CN1047681A

CN1047681A - Painted mineral color and application

Info

Publication number: CN1047681A
Application number: CN89103635A
Authority: CN
Inventors: 戴维·休·德拉姆
Original assignee: JM Huber Corp
Current assignee: JM Huber Corp
Priority date: 1988-04-05
Filing date: 1989-05-29
Publication date: 1990-12-12
Also published as: WO1989009804A1; JPH03500059A; EP0363471A4; EP0363471A1; AU3449789A

Abstract

A kind of to be used for printing ink, coating, plastics and rubber dyeing or painted tinting pigment be positively charged ion organic dye and mineral, preferably the reaction product of hectorite.These mineral have very thin mean particle size and very high cation exchange capacity (CEC).This pigment has good colouring intensity, can imbibition in water or oil, and be easy to be dispersed in the aqueous solution and the organic medium.

Description

Painted mineral color and application

The present invention relates to be used for the pigment of printing ink, coating, plastics and rubber coloring, relate in particular to by as mineral and positively charged ion organic dye reaction product and this class pigment of making.

Always mineral have many purposes, such as all making tackifier, antisettling agent, thixotrope or rheologic additive at the aqueous solution and organic system.The many patents that relate to the mineral purposes disclosed, and comprised that the montmorillonite type mineral are in coating, lubricating grease, makeup, printing ink, polyester and other Application for Field.Also known for many years, layer silicate mineral such as kaolin, mica, vermiculite and montmorillonite and so on have natural exchange capacity to the cation compound of inorganic or organic type.This just natural exchange capacity characteristic makes the clay of smectites become organic system thixotrope of great use.Know also that for many years the organic cation dye resemble the methylenum coeruleum can be used for obtaining the approximate measure of the cation exchange capacity of these mineral.In this step, organic cation dye is switched on the surface of clay.Know that also organic cation dye can be fixed to anyly to has on the ionic layer silicate mineral.

Treat that painted pigment not only must admit and keep dyestuff in the dyeing stage but also in the follow-up process segment.Keep incessantly that dyestuff can lower treatment effect, and the recirculation of painted filtrate or dispose uneconomical economically.

The product of knowing in the prior art is the tinting material of printing-ink, and for example United States Patent (USP) discloses a kind of printing-ink No. 4410364, and it is made up of the ink colorant and a kind of organophilic clay gelling agent that are dispersed in the printing ink.In this patent, organophilic clay gelling agent is the reaction product by organic cation, organic anion and polynite type clay.The cation exchange capacity (CEC) of this polynite type clay is that per 100 gram clays have 75 milligramequivalents at least, so that organic cation one organic anion complex compound can be added in the polynite type clay, the cation exchange site of the clay of polynite type simultaneously, is replaced by organic cation.

A series of patent disclosures more early draw thixotropic agent or rheological agent by various clay minerals and cationoid reagent reaction, still, these products are not tinting materials.Therefore, United States Patent (USP) discloses the reactor product of a kind of clay and quaternary ammonium cation compound for No. 4116866.Disclosed clay has wilkinite and hectorite in this patent, and the latter is stated as a kind of swollen magnesium-lithium silicates clay.In this patent, other polynite type clay that is disclosed that is used to react comprises: polynite, beidellite, talcum powder and rich magnesium montmorillonite.A kind of similar product is disclosed in No. 4287086, United States Patent (USP).

The United States Patent (USP) of authorizing Fen Laixun (Finlayson) discloses organophilic clay and the thixotropy polymer blend that contains these clays for No. 4216135 and No. 4081496.This product is the reaction product of a kind of polynite type clay and xylyl dialkyl ammonium compound.Allegedly these products are dispersed in and form gel in the organic liquor, and this gel can be used as jelling agent and is added in the polymer blend.

The United States Patent (USP) of authorizing people such as Fen Laixun discloses the organophilic clay gelling agent with the reaction product preparation of polynite type clay and quarternary ammonium salt compound for No. 4105578.It is said that these products also have good dispersiveness in organic liquor, and form gel, be used for lubricating grease, ointment mud, oil base packing liquid, coating-varnish-lacquer simultaneously and remove agent, coating and casting type sand adhesvie etc.

