JPH03500059A - Colored mineral pigments and uses - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Colored mineral pigments and uses 〔Technical field〕 The present invention is useful for coloring or dyeing inks, paints, plastics and rubber. Regarding pigments for use, more specifically, they are reaction products of minerals and cationic organic dyes. The present invention relates to such pigments made by

[Background technology]

Minerals serve as viscosifiers in both aqueous and aqueous systems. )% Many such as anti-settling agents, thixotropic additives or rheological additives It has been used historically in various applications. A large number of patents have been issued and they are Paints, greases, cosmetics, inks, and polyesters containing smectite-type minerals Covers esters and their uses in other fields. Also, layered silicate minerals , such as kaolinite, mica, vermiculite and smectite, It has an inherent exchange capacity for cationic compounds of both inorganic and organic types. It has been known for many years that Smectite type clay versus organic system It is this characteristic of having an inherent exchange capacity that makes it a useful addition to thixotropes. It is. Furthermore, organic cationic dyes such as methylene blue can be used to dye these minerals. It has also been known for many years that it can be used to obtain a rough measure of thione exchange capacity. there were. In this procedure, the cationic dye is exchanged at the clay surface.

Additionally, organic cationic dyes can be immobilized on any charged layered silicate minerals. It is also known that

The pigment to be colored must be capable of receiving the dye not only in the coloring stage but also in the subsequent descending stage. need to be maintained and maintained. Failure to maintain the dye reduces the efficiency of this coloring process. and discarding or recycling the colored filtrate is economically undesirable. In the prior art, substances are known that are colorants in printing inks.

For example, U.S. Pat. No. 4,410,364 describes an ink coloring material and an organophilic clay gel. Discloses a printing ink formed by dispersing a curing agent. This patent In the organophilic clay gelling agent, an organic cation, an organic anion, and It is a reaction product with kutite-type clay, and the clay has a small amount per 100g (both 7 It has a cation exchange capacity of 5 meq, resulting in an organic cation-organic anion complex. The body is inserted into the smectite clay, and the cation of the smectite clay is inserted into the smectite clay. One exchange site for the organic cation is imitated.

A series of early patents described thixotropy by the reaction of various clay minerals with cationic reagents. Disclose the agent or rheology analysis. However, these products are colorants That is, U.S. Pat. No. 4,116°866 deals with clay and quaternary ammonium Discloses reaction products with onic compounds. The clay disclosed in this patent These include bentonite and hectorite, the latter being swollen magnesium. For this reaction, the lithium-lithium silicate clay is described as Other types of smectite type I2i described in Similar products, including idellite, sabotite and stevensite, are patented in the U.S. No. 4.287.086.

U.S. Patent No. 4,216,1 to Finlayson No. 35 and No. 4.081,496 contain organophilic clays and these clays, including soil. Discloses a thixotropic polyester composition having a Kutite-type clay and methylbenzine dialkyl ammonium It is a reaction product with a substance. These products are dispersed in organic liquids to form gels. The gel can be added to the polyester composition as a gelling agent.

U.S. Patent No. 4,105.578 to Finlayson et al. An organophilic viscosity prepared as a reaction product of a clay and a quaternary ammonium compound. A soil gelling agent is disclosed. These products also have good dispersibility in organic liquids. However, it forms a gel, and is also suitable for lubricating grease, oil paste, etc. e + mud), oil-based backer liquid, paint-varnish-lacquering It is believed to be useful in paints, mold making, Sunagawa binder, etc. ).

U.S. Patent No. 2,531,440, U.S. Patent No. 2.531.427 and U.S. Patent No. 2,9 A series of earlier U.S. patents, including No. 66,506, cover modified clays compatible with organic liquids. Discloses a complex. These organoclay complexes are composed of clays, e.g. or bentonite and hectorite, and quaternary ammonium type organic compounds Contains reaction products with The clay used in this series of patents is Clay 1 Exchangeable basic 15-100 meq. per 00g. base exchange capacity in the range of It is said to have These products can be used as gelling agents (disclosure). has been done.

U.S. Pat. No. 4,382,868 discloses an organophilic compound with improved dispersibility in organic liquids. Discloses clay. This organophilic clay is a smectite clay, a quaternary cationic clay. It is prepared by extruding a mixture of organic compounds, water and alcohol. rice National Patent No. 3, 974. No. 125 Dialkyldimethylammonium quaternary salt Thixotropic agents consisting of clays reacted with and polyesters of these products The formulation is disclosed. U.S. Pat. No. 3,864,294 describes a gel-like coating. Discloses a composition comprising an amine-modified montmorillonite clay, for which swelling This product contains a lubricant and a non-volatile oily chemical to moisten the clay. It is said to be suitable for pigment-containing coating systems such as nail polish enamel compositions. There is.

