that is illustrated in as determination object, and the particle of all size (particle diameter) accounts for the index of the ratio of total number of particles, is the size-grade distribution of measuring based on the laser diffraction and scattering method in this manual.So-called laser diffraction and scattering method is to utilize scattered light when particle carried out laser radiation to obtain the method for size-grade distribution, in the size-grade distribution in this specification sheets, adopts volume as the benchmark of particle weight.In addition, the definition of D10 and D90 as mentioned above.D50 (volume of size-grade distribution is accumulated as 50% o'clock pairing particle diameter) refers to median size.D90/D10 can be used as the index of width of expression size-grade distribution, and under median size (D50) be situation with degree, the value of D90/D10 was big more, and the width of size-grade distribution is just big more; The value of D90/D10 is the width that distributes of small grain size just narrow more (content of micro mist and meal is little) more.In addition, so-called maximum particle diameter is that the volume of size-grade distribution is accumulated as 100% o'clock pairing particle diameter.
The value of the D90/D10 of lamelliform particle of the present invention is 2.0～3.0, and D10 is 4.7 μ m～25 μ m, and maximum particle diameter is that the width of its size-grade distribution is narrow below the 90 μ m.Therefore, the micro mist and the meal that comprise are few.By reducing the content of micro mist, and D10 is made as more than the 4.7 μ m, for example is being used under the situation of pigment, can realize high particle sense and light sense.In addition, by reducing the content of meal, and maximum particle diameter is made as below the 90 μ m, for example under the situation that the pigment as coating uses, can suppresses the obstruction of strainer and be taken as the generation that foreign matter such as discerns at problem.In addition,, therefore be not partial to the coarse grain footpath, can obtain the light sense of appropriateness because D10 is below the 25 μ m.
Bright pigment of the present invention comprises at least a in metal level that lamelliform particle and being selected from forms and the metal oxide layer on lip-deep at least a portion of above-mentioned lamelliform particle.This bright pigment is in size-grade distribution, to be accumulated as 10% o'clock pairing particle diameter by the volume that the little side of particle diameter begins is set at D10, will be accumulated as 90% o'clock pairing particle diameter by the volume that the little side of particle diameter begins and be set at D90, in the case, the value of D90/D10 is 2.0～3.0, D10 is 4.7 μ m～25 μ m, and maximum particle diameter is below the 90 μ m.About the measuring principle of the size-grade distribution in the bright pigment of the present invention, identical with the measuring principle of the size-grade distribution of lamelliform particle of the present invention.In addition, the index of D90/D10 demonstration is also as described above.In addition, the situation of the definition of the particle diameter of the lamelliform particle that uses in the bright pigment of the present invention, lamelliform particle and maximum particle diameter and lamelliform particle of the present invention is identical.
The value of the D90/D10 of bright pigment of the present invention is 2.0～3.0, and D10 is 4.7 μ m～25 μ m, and maximum particle diameter is that the width of its size-grade distribution is narrow below the 90 μ m.Therefore, the micro mist and the meal that contain are few.By reducing the content of micro mist, and D10 is made as more than the 4.7 μ m, can realizes high particle sense and light sense.In addition, by reducing the content of meal, and maximum particle diameter is made as below the 90 μ m, for example is used under the situation of pigment of coating, can suppress the obstruction of strainer and be taken as the generation that foreign matter such as discerns at problem.In addition,, therefore be not partial to the coarse grain footpath, can obtain the light sense of appropriateness because D10 is below the 25 μ m.
Cosmetic material of the present invention contains and is selected from least a in lamelliform particle of the present invention and the bright pigment of the present invention.
Coating composition of the present invention contains and is selected from least a in lamelliform particle of the present invention and the bright pigment of the present invention.
Resin combination of the present invention contains and is selected from least a in lamelliform particle of the present invention and the bright pigment of the present invention.
Ink composite of the present invention contains and is selected from least a in lamelliform particle of the present invention and the bright pigment of the present invention.
Be selected from least a in lamelliform particle of the present invention and the bright pigment of the present invention because cosmetic material of the present invention, coating composition, resin combination and ink composite comprise, therefore can realize problems such as high light sense and particle sense, the filter stoppage in the time of can suppressing to filter and foreign matter be outstanding.
Description of drawings
Fig. 1 schematically shows the fragmentary cross-sectional view of manufacturing as an example of the device of the flake glass of lamelliform particle of the present invention.
Has embodiment
Below, the specific embodiment of the present invention is described.
Embodiment 1
In the embodiment 1 lamelliform particle of the present invention is described.
In the size-grade distribution of the lamelliform particle of present embodiment, the value of D90/D10 is 2.0～3.0 scope, and the value of D10 is 4.7 μ m～25 μ m, and maximum particle diameter is the following scopes of 90 μ m.The width of the size-grade distribution of such lamelliform particle is narrow, and be set in the above-mentioned scope by value and maximum particle diameter with D10, for example in pigment, use under the situation of lamelliform particle, high light sense and granularity sense can be obtained, and make up material and problems such as isochronous foreign body sensation of coating and filter stoppage can be prevented to be used for.Therefore, for the width that makes size-grade distribution becomes narrower, for example also the value of D90/D10 can be set in 2.4～2.9 scope.The lower value of maximum particle is not particularly limited, but can be set at for example 75 μ m, is preferably set to 45 μ m.
The lamelliform particle of present embodiment for example can use separately and himself also can use himself base material as bright pigment such as pearlescent pigment and metalluster pigment separately as pearlescent pigment and metalluster pigment.Under the situation that the base material as bright pigment uses, formation metal level and metal oxide layer get final product at least a portion in its surface, preferably cover whole substrate surface with metal level and metal oxide layer.As the lamelliform particle of present embodiment, for example under the situation that the base material as bright pigment uses, for example have: mica, synthetic mica, talcum, flake glass, laminar silica and laminar pearl white etc.In addition, using under the situation of lamelliform particle as bright pigment of present embodiment separately, can use the thin slice that constitutes by metals such as aluminium or copper (below, be called sheet metal sometimes.), guanin and laminar pearl white etc.
The median size of the lamelliform particle of present embodiment (D50) can be for example 7 μ m～80 μ m.By median size being set in this scope, can be preferably used as the pigment such as material and coating of for example making up.
Secondly, in the present embodiment, the value that making is had a D90/D10 is 2.0～3.0, the value of D10 is that 4.7 μ m～25 μ m and maximum particle diameter are that the method for lamelliform particle of the size-grade distribution of the scope below the 90 μ m describes.
In the present embodiment, for example regulate the granularity of lamelliform particle, realize size-grade distribution as noted above by classification.At this, the example that for example utilizes sieve classification is described.For example can use the dry type vibratory sieve in the sieve classification.At first, adopt size (thick eye) sieve more than regulation of mesh to remove meal, secondly, adopt size (thin eye) sieve below regulation of mesh to remove micro mist, can obtain having the lamelliform particle of the size-grade distribution in the present embodiment thus.Under this situation,, can further improve the effect of removing micro mist by the dual-purpose ultrasonic vibration.Need to prove that the size of sieve mesh as used herein waits according to the value (width of the width of size-grade distribution) of the median size of the granularity of the particle before the screening and the lamelliform particle that hope obtains and D90/D10 and suitably to select to get final product.In addition, the meal of removing by pulverize again and again classification can utilize once again.In addition, the micro mist of removing also can be used for other product.
With the flake glass is example, and the method for the lamelliform particle of making present embodiment is described.At first, for example adopt in Japanese Patent Publication 45-3541 communique in converting process of publicity (Block ロ one method) and the Japanese Patent Publication 41-17148 communique method of publicity to make flake glass.At this method that adopts converting process to make flake glass is described.So-called converting process is the melten glass blank of supplying with continuously from the melten glass source by stretching and it is expanded go the method that makes thin glass film into hollow form.Can make the flake glass weighting material of present embodiment by pulverizing glass film obtained by this method.
