JPH0457709B2 - - Google Patents
Info
- Publication number
- JPH0457709B2 JPH0457709B2 JP13171986A JP13171986A JPH0457709B2 JP H0457709 B2 JPH0457709 B2 JP H0457709B2 JP 13171986 A JP13171986 A JP 13171986A JP 13171986 A JP13171986 A JP 13171986A JP H0457709 B2 JPH0457709 B2 JP H0457709B2
- Authority
- JP
- Japan
- Prior art keywords
- goethite
- particles
- pigment
- silica
- yellow pigment
- 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.)
- Expired
Links
- 229910052598 goethite Inorganic materials 0.000 claims description 56
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 claims description 56
- 239000002245 particle Substances 0.000 claims description 53
- 239000001052 yellow pigment Substances 0.000 claims description 26
- 239000002131 composite material Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000010954 inorganic particle Substances 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 45
- 239000000843 powder Substances 0.000 description 21
- 239000000049 pigment Substances 0.000 description 18
- 239000000377 silicon dioxide Substances 0.000 description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 13
- 238000010521 absorption reaction Methods 0.000 description 11
- 239000003921 oil Substances 0.000 description 11
- 235000019198 oils Nutrition 0.000 description 11
- 238000004040 coloring Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000011521 glass Substances 0.000 description 7
- 239000004408 titanium dioxide Substances 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 235000021388 linseed oil Nutrition 0.000 description 5
- 239000000944 linseed oil Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 241000276425 Xiphophorus maculatus Species 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000005355 lead glass Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000010303 mechanochemical reaction Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Description
「産業上の利用分野」
本発明は、SiO2分を15重量％以上含有する無
機粒子（以下、シリカ系粒子と記載する）を核と
し、その表面にゲーサイト粒子層を形成させた新
規な複合黄色顔料及びその製造法に関するもので
ある。
「従来の技術」
ゲーサイトは、一名針鉄鉱と呼ばれ、天然、合
成ともに針状粒子であり、耐光性、安定性、無毒
性であつて、黄色顔料として古くから広く使用さ
れてきた。1920年、その合成法が発明されて以
来、特性の優れた合成品が普及している。製造品
は多く知られているが、公知の方法で得られるも
のは、針状粉である。その後、この針状粒子の特
性を生かして記録用磁性粉の原料としても多量に
使用されるようになつた。
黄色顔料としてのゲーサイトの最適粒子径は、
短軸方向で0.1〜0.2μｍの範囲にある。これより
大きくなると分散性は良くなるが順次、黄褐色、
褐色、暗褐色と明度が小さくなる。粒子径1μｍ
付近では暗褐色となり黄色顔料としては不適当で
ある。これらの顔料の粒子径と色との関係につい
ては、信岡、色材、55、〔10〕758（1982）に詳述
されている。ゲーサイトの黄色顔料としての最適
粒子径である短軸方向で0.1〜0.2μｍの針状粒子
は、微細なので吸油量が大きく、かつ凝集性が強
いので分散性が悪いという大きな難点がある。分
散性の良い粒子径1μｍ以上にすると暗褐色とな
り顔料として不適当である。
近年、針状ゲーサイトとは別に、楕円体ゲーサ
イト（特公昭60−13975号公報、特公昭60−15580
号公報）、盤状ゲーサイト（大工試ニユース、
vol・29、1985、No.11）等が提案されているが、
やはり顔料としては上記針状ゲーサイトの場合と
同様の難点を有している。
「発明が解決しようとする問題点」
本発明の目的は、ゲーサイトの黄色顔料として
の美しい色調、耐光性、安定性、無毒性を維持し
