JPH0366764A - Color pigment - Google Patents
Color pigmentInfo
- Publication number
- JPH0366764A JPH0366764A JP1204214A JP20421489A JPH0366764A JP H0366764 A JPH0366764 A JP H0366764A JP 1204214 A JP1204214 A JP 1204214A JP 20421489 A JP20421489 A JP 20421489A JP H0366764 A JPH0366764 A JP H0366764A
- Authority
- JP
- Japan
- Prior art keywords
- silicon dioxide
- organic
- pigment
- solution
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000049 pigment Substances 0.000 title claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000003086 colorant Substances 0.000 claims abstract description 24
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 24
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 239000008187 granular material Substances 0.000 claims description 10
- 229910010272 inorganic material Inorganic materials 0.000 claims description 5
- 239000011147 inorganic material Substances 0.000 claims description 5
- 239000011368 organic material Substances 0.000 claims description 3
- 239000000243 solution Substances 0.000 abstract description 17
- 239000011521 glass Substances 0.000 abstract description 9
- 239000002245 particle Substances 0.000 abstract description 6
- 239000001023 inorganic pigment Substances 0.000 abstract description 5
- 239000002537 cosmetic Substances 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011324 bead Substances 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 15
- 239000000975 dye Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 239000012860 organic pigment Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000004040 coloring Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000003980 solgel method Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- IOOMXAQUNPWDLL-UHFFFAOYSA-N 2-[6-(diethylamino)-3-(diethyliminiumyl)-3h-xanthen-9-yl]-5-sulfobenzene-1-sulfonate Chemical compound C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=C(S(O)(=O)=O)C=C1S([O-])(=O)=O IOOMXAQUNPWDLL-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- VBVAVBCYMYWNOU-UHFFFAOYSA-N coumarin 6 Chemical compound C1=CC=C2SC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 VBVAVBCYMYWNOU-UHFFFAOYSA-N 0.000 description 2
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- KQSBZNJFKWOQQK-UHFFFAOYSA-N hystazarin Natural products O=C1C2=CC=CC=C2C(=O)C2=C1C=C(O)C(O)=C2 KQSBZNJFKWOQQK-UHFFFAOYSA-N 0.000 description 2
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 2
- 229940107698 malachite green Drugs 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- AZXGXVQWEUFULR-UHFFFAOYSA-N 2',4',5',7'-tetrabromofluorescein Chemical compound OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 AZXGXVQWEUFULR-UHFFFAOYSA-N 0.000 description 1
- ZTKQHJHANLVEBM-UHFFFAOYSA-N 2-[3-(ethylamino)-6-ethylimino-2,7-dimethylxanthen-9-yl]benzoic acid Chemical compound C1=2C=C(C)C(NCC)=CC=2OC2=CC(=NCC)C(C)=CC2=C1C1=CC=CC=C1C(O)=O ZTKQHJHANLVEBM-UHFFFAOYSA-N 0.000 description 1
- PGRMUEVKABEERE-UHFFFAOYSA-N 2-[3-(methylamino)-6-methyliminoxanthen-9-yl]benzoic acid;perchloric acid Chemical compound [O-]Cl(=O)(=O)=O.C=12C=CC(=[NH+]C)C=C2OC2=CC(NC)=CC=C2C=1C1=CC=CC=C1C(O)=O PGRMUEVKABEERE-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 235000002566 Capsicum Nutrition 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000006002 Pepper Substances 0.000 description 1
- 235000016761 Piper aduncum Nutrition 0.000 description 1
- 235000017804 Piper guineense Nutrition 0.000 description 1
- 244000203593 Piper nigrum Species 0.000 description 1
- 235000008184 Piper nigrum Nutrition 0.000 description 1
- 240000004713 Pisum sativum Species 0.000 description 1
- 235000010582 Pisum sativum Nutrition 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- 101150113227 RED3 gene Proteins 0.000 description 1
