JPH0296511A - Colored laminar compound and its production - Google Patents
Colored laminar compound and its productionInfo
- Publication number
- JPH0296511A JPH0296511A JP24738888A JP24738888A JPH0296511A JP H0296511 A JPH0296511 A JP H0296511A JP 24738888 A JP24738888 A JP 24738888A JP 24738888 A JP24738888 A JP 24738888A JP H0296511 A JPH0296511 A JP H0296511A
- Authority
- JP
- Japan
- Prior art keywords
- cation
- polynuclear complex
- colored
- dye
- clay mineral
- 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
- 150000001875 compounds Chemical class 0.000 title claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 150000001768 cations Chemical class 0.000 claims abstract description 53
- 239000002734 clay mineral Substances 0.000 claims abstract description 36
- 238000005341 cation exchange Methods 0.000 claims abstract description 13
- 239000002798 polar solvent Substances 0.000 claims abstract description 7
- 125000000129 anionic group Chemical group 0.000 claims description 19
- 238000005342 ion exchange Methods 0.000 claims description 16
- 239000011229 interlayer Substances 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims 1
- 239000000975 dye Substances 0.000 abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 238000010828 elution Methods 0.000 abstract description 10
- 229910052618 mica group Inorganic materials 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 abstract description 5
- 150000001450 anions Chemical class 0.000 abstract description 3
- 239000002537 cosmetic Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000003973 paint Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 229910052901 montmorillonite Inorganic materials 0.000 abstract description 2
- 235000019354 vermiculite Nutrition 0.000 abstract description 2
- 241000234282 Allium Species 0.000 abstract 1
- 235000002732 Allium cepa var. cepa Nutrition 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004040 coloring Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000010445 mica Substances 0.000 description 5
- XYOWBKPNPPIQLH-UHFFFAOYSA-N [Na].[Si].[Si].[Si].[Si] Chemical compound [Na].[Si].[Si].[Si].[Si] XYOWBKPNPPIQLH-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- LTGPFZWZZNUIIK-LURJTMIESA-N Lysol Chemical compound NCCCC[C@H](N)CO LTGPFZWZZNUIIK-LURJTMIESA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 2
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- -1 etc. Substances 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229940063656 aluminum chloride Drugs 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000982 direct dye Substances 0.000 description 1
- 238000007922 dissolution test Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- UJMBCXLDXJUMFB-GLCFPVLVSA-K tartrazine Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=NN(C=2C=CC(=CC=2)S([O-])(=O)=O)C(=O)C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 UJMBCXLDXJUMFB-GLCFPVLVSA-K 0.000 description 1
- 235000012756 tartrazine Nutrition 0.000 description 1
- 239000004149 tartrazine Substances 0.000 description 1
- 229960000943 tartrazine Drugs 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
Landscapes
- Cosmetics (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はカチオン交換能を有する層状化合物を主体とす
る粘土鉱物（以下層状粘土鉱物と略称する）中の層間カ
チオンを多核錯カチオンとイオン交換したのち、アニオ
ン性染料を結合させることによって得られる着色層状化
合物およびその製造方法に関する。[Detailed Description of the Invention] [Field of Industrial Application] The present invention is an ion exchange method for interlayer cations in clay minerals (hereinafter abbreviated as layered clay minerals) mainly composed of layered compounds having cation exchange ability with polynuclear complex cations. The present invention then relates to a colored layered compound obtained by binding an anionic dye and a method for producing the same.