Fig. 1 is an example that is used for making by converting process the device of glass film.Among Fig. 1,1 is the melten glass blank; 2 is refractory furnace chamber (furnace bath: Kiln groove) furnace chamber; 3 for being arranged on the hole bottom the refractory furnace chamber; 4 for having the feeder parts (feeder block) of the circular glass conveying end 5 littler than hole 3, and its casting refractory brick by embedding heating wire 6 constitutes.Importing and exporting the temperature of the melten glass blank in 5 at glass utilizes heating wire 6 to remain on certain temperature.7 is to import and export 5 blow gun by the upper end of refractory furnace chamber 2 through via hole 3 arrival glass, forms circular slit 9 by its top ends 8 at the glass import and export.The gas (for example air) that is blown into from blow gun 7 by slit 9 effusive melten glass blank utilizations expands and forms hollow form, thereunder further stretches downwards and is elongated, and the thickness of this film is become extremely thin.11 is extrusion roll; 12 is draw roll.13 for the tubular steel plate system reflector of fan out.Hollow form glass 10 can be incubated when utilizing reflector 13 to block outer gas stream preferably, and is expanded thinly equably.Utilize 11 pairs of the extrusion rolls hollow form glass 10 that forms that expands thus to push, form plate glass film 14 and also transfer out.For example use roller to pulverize thus obtained glass film, can obtain flake glass.Need to prove, state device in the use and make under the situation of flake glass that the pressure of draw speed by suitable adjusting hollow form glass and the gas that is blown into by blow gun can be made the flake glass of desired thickness.
To the flake glass that as above makes, consider to carry out classification from desirable median size and size-grade distribution aspect, can make flake glass as the lamelliform particle in the present embodiment.
Need to prove, adopt sieve classification as the fractionated method in the present embodiment, but also can adopt other stage division to remove micro mist and meal.
Under the situation of dry classification, for example, can adopt airflow classification devices such as gravity type boat davit classification, the classification of mass force formula and centrifugal force type classification.As the gravity type boat davit classification, for example, can adopt horizontal flow pattern, vertical flow pattern and inclination flow pattern etc.As the classification of mass force formula, for example, can adopt linear pattern, shaped form, flap type, elbow type jet classifying (Elbow-Jet) and variable impact type classification (Variableimpactor) etc.As the centrifugal force type classification, for example, can adopt cyclonic separator (cyclone), blowing-type cyclone classifier (Off ア Application ト Application ゲ レ Application), whirlwind (powder) classifier (classiclone), diffusion type cyclonic separator (Dispersion Separator) and the air classifier (Microplex) of the rotation principle manufacturing that utilizes air-flow; Eddy flow particle separator (micronseparator), turbo separator (turboplex), Ai Qiukate grading machine (acucut) and the vortex classifier (turbo classifier) etc. that utilize the mechanical rotation principle to make.
Under the wet classification situation, for example can adopt airflow classification devices such as gravity type boat davit classification and centrifugal force type classification.The gravity type boat davit classification can be adopted settling bath, taper sedimentation tank, spitzkasten (spitzkasten) and the hydroseparator (hydroseparator) that utilizes gravitational settling groove principle to make; Utilize chain-plate type (drag chain) grading machine that the mechanical type classification principle makes, rake formula (rake) grading machine, floating trough (bowl) grading machine, spiral (Spiral) grading machine etc.Hydraulic classification can be adopted Dorrco sizer (Dorrco sizer), Fahrenwald sizer (Fahrenwald Sizer), hydrocone type grading machine (siphon sizer) and floating trough cake formula composite ratings machine (hydroscillator) etc.The centrifugal force type classification can be adopted hydraulic cyclone, centrifugal classifier (collar plate shape, precipitation are got type) etc.
In embodiment 2, bright pigment of the present invention is described.
For the bright pigment of present embodiment, on lip-deep at least a portion as the lamelliform particle of base material, be provided with and be selected from least a in metal level and the metal oxide layer, preferably cover whole lamelliform particle with these metal levels and metal oxide layer.Bright pigment in the present embodiment, the value of the D90/D10 in its size-grade distribution are 2.0～3.0, and the value of D10 is 4.7 μ m～25 μ m, and maximum particle diameter is the following scopes of 90 μ m.The width of the size-grade distribution of this bright pigment is narrow, and be set in the above-mentioned scope by value and maximum particle diameter with D10, under the situation that this bright pigment is used as the stopping composition such as material and coating of making up, the goods of high light sense and particle sense can be realized having, and also problems such as foreign body sensation and filter stoppage can be suppressed.Therefore, in order further to make the narrowed width of size-grade distribution, for example also the value of D90/D10 can be set in 2.4～2.9 scope.The lower value of maximum particle is not particularly limited, and can be set at for example 75 μ m, is preferably set to 45 μ m.
Be used for the lamelliform particle of the bright pigment of present embodiment, for example have: mica, synthetic mica, talcum, flake glass, laminar silica and laminar pearl white etc.Wherein, compare with other materials and can realize higher transparent feel, in addition,, emphasize this high transparent feel,, preferably use the base material of flake glass as bright pigment from this reason in the few situation of micro mist that the bright pigment of present embodiment contains.
In addition, in the bright pigment of present embodiment,, preferably adopt the lamelliform particle of introducing in the embodiment 1 as base material in order more easily to regulate the size-grade distribution of bright pigment.
The metal level that uses in the pigment of present embodiment, for example can utilizing, metals such as silver, gold and nickel form.Utilize this metal level cover sheet shape particle can obtain metalluster pigment.In addition, metal oxide layer for example can utilize that metal oxide such as titanium oxide or ferric oxide forms.Utilize this metal oxide layer cover sheet shape particle can obtain pearlescent pigment.
The median size of the bright pigment of present embodiment (D50) also can be for example 7 μ m～80 μ m.By median size being set in this scope, can be suitable as the pigment such as material and coating of for example making up.
Method with cover sheet shape particles such as metal levels uses well-known method to get final product, and for example can use disclosed method in TOHKEMY 2001-031421 communique and the TOHKEMY 2001-11340 communique.Particularly be following method,, make lamelliform particle outstanding turbid in titanyl sulfate or titanium tetrachloride solution, titanium dioxide is separated out, on the surface of lamelliform particle, form overlay film by this solution is heated up when for example using titanium oxide layer cover sheet shape particle.But be not limited to this method, so long as the method for thin overlay film can be set on the surface of lamelliform particle, can with arbitrary method.The thickness of metal level and metal oxide layer is not particularly limited, but when realizing that light sense and cost aspect are considered, under the situation of covering metal, the thickness of its overlay film for example is preferably 0.04～2 μ m; Under the situation that covers metal oxide, the thickness of its overlay film for example is preferably 0.01～1 μ m.
In addition, be 2.0～3.0 in the value that making has a D90/D10, the value of D10 is that 4.7 μ m～25 μ m and maximum particle diameter are in the method for bright pigment of size-grade distribution of the scope below the 90 μ m, can utilize the control method (stage division) of the size-grade distribution of the lamelliform particle of introducing in the embodiment 1.That is, carry out classification, can make the bright pigment of size-grade distribution with present embodiment by the material that is formed with metal level etc. on the surface to lamelliform particle.
In the present embodiment, describe containing at least a cosmetic material, coating composition, resin combination and the ink composite that are selected from the embodiment 1 in the bright pigment of introducing in the lamelliform particle introduced and the embodiment 2.Need to prove that cosmetic material, coating composition, resin combination and the ink composite of following explanation can contain any in lamelliform particle and the bright pigment, also can contain two kinds.
In the cosmetic material of present embodiment and since be combined with in the bright pigment of the lamelliform particle that is selected from embodiment 1 particle of pigment use (can be separately as) and embodiment 2 at least a (below, be sometimes referred to as stopping composition.), therefore the colour developing higher can be realized, and the cosmetic material that sense of touch is also excellent can be realized than former light sense.The content of stopping composition in the material of making up (is the total of content separately when containing lamelliform particle and bright pigment.Below too.) be not particularly limited, can select according to product is suitable.In addition, can suit to cooperate other compositions that contain in the stopping composition cosmetic material in addition, common in the cosmetic material as required.
In the coating composition of present embodiment, because therefore the same stopping composition of material that is combined with and makes up can be realized than higher in the past light sense.The content of stopping composition is not particularly limited in the coating composition, but considers from the sufficient bright sense aspect of filming, and can be set to be for example 0.05～30 quality %.In addition, can suit to cooperate other compositions that contain in the stopping composition coating composition in addition, common in the coating composition as required.
