JPH04249584A - Scaly pigment composition excellent in resistance to ultraviolet discoloration and use thereof - Google Patents
Scaly pigment composition excellent in resistance to ultraviolet discoloration and use thereofInfo
- Publication number
- JPH04249584A JPH04249584A JP41685490A JP41685490A JPH04249584A JP H04249584 A JPH04249584 A JP H04249584A JP 41685490 A JP41685490 A JP 41685490A JP 41685490 A JP41685490 A JP 41685490A JP H04249584 A JPH04249584 A JP H04249584A
- Authority
- JP
- Japan
- Prior art keywords
- pigment composition
- weight
- oxide
- hydroxide
- tio2
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 25
- 239000000049 pigment Substances 0.000 title claims abstract description 25
- 238000002845 discoloration Methods 0.000 title claims abstract description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000000463 material Substances 0.000 claims abstract description 19
- 239000010445 mica Substances 0.000 claims abstract description 19
- 229910052618 mica group Inorganic materials 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 8
- 239000000057 synthetic resin Substances 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 6
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 239000005995 Aluminium silicate Substances 0.000 claims abstract 2
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000000454 talc Substances 0.000 claims abstract 2
- 229910052623 talc Inorganic materials 0.000 claims abstract 2
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 7
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims 1
- 150000004679 hydroxides Chemical class 0.000 abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000002002 slurry Substances 0.000 description 12
- 239000010936 titanium Substances 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 4
- 229910018404 Al2 O3 Inorganic materials 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- 229910017895 Sb2 O3 Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- -1 aluminum compound Chemical class 0.000 description 3
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002932 luster Substances 0.000 description 3
- 238000009283 thermal hydrolysis Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910003556 H2 SO4 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 2
- 229910020187 CeF3 Inorganic materials 0.000 description 1
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- 229910000355 cerium(IV) sulfate Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、耐紫外線変色性に優れ
た真珠光沢を有する鱗片状顔料組成物及び、該鱗片状顔
料組成物を化粧板原紙に混入抄紙することにより製する
ことができる耐紫外線変色性に優れた真珠光沢を有する
合成樹脂化粧板に関する。[Industrial Application Field] The present invention provides a scaly pigment composition having a pearlescent luster with excellent ultraviolet discoloration resistance, and a scaly pigment composition that can be produced by mixing the scaly pigment composition into decorative laminate base paper. This invention relates to a synthetic resin decorative board with pearlescent luster and excellent ultraviolet discoloration resistance.
【０００２】0002
【従来の技術】従来より、ＣｅＯ２ 、Ｓｂ２ Ｏ３
を各々単独で又は他の金属酸化物と組み合わせて被覆す
ることで、ＴｉＯ２ 被覆雲母真珠光沢顔料の耐候性を
改善する方法（特開昭６２−９１５６７号、特開平１−
２９２０６７号）が開示されているが、耐紫外線変色性
に関するかぎり現在の高い要求レベルを満たすものを製
造しうるまでには至っていなかった。また、Ｓｂ２ Ｏ
３ を被覆し焼成することで耐紫外線変色性は改善され
るが、かかる処理によればこの顔料の特徴である真珠光
沢（光輝）感を大幅に損なってしまうという問題があり
、耐紫外線変色性と真珠光沢とを同時に得ることは困難
であった。例えば車輛（電車・バス）の内装用に使用さ
れる合成樹脂化粧板には高い耐紫外線変色性が要求され
るが、上記の事情から、これに使用しうる性能を有する
顔料としては顔料級の二酸化チタンにほぼ限られてしま
い、このためかかる合成樹脂化粧板の意匠性は極めて乏
しいものとならざるを得なかった。[Prior Art] Conventionally, CeO2, Sb2 O3
A method for improving the weather resistance of TiO2-coated mica pearlescent pigments by coating each of them alone or in combination with other metal oxides (JP-A-62-91567, JP-A-1-1999)
No. 292,067), but it has not yet been possible to produce a product that satisfies the current high requirements as far as ultraviolet discoloration resistance is concerned. Also, Sb2O
3. Although UV discoloration resistance can be improved by coating and firing, such treatment has the problem of significantly impairing the pearlescent (brilliance) characteristic of this pigment. It was difficult to obtain both pearlescent and pearlescent luster at the same time. For example, synthetic resin decorative laminates used for the interior of vehicles (trains and buses) are required to have high resistance to ultraviolet discoloration, but due to the above circumstances, pigment-grade pigments with the performance that can be used for these are required. It is almost limited to titanium dioxide, and as a result, the design of such synthetic resin decorative laminates has been extremely poor.
【０００３】0003
【発明が解決しようとする課題】本発明は、上記の問題
点に鑑み、無機鱗片状物質に被覆したＴｉＯ２ 又はＴ
ｉＯ２ とＣｏ、Ｆｅ、Ｎｉ、Ｃｕ、Ｍｎ等よりなる被
覆層の紫外線に対する活性を抑制することを課題とする
ものである。Problems to be Solved by the Invention In view of the above-mentioned problems, the present invention has been made to provide TiO2 or T
The object of this invention is to suppress the activity of a coating layer made of iO2 and Co, Fe, Ni, Cu, Mn, etc. against ultraviolet rays.