つつ、吸油性が小さく分散性に優れた複合黄色顔
料とその製造方法を提供することにある。
本発明者等は種々検討の結果、シリカ系粒子を
核として、該粒子表面にゲーサイトを被着させて
ゲーサイト粒子層を形成させることにより上記目
的を達成し得ることを見出し本発明を完成するに
至つた。
本発明の如き複合顔料としてのゲーサイト、及
びその製造法は未だ見出されていない。
「問題点を解決するための手段」
本発明は、シリカ系粒子を核とし、その表面に
ゲーサイト粒子層が形成されていることを特徴と
する複合黄色顔料に関するものである。
更に本発明はゲーサイト粒子の存在下、シリカ
系粒子を粉砕し、破砕表面にゲーサイト粒子を被
着させることによりシリカ系粒子の表面にゲーサ
イト粒子層を形成させることを特徴とする複合黄
色顔料の乾式製造法に関するものである。
また、本発明はシリカ系粒子とゲーサイト粒子
をアルカリ水溶液中において混合、分散、加熱す
ることによつてシリカ系粒子の表面にゲーサイト
粒子層を形成させることを特徴とする複合黄色顔
料の湿式製造法に関するものである。
以下、本発明を詳細に説明する。
本発明に用いられるゲーサイト粒子は顔料とし
ての黄色を有するものであれば特に限定されな
い。ゲーサイトは、自形として針状粒子に成長す
る本性をもつており、多くは針状粒子であるが調
製条件によつては楕円体、盤状等非針状のものも
得られ、本発明においては、それ等のいずれでも
よく、なかでも盤状ゲーサイトは好適である。盤
状ゲーサイトは、塩化第二鉄、硫酸第二鉄の如き
第二鉄塩と水酸化ナトリウムの如き水酸化アルカ
リを水媒体中で反応させる際にモノエタノールア
ミンの如きオキシアルキルアミン（炭素数２〜
６）を添加して反応させ、生成した水酸化第二鉄
のスラリを100〜250℃で水熱処理し、母液から生
成物をろ別、洗浄、乾燥することによつて得られ
る。盤状ゲーサイトの粒子径（盤径）は、調製条
件でコントロールできるが、平均粒子径があまり
大きすぎると褐色がかつてくるので本発明におい
ては0.2μｍ以下、0.03〜0.2μｍのものが好適に使
用される。（なおゲーサイトは、1μｍが限界粒子
径である。）
但し、ゲーサイト粒子が針状の場合は好ましく
は平均短軸径が0.2μｍ以下であればよい。という
のは黄色が濃くなつて褐色がかつてくるのは、針
状の場合は短軸径が増すことにより生じ、長軸径
の増減は余り影響しないからである。
本発明においてシリカ系粒子は核として作用
し、顔料の分散性に寄与する。
この点から核としてのシリカ系粒子の平均粒子
径は、１〜18μｍ、特に３〜15μｍの範囲にある
ことが望ましい。
本発明においてシリカ系粒子は、顔料としたと
きにゲーサイトの黄色を防げないものが好適であ
り、一般には透明ないし白色または淡黄色のもの
が使用される。
本発明で使用するシリカ系粒子、即ちSiO2分
を15重量％以上含有する無機粒子としては、粒子
表面がアルカリにおかされやすく、表面活性が高
く、軽くて安価なものが選択され、そのようなシ
リカ系粒子としては、例えば、シリカ、ソーダ石
灰系ガラス、ホウケイ酸系ガラス、鉛系ガラス、
無アルカリ系ガラスがある。
本発明にかかる黄色複合顔料におけるゲーサイ
トの含有量は、過度に少いと着色力が低下し、過
度に多いと分散性が悪くなるので、好ましくは５
〜40重量％である。
本発明のシリカ系粒子を核とし、その表面にゲ
ーサイト粒子層が形成されている複合黄色顔料の
平均粒子径は、使用する核の大きさ、ゲーサイト
の種類、製造条件等によつてもかえることができ
るが、分散性の向上の点から１〜20μｍ、好まし
くは２〜17μｍである。
本発明にかかる複合黄色顔料は以下に詳述の如
く乾式法および湿式法のいずれによつても製造す
ることができる。
(1) 乾式法：シリカ系粒子またはその塊状物とゲ
ーサイト粉末とを乾式において混合、粉砕する
と、ゲーサイトは微細なのでそれ以上粉砕され
ないが、固溶体が粉砕されて新しい表面がで
き、その表面にゲーサイト粉末が被着し、ゲー
サイト粒子層が形成された複合黄色顔料が得ら
れる。小規模では、例えば自動乳鉢を用いて混
合、摩砕を行うと容易にシリカ系粒子が核とな
りその表面にゲーサイト粉末の披着することが
観察される。この現象は、乾式混合に際し、接
触、摩擦帯電が起こり付着作用に有効に働くた
めである。また、摩砕直後のシリカ系粒子表面
は、極めて活性であり吸着性が強いから微粒子
ゲーサイト粉末をよく吸着させるというメカノ
ケミカルな反応が考えられる。これらの機構に
ついては、山口、色材、58、〔８〕476（1985）
に解説されている。工業的には例えば遠心回転
型ボールミルの如きを用いる。その際、乾燥空
気、不活性ガス気流、真空中で行なうと、さら
に被着効果が良好である。
(2) 湿式法：核となるシリカ系粒子とゲーサイト
粉末とを水酸化ナトリウム水溶液中に入れ、よ
く混合、分散させる。次に、混合、分散させな
がら加熱、通常50〜90℃に２〜３時間加熱し、
その後、水洗、乾燥する。この乾燥によつてシ
リカ系粒子表面にゲーサイト粉末が均一に被着
しゲーサイト粒子層が形成された複合黄色顔料
を得ることができる。この被着現象は、シリカ
系粒子表面がアルカリによつてやや溶解、侵食
され、僅かに生成したケイ酸ナトリウムの如き
ケイ酸塩が糊の接着作用を行ない、ゲーサイト
粉末を核表面に付着させるものと考案される。
分散機は、小規模では超音波分散機が良いが、
より工業的には例えばアトライター（ビーズミ
ル）などが好適である。
上記のようにして得られる本発明の易分散性
複合黄色顔料は、従来からの顔料の特性を改良
し一歩前進させた新規顔料である。
本発明の複合黄色顔料は、粒子系が１〜20μ
ｍと従来のものに比べて大きいので、特に分散
性に優れた無毒性黄色顔料として塗料、印刷イ
ンキ、合成樹脂、化粧品、建築材料、絵具など
に利用することができる。特に簡易に分散を要
求されるメークアツプ化粧品、合成樹脂、セメ
ントなどへの適応性がある。
実施例
以下、実施例により本発明を更に具体的に説明
する。
実施例 １
（湿式法）
盤状ゲーサイト（平均粒子径0.18μｍ、吸油量
24％）3.0ｇを蒸留水50mlに加え超音波分散機で
分散させた。この分散液に破砕シリカ（２〜7μ
ｍ）８ｇを添加し、70℃に加温したのち、撹拌し