（従来の技術）
雲母、モンモリロナイト、カオリン等のカチオン交換能
を有する層状粘土鉱物の層間カチオンとカチオン性染料
をイオン交換させることによって着色層状化合物が得ら
れることは公知である（特開昭５１−４１４４３、特開
昭５３−９６０：１４）。これらの着色層状化合物は優
れた潤滑性を有し、塗料、インキ、絵の具、化粧品等に
有用であり、さらにその色相範囲を拡大する目的でアニ
オン性染料による着色が試みられている。しかしながら
、カチオン交換能を有する層状粘土鉱物の層間カチオン
とアニオン性染料の発色団イオンとではその電荷が異な
るためイオン交換はできず、通常の方法では良好な着色
層状化合物は得られないため、いくつかの改善方法が提
案されている。例えば粘土鉱物を金属陽イオンもしくは
染料で前処理したのち、染料もしくは金属陽イオンの塩
で処理する方法（特開昭５Ｏ−１２６８４０） 、ある
いは粘土鉱物とアニオン性染料を多価金属イオンを媒体
として結合させる方法（特開昭５ｌ−４１４４４）など
がある。(Prior Art) It is known that a colored layered compound can be obtained by ion-exchanging a cationic dye with an interlayer cation of a layered clay mineral having cation-exchanging ability such as mica, montmorillonite, or kaolin (Japanese Patent Laid-Open No. 1983-1973). 41443, Japanese Unexamined Patent Publication No. 53-960:14). These colored layered compounds have excellent lubricity and are useful in paints, inks, pigments, cosmetics, etc., and attempts have been made to color them with anionic dyes in order to further expand their hue range. However, since the interlayer cations of layered clay minerals with cation exchange ability and the chromophoric ions of anionic dyes have different charges, ion exchange is not possible, and good colored layered compounds cannot be obtained using normal methods. Improvement methods have been proposed. For example, a method in which clay minerals are pretreated with metal cations or dyes and then treated with dyes or salts of metal cations (JP-A-5O-126840), or clay minerals and anionic dyes are mixed using polyvalent metal ions as a medium. There is a method of combining (Japanese Unexamined Patent Publication No. 51-41444).
従来の方法に従って、アニオン性染料により着色した着
色層状化合物は、いずれも層状化合物と染料との結合が
不充分で水等の溶媒中への染料イオンの溶出が認められ
、濃度が低下するという欠点を有していた。Colored layered compounds colored with anionic dyes according to conventional methods have the disadvantage that the bond between the layered compound and the dye is insufficient, and dye ions are eluted into solvents such as water, resulting in a decrease in concentration. It had
本発明の目的はこのような問題点を解決し、長期間の使
用に際し安定した色調を示す着色層状化合物およびその
製造方法を提供することにある。An object of the present invention is to solve these problems and provide a colored layered compound that exhibits a stable color tone during long-term use, and a method for producing the same.
本発明者らは層状化合物を主体とする粘土鉱物とアニオ
ン性染料を結合させて着色層状化合物を製造するに際し
、結合媒体として多核錯カチオンを用いることにより粘
土鉱物と染料の結合力を飛躍的に高めることができ、染
料の溶媒への溶出が無い安定した着色層状化合物が得ら
れることを見出し、本発明に到達した。The present inventors dramatically increased the bonding force between the clay mineral and the dye by using a polynuclear complex cation as a binding medium when producing a colored layered compound by bonding a clay mineral mainly composed of a layered compound with an anionic dye. The inventors have discovered that it is possible to obtain a stable colored layered compound in which dyes are not eluted into solvents, and the present invention has been achieved.
本発明の第１はカチオン交換能を有する層状化合物を主
体とする粘土鉱物中の層間カチオンが多核錯カチオンで
イオン交換され、更に該カチオンにアニオン性染料が結
合している着色層状化合物である。The first aspect of the present invention is a colored layered compound in which interlayer cations in a clay mineral mainly composed of a layered compound having cation exchange ability are ion-exchanged with a polynuclear complex cation, and an anionic dye is further bonded to the cation.
本発明の第２はカチオン交換能を有する層状化合物を主
体とする粘土鉱物を極性溶媒中に分散させ、多核錯カチ
オンの溶液を添加して反応させ粘土鉱物中の層間カチオ
ンと多核錯カチオンとをイオン交換させたのち、アニオ
ン性染料を添加、混合して反応せしめ、粘土鉱物と多核
錯カチオンおよびアニオン性染料の複合体とすることに
よる着色層状化合物の製造方法である。The second aspect of the present invention is to disperse a clay mineral mainly composed of a layered compound having cation exchange ability in a polar solvent, add a solution of a polynuclear complex cation, and react with the interlaminar cation in the clay mineral and the polynuclear complex cation. After ion exchange, an anionic dye is added, mixed, and reacted to form a complex of clay mineral, polynuclear complex cation, and anionic dye, thereby producing a colored layered compound.