【０００４】0004
【課題を解決するための手段】種々の検討を行った結果
、ＴｉＯ２ で被覆し又はＴｉＯ２ 及びＣｏ、Ｆｅ、
Ｎｉ、Ｃｕ、Ｍｎ等の着色金属元素の酸化物若しくは水
酸化物で被覆した無機鱗片状物質を、Ｃｅ及びＳｂの水
酸化物又は酸化物で更に被覆することで、耐紫外線変色
性が大幅に向上することを見出した。また、Ｃｅ及びＳ
ｂの水酸化物又は酸化物で被覆した後、Ａｌ及びＳｉの
水酸化物又は酸化物を更に被覆することによ、より一層
耐紫外線変色性が向上することを見出した。特に、Ｃｅ
及びＳｂの水酸化物又は酸化物を被覆した後、Ａｌ及び
Ｓｉの水酸化物又は酸化物を複合体の形で被覆した場合
に最も大きな効果を得ることができる。[Means for solving the problem] As a result of various studies, we found that coating with TiO2 or coating with TiO2 and Co, Fe,
By further coating an inorganic scale-like material coated with an oxide or hydroxide of a colored metal element such as Ni, Cu, or Mn with a hydroxide or oxide of Ce and Sb, the resistance to ultraviolet discoloration can be greatly improved. I found that it can be improved. Also, Ce and S
It has been found that after coating with the hydroxide or oxide of (b), the ultraviolet discoloration resistance can be further improved by further coating with the hydroxide or oxide of Al and Si. In particular, Ce
The greatest effect can be obtained when the hydroxides or oxides of Al and Si are coated in the form of a composite after the hydroxides or oxides of Al and Si are coated.
【０００５】本発明の鱗片状顔料組成物の製造において
は先ず、（１）無機鱗片状物質に硫酸チタニル又は四塩
化チタン等の水溶性チタン化合物（Ｓｎ化合物のような
ルチル型ＴｉＯ２ への転位促進剤を含んでもよい。）
を加えこれを熱加水分解又は中和加水分解することによ
って、該無機鱗片状物質上にチタンの水和酸化物をＴｉ
Ｏ２ として無機鱗片状物質重量に対し５乃至５０重量
％沈着させ、（２）所望により更に、ポリ塩化アルミニ
ウム等の水溶性アルミニウム化合物を加え、これを熱加
水分解又は中和加水分解することによって、Ａｌ２ Ｏ
３ として沈着させた後、（３）更に所望により、これ
にＣｏ、Ｆｅ、Ｎｉ、Ｃｕ、Ｍｎ等の着色金属化合物の
水溶性塩を加えこれを中和又は熱加水分解することによ
り、Ｃｏ、Ｆｅ、Ｎｉ、Ｃｕ、Ｍｎ等の水酸化物又は酸
化物を無機鱗片状物質重量に対し各々ＣｏＯ、Ｆｅ２
Ｏ３ 、ＦｅＯＯＨ、ＮｉＯ、ＣｕＯとして２乃至４０
重量％沈着させ、これを３００乃至９００℃で３０分乃
至６０時間焼成することにより、目的とする鱗片状顔料
組成物のための基材を製する。被覆されたＴｉＯ２ の
結晶形態はアナタース型、ルチル型のどちらでもよい。In the production of the scaly pigment composition of the present invention, first, (1) an inorganic scaly substance is treated with a water-soluble titanium compound such as titanyl sulfate or titanium tetrachloride (to promote rearrangement to rutile-type TiO2 such as a Sn compound); (May also contain agents.)
The hydrated oxide of titanium is formed on the inorganic scale material by thermal hydrolysis or neutralization hydrolysis.
By depositing 5 to 50% by weight of O2 based on the weight of the inorganic scale-like substance, (2) optionally further adding a water-soluble aluminum compound such as polyaluminum chloride, and subjecting it to thermal hydrolysis or neutralization hydrolysis, Al2O
After depositing as Co, Hydroxides or oxides of Fe, Ni, Cu, Mn, etc. are added to CoO and Fe2, respectively, based on the weight of the inorganic scale material.
2 to 40 as O3, FeOOH, NiO, CuO
By depositing % by weight and firing it at 300 to 900° C. for 30 minutes to 60 hours, a base material for the intended flaky pigment composition is manufactured. The crystal form of the coated TiO2 may be either anatase type or rutile type.