- IVHDZUFNZLETBM-IWSIBTJSSA-N acridine red 3B Chemical compound [Cl-].C1=C\C(=[NH+]/C)C=C2OC3=CC(NC)=CC=C3C=C21 IVHDZUFNZLETBM-IWSIBTJSSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical compound Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- FTZLWXQKVFFWLY-UHFFFAOYSA-L disodium;2,5-dichloro-4-[3-methyl-5-oxo-4-[(4-sulfonatophenyl)diazenyl]-4h-pyrazol-1-yl]benzenesulfonate Chemical compound [Na+].[Na+].CC1=NN(C=2C(=CC(=C(Cl)C=2)S([O-])(=O)=O)Cl)C(=O)C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 FTZLWXQKVFFWLY-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical class [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- 231100000299 mutagenicity Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- MYIOYATURDILJN-UHFFFAOYSA-N rhodamine 110 Chemical compound [Cl-].C=12C=CC(N)=CC2=[O+]C2=CC(N)=CC=C2C=1C1=CC=CC=C1C(O)=O MYIOYATURDILJN-UHFFFAOYSA-N 0.000 description 1
- TUFFYSFVSYUHPA-UHFFFAOYSA-M rhodamine 123 Chemical compound [Cl-].COC(=O)C1=CC=CC=C1C1=C(C=CC(N)=C2)C2=[O+]C2=C1C=CC(N)=C2 TUFFYSFVSYUHPA-UHFFFAOYSA-M 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 208000017520 skin disease Diseases 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- FKVXIGHJGBQFIH-UHFFFAOYSA-K trisodium 5-amino-3-[[4-[4-[(7-amino-1-hydroxy-3-sulfonatonaphthalen-2-yl)diazenyl]phenyl]phenyl]diazenyl]-4-hydroxynaphthalene-2,7-disulfonate Chemical compound C1=CC(=CC=C1C2=CC=C(C=C2)N=NC3=C(C=C4C=CC(=CC4=C3[O-])N)S(=O)(=O)O)N=NC5=C(C6=C(C=C(C=C6C=C5S(=O)(=O)O)S(=O)(=O)[O-])N)[O-].[Na+].[Na+].[Na+] FKVXIGHJGBQFIH-UHFFFAOYSA-K 0.000 description 1
- JEVGKYBUANQAKG-UHFFFAOYSA-N victoria blue R Chemical compound [Cl-].C12=CC=CC=C2C(=[NH+]CC)C=CC1=C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 JEVGKYBUANQAKG-UHFFFAOYSA-N 0.000 description 1
- 235000019235 yellow 2G Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
- C03C2217/45—Inorganic continuous phases
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/48—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase having a specific function
- C03C2217/485—Pigments
Landscapes
- Cosmetics (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は粉粒体の表面に着色層を形成して成る着色顔料
に関し、更に詳しくは粉粒体表面に有機着色剤を含有す
る二酸化ケイ素被膜を形成して成る化学的・機械的耐久
性にすぐれた着色顔料の提供に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a colored pigment formed by forming a colored layer on the surface of a powder or granule, and more specifically to a silicon dioxide containing an organic colorant on the surface of the powder or granule. The present invention relates to a colored pigment having excellent chemical and mechanical durability formed by forming a film.
今日、顔料は塗料・印刷インキ・化粧品・合成樹脂など
多くの応用分野で着色剤としてその重要はますます高ま
りつつある。 ところで顔料には無機材料から成る無機
顔料と、有機材料から成る有機顔料がある。無機顔料は
化学的に安定でありかつ無害なものが多く、塗料・印刷
インキ・化粧品・建材など広範な用途に使われている。Today, pigments are becoming increasingly important as coloring agents in many applied fields such as paints, printing inks, cosmetics, and synthetic resins. By the way, pigments include inorganic pigments made of inorganic materials and organic pigments made of organic materials. Many inorganic pigments are chemically stable and harmless, and are used in a wide range of applications, including paints, printing inks, cosmetics, and building materials.
しかしながら、無機顔料は色の種類が少ない、色の鮮や
かさに欠けるなどの問題があり、特に色の特質を重要視
する分野、例えば、口紅・ネイルエナメルなどのポイン
トメ−キャップに用いられるメーキャップ化粧品、ある
いは画像用印刷インキでは有機顔料に依らざるを得ない
場合が少なくなかった。However, inorganic pigments have problems such as a limited number of color types and a lack of color vibrancy, and are used in areas where color characteristics are particularly important, such as makeup cosmetics used in point makeup such as lipstick and nail enamel. In many cases, printing inks for images have no choice but to rely on organic pigments.
これに対し有機顔料は色の種類の豊富さ、色彩などの特
徴はあるものの、多くがタール色素であり、皮膚障害・
発ガン性・変異原性など人体への安全面の問題から、そ
の使用については法律的に厳しい規制が設けられ、実用
上大きな制約があった。On the other hand, although organic pigments have characteristics such as a rich variety of colors and colors, most of them are tar pigments, which can cause skin disorders and
Due to safety issues for the human body, such as carcinogenicity and mutagenicity, strict legal regulations have been established regarding its use, and there are significant practical limitations.