本発明の着色層状化合物の原料としては、カチオン交換
能を有する天然または合成の層状粘土鉱物が用いられる
。これらの粘土鉱物の代表例としてはバーミキュライト
群、モンモリロナイト群、雲母群などの粘土鉱物が挙げ
られる。As a raw material for the colored layered compound of the present invention, a natural or synthetic layered clay mineral having cation exchange ability is used. Representative examples of these clay minerals include clay minerals such as vermiculite group, montmorillonite group, and mica group.
カチオン交換反応に用いる極性溶媒としては水、アルコ
ール類、ケトン類などが挙げられるが、特に水が好適で
ある。Examples of the polar solvent used in the cation exchange reaction include water, alcohols, ketones, etc., and water is particularly preferred.
本発明の最大の特徴は層状粘土鉱物とアニオン性染料の
結合媒体として多核錯カチオンを用いることにある６多
核錯カチオンとは二つ以上の中心金属を含む錯体をもつ
化合物の塩のイオンをいうか、本発明における多核錯カ
チオンとしては中心金属としてＡＡ 、 Ｇｒ、 Ｂｉ
、 Ｚｒなどを含む多核錯カチオンが好適である。The greatest feature of the present invention is the use of polynuclear complex cations as a binding medium for layered clay minerals and anionic dyes.6 Polynuclear complex cations refer to ions of salts of compounds having complexes containing two or more central metals. Alternatively, the polynuclear complex cation in the present invention includes AA, Gr, Bi as the central metal.
, Zr, and the like are preferred.
多核錯カチオンには種々のタイプがあり、それらの構造
は未だ完全に解明されていないが、本発明においては、
通常、上記の金属の塩の水溶液にカセイソーダ等を添加
してｐＨを調整することによって得られる多核錯カチオ
ンを使用するのが最も簡単で好ましい。この場合も得ら
れる多核錯カチオンの構造は明確ではないが金属として
ＡＡを使用すれば［八Ａ ｓ （ＯＨ） ＋２ （）１
２０） １２］”あるいは［ＡＡ １３０４ （ＯＨ）
ｚ４（Ｈ２ｃｌ） １２１’″″等の如き構造のもので
あろうと言われている。多核錯カチオンを調整するため
の金属塩としては、塩化物、硝酸塩等水溶性のものであ
ればいずれを用いても良い。既に多核錯イオンになって
いる市販の塩基性アルミニウム等を用いても良いことは
もちろんである。There are various types of polynuclear complex cations, and their structures have not yet been completely elucidated, but in the present invention,
Usually, it is easiest and preferable to use a polynuclear complex cation obtained by adding caustic soda or the like to an aqueous solution of the above-mentioned metal salt to adjust the pH. The structure of the polynuclear complex cation obtained in this case is not clear, but if AA is used as the metal, [8A s (OH) +2 ()1
20) 12]” or [AA 1304 (OH)
It is said to have a structure such as z4(H2cl) 121'''''. As the metal salt for preparing the polynuclear complex cation, any water-soluble salt such as chloride or nitrate may be used. Of course, commercially available basic aluminum or the like which is already a polynuclear complex ion may be used.
着色用の染料として使用するアニオン性染料は、一般に
染料分子中にスルホン酸基、カルボン酸基などの陰性基
を含んでおり、具体的には酸性染料、直接染料、反応染
料あるいは一部の蛍光増白剤などが使用できる。Anionic dyes used as coloring dyes generally contain negative groups such as sulfonic acid groups and carboxylic acid groups in the dye molecule, and specifically include acid dyes, direct dyes, reactive dyes, and some fluorescent dyes. Brighteners, etc. can be used.
