JPS59156913A - Extender pigment and its manufacture - Google Patents

Abstract

PURPOSE:To obtain an extender pigment having high transparency, high dispersibility and a significant filling effect by treating the surface of zeolite with an acid so as to prepare amorphous alumino-silicate having a specified oil absorption value and a specified refractive index. CONSTITUTION:Uniform and fine grains of zeolite having 10-80ml/100g oil absorption value and 1.42-1.53 refractive index such as A-type zeolite, X-type zeolite or analcime are dispersed in water, and an acid or an acidic substance is added to the resulting aqueous suspension and stirred to adjust the suspension to <=about 4.5pH. The amount of grains of >=10mum grain size in said zeolite grains is <= about 1%, and the amount of grains of <=6mum grain size is >= about 85%. Solid matter is separated from the adjusted suspension, washed, dried, and pulverized to obtain an extender pigment.

Description

[Detailed description of the invention] Regarding extender pigments.

In general, extender pigments are non-pigmenting pigments that are used together with other coloring pigments as base materials for paints and printing ink formulations or lake pigments to improve the spread of color pigments.4. It exerts effects such as reinforcing the paint film, smoothing the surface of the base and paint film, and giving appropriate viscosity and fluidity to the paint and printing ink. It is necessary for the pigment to meet the following requirements.

■ Must be as transparent as possible in vehicles such as linseed oil or varnish; ■ Pigment particles should be fine-grained (easily mixed with vehicles and other pigments, and have good dispersibility); ■ Oil absorption It must have an appropriate value and the desired flow characteristics can be obtained with an appropriate amount; ■ It must be insoluble in vehicles and solvents, and it must not be reactive with them; ■ It must be resistant to light, heat, chemicals, etc. ■Printing°
It must not inhibit the drying properties of the ink; ■ It must be non-toxic; etc.

Traditionally, barium sulfate, calcium carbonate, alumina white, white carbon, etc. have been mainly used as extender pigments, but these extender pigments have advantages and disadvantages.
Overall, nothing was satisfactory.

That is, barium sulfate has been used as an extender pigment for a long time, but when kneaded with linseed oil, it becomes a translucent paste, which is easy to knead, but is not very suitable as a general-purpose ink.

Calcium carbonate is also easy to knead, but it is translucent in linseed oil, making it unsuitable for printing inks that require a high degree of transparency. It also has the disadvantage that it tends to produce a slightly matte coating.

When alumina white is kneaded with linseed oil, a nearly transparent paste is obtained, but when kneaded with a varnish with a high acid value, it has the disadvantage of causing reburring and slowing down the drying of the ink.

Furthermore, the gloss of the coating film is likely to be lost, and other pigments may become discolored.

On the other hand, white carbon is slightly transparent in a vehicle, but its oil absorption value is extremely large (100~koθθl/1o
Since the viscosity increases with the addition of a small amount of oli), the amount added is limited to a small amount, and there is a drawback that a sufficient color spreading effect on colored or white pigments and a reinforcing effect on the coating film cannot be obtained.

In addition, it has been known that a certain type of amorphous aluminosilicate fine powder (Zeolex) is used as a filler in paints, but this type of aluminosilicate is different from zeolite and is rather similar to white carbon. It is composed of ultrafine particles with a primary particle diameter of 0.02 to 0.041μ, and the oil absorption value is about 100 to /jOg/lθθg,
The structure and properties of the substance, the purpose of use, effects, etc. are also significantly different from the extender pigment of the present invention.

The present inventors conducted various experiments and studies in order to develop a new high-performance extender pigment that overcomes many of the drawbacks of conventional extender pigments. The present invention was completed based on the discovery that amorphous aluminum/silicate and its surface-modified product are extremely suitable as extender pigments.

That is, the present invention uses amorphous aluminosilicate obtained by acid treatment of zeolite as a main component, has an oil absorption value of 10 to 0 g Oml//0θg, and a refractive index of 8 lIJ to// , S3.

Generally, zeolite has the general formula (1, θ 〇, ko) M2O
-M,,0. -xsio, -yH,O (where M is H& or an equivalent heptavalent or polyvalent metal, Aluminosilicates with unique crystal structures that can be identified by X-ray diffraction are known in a variety of forms, including natural minerals and synthetics (usually M
is Na).