ながら2N NaOH水溶液150mlを加えて２時間撹
拌した。生成した黄色沈殿物を水洗、濾過、乾燥
を行ない盤状ゲーサイト単独よりも着色力に優れ
分散性の良い複合黄色顔料粉末を得た（ゲーサイ
ト含有量27重量％）。
この粉末の走査型電子顕微鏡写真（１万倍）を
第１図に示す。
なお、着色力、吸油量、隠ぺい力について以下
の如く測定した。
着色力：
べんがら（顔料）JISK5109の表２に準じ、調
製した複合黄色顔料0.3ｇ（盤状ゲーサイト粉
0.0818ｇをシリカ粉0.2182ｇに被覆）を採取し、
これにアマニ油１〜２ｇ（練り具合をみて加減）
および二酸化チタン（ルチル型）3.0ｇを加え、
鋼べらで均一になるまでガラス板上で練る。
均一なノリ状態となつたものをガラス板上に塗
布した。
この時の色の濃さを一応100とした。
つぎに、上記配合量に二酸化チタンを0.5ｇ、
1.0ｇ、1.5ｇ、2.0ｇ、2.5ｇおよび3.0ｇを追加し、
同様な操作でガラス板上に塗布した。
数値化
0.5ｇ追加の場合、0.3＋3.0／0.3＋3.0＋0.5×100＝8
7
同様に1.0ｇ追加の場合 77
〃 1.5 〃 69
〃 2.0 〃 62
〃 2.5 〃 57
〃 3.0 〃 52
とした。（標準試料）
吸油量：
顔料試験方法（JIS K5101）の19に準ずる。
試料は１ｇ採取し、鋼ベラでラセン形に巻き起
こされる程度になつた時を終点とした。
吸油量は（ml／ｇ）％の単位で表わされる。
隠ぺい力：
隠ぺい力は、次式で表わされる。
HP＝v1＋v2＋v3／ｗ・ｋ・ｌ （cm2／ｇ）
ｗ：試料重量（ｇ）
ｋ：定数（ここでは0.01）
ｌ：目盛（cm）
v1：試料体積（ｗ／ρ4.2）
v2：エアロジル体積（w1／ρ2.0）
v3：アマニ油の所要量
試料0.1ｇを秤量し、これにエアロジル（SiO2）
0.3ｇおよびアマニ油3.0mlをガラス板にとり、鋼
ベラで混練し、ノリ状態となつたものをクリプト
メーター（顔料試験方法JIS K5101図３）を使用
し、隠ぺい力を測定した。（甲法）
結果を表１に示した。
実施例 ２〜４
実施例１において、針状ゲーサイト（平均粒子
径0.5μｍ）の含有量27重量％を15重量％（実施例
２）、35重量％（実施例３）及び50重量％（実施
例４）に変えたほかは、実施例１と同様に調製し
分散性の良い複合黄色顔料を得た。走査型電子顕
微鏡写真を観察したところ、実施例４は余剰のゲ
ーサイト粒子が認められ、実施例２お及び３は相
当の着色力を与えた。吸油量は表１に示す通りで
ある。
実施例 ５
（乾式法）
実施例１と同様のゲーサイト（平均粒子径
0.18μｍ）1.5ｇ及び破砕シリカ（２〜7μｍ）4.0ｇ
を擂潰機にて30分間擂潰して複合黄色顔料粉を得
た。
その粉の走査型電子顕微鏡写真（１万倍）を第
２図に示す。また得られた黄色複合顔料粉を顔料
試験法に基いて着色力及び吸油量を調べたとこ
ろ、被覆しないものと比べて着色力は大きく、吸
油量も12重量％と良好な結果を与えた。
つぎに、実施例５で調製した複合黄色顔料粉の
0.3ｇ（盤状ゲーサイトおよびシリカは、実施例
１と同量）、二酸化チタン3.0ｇおよびアマニ油
（適量）を鋼ベラで練りガラス板上に塗布した。
この時の黄色の濃さと、先の二酸化チタン0.5ｇ
追加したものの黄色の濃さがほぼ一致するため、
表１の実施例５の着色力を90とした。結果を表１
に示す。
比較例
盤状ゲーサイト（平均粒子径0.18μｍ）1.5ｇ及
び破砕シリカ（２〜7μｍ）の混合物を顔料試験
法に基づいて着色力、吸油量並びに隠ぺい力を調
べた。
盤状ゲーサイト粉0.0818ｇおよびシリカ粉
0.2182ｇ（トータル0.3ｇ）を採取し、二酸化チ
タン3.0ｇおよびアマニ油とともに鋼ベラで練り
ガラス板上に塗布した。この時の黄色の濃さと、
先の標準試料の中の二酸化チタン3.0ｇ追加した
ものの色の濃さがほぼ一致したため、着色力50と
した。結果を表１に示す。
"Industrial Application Field" The present invention is a novel technology that uses inorganic particles (hereinafter referred to as silica particles) as cores containing 15% by weight or more of SiO 2 and on which a goethite particle layer is formed. This invention relates to a composite yellow pigment and its manufacturing method. "Prior Art" Goethite, also known as goethite, is a needle-shaped particle in both natural and synthetic forms, is light-fast, stable, and non-toxic, and has been widely used as a yellow pigment since ancient times. Since the synthesis method was invented in 1920, synthetic products with excellent properties have become widespread. Although many manufactured products are known, the one obtained by known methods is needle-shaped powder. Later, taking advantage of the characteristics of these acicular particles, they came to be used in large quantities as a raw material for magnetic recording powder. The optimum particle size of goethite as a yellow pigment is
