CN101525502A - Infrared reflecting blue pigment, infrared reflecting green pigment, paint and resin composition using the infrared reflecting blue pigment, and paint and resin composition using the infrared reflecti - Google Patents
Infrared reflecting blue pigment, infrared reflecting green pigment, paint and resin composition using the infrared reflecting blue pigment, and paint and resin composition using the infrared reflecti Download PDFInfo
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- CN101525502A CN101525502A CNA2009101178369A CN200910117836A CN101525502A CN 101525502 A CN101525502 A CN 101525502A CN A2009101178369 A CNA2009101178369 A CN A2009101178369A CN 200910117836 A CN200910117836 A CN 200910117836A CN 101525502 A CN101525502 A CN 101525502A
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- infrared reflectivity
- veridian
- blue pigments
- reflectivity
- infrared
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Landscapes
- Paints Or Removers (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to an infrared reflecting blue pigment comprising a composite oxide comprising Co, Al and Mg, wherein a content of Mg in the blue pigment is 11 to 22% in terms of a molar ratio thereof based on whole metal element present in the blue pigment, and the blue pigment has a BET specific surface area of 10 to 100 m 2 /g; and an infrared reflecting green pigment comprising a composite oxide comprising Co, Al, Mg and Fe, wherein a content of Mg in the green pigment is 11 to 22% in terms of a molar ratio thereof based on whole metal element present in the green pigment, a content of Fe in the green pigment is 0.5 to 20% in terms of a molar ratio thereof based on whole metal element present in the green pigment, and the green pigment has an average particle diameter of 0.02 to 1.2 [mu]m.
Description
Technical field
The present invention relates to not contain harmful element and can access the infrared reflectivity blue pigments and the infrared reflectivity veridian of covering property of heat coating with good infrared reflectivity.
Background technology
At the road of outdoor application, buildings, storage tank, automobile, boats and ships etc. because of sunshine of the sun internal temperature being raise.Therefore, take following measure: extremely light by the outward appearance of buildings and automobile etc. is covered with paint, lacquer, colour wash, etc. to white, reflected sunlight improves hot screening effect to a certain degree.
Yet, roof of outdoor architecture thing etc. especially is unshowy and to be dark colour a lot of to the situation of black in order to make dirt.Have buildings that dark colour to the outward appearance of black covers with paint, lacquer, colour wash, etc. and automobile etc., the buildings of covering with paint, lacquer, colour wash, etc. with the outward appearance with light-coloured to white and automobile etc. are compared, and absorb sunlight easily, have the tendency that indoor temperature significantly raises.When carrying, when preserving article, not expecting that internal temperature rises to high temperature.
Therefore, from the viewpoint of the conserve energy in order to prevent greenhouse effects of the earth, also expectation suppresses to have the rising of dark colour to the internal temperature of the buildings of the outward appearance of black and automobile etc. consumingly.Though, for example developed a kind of containing by CoO, Cr as existing covering property of heat blackwash
2O
3And Fe
2O
3The black that constitutes and have a spinel structure is fired covering property of the heat blackwash (opening the 2000-72990 communique with reference to the spy) of pigment, but in pigment, contain Cr, so seek a kind of infrared reflectivity blackwash that does not contain harmful element and have good infrared reflectivity.To this, applicant of the present invention develops a kind of infrared reflectivity blackwash that does not contain harmful element and have good infrared reflectivity, has proposed patent application (opening the 2007-197570 communique with reference to the spy).
As everyone knows, as coating, except using blackwash, also use multiple pigmented coatinges such as blueness, green, redness.As the mineral dye of the blueness of in coating etc., using, use the pigment of cobalt blue system up to now widely.As the pigment of cobalt blue system, motion has the blue pigments of various improvement.For example, as the manufacture method of reddish particle type cobalt blue series pigments, motion has the method (opening the 2000-80301 communique with reference to the spy) that makes the phosphorus compound coexistence when using yellow soda ash as alkaline agent, the oxyhydroxide that makes aluminium and cobalt and carbonate deposition.In addition, also motion has: the pulverizing of starting raw material applies the energy that is enough to obtain the chemomotive force effect when mixing, make cobalt and aluminium become the second particle of even existence, this second particle is fired in heating, makes the cobalt blue series pigments (opening flat 10-219132 communique with reference to the spy) of high transparent.
In addition, as the mineral dye of the green of in coating etc., using, the known pigment that the spinelle type composite oxides of cobalt, aluminium, chromium, titanium system is arranged.With regard to veridian, expect not contain in the pigment chromium too.As the veridian that does not contain chromium, motion has the composite oxides veridian (opening the 2000-86246 communique with reference to the spy) that is made of cobalt, aluminium and titanyl compound.