Zeolites are also generally known to have unique adsorption and ion exchange properties based on their unique crystal structures), and a variety of uses are being developed that take advantage of these properties.

Therefore, the extender pigment according to the present invention is an acid-treated product of the zeolite that substantially has a skeleton in the form of basic particles, and is an amorphous product having an oil absorption amount and a refractive index desirable as an extender pigment. It is a high quality aluminosilicate. Therefore, the extender pigment of the present invention will be described in detail below along with its manufacturing method.

According to the study results of the present inventors, surprisingly, A-type zeolite (Na!O-IJ, 03・J 5in2-+
, j H, O) and X-type zeolite (Ha, O-Al!,
03-a, s sio, , A, / H, o) etc. Zeolite with a relatively small value of the component ratio (5ioV/M, Q3) can be treated with an appropriate amount of acid to make it resistant to X-rays. Although the particles become clearly amorphous, the shape and size of the secondary particles hardly change due to the acid treatment, and the particle state before the acid treatment is almost the same. It turned out that it was retained.

The present invention is based on the application of such facts,
Even though the acid treatment of zeolite makes the chemical characteristics completely different from that of amorphous aluminosilicate, it maintains the basic particle characteristics of the raw zeolite, so it can be used as an extender pigment. The dependence of various physical properties is large, and it is necessary that the particle state of the zeolite itself, as well as properties such as oil absorption and refractive index, be appropriate.

Therefore, the zeolite as a raw material used in the present invention is first prepared at a component molar ratio (51 ot/M t
It is necessary that the particle size (o s ) is relatively small and that the particle state is uniform and fine.

In this case, the term "uniform and fine particles" means a particle size distribution in which the particle size portion of 10 μm or more is 7% or less, and the particle size portion of 6 μm or less is 359 or more.

Moreover, the zeolite used as a raw material in the present invention has an oil absorption value of 10 to 1 g.

A value of the order of vrl/　/0011 is desirable.

From this point of view, various types of zeolite have been suggested as suitable as raw materials for producing the extender pigment of the present invention, including A-type zeolite, X-type zeolite, and P-type zeolite.
Particularly preferred are zeolite, sodalite, analcyme, etc. Some or more of these types can be used.

Further, uniform fine zeolite particles having the above particle size and oil absorption values can be prepared by various methods, such as JP-A-17-J7/J and JP-A-Sho! ;'/-1443
Synthetic zeolites such as A-type zeolite and X-type zeolite obtained by methods such as // are particularly suitable.

Furthermore, it is also possible to use metal-substituted zeolites in which part or most of the Na2O component in these zeolites is replaced with cations other than Na2 through an ion exchange reaction.

In this case, the types of cations other than Na+ are H soil,
Li+, heptavalent cations such as K10, Mg” +Oa
2+* Sr 2+, Ba' 10* Zn 2+m
Various divalent cations such as Od' +m Pb 2+ can be used, and it is possible to adjust the refractive index of the zeolite particles depending on the type of cation and the degree of substitution.

Although various methods are possible for acid-treating such zeolite, it can usually be carried out as follows.

That is, the above-mentioned zeolite particles are dispersed in water to form an aqueous suspension, and an acid or acidic salt solution is gradually added to this with stirring until the pH value of the suspension is at least 1. ．． After adjusting the amount added so that up to S,
The same liquid is separated and washed, and processes such as drying and pulverization are added as necessary.

Examples of acids or acidic substances used here include mineral acids such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, carbonic acid, and sulfurous acid; formic acid;
Examples include, but are not limited to, organic acids such as acetic acid and oxalic acid, and acid salts such as sodium bisulfate and acidic sodium phosphate.

If the final pH value is less than 9.5, the whole multiparticles in which the zeolite particle state has changed significantly will dissolve or disappear, and the skeleton of the bulk zeolite will be destroyed, which is unsuitable. If the temperature is higher, the degree of amorphization will be insufficient.

Therefore, a weakly acidic pH range of 5-5 is particularly preferred. The degree of amorphousness is evaluated by the presence or absence and strength of diffraction lines in an X-ray diffraction diagram, and in the extender pigment of the present invention, the height of the diffraction line is approximately equal to or less than that of the original zeolite. It means something.