It is in the range of 0.1 to 0.2 μm in the minor axis direction. When the size is larger than this, the dispersibility improves, but the color becomes yellow-brown, yellowish-brown,
Brown, dark brown and lightness decreases. Particle size 1μm
In the vicinity, it becomes dark brown and is unsuitable as a yellow pigment. The relationship between the particle size and color of these pigments is detailed in Nobuoka, Shikizai, 55, [10] 758 (1982). The acicular particles of 0.1 to 0.2 μm in the minor axis direction, which is the optimum particle diameter for goethite as a yellow pigment, have the major drawbacks of being fine and therefore having a large oil absorption capacity, and having strong agglomeration and poor dispersibility. If the particle size is 1 μm or more, which has good dispersibility, the color becomes dark brown and is unsuitable as a pigment. In recent years, apart from acicular goethite, ellipsoidal goethite (Special Publication No. 13975, No. 60-15580)
Publication), board game site (carpentry exam news,
vol. 29, 1985, No. 11) etc. have been proposed,
As a pigment, it still has the same drawbacks as the acicular goethite mentioned above. "Problems to be Solved by the Invention" The purpose of the present invention is to maintain the beautiful color tone, light resistance, stability, and non-toxicity of goethite as a yellow pigment, while also creating a complex yellow color with low oil absorption and excellent dispersibility. The purpose of this invention is to provide a pigment and a method for producing the same. As a result of various studies, the present inventors discovered that the above object could be achieved by forming a goethite particle layer by using silica-based particles as cores and depositing goethite on the particle surface, thereby completing the present invention. I came to the conclusion. Goethite as a composite pigment such as the one of the present invention and a method for producing the same have not yet been discovered. "Means for Solving the Problems" The present invention relates to a composite yellow pigment characterized by having silica-based particles as a core and a goethite particle layer formed on the surface thereof. Furthermore, the present invention provides a composite yellow powder characterized in that a goethite particle layer is formed on the surface of the silica particles by pulverizing silica particles in the presence of goethite particles and depositing the goethite particles on the crushed surface. This invention relates to a dry manufacturing method for pigments. The present invention also provides a wet method for producing a composite yellow pigment, which is characterized in that a goethite particle layer is formed on the surface of the silica particles by mixing, dispersing, and heating silica