JP-A-50-72926 published on June 16, 1975 describes pigments containing organic colorants. discloses a manufacturing method. These pigments have clay properties and ion exchange capabilities Obtained by dispersing minerals in water. This slurry contains an aqueous organic coloring element. The solution is added to chemically combine the resulting products, which are uncontained in the water that is recovered. Make it soluble. The clay disclosed for use in this patent is montmorillonite, Includes zeolites and bentonites. The colorant is primarily an organic dye .

European Patent Application No. 206.800 (published March 30, 1986) is a water-insoluble pigment. discloses a water-insoluble inorganic anion exchange material with a layered structure and a water-soluble Contains complexes with sex dyes. This anion exchange material with a layered structure is magnesium chloride. can include any of a number of known mineral materials, including aluminum; The dye is an organic dye.

The present invention relates to improvements over the previously known products mentioned above for coloring materials. Provide useful colored pigments.

[Disclosure of the invention]

Therefore, one of the objects of the present invention is to color inks, paints, plastics and rubber. The object of the present invention is to provide pigments useful for coloring or dyeing.

Another object of the invention is to color materials containing the reaction products of organic dyes and minerals. The goal is to provide pigments for

Yet another object of the invention is a method for preparing pigments useful for coloring or dyeing various products. The method has a small particle size and a high cation exchange capacity. Involves the reaction of minerals with cationic organic dyes.

Another object of the invention is to produce colored or dyed inks, paints, plastics and rubbers. The colorant is a cationic dye and a hectorite mineral. A pigment that is the product of a reaction with a substance, hectorite mineral has a small average particle size and It is characterized by having novel morphological properties and high cation exchange capacity.

This pigment has the same color strength as commercially available pigments and does not leach into water or oil. and can be easily dispersed in aqueous as well as organic media.

Other objects and advantages of the present invention will become apparent as the cough invention progresses.

According to the invention, coloring or dyeing inks, paints, plastics and rubbers Colored pigments useful for contains the reaction product with the hectorite mineral, which has a small average particle size and high titer. It has an on-exchange capacity.

The invention also applies to coloring or dyeing inks, paints, plastics and rubbers. The present invention also provides a method for producing pigments useful in and recovering the reaction product, wherein the mineral has a small average particle size and , has novel morphological characteristics and high cation exchange capacity, and the reaction is dry-phase. or in an aqueous medium.

According to the invention, colored or dyed printing inks, paints, plastics and rubber compositions are also provided, the compositions comprising the reaction of a cationic organic dye with a mineral. The mineral contains a colored pigment containing a product, where the mineral has a small average particle size and high cation exchange. It has a conversion capacity.

Brief description of the drawing Reference will now be made to the drawings attached to this application. Here, FIG. 1 shows the adhesive used in the present invention. Da 0! This is an enlarged photograph (40°000X) of hectorite mineral (evada), and call Figure 2 is an enlarged photo of California hectorite (4 0,0OOX).

[BEST MODE FOR CARRYING OUT THE INVENTION]

The present invention can be used to color or color a variety of materials including inks, paints, plastics and rubber. Relating to pigments useful for dyeing. This pigment is characterized by unique physicochemical properties With cationic organic dye that can be attached! @)' It is a reaction product with I. To the present invention This pigment made from It has the same color strength as organic and Ia-free pigments. Thus, the pigment of the invention is only about 40-100% of the amount required for commercially available organic and inorganic pigments. Even when used in color formulations, the color is equivalent to that of industrially used organic and inorganic additives. When treated with an appropriate amount of cationic dye, these unique pigments have a deep color. , does not seep into water or oil, and when properly crushed It was unexpectedly possible to create a pigment that is easily dispersed in any organic medium.

The pigments of the invention can be used in any application where coloring or dyeing of finished materials is desired. Wear. The main systems in which this new dye/mineral material can be used are inks and paints. , plastic and rubber.