A series of older United States Patent (USP)s comprise United States Patent (USP) to disclose the modified clay mixture No. 2531440, No. 2531427 and No. 2966506 that these mixtures and organic liquid phase are miscible.These organoclay composites if you would take off soil by a kind of clay or wilkinite is formed with the reaction product that comprises hectorite and a kind of quaternary ammonium type organic compound.The clay that allegedly is used in this series of patents has the most basic exchange capacity, and its scope approximately is 15-100 milligramequivalent/100 gram clays.Disclosed these products are as jelling agent.

United States Patent (USP) disclose for No. 4382868 organophilic clay in organic liquor, can improve dispersed, these organophilic clays be by montmorillonite clay, season positively charged ion organic compound, water and a kind of mixture extruding of alcohol form.United States Patent (USP) discloses a kind of thixotropic agent that contains clay for No. 3974125, and this clay reacts with the dialkyl dimethyl quaternary ammonium, and this product is mixed in the polyester.United States Patent (USP) discloses a kind of colloidal state coating composition for No. 3864294, and the non-volatile finish that it is a kind of swelling and a kind of wetting this clay by a kind of amine modification illiteracy unsticking soil is formed.This product can be used for containing the coating system of pigment, as is used for enamel composition.

Application number 50-72926, date of publication are the announcement on June 16th, 1975 but uncensored Japanese Patent discloses a kind of manufacture method that contains the pigment of organic colorant.These pigment are to make by a kind of mineral with clay property and ion-exchange capacity are dispersed in the water.A kind of aqueous solution of organic coloring composition is added in these slurries,, simultaneously, from water, water-fast resultant is extracted, so just it has been reclaimed to produce chemical bonding.The clay that is used in this patent according to announcement comprises polynite, zeolite and wilkinite.The most basic tinting material is an organic dye.

The application number of announcing on March 30th, 1986 is that 206800 European patent discloses a kind of water-insoluble pigment, it by have laminate structure, the material of water-insoluble inorganic anion exchange and a kind of mixture of water-soluble dye formed.This anionresin material with laminate structure can comprise any in many essential minerals, comprise the chlorination magnalium, and this dyestuff is an organic dye.

The invention provides a kind of tinting pigment that is used for coloring material, this product is a kind of improvement to above-mentioned prior art known product.

One of purpose of the present invention provides a kind of pigment, is used for the dyeing of printing ink, coating, plastics and rubber or painted.

Two of purpose of the present invention provides a kind of pigment that is used for tinting material, and it comprises the reaction product of a kind of organic dye and a kind of mineral.

Three of purpose of the present invention provides the preparation method of pigment.This class pigment is used for the dyeing of various products or painted, and this method comprises that the mineral and a kind of cationic organic dye that make a kind of small grain size and high-cation exchange capacity react.

Four of purpose of the present invention provides painted or painted printing ink, coating, plastics and rubber, and wherein, tinting material is a kind of pigment, and it is the reaction product of positively charged ion organic dye and hectorite mineral.These hectorite mineral are characterised in that to have very thin mean particle size, novel form and high-cation exchange capacity very.The colouring intensity of this pigment is equivalent to industrial pigment, and can imbibition in water or oil, and simultaneously, it is easy to be dispersed in the aqueous solution and the organic medium.Along with the narration of process, other purpose of the present invention and advantage will become apparent.

The invention provides a kind of printing ink, coating, plastics and rubber dyeing or painted tinting pigment of being used for.This pigment is the reaction product that comprises a kind of positively charged ion organic dye and a kind of mineral.This mineral are the hectorite mineral preferably, and these mineral will have very thin mean particle size and high-cation exchange capacity very.

The present invention also provides a kind of preparation method who is used for printing ink, coating, plastics and rubber dyeing or painted pigment.This method comprises makes a kind of positively charged ion organic dye and the reaction of a kind of mineral.These mineral have the form and the very high cation exchange capacity (CEC) of very thin mean particle size, novelty.This is reflected in dry state or the water medium and carries out, and then, reclaims this reaction product.