particles and goethite particles in an alkaline aqueous solution. It concerns the manufacturing method. The present invention will be explained in detail below. The goethite particles used in the present invention are not particularly limited as long as they have a yellow pigment. Goethite has the property of growing into acicular particles as euhedral particles, and most of them are acicular particles, but depending on the preparation conditions, non-acicular particles such as ellipsoids and discs can also be obtained. In this case, any of them may be used, and plate-shaped goethite is particularly suitable. Platy-like goethite is produced when ferric salts such as ferric chloride and ferric sulfate are reacted with alkali hydroxides such as sodium hydroxide in an aqueous medium. 2～
6) is reacted, the resulting slurry of ferric hydroxide is hydrothermally treated at 100 to 250°C, and the product is filtered from the mother liquor, washed, and dried. The particle size (disk diameter) of platy goethite can be controlled by the preparation conditions, but if the average particle size is too large, it will turn brown, so in the present invention, it is preferably 0.2 μm or less, 0.03 to 0.2 μm. used. (The limiting particle diameter of goethite is 1 μm.) However, if the goethite particles are acicular, the average minor axis diameter may preferably be 0.2 μm or less. This is because, in the case of needles, the yellow becomes darker and the brown becomes more brown due to an increase in the minor axis diameter, and an increase or decrease in the major axis diameter does not have much of an effect. In the present invention, the silica particles act as a nucleus and contribute to the dispersibility of the pigment. From this point of view, it is desirable that the average particle diameter of the silica-based particles as the core be in the range of 1 to 18 μm, particularly 3 to 15 μm. In the present invention, the silica-based particles are preferably those that do not prevent the yellowing of goethite when used as a pigment, and those that are transparent, white, or pale yellow are generally used. The silica-based particles used in the present invention, that is, the inorganic particles containing 15% by weight or more of SiO 2 , are selected from those whose particle surfaces are easily attacked by alkali, have high surface activity, are light, and are inexpensive. Examples of silica particles include silica, soda lime glass, borosilicate glass, lead glass,
There is alkali-free glass. The content of goethite in the yellow composite pigment according to the present invention is preferably 5.5%, because if it is too small, the coloring power will be reduced, and if it is too large, the dispersibility will be poor.