This colored pigment can be prepared by any of a number of reaction routes, and indeed, organic reaction Materials: rheology agents, thixotropic agents, thickeners and anti-settling agents Any preparative power of the agent can be successfully utilized. End use of this new dye/mineral pigment Depending on the circumstances, some of the steps may be utilized or omitted. Thus, the book The novel pigments of the invention can be prepared by an essentially dry process or a wet slurry process. Ru. Any method that can exchange the organic dye with naturally occurring counterions on the ore Can be used to prepare foods. If high grade colored pigments are desired, additional steps, e.g. Examples include sodium exchange of clays, heating, shearing of mineral slurries, and shearing of dye/mineral products. Special drying and grinding conditions can be used. Many of these processes For the production of organoclays for silica, thixotropes, thickeners and anti-settling agents. It has been used for a long time.

However, there are many differences between the conventional organoclay material and the pigment of the present invention. You should understand that. First, known organic clays are materials that require pigment coloring. In fact, it cannot be used to impart color to materials; The base material used is often of a sufficiently high temperature that it does not interfere with color development in the system in which the organoclay is used. Selected for its high luster. The dyes/mineral pigments of the present invention are based on the systems in which they are used. chosen to give color to. Second, organoclays add viscosity to conventional acid systems. However, the dyes/mineral pigments of the present invention cause as little clay increase as possible in the systems in which they are used. You can choose as low as possible. Third, the starting materials used in organoclays are It is chosen to have the best degree of swelling when converted into the organoclay. but, In the dyes/mineral pigments of the invention, the mineral is present at any given viscosity or degree of swelling. can be chosen to give an increase of 10% or no increase at all. .

One of the important aspects of the present invention is that the minerals used to prepare the pigments include The minerals used to prepare the inventive pigments have a small particle size and extremely high cation exchange. includes any mineral that has a capacitance and a unique charge density distribution as defined herein. do. Preferred minerals are hectorite, bentonite, montmorillonite, and zeola. and mixtures thereof. The preferred mineral is hectra Also within the scope of this invention are minerals whose properties have been artificially altered.

Hectorite is known as a magnesium/lithium/silicate clay in -i ing. The hectorite used to form the products of this invention is small particle size hectorite. It has an extremely high cation exchange capacity and a unique charge density distribution. Ru. This charge density distribution can be understood or detected by the difference in the X-ray diffraction plane spacing. I can know. The interplanar spacing obtained in this measurement is based on the dimensions and charge density distribution of the molecules used. 0 Hectorite used in the present invention has this effect when treated in the same way. Gives greater spacing than other clays of the species.

The hectorite preferably used in the present invention is McDermid (McDermid). mitt), Nevada hectorite, preferably sticky It is a type of hectorite that is mined in the state and is different from other known hectorites. . This hectorite has an extremely fine grain size, and the average grain size is approximately 0.1 to 0. 6, preferably about 0.4μ. This hectorite is calcium magnesium hectorite, which means it contains more calcium than known hectorites. It means to include. This hectorite is therefore as strong as sodium hectorite. does not swell in aqueous systems, this hectorite contains large amounts of calcium and minerals. Since it contains gnesium, according to the present invention, it can be used in combination with known sodium carbonate. Exchange reaction and/or exchange reaction with sodium exchange resin to release calcium form. The resulting product, preferably converted to the sodium form, is It has a very high cation exchange capacity in the range of 110-150 meq. this The cation exchange capacity expressed in milliequivalents per 100 g of dry clay is ammonium acetate. Calculated based on the Mu/Kjeldahl cation exchange capacity test.

The hectorite preferably used in the present invention to prepare the colorant is native to Nevada. In this invention, it is described as McDermitt, Nevada hectorite. do. Second hectorite is mined as a crude product in Nevada, and is known for its clay processing. Processed into products suitable for use in the present invention by methods. That is, to the crude The chtolites are dried and crushed or ground to reduce particle size. Then this crude mineral is mixed with water and soda ash or other forms of sodium carbonate, which imparts shear forces to this mineral. Extrude through an extruder that gives.

To achieve good mixing conditions, and also replace the sodium carbonate at this point. 1 to 3 to convert at least a portion of the calcium form into the sodium form. It is preferable to extrude twice. At this stage, the optimal process then converts the resulting product into It means pulverizing it over and over again.

The second hectorite is then treated with water, usually steam, and then sieved to form coarse particles. Next, the obtained product is centrifuged to ensure that it contains only about 1 to 2% foreign matter. Remove fines so as to collect no clean clay fraction.

This hectorite has particles that are generally square or plate-like in shape; And it has a fine particle size in the range of about 0.1 to 0.6μ, which is different from other public products. It is morphologically different from the knowledge hectorite. This means that -a has a narrow tree It contrasts sharply with other hectorites in the shape of ridges.