【０００６】次いで、該基材をサンプルミル又はエック
アトマイザー等の粉砕機で粉砕した後、５０乃至２００
ｇ／Ｌの固形分濃度の水スラリーにする。加熱すること
により該スラリー温度を４０乃至６０℃とし、これに無
機鱗片状物質に対しＣｅＯ２ 換算で０．１乃至５重量
％、好ましくは０．３乃至１重量％相当量のＣｅの水溶
性塩、及び無機鱗片状物質に対しＳｂ２ Ｏ３ 換算で
０．１乃至５重量％、好ましくは１乃至３重量％相当量
のＳｂの水溶性塩をそれぞれ加えて、逐次的に又は同時
に沈着せしめ、更に所望により、無機鱗片状物質に対し
ＳｉＯ２ 換算で２乃至２０重量％、好ましくは４乃至
１０重量％相当量のＳｉの水溶性化合物、及び無機鱗片
状物質に対しＡｌ２ Ｏ３ 換算で２乃至２０重量％、
好ましくは４乃至１０重量％相当量のＡｌの水溶性化合
物を加えて、加熱加水分解又はＨ２ ＳＯ４ 等の酸若
しくはＮａＯＨ、ＮＨ４ ＯＨ等のアルカリを使用して
中和加水分解することにより、上記ＴｉＯ２ 等が被覆
された無機鱗片状物質表面にＣｅ、Ｓｂ、Ｓｉ、Ａｌの
各水酸化物又は酸化物を沈着させる。これを一般的な方
法で濾過し洗浄して系内の塩類を除いた後、１５０℃以
下で乾燥し、サンプルミル等の粉砕機で粉砕して目的物
たる鱗片状顔料組成物とする。[0006] Next, after pulverizing the base material with a pulverizer such as a sample mill or an Ec atomizer,
Make a water slurry with a solids concentration of g/L. The slurry temperature is brought to 40 to 60°C by heating, and a water-soluble salt of Ce is added thereto in an amount equivalent to 0.1 to 5% by weight, preferably 0.3 to 1% by weight, based on the inorganic scale-like substance in terms of CeO2. , and a water-soluble salt of Sb in an amount equivalent to 0.1 to 5% by weight, preferably 1 to 3% by weight in terms of Sb2O3 based on the inorganic scale-like material, and deposited sequentially or simultaneously, and further as desired. Accordingly, a water-soluble compound of Si in an amount equivalent to 2 to 20% by weight in terms of SiO2, preferably 4 to 10% by weight based on the inorganic scale-like material, and 2 to 20% by weight in terms of Al2O3 based on the inorganic scale-like material,
The above TiO2 is preferably added with a water-soluble compound of Al in an amount equivalent to 4 to 10% by weight, and subjected to thermal hydrolysis or neutralization hydrolysis using an acid such as H2SO4 or an alkali such as NaOH or NH4OH. Each hydroxide or oxide of Ce, Sb, Si, and Al is deposited on the surface of the inorganic scale-like material coated with the like. This is filtered and washed using a general method to remove salts from the system, then dried at 150° C. or below, and ground with a grinder such as a sample mill to obtain the target flaky pigment composition.
【０００７】Ｃｅの水溶性塩としては例えば、Ｃｅ（Ｓ
Ｏ４ ）２、Ｃｅ２ （ＳＯ４ ）３ 、ＣｅＣｌ３
、Ｃｅ（ＣＯ３ ）３ 、ＣｅＦ３ 、Ｃｅ（ＮＯ２
）３ 又はＣｅ（Ｃ２ Ｏ４ ）３ が使用できるが、
Ｃｅ（ＳＯ４ ）２ が最も好ましい。またＳｂの水溶
性塩としては例えばＳｂＣｌ３ が、Ｓｉの水溶性化合
物としては例えばＳｉＮａ２ Ｏ３ が、Ａｌの水溶性
化合物としては例えばＡｌＮａＯ２ 又はＡｌ２ （Ｓ
Ｏ４）３ が使用できるが、これらの化合物に限定され
るものではない。なお、Ｃｅ以外にＬａ、Ｌｕ、Ｖにも
効果が認められた。本発明による鱗片状顔料組成物は例
えば、ポリエチレン、ポリプロピレン、ポリ塩化ビニル
等の熱可塑性樹脂又は例えば尿素樹脂、フェノール樹脂
等の熱硬化性樹脂に配合することにより、格調ある色彩
を有する成型物を提供することができるほか、塗料、イ
ンキ、紙等にも使用することができ、特に、合成樹脂化
粧板に用いると耐紫外線変色性を大きく改善できる点で
有利である。以下に実施例を挙げて本発明をより詳細に
説明するが、本発明はこれらの実験条件等によって限定
されるものではない。Examples of water-soluble salts of Ce include Ce(S).
O4 )2, Ce2 (SO4)3, CeCl3
, Ce(CO3)3, CeF3, Ce(NO2
)3 or Ce(C2O4)3 can be used, but
Ce(SO4)2 is most preferred. Examples of water-soluble salts of Sb include SbCl3, examples of water-soluble compounds of Si include SiNa2O3, and examples of water-soluble compounds of Al include AlNaO2 and Al2(S).
O4)3 can be used, but is not limited to these compounds. In addition to Ce, effects were also observed on La, Lu, and V. The scaly pigment composition according to the present invention can be blended with thermoplastic resins such as polyethylene, polypropylene, and polyvinyl chloride, or thermosetting resins such as urea resins and phenolic resins, to produce molded products with magnificent colors. In addition, it can also be used in paints, inks, papers, etc. It is especially advantageous when used in synthetic resin decorative boards because it can greatly improve the resistance to ultraviolet discoloration. The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited by these experimental conditions.