以下本発明の着色層状化合物の製造方法について説明す
る。The method for producing the colored layered compound of the present invention will be explained below.
ます面述のカチオン交換能を有する層状粘土鉱物を必要
により十分粉砕したのち極性溶媒中に投入して撹拌する
。この段階でほとんどの粘土鉱物は膨潤し、イオン交換
の進み易い形態となる。粉砕の程度は特に限定されるも
のではないが、粘土鉱物の粒子が大きすぎるとイオン交
換反応に長時間を要するので、通常５０μ以下程度とす
るのが好ましい。使用する極性溶媒の量は、膨潤後も十
分な流動性を保つために、原料の粘土鉱物の１容量部当
りｌＯ容量部以十が好ましく、さらに好ましくは３０容
量部以上を使用する。The layered clay mineral having cation exchange ability as described above is sufficiently ground if necessary, and then put into a polar solvent and stirred. At this stage, most clay minerals swell and become in a form that facilitates ion exchange. The degree of pulverization is not particularly limited, but if the clay mineral particles are too large, the ion exchange reaction will take a long time, so it is usually preferable that the size is about 50 μm or less. The amount of polar solvent used is preferably 10 parts by volume or more, more preferably 30 parts by volume or more per 1 part by volume of the raw clay mineral, in order to maintain sufficient fluidity even after swelling.
別に、多核錯カチオンを形成する金属の塩の水溶液にカ
セイソーダ等のアルカリ水溶液を添加してｐ）Ｉを調整
することによフて多核錯カチオン溶液を調整する。最適
ｐＨは使用する金属の種類や生成する多核錯カチオンの
種類により異なるがおよそｐＨ２〜７の範囲である。Separately, a polynuclear complex cation solution is prepared by adding an alkaline aqueous solution such as caustic soda to an aqueous solution of a metal salt forming a polynuclear complex cation to adjust p)I. The optimum pH varies depending on the type of metal used and the type of polynuclear complex cation produced, but is approximately in the range of pH 2 to 7.
層状粘土鉱物の分散液に、前記のようにして調整した多
核錯カチオンの水溶液あるいは市販の多核錯カチオン化
合物の溶液を添加しイオン交換反応を行わせる。An aqueous solution of a polynuclear complex cation prepared as described above or a solution of a commercially available polynuclear complex cation compound is added to the dispersion of the layered clay mineral to carry out an ion exchange reaction.
多核錯カチオンの交換量は、層状化合物のカチオン交換
能の１〜８０％程度を置換することが望ましく、そのた
めの多核錯カチオンの使用量は、層状化合物のカチオン
交換能に対して１〜２０当量倍である。The amount of polynuclear complex cation exchanged is preferably about 1 to 80% of the cation exchange capacity of the layered compound, and the amount of polynuclear complex cation used for this purpose is 1 to 20 equivalents relative to the cation exchange capacity of the layered compound. It's double.
使用原料あるいは反応条件によってはイオン交換反応に
際し適当な界面活性剤の添加が反応の円滑な進行あるい
は最終生成物の色相改善に効果がある。イオン交換反応
を速やかかつ十分に進行させるためにイオン交換反応時
のｐＨは２〜７、好ましくは２．５〜４．５に保持する
ことが必要である。Depending on the raw materials used or the reaction conditions, addition of an appropriate surfactant during the ion exchange reaction is effective in smoothing the reaction or improving the hue of the final product. In order to allow the ion exchange reaction to proceed quickly and sufficiently, it is necessary to maintain the pH during the ion exchange reaction at 2 to 7, preferably 2.5 to 4.5.