In the resin combination of present embodiment, because therefore the same stopping composition of material that is combined with and makes up can be realized than higher in the past light sense.The content of stopping composition is not particularly limited in the resin combination, but from the sufficient light sense of resin combination and the aspect that influences of physical property being considered, can be set to be for example 0.05～30 quality %.In addition, can suit to cooperate other compositions that contain in the stopping composition resin combination in addition, common in the resin combination as required.Need to prove,, be not particularly limited, for example have: polyolefin resines such as polyethylene, polypropylene as resin as used herein; Thermoplastic resins such as vinyl chloride resin, polystyrene resin, acrylic resin, methacrylic resin, ABS resin, AES resin, AS resin, polymeric amide, polycarbonate resin, polybutylene terephthalate resin, polyethylene terephthalate resin, polyacetal resin, polyhenylene ether resin, polysulfone resin, fluoro-resin.In addition, also can use the interpolymer, mixture, modifier etc. of their polymkeric substance.
In the ink composite of present embodiment, because therefore the same stopping composition of material that is combined with and makes up can be realized than higher in the past light sense.The content of stopping composition is not particularly limited in the ink composite, but considers from sufficient bright sense aspect, can be set to be for example 0.05～30 quality %.In addition, can suit to cooperate other compositions that contain in the stopping composition ink composite in addition, common in the ink composite as required.Need to prove, for example have as ink composite: lettering pen printing ink such as ballpoint pen, gel ink pen, advertising pen reach printing inks such as intaglio printing, letterpress, intaglio printing, silk screen printing.
Embodiment
Below, adopt embodiment that the present invention is illustrated in further detail.In addition, embodiment shown below is to use the example of flake glass as the lamelliform particle situation, but the present invention is not limited to these examples, also can adopt mica, synthetic mica and laminar pearl white etc. as lamelliform particle.
In embodiment and comparative example as follows, the pulverizing when making flake glass, the evaluation for mensuration, light sense and the particle sense of regulating classification that size-grade distribution carries out, size-grade distribution, the evaluation of filter stoppage, the evaluation of coating foreign body sensation are carried out with the following method.
(pulverizing)
Use micronizer mill (ProductName " ラ ボ ジ
The エ Starト LJ " (Japanese PNEUMATIC (ニ ユ-マ チ
StarNetwork) Co., Ltd.'s system)) pulverizes flake glass.
(classification)
Utilize sieve classification to regulate granularity.
Use hummer screen (ProductName " RETSCH SIEVESHAKER, typeVIBRO " (RETSCH Co., Ltd. system) as vibratory screening apparatus.The testing sieve that uses is Φ 200mm, height 45mm.Can prepare the sieve (Co., Ltd. meal field make made) of the various meshes of 16,20,25,32,38,45 μ m as testing sieve, select suitable sieve according to required size-grade distribution.
As method for sieving, exactly that specified mesh is thick sieve be arranged on epimere, sieve that specified mesh is thin be arranged on stage casing, pallet be arranged on hypomere and with 3 sections overlapping, this structure is arranged in the hummer screen, carry out the screening of specified time.Sieve with epimere is removed meal, and the flake glass that meal tails off falls into the sieve in stage casing.Remove micro mist with this stage casing sieve, micro mist is fallen under the sieve.Thus, the flake glass of having removed meal and micro mist remains on the sieve in stage casing, and they promptly become as the narrow flake glass of the size-grade distribution width of lamelliform particle of the present invention.By suitable granularity, the mesh of sieve, screening intensity, the screening time of regulating the preceding initial sheet shape glass of screening, can change the size-grade distribution of the flake glass of recovery diversifiedly.
(measuring method of size-grade distribution)
Use laser diffraction granularity measure of spread device (" ProductName マ イ Network ロ ト ラ in the mensuration of size-grade distribution
StarNetwork HRA " (Nikkiso Company Limited's system)).Read the value of median size D50, maximum particle, D90 and D10 by its measurement result, further calculate the value of D90/D10 of the width of the width of judging size-grade distribution.
(evaluation of transparent feel)
Prepare following two kinds of cold coatings: acrylic resin paint (ProductName " ア Network リ Le オ-ト Network リ ア ス-パ-", (Japanese PAINT Co., Ltd. system), the about 50 quality % of solids component) (cold coating that does not have lamelliform particle); And in this acrylic resin paint, add the sample lamelliform particle and make its content in resin reach 10 quality %, mix the material (cold coating) that obtains after the stirring fully with lamelliform particle.Utilize the material feeder of gap 9 mils (9/1000 inch) on hiding rare mensuration paper, to apply 2 these two kinds of cold coatings side by side and make its drying.Use color colour-difference meter (CR300, MINOLTA Co., Ltd. system) that the black part of this coating plate is carried out the mensuration of tone L value, obtain poor (the △ L) of the L value that having or not of lamelliform particle cause.It is higher that the side that △ L is little is considered to the transparency.
(evaluation of light sense and particle sense)
In acrylic resin paint (ProductName " ア Network リ Le オ-ト Network リ ア ス-パ-" (Japanese PAINT Co., Ltd. system), the about 50 quality % of solids component), add sample pigment and make its content in resin reach 10 quality %, after thorough mixing stirs, utilize the material feeder of gap 9 mils (9/1000 inch) to apply, and make its drying.Use color colour-difference meter (CR300, MINOLTA Co., Ltd. system) this coating plate to be carried out the mensuration of tone L value.It is higher that the high side of L value of expression brightness is considered to the light sense.
In addition, the coating plate that uses above-mentioned brightness measuring to use, the visual observation coating plate is also judged its particle sense and the light sense.Criterion is as follows.
(criterion (visual observation coating plate))
Particle sense, light sense are divided into following 5 grades and estimate.
5: particle sense, light feel very high.Can observe each pigment, and feel that the light sense of this each particle is all strong.
4: particle sense height.Can observe each pigment, and feel the light sense of this each particle.
3: the particle sense of middle degree.Can observe each particle, but the almost light sense of imperceptible this each particle.
2: the particle sense is few.Carefully observe each pigment and can feel the particle sense, but do not see Chu and present smooth outward appearance.
1: do not have the particle sense.Complete imperceptible particle sense, integral body are faced the wall and meditated like one, and integral body presents bright slightly state.
(evaluation of filter stoppage)
An amount of thinner that adds in 78 quality % acrylic resins (ProductName " ACRIDECA-322 " (Dainippon Ink. ﹠ Chemicals Inc's system)), 16 quality % butylated melamine resins (ProductName " SUPERBECKAMINEL-117-60 " (Dainippon Ink. ﹠ Chemicals Inc's system)), 6 quality % sample pigment, use stirrer so that viscosity is the mode of 13 seconds (Co., Ltd.'s smart mechanism in peace field is made No.4/20 ℃ of obtained Ford Cup) mixes, regulate light coating.Triangle strainer (nylon system, #200 grid (mesh: about 75 μ m)) chocking-up degree of strainer when filtering this light coating are used in visual observation.
(criterion (obstruction of visual observation strainer))
The obstruction of strainer is divided into following 3 grades to be estimated.
3: think not have and stop up.
2: think that obstruction is less.
1: think and stop up significantly.
(evaluation of coating foreign body sensation)
Acrylic resin (ProductName " ACRIDEC (ア Network リ デ at 78 quality %
StarNetwork) A-322 " (Dainippon Ink. ﹠ Chemicals Inc's system)), butylated melamine resins (ProductName " SUPER BECKAMINE (ス-パ-ベ of 16 quality %
Starカ ミ Application) L-117-60 " (Dainippon Ink. ﹠ Chemicals Inc's system)), an amount of thinner that adds in the sample pigment of 6 quality %; use stirrer so that viscosity is the mode of 13 seconds (Co., Ltd.'s smart mechanism in peace field is done obtained Ford CupNo.4/20 ℃) mixes, regulate light coating as basic coating.Use spray gun (the system W-100 of ANEST rock field Co., Ltd.) after dull-finish steel (thickness 0.8mm * width 100mm * length 500mm) is gone up, to fire (130 ℃ * 10 minutes) by the light applying coating, form the basal layer of thickness 15 μ m.