The present invention also provides painted or painted printing-ink, coating, plastics and rubber combination.Above-mentioned composition has comprised a kind of tinting pigment, and this pigment is a kind of positively charged ion organic dye and a kind of reaction product with mineral of very thin mean particle size and very high cation exchange capacity (CEC).

Now the accompanying drawing of the application's book is done following explanation:

Fig. 1 is the enlarged photograph (40000 times) of Nevada used in this invention hectorite mineral

Fig. 2 is the enlarged photograph (40000 times) of California hectorite

The present invention relates to a kind of pigment, the various materials of Yong Yu comprise dyeing or the look of You China ink, coating, plastics and rubber. Zhe pigment is the product of cation You organic dye and mineral. These mineral are characterised in that the physico-chemical property that it is unique. The pigment that the present invention produces, its price is lower and have a colouring intensity identical with inorganic pigment with the You machine of industry. Therefore, when Yong Zai Zai colo(u)r specification Zhi needed industry amount inorganic or organic pigment to be about 40-100%, this paint color intensity equaled You machine and the inorganic pigment of industrial Yong. Simultaneously, be surprised to find that also that the some unique pigment of Zhe can imbibition Zai water or You Zhong, when an amount of dye of positive ion of Yong was processed, when suitably grinding simultaneously, the pigment that generates was easy to be dispersed in water and organic media Zhong.

Can the Yong Yu any Yong of pigment of the present invention way, final products are colored or the look there.

Zhu Yao is that You China ink, coating, plastics and rubber can use this reactive monoazo dyestuffs/coloring earth.

This dyeing pigment can the many reaction paths of Yong anyly come Zhi standby. And thing All Preparation Methods processed can both successfully use reaction material-rheological agent, thixotropic agent, tackify agent or the antisettling agent of You machine on the reality. According to Zui Zhong Yong way of this reactive monoazo dyestuffs/coloring earth, some step can Yong, also can. Therefore, new pigment can Yong one Zhong be that the method for dry method or a kind of wet pulp liquid comes Zhi to get basically. The Zao Zhong processed of Zai pigment, any can make organic dye Yu on the mineral method of the counter ion of natural generation exchange can both use. If need high-quality dyeing pigment, some additional steps all can use such as the drying of the shearing of the shearing of the sodium exchange of Nian soil, heating, mineral slurry, dyeing mineral products or Zhuan door and pulverizing etc. For the organic clay of Zao Yong Yu rheological agent processed, tackify agent and antisettling agent, many steps of a little step Zhong of Zhe, general equal the employing.

, there are many differences between Zhi must understanding the organic clay of above disclosed prior art and pigment of the present invention. The first, the organic clay of prior art can not go by next color is added to Zhong those materials that need to dye of Yong. In fact Zai system Zhong Yong, usually the basic substance with the enough strong brightness of Zu is elected to be organic clay, so that during to organic clay, can not disturb the development of color. And dyestuff/coloring earth of the present invention is the material that color can be provided when selecting those Zai systems Zhong to use them. The second, organic clay is to make the system tackify usually, and dyestuff/coloring earth of the present invention when Zai system Zhong uses them, makes system viscosity Zeng add as much as possible little. The 3rd, the initiation material of Yong Zai organic clay Zhong normally selects those swellabilities the best, so that Zhuan changes into organic clay,, Zai dyestuff of the present invention/coloring earth Zhong, selected ore the most fortunately Nian or swellability aspect Zhi You slightly Zeng add or even do not have Zeng to add at all.

Of the present invention one want very much aspect Zai Yu Yong mineral of Chong come the standby pigment of Zhi. The mineral of the standby pigment of Yong Yu Zhi comprise anyly having very thin granularity, very high cation exchange capacity (CEC) according to the present invention, and the mineral that are defined as uniform Density Distribution in the Zhe. Therefore, the best mineral are selected from hectorite, bentonite, imvite, zeolite etc. and their mixture. The water brightness Stone is the best mineral. The mineral that changed artificially its characteristic also belong to scope of the present invention.