On the other hand, the refractive index value is an important property that governs the transparency of extender pigments, and the closer the refractive index value of the linseed oil or phenol used, the better the transparency. In order to obtain sufficient transparency, the refractive index value (n, ) should be 1. llλ to 7.33.

In this regard, the refractive index of the product obtained by the above acid treatment of zeolite will be within this range, but if necessary, the degree of substitution with cations and the quantitative ratio of silica in the silica coating treatment described below may be adjusted. Since the value of the refractive index can be adjusted to a certain degree, a higher degree of transparency can be achieved for a particular vehicle.

The extender pigment according to the present invention is the above-mentioned specific amorphous aluminum/silicate, but it also includes those modified as necessary to further improve the pigment properties.

Typical examples of such modified substances include:
A continuous coating of dense and fine amorphous silica, or a deposit of fine white metal hydrated oxides, such as aluminum, titanium, zirconium, antimony, etc., or a surface active agent, or a dispersion. Examples include modifying the surface of particles such as agents.

Therefore, for example, when applying silica coating treatment, acid or acidic salts are added to an aqueous suspension of zeolite for acid treatment, and then activated silica sol is gradually added at a temperature of 10°C or higher, or an alkali silicate solution is applied. By gradually adding silica and acid to generate active silica, the particle surface can be covered with a dense amorphous silica film.

In most cases, the amount of silica added or generated is 1 to 30% by weight for the amorphous aluminosilicate to obtain a sufficient coating effect, but as the amount of silica increases, the refractive index of the particles increases. The value of tends to increase somewhat.

Amorphous aluminosilicate particles coated with silica have extremely inert surfaces and are more resistant to light, heat, and chemicals, regardless of the type of zeolite used as raw material. However, even when mixed with a vehicle with a high acid value or various formulations, the properties of paints and printing inks do not deteriorate. Similarly, in the coating treatment of metal hydrated oxides, a corresponding aqueous metal salt solution may be added to deposit the hydroxides produced by hydrolysis.

As is clear from the above description, the following points are pointed out as characteristics of the extender pigment of the present invention.

■ It is far more transparent than conventional extender pigments such as barium sulfate and calcium carbonate.

In particular, the extender pigment of the present invention, whose refractive index is adjusted to a value similar to that of linseed oil and phenol used in paints and printing inks, is almost completely transparent in these vehicles. .

■ Pigment particles are fine-grained, have an oil absorption value equal to that of general pigments, are easily mixed with vehicles and other pigments, and have good particle dispersibility. This point is markedly different from alumina white and white carbon, which have large oil absorption values.

■ Since the specific gravity value is relatively small at approximately λ, the same filling effect can be obtained with the amount used in fishing equipment compared to barium sulfate.

■ Insoluble in vehicles and solvents.

■ It is resistant to light and heat. The surface of the zeolite particles coated with amorphous silica, which is extremely dense, is extremely inert and will not be attacked by various chemicals, nor will it affect the drying properties of printing ink. Therefore, even if kneaded with oil with a high acid value,
It does not cause song formation, solidify the surface, or promote gelation.

■ Non-toxic.

The extender pigment of the present invention, which has many of these characteristics, can be used not only for general paints and printing inks, but also for special paints and high-grade printing inks characterized by high quality characteristics, or as transparent pigments for lake pigments. It can be said that it is an epoch-making extender pigment that can be widely used as a sexual base material.

Examples will be shown below, and the results were evaluated using the following test method.

Oil absorption: 19 of K3i0i-qg from J Specific gravity: 17 Refractive index: Measured by Lar8en's oil immersion method using an Atsube refractometer.

Particle size distribution: Measured using a Coulter Counter (manufactured by Coulter Electronics) with an aperture tube diameter of 20 μm.

Color difference: Color difference was measured using a digital colorimeter (manufactured by Suga Test Instruments).

Transparency: Based on the black side of the hiding power measurement paper (note),
The color difference of each sample pigment applied on the black surface was measured, and those with a small color difference were defined as having high transparency.

(Note) Hiding power measurement paper Art paper with white and black sides (approximately 277X, 17m+x)
The +j degree diffuse reflectance was 79.49% on the white surface and 8yg% on the black surface.