Reference is now made to the drawings accompanying the present invention, which illustrate the adhesive structure according to the invention shown in FIG. Dahectolite is compared with the conventional type of California hectorite shown in Figure 2. It is a comparison. No. 11i (1 includes Macda dispersion in water on a mica substrate) - I would like to mention that the Mitt Nevada hectorite is shown in the diagram. Both figures showing California hectorite dispersed in water on a mosquito substrate. It is 40.0OOX. From the comparison between Figure 1 and Figure 2, the hectorite ore in Figure 1 is While stones are generally square or plate-shaped, the hectorite shown in Figure 2 is It is a long, thin product with laminar features.

The hectorite of the present invention has a charge that produces a (001) plane spacing greater than 28.5 It has density. This charge density is equal to the cation exchange capacity of the material. D(001) on the material using hydrogenated tallow ammonium chloride treatment. It is measured by X-ray diffraction based on the interplanar spacing. This measurement implements an X-ray diffraction pattern measurement. This is done by applying

Generally, as the cation exchange capacity increases, the charge density also increases. in this case The charge density of the hectorite of the present invention is so high that it is difficult to actually measure the molecule. It's so bad that he ends up standing vertically or erect during the test. Therefore, the hector used in the present invention Wright distinguishes this from other hectorite and other smectite-type minerals. It has the following characteristics. It has unexpected advantages including high cation exchange capacity. , contribute to the substantial advantages achieved in making the colorants of the present invention.

This hectorite is reacted with a dye, preferably a cationic organic dye, to produce the present invention. Form the product. The dye may be any known dye, preferably a cationic dye. These react with hectorite-based minerals. These cations The sex dyes are well known and include methyl violet, methylene blue, and Victoria blue. , rhodamine red, auramine yellow and certain dyes listed below. Contains materials.

Victoria Blue B methylene blue Methylbiolev)X rhodamine 6g red auramine yellow In a preferred method of preparation, an aqueous hectorite slurry is formed, which contains about 1- This hectorite can then contain 10% by weight of hectorite solids. Heat the slurry to about 50-100℃ while thoroughly mixing it, then dissolve the dye in water. The dye solution is then added to the slurry for about 10 minutes to 1 hour with thorough mixing. Allow time to react with hectorite. To complete this reaction, the dye/hector The light pigment is subjected to shearing action, preferably under conditions of vigorous stirring for a short period of time to produce a final This sheared material is then filtered and washed to remove excess salt. The resulting filter cake is then dried and preferably ground to a very fine powder. particle size.

One of the important aspects of the present invention is to react the colored pigments of the present invention with hectorite. The next step is to determine the amount of dye formed. Must be done to determine the amount of dye Not the preferred procedure for determining the maximum amount of dye that can adhere to a pigment The hands of the Petroleum Institute It is to use order. In order to achieve the maximum input amount of dyed rice, API RP13 Any dye can be prepared using the American Petroleum Institute procedure based on the cation exchange capacity shown in 6. It is preferable to measure the maximum amount of input material. This procedure is recommended by “Recommended Bra Kuchisu Standard Procedure Four Testing Drilling Full (Reco+++mended Practice-Staodard P rocedure for Testing Drilling Fluids )'', 3rd edition (May 1981), P. 23, chapters 9.60 and 9.61. I can put it out.

If it is not desirable to pass the maximum amount of dye through the mineral, use the following formula: be able to.

Where A: Weight of hectorite to be treated (dry weight); B: Dye to be added Mi: no equivalent number; C: equivalent weight of dye; D: Dye activity expressed as %; E: Quantity required to convert equivalent to milliequivalent; 1000; F: Dye necessary for reaction weight.

In carrying out this reaction, the water used can be tap water or deionized water. anti Although it is not necessary to heat the reaction slurry, better results are obtained by heating.

Shearing improves clay dispersibility and processing effectiveness while creating products of the invention is not required. Drying is carried out under controlled low temperature conditions to avoid excessive hardness of the material. It can prevent it from drying out. Preferably, the mixing is carried out; This provides the desired fineness for each application.

When incorporated into inks, the preferred loading is up to about 12% by weight, which This corresponds to approximately 7% by weight of hectorite in the pigment. The amount added to the plastic is It ranges from about 0.50 to 0.75% by weight.

Although the following examples are given to illustrate the invention, it is understood that the invention should not be considered to be limited by the above.

In the following examples and throughout the specification, parts are by weight unless otherwise stated.