In general, the Zhou Zhi of Zhong institute hectorite is magnesium/Li/silicate clay. It is the small grain size hectorite that Yong comes the hectorite of the standby product of the present invention of Zhi, and it has very high cation exchange capacity (CEC), and has well-proportioned load density distribution. Load density distributes and can estimate, and difference that also can Yong X-ray diffraction detects. The spacing of this measurement gained of Yong is that the used molecular size of Yu and load density are distributed with the pass. When the identical method of Yong was processed, the used hectorite of the present invention had consisted of more much bigger spacing than other Nian soil of Zhe class.

The hectorite of Yong Zai Zhong of the present invention is the best to be Mike De Mite (McDermitt), the Nevada hectorite, it is the typical ore of the easy exploitation of state of Nevada Zui, it with form Yu other known hectorite is not all feature. The granularity of this hectorite is very thin, and particle mean size approximately is the 0.1-0.6 micron, and optimal average particle size Yue is 0.4 micron. This hectorite is a kind of calcium-magnesium hectorite, this means that it contains more substantial calcium than the hectorite of routine. Therefore, this hectorite do not resemble can expand Zhong the Zai water solution system the sodium hectorite so much. This hectorite Zhong of You Yu Zai contains a large amount of calcium and magnesium, carries out conventional exchange reaction according to the best it and sodium carbonate and/or sodium exchanger resin of making of the present invention, makes it to become the sodium type from calcium type Zhuan. The product that generates has very high cation exchange capacity (CEC), that is, and and the commutative 110-150 milliequivalent of per 100 gram dry clays. Cation exchange capacity (CEC) (the milliequivalent numerical table with 100 gram dry clays shows) is according to Ammonium Acetate-Kjeldahl Cation Exchange Capacity experiment calculation.

Only found to be used for the best hectorite of the present invention's preparation tinting material in the state of Nevada, the present invention is called Mike De Mite, the Nevada hectorite.This hectorite is exploited out as original prod in the locality, Nevada, then, processes by the clay course of processing of routine, to obtain to be applicable to product of the present invention.Therefore, this hectorite raw ore is dried, crushes or grinds, to reduce its granularity.After this, this raw ore mixes mutually with the yellow soda ash of water, alkali end or other form again, by extrusion machine it is extruded, and extrudate is cut into starting material with shears.For the material that obtains mixing, preferably extrude about 1-3 time, simultaneously, this stage also because of and the yellow soda ash permutoid reaction, make a part of calcium type transform into the sodium type at least.In this stage arbitrary step on probation, grind this resultant again.

Then, hectorite is contacted usually with water under steam, rescreen coarse particles.The product that generates centrifugation again removes fine powder, so that reclaim clean clay composition, its foreign matter content is not more than about 1-2%.

The form of this hectorite is different from other hectorite of prior art, that is, this hectorite particle generally is being quadrate or is resembling plate shapedly that the mean particle size of powdered granule approximately is between the 0.1-0.6 micron in shape.This and other hectorite differs widely, and in general, other hectorite is the narrow boards stripe shape.

With reference to accompanying drawing of the present invention.Fig. 1 is a Nevada of the present invention hectorite, and Fig. 2 is California hectorite of prior art, and these two kinds of hectorites differ widely.Fig. 1 is Mike De Mite, and the Nevada hectorite places the water on the mica backing plate, and Fig. 2 is that California hectorite places the water on the mica backing plate.These two pictures all are to amplify 40000 times.From Fig. 1 and Fig. 2 more as can be seen, in general, in shape, the hectorite ore deposit of Fig. 1 is square or resembles plate shapedly that and the hectorite of Fig. 2 is long narrow product, it has the feature that resembles strap.

Hectorite of the present invention has the load density that causes producing greater than the space D (001) of 28.5 dusts.With the X-ray diffraction at mineral D(001) load density measured on the face, mineral are handled with dimethyl dihydro tallow ammonium chloride during measurement, are equivalent to the cation exchange capacity of this material.This mensuration is to be undertaken by continuous X-ray grating spectrum.When cation exchange capacity increases, load density also will increase substantially.In the case, during measuring, to such an extent as to that the load density of hectorite of the present invention is that in fact so high molecule can become is vertical or axial.Therefore, hectorite used in this invention has a lot of features, and it is different from other mineral of hectorite and polynite type.Usually, this is very favourable, comprises very high cation exchange capacity (CEC), and when forming tinting material of the present invention, it has played the effect that realizes desired result.