ｐＨ２未満では粘土鉱物自体の構造が破壊される恐れが
あり、またｐＨが７を超えると多核錯カチオンの重合に
よるゲル化が起ったり、粘土鉱物のイオン交換特性が低
下するなどによってイオン交換反応が十分に進まなくな
るので好ましくない。イオン交換反応は室温から、用い
る溶媒の沸点付近まで任意の温度範囲で実施できるが、
温度が低過ぎるとイオン交換に長時間を要したり、ある
いはイオン交換がわずかしか進行しない場合もあるので
、通常は溶媒の沸点付近でかきまぜるのが好ましい。If the pH is less than 2, the structure of the clay mineral itself may be destroyed, and if the pH exceeds 7, gelation may occur due to polymerization of polynuclear complex cations, or the ion exchange properties of the clay mineral may deteriorate, resulting in ion exchange reactions. This is not preferable because it will not progress sufficiently. Ion exchange reactions can be carried out at any temperature range from room temperature to around the boiling point of the solvent used, but
If the temperature is too low, ion exchange may take a long time or ion exchange may proceed only slightly, so it is usually preferable to stir the mixture near the boiling point of the solvent.
得られた層状粘土鉱物と多核錯カチオンの結合体の分散
液あるいは必要により結合体を一旦ろ別洗浄して未反応
の多核錯カチオンを除去したのち再度極性溶媒中に分散
させた分散液にアニオン性染料の水溶液を添加し室温な
いし溶媒の沸点付近までの任意の温度範囲内で１〜２４
時間かきまぜて反応させる。アニオン性染料の使用量は
、目的物の着色濃度にもよるが、層状化合物１００重量
部に対して０．０１〜５０重量部程度を使用するのが好
ましい。反応時のｐｌ＋は２〜７が好ましい。また、必
要によりＣａ”、Ａ７３３等の金属多価イオンを添加す
ることによって、より着色を安定させることもできる。The obtained dispersion of the combined layered clay mineral and polynuclear complex cation, or if necessary, the combined body is once filtered and washed to remove unreacted polynuclear complex cations, and then the anion is added to the dispersion liquid again dispersed in a polar solvent. Add an aqueous solution of a color dye and heat it at any temperature range from room temperature to around the boiling point of the solvent.
Stir and react for some time. The amount of anionic dye to be used depends on the coloring density of the object, but it is preferably about 0.01 to 50 parts by weight based on 100 parts by weight of the layered compound. pl+ during the reaction is preferably 2 to 7. Furthermore, if necessary, the coloring can be further stabilized by adding metal multivalent ions such as Ca'' and A733.
このようにして得られた層状粘土鉱物と多核錯カチオン
およびアニオン性染料の結合体の沈澱をろ過、洗浄して
乾燥したのち所望の粒度に粉砕することによって着色層
状化合物を得ることができる。A colored layered compound can be obtained by filtering, washing and drying the thus obtained precipitate of a combination of a layered clay mineral, a polynuclear complex cation, and an anionic dye, and then pulverizing it to a desired particle size.
（実施例） 以下、実施例により本発明の内容を具体的に説明する。(Example) Hereinafter, the content of the present invention will be specifically explained with reference to Examples.
本実施例における色彩の表示方法としては日本重色工業
社製色差計ｒ ＭＯＤＥＬ−１００１０Ｐ」によりＬａ
ｂ表示系で表示した。ここで染料溶出試験は着色層状化
合物を水溶液中に１ｗｔ、％分散させ６時間煮沸させた
後ろ過乾燥し、処理前後の試料の色差（ΔＥ）を測定す
ることによって行なった。In this example, the color display method is La
Displayed using the b display system. Here, the dye elution test was conducted by dispersing the colored layered compound at 1 wt% in an aqueous solution, boiling it for 6 hours, over-drying it, and measuring the color difference (ΔE) of the sample before and after the treatment.