【０００８】[0008]
【実施例】実施例−１
平均粒子径３０μｍの天然雲母２７０ｇに水２８００ｍ
ｌを加えたスラリーを加熱して、温度が９０℃になった
時、ＴｉＯ２ 換算で２３０ｇ／Ｌの硫酸チタニル水溶
液を３９１ｍｌ（ＴｉＯ２ として９０ｇ、天然雲母に
対して３３．３重量％）を添加する。そのまま昇温して
沸騰させ、その状態を３時間維持した後、濾過、水洗、
脱水する。再び、該脱水ケーキ全量を３Ｌの水スラリー
にした後、８０℃まで昇温し、ＮａＯＨでｐＨを７に調
整し、３０分間熟成した後、濾過、水洗、加熱乾燥して
９００℃で２時間焙焼し、サンプルミル粉砕することに
より、基材となる雲母チタン（試料１）を作成した。試
料１のチタンの結晶形はＸ線回折によりアナタース型で
あることが確認された。試料１の２００ｇを全量で２Ｌ
のスラリーとし、６０℃まで加熱し、ＣｅＯ２ 換算で
１００ｇ／ＬのＣｅ（ＳＯ４ ）２ 水溶液を６ｍｌ（
ＣｅＯ２ として０．６ｇ、試料１に対して０．３重量
％）を添加し、ＮａＯＨでｐＨを８に調整する。続いて
、Ｓｂ２ Ｏ３ として５１重量％のＳｂＣｌ３ 水溶
液を４．７ｇ（Ｓｂ２ Ｏ３ として２．４ｇ、試料１
に対して１．２重量％）添加し、ＮａＯＨでｐＨを７に
調整し、系の温度を６０℃に維持して３０分間熟成した
後、濾過、水洗、乾燥及びサンプルミル粉砕することに
より、目的の鱗片状顔料組成物（試料２）を得た。[Example] Example-1 270 g of natural mica with an average particle size of 30 μm and 2800 m of water
1 is heated, and when the temperature reaches 90°C, 391 ml of an aqueous titanyl sulfate solution containing 230 g/L in terms of TiO2 (90 g as TiO2, 33.3% by weight based on natural mica) is added. . Raise the temperature and bring it to a boil, maintain that state for 3 hours, then filter, wash with water,
Dehydrate. Again, the entire amount of the dehydrated cake was made into a 3L water slurry, heated to 80°C, adjusted to pH 7 with NaOH, aged for 30 minutes, filtered, washed with water, heated and dried at 900°C for 2 hours. A titanium mica (sample 1) serving as a base material was prepared by roasting and pulverizing with a sample mill. The crystal form of titanium in Sample 1 was confirmed to be anatase type by X-ray diffraction. 200g of sample 1 in total 2L
slurry, heated to 60°C, and added 6 ml (
0.6 g of CeO2 (0.3% by weight based on sample 1) was added, and the pH was adjusted to 8 with NaOH. Subsequently, 4.7 g of a 51% by weight SbCl3 aqueous solution as Sb2 O3 (2.4 g as Sb2 O3, sample 1
1.2% by weight), adjusted the pH to 7 with NaOH, maintained the temperature of the system at 60°C and aged for 30 minutes, and then filtered, washed with water, dried and pulverized with a sample mill. The desired flaky pigment composition (Sample 2) was obtained.
【０００９】実施例−２
実施例−１おいて、ＳｂＣｌ３ 水溶液の添加後、Ｎａ
ＯＨでｐＨを１０に調整する。引続いて、系の温度を６
０℃に維持して３０分間熟成した後、ＳｉＯ２ 換算で
２００ｇ／ＬのＳｉＮａ２ Ｏ３ 水溶液を４０ｍｌ（
ＳｉＯ２ として８ｇ、試料１に対して４重量％）添加
、更にＡｌ２ Ｏ３ 換算で２５０ｇ／ＬのＡｌＮａＯ
２ 水溶液を３２ｍｌ（Ａｌ２ Ｏ３ として８ｇ、試
料１に対して４重量％）添加し、Ｈ２ ＳＯ４ でｐＨ
を５に調整し、３０分間熟成させた後、濾過、水洗、脱
水する。再び、該脱水ケーキ全量を２Ｌのスラリーにし
８０℃まで加熱し、ＮａＯＨ又はＨ２ ＳＯ４ でｐＨ
を５に調整して３０分間熟成後、濾過、水洗、加熱乾燥
及びサンプルミル粉砕して、目的の鱗片状顔料組成物（
試料３）を得た。Example 2 In Example 1, after adding the SbCl3 aqueous solution, Na
Adjust pH to 10 with OH. Subsequently, the temperature of the system was increased to 6
After aging at 0°C for 30 minutes, add 40ml of SiNa2O3 aqueous solution containing 200g/L in terms of SiO2 (
8g of SiO2 (4% by weight based on sample 1) was added, and 250g/L of AlNaO was added in terms of Al2O3.
2 Add 32 ml of aqueous solution (8 g as Al2 O3, 4% by weight based on sample 1) and adjust the pH with H2 SO4.
5 and aged for 30 minutes, filtered, washed with water, and dehydrated. Again, the entire amount of the dehydrated cake was made into a 2L slurry, heated to 80°C, and adjusted to pH with NaOH or H2SO4.
5 and aged for 30 minutes, filtered, washed with water, heated and dried, and ground in a sample mill to obtain the desired flaky pigment composition (
Sample 3) was obtained.
【００１０】実施例−３
Ｃｅ、Ｓｂ、Ｓｉ、Ａｌの量を各々ＣｅＯ２ として０
．６重量％、Ｓｂ２ Ｏ３ として１．２重量％、Ｓｉ
Ｏ２ として８重量％、Ａｌ２ Ｏ３ として８重量％
に変更した以外は実施例−２と同一の処理を行い、目的
の鱗片状顔料組成物（試料４）を得た。Example 3 The amounts of Ce, Sb, Si, and Al are each set to 0 as CeO2.
．． 6% by weight, 1.2% by weight as Sb2O3, Si
8% by weight as O2, 8% by weight as Al2O3
The same treatment as in Example 2 was performed except that the desired scaly pigment composition (Sample 4) was obtained.
【００１１】実施例−４
の天然雲母の平均粒子径を５５μｍ、ＴｉＯ２ の被覆
量を２２重量％に変更した以外は実施例−３と同一処理
を行い、基材となる雲母チタン（試料５）及び目的の鱗
片状顔料組成物（試料６）を得た。[0011] The same treatment as in Example 3 was carried out except that the average particle diameter of natural mica in Example 4 was changed to 55 μm and the coating amount of TiO2 was changed to 22% by weight. And the desired flaky pigment composition (Sample 6) was obtained.