Nowadays, from preventing the viewpoint of greenhouse effects of the earth, seeking a kind of blue pigments and veridian also with the same covering property of the heat coating of black pigment with good infrared reflectivity.The pigment of the blueness that in blue paste, can use, though except the spy opens 2000-80301 communique and the Te Kai described manufacture method of flat 10-219132 communique and adopts the blue pigments that these methods make, there are many manufacture method and pigment open in patent disclosure communique etc., but do not make the infrared reflectivity blue pigments that does not contain harmful element and have good infrared reflectivity as yet.In addition, the pigment of the green that in green coating, can use, though except the spy opens the described manufacture method of 2000-86246 communique and adopts the veridian that these methods make, there are many manufacture method and pigment open in patent disclosure communique etc., but do not make the infrared reflectivity veridian that does not contain harmful element and have good infrared reflectivity as yet.
Summary of the invention
First purpose of the present invention is: provide a kind of and do not contain harmful element and be blue pigments and the infrared reflectivity blue pigments with good infrared reflectivity.
Second purpose of the present invention is: provide a kind of and do not contain harmful element and be veridian and the infrared reflectivity veridian with good infrared reflectivity.
By the present invention as described below, can reach first purpose of the present invention.
The invention provides a kind of infrared reflectivity blue pigments, it is characterized in that: constitute by the composite oxides that contain Co, Al and Mg, the Mg content of this blue pigments is 11～22% with the molar ratio computing with respect to whole metallic elements, and the BET specific surface area of this blue pigments is 10～100m
2/ g (the present invention 1).
As the present invention's 1 described infrared reflectivity blue pigments, the crystalline structure of infrared reflectivity blue pigments is spinel type (the present invention 2).
As the present invention's 1 described infrared reflectivity blue pigments, the luminance brightness (L of infrared reflectivity blue pigments
*) be 35～50 (the present invention 3).
As the present invention's 1 described infrared reflectivity blue pigments, the reflectivity at sunshine of infrared reflectivity blue pigments is 45～60% (the present invention 4).
As the present invention's 1 described infrared reflectivity blue pigments, more than one the compound that the surface of infrared reflectivity blue pigments is selected among Si, Al, Zr, the Ti covers (the present invention 5).
The invention provides a kind of coating, it constitutes cooperation the present invention's 1 described infrared reflectivity blue pigments in the base material and obtains (the present invention 6) at coating.
The invention provides a kind of resin combination, it is to use the present invention's painted obtaining of 1 described infrared reflectivity blue pigments (the present invention 7).
By the present invention as described below, can reach second purpose of the present invention.
The invention provides a kind of infrared reflectivity veridian, it is characterized in that: constitute by the composite oxides that contain Co, Al, Mg and Fe, the Mg content of this veridian is 11～22% with the molar ratio computing with respect to whole metallic elements, Fe content is 0.5～20% with the molar ratio computing with respect to whole metallic elements, and the median size of this veridian is 0.02～1.2 μ m (the present invention 8).
As the present invention's 8 described infrared reflectivity veridians, the crystalline structure of infrared reflectivity veridian is spinel type (the present invention 9).
As the present invention's 8 described infrared reflectivity veridians, the luminance brightness (L of infrared reflectivity veridian
*) surpass 30 and be (the present invention 10) below 40.
As the present invention's 8 described infrared reflectivity veridians, the reflectivity at sunshine of infrared reflectivity veridian is 35～50% (the present invention 11).
As the present invention's 8 described infrared reflectivity veridians, more than one the compound that the surface of infrared reflectivity veridian is selected among Si, Al, Zr, the Ti covers (the present invention 12).
The invention provides a kind of coating, it constitutes cooperation the present invention's 8 described infrared reflectivity veridians in the base material and obtains (the present invention 13) at coating.
The invention provides a kind of resin combination, it is to use the present invention's painted obtaining of 8 described infrared reflectivity veridians (the present invention 14).
Embodiment
Below, illustrate in greater detail structure of the present invention.
At first, the infrared reflectivity blue pigments that reaches the present invention's first purpose is described.
The infrared reflectivity blue pigments that the present invention relates to is made of the composite oxides that contain Co, Al and Mg, and the Mg content of this blue pigments is 11～22% with the molar ratio computing with respect to whole metallic elements, and the BET specific surface area of this blue pigments is 10～100m
2/ g.