〈実施例１〉
塩化アルミニウム６水和物（Ａ７Ｇ）、・６＋１２０）
２３．０ｇを水５００ｄ中に溶解させたのち、ＩＮ Ｎ
ａＯＨ水溶液を加えてｐｌ＋を４．５とすることにより
アルミニウム多核錯カチオン溶液を：Ｊ！４製した。層
状粘土鉱物としてナトリウム四ケイ素雲母５０ｇを水２
１中に分散させ、室温にて２４時間かきまぜて十分膨溜
させ、得られた分散液に前記アルミニウム多核錯カチオ
ン溶液を添加し室温で１時間かきまぜた。この間ＩＮＨ
（ニア水溶液を用いてｐＨを４．５に保持した。次いで
リソールルビンＢ（４−（ｏ−スルホ−ｐトリルアゾ）
−３−ヒドロキシ−２−ナフトエ酸のナトリウム塩）
３．８７ｇを水１１に溶解させた溶液を加え８０℃にて
１時間撹拌した。ざらにｆ；ａ（：４２１．８ｇを水］
００Ｉａｆに溶解させた溶液を加え、８０℃で１時間撹
拌したのち室温にて１２時間撹拌し、生成した赤色の沈
澱物をろ過、洗浄、乾燥し、次いで粉砕することにより
赤色の着色層状化合物の粉末５Ｌｇを得た。得られた着
色層状化合物の色および前記の方法に従って染料溶出試
験を行った結果を表１に示す。<Example 1> Aluminum chloride hexahydrate (A7G), 6+120)
After dissolving 23.0g in 500d of water, IN N
By adding aOH aqueous solution and setting pl+ to 4.5, an aluminum polynuclear complex cation solution is prepared: J! 4 were made. As a layered clay mineral, add 50 g of sodium tetrasilicon mica to 2 ml of water.
1 and stirred at room temperature for 24 hours to sufficiently swell, the aluminum polynuclear complex cation solution was added to the obtained dispersion, and the solution was stirred at room temperature for 1 hour. During this time INH
(The pH was maintained at 4.5 using an aqueous solution of lysolrubin B (4-(o-sulfo-p-tolylazo)).
-3-hydroxy-2-naphthoic acid sodium salt)
A solution of 3.87 g dissolved in water 11 was added and stirred at 80° C. for 1 hour. Rough f;a (: 421.8g water)
A solution dissolved in 00Iaf was added, stirred at 80°C for 1 hour and then at room temperature for 12 hours, and the red precipitate formed was filtered, washed, dried, and then ground to obtain a red colored layered compound. 5Lg of powder was obtained. Table 1 shows the color of the colored layered compound obtained and the results of a dye elution test conducted according to the method described above.
〈実施例２）
実施例１のナトリウム四ケイ素雲母５０ｇの代わりにベ
ントナイト（クニミネ工業社製りニピャ）５０ｇを用い
て同様の操作を行なって着色層状化合物を得た。また同
様に染料溶出試験を行なった。<Example 2> A colored layered compound was obtained by carrying out the same operation using 50 g of bentonite (Nipya manufactured by Kunimine Kogyo Co., Ltd.) in place of 50 g of sodium tetrasilicon mica in Example 1. A dye elution test was also conducted in the same manner.
その結果を表１に示す。The results are shown in Table 1.
（実施例３〜４〉
実施例１のリソールルビンＢの代わりにブリリアントブ
ルーＦＣＦおよびタートラジンをそれぞれ３．３１ｇお
よび２．５３ｇずつ用いて同様の操作を行なって着色層
状化合物を得た。また同様に染料溶出試験を行ないその
結果を表１に示す。(Examples 3 to 4) A colored layered compound was obtained by performing the same operation using 3.31 g and 2.53 g of Brilliant Blue FCF and 2.53 g of tartrazine, respectively, in place of Lysol Rubin B in Example 1. A dissolution test was conducted and the results are shown in Table 1.
（実施例５）
実施例１においてアルミニウム多核錯カチオンを合成す
る代わりに市販の塩基性塩化アルミニウム（多水化学社
製 タキパイン＄１５００） ２０．７ｇを用いて同様
の操作を行なフて着色層状化合物を得た。また同様に染
料溶出試験を行なった。その結果を表１に示す。(Example 5) Instead of synthesizing the aluminum polynuclear complex cation in Example 1, 20.7 g of commercially available basic aluminum chloride (Tachypain, manufactured by Tasui Kagaku Co., Ltd., $1500) was used and the same operation was carried out to form a colored layer. The compound was obtained. A dye elution test was also conducted in the same manner. The results are shown in Table 1.