【００１２】実施例−５
平均粒子径２２μｍの天然雲母２７０ｇに水２８００ｍ
ｌを加えたスラリーを加熱して、液温を９０℃とし、こ
れにＴｉＯ２ 換算で２３０ｇ／Ｌの硫酸チタニル水溶
液４３５ｍｌ（ＴｉＯ２ として１００ｇ、天然雲母に
対して３７重量％）とＳｎＯ２ 換算で５５重量％のＳ
ｎＣｌ４ 水溶液２７．３ｇ（ＳｎＯ２ として１５．
０ｇ、ＴｉＯ２ に対して１５重量％）との混合物を添
加する。そのまま昇温して沸騰させ、その状態を３時間
維持した後、濾過、水洗、脱水する。再び、該脱水ケー
キ全量を３Ｌの水スラリーにした後、８０℃まで昇温し
、ＮａＯＨでｐＨを７に調整し、３０分間熟成した後、
濾過、水洗、加熱乾燥して９００℃で２時間焙焼しサン
プルミル粉砕することにより、基材である雲母チタン（
試料７）を作成した。試料７のチタンの結晶形はＸ線回
折によりルチル型であることが確認された。これについ
て実施例−３と同一の処理を行い、目的の鱗片状顔料組
成物（試料８）を得た。Example 5 270 g of natural mica with an average particle size of 22 μm and 2800 m of water
1 was added to the slurry to bring the liquid temperature to 90°C, and to this was added 435 ml of an aqueous titanyl sulfate solution of 230 g/L in terms of TiO2 (100 g as TiO2, 37% by weight based on natural mica) and 55 weight in terms of SnO2. %S
27.3 g of nCl4 aqueous solution (15.3 g as SnO2.
0 g, 15% by weight based on TiO2) is added. The temperature is raised to boil, and this state is maintained for 3 hours, followed by filtration, washing with water, and dehydration. Again, the entire amount of the dehydrated cake was made into a 3L water slurry, heated to 80°C, adjusted to pH 7 with NaOH, aged for 30 minutes,
The base material mica titanium (
Sample 7) was created. The crystal form of titanium in Sample 7 was confirmed to be rutile by X-ray diffraction. This was subjected to the same treatment as in Example 3 to obtain the desired flaky pigment composition (Sample 8).
【００１３】実施例−６
平均粒子径２５μｍの天然雲母２７０ｇに水２８００ｍ
ｌを加えたスラリーを加熱して液温を９０℃とし、これ
にＴｉＯ２ 換算で２３０ｇ／Ｌの硫酸チタニル水溶液
１３５ｍｌ（ＴｉＯ２ として３１ｇ、天然雲母に対し
て１１．５重量％）を添加する。そのまま昇温し沸騰さ
せ、沸騰状態を３時間維持した後、濾過、水洗、脱水す
る。
再び、該脱水ケーキ全量を３Ｌのスラリーにし、８０℃
まで昇温し、Ａｌ２ Ｏ３ 換算で１２重量％のポリ塩
化アルミニウム２５９ｇ（Ａｌ２ Ｏ３ として３１ｇ
、天然雲母に対して１１．５重量％）を添加する。ＮＨ
４ ＯＨでｐＨを８に調整し、３０分間熟成後、濾過、
水洗、脱水する。再度、該脱水ケーキ全量を３Ｌのスラ
リーにし、８０℃まで昇温し、ＮＨ４ ＯＨ及びＨ２Ｓ
Ｏ４ でｐＨを８に調整し、３０分間熟成した後、濾過
、水洗、脱水、乾燥して９００℃で２時間焙焼後サンプ
ルミル粉砕し、基材である雲母−ＴｉＯ２ −Ａｌ２
Ｏ３ 組成物（試料９）を得た。被覆されたＴｉＯ２
の結晶形はＸ線回折によりアナタース型であることが確
認された。水１．２５ＬにＦｅ２ Ｏ３ 換算で１６．
６重量％のＦｅ（ＮＨ４ ）（ＳＯ４ ）２ ２４１．
５ｇ（Ｆｅ２ Ｏ３ として４０ｇ、試料９に対して２
０重量％）を添加する。３０重量％のＨ２ ＳＯ４ １
０ｍｌを添加し、Ｆｅ（ＮＨ４ ）（ＳＯ４ ）２ が
溶解していることを確認した後、徐中和用の尿素７５ｇ
を添加する。更に、試料９の２００ｇを投入し、全体の
液量を２Ｌにする。沸騰するまで加熱し、ｐＨが ５
．５になるまで沸騰状態を維持し、濾過、水洗、脱水後
、再び、該脱水ケーキ全量を２．５Ｌのスラリーにし、
６０℃まで加熱し、ＮａＯＨでｐＨを５に調整し、３０
分間熟成した後、濾過、水洗、脱水、乾燥して９００℃
で２時間焼成後サンプルミル粉砕することにより、赤色
に着色された基材である着色鱗片状物質（試料１０）を
得た。試料１０を実施例−２と同じ方法で且つ同量のＣ
ｅＯ２ 、Ｓｂ２ Ｏ３ 、ＳｉＯ２ 、Ａｌ２ Ｏ３
で被覆することにより、目的の鱗片状顔料組成物（試
料１１）を得た。Example 6 270 g of natural mica with an average particle size of 25 μm and 2800 m of water
1 of the slurry was heated to a liquid temperature of 90° C., and 135 ml of an aqueous titanyl sulfate solution containing 230 g/L in terms of TiO2 (31 g as TiO2, 11.5% by weight based on natural mica) was added thereto. The temperature is raised to boil, and the boiling state is maintained for 3 hours, followed by filtration, washing with water, and dehydration. Again, the entire amount of the dehydrated cake was made into a 3L slurry and heated to 80°C.