Then, in the butylated melamine resins (ProductName " SUPER BECKAMINEL-117-60 " (Dainippon Ink. ﹠ Chemicals Inc's system)) of the acrylic resin (ProductName " ACRIDECA-345 " (Dainippon Ink. ﹠ Chemicals Inc's system)) of 72 quality %, 28 quality %, add thinner, use stirrer so that viscosity is the mode of 13 seconds (Co., Ltd.'s smart mechanism in peace field is made No.4/20 ℃ of obtained Ford Cup) mixes, regulate high bright based coating composition.Use spray gun (the system W-100 of ANEST rock field Co., Ltd.) to be coated on the dull-finish steel that is formed with basal layer by the light based coating composition, fire (140 ℃, 30 minutes) thereafter, form high light (top clear) layer of thickness 30 μ m.
(criterion (frequency that visual observation coating foreign matter takes place))
The surface of the dull-finish steel (thickness 0.8mm * width 100mm * length 500mm) that visual observation has applied goes out to be taken as the number that foreign matter is discerned by number, estimates.
(embodiment 1～3)
Substrate sheet shape glass adopts device shown in Figure 1 to make.That is,, and when making it expand into hollow form, stretch and make its filming, carry out cooling curing at last at 1,200 ℃ of following melten glass.With roller its pulverizing is obtained the thick flake glass of 1.3 μ m.Use micronizer mill to pulverize as the flake glass that standard will obtain thus, be made into the lamelliform particle of median size D50=21.7 μ m with median size 20 μ m.Maximum particle diameter=96.0 μ m of this moment; D90=37.2 μ m; D10=10.8 μ m; D90/D10 is 3.44.
It is that to use mesh be under the sieve, the situation of hypomere as pallet of 20 μ m for testing sieve, the stage casing of 32 μ m that this flake glass is used mesh at epimere, in the screening time of regulation, sieve, remove meal and micro mist, be determined at the size-grade distribution of the flake glass that is recovered on its stage casing sieve.By changing the flake glass that the screening time obtains various size-grade distribution.With their table 1 that the results are shown in.So-called in the table 1 " initial sheet " is meant initial (being in unsized state) flake glass.Each following table is also identical.
Table 1
| Initial sheet | Embodiment 1 | |
|
|
| The screening time | — | 30 | 45 | 60 |
| Median size D50 (μ m) | 21.7 | 24.4 | 22.5 | 21.0 |
| Maximum particle diameter (μ m) | 96.0 | 74.0 | 80.7 | 88.0 |
| D90(μm) | 37.2 | 38.8 | 36.3 | 34.5 |
| D10(μm) | 10.8 | 15.5 | 13.4 | 11.7 |
| D90/D10 | 3.44 | 2.50 | 2.71 | 2.95 |
| No lamelliform particle black part L value | 20.8 | 20.8 | 20.8 | 20.8 |
| Lamelliform particle black part L value is arranged | 24.1 | 22.0 | 22.7 | 23.3 |
| △L | 3.3 | 1.2 | 1.9 | 2.5 |
In the table 1, in embodiment 1,2 and 3, the value of D90/D10 is respectively 2.50,2.71,2.95 with respect to the D90/D10=3.44 of initial sheet shape glass, can confirm to have obtained the narrow flake glass of width of size-grade distribution.In addition, 96.0 μ m of embodiment 1,2 and 3 the relative initial sheet of maximum particle diameter are respectively 74.0 μ m, 80.7 μ m, 88.0 μ m.10.8 μ m of embodiment 1,2 and 3 the relative initial sheet of D10 are respectively 15.5 μ m, 13.4 μ m, 11.7 μ m.3.3 of embodiment 1,2 and 3 the relative initial sheet of △ L is respectively 1.2,1.9,2.5.Hence one can see that, utilizes aforesaid method to remove meal effectively and micro mist uprises the transparency.
(embodiment 4～6, comparative example 1 and 2)
Utilize titanium oxide to cover the classified flake glass of embodiment 1～3.Add ion exchanged water and be 0.5 liter in the 50g flake glass, the hydrochloric acid with 35 quality % is adjusted to 1.0 with PH afterwards, is warmed to 75 ℃ simultaneously.Quantitatively add titanium tetrachloride aqueous solution (containing 16.5 quality %) with the ratio of 12g per hour while stirring as the Ti composition, simultaneously add the sodium hydroxide of being dissolved into 10 quality %, till the silver gray tone product that obtain the light sense with 60 milliliters ratio per hour.
Obtain after the ideal tone product, filter to extract resultant, clean with pure water with decompression, 150 ℃ dry down and under 600 ℃, fire, obtain to possess the flake glass of titanium oxide overlay film as pearlescent pigment.Use the flake glass of embodiment 1,2,3, make the pearlescent pigment (bright pigment) of embodiment 4,5,6 respectively.The evaluation result of these pearlescent pigments is shown in table 2.
As a comparative example, to commercially available, the median size D50 that is divided into 2 groups is bright pigment メ シ ャ イ Application (registered trademark) MC1020RS (Nippon Sheet Glass Co Ltd's system) about 20 μ m, be coated with titanium oxide on the thick flake glass of 1.3 μ m, measures its size-grade distribution (median size, maximum particle diameter, D90, D10 and D90/D10), L value.In addition, the bright sense of particle sensitization, the property stopped up and coating foreign matter are estimated.These be the results are shown in table 2.
Table 2
| |
|
|
Comparative example 1 | Comparative example 2 | |
| Median size D50 (μ m) | 24.3 | 22.8 | 21.2 | 22.0 | 20.7 |
| Maximum particle diameter (μ m) | 74.0 | 80.7 | 88.0 | 96.0 | 96.0 |
| D90(μm) | 38.2 | 36.0 | 34.9 | 36.1 | 35.1 |
| D10(μm) | 15.4 | 13.3 | 11.8 | 11.7 | 10.4 |
| D90/D10 | 2.48 | 2.71 | 2.96 | 3.09 | 3.38 |
| The L value | 70.5 | 70.9 | 71.2 | 68.5 | 68.7 |
| The bright sense of |
5 | 5 | 5 | 3 | 3 |
| The property stopped up | 3 | 3 | 3 | 2 | 2 |
| Coating foreign matter (individual) | 0 | 0 | 0 | 3 | 2 |
At D90/D10 is 3.09,3.38; D10 is that the L value is about 68 in the comparative example 1,2 of 11.7 μ m, 10.4 μ m.D90/D10 among the embodiment 4,5,6 is respectively 2.48,2.71,2.96; D10 is respectively 15.4 μ m, 13.3 μ m, 11.8 μ m, and the L value is brought up to about 71.Hence one can see that, and the bright pigment of embodiment 4～6 is because micro mist reduces, the narrowed width of size-grade distribution, so brightness increases to some extent than the brightness of comparative example 1 and 2.In addition also as can be known, be evaluated as 5 among the relative embodiment 4～6 of the bright sense of particle sensitization, in comparative example 1 and 2, be evaluated as 3; Because micro mist reduces, the narrowed width of size-grade distribution, therefore in particle sense and light sense, have very big-difference.
Be all 96.0 μ m, D90 in maximum particle diameter and be respectively in the comparative example 1,2 of 36.1 μ m, 35.1 μ m, the property stopped up is 2, thinks that there is obstruction in strainer and the coating foreign matter has taken place.Maximum particle diameter among the embodiment 4,5,6 is respectively 74.0 μ m, 80.7 μ m, 88.0 μ m, and the property stopped up is 3, thinks that strainer does not stop up and do not apply foreign matter.
In addition, filter stoppage, coating foreign matter take place in the comparative example 1 and 2 of D90=36.1 μ m, 35.1 μ m, obstruction, the coating foreign matter of strainer do not take place in the embodiment 4 of D90=38.2 μ m, hence one can see that, the value of maximum particle diameter more can reflect the effect of removing meal than the value of D90, can improve the obstruction and the coating foreign matter of strainer by adjusting maximum particle diameter.