（実施例６〉
ナトリウム四ケイ素雲母を膨潤させるための水およびリ
ソールルビンＢを溶解させるための水の代わりに、それ
ぞれメタノール２ＩｌおよびＩＩＬを使用し、８０℃で
の撹拌を５０℃に替えたほかは実施例１と同様に操作し
、赤色の着色層状化合物５１．５ｇを得た。このものの
染料溶出試験の結果は表１のとおりであった。(Example 6) Methanol 2Il and IIL were used instead of water for swelling sodium tetrasilicon mica and water for dissolving Lysol Rubine B, respectively, and stirring at 80°C was replaced with 50°C. The same procedure as in Example 1 was carried out to obtain 51.5 g of a red colored layered compound.The results of the dye elution test for this compound were as shown in Table 1.
〈比較例１）
ナトリウム四ケイ素雲母５０ｇを水２２中に分散させ、
室温にて２４時間撹拌し十分膨潤させた。得られた分散
液にあらかじめリソールルビン８３．８７ｇを水ｌＩＬ
に溶解させた溶液を添加し、つづいて撹拌しながら塩化
アルミニウム六水和物２３．０ｇを水５００ｍ１に溶解
した水溶液を加えて８０℃にて１時間、さらに室温にて
１２時間撹拌し、生成した赤色の沈澱物をろ過、洗浄、
乾燥し、次いで粉砕することにより約５１ｇの赤色層状
化合物を得た。このものの色調および染料溶出試験結果
を表２に示す。表２の結果から従来の結合媒体として多
価金属イオンを用いて酸性染料とカチオン交換能を有す
る粘土鉱物を結合させる方法に従って得られた本比較例
の着色層状化合物は溶出試験前後の色差（ΔＥ）が大き
く、層状化合物と染料との結合が弱く洗浄による染料の
溶出量が多いことがわかる。<Comparative Example 1) 50 g of sodium tetrasilicon mica was dispersed in 22 ml of water,
The mixture was stirred at room temperature for 24 hours to allow sufficient swelling. Add 83.87 g of Lysol Rubin to the resulting dispersion in advance and add 1 L of water.
Then, with stirring, an aqueous solution of 23.0 g of aluminum chloride hexahydrate dissolved in 500 ml of water was added, and the mixture was stirred at 80°C for 1 hour and then at room temperature for 12 hours to produce a Filter and wash the red precipitate.
Approximately 51 g of a red layered compound was obtained by drying and then grinding. The color tone and dye elution test results of this product are shown in Table 2. From the results in Table 2, the colored layered compound of this comparative example obtained according to the conventional method of binding an acidic dye and a clay mineral having cation exchange ability using polyvalent metal ions as a binding medium has a color difference (ΔE) before and after the elution test. ) is large, indicating that the bond between the layered compound and the dye is weak and the amount of dye eluted by washing is large.
これにくらべて、本発明の着色層状化合物の場合は、表
１に示す如く、溶出試験前後の色差（ΔＥ）がきわめて
小さく、層状化合物と染料との結合が顕著に強くなって
いることがわかる。In comparison, in the case of the colored layered compound of the present invention, as shown in Table 1, the color difference (ΔE) before and after the elution test is extremely small, indicating that the bond between the layered compound and the dye is significantly stronger. .
（発明の効果）
本発明の着色層状化合物は層状粘土鉱物がもっているカ
チオン吸着座席に、−旦多核錯カチオンを吸着させ層間
を広げた後、多核錯カチオンの持っているアニオン吸着
座席にアニオン性染料を吸着させて得られるものである
。(Effects of the Invention) The colored layered compound of the present invention first adsorbs polynuclear complex cations to the cation adsorption seats possessed by the layered clay mineral to widen the interlayer gap, and then adsorbs the anionic complex cations to the anion adsorption seats possessed by the polynuclear complex cations. It is obtained by adsorbing dye.