259 g of polyaluminum chloride (31 g as Al2 O3) with a concentration of 12% by weight in terms of Al2 O3
, 11.5% by weight based on natural mica). N.H.
4 Adjust the pH to 8 with OH, age for 30 minutes, filter,
Wash and dehydrate. Again, the entire amount of the dehydrated cake was made into a 3L slurry, heated to 80°C, and mixed with NH4OH and H2S.
After adjusting the pH to 8 with O4 and aging for 30 minutes, it was filtered, washed with water, dehydrated, dried, roasted at 900°C for 2 hours, and then ground in a sample mill to obtain the base material mica-TiO2-Al2.
An O3 composition (Sample 9) was obtained. coated TiO2
The crystal form was confirmed to be anatase type by X-ray diffraction. 1.25L of water is equivalent to 16.
6% by weight of Fe(NH4)(SO4)2 241.
5g (40g as Fe2O3, 2 for sample 9
0% by weight). 30% by weight H2 SO4 1
After confirming that Fe(NH4)(SO4)2 is dissolved, add 75g of urea for gradual neutralization.
Add. Furthermore, 200 g of sample 9 is added to bring the total liquid volume to 2 L. Heat until boiling and pH is 5.
．． After maintaining the boiling state until the temperature reaches 5, filtration, washing with water, and dehydration, the entire amount of the dehydrated cake is made into a 2.5L slurry again.
Heat to 60°C, adjust pH to 5 with NaOH,
After aging for a minute, filter, wash with water, dehydrate, and dry at 900℃.
After baking for 2 hours, the sample was pulverized in a sample mill to obtain a colored scaly material (sample 10), which was a red colored base material. Sample 10 was treated with the same method as in Example-2 and with the same amount of C.
eO2, Sb2O3, SiO2, Al2O3
By coating with , the target flaky pigment composition (Sample 11) was obtained.
【００１４】評 価
各実施例において得られた試料を用いて下記の方法にて
製した低圧メラミン樹脂含浸紙を、シャワーなしのサン
シャインウエザオメーターに３６時間暴露して、その耐
紫外線変色性を評価した。結果は表１に示す。
低圧メラミン樹脂含浸紙の作成条件：叩解度３２°ＳＲ
のパルプを紙として１．４ｇ計量し、歩留向上剤として
サンド（株）製のＣａｒｔａｒｅｔｉｎ Ｆ Ｌｉ
ｑｕｉｄ溶液（１％）をパルプに対して２％混合する。
５０ｇ／Ｌのチタンマイカスラリーをパルプに対してチ
タンマイカとして２０％添加し混合した後、湿潤紙力向
上剤としてディック・ハーキュレス（株）製のＥＰＩＮ
ＯＸ Ｐ−１３０（１％）をパルプに対して２％混合
し、全量を２００ｍｌにする。３０分間放置した後、抄
紙し、３分間３０ｋｇ／ｃｍ２ でプレスし、一晩放置
する。サントップＭ−７００（ＮＶ＝５８％）を含浸さ
せ、乾燥させた後、同様に含浸させたベース紙と重ねて
１５０℃・１５０ｋｇ／ｃｍ２ の条件で５分間プレス
して低圧メラミン樹脂化粧板とする。Evaluation A low-pressure melamine resin-impregnated paper produced by the following method using the samples obtained in each example was exposed to a sunshine weather meter without a shower for 36 hours to evaluate its ultraviolet discoloration resistance. evaluated. The results are shown in Table 1. Conditions for making low-pressure melamine resin-impregnated paper: Beating degree 32°SR
Weighed 1.4g of the pulp as paper, and used Cartaretin F Li manufactured by Sandoz Co., Ltd. as a retention aid.
Mix 2% of Quid solution (1%) to the pulp. After adding and mixing 50 g/L of titanium mica slurry to the pulp as 20% titanium mica, EPIN manufactured by Dick Hercules Co., Ltd. was added as a wet paper strength improver.
Mix 2% of OX P-130 (1%) to the pulp to make the total volume 200ml. After standing for 30 minutes, paper is made, pressed at 30 kg/cm2 for 3 minutes, and left overnight. After impregnating it with Suntop M-700 (NV=58%) and drying it, it was layered with base paper impregnated in the same way and pressed for 5 minutes at 150℃ and 150kg/cm2 to form a low-pressure melamine resin decorative board. do.