~40% by weight. The average particle diameter of the composite yellow pigment of the present invention, which has silica-based particles as a core and has a goethite particle layer formed on its surface, varies depending on the size of the core used, the type of goethite, manufacturing conditions, etc. Although the thickness can be changed, the thickness is 1 to 20 μm, preferably 2 to 17 μm, from the viewpoint of improving dispersibility. The composite yellow pigment according to the present invention can be produced by either a dry method or a wet method, as detailed below. (1) Dry method: When silica particles or their agglomerates and goethite powder are mixed and crushed in a dry method, the goethite is so fine that it is not crushed any further, but the solid solution is crushed and a new surface is formed, and the surface A composite yellow pigment is obtained in which the goethite powder is adhered and a goethite particle layer is formed. On a small scale, for example, when mixing and grinding are carried out using an automatic mortar, it is observed that silica-based particles easily form a nucleus and goethite powder is deposited on the surface thereof. This phenomenon occurs because during dry mixing, contact and frictional electrification occur and work effectively for adhesion. Furthermore, since the surface of the silica-based particles immediately after grinding is extremely active and has strong adsorption properties, a mechanochemical reaction is thought to occur in which the fine goethite powder is well adsorbed. Regarding these mechanisms, see Yamaguchi, Shikizai, 58, [8] 476 (1985).
It is explained in Industrially, for example, a centrifugal rotary ball mill is used. At this time, the adhesion effect is even better if it is carried out in dry air, an inert gas stream, or a vacuum. (2) Wet method: Put the core silica particles and goethite powder into an aqueous sodium hydroxide solution, mix well, and disperse. Next, heat while mixing and dispersing, usually at 50 to 90°C for 2 to 3 hours.
Then wash with water and dry. By this drying, goethite powder is uniformly adhered to the surface of the silica-based particles to obtain a composite yellow pigment in which a goethite particle layer is formed. This adhesion phenomenon occurs when the surface of the silica particles is slightly dissolved and eroded by the alkali, and a small amount of silicate such as sodium silicate acts as a glue, causing the goethite powder to adhere to the core surface. It is conceived as a thing.
As for the dispersion machine, an ultrasonic dispersion machine is good on a small scale, but
For example, an attritor (bead mill) is more suitable from an industrial perspective. The easily dispersible composite yellow pigment of the present invention obtained as described above is a new pigment that improves the characteristics of conventional pigments and takes them one step further. The composite yellow pigment of the present invention has a particle size of 1 to 20 μm.
m, which is larger than conventional pigments, so it can be used as a non-toxic yellow pigment with particularly excellent dispersibility in paints, printing inks, synthetic resins, cosmetics, building materials, paints, etc. It is particularly applicable to make-up cosmetics, synthetic resins, cement, etc. that require easy dispersion. Examples Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 (Wet method) Platy-shaped goethite (average particle size 0.18 μm, oil absorption
24%) was added to 50 ml of distilled water and dispersed using an ultrasonic disperser. Add crushed silica (2 to 7μ) to this dispersion.