従来、提案されていた多価金属イオンを用いる方法等で
は層状粘土鉱物の層間距離があまり拡がらず（約９人前
後）、かつ多価金属イオンとアニオン性染料の結合が弱
く、得られた着色化合物は洗浄を繰り返すことによって
染料が徐々に溶出し、最終的にはほとんど無彩色となっ
てしまう。In the previously proposed methods using polyvalent metal ions, the distance between the layers of layered clay minerals did not increase much (about 9 people), and the bond between the polyvalent metal ions and anionic dye was weak, resulting in poor results. As the colored compound is repeatedly washed, the dye gradually dissolves out, and in the end it becomes almost achromatic.
しかし、本発明の多核錯カチオンを用いる方法では層間
がかなり拡がり（約１４人前後）さらに多核錯カチオン
とアニオン性染料との結合も強いため、得られた着色化
合物は彩やかでかつ染料の溶出がないという特性を有し
ている。However, in the method using the polynuclear complex cation of the present invention, the interlayer distance is considerably widened (approximately 14 people), and the bond between the polynuclear complex cation and the anionic dye is also strong, so the colored compound obtained is colorful and has a strong dyestuff. It has the characteristic of no elution.
また染料を複数種組合わせて使用し、その比率を変える
ことによって任意の色相の層状化合物を得ることができ
る。Furthermore, by using a combination of a plurality of dyes and changing the ratio, a layered compound of any hue can be obtained.
本発明の着色層状化合物は今まで得られなかった色調の
、彩かで安定した発色を示し、しかも潤滑性を有する色
材であり、塗料、インク、絵の具、化粧品等の着色材と
して有用なものである。The colored layered compound of the present invention is a coloring material that exhibits a colorful and stable coloring that has not been available until now, and has lubricating properties, and is useful as a coloring material for paints, inks, pigments, cosmetics, etc. It is.
特許出願人 三井鉱山株式会社Patent applicant: Mitsui Mining Co., Ltd.
Claims (2)
粘土鉱物中の層間カチオンが多核錯カチオンで交換され
、更に該カチオンにアニオン性染料が結合していること
を特徴とする着色層状化合物。(1) A colored layered compound characterized in that interlayer cations in a clay mineral mainly composed of a layered compound having cation exchange ability are exchanged with a polynuclear complex cation, and an anionic dye is further bonded to the cation.
粘土鉱物を極性溶媒中に分散させ、多核錯カチオンの溶
液を添加して反応させ粘土鉱物中の層間カチオンと多核
錯カチオンとをイオン交換させたのち、アニオン性染料
を添加、混合して反応せしめ、粘土鉱物と多核錯カチオ
ンおよびアニオン性染料の複合体とすることを特徴とす
る着色層状化合物の製造方法。(2) Clay minerals mainly composed of layered compounds with cation exchange ability are dispersed in a polar solvent, and a solution of polynuclear complex cations is added and reacted to cause ion exchange between the interlaminar cations in the clay mineral and the polynuclear complex cations. A method for producing a colored layered compound, characterized in that an anionic dye is then added, mixed, and reacted to form a composite of a clay mineral, a polynuclear complex cation, and an anionic dye.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24738888A JPH0296511A (en) | 1988-10-03 | 1988-10-03 | Colored laminar compound and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24738888A JPH0296511A (en) | 1988-10-03 | 1988-10-03 | Colored laminar compound and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0296511A true JPH0296511A (en) | 1990-04-09 |
Family
ID=17162688
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24738888A Pending JPH0296511A (en) | 1988-10-03 | 1988-10-03 | Colored laminar compound and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0296511A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013133091A1 (en) * | 2012-03-07 | 2013-09-12 | 株式会社ヤマグチマイカ | Thixotropic agent and method for producing same |
-
1988
- 1988-10-03 JP JP24738888A patent/JPH0296511A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013133091A1 (en) * | 2012-03-07 | 2013-09-12 | 株式会社ヤマグチマイカ | Thixotropic agent and method for producing same |
| JP2013185061A (en) * | 2012-03-07 | 2013-09-19 | Yamaguchi Mica Co Ltd | Thixotropic agent and method for producing the same |
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