【００１５】
表１
試料 雲母粒
子 表面処理物質および処理量（％）
耐紫外線 径
（対雲母） ： （対雲母チタ
ン） 変色性Ｎｏ． （μｍ） Ｔｉ
Ｏ２ Ａｌ２Ｏ３ Ｆｅ２Ｏ３ ＣｅＯ２
Ｓｂ２Ｏ３ ＳｉＯ２ Ａｌ２Ｏ３ ΔＥ
１ ３０ ３３．３ −
− − − −
− １３ ２ ３０ ３３．
３ − − ０．３ １．
２ − − ７ ３
３０ ３３．３ − −
０．３ １．２ ４
４ ５ ４ ３０ ３３
．３ − − ０．６ ２
．４ ８ ８ ３
５ ５５ ２２ −
− − − − −
８ ６ ５５ ２２
− − ０．６ ２．
４ ８ ８ ２
７ ２２ ３７ − −
− − − −
７ ８ ２２ ３７
− − ０．６ ２．４
８ ８ ３ ９
２５ １１．５ １１．５ −
− − − −
８ １０ ２５ １１．
５ １１．５ ２４．６ − −
− − ７ １１
２５ １１．５ １１．５ ２４
．６ ０．６ ２．４ ８
８ ３ サンシャインウエザオ
メーター曝露条件 耐紫外線変色性の判定方法
色差計 型式 ：ＳＭカラーコン
ピューター ＳＭ−５ メー
カー ：スガ試験機（株） ΔＥの求め方
ΔＥ＝｛（Ｌ２ −Ｌ１ ）２ ＋（ａ２ −
ａ１ ）２ ＋（ｂ１ −ｂ２ ）２ ｝１／２
但し、Ｌ１ ，ａ１ ，ｂ１ ：曝露前
Ｌ２ ，ａ２ ，ｂ２ ：曝露後Table 1
Sample Mica particles Surface treatment substance and treatment amount (%)
UV resistant Diameter
(Against mica): (Against mica titanium) Discoloration No. (μm) Ti
O2 Al2O3 Fe2O3 CeO2
Sb2O3 SiO2 Al2O3 ΔE
1 30 33.3 -
− − − −
- 13 2 30 33.
3 - - 0.3 1.
2 - - 7 3
30 33.3 - -
0.3 1.2 4
4 5 4 30 33
．． 3 - - 0.6 2
．． 4 8 8 3
5 55 22 -
− − − − −
8 6 55 22
- - 0.6 2.
4 8 8 2
7 22 37 - -
− − − −
7 8 22 37
− − 0.6 2.4
8 8 3 9
25 11.5 11.5 -
− − − −
8 10 25 11.
5 11.5 24.6 - -
- - 7 11
25 11.5 11.5 24
．． 6 0.6 2.4 8
8 3 Sunshine Weather-Ometer exposure conditions Method for determining ultraviolet discoloration resistance Color difference meter Model: SM Color Computer SM-5 Manufacturer: Suga Test Instruments Co., Ltd. How to determine ΔE ΔE={(L2 −L1)2 +(a2 −)
a1 )2 + (b1 - b2 )2 }1/2
However, L1, a1, b1: before exposure
L2, a2, b2: after exposure
【
００１６】[
0016
【発明の効果】本発明の耐紫外線変色性に優れた鱗片状
顔料組成物は、高い耐紫外線変色性が要望されている合
成樹脂成型品やフィルム、塗料等の製造を可能にするも
のである。特に、本発明によれば、車輛の内装その他高
度の耐紫外線変色性が要求される用途にも用いうる、意
匠性に富み且つ優れた耐紫外線変色性を有する合成樹脂
化粧板を提供することができる。[Effects of the Invention] The flake-like pigment composition of the present invention with excellent ultraviolet discoloration resistance enables the production of synthetic resin molded products, films, paints, etc. that require high ultraviolet discoloration resistance. . In particular, according to the present invention, it is possible to provide a synthetic resin decorative board that is rich in design and has excellent ultraviolet discoloration resistance and can be used for vehicle interiors and other applications that require a high degree of ultraviolet discoloration resistance. can.
Claims (5)
びＣｏ、Ｆｅ、Ｎｉ、Ｃｕ、Ｍｎその他の着色金属元素
のうち少なくとも一の酸化物若しくは水酸化物で被覆さ
れた無機鱗片状物質よりなる基材を、Ｃｅの酸化物又は
水酸化物及びＳｂの酸化物又は水酸化物で被覆してなる
ことを特徴とする、耐紫外線変色性に優れた鱗片状顔料
組成物。Claim 1: A base material made of an inorganic scale-like substance coated with TiO2 or coated with an oxide or hydroxide of at least one of TiO2 and other colored metal elements such as Co, Fe, Ni, Cu, Mn, etc. A scaly pigment composition having excellent ultraviolet discoloration resistance, characterized in that it is coated with an oxide or hydroxide of Ce and an oxide or hydroxide of Sb.
の被覆量が５乃至５０重量％であり且つＣｅ及びＳｂ
の酸化物又は水酸化物の該被覆量がそれぞれ０．１乃至
１０重量％であることを特徴とする、請求項１に記載の
耐紫外線変色性に優れた鱗片状顔料組成物。Claim 2: TiO2 based on the weight of the inorganic scale-like material
The coating amount of Ce and Sb is 5 to 50% by weight, and
The scaly pigment composition with excellent ultraviolet discoloration resistance according to claim 1, wherein the coating amount of the oxide or hydroxide is 0.1 to 10% by weight, respectively.
物又は水酸化物で更に被覆し、且つ該無機鱗片状物質の
重量に対し、Ｓｉ及びＡｌの酸化物又は水酸化物の被覆
量がＳｉＯ２ 及びＡｌ２ Ｏ３ としてそれぞれ１乃
至１５重量％であることを特徴とする、請求項１又は２
に記載の耐紫外線変色性に優れた鱗片状顔料組成物。3. Further coating with Si oxide or hydroxide and Al oxide or hydroxide, and coating with Si and Al oxide or hydroxide based on the weight of the inorganic scale-like material. Claim 1 or 2, characterized in that the amount of SiO2 and Al2O3 is 1 to 15% by weight, respectively.
A scaly pigment composition having excellent ultraviolet discoloration resistance as described in .
タルク、カオリン、セリサイト及びガラスフレークから
選ばれたものであることを特徴とする、請求項１、２又
は３に記載の耐紫外線変色性に優れた鱗片状顔料組成物
。4. The inorganic scale-like substance is natural mica, artificial mica,
The scaly pigment composition having excellent ultraviolet discoloration resistance according to claim 1, 2 or 3, characterized in that it is selected from talc, kaolin, sericite and glass flakes.