After adding 8 g of m) and heating to 70°C, 150 ml of 2N NaOH aqueous solution was added while stirring, and the mixture was stirred for 2 hours. The produced yellow precipitate was washed with water, filtered, and dried to obtain a composite yellow pigment powder with better coloring power and better dispersibility than platy goethite alone (goethite content: 27% by weight). A scanning electron micrograph (10,000 times magnification) of this powder is shown in FIG. The coloring power, oil absorption, and hiding power were measured as follows. Coloring power: Red pigment (pigment) 0.3g of composite yellow pigment prepared according to Table 2 of JISK5109 (platy-shaped goethite powder)
0.0818g coated with 0.2182g of silica powder) was collected,
Add 1 to 2 g of linseed oil (adjust according to the consistency of kneading)
Add 3.0g of titanium dioxide (rutile type) and
Knead on a glass plate with a steel spatula until homogeneous. Once the paste had become uniform, it was applied onto a glass plate. The color depth at this time was set to 100. Next, add 0.5g of titanium dioxide to the above amount,
Add 1.0g, 1.5g, 2.0g, 2.5g and 3.0g,
It was coated on a glass plate using the same procedure. Numericalization If 0.5g is added, 0.3+3.0/0.3+3.0+0.5×100=8
7 Similarly, when adding 1.0g, 77 〃 1.5 〃 69 〃 2.0 〃 62 〃 2.5 〃 57 〃 3.0 〃 52. (Standard sample) Oil absorption: According to Pigment Test Method (JIS K5101) 19. 1 g of the sample was taken, and the end point was when it could be rolled up into a spiral shape with a steel spatula. Oil absorption is expressed in units of (ml/g)%. Hiding power: Hiding power is expressed by the following formula. HP=v 1 +v 2 +v 3 /w・k・l (cm 2 /g) w: Sample weight (g) k: Constant (here 0.01) l: Scale (cm) v 1 : Sample volume (w/ρ 4.2 ) v 2 : Aerosil volume (w 1 /ρ 2.0 ) v 3 : Required amount of linseed oil Weigh 0.1 g of sample and add Aerosil (SiO 2 ) to it.
0.3 g and 3.0 ml of linseed oil were placed on a glass plate, kneaded with a steel spatula, and the resulting paste was measured for hiding power using a cryptometer (pigment test method JIS K5101 Figure 3). (Method A) The results are shown in Table 1. Examples 2 to 4 In Example 1, the content of acicular goethite (average particle size 0.5 μm) was changed from 27% by weight to 15% by weight (Example 2), 35% by weight (Example 3), and 50% by weight ( A composite yellow pigment with good dispersibility was prepared in the same manner as in Example 1 except that Example 4) was used. When scanning electron micrographs were observed, excess goethite particles were observed in Example 4, and Examples 2 and 3 provided considerable tinting power. The oil absorption amount is as shown in Table 1. Example 5 (Dry method) Same goethite as in Example 1 (average particle size
0.18μm) 1.5g and crushed silica (2-7μm) 4.0g
The mixture was crushed in a crusher for 30 minutes to obtain a composite yellow pigment powder. A scanning electron micrograph (10,000x magnification) of the powder is shown in Figure 2. In addition, when the obtained yellow composite pigment powder was examined for coloring power and oil absorption based on the pigment test method, the coloring power was greater than that of the uncoated powder, and the oil absorption was 12% by weight, giving good results. Next, the composite yellow pigment powder prepared in Example 5 was prepared.
0.3 g (the same amounts of platy goethite and silica as in Example 1), 3.0 g of titanium dioxide, and linseed oil (appropriate amount) were kneaded with a steel spatula and applied onto a glass plate.
The intensity of the yellow color at this time and the 0.5g of titanium dioxide
The yellow color of the added item is almost the same, so
The coloring strength of Example 5 in Table 1 was set at 90. Table 1 shows the results.
Shown below. Comparative Example A mixture of 1.5 g of platy goethite (average particle size 0.18 μm) and crushed silica (2 to 7 μm) was examined for coloring power, oil absorption, and hiding power based on the pigment test method. Plate-shaped goethite powder 0.0818g and silica powder
0.2182 g (total 0.3 g) was collected, mixed with a steel spatula, and coated on a glass plate together with 3.0 g of titanium dioxide and linseed oil. The depth of yellow at this time,
Since the color depth of the standard sample to which 3.0g of titanium dioxide was added was almost the same, the coloring strength was set at 50. The results are shown in Table 1.