Containing of Mg in the infrared reflectivity blue pigments that the present invention relates to is proportional, is 11～22mol% with respect to the whole metallic elements in the blue pigments, is preferably 12～20mol%, more preferably 13～20mol%.If proportional less than 11mol% with respect to containing of the Mg of whole metallic elements, then sunshine, reflectivity was difficult to say enough.On the other hand, if proportional with respect to containing of the Mg of whole metallic elements greater than 22mol%, luminance brightness (L then
*) become too high.Containing of Co in the infrared reflectivity blue pigments that the present invention relates to is proportional, is preferably 12～22mol% with respect to the whole metallic elements in the blue pigments.In addition, though the infrared reflectivity blue pigments that the present invention relates to is sneaked into the impurity from various raw materials sometimes inevitably, but its amount is trace, Mg in blue pigments and the metallic element the Co, come down to Al, the ratio of the content of Co and Mg and the content of Al is preferably 1: 2 with molar ratio computing.
The BET specific surface area of the infrared reflectivity blue pigments that the present invention relates to is 10～100m
2/ g is preferably 15～90m
2/ g, more preferably 20～80m
2/ g, more preferably 36～80m
2/ g.In the BET specific surface area less than 10m
2During/g, particle is thick, perhaps becomes sintering between particle and the particle and the particle that generates, and tinting strength reduces.In addition, if the BET specific surface area greater than 100m
2/ g, the aggegation that easy generation causes because of the particulate miniaturization, the dispersion in vehicle (vehicle) become difficult, thereby not preferred.
The crystalline structure of the infrared reflectivity blue pigments that the present invention relates to is preferably spinel type.
Though sneak into the impurity from various raw materials sometimes inevitably in the infrared reflectivity blue pigments that the present invention relates to, even in this case, for example the content of Cr is below the 1wt%, especially Cr
6+Content be below the 10ppm.
The median size of the infrared reflectivity blue pigments that the present invention relates to is preferably 0.02～1.2 μ m, under the situation of median size greater than 1.2 μ m of infrared reflectivity blue pigments, because particle size is excessive, so tinting strength reduces.Under the situation of median size less than 0.02 μ m, it is difficult that the dispersion in vehicle becomes.More preferably 0.02～1.1 μ m, more preferably 0.02～1.0 μ m.
Luminance brightness (the L of the infrared reflectivity blue pigments that the present invention relates to
*) be preferably 35～50.As luminance brightness (L
*) beyond the above-mentioned scope time, being difficult to say to be excellent blueness, its purposes is defined easily.More preferably 40～50.
The a of the infrared reflectivity blue pigments that the present invention relates to
*Be preferably 15～30.Work as a
*In the time of beyond above-mentioned scope, be difficult to say to be excellent blueness, its purposes is defined easily.More preferably 17～28.
The b of the infrared reflectivity blue pigments that the present invention relates to
*Be preferably-40～-60.Work as b
*In the time of beyond above-mentioned scope, be difficult to say to be excellent blueness, its purposes is defined easily.More preferably-45～-60.
The reflectivity at sunshine of the infrared reflectivity blue pigments that the present invention relates to is preferably 45～60%.Under less than 45% situation, infrared reflectivity is difficult to say enough.More preferably 50～60%
In the present invention, particle surface one or more the compound that can be selected among Si, Al, Zr, the Ti covers.Overlay capacity is preferably 0.1～10wt% with respect to the infrared reflectivity blue pigments, more preferably 0.2～5wt%.
Secondly, the infrared reflectivity veridian that reaches the present invention's second purpose is described.
The infrared reflectivity veridian that the present invention relates to is made of the composite oxides that contain Co, Al, Mg and Fe, the Mg content of this veridian is 11～22% with the molar ratio computing with respect to whole metallic elements, Fe content is 0.5～20% with the molar ratio computing with respect to whole metallic elements, and the median size of this veridian is 0.02～1.2 μ m.
Containing of Mg in the infrared reflectivity veridian that the present invention relates to is proportional, with respect to the whole metallic elements in the veridian is 11～22mol%, and containing of the Fe in the infrared reflectivity veridian that the present invention relates to is proportional, is 0.5～20mol% with the molar ratio computing with respect to the whole metallic elements in the veridian.If proportional beyond above-mentioned scope with respect to containing of the Mg of the whole metallic elements in the veridian and Fe, then tone and/or sunshine reflectivity insufficient, can not obtain excellent color tone and the good veridian of reflectivity at sunshine.Contain the proportional 12～20mol% that is preferably, more preferably 13～20mol% with respect to the Mg of the whole metallic elements in the veridian.In addition, contain the proportional 0.6～15mol% that is preferably, more preferably 2～12mol% with respect to the Fe of the whole metallic elements in the veridian.Co in the infrared reflectivity veridian that the present invention relates to contains the proportional 12～22mol% that is preferably.In addition, though the infrared reflectivity veridian that the present invention relates to is sneaked into the impurity from various raw materials sometimes inevitably, but its amount is trace, metallic element Mg in veridian, Fe and the Co, come down to Al, the ratio of the content of the content of Co and Mg and Fe and Al is preferably 1: 2 with molar ratio computing.