このため、有機顔料表面を無機材料で被覆したり、有機
顔料を無機質微小カプセル球内に封じ込めたりすること
が試みられて来た。しがしながらこれら無機材料による
保護層も厳密には多孔質あるいは超微小コロイドから成
るクラスター状構造であり、水分・溶剤・酸素などから
有機顔料を保護するには必ずしも十分ではなかった。For this reason, attempts have been made to coat the surface of organic pigments with inorganic materials or to confine organic pigments within inorganic microcapsules. However, these protective layers made of inorganic materials are strictly porous or have cluster-like structures made of ultrafine colloids, and are not necessarily sufficient to protect organic pigments from moisture, solvents, oxygen, etc.
すなわち、色の種類が豊富であり、色も鮮やかで、かつ
、化学的に安定・安全に顔料を実現する手段は殆どなか
った。In other words, there has been almost no means to produce pigments that come in a wide variety of colors, are vivid, and are chemically stable and safe.
〔発明が解決しようヒする問題点〕
本発明者らは、かかる着色顔料の問題点に鑑み鋭意研究
の結果、無機質あるいは有機質の粉粒体表面に有機着色
剤を含有する二酸化ケイ素被膜を形成することにより、
有機着色剤の特徴すなわち豊富な色の種類・色の鮮やか
き等を維持しつつ、無機顔料並の安定性・安全性を確保
できることを見出した。[Problems to be Solved by the Invention] In view of the problems of coloring pigments, the present inventors have conducted extensive research and found that a silicon dioxide film containing an organic colorant is formed on the surface of inorganic or organic powder particles. By this,
We have discovered that it is possible to maintain the characteristics of organic colorants, such as a wide variety of colors and vivid colors, while ensuring stability and safety comparable to inorganic pigments.
本発明は、有機染料・顔料などの有機着色剤を含む二酸
化ケイ素被膜で粉粒体表面を被覆することで実現される
。このような方法としては、金属アルコキシドの加水分
解溶液中に有機着色剤を添加した溶液と粉粒体を接触さ
せる、いわゆるゾル・ゲル法があげられる。The present invention is realized by coating the surface of the powder with a silicon dioxide coating containing an organic coloring agent such as an organic dye or pigment. An example of such a method is the so-called sol-gel method, in which the powder is brought into contact with a solution in which an organic colorant is added to a hydrolyzed solution of a metal alkoxide.
例えば、この製造方法に関する文献としてはＦＪ、Ｎｏ
ｎ−Ｃｒｙｓｔ、 ５ｏｌｉｄｓ、 ７４（１９８５）
３９５Ｊ があり、二酸化ケイ素薄膜中に有機蛍光
色素を導入してｂする。また、「セラミックス、２１．
Ｎｏ、２（１９８６） １１１」では、ゾル・ゲル法
によって有機分子を非晶質石英にドープしている。For example, as a document regarding this manufacturing method, FJ, No.
n-Cryst, 5olids, 74 (1985)
395J, which involves introducing an organic fluorescent dye into a silicon dioxide thin film. Also, “Ceramics, 21.
No. 2 (1986) 111'', amorphous quartz is doped with organic molecules by a sol-gel method.
しかしながら、ゾル・ゲル法では、被膜を基祠に固着さ
せるために最終工程で加熱する必要があり、有機物が分
解するような高い温度で加熱処理することはできないの
で、生成した膜はどうしても多孔質となる問題があった
。また、低い温度での加熱によっても分解してしまうよ
うな有機物は膜中に導入することができなかった。さら
に、低い温度でしか加熱できないことは、ゾル・ゲル法
固有の問題をいっそう大きなものにし、膜中には未分解
の原料や溶媒等の不純物が残存していた。However, in the sol-gel method, it is necessary to heat the film in the final step in order to fix it to the base, and it cannot be heated at a high temperature that would decompose organic substances, so the resulting film is inevitably porous. There was a problem. Furthermore, it was not possible to introduce into the film organic substances that would decompose even when heated at low temperatures. Furthermore, the fact that heating can only be done at low temperatures exacerbates the problems inherent in the sol-gel method, and impurities such as undecomposed raw materials and solvents remain in the membrane.
その他の問題としては、出発原料として高価な金属アル
コキシドを用いるため、膜の製造コストが高くなること
である。また、コーティング方法としてはデイツプコー
ト等が用いられ１、この方法では、複雑な形状を持った
基材には適用できなかった。Another problem is that the use of expensive metal alkoxides as starting materials increases the cost of membrane production. Further, as a coating method, a dip coat or the like is used1, but this method cannot be applied to a base material having a complicated shape.