This hectorite and a kind of dyestuff preferably positively charged ion organic dye react to generate product of the present invention.The dyestuff of energy and hectorite raw material reaction can be any conventional dyestuff, still, and preferably a kind of cationic dyestuff.These cationic dyestuff are known, and comprise following material: methyl violet, and methylenum coeruleum, victoria blue, rhodamine reds, auramine and following dedicated dye:

Victoria blue B

Methylenum coeruleum

Methyl violet X

Rhodamine reds 6G

Auramine

In a kind of preferred preparation method, the hectorite slurries of formation, its solid content is about 1-10%(weight).Then, these hectorite slurries are heated to about 50-100 ℃ under the good mixing condition, simultaneously, dyestuff is dissolved in the water, then this dye solution is joined in the hectorite slurries, make it under well blend, reacted about 10 minutes to 1 hour with hectorite.After reaction was finished, this dyestuff/hectorite pigment was preferably in the shearing of following short period of time of high-speed stirring, to reach last mixing.Then, the filtration of material that this was sheared, washing is to remove superfluous salt.Then, filtration cakes torrefaction, preferably be ground into very thin particle.

An importance of the present invention is to measure the amount of dyestuff, and it is to form tinting pigment of the present invention with the hectorite reaction.The best method of measuring amount of dye is to use the method for American Petroleum Institute (API) (API) to measure the maximum amount of dye that pigment can reach.In order to realize importing maximum amount of dye, preferably the maximum of measuring any dyestuff with the method for American Petroleum Institute (API) is carried colo(u)r specification, and this method is based on the described cation exchange capacity (CEC) of API RP13b.This method can be referring to " the practical standard method of recommendation is used to test drilling fluid " (Recommended Practice-Standard Procedure for Testing Drilling Fluids ") the 8th edition (in May, 1981), the 23rd page, 9.60 and 9.61 sections.

If can not use maximum amount of dye method well to mineral, so, also available following formula is measured:

(（A）（B）（C）)/(（D）（E）) ＝（F）

In the formula:

A=hectorite weight to be measured (butt)

The milligramequivalent number of the dyestuff that B=added

The suitable weight of this dyestuff of C=

The activity of D=dyestuff is represented with percentage ratio

E=1000(changes into millinormal transformation ratio from gram equivalent)

The dyestuff weight that the F=reaction is required

When carrying out this reaction, used water can be tap water or deionized water.Need not to heat this reacting slurry, but resultant is to want heat supply preferably.Shearing has improved this Dispersion of Clay and treatment effect, but is not deciding factor for producing this product.Under controlled cold condition, carry out drying, in drying, become really up to the mark to prevent material.Preferably grind, to obtain the required fine powder of each purposes.

When in being incorporated into printing ink, going, best loading level with height to about 12%(weight) it is equivalent to that 7%(weight is arranged in the final pigment approximately) and hectorite.Its loading level scope in plastics approximately is 0.5% to 0.75%(weight).

Following example is used for illustrating the present invention, rather than is limited.Except as otherwise noted, at example and whole declaratives, all be to be unit with weight.

Example 1

A kind of hectorite clay slurry is to make by 15 gram solid carbon dioxide pyroxenes are added in the entry.Then, these slurries are under agitation in 80 ℃ of heating 30 minutes.Then, get the cationic MBD of 5.05 grams and make it to form a kind of aqueous solution, and add in the hectorite clay slurry.At 80 ℃ heating one-period, filter again by cooling for this mixture.Reclaim this dyestuff treated water pyroxene at last.

Example 2

Composition:

80 milligramequivalent methyl violet (cationic dyestuff) * dye strengths=142.92 grams

48.40 the pound solids content is hectorite slurries=454.0 gram clays of 2.0662%

These hectorite slurries are heated to 60-80 ℃, in Lai Tening (Lightnin) mixing tank, mix simultaneously

This dyestuff is dissolved in the water, and solids content is 5%.Then, this dye solution is added in the hectorite slurries, and 60-80 ℃ of following reacting by heating 30 minutes.