The median size of the infrared reflectivity veridian that the present invention relates to is preferably 0.02～1.2 μ m, under the situation of median size greater than 1.2 μ m, because particle size is excessive, so tinting strength reduces.Under the situation of median size less than 0.02 μ m, it is difficult that the dispersion in vehicle becomes.Be preferably 0.02～1.1 μ m, more preferably 0.02～1.0 μ m.
The crystalline structure of the infrared reflectivity veridian that the present invention relates to is preferably spinel type.
Though sneak into the impurity from various raw materials sometimes inevitably in the infrared reflectivity veridian that the present invention relates to, even in this case, for example the content of Cr is below the 1wt%, especially Cr
6+Content be below the 10ppm.
The BET specific surface area of the infrared reflectivity veridian that the present invention relates to is preferably 5～100m
2/ g, more preferably 8～90m
2/ g.In the BET specific surface area less than 5m
2Under the situation of/g, particle is thick, perhaps becomes sintering between particle and the particle and the particle that generates, and tinting strength reduces.
Luminance brightness (the L of the infrared reflectivity veridian that the present invention relates to
*) preferably surpass 30 and be below 40.As luminance brightness (L
*) beyond the above-mentioned scope time, being difficult to say to be excellent green, its purposes is defined easily.More preferably 32～40.
The a of the infrared reflectivity veridian that the present invention relates to
*Be preferably-2～0.Work as a
*In the time of beyond above-mentioned scope, be difficult to say to be excellent green, its purposes is defined easily.More preferably-1.5～-0.2.
The b of the infrared reflectivity veridian that the present invention relates to
*Be preferably-5～-15.Work as b
*In the time of beyond above-mentioned scope, be difficult to say to be excellent green, its purposes is defined easily.More preferably-7～-12.
The reflectivity at sunshine of the infrared reflectivity veridian that the present invention relates to is preferably 35～50%.Under less than 35% situation, infrared reflectivity is difficult to say enough.More preferably 37～48%.
In the present invention, particle surface one or more the compound that can be selected among Si, Al, Zr, the Ti covers.Overlay capacity is preferably 0.1～10wt% with respect to the infrared reflectivity veridian, more preferably 0.2～5wt%.
Then, the infrared reflectivity blue pigments that the present invention relates to and the manufacture method of infrared reflectivity veridian are described.
Infrared reflectivity blue pigments that the present invention relates to and infrared reflectivity veridian can be by mixing, firing various raw materials and make.
As starting raw material, can use oxide compound, carbonate, nitrate, vitriol of above-mentioned each metallic element etc.
If the mixing of starting raw material can mix equably, just be not particularly limited, both can be wet mixing, also can be dry type is mixed.Can also be that wet type is synthetic in addition.
Heating firing temperature in the manufacturing of infrared reflectivity blue pigments is preferably 800～1200 ℃, more preferably 800～1050 ℃.Heating atmosphere is in the atmosphere.
Heating firing temperature in the manufacturing of infrared reflectivity veridian is preferably 800～1200 ℃, more preferably 800～1150 ℃.Heating atmosphere is in the atmosphere.
Powder after the heating can be washed, pulverize according to usual method.
In the present invention, the particle surface of infrared reflectivity blue pigments or infrared reflectivity veridian one or more the compound that can be selected among Si, Al, Zr, the Ti covers.Surface treatment method can be implemented according to usual methods such as wet type or dry methods.For example: while wet method be in the slurry of wet type dispersive infrared reflectivity blue pigments or infrared reflectivity veridian, use acid or alkali adjust pH, add, mix be selected among Si, Al, Zr, the Ti one or more soluble compound and the method that covers.Dry method is in devices such as Henschel mixer infrared reflectivity blue pigments or infrared reflectivity veridian to be covered the method for processing by one or more the coupling agent etc. that is selected among Si, Al, Zr, the Ti.
Then, the coating that cooperates the infrared reflectivity blue pigments that the present invention relates to or infrared reflectivity veridian and obtain is described.