成物を、化粧板原紙に混入抄紙することを特徴とする、
耐紫外線変色性に優れた合成樹脂化粧板。5. A paper making process characterized by mixing the scaly pigment composition according to claim 1, 2 or 3 into decorative board base paper,
A synthetic resin decorative board with excellent UV discoloration resistance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP41685490A JPH04249584A (en) | 1990-12-28 | 1990-12-28 | Scaly pigment composition excellent in resistance to ultraviolet discoloration and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP41685490A JPH04249584A (en) | 1990-12-28 | 1990-12-28 | Scaly pigment composition excellent in resistance to ultraviolet discoloration and use thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04249584A true JPH04249584A (en) | 1992-09-04 |
Family
ID=18525040
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP41685490A Pending JPH04249584A (en) | 1990-12-28 | 1990-12-28 | Scaly pigment composition excellent in resistance to ultraviolet discoloration and use thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04249584A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0596442A1 (en) * | 1992-11-06 | 1994-05-11 | NIPPON INORGANIC COLOUR & CHEMICAL CO., LTD. | Ultraviolet-shielding agent, method for the preparation thereof and cosmetic composition compounded therewith |
| JPH07268241A (en) * | 1993-10-21 | 1995-10-17 | Mearl Corp:The | Improvement of weatherability of nacreous pigment |
| EP0719843A1 (en) | 1994-12-29 | 1996-07-03 | MERCK PATENT GmbH | Gray interference pigment and process for producing the same |
| WO1997046624A1 (en) * | 1996-06-03 | 1997-12-11 | Engelhard Corporation | Pearlescent glass |
| EP0761773A3 (en) * | 1995-08-31 | 1998-04-15 | Shiseido Company Limited | Yellowish scaly powder |
| EP0837114A4 (en) * | 1996-04-25 | 1998-08-05 | Sakai Chemical Industry Co | Ultraviolet absorber composition and process for production thereof |
| EP0905205A2 (en) * | 1997-09-30 | 1999-03-31 | Shiseido Company Limited | Coloured titanium dioxide coated mica pigment and article coated using the same |
| EP1038926A2 (en) * | 1999-03-23 | 2000-09-27 | Shiseido Company Limited | Pleochroism powder and pleochroism printed article |
| JP2004067773A (en) * | 2002-08-02 | 2004-03-04 | Sk Kaken Co Ltd | Coloring particle |
| JP2009527605A (en) * | 2006-02-24 | 2009-07-30 | エッカルト ゲゼルシャフト ミット ベシュレンクテル ハフツング | Weather-stable pearlescent pigments based on thin glass platelets and process for preparing them |
| USRE41858E1 (en) | 1993-06-24 | 2010-10-26 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Pearlescent pigment for water-borne surface-coating systems |
-
1990
- 1990-12-28 JP JP41685490A patent/JPH04249584A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0596442A1 (en) * | 1992-11-06 | 1994-05-11 | NIPPON INORGANIC COLOUR & CHEMICAL CO., LTD. | Ultraviolet-shielding agent, method for the preparation thereof and cosmetic composition compounded therewith |
| US5478550A (en) * | 1992-11-06 | 1995-12-26 | Nippon Inorganic Colour & Chemical Co., Ltd. | Ultraviolet-shielding agent, method for the preparation thereof and cosmetic composition compounded therewith |
| USRE41858E1 (en) | 1993-06-24 | 2010-10-26 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Pearlescent pigment for water-borne surface-coating systems |
| JPH07268241A (en) * | 1993-10-21 | 1995-10-17 | Mearl Corp:The | Improvement of weatherability of nacreous pigment |
| EP0719843A1 (en) | 1994-12-29 | 1996-07-03 | MERCK PATENT GmbH | Gray interference pigment and process for producing the same |
| US5693134A (en) * | 1994-12-29 | 1997-12-02 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Gray interference pigment and process for producing the same |
| EP0761773A3 (en) * | 1995-08-31 | 1998-04-15 | Shiseido Company Limited | Yellowish scaly powder |
| EP0837114A4 (en) * | 1996-04-25 | 1998-08-05 | Sakai Chemical Industry Co | Ultraviolet absorber composition and process for production thereof |
| WO1997046624A1 (en) * | 1996-06-03 | 1997-12-11 | Engelhard Corporation | Pearlescent glass |
| EP0905205A2 (en) * | 1997-09-30 | 1999-03-31 | Shiseido Company Limited | Coloured titanium dioxide coated mica pigment and article coated using the same |
| EP0905205A3 (en) * | 1997-09-30 | 1999-10-20 | Shiseido Company Limited | Coloured titanium dioxide coated mica pigment and article coated using the same |
| EP1038926A2 (en) * | 1999-03-23 | 2000-09-27 | Shiseido Company Limited | Pleochroism powder and pleochroism printed article |
| EP1038926A3 (en) * | 1999-03-23 | 2002-11-06 | Shiseido Company Limited | Pleochroism powder and pleochroism printed article |
| JP2004067773A (en) * | 2002-08-02 | 2004-03-04 | Sk Kaken Co Ltd | Coloring particle |
| JP2009527605A (en) * | 2006-02-24 | 2009-07-30 | エッカルト ゲゼルシャフト ミット ベシュレンクテル ハフツング | Weather-stable pearlescent pigments based on thin glass platelets and process for preparing them |
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