Example-1 Na-A zeolite sog was weighed in a SOCC beaker and 2001/ml of water was added to prepare a slurry-5oz with a zeolite concentration of -0%. The pH of this slurry is l
/, 7. While stirring the slurry, add 9%
Sulfuric acid 2! ; After adding Ill and continuing stirring for 1 hour after addition, filtering, washing with water, drying, and pulverization were carried out in the usual manner,
An acid-treated product of Na-A type zeolite was obtained. An electron microscope (SEM) photograph of this acid-treated product is shown in Figure O1. When this acid-treated product was subjected to X-ray diffraction (X, RoD) analysis, no diffraction peak was observed, and it was clear that it was an amorphous aluminosilicate. Table 7 shows the specific gravity, refractive index, oil absorption, acid treatment conditions, composition, etc. of this acid-treated product.

Particle size distribution of Na-A zeolite The raw material Na-A zeolite is obtained by reacting a sodium silicate solution and a sodium aluminate solution without back-mixing to form a gel, and then heating and aging the gel. 1971-ibtJii issue). An electron microscopy (SEM) photograph of the obtained Na-X type zeolite is shown in the diagram. It is clear from these photographs that the state of the zeolite particles remains almost unchanged before and after acid treatment.

Example-2 Using Ha-A type zeolite similar to Example-7, t
Example-l except that 2% sulfuric acid is used instead of % sulfuric acid
Acid treatment was carried out in exactly the same manner. X, R, and D analysis of the acid-treated product revealed that the intensity of each diffraction peak of Ha-Affl zeolite was reduced to about 10 to 100%, and it was clear that it contained a large amount of amorphous aluminosilicate. It is. The specific gravity, refractive index, oil absorption, acid treatment conditions, composition, etc. of this acid-treated product are also shown in Table 1.

Example-3 Using the same Na-Am zeolite as in Example-7, l
Acid treatment was carried out in exactly the same manner as in Example 7, except that 10% phosphoric acid was used instead of I% sulfuric acid. The obtained acid-treated product showed no diffraction peaks at all in X and R6D0 analysis, and it is clear that it is an amorphous aluminosilicate. The specific gravity, refractive index, oil absorption, acid treatment conditions, composition, etc. of this acid-treated product are also shown in Table 1.

Example - DA The same Na-A zeolite as in Example-7 was used, and q
Example except that 1% phosphoric acid was used instead of sulfuric acid.
Acid treatment was carried out in exactly the same manner as in 1. The obtained acid-treated product was analyzed for X, R, and D, and the intensity of each diffraction peak of Na-A type zeolite was reduced to about %, and it was clear that the main component was amorphous aluminosilicate. It is. The specific gravity, refractive index, oil absorption, acid treatment conditions, composition, etc. of this acid-treated product are also shown in Table 7.

Example 5 In the same manner as in Example 7, Na-X type zeolite sog was weighed in a 50[theta] beaker, and water cog was added to prepare slurry 23OI with a zeolite concentration of 20%. Note that the pH of this slurry was / /, g. While stirring the slurry, add da% sulfuric acid sop to it, and after addition,
After continuing stirring for a period of time, FO filtration, water washing, drying, and pulverization were performed in a conventional manner to obtain an acid-treated Na-X type zeolite. An electron microscope (SEM) photograph of this acid-treated product is shown in FIG. When this acid-treated product was analyzed for X, R, and D0, a slight diffraction peak of Na-X type zeolite was observed, but its intensity was below that of the strongest peak (-〇=6°). 9. It is clear that the main component is amorphous aluminosilicate. The specific gravity, refractive index, oil absorption, acid treatment conditions, composition, etc. of this acid-treated product are also shown in Table 7.

The Na-X1 zeolite used as a raw material was prepared by reacting a silicate-soda solution and a sodium aluminate solution without back-mixing to form a gel, and then heating and aging the gel (Japanese Unexamined Patent Application Publication No. 1983-37-/At, 3). / No. 1). This Na
An electron microscopy (8EM) photograph of -X type zeolite is shown in FIG.

Comparative Example-/For comparison, a commercially available amorphous aluminosilicate (Zeol
Fig. 5 shows an electron microscopy (EIM) photograph of
The refractive index, oil absorption, composition, etc. are also shown in Table-1. Table 7 also shows the physical properties of commercially available extender pigments such as white carbon, precipitated barium sulfate, and calcium carbonate.