(embodiment 7 and 8, comparative example 3)
With making thickness 1.3 μ m flake glass with embodiment 1～3 identical method.Pulverize with micronizer mill, 30 μ m are standard with median size, are made into the flake glass (initial sheet) of D50=30.1 μ m, maximum particle diameter=114.1 μ m, D90=51.7 μ m, D10=16.1 μ m, D90/D10=3.21.At the epimere mesh is that 38 μ m, stage casing mesh are that 20 μ m, hypomere are under the situation of pallet, sieves in the screening time of the regulation identical with embodiment 1～3 situation, obtains embodiment 7 and 8 and the flake glass of comparative example 3.The results are shown in table 3.
Table 3
| Initial sheet | Embodiment 7 | |
Comparative example 3 | |
| The screening time (branch) | — | 30 | 60 | 90 |
| Median size D50 (μ m) | 30.1 | 32.1 | 30.7 | 31.2 |
| Maximum particle diameter (μ m) | 114.1 | 88.0 | 88.0 | 104.7 |
| D90(μm) | 51.7 | 47.8 | 50.5 | 51.4 |
| D10(μm) | 16.1 | 22.5 | 18.7 | 17.8 |
| D90/D10 | 3.21 | 2.12 | 2.70 | 2.89 |
As shown in table 3, embodiment 7 and 8 compares with the D90/D10=3.21 of initial sheet shape glass, and the value of D90/D10 is respectively 2.12,2.70.In addition, the relative maximum particle diameter 114.1 μ m of initial sheet shape glass, embodiment 7 and 8 maximum particle diameter are 88.0.In addition, relatively the D10 of initial sheet shape glass is 16.1 μ m, and embodiment 7 and 8 D10 are respectively 22.5 μ m, 18.7 μ m, and affirmation can obtain the narrow flake glass of width of size-grade distribution.
In addition, with the comparative example 3 of the screening asynchronism(-nization) of embodiment 7 and 8 in, the D90/D10=3.21 of the value of D90/D10 and initial sheet shape glass is in a ratio of 2.89, the maximum particle diameter 114.1 μ m of maximum particle diameter and initial sheet shape glass are in a ratio of 104.7 μ m, the D10=16.1 μ m of D10 and initial sheet shape glass is in a ratio of 17.8 μ m, though can confirm to obtain from the width of the value size-grade distribution of D90/D10 narrow, the flake glass that maximum particle diameter may not reduce.
(embodiment 9 and 10, comparative example 4 and 5)
To using titanium oxide to cover embodiment 7 and 8 and the embodiment 9,10 of the flake glass of comparative example 3 and the bright pigment of comparative example 4, adopt and embodiment 4～5 identical methods are estimated size-grade distribution, L value, the bright sense of particle sensitization, obstruction property and applied foreign matter.
And, as a comparative example 5, using the thickness of substrate glass is that 1.3 μ m, median size are commercially available bright pigment メ シ ャ イ Application (registered trademark) MC1030RS (Nippon Sheet Glass Co Ltd's system) about 30 μ m, carries out same evaluation.The result gathered be shown in table 4.
Table 4
| Embodiment 9 | |
Comparative example 4 | Comparative example 5 | |
| Median size D50 (μ m) | 31.9 | 30.9 | 31.5 | 32.0 |
| Maximum particle diameter (μ m) | 88.0 | 88.0 | 96.0 | 104.7 |
| D90(μm) | 47.5 | 50.8 | 51.9 | 54.6 |
| D10(μm) | 22.2 | 18.8 | 17.9 | 17.2 |
| D90/D10 | 2.14 | 2.70 | 2.90 | 3.17 |
| The L value | 71.6 | 72.8 | 72.2 | 68.5 |
| The bright sense of |
5 | 5 | 5 | 4 |
| The property stopped up | 3 | 3 | 2 | 1 |
| Coating foreign matter (individual) | 0 | 0 | 3 | 5 |
Be 3.17 at D90/D10, D10 is in the comparative example 5 of 17.2 μ m, the L value is about 68.In embodiment 9 and 10, D90/D10 is 2.14,2.70, and D10 is 22.2 μ m, 18.8 μ m, and the L value is about 72, and hence one can see that, because micro mist reduces, the narrowed width of size-grade distribution, so brightness increases to some extent than comparative example 5.In addition, the bright sense of particle sensitization among the embodiment 9 and 10 is evaluated as 5, and the bright sense of particle sensitization in the comparative example 5 is evaluated as 4, and hence one can see that, because micro mist reduces, the narrowed width of size-grade distribution, therefore has gap.
In maximum particle diameter is in the comparative example 5 of 104.7 μ m, and the property stopped up is 1, thinks that the coating foreign matter takes place to stop up and takes place strainer.In embodiment 9,10, maximum particle diameter is 88.0 μ m, and the property stopped up is 3, thinks that foreign matter does not take place to stop up and do not apply strainer.Hence one can see that, can improve the obstruction of strainer, the generation of coating foreign matter by adjusting by the maximum particle diameter of the effect decision of removing meal.
In addition, with respect to the L value in the comparative example 4 be about 72, the bright sense of particle sensitization is 5 evaluation, embodiment 9 and 10 degree same with it, the property stopped up is 2, thinks that the coating foreign matter takes place to stop up and takes place strainer.In the comparative example 4, D90/D10 is 2.90, and D10 is 17.9 μ m, and maximum particle diameter is 96.0 μ m; D90/D10 is 2.14,2.70 among the embodiment 9 and 10, and D10 is 22.2,18.8 μ m, and maximum particle diameter is 88.0 μ m.These are compared as can be known,, not only will make the narrowed width of size-grade distribution, also will adjust maximum particle diameter by the effect decision of removing meal in order to satisfy all brightness, particle sense, light sense, the property stopped up, coating foreign matter.
(embodiment 11, comparative example 6)
With the thickness of substrate glass is that 1.3 μ m, median size are the bright pigment メ シ about 40 μ m
ャイ Application (registered trademark) MC1040RS (flake glass of capping oxidation titanium) (Nippon Sheet Glass Co Ltd's system) carries out screening in 30 minutes with the screening machine of epimere mesh 45 μ m, hypomere mesh 20 μ m.The bright pigment that screening is obtained is as the pigment of embodiment 11, and the bright pigment before will screening is 6 pigment as a comparative example.Size-grade distribution and L value and the bright sense of particle sensitization, property stopped up that records respectively and the evaluation result that applies foreign matter are shown in table 5.Because the median size of initial sheet shape glass is big, therefore there is not big difference in the particle sense of seeing.But for the light sense, embodiment 11 is because micro mist reduces, the narrowed width of size-grade distribution, and micropartical reduced and then scattering is reduced, therefore than the brightness height of comparative example 6.This result also can obtain confirming by the high situation of the L value of embodiment 11.In addition, can confirm,, can improve the property stopped up, coating foreign matter by adjusting maximum particle diameter by the effect decision of removing meal.
Table 5
| |
Comparative example 6 | |
| The screening time (branch) | 30 | — |
| Median size D50 (μ m) | 38.9 | 39.6 |
| Maximum particle diameter (μ m) | 88.0 | 124.5 |
| D90(μm) | 66.6 | 66.9 |
| D10(μm) | 23.8 | 21.1 |
| D90/D10 | 2.80 | 3.17 |
| The L value | 74.2 | 70.2 |
| The bright sense of |
5 | 4～5 |
| The property stopped up | 3 | 1 |
| Coating foreign matter (individual) | 0 | 7 |
(embodiment 12 and comparative example 7)
Make the flake glass of thickness 1.3 μ m of the method identical with embodiment 1～3.Pulverize with micronizer mill, 10 μ m are standard with median size, are made into the flake glass (initial sheet) of D50=8.5 μ m, maximum particle diameter=37.0 μ m, D90=15.2 μ m, D10=4.4 μ m, D90/D10=3.45.At the epimere mesh is that 25 μ m, stage casing mesh are that 16 μ m, hypomere are under the situation of pallet, uses the screening time of the regulation identical with embodiment 1～3 situation to sieve.The results are shown in table 6.