本願発明の方法では、二酸化ケイ素を過飽和に含む珪弗
化水素酸の水溶液に染料・顔料などの有機着色剤を添加
して成る処理液と粉粒体を接触させることで、該粉粒体
表面に有機着色剤を含有する二酸化ケイ素被膜を形成さ
せることを利用するものである。この場合、二酸化ケイ
素を過飽和に含む珪弗化水素酸の水溶液は、珪弗化水素
酸の水溶液に二酸化ケイ素を飽和した溶液にホウ酸・ア
ンモニア水・金属ハライドあるいは水素よりもイオン化
傾向の大きい金属を添加することによって得られる。あ
るいは低温の珪弗化水素酸の水溶液に二酸化ケイ素を添
加した後、該溶液の温度を上昇させること（温度差法）
によっても得られる。In the method of the present invention, the surface of the powder is brought into contact with a treatment liquid prepared by adding an organic coloring agent such as a dye or pigment to an aqueous solution of hydrosilicic acid containing supersaturated silicon dioxide. This method utilizes the formation of a silicon dioxide film containing an organic colorant. In this case, an aqueous solution of hydrosilicofluoric acid containing supersaturated silicon dioxide is prepared by adding boric acid, aqueous ammonia, metal halides, or metals with a larger ionization tendency than hydrogen to an aqueous solution of hydrosilicofluoric acid and a solution saturated with silicon dioxide. Obtained by adding. Alternatively, silicon dioxide is added to a low-temperature aqueous solution of hydrosilicofluoric acid and then the temperature of the solution is raised (temperature difference method).
It can also be obtained by
有機着色剤の添加は、水溶性のものであれば、直接処理
液に添加することができ、水に不溶のものであってもア
ルコールなど水溶性有機溶媒中に溶解させた後、処理液
に添加するこヒもできる。また、添加の仕方は、珪弗化
水素酸の二酸化ケイ素飽和溶液に有機着色剤を加えても
よく、二酸化ケイ素を過飽和に含む状態とした後の溶液
に添加してもよい、 条件的には珪弗化水素酸の濃度
は１．０モル／９．以上、望ましくは１６５〜３．０モ
ル／党 が使われる。また、粉粒体を接触させる時の処
理液の温度は１５〜６０℃望ましくは２５〜４０℃であ
り、温度差法では通常１．０℃以下の温度で二酸化ケイ
素を飽和させ、２０℃以上、好ましくは４０〜６０℃の
温度で処理液と粉粒体を接触させる。接触の方法は、−
膜内には処理液の中に粉粒体を分散・攪拌する方法がと
られる。When adding an organic colorant, if it is water-soluble, it can be added directly to the processing solution, or even if it is insoluble in water, it can be added to the processing solution after being dissolved in a water-soluble organic solvent such as alcohol. You can also add pepper. In addition, the organic colorant may be added to a saturated silicon dioxide solution of hydrosilicofluoric acid, or it may be added to a solution that has been made to contain silicon dioxide in a supersaturated state.Conditions include: The concentration of hydrosilicofluoric acid is 1.0 mol/9. Above, 165 to 3.0 mol/part is preferably used. In addition, the temperature of the treatment liquid when bringing the powder or granules into contact is 15 to 60 degrees Celsius, preferably 25 to 40 degrees Celsius, and in the temperature difference method, silicon dioxide is usually saturated at a temperature of 1.0 degrees Celsius or lower, and 20 degrees Celsius or higher. The treatment liquid and the powder are brought into contact, preferably at a temperature of 40 to 60°C. The method of contact is -
A method is used in which particles are dispersed and stirred in the processing liquid within the membrane.
有機着色剤としては、染料・顔料などがあげられ、例え
ば、ローダミン６ Ｇ ［Ｒ）ＩＯＤＡＭＩＮＥ ６Ｇ
コ、フルオレセイン［ＦＬＯＯＲＥＳＣＥＩＮ］、マラ
カイトグリーン［ＭＡＬＡＣＨＩＴＥ ＧＲＥＥＮコ（
保土谷化学）、クマリン６ ［ＣＯＵＭＡＲＩＮ ６
コ、スルホローダミンＢ ［ＳＵＬＦＯ−ＲＨＯＤＡＭ
ＩＮＥ Ｂ］、ローダミン １２３、ローダミン１１０
、ローダミン １１６、ローダミン １９、カヤシルイ
エローＧＯ［ＫＡＹＡＣＹＬ ＹＥＬＬＯＷ ＧＧ］（
日本化薬）、レッド２１ Ｐ Ｓ−０１１［ＲＥＤ
２１Ｐ Ｓ−０１１コ（東京化成）、アクリジン レッ
ド［ＡＣＲＤＩＮ ＲＥＤ］、カヤシルローダミ゛ン
Ｆ Ｂ ［ＫＡＹＡＣＹＬ ＲＨＯＤＡＭＩＮＥＦＢコ
（日本化薬）、レッド ３Ｐ Ｔ−０１６［ＲＥＤ３
Ｐ Ｔ−０１６］（東京化成）、ビクトリアブルーＢＨ
［ＶＩＣＴＯＲＩＡ ＢＬＵＥ ＢＨコ（保土谷化学）
、アリサリンアストーｆｉｖ ［ＡＬＩＺＡＲＩＮＥ
ＡＳＴＯＬ］（東京化成）、メチｈ バイオＬ／ ット
ヒュ７− Ｓ Ｐ ［ＭＥＴＨＹＬ’ＶＩＯＬＥＴＰＵ
ＲＥ ＳＰ］（保土谷化学）、グリーン ＩＯＰ Ｐ
−００５［ＧＲＥＥＮ ＩＯＰ Ｐ−００５］（東京化
成）、などがあげられる。Examples of organic colorants include dyes and pigments, such as rhodamine 6G [R) IODAMINE 6G.