The infrared reflectivity blue pigments that the present invention relates to or the cooperation ratio of infrared reflectivity veridian can be used in the scope that with respect to coating formation base material 100 weight parts is 0.5～100 weight part.If consider the operability of coating, then preferred 1.0～100 weight parts.
Constitute base material as coating, cooperate resin, solvent, grease as required, defoamer, filler pigment, dry promotor, tensio-active agent, curing catalyst, auxiliary agent etc.
As resin, can use and be generally used for solvent be coating with and modified rosin resin, petroleum resin etc. such as rosin based resin, maleic acid resin, polyamide resin, soluble cotton, ethane-acetic acid ethyenyl copolymer resins, rosin modified phenolic resin, Abietyl modified maleic acid resin such as the acrylic resin of oiliness printing-ink, Synolac, vibrin, urethane resin, Resins, epoxy, resol, melamine resin, aminoresin, vinyl chloride resin, silicone resin, rosin, limed rosin.As aqueous coating usefulness, can use be generally used for aqueous coating with and the water soluble acrylic resin of water color ink, water-soluble phenylethene-maleic acid resin, water soluble alkyd resin, water-soluble melamine resin, aqurous ployurethane emulsion resin, water-soluble epoxy resin, Polyester Resin Water Soluble etc.
As solvent, can use and be generally used for solvent is the soybean oil that coating is used, toluene, dimethylbenzene, thinner, butylacetate, methyl acetate, methyl iso-butyl ketone (MIBK), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, glycol ethers solvents such as propylene glycol monomethyl ether, ethyl acetate, butylacetate, esters solvents such as pentyl acetate, hexane, heptane, aliphatic hydrocarbon kind solvents such as octane, clicyclic hydrocarbon kind solvents such as hexanaphthene, petroleum-type solvents such as petroleum solvent, acetone, ketones solvents such as methylethylketone, methyl alcohol, ethanol, propyl alcohol, alcoholic solvents such as butanols, aliphatic hydrocarbon etc.
As the aqueous coating solvent, can be generally used for ethylene oxides such as glycol ethers solvent, glycol ether, Triethylene glycol, polyoxyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycols such as alcoholic solvent, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether such as ethanol that water and aqueous coating use, propyl alcohol, butanols or propylene oxide addition polymer, ethylene glycol, propylene glycol, 1,2, water-miscible organic solvents such as aklylene glycols such as 6-hexanetriol, glycerol, 2-Pyrrolidone mix use.
As grease, can use linseed oil, tung oil, oiticica oil, safflower wet goods siccative oil are processed the stand oil that makes.
As defoamer, can use Nopco 8034 (trade(brand)name), SN Defoamer 477 (trade(brand)name), SN Defoamer 5013 (trade(brand)name), SN Defoamer 247 (trade(brand)name), SN Defoamer382 (trade(brand)name) (above commodity are SAN NOPCO Co., Ltd. and make), ア Application チ ホ one system 08 (trade(brand)name), エ マ Le ゲ Application 903 (trade(brand)names) commercially available products such as (above commodity are Kao Corp and make).
Secondly, illustrate and contain the infrared reflectivity blue pigments that the present invention relates to or the resin combination of infrared reflectivity veridian.
The infrared reflectivity blue pigments in the resin combination that the present invention relates to or the blending ratio of infrared reflectivity veridian can be used in the scope that with respect to resin 100 weight parts is 0.01～200 weight part.If consider the operability of resin combination, then be preferably 0.05～150 weight part, more preferably 0.1～100 weight part.
Formation base material as the resin combination that the present invention relates to, cooperate infrared reflectivity blue pigments or infrared reflectivity veridian and known thermoplastic resin, and cooperate additives such as lubricant, softening agent, antioxidant, UV light absorber, various stablizers as required.
As resin, can use polyethylene, polypropylene, polybutene, polyolefine such as polyisobutene, polyvinyl chloride, polymethylpentene, polyethylene terephthalate, polybutylene terephthalate, polystyrene, copolymer in cinnamic acrylic ester, vinylbenzene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene copolymer, vinyl cyanide-EPDM-styrol copolymer, acrylic resin, polymeric amide, polycarbonate, polyacetal, thermoplastic resins such as urethane, Abietyl modified maleic acid resin, resol, Resins, epoxy, vibrin, silicone resin, rosin-ester, rosin, natural rubber, synthetic rubber etc.
Content of additive is if be just passable below the 50 weight % with respect to the summation of infrared reflectivity blue pigments or infrared reflectivity veridian and resin.Under the situation of content of additive greater than 50 weight %, formability reduces.