After this, this painted hectorite pigment was sheared 1 minute in a large-scale Wo Lin (Waring) mixing tank.

The material of shearing is poured into strainer, vacuum filtration, the salt of water flush away surplus simultaneously.This filter cake is put into stove, 80 ℃ of dryings, then it is ground, and crosses the aperture and be 0.062 inch sieve, and again in sieve's Mike sample mill (Mikro Sampl Mill), four times is 0.020 inch sieve by an aperture.Making another duplicate samples according to last method, and grind in sieve's Mike sample mill, only once is the sieve of 0.062 inch and 0.020 inch by the aperture.This second duplicate samples in the 100AFG of A Erpei America company (Alpine American Corporation) mill by abrasive blasting.These two parts of materials are blended in the acrylic plastering, simultaneously spray up n..Test result shows, except drip heavy effect Gardner (Gardner) aspect, have the difference, it is suitable that the character of not abrasive blasting sample is compared with the polypropylene of not filling, and the Gardner that the abrasive blasting sample increases is dripped polyacrylic Gardner that heavy effect also comes not filling and dripped heavily after the value.

Because the sample of not abrasive blasting is transparent, and the sample of abrasive blasting is opaque, the methyl violet sample of abrasive blasting has improved tinting strength.

Example 3

In this example, join effect in the plastics with different amounts, carried out the bulk testing and the physical test of dyestuff of the present invention-hectorite pigment in order to estimate this pigment.In these were estimated, dyestuff-hectorite pigment added in the polyolefine with two kinds of different consumptions, and used polyolefine is the Himont pp6601 of commercial sale.Dyestuff of the present invention-hectorite pigment is by example 2 preparations, and it adds as weighting agent, and its add-on is a 0.5%(weight) and 0.75%(weight).After this, the polyolefine of filling is estimated with regard to aspects such as tensile modulus, extensibility, stretching peak value, extension at break degree, modulus of elasticity and elastic strengths, it the results are shown in table 1, and table 2 is the evaluation results about aspects such as IZOD impact, Gardner DWI, thermal distortion, density and fusings.Table 3 is results of the polyolefine colourity that evaluation was filled according to Chinese spy (Hunter) colourimetric number.

From table 1,2 and 3 evaluating data as can be seen, these data show that the dyestuff-adding of hectorite pigment can't strengthen the physical properties of compound on the stable base resin.As if also reduce to some extent aspect some character such as extensibility, otch IZOD and Gardner's value as can be seen, this must consider when selecting suitable industrial use for this compound.It can also be seen that in these were estimated, the abrasive blasting sample almost be can't see caking phenomenon, for example, abrasive blasting sample 11 is compared with not abrasive blasting sample 6 and has also been strengthened physical properties.Also almost can't see caking in abrasive blasting sample 11 and 12, not abrasive blasting sample 5 and 6 lumps a lot.By abrasive blasting the colouring intensity of pigment or dyestuff is seemingly enlarged widely, it seems that abrasive blasting can enlarge color system.Table 1,2,3 as follows:

Table 1

Dyestuff-hectorite pigment is filled in polyolefine with 0.5% and 0.75%

Evaluation result among the Himont pp6601

Tension fracture

Tensile modulus extensibility tension fracture modulus of elasticity elastic strength

The peak value extensibility

Sample loading level PS1 PS1 % PS1 % PS1 PS1

1 0.5X 227300 5221 7.7 2869 25.7 260500 1415

2 0.75X 230200 5229 7.9 2993 17.1 264400 7468

3 0.5X 224200 5194 8.0 2486 35.0 252900 7129

4 0.75X 220500 5181 8.0 2608 23.9 257400 7279

5 0.5X 221100 5141 8.0 2732 34.5 257000 7271

6 0.75X 222900 5181 8.2 2842 24.7 261700 7393

Table 1(is continuous)