, fluorescein [FLOORESCEIN], malachite green [MALACHITE GREEN]
Hodogaya Chemical), Coumarin 6 [COUMARIN 6
Co, Sulforhodamine B [SULFO-RHODAM
INE B], Rhodamine 123, Rhodamine 110
, Rhodamine 116, Rhodamine 19, Kayacyl Yellow GO [KAYACYL YELLOW GG] (
Nippon Kayaku), Red 21 P S-011 [RED
21P S-011 (Tokyo Kasei), Acridine Red [ACRDIN RED], Kayasil Rhodamine
F B [KAYACYL RHODAMINE FB Co (Nippon Kayaku), Red 3P T-016 [RED3
PT-016] (Tokyo Kasei), Victoria Blue BH
[VICTORIA BLUE BH Co. (Hodogaya Chemical)
, ALIZARINE fiv [ALIZARINE
ASTOL] (Tokyo Kasei), METHYL'VIOLETPU
RE SP] (Hodogaya Chemical), Green IOP P
-005 [GREEN IOP P-005] (Tokyo Kasei), etc.
一方、粉粒体としては、酸化チタン・酸化第二鉄・硫酸
バリウム・雲母など無機結晶から戒るものでもよく、ガ
ラスピーズ・ガラスバルーン・フレークなど非晶質無機
材料から戒るものでもよい。On the other hand, the powder or granules may be made from inorganic crystals such as titanium oxide, ferric oxide, barium sulfate, or mica, or may be made from amorphous inorganic materials such as glass peas, glass balloons, and flakes.
更には、ポリカーボネート樹脂・アクリル樹脂など有機
材料から成る粉粒体でもよい、この場合、密着力のよい
着色層を形成するためには、有機粉粒体の表面をシラン
カップリング剤から戒る有機ケイ素化合物、それらの加
水分解物およびコロイダルシリカ等から成る群より選ば
れた少なくとも１種のケイ素化合物で被覆した後、処理
液中に浸漬・分散させ有機着色剤含有二酸化ケイ素被膜
を形成することが望ましい。Furthermore, powder or granules made of organic materials such as polycarbonate resin or acrylic resin may also be used. After coating with at least one silicon compound selected from the group consisting of silicon compounds, their hydrolysates, colloidal silica, etc., it is immersed and dispersed in a treatment liquid to form a silicon dioxide film containing an organic colorant. desirable.
〔実施例、１〕
第１図に示す装置によりＴｉｅ、微粒子表面に第１表に
示す有機色素含有二酸化ケイ素被膜を形成し、着色Ｔ
ｉ Ｏ２微粒子を得た。[Example 1] An organic dye-containing silicon dioxide coating shown in Table 1 was formed on the surface of Tie and fine particles using the apparatus shown in FIG.
iO2 fine particles were obtained.
ｍ１表
第２表
＊膜厚はガラス板上での膜厚
この場合、２Ｑの外槽■に満たしである水■はヒーター
■により３５℃に維持した。m1 Table 2 *Film thickness is the film thickness on the glass plate In this case, the water (2) filled in the outer tank (2) of 2Q was maintained at 35° C. by the heater (3).