[Example I]

Hectorite clay slurry by adding 15g of dry hectorite to water was prepared. This slurry was then heated at 80°C for 30 minutes while stirring. Ta. Then, 5.05 g of cationic methylene blue dye was prepared as an aqueous solution. This mixture was prepared and added to the hectorite clay slurry and then heated to 80"C. The mixture was heated for an additional period of time, then cooled and filtered. Thus, the dye-treated hex Trites were collected.

[Example ■]

bottom - hill 80+aeq, methyl violet (cationic dye) x dye concentration = 142. 92g; Hectorite slurry containing 2.0662% solids of 48°40 bond = 454 ．． 0g clay.

This hectorite slurry was mixed with a lightnin mixer. r) and heated to 60-80°C while mixing.

The dye number was dissolved in water to a solid content of 5%. This dye solution is then added to the Add to trito slurry and heat to 60-80°C for 30 minutes while mixing and heating to 60-80°C. Allowed to react for minutes.

This dyed hectorite pigment was then applied to a large Waring blender O1ar. Shearing was carried out for 1 minute in a mixing blender.

Pour the second sheared material onto the filter, vacuum filter, add wash water and filter. Removed excess salt. The obtained filter cake was dried at 80℃ in an open oven, and 0.062 inch on Mikro Sample Mill 4 times through a 0.020 inch round hole screen and a 0.020 inch round hole screen. It was crushed. Another sample was prepared as above and microsaved. One pass each through 0.062 and 0.020 inch round hole screens on a sample mill. It was ground by grinding. This second sample was prepared using Alpine American (Alpi). Jet milling was carried out in a 100 AFG mill at the American Co., Ltd. child Both materials were blended into polypropylene plastic and injection molded. test results The non-jet-milled sample was subjected to Gardner (Cardnet) falling weight impact. Except for polypropylene, the results showed that the results were almost comparable to polypropylene without this material; The results for the et-pulverized sample showed that the Gardner fall impact value was higher than that of unblended polypropylene. It was shown that the value of

Jet milling of methyl violet samples improved the coloring ability. I mean, The non-jet-milled sample is translucent, while the jet-milled sample is translucent. This is because the information was not transparent.

[Example ■]

This example describes the formulation and physical testing of the dye-Hectry HJI material of the present invention. and evaluated the pigment at different dosages when added to plastics. . In this evaluation, the dye-hectorite pigment was tested at two different loadings. Added to polyolefin commercially available as Himont PP6601. The dye-hectorite pigment prepared in Example 2 of the present invention was added at a dosage of 0 ．． It was added as a filler at 5wt% and 0.75wt%. Then add poly Olefins have tensile modulus, tensile yield strength, peak elongation, tensile strength at break, Bending modulus (flexible modulus) and bending strength (f Flexible strength) was evaluated as shown in Table 1. No. ■In the table, Izotsu impact strength, Gardner DWl, heat distortion temperature, density , and evaluations regarding melt flow are shown. In Table ■, filled polyolefin The fins were evaluated for color based on Hunter color values.

1st. In evaluating the data from the II and m tables, the dye of the invention - Hectorai ) The addition of II ingredients increases the physical properties of the formulation beyond the stabilized main resin. You will notice that the data show that this formulation also does not Some characteristics that must be considered when choosing a suitable industrial application, For example, elongation, notched isot, and Gardner grade. It should be mentioned that there has been a decrease in the number of patients (Bting) etc.

During these evaluations, in jet-pulverized samples such as jet-pulverized sample 11, Almost no agglomerates were observed in the sample 6, which was not jet-milled. It is also noticed that the physical properties of the jet-milled samples 11 and 11 have increased. and 12 are polar (only a few agglomerates are seen, but they are not jet-pulverized). Many aggregates were observed in Samples 5 and 6. Color density of pigment or dye appears to be significantly enhanced by jet crushing. This jet grinding Seems to expand the color system. 1st. II and ■Tables are as follows .

[Example ■]

In this evaluation, various dyes (Victoria blue, methylene blue, methyl dyes (including violet, rhodamine red and auramine yellow) - A hectorite pigment was prepared.

Samples of these dye-hectorite pigments were prepared at concentrations of 0.5 and 0.75 wt%. It was blended into Highmont PP6601. All samples contain 0 thioester ．． 075% and phenolic Goodrite 3114 It was stabilized at 0.1%. These products are shown in Table 2.