About the resin combination that the present invention relates to, thorough mixing resin raw material and infrared reflectivity blue pigments or infrared reflectivity veridian in advance, then use mixing roll or forcing machine, under the condition of heating, apply strong shearing action, destroy the aggregate of infrared reflectivity blue pigments or infrared reflectivity veridian, make infrared reflectivity blue pigments or infrared reflectivity veridian be scattered in the resin combination equably, then, forming process is and the corresponding shape of purpose, uses.
In addition, the resin combination that the present invention relates to can also obtain via masterbatch pellet.
The masterbatch pellet that the present invention relates to can adopt following method to make.That is: as required, use mixing machines such as ribbon blender, nauta mixer, Henschel mixer, high-speed mixer, mixing is as jointing material resin and the above-mentioned infrared reflectivity blue pigments or the infrared reflectivity veridian of the formation base material of coating and resin combination, then, use known single screw mixing forcing machine or twin-screw mixer forcing machine etc. mixing, cut off after the moulding, perhaps, use mixing said mixtures such as Banbury, adding pressure type kneader, the mixing thing that pulverizing or moulding, cut-out obtain.
Jointing material resin and infrared reflectivity blue pigments or infrared reflectivity veridian are to the supply of mixing roll, and both ratio was supplied with respectively quantitatively according to the rules, also can supply with the mixture of the two.
The masterbatch pellet that the present invention relates to, its average major diameter is the scope of 1～6mm, is preferably the scope of 2～5mm.Average minor axis is the scope of 2～5mm, is preferably the scope of 2.5～4mm.Under the average situation of major diameter less than 1mm, the operability deterioration during granule manufacture, thereby not preferred.Under the average situation of major diameter greater than 6mm, become greatly with the difference of dilution with the size of jointing material resin, be difficult to make it to disperse fully.In addition, its shape can present different shape, can present the granular, cylindrical, laminar etc. of unsetting and sphere etc.
As the jointing material resin that in the masterbatch pellet that the present invention relates to, uses, can use and the described resin combination identical resin of resin.
Moreover, the composition of the jointing material resin in the masterbatch pellet, both can use and diluted with bond material resin identical resin, also can use different resins in addition, yet, under the situation of using different resins, set just passable if consider to depend on each characteristic of resin intermiscibility each other.
The infrared reflectivity blue pigments that cooperates in masterbatch pellet or the amount of infrared reflectivity veridian are 1～200 weight part with respect to jointing material resin 100 weight parts, are preferably 1～150 weight part, more preferably 1～100 weight part.Under the situation less than 1 weight part, it is difficult that the melt viscosity deficiency when mixing, the good dispersing and mixing of infrared reflectivity blue pigments or infrared reflectivity veridian become.Under situation greater than 200 weight parts, because with respect to infrared reflectivity blue pigments or infrared reflectivity veridian, the jointing material resin is few, the difficulty so the good dispersing and mixing of infrared reflectivity blue pigments or infrared reflectivity veridian becomes; In addition, also because the small variation of the addition of masterbatch pellet can cause the infrared reflectivity blue pigments that cooperates in resin combination or the content of infrared reflectivity veridian to have greatly changed, so it is not be difficult to be adjusted into desired content, thereby preferred.Moreover, seriously not preferred because of mechanical wear yet.
Most important inventive point is among the present invention: infrared reflectivity blue pigments or the infrared reflectivity veridian that the present invention relates to do not contain harmful element, and have the high IR line reflection.
The infrared reflectivity blue pigments that the present invention relates to is blue and has the reason of high IR line reflection, though it be unclear that, but embodiment described as follows and comparative example are expressed, by containing Co, Al, Mg, the content of Mg is 11～22% and to make the BET specific surface area of this blue pigments be 10～100m with the molar ratio computing with respect to whole metallic elements of this blue pigments
2/ g can make it be blue and the sunshine reflectivity is improved.
The infrared reflectivity veridian that the present invention relates to is green and has the reason of high IR line reflection, though it be unclear that, but embodiment described as follows and comparative example are expressed, by containing Co, Al, Mg and Fe, Mg content in this veridian with the molar ratio computing with respect to whole metallic elements be 11～22%, Fe content is 0.5～20% and to make the median size of this veridian be 0.02～1.2 μ m with the molar ratio computing with respect to whole metallic elements, can make it be green and the sunshine reflectivity is improved.
In addition, infrared reflectivity blue pigments that the present invention relates to and infrared reflectivity veridian are a kind of Cr that do not contain
6+Pigment Deng poisonous metal element, safety.