この外槽中に５００ｃｃの内槽■を設け、この中にシリ
カゲルを飽和に含む２．５モル／党 の珪弗化水素酸の
水溶液２５０ｃｃに０．５モル／党のホウ酸水溶液１５
ｃｃを添加した処理液■を入れ、３４℃に維持している
。更に、処理液に着色剤を添加するため、第１表に示す
色素を水に室温にて溶解させ、５重量％または飽和の添
加溶液とし、珪弗化水素酸水溶液１００ｃｃ当りｌｃｃ
を添加し、別表１に示す色素毎に着色操作を行なった。A 500 cc inner tank (1) was provided in this outer tank, in which 250 cc of an aqueous solution of 2.5 mol/part of hydrosilicic acid containing saturated silica gel and 150 cc of a 0.5 mol/part of boric acid aqueous solution were added.
A processing solution (2) containing cc was added and maintained at 34°C. Furthermore, in order to add a coloring agent to the treatment solution, the dyes shown in Table 1 are dissolved in water at room temperature to make a 5% by weight or saturated solution, and the amount is 1cc per 100cc of the hydrosilicofluoric acid aqueous solution.
was added, and coloring operations were performed for each dye shown in Attached Table 1.
着色操作は、処理液中に平均粒径約１くクロンのＴ ｉ
Ｏ２微粒子１０ｇを添加、２０時間攪拌しなからＴｉ
ｅ、表面に着色層すなわち色素含有二酸化ケイ素被膜を
形成した。また、この際、色素含有二酸化ケイ素被膜の
膜厚・膜質評価のため、１．１ｍｍ厚昧Ｘ２０ｍｍＸ５
０ｍｍのガラス板も同時に浸漬し、その表面に着色層を
形成した。The coloring operation is performed by adding Ti having an average particle size of about 1 cm to the processing solution.
Add 10g of O2 fine particles and stir for 20 hours.
e. A colored layer, that is, a dye-containing silicon dioxide coating was formed on the surface. In addition, at this time, in order to evaluate the film thickness and film quality of the dye-containing silicon dioxide coating, a 1.1 mm thickness x 20 mm x 5
A 0 mm glass plate was also immersed at the same time to form a colored layer on its surface.
添加色素の種類及び実験結果を第１表に示す。Table 1 shows the types of dyes added and the experimental results.
二酸化ケイ素膜の膜厚は接触針式膜厚測定機にて測定し
た。The thickness of the silicon dioxide film was measured using a contact needle type film thickness measuring device.
これらの色素は、Ｘ線光電子分光法（ＥＳＣＡ）、二次
イオン質量分析法（ＳＩＭＳ）、赤外線分光法（ＩＲ）
などにより分析した結果、膜中に均一に取り込まれてい
ることが確認された。さらに、二酸化ケイ素戒膜後のＴ
ｉＯ２粒子を９９．５％アルコール溶液の中に２４時間
浸漬したが、有機染料の溶出はみられなかった。These dyes can be used for X-ray photoelectron spectroscopy (ESCA), secondary ion mass spectrometry (SIMS), and infrared spectroscopy (IR).
As a result of analysis, it was confirmed that it was evenly incorporated into the membrane. Furthermore, T after silicon dioxide film
Although the iO2 particles were immersed in a 99.5% alcohol solution for 24 hours, no elution of the organic dye was observed.
〔実施例、２〕
第１図に示す装置により、ガラスフレーク表面に第２表
に示す有機色素含有二酸化ケイ素被膜を形成し、着色ガ
ラスフレークを得た。この場合、処理液は一３℃の珪弗
化水素酸の水溶液に約２時間かけてシリカゲルを飽和し
、しかる後、第２表に示す染料を珪弗化水素酸水溶液１
００ｃｃ当りｌｃｃ添加して調整した。この後、該処理
液を第１図に示す内槽へ移し、５０℃となるよう外槽中
の水を加温し、同時にガラスフレーク１０ｇ及び実施例
１ヒ同様、評価用にガラス板を浸漬した。[Example 2] Using the apparatus shown in FIG. 1, an organic dye-containing silicon dioxide coating shown in Table 2 was formed on the surface of glass flakes to obtain colored glass flakes. In this case, the treatment solution is to saturate the silica gel with an aqueous solution of hydrosilicofluoric acid at -3°C for about 2 hours, and then add the dyes listed in Table 2 to the aqueous solution of hydrosilicofluoric acid for 1 hour.
It was adjusted by adding lcc per 00cc. After that, the treatment solution was transferred to the inner tank shown in Fig. 1, and the water in the outer tank was heated to 50°C, and at the same time, 10 g of glass flakes and a glass plate were immersed for evaluation in the same manner as in Example 1H. did.
２０時間攪拌しながら着色操作を行ない、第２表に示す
結果が得られた。得られた着色フレークを９９．５％ア
ルコール溶液中に２４時間浸漬したが、有機染料の溶出
は見られなかった。The coloring operation was carried out while stirring for 20 hours, and the results shown in Table 2 were obtained. The obtained colored flakes were immersed in a 99.5% alcohol solution for 24 hours, but no elution of the organic dye was observed.