1 0.5 Victoria Blue 8 2 0, 75 Victoria Blue B 3 0.5 Methylene blue 4 0.75 Methylene blue 5 0.5 Methyl violet X 6 0.75 Methyl violet X 7 0.5 Rhodamine 60 Red 8 0, 75 Rhodamine 60 Red 9 0.5 Auramine Yellow 10 0.75 Auramine Yellow 13 Control Pure resin Highmont PP6601 control The invention has been described herein with reference to several preferred embodiments. death However, it will be obvious to those skilled in the art that obvious modifications may be made, and the present invention does not cover these modifications. It should not be thought of as limiting.

Figure 1 Figure 2 international search report

Claims (23)

[Claims] (1) Contains a reaction product of a cationic organic dye and a mineral, and the mineral has small average particles. diameter, novel morphological characteristics, and 100 to 150 meq. per 100 g of dry mineral. of High cation exchange capacity in the range and D(0 01) A colored pigment characterized by having a charge density that provides a planar spacing. (2) The pigment according to claim 1, wherein the mineral is hectorite. (3) The hectorite has an average particle size of about 0.1 to 0.6μ, and the particles are 3. A pigment according to claim 2 in a generally square or plate-like physical shape. (4) The hectorite that reacts with the organic cationic dye reacts with sodium ions. The calcium magnesium hectorite according to claim 3, which is a reacted calcium magnesium hectorite. pigment. (5) The organic cationic dye is Victoria Blue, Methylene Blue, Methyl Bai selected from the group consisting of olette, rhodamine red and auramine yellow The pigment according to claim 1. (6) Contains a reaction product of a cationic organic dye and a mineral as a coloring agent, and the mineral 100 to 1 per 100 g of dry mineral with small average particle size and novel morphological characteristics. 50meq. With high cation exchange capacity in the range of A plastic containing a pigment having a charge density that gives the measured D(001) spacing. nine. (7) The plastic according to claim 6, wherein the mineral is hectorite. (8) the hectorite has an average particle size of about 0.1 to 0.6 μ; 8. A plastic according to claim 7, which is generally square or plate-like in shape. (9) The hectorite that reacts with the organic cationic dye is made of sodium carbonate or is a calcium matrix that has been converted to the sodium form by reaction with a sodium exchange resin. The plastic according to claim 7, which is magnesium hectorite. (10) The organic cationic dye is Victoria Blue, methylene blue, methylba selected from the group consisting of iolet, rhodamine red and auramine yellow. The plastic according to claim 6. (11) The pigment according to claim 6, containing about 0.5 to 0.75% by weight of the pigment. Rustic composition. (12) A paint containing the pigment according to claim 1 as a colorant. (13) A rubber containing the pigment according to claim 1 as a colorant. (14) Reaction of cationic organic dye and Nevada hectorite mineral as a coloring agent the hectorite mineral has a small average grain size and novel morphological characteristics; 100-150 meq. per 100g of dry hectorite. High cation exchange capacity of quantity and charge giving the D(001) spacing measured by X-ray diffraction over 28.5 Å A printing ink comprising a pigment having a density. (15) A claim in which the hectorite has an average particle size in the range of about 0.1 to 0.6μ. 14. Printing ink according to item 14. (16) The hectorite that reacts with the organic cationic dye is is a calcium matrix that has been converted to the sodium form by reaction with a sodium exchange resin. 15. The printing ink according to claim 14, which is gnesium hectorite. (17) The organic cationic dye is Victoria Blue, Methylene Blue, Methylba selected from the group consisting of iolet, rhodamine red and auramine yellow. The printing ink according to claim 14. (18) Claims characterized in that the pigment is pulverized before being blended into the ink. 14. Printing ink according to item 14. (19) Contains a reaction product of an organic cationic dye and Nevada hectorite mineral, The hectorite mineral has a small average particle size, novel morphological characteristics, and dry hectorite 100-150 meq. per 100g. High cation exchange capacity of 28.5 and a charge density giving a D(001) plane spacing measured by X-ray diffraction exceeding Å. Paper or board printed with printing inks containing colored pigments. (20) A claim in which the hectorite has an average particle size in the range of about 0.1 to 0.6μ. The paper described in box 19. (21) The hectorite that reacts with the organic cationic dye is and/or converted to the sodium form by reaction with a sodium exchange resin. The paper according to claim 19, which is calcium magnesium hectorite. (22) The organic cationic dye is Victoria blue, methylene blue, methylba selected from the group consisting of iolet, rhodamine red and auramine yellow. The paper according to claim 19. (23) The pigment is jet-pulverized before being blended into the ink. Paper described in item 19.