Table 6
| | Embodiment | 12 | Comparative example 7 | |
| The screening time (branch) | — | 60 | 30 | |
| Median size D50 (μ m) | 8.5 | 8.2 | 84 | |
| Maximum particle diameter (μ m) | 37.0 | 33.9 | 33.9 | |
| D90(μm) | 15.2 | 14.0 | 13.3 | |
| D10(μm) | 4.4 | 4.7 | 4.5 | |
| D90/D10 | 3.45 | 2.98 | 2.96 |
Can confirm by table 6, the D90/D10 of former flake glass is 3.45 and the value of D90/D10 among the embodiment 12 is 2.98, the maximum particle diameter of former flake glass is 37.0 μ m and maximum particle footpath 33.9 μ m among the embodiment 12, the D10 of former flake glass is 4.4 μ m and D10 among the embodiment 12 is 4.7 μ m, can obtain the narrow flake glass of width of size-grade distribution.
In addition, the D90/D10 of initial sheet shape glass is 3.45 and the value of D90/D10 in the comparative example 7 is 2.96, the maximum particle diameter 37.0 μ m of initial sheet shape glass and the value of maximum particle diameter in the comparative example 7 is 33.9 μ m, the D10 of initial sheet shape glass is 4.4 μ m and the value of D10 in the comparative example 7 is 4.5 μ m, though can confirm to obtain from the width of the value size-grade distribution of D90/D10 narrow, the flake glass that D10 not necessarily increases.
(embodiment 13, comparative example 8 and 9)
With the method identical, make and use titanium oxide to cover the bright pigment of the flake glass of embodiment 12 and comparative example 7, as embodiment 13 and comparative example 8 with embodiment 4～5.These bright pigment are estimated its size-grade distribution, L value, the bright sense of particle sensitization, the property stopped up, coating foreign matter.
As a comparative example 9, the bright pigment of using initial sheet to make is carried out same evaluation.The result gathered be shown in table 7.
Table 7
| |
Comparative example 8 | Comparative example 9 | |
| Median size D50 (μ m) | 8.0 | 8.3 | 8.4 |
| Maximum particle diameter (μ m) | 33.9 | 33.9 | 37.0 |
| D90(μm) | 14.2 | 13.2 | 14.8 |
| D10(μm) | 4.8 | 4.5 | 4.4 |
| D90/D10 | 2.96 | 2.93 | 3.36 |
| The L value | 67.1 | 64.4 | 63.8 |
| The bright sense of |
4 | 2 | 1 |
| The property stopped up | 3 | 3 | 3 |
| Coating foreign matter (individual) | 0 | 0 | 0 |
Be 3.36 at D90/D10, D10 is in the comparative example 9 of 4.4 μ m, the L value is about 64.D90/D10 among the embodiment 13 is 2.96, and D10 is 4.8 μ m, and the L value rises to about 67, and hence one can see that, because micro mist reduces, the effect of the narrowed width of size-grade distribution, brightness increases to some extent than comparative example 9.In addition, the bright sense of particle sensitization is be evaluated as 4 and be evaluated as 1 in comparative example 9 in embodiment 13, and hence one can see that, because micro mist reduces, the effect of the narrowed width of size-grade distribution, therefore has difference.
Maximum particle diameter is that the comparative example 9 of 37.0 μ m, the obstruction of embodiment 13 that maximum particle diameter is 33.9 μ m are 3, thinks that foreign matter does not take place to stop up and do not apply strainer.
In addition, in comparative example 8, stop up, the coating foreign matter do not take place, but the L value be reduced to about 64 and comparative example 9 almost do not have difference.With the D90/D10 in the comparative example 8 be 2.93, D10 is that 4.5 μ m, maximum particle diameter are that D90/D10 among 33.9 μ m and the embodiment 13 is 2.96, D10 is that 4.8 μ m, maximum particle diameter are that 33.9 μ m compare as can be known, in order to satisfy all brightness, particle sense, light sense, the property stopped up, coating foreign matter, not only to make the narrowed width of size-grade distribution by D90/D10, also will adjust the D10 that removes the effect decision by micro mist.
(embodiment 14)
Making the flake glass of thickness 0.7 μ m with the method identical with the mode of embodiment 1～3, is that standard is pulverized with micronizer mill with these flake glass about with median size 10 μ m.The flake glass that pulverizing is obtained is the sieve screening 2 minutes of 20 μ m with one deck mesh.The measured value of D50, the maximum particle diameter of the flake glass (embodiment 14) after initial sheet shape glass and the screening, D90, D10, D90/D10 is shown in table 8.
Table 8
| | Embodiment | 14 | |
| The screening time (branch) | — | 2 | |
| Median size D50 (μ m) | 8.3 | 7.9 | |
| Maximum particle diameter (μ m) | 52.3 | 48.0 | |
| D90(μm) | 14.7 | 13.9 | |
| D10(μm) | 4.5 | 4.7 | |
| D90/D10 | 3.27 | 2.96 |
(embodiment 15, comparative example 10)
Silver about utilizing non-electrolytic plating method with thickness 50nm covers the flake glass of embodiment 14, makes bright pigment (embodiment 15) thus.In addition, the silver that sieves about preceding flake glass (initial sheet in the table 8) utilizes non-electrolytic plating method with thickness 50nm is equally covered it, make bright pigment (comparative example 10) thus.The evaluation result of size-grade distribution, L value and the bright sense of particle sensitization that records respectively, the property stopped up and coating foreign matter is shown in table 9.By table 9 as can be known, the L value of the pigment of embodiment 15 and the bright sense of particle sensitization are all than the pigment height of comparative example 10.In addition, mesh obstruction and coating foreign matter all do not take place in embodiment 15 and comparative example 10.
Table 9
| Embodiment 15 | Comparative example 10 | |
| Median size D50 (μ m) | 8.8 | 8.8 |
| Maximum particle diameter (μ m) | 44.0 | 52.3 |
| D90(μm) | 16.0 | 14.9 |
| D10(μm) | 5.4 | 4.5 |
| D90/D10 | 2.96 | 3.31 |
| The L value | 70.0 | 67.1 |
| The bright sense of |
5 | 3 |
| The property stopped up | 3 | 3 |
| Coating foreign matter (individual) | 0 | 0 |
(embodiment 16, comparative example 11)
Will be as the メ シ of the metalluster pigment that on flake glass, is coated with silver
ャイ Application (registered trademark) ME2040PS (Nippon Sheet Glass Co Ltd's system), with the sieve screening of epimere mesh 32 μ m, hypomere mesh 20 μ m 30 minutes, the pigment that screening is obtained was as the bright pigment of embodiment 16.In addition, preceding pigment 11 pigment as a comparative example will be sieved.The evaluation result of size-grade distribution, L value and the bright sense of particle sensitization that will record respectively each pigment, the property stopped up and coating foreign matter is shown in table 10.By table 10 as can be known, the L value of the pigment of embodiment 16 and the bright sense of particle sensitization are all than the pigment height of comparative example 11.In addition, do not stop up and do not apply foreign matter among the embodiment 16.
Table 10
| Embodiment 16 | Comparative example 11 | |
| The screening time | 30 | — |
| Median size D50 (μ m) | 34.5 | 33.5 |
| Maximum particle diameter (μ m) | 88.0 | 124.5 |
| D90(μm) | 58.6 | 58.4 |
| D10(μm) | 20.1 | 15.9 |
| D90/D10 | 2.92 | 3.67 |
| The L value | 83.9 | 80.2 |
| The bright sense of |
5 | 4 |
| The property stopped up | 3 | 1 |
| Coating foreign matter (individual) | 0 | 6 |
(embodiment 17, comparative example 12)
Utilize shown below each to become to assign to modulate oil-in-water type Mascara as embodiment 17.Unit is quality %.
(1) Natvosol 1.0
(2) methyl p-hydroxybenzoate 0.2
(3) glycerine 0.3
(4) high-polymerization degree polyoxyethylene glycol
(molecular-weight average 2,000,000) 0.5
(5) distilled water 60.0
(6) bright pigment 5.0 of embodiment 11
(7) Black Rouge pigment 3.0
(8) trolamine 3.0
(9) stearic acid 5.0
(10) beeswax 9.0
(11) carnauba wax 3.0
(12) paraffin 10.0
Mix mentioned component (1)～(5), be heated to 75 ℃ and dissolve, make its homogenization.To bright pigment, (7) Black Rouge pigment of this mixture added ingredients (6), enter colloid mill its homogeneous is disperseed.Further mix the composition dissolving of (8) and be heated to 75 ℃, emulsification, cooling are also carried out in (9)～(12) after the homogenization of interpolation heating for dissolving, obtain the oil-in-water type Mascara.