第１図は、実施例において使用した二酸化珪素被膜製造
装置である。
１・・・・・外槽、 ２ ・・・・・水、３
・・−・・電熱ヒーター ４ ・・・・・内槽、
５ ・・・・・処理液、 ６・・・・・粉粒
体、７・・・・・攪拌器FIG. 1 shows a silicon dioxide film manufacturing apparatus used in Examples. 1...Outer tank, 2...Water, 3
・・・・Electric heater 4 ・・・Inner tank,
5... Processing liquid, 6... Powder, 7... Stirrer
Claims (5)
イ素被膜を形成して成る着色顔料。(1) A colored pigment formed by forming a silicon dioxide film containing an organic colorant on the surface of powder or granules.
とを特徴とする特許請求の範囲第１項に記載の着色顔料
。(2) The colored pigment according to claim 1, wherein the powder or granule is a crystalline or amorphous inorganic material.
請求の範囲第１項に記載の着色顔料。(3) The colored pigment according to claim 1, wherein the powder or granules are made of an organic material.
特許請求の範囲第１項に記載の着色顔料。(4) The colored pigment according to claim 1, wherein the organic colorant is a dye/pigment.
ケイ素の過飽和状態となった珪弗化水素酸水溶液に染料
・顔料など有機着色剤を添加して成る処理液と、粉粒体
を接触させることで該粉粒体表面に形成されることを特
徴とする特許請求の範囲第１項乃至第４項に記載の着色
顔料。(5) A silicon dioxide film containing an organic colorant is brought into contact with a treatment liquid made by adding an organic colorant such as a dye or pigment to an aqueous solution of hydrosilicofluoric acid in which the silicon dioxide film is supersaturated with silicon dioxide, and the powder or granules are brought into contact with it. The colored pigment according to any one of claims 1 to 4, wherein the colored pigment is formed on the surface of the powder or granular material.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20421489A JPH0794615B2 (en) | 1989-08-07 | 1989-08-07 | Color pigments |
| DE1990610537 DE69010537T2 (en) | 1989-04-01 | 1990-03-28 | Process for producing a layered material with an organic dye-containing silicon dioxide film and the product thus produced. |
| EP19900105873 EP0391226B1 (en) | 1989-04-01 | 1990-03-28 | Method for manufacturing layer-built material with silicon dioxide film containing organic colorant and the layer-built material manufactured thereby |
| US07/500,987 US5114760A (en) | 1989-04-01 | 1990-03-29 | Method for manufacturing layer-built material with silicon dioxide film containing organic colorant and the layer-built material manufactured thereby |
| CN90101766A CN1040740C (en) | 1989-04-01 | 1990-03-31 | Method for production of layered material having organic colorant of silica film and obtained layered material from them |
| KR1019900004535A KR0160125B1 (en) | 1989-04-01 | 1990-03-31 | Method for manufacturing layer-built material with silicon dioxide film containing organic colorant and the layer-built thereof |
| CA002013660A CA2013660C (en) | 1989-06-29 | 1990-04-02 | Method for manufacturing layer-built material with silicon dioxide film containing organic colorant and the layer-built material manufactured thereby |
| US07/834,455 US5232781A (en) | 1989-04-01 | 1992-02-12 | Method for manufacturing layer-built material with silicon dioxide film containing organic colorant and the layer-built material manufactured thereby |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20421489A JPH0794615B2 (en) | 1989-08-07 | 1989-08-07 | Color pigments |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0366764A true JPH0366764A (en) | 1991-03-22 |
| JPH0794615B2 JPH0794615B2 (en) | 1995-10-11 |
Family
ID=16486727
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20421489A Expired - Fee Related JPH0794615B2 (en) | 1989-04-01 | 1989-08-07 | Color pigments |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0794615B2 (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07133211A (en) * | 1993-11-11 | 1995-05-23 | Kira Keshohin Kk | Pigment for color cosmetic |
| JPH09227114A (en) * | 1996-02-22 | 1997-09-02 | Mori Sadayoshi | Pigment for colored cosmetic material |
| JPH1160444A (en) * | 1997-08-19 | 1999-03-02 | Pola Chem Ind Inc | Silica-coating powder containing pigment |
| JP2000160050A (en) * | 1998-11-27 | 2000-06-13 | Nittetsu Mining Co Ltd | Fluorescent pigment composition |
| KR20020052663A (en) * | 2000-12-26 | 2002-07-04 | 이지중 | A writing element in which double color-inks flow round a ball and a ball pen with the same |