【表】
以上の結果から、単に混合した場合（比較例）
や盤状ゲーサイト単独と比べて、複合化したもの
は着色力が高いことが伺える。
「発明の効果」
以上から明らかな如く、本発明によればゲーサ
イトの黄色顔料としての色調、耐光性、安定性、
無毒性を維持とつつ、吸油性が小さく分散性に優
れた複合黄色顔料とその製造方法を提供すること
ができる。[Table] From the above results, when simply mixed (comparative example)
It can be seen that the composite material has higher coloring power than the disc-shaped goethite alone. "Effects of the Invention" As is clear from the above, according to the present invention, goethite has excellent color tone, light resistance, and stability as a yellow pigment.
It is possible to provide a composite yellow pigment that has low oil absorption and excellent dispersibility while maintaining non-toxicity, and a method for producing the same.
第１図及び第２図は本発明にかかる複合黄色顔
料の各例のシリカ系粒子の表面にゲーサイト粒子
層が形成されている粒子構造を示す走査型電子顕
微鏡写真（×10，000）である。
Figures 1 and 2 are scanning electron micrographs (x10,000) showing the particle structure in which a goethite particle layer is formed on the surface of the silica particles of each example of the composite yellow pigment according to the present invention. be.
１ 着色剤と高級脂肪酸のａ，ｂ族金属塩、
およびａ，ｂ族金属塩の酸化物を含有してな
る熱可塑性樹脂の成形加工用着色剤組成物。
1 Coloring agent and group A and B metal salts of higher fatty acids,
and a colorant composition for molding a thermoplastic resin, comprising an oxide of a metal salt of group A or group B.
Claims (1)
ることにより該無機粒子の表面にゲーサイト粒子
層を形成させることを特徴とする複合黄色顔料の
乾式製造法。 ９ SiO2分を15重量％以上含有する無機粒子と
ゲーサイト粒子とをアルカリ水溶液中において混
合、分散、加熱することによつて該無機粒子の表
面にゲーサイト粒子層を形成させることを特徴と
する複合黄色顔料の湿式製造法。A method for dry producing a composite yellow pigment, which comprises: forming a layer of goethite particles on the surface of the inorganic particles by depositing the goethite particles on the crushed surfaces of the inorganic particles. 9. A goethite particle layer is formed on the surface of the inorganic particles by mixing, dispersing, and heating inorganic particles containing 15% by weight or more of SiO 2 and goethite particles in an alkaline aqueous solution. A wet manufacturing method for a composite yellow pigment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13171986A JPS62288662A (en) | 1986-06-09 | 1986-06-09 | Complex yellow pigment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13171986A JPS62288662A (en) | 1986-06-09 | 1986-06-09 | Complex yellow pigment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62288662A JPS62288662A (en) | 1987-12-15 |
| JPH0457709B2 true JPH0457709B2 (en) | 1992-09-14 |
Family
ID=15064600
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13171986A Granted JPS62288662A (en) | 1986-06-09 | 1986-06-09 | Complex yellow pigment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62288662A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3160627B2 (en) * | 1993-04-21 | 2001-04-25 | 一 岡崎 | Fine particles and decorative plates for painting or printing |
| DE102009051171A1 (en) | 2009-10-29 | 2011-05-05 | Merck Patent Gmbh | pigments |
| DE102013012023A1 (en) | 2013-07-19 | 2015-01-22 | Merck Patent Gmbh | pigment mixture |
| EP3383957B1 (en) | 2015-11-30 | 2021-02-17 | Anomera Inc. | Cellulose-based organic pigments |
| DE102016004164A1 (en) | 2016-04-11 | 2017-10-12 | Merck Patent Gmbh | pigment mixture |
-
1986
- 1986-06-09 JP JP13171986A patent/JPS62288662A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62288662A (en) | 1987-12-15 |
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