In the prescription of embodiment 17, substitute the bright pigment of composition (6), all the other and embodiment 17 same operation, the oil-in-water type Mascara of making comparative example 12 with the bright pigment of comparative example 4.
The evaluation result of the bright sense of particle sensitization of embodiment 17 and comparative example 12 is shown in table 11.
Table 11
| Embodiment 17 | Comparative example 12 | |
| The bright sense of |
5 | 4 |
By the result shown in the comparison sheet 11 as can be known, the Mascara that contains the oil-in-water type Mascara of embodiment 17 of bright pigment of the present invention and present comparative example 12 is the more distinct sparkling Mascara of particle relatively.
(embodiment 18, comparative example 13)
Utilize shown below each to become to assign to modulate eye shadow as embodiment 18.Unit is quality %.
(1) talcum 21
(2) white mica 20
(3) bright pigment 40 of embodiment 11
(4) pigment 12
(5) three decanes 4
(6) the cetostearyl alcohol octanoate 1.9
(7) Span-83 0.8
(8) sanitas 0.1
(9) spices 0.2
Use Henschel mixer mixing mentioned component (1)～(4), the mixture that obtains mixes to wherein spraying heating mixing (5)～(9), pulverizes afterwards.The material that pulverizing is obtained is sprayed onto in the vessel of regulation, obtains eye shadow.
In the prescription of embodiment 18, use the bright pigment of the alternative composition (3) of bright pigment of comparative example 4, all the other and embodiment 18 same operation, the eye shadow of making comparative example 13.
The evaluation result of the bright sense of particle sensitization of the eye shadow of embodiment 18 and comparative example 13 is shown in table 12.
Table 12
| Embodiment 18 | Comparative example 13 | |
| The bright sense of |
5 | 4 |
By the result shown in the table 12 as can be known, the eye shadow that contains the eye shadow of embodiment 18 of bright pigment of the present invention and present comparative example 13 is the more distinct sparkling eye shadow of particle relatively.
(embodiment 19, comparative example 14)
Utilize the Colour nail polish of each composition modulation shown below as embodiment 19.Unit is quality %.
(1) soluble cotton 18.0
(2) the tolylsulfonyl polyimide resin 6.0
(3) tributyl acetylcitrate 6.0
(4) the alkyl acrylic multipolymer 2.0
(5) Virahol 5.0
(6) benzyl dimethylammonium hectorite 2.0
(7) vinyl acetic monomer 20.0
(8) N-BUTYL ACETATE 30.9
(9) dark blue pigment 0.1
(10) bright pigment 10.0 of embodiment 10
, add (5)～(8) and fusion diffusion its homogeneous is disperseed with mentioned component (1)～(4) and after (9)～(10) are mixing with roller mill, the mixture that obtains after disperseing is filled in the container of regulation and obtains Colour nail polish.
In the prescription of embodiment 19, use the bright pigment of the alternative composition (10) of bright pigment of comparative example 3, all the other and embodiment 19 same operation, the Colour nail polish of making comparative example 14.
The evaluation result of the bright sense of particle sensitization of the Colour nail polish of embodiment 19 and comparative example 14 is shown in table 13.
Table 13
| Embodiment 19 | Comparative example 14 | |
| The bright sense of |
5 | 4 |
By the result shown in the table 13 as can be known, the Colour nail polish that contains the Colour nail polish of embodiment 19 of bright pigment of the present invention and present comparative example 14 is the more distinct sparkling Colour nail polish of particle relatively.
(embodiment 20, comparative example 15)
Utilize the lipstick of each composition modulation shown below as embodiment 20.Unit is quality %.
(1) chloroflo 20
(2) candy lira wax (candelilla wax) 3
(3) Tegin ISO 40
(4) liquid wax 26.8
(5) titanium dioxide 4
(6) bright pigment 0.2 of embodiment 16
(7) pigment dyestuff 5.8
(8) spices 0.2
In 85 ℃ of following heating and melting mentioned components (1)～(4), in them, add (5)～(7) and mix, remix (8) and stirring afterwards fills it into thereafter in the container of regulation and obtains lipstick.
In the prescription of embodiment 20, use the bright pigment of the alternative composition (6) of bright pigment of comparative example 11, all the other and embodiment 20 same operation, the lipstick of making comparative example 15.
The evaluation result of the bright sense of particle sensitization of the lipstick of embodiment 20 and comparative example 15 is shown in table 14.
Table 14
| Embodiment 20 | Comparative example 15 | |
| The bright sense of |
5 | 4 |
By the result shown in the table 14 as can be known, the lipstick that contains the lipstick of embodiment 20 of bright pigment of the present invention and present comparative example 15 is the more distinct sparkling lipstick of particle relatively.
(embodiment 21, comparative example 16)
Utilize the coating composition of each composition modulation shown below as embodiment 21.Unit is quality %.
At first, composition as follows is made paint the dispersion that shaking machine (Paint shaker) carried out 60 minutes and make dispersible carrier.Following:
(1) Synolac class lacquer 20.6
(2) melanocyte resene lacquer 10.6
(3)スワゾ—ル 15.6
(4) in the dispersible carrier that the bright pigment 15.6 of embodiment 5 forms, further add following composition:
(5) Synolac class lacquer 26.3
(6) melanocyte resene lacquer 11.3
And stir and make coating composition.
In the coating composition shown in the embodiment 21, use the bright pigment of the alternative composition (4) of bright pigment of comparative example 1, all the other and embodiment 21 same operation, the coating composition of making comparative example 16.
Respectively the bright sense of particle sensitization of the coating composition of embodiment 21 and comparative example 16 is judged.It is the results are shown in table 15.
Table 15
| Embodiment 21 | Comparative example 16 | |
| The bright sense of |
5 | 3 |
By the result shown in the table 15 as can be known, the coating composition that contains the coating composition of embodiment 21 of bright pigment of the present invention and present comparative example 16 relatively, for having the distinct more coating product of particle sense.In addition, the coating of embodiment 21 since in the bright pigment of (4) meal few, therefore with the coating ratio of comparative example 16, the obstruction that can lower strainer when filtering.
(embodiment 22, comparative example 17)
Use Henschel mixer, the bright pigment that the methyl methacrylate copolymer of 98 quality % is closed the embodiment 6 of microballon, 2 quality % is mixed and is stirred the resin combination that obtains embodiment 22.This resin combination is made into the acrylic resin shaping thing of thickness 0.5mm with forcing machine.
Except that bright pigment with the bright pigment of using in the bright pigment alternate embodiment 22 of comparative example 2, with embodiment 22 same operation, make the resin combination of comparative example 17, use this resin combination to make the acrylic resin shaping thing of thickness 0.5mm.
The evaluation result of the bright sense of particle sensitization of the resin forming article of embodiment 22 and comparative example 17 is shown in table 16.
Table 16
| Embodiment 22 | Comparative example 17 | |
| The bright sense of |
5 | 3 |
By the result shown in the table 16 as can be known, the resin forming article that contains the resin forming article of embodiment 22 of bright pigment of the present invention and present comparative example 17 relatively presents the tone with particle sense and rich light sense.
(embodiment 23, comparative example 18)
With each composition thorough mixing shown below, modulation is as the printing ink of embodiment 23.Unit is quality %.
(1) bright pigment 12 of embodiment 9
(2) ketone resin 19
(3) ethanol 59
(4) propylene glycol monomethyl ether 10
In the ink composite of embodiment 23, except that the bright pigment with comparative example 5 substitutes the bright pigment of composition (1), all the other and embodiment 23 same operation, the ink composite of making comparative example 18.
Use the ink composite of embodiment 23 and comparative example 18 on blank sheet of paper, to write, respectively the bright sense of its particle sensitization is judged.Result of determination is shown in table 17.
Table 17
| Embodiment 23 | Comparative example 18 | |
| The bright sense of |
5 | 3 |
By the result shown in the table 17 as can be known, the ink composite that contains the ink composite of embodiment 23 of bright pigment of the present invention and comparative example 18 relatively can present the person's handwriting that has the particle sense and have the tone of distinct light sense.