7 0.5X 229000 5310 7.0 3104 18.3 266500 7572

8 0.75X 222100 5213 8.2 2909 43.0 254000 7207

9 0.5X 218300 5179 8.2 2851 46.1 256800 7315

10 0.75X 220300 5179 8.2 2934 37.1 200600 7323

11 0.5X 226600 5306 7.9 1592 36.7 262000 7448

12 0.78X 227200 5312 7.9 1742 33.2 272400 7655

13 contrasts 190,600 4,837 9.1 2,976 388.3 210,400 6072

Himont 6601

PP

Table 2

Dyestuff-hectorite pigment is filled in polyolefine with 0.5% and 0.75%

Evaluation result among the Himont pp6601

Gardner's thermal distortion

IZOD impacts the fusing of DW1 66PSl density

Sample loading level ft-lb/inch inch/pound ℃ gram per centimeter ³(conD.L)

1 0.5X 0.89 3.0 92.2 0.9072 1.73

2 0.75X 0.80 2.9 92.1 0.9060 2.02

3 0.5X 0.83 3.6 85.5 0.9061 1.95

4 0.75X 0.92 2.6 81.7 0.9070 2.01

5 0.6X 0.91 3.8 96.4 0.9068 1.87

6 0.76X 0.95 3.6 87.6 0.9078 1.38

Table 2(is continuous)

7 0.5X 0.92 3.1 94.9 0.9079 1.66

8 0.75X 0.81 3.0 90.5 0.9086 1.84

9 0.5X 0.91 3.3 94.1 0.9091 2.55

10 0.75X 0.93 3.1 81.4 0.9093 1.74

11 0.5X 0.99 5.9 82.4 0.9078 1.41

12 0.75X 0.76 4.8 96.8 0.9094 1.25

13 contrasts 0.87 7.7 80.1 0.9040 3.31

Himont 6601

PP

Table 3

Dyestuff-hectorite pigment is filled in polyolefine with 0.5% and 0.75%

Evaluation result among the Himont pp6601

Chinese spy (Hanter) colourimetric number

Sample loading level L: a: b

1 0.5X 23.6 7.8 -12.0

2 0.75X 23.7 3.4 -4.4

3 0.5X 23.8 2.3 -3.9

4 0.75X 23.7 0.4 -0.2

5 0.5X 23.7 3.4 -2.6

Table 3(is continuous)

6 0.75X 23.7 1.0 0.3

7 0.5X 37.4 39.5 20.6

8 0.75X 34.5 35.0 18.5

9 0.6X 58.6 1.3 57.1

10 0.75X 53.8 2.6 49.8

11 0.5X 23.6 0.1 1.4

12 0.75X 23.5 0.2 1.4

13 contrasts

Himont 6601

PP

Example 4

In this is estimated, prepared the dyestuff-hectorite pigment that contains various dyestuff and comprise victoria blue, methylenum coeruleum, methyl violet, rhodamine reds and auramine.The sample of these dyestuffs-hectorite pigment is respectively with 0.5%(weight) and 0.75%(weight) add among the Himont PP6601.All sample all uses 0.075% thioester and 0.1% phenol brother to come 3114(phenolic Goodrlte) make it stable.These products are shown in table 4.

Table 4

Dyestuff-hectorite pigment is filled in polyolefine with 0.5% and 0.75%

Evaluation result among the Himont PP6601

The number of sample loading level pigment

1 0.5% victoria blue B

2 0.75% victoria blue Bs

3 0.5% methylenum coeruleum

4 0.75% methylenum coeruleum

5 0.5% methyl violet X

6 0.75% methyl violet X

7 0.5% rhodamine reds 6G

8 0.75% rhodamine reds 6G

9 0.5% auramines

10 0.75% auramines

11 0.5% methyl violet X(abrasive blastings)

12 0.75% methyl violet X(abrasive blastings)

13 contrast barren resin Himont

The PP6601 contrast

Above-mentioned preferred examples has been described the present invention., know those skilled in the art for those, it is conspicuous making various changes, and therefore, above-mentioned explanation should not be considered as limitation of the present invention.

Claims

1, a kind of tinting pigment, it is characterized in that this pigment is the reaction product of a kind of positively charged ion organic dye and a kind of mineral, above-mentioned mineral have very thin mean particle size, novel form and very high cation exchange capacity (CEC), its scope is that the dried mineral of per 100 grams have 100 to 150 milligramequivalents, simultaneously, load density with x-ray diffraction method measure its spacing greater than 28.5 dust D (001).