Infrared reflectivity blue pigments that the present invention relates to or infrared reflectivity veridian, because it is blue pigments and the veridian that does not contain harmful element, and, its infrared reflectivity is good, so as infrared reflectivity blue pigments and infrared reflectivity veridian and preferred.
Embodiment
Representative embodiment of the present invention, as described below.Moreover in following embodiment, the comparative example, embodiment 1～6 and comparative example 1～4 relate to the infrared reflectivity blue pigments.Embodiment 5～13 and comparative example 5～11 relate to the infrared reflectivity veridian.
About the particulate median size, measure respectively 350 of the particles be shown on the electron micrograph particle diameter, represent with its mean value.
About specific surface area, with the numeric representation of adopting the BET method to record.
The content of the metallic element of infrared reflectivity blue pigments and infrared reflectivity veridian, use " fluorescent x-ray analyzer 3063M type " (manufacturing of electric machine industry Co., Ltd. of Ricoh), and measure according to JIS K 0119 " x-ray fluorescence analysis general rule ".
Cr
6+Measuring method, use " ICP Emission Spectrophotometer device " (manufacturing of SSINanotechnoledgy Co., Ltd.), and measure according to JIS K 0102 65.2.4 " ICP Emission Spectrophotometer method ".
Tone (the L of infrared reflectivity blue pigments and infrared reflectivity veridian
*Value, a
*Value, b
*Value), adopt following method to record.Use laboratory shredder (Hoover muller), mixing sample 0.5g and Viscotrol C 0.5ml, make it become pulp-like, in this slurry, add the clear lacquer (clear lacquer) 4.5g, mixing, coatingization use the spreader of 150 μ m (6mil) to be coated with on cast-coated paper, make coated sheets (coating thickness: about 30 μ m), use " multiple light courcess spectral photometric colour measuring meter MSC-IS-2D " (manufacturing of Sugatest Co., Ltd.), measure.According to the regulation of JIS Z 8729, with table colour index (L
*Value, a
*Value, b
*Value) expression.
The characteristic at sunshine of infrared reflectivity blue pigments and infrared reflectivity veridian, adopt following method evaluation: to the pellicula of making in order to measure above-mentioned tone, use " spectrophotometer U-4100 " (High-Technologies of Co., Ltd. Hitachi), measure.Regulation according to JIS R3106-1998, under the situation of infrared reflectivity blue pigments, with reflectivity at sunshine (%) expression of wavelength 300～2100nm, under the situation of infrared reflectivity veridian, with reflectivity at sunshine (%) expression of wavelength 300～2100nm.
Embodiment 1
According to CoO
xMgO
1-xNAl
2O
3(x=0.5 n=1), takes by weighing CoO and MgO, Al
2O
3, mix, in electric furnace, under 1050 ℃, fired 2 hours.Burned product is pulverized, and making median size is that 0.2 μ m, BET specific surface area are 36m
2The blue pigments of/g.The crystalline structure of the blue pigments that obtains is a spinel type.
This pigment and varnish are made colored coating, make the color card sample, use U-4100 Hitachi spectrophotometer, in the scope of wavelength 250nm～2500nm, estimate reflectivity.As a result of, the reflectivity of wavelength 300～2100nm is 50%.
Embodiment 2～3, comparative example 1～4
Change proportion of composing and firing temperature, in addition, operate equally, make blue pigments with the foregoing description 1.
With the creating conditions and be shown in table 1 of this moment, each property list of the infrared reflectivity blue pigments that makes is shown in table 2.
Embodiment 4
Operate equally with the foregoing description 1, make blue pigments.Then, the blue pigments wet type that makes is scattered in the water, to insulation in the slurry of 70 ℃ blue pigments drip water glass 0.5wt% on one side, use hydrochloric acid and sodium hydroxide to adjust pH to 7 on one side, and kept 1 hour.Then, wash, dry, pulverization process.
Embodiment 5 and embodiment 6
Change the surface treatment condition, in addition, operate equally, make blue pigments with the foregoing description 4.
In the crystalline structure of table 2, " spinel " represents spinel type.In addition, so-called Cr
6+Content " less than 5ppm ", be illustrated in below the said determination Device Testing limit.
[table 1]
Embodiment 7
According to CoO
xMgO
1-xN[(Al
2O
3)
y(Fe
2O
3)
1-y] (x=0.5, y=0.9 n=1), take by weighing CoO and MgO, Al
2O
3, Fe
2O
3, mix, in electric furnace, under 1050 ℃, fired 2 hours.Burned product is pulverized, and making median size is that 0.25 μ m, BET specific surface area are 20m
2The veridian of/g.The crystalline structure of the veridian that obtains is a spinel type.