| KR20030011003A (en) * | 2001-07-28 | 2003-02-06 | 이지중 | The triple color ball point pen in which triple color-inks flow round on the three balls at the same time |
| KR100478880B1 (en) * | 2001-09-08 | 2005-03-23 | 윤기태 | Writting instrument for 3-dimensional expression |
| JP2006104362A (en) * | 2004-10-06 | 2006-04-20 | Toda Kogyo Corp | Composite particle powder, its manufacturing method and coating material and resin composition using the composite particle powder |
| JP2006206681A (en) * | 2005-01-26 | 2006-08-10 | Toda Kogyo Corp | Composite particle powder and colored composition and resin composition using the composite particle powder |
| JP2007099774A (en) * | 2005-10-03 | 2007-04-19 | L'oreal Sa | Fluorescent cosmetic composition |
| JP2008231401A (en) * | 2007-02-19 | 2008-10-02 | Sanyo Chem Ind Ltd | Fluorescent material-including multilayer-structured spherical particles |
| US8273171B2 (en) | 2006-08-29 | 2012-09-25 | Nippon Sheet Glass Company, Limited | Pearlescent pigment |
| US8409708B2 (en) | 2007-10-18 | 2013-04-02 | Nippon Sheet Glass Company, Limited | Bright pigment |
| US8440014B2 (en) | 2007-04-27 | 2013-05-14 | Nippon Sheet Glass Company, Limited | Bright pigment, and bright coating composition and automotive body coating each containing the same |
| US9045643B2 (en) | 2006-04-21 | 2015-06-02 | Nippon Sheet Glass Company Limited | Bright pigment, method for producing the pigment, and waterborne resin composition containing the pigment |
| US9107834B2 (en) | 2007-04-18 | 2015-08-18 | Nippon Sheet Glass Company, Limited | Bright pigment and cosmetic composition using the same |
-
1989
- 1989-08-07 JP JP20421489A patent/JPH0794615B2/en not_active Expired - Fee Related
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07133211A (en) * | 1993-11-11 | 1995-05-23 | Kira Keshohin Kk | Pigment for color cosmetic |
| JPH09227114A (en) * | 1996-02-22 | 1997-09-02 | Mori Sadayoshi | Pigment for colored cosmetic material |
| JPH1160444A (en) * | 1997-08-19 | 1999-03-02 | Pola Chem Ind Inc | Silica-coating powder containing pigment |
| JP2000160050A (en) * | 1998-11-27 | 2000-06-13 | Nittetsu Mining Co Ltd | Fluorescent pigment composition |
| KR20020052663A (en) * | 2000-12-26 | 2002-07-04 | 이지중 | A writing element in which double color-inks flow round a ball and a ball pen with the same |
| KR20030011003A (en) * | 2001-07-28 | 2003-02-06 | 이지중 | The triple color ball point pen in which triple color-inks flow round on the three balls at the same time |
| KR100478880B1 (en) * | 2001-09-08 | 2005-03-23 | 윤기태 | Writting instrument for 3-dimensional expression |
| JP2006104362A (en) * | 2004-10-06 | 2006-04-20 | Toda Kogyo Corp | Composite particle powder, its manufacturing method and coating material and resin composition using the composite particle powder |
| JP2006206681A (en) * | 2005-01-26 | 2006-08-10 | Toda Kogyo Corp | Composite particle powder and colored composition and resin composition using the composite particle powder |
| JP2007099774A (en) * | 2005-10-03 | 2007-04-19 | L'oreal Sa | Fluorescent cosmetic composition |
| US9045643B2 (en) | 2006-04-21 | 2015-06-02 | Nippon Sheet Glass Company Limited | Bright pigment, method for producing the pigment, and waterborne resin composition containing the pigment |
| US8273171B2 (en) | 2006-08-29 | 2012-09-25 | Nippon Sheet Glass Company, Limited | Pearlescent pigment |
| JP2008231401A (en) * | 2007-02-19 | 2008-10-02 | Sanyo Chem Ind Ltd | Fluorescent material-including multilayer-structured spherical particles |
| US9107834B2 (en) | 2007-04-18 | 2015-08-18 | Nippon Sheet Glass Company, Limited | Bright pigment and cosmetic composition using the same |
| US8440014B2 (en) | 2007-04-27 | 2013-05-14 | Nippon Sheet Glass Company, Limited | Bright pigment, and bright coating composition and automotive body coating each containing the same |
| US8409708B2 (en) | 2007-10-18 | 2013-04-02 | Nippon Sheet Glass Company, Limited | Bright pigment |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0794615B2 (en) | 1995-10-11 |
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