(embodiment 24, comparative example 19)
Utilize the muffin of each composition modulation shown below as embodiment 24.Unit is quality %.
(1) lamelliform particle 35 of embodiment 1
(2) talcum 20
(3) flake glass 20 of covering titanium
(4) titanium dioxide 10
(5) spherical polyethylene powders 5
(6) red iron oxide 1
(7) Zh 13
(8) black iron oxide 0.1
(9) silicone oil 1
(10) 2-ethylhexyl Palmitate
(Wickenol 155) 9
(11) sesquialter oleic acid sorbitanic 1
(12) sanitas 0.3
(13) spices 0.1
With Henschel mixer mixing mentioned component (1)～(8), this mixture is added that heating and melting mixes (9)～(13) and the mixture that obtains is pulverized with pulverizer afterwards, the mixture that pulverizing is obtained is packed in the vessel of diameter 6cm, at 1.5kg/cm
2Pressure be shaped down, be made into muffin.
In the prescription of embodiment 24, use the lamelliform particle of the alternative composition (1) of lamelliform particle of initial sheet, all the other and embodiment 24 same operation, the muffin of making comparative example 19.
The organoleptic test of muffin is, is made as the evaluation point of following 5 grades, reinstates 10 experimenters, and the mean value of selecting with this 10 people's evaluation is estimated the transparent feel of muffin.
(criterion)
1: do not have transparent feel, be regarded as muddiness.
2: sub-translucent, be regarded as muddy slightly.
3: transparent feel is general.
4: have suitable transparent feel.
5: the transparent feel height.
The evaluation result of the transparent feel of the muffin of embodiment 24 and comparative example 19 is shown in table 18.
Table 18
| Embodiment 24 | Comparative example 19 | |
| |
5 | 3.8 |
For the muffin of embodiment 24, because 10 experimenters all are evaluated as 5 points, the mean value of therefore estimating point is 5.On the contrary, for the muffin of comparative example 19, owing to 8 experimenters are evaluated as 4 points, 2 people experimenters are evaluated as 3 points, the mean value of therefore estimating point is 3.8.Relatively this result as can be known, the muffin that contains the muffin of embodiment 24 of lamelliform particle of the present invention and present comparative example 19 relatively is the higher muffin of transparent feel.
Applicability on the industry
Flaky particle of the present invention and pigment owing to can realize high particle sense and light sense, therefore can be preferably used as the filler of light senses such as giving cosmetic preparation, coating composition, resin combination and ink composite. In addition, cosmetic preparation of the present invention, coating composition, resin combination and ink composite owing to have high light sense and particle sense, therefore can preferably be used in such as in the goods that require to have senior outward appearance etc.
Claims (8)
1, a kind of lamelliform particle, wherein, in its size-grade distribution, to be accumulated as that 10% o'clock pairing particle diameter is set at D10, the volume that begun by the little side of particle diameter is accumulated as 90% o'clock pairing particle diameter and is set at D90 by the volume that the little side of particle diameter begins, in the case, the value of D90/D10 is 2.0～3.0, and D10 is 4.7 μ m～25 μ m, and maximum particle diameter is below the 90 μ m.
2, as claim item 1 described lamelliform particle, wherein, above-mentioned lamelliform particle is made of glass.
3, a kind of bright pigment, it comprises at least a in lamelliform particle and metal level that forms and the metal oxide layer on lip-deep at least a portion of above-mentioned lamelliform particle;
Wherein, in size-grade distribution, to be accumulated as that 10% o'clock pairing particle diameter is set at D10, the volume that begun by the little side of particle diameter is accumulated as 90% o'clock pairing particle diameter and is set at D90 by the volume that the little side of particle diameter begins, in the case, the value of D90/D10 is 2.0～3.0, D10 is 4.7 μ m～25 μ m, and maximum particle diameter is below the 90 μ m.
4, as claim item 3 described bright pigment, wherein, in the size-grade distribution of above-mentioned lamelliform particle, being accumulated as 10% o'clock pairing particle diameter is set at D10, a little side begins by particle diameter volume at volume that will a little side begins by particle diameter is accumulated as 90% o'clock pairing particle diameter and is set under the situation of D90, the value of D90/D10 is 2.0～3.0, D10 is 4.7 μ m～25 μ m, and maximum particle diameter is below the 90 μ m.
5, a kind of cosmetic material wherein, contains at least a in claim item 1 described lamelliform particle and the claim item 3 described bright pigment.
6, a kind of coating composition wherein, contains at least a in claim item 1 described lamelliform particle and the claim item 3 described bright pigment.
7, a kind of resin combination wherein, contains at least a in claim item 1 described lamelliform particle and the claim item 3 described bright pigment.
8, a kind of ink composite wherein, contains at least a in claim item 1 described lamelliform particle and the claim item 3 described bright pigment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510068340.2A CN104761927A (en) | 2006-04-05 | 2007-04-03 | Flaky particles and luster pigment, and cosmetic, coating composition, resin composition and ink composition each containing the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006104509 | 2006-04-05 | ||
| JP104509/2006 | 2006-04-05 | ||
| JP278656/2006 | 2006-10-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510068340.2A Division CN104761927A (en) | 2006-04-05 | 2007-04-03 | Flaky particles and luster pigment, and cosmetic, coating composition, resin composition and ink composition each containing the same |
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| Publication Number | Publication Date |
|---|---|
| CN101415783A true CN101415783A (en) | 2009-04-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200780012034 Pending CN101415783A (en) | 2006-04-05 | 2007-04-03 | Flaky particle and brightening pigment, and cosmetic preparation, coating composition, resin composition, and ink composition each containing these |
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| CN (1) | CN101415783A (en) |
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| CN102391693A (en) * | 2011-09-01 | 2012-03-28 | 江苏双乐化工颜料有限公司 | Pigment with metal luster and preparation method for pigment with metal luster |
| CN102762673A (en) * | 2010-02-18 | 2012-10-31 | 巴斯夫涂料有限公司 | Aqueous coating compositions pigmented with flake-form metallic effect pigments, processes for preparing them and use thereof for producing multicoat paint finish |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2014159584A (en) * | 2008-02-20 | 2014-09-04 | Eckart Gmbh | Effect pigment based on artificially manufactured base material having narrow size distribution |
| CN102317379A (en) * | 2009-08-19 | 2012-01-11 | 埃卡特有限公司 | Has high gloss multiple layering effect pigment of colored interference look and narrow size distribution and preparation method thereof |
| US8728226B2 (en) | 2009-08-19 | 2014-05-20 | Eckart Gmbh | High-gloss multilayer effect pigments having a chromatic interference color and a narrow size distribution, and method for the production thereof |
| CN102762673A (en) * | 2010-02-18 | 2012-10-31 | 巴斯夫涂料有限公司 | Aqueous coating compositions pigmented with flake-form metallic effect pigments, processes for preparing them and use thereof for producing multicoat paint finish |
| CN102762673B (en) * | 2010-02-18 | 2016-01-27 | 巴斯夫涂料有限公司 | The aqueous coating agent adopting platelet-like metal effect pigment painted, its preparation method and the purposes for the preparation of multilayer japanning thereof |
| CN102391693A (en) * | 2011-09-01 | 2012-03-28 | 江苏双乐化工颜料有限公司 | Pigment with metal luster and preparation method for pigment with metal luster |
| CN102391693B (en) * | 2011-09-01 | 2013-12-04 | 江苏双乐化工颜料有限公司 | Pigment with metal luster and preparation method for pigment with metal luster |
| CN110678424A (en) * | 2017-05-29 | 2020-01-10 | 日本板硝子株式会社 | Sheet glass and resin composition |
| CN110678424B (en) * | 2017-05-29 | 2022-04-29 | 日本板硝子株式会社 | Sheet glass and resin composition |
| CN109855411A (en) * | 2019-03-26 | 2019-06-07 | 浙江林奈新能源有限公司 | A kind of pretreating device in anode material for lithium-ion batteries production |
| CN115003270A (en) * | 2020-02-28 | 2022-09-02 | 株式会社资生堂 | Powdery solid cosmetic |
| CN113604182A (en) * | 2021-08-16 | 2021-11-05 | 广东生益科技股份有限公司 | Resin composition and application thereof |
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Application publication date: 20090422 |