2,, it is characterized in that described mineral are hectorites according to the described pigment of claim 1.

3, according to the described pigment of claim 2, it is characterized in that described hectorite has about 0.1 to 0.6 micron of mean particle size, these particles generally are square or are plate shaped.

4,, it is characterized in that hectorite with organic cation dye reaction is a kind of calcium-magnesium hectorite that had reacted with sodium ion according to the described pigment of claim 3.

5,, it is characterized in that described organic cation dye is selected from victoria blue, methylenum coeruleum, methyl violet, rhodamine reds and auramine according to the described pigment of claim 1.

6, a kind of plastics that contain as colorant pigment, this pigment is characterised in that it comprises the reaction product of positively charged ion organic dye and mineral, above-mentioned mineral have very thin mean particle size, novel form, very high cation exchange capacity (CEC), its scope is 100-150 milligramequivalent/dried mineral of 100 grams, and load density records spacing with the X-ray diffraction, greater than 28.5 dust D(001).

7,, it is characterized in that described mineral are hectorites according to the described plastics of claim 6.

8, according to the described plastics of claim 7, it is characterized in that described hectorite has about 0.1 to 0.6 micron of mean particle size, those particles generally are square or are plate shaped.

9, according to the described plastics of claim 7, it is characterized in that the hectorite that reacts with organic cation dye is a kind of calcium-magnesium hectorite, it by reacting with yellow soda ash or sodium exchange resin, transforms into the sodium type.

10,, it is characterized in that described organic cation dye is selected from victoria blue, methylenum coeruleum, methyl violet, rhodamine reds and auramine according to the described plastics of claim 6.

11,, it is characterized in that it contains about 0.5% to 0.75%(weight according to the described plastics of claim 6) pigment.

12, a kind of coating is characterized in that it contains the pigment of claim 1 as a kind of tinting material.

13, a kind of rubber, the pigment that contains claim 1 is as a kind of tinting material.

14, a kind of color-printed printing ink that contains as tinting material, this pigment is characterised in that it comprises the reaction product of a kind of positively charged ion organic dye and a kind of Nevada hectorite mineral, above-mentioned hectorite mineral have very thin mean particle size, novel form, very high cation exchange capacity (CEC), its scope is at 100-150 milligramequivalent/100 gram solid carbon dioxide pyroxenes, and its load density records spacing greater than 28.5 dust D(001 with the X-ray diffraction).

15, according to claim 14, described printing-ink is characterized in that described hectorite has the mean particle size of about 0.1-0.6 micron.

16, printing-ink according to claim 14 is characterized in that described hectorite with the organic cation dye reaction is calcium-magnesium hectorite, and it by reacting with yellow soda ash or sodium exchange resin, transforms into the sodium type.

17, printing-ink according to claim 14 is characterized in that described organic cation dye is selected from victoria blue, methylenum coeruleum, methyl violet, rhodamine reds and auramine.

18, printing-ink according to claim 14 is characterized in that grinding before described pigment is in being incorporated into printing ink.

19, a kind of usefulness contains a kind of paper or cardboard of printing-ink printing of tinting pigment, it is characterized in that this pigment comprises the reaction product of positively charged ion organic dye and Nevada pyroxene mineral, above-mentioned hectorite mineral have very thin mean particle size, novel form, very high cation exchange capacity (CEC), its scope is at 100-150 milligramequivalent/100 gram solid carbon dioxide pyroxenes, its load density, recording with x-ray diffraction method is that spacing is greater than 28.5 dust D(001).

20, paper according to claim 19 is characterized in that described hectorite has the about 0.1-0.6 micron of mean particle size.

21, paper according to claim 19 is characterized in that described hectorite with the organic cation dye reaction is calcium-magnesium hectorite, and it by reacting with yellow soda ash and/or sodium exchange resin, changes into the sodium type.

22, paper according to claim 19 is characterized in that described organic cation dye is selected from victoria blue, methylenum coeruleum, methyl violet, rhodamine reds and auramine.

23, paper according to claim 19, it is characterized in that described pigment is in being incorporated into printing ink before, earlier through abrasive blasting.