This pigment and varnish are made colored coating, make the color card sample, use U-4100 Hitachi spectrophotometer, in the scope of wavelength 250nm～2500nm, estimate reflectivity.As a result of, the reflectivity of wavelength 300～2100nm is 44%.
Embodiment 8～9, embodiment 7 and comparative example 5～11
Change proportion of composing and firing temperature, in addition, operate equally, make veridian with the foregoing description 7.
With the creating conditions and be shown in table 3 of this moment, each property list of the infrared reflectivity veridian that makes is shown in table 4.
Embodiment 10
Operate equally with the foregoing description 7, make veridian.Then, the veridian wet type that makes is scattered in the water, to insulation in the slurry of 70 ℃ veridian drip water glass 0.5wt% on one side, use hydrochloric acid and sodium hydroxide to adjust pH to 7 on one side, and kept 1 hour.Then, wash, dry, pulverization process.
Embodiment 11 and embodiment 12
Change the surface treatment condition, in addition, operate equally, make veridian with the foregoing description 10.
In the crystalline structure of table 4, " spinel " represents spinel type.In addition, so-called Cr
6+Content " less than 5ppm ", be illustrated in below the said determination Device Testing limit.
[table 3]
Claims (14)
1. infrared reflectivity blue pigments is characterized in that:
Constitute by the composite oxides that contain Co, Al and Mg,
The Mg content of this blue pigments is 11～22% with the molar ratio computing with respect to whole metallic elements, and the BET specific surface area of this blue pigments is 10～100m
2/ g.
2. infrared reflectivity blue pigments as claimed in claim 1 is characterized in that:
The crystalline structure of infrared reflectivity blue pigments is a spinel type.
3. infrared reflectivity blue pigments as claimed in claim 1 is characterized in that:
Luminance brightness (the L of infrared reflectivity blue pigments
*) be 35～50.
4. infrared reflectivity blue pigments as claimed in claim 1 is characterized in that:
The reflectivity at sunshine of infrared reflectivity blue pigments is 45～60%.
5. infrared reflectivity blue pigments as claimed in claim 1 is characterized in that:
More than one the compound that the surface of infrared reflectivity blue pigments is selected among Si, Al, Zr, the Ti covers.
6. coating is characterized in that:
It cooperates the described infrared reflectivity blue pigments of claim 1 and obtains in coating formation base material.
7. resin combination is characterized in that:
It is to use painted the obtaining of the described infrared reflectivity blue pigments of claim 1.
8. infrared reflectivity veridian is characterized in that:
Constitute by the composite oxides that contain Co, Al, Mg and Fe,
The Mg content of this veridian is 11～22% with the molar ratio computing with respect to whole metallic elements, and Fe content is 0.5～20% with the molar ratio computing with respect to whole metallic elements, and the median size of this veridian is 0.02～1.2 μ m.
9. infrared reflectivity veridian as claimed in claim 8 is characterized in that:
The crystalline structure of infrared reflectivity veridian is a spinel type.
10. infrared reflectivity veridian as claimed in claim 8 is characterized in that:
Luminance brightness (the L of infrared reflectivity veridian
*) surpass 30 and be below 40.
11. infrared reflectivity veridian as claimed in claim 8 is characterized in that:
The reflectivity at sunshine of infrared reflectivity veridian is 35～50%.
12. infrared reflectivity veridian as claimed in claim 8 is characterized in that:
More than one the compound that the surface of infrared reflectivity veridian is selected among Si, Al, Zr, the Ti covers.
13. a coating is characterized in that:
It cooperates the described infrared reflectivity veridian of claim 8 and obtains in coating formation base material.
14. a resin combination is characterized in that:
It is to use painted the obtaining of the described infrared reflectivity veridian of claim 8.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008058775A JP5392453B2 (en) | 2008-03-07 | 2008-03-07 | Infrared reflective blue pigment, paint and resin composition using the infrared reflective blue pigment |
| JP2008058776 | 2008-03-07 | ||
| JP2008058775 | 2008-03-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101525502A true CN101525502A (en) | 2009-09-09 |
Family
ID=41093577
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2009101178369A Pending CN101525502A (en) | 2008-03-07 | 2009-03-06 | Infrared reflecting blue pigment, infrared reflecting green pigment, paint and resin composition using the infrared reflecting blue pigment, and paint and resin composition using the infrared reflecti |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP5392453B2 (en) |
| CN (1) | CN101525502A (en) |
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2009
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| JP5392453B2 (en) | 2014-01-22 |
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