According to Table 7, the acid-treated zeolite has a specific gravity of about 100%, which is also smaller than that of the extender pigment of the comparative example. Furthermore, the refractive index is close to that of linseed oil, and it is clear that when mixed with linseed oil, a nearly transparent coating film can be obtained.

All of the acid-treated zeolites shown in Table 1 maintain a particle shape close to a spherical shape with a particle size of O, S-t μm.
Since the oil absorption amount is less than g Oml/100//, commercially available amorphous aluminosilicate (particle size 0.02 to 0.011
tin, oil absorption amount ioθrnl/1oo1 or more). As can be seen from Figures O/S to OS, the particle shape of the zeolite acid-treated product of the present invention maintains the original zeolite shape, whereas the commercially available amorphous aluminosilicate It is evident that the salt is an irregular agglomeration of fine particles of less than 0.02μ.

Comparative Example - Using the same Na-A zeolite as in Example 1, adding 2% sulfuric acid for acid treatment in the same manner as in Example 1, and further adding sulfuric acid to adjust the pH of the mixed slurry. After adjusting the temperature to 3.0, stirring was continued for 1 hour. Thereafter, the acid-treated product was obtained by filtration, washing with water, drying, and pulverization using conventional methods. An electron microscope (SKM) photograph of the obtained acid-treated product is shown in FIG. In FIG. 6, an irregular shape due to dissolution and aggregation of particles was observed due to the pH drop during acid treatment, and the skeleton of the bulk zeolite had disappeared. In this comparative example, the yield of the acid-treated product was not only low, but also the dispersibility as a pigment was poor.

Test Example-7 The hiding power of precipitated barium sulfate and calcium carbonate in Example/-3 and Comparative Example was measured using a cryptometer according to the method described in JxsKgtol (Pigment Test Method) 6. Use T linseed oil as the vehicle and J
When measuring the hiding power of acid-treated zeolite or calcium carbonate, make a paste by matching the pigment volume concentration to the mixed paste of precipitated barium sulfate. Tested. The results are shown in Table 1.

Table - The amorphous aluminosilicate obtained by acid treatment of Koyoshi zeolite has a hiding power of 11111 or more,
It is clear that it has extremely superior transparency compared to precipitated barium sulfate and calcium carbonate.

Table 1 Example 6 After acid-treating Na-A zeolite with an average particle diameter of i, ox μm in the same manner as in Example 1, the slurry with a slurry concentration of 20% by weight was kept at a temperature of 90°C and stirred. 8
10. A 6% by weight sodium silicate aqueous solution and 1I% sulfuric acid were simultaneously gradually added to carry out a silica deposition treatment.

Next, the above deposited product was washed with water, dried and pulverized in a conventional manner to obtain an extender pigment.

The amount of silica in this pigment is S10. As / LO! The acid resistance was significantly improved at r weight %.

Further, in the same manner as in Test Example 1 above, when its characteristics were examined, the cryptometer scale was s o mlA or more, and the hiding power was 7 or more.

The Na-A type zeolite used as a raw material was prepared as follows: A sodium silicate aqueous solution and a sodium aluminate aqueous solution were maintained at a molar ratio of 5 iOt/u, o, x, o to form a gel without back mixing. Then, Na-A type zeolite was synthesized. The average particle size of this zeolite was 80-μm.

Test Example - Regarding the ceolite acid treated product of Example 1/-j- and the extender pigment of Comparative Example, a paste was prepared by kneading each of y, o and y in No. linseed oil with No. 0.071m with a film applicator on the measuring paper
It was applied to a thickness of π (3 mils). After drying at room temperature, use a color difference meter to measure the tristimulus values X and Y of the color of the black side of the hiding power measurement paper.
, Z were measured, and from this, pL, a, b values, and color difference ΔE were determined.

The results are shown in Table-3. In Table 3, the color difference (△E) with respect to the blank (black side of the hiding power measurement paper) is excellent, and the transparency is excellent, whereas the black side coated with acid-treated zeolite has a color difference of about 10 or less. On the other hand, precipitated barium sulfate and calcium carbonate have a transparency of 20 or more, and it is clear that the amorphous aluminosilicate obtained by acid treatment of zeolite has excellent transparency.

Test Example-3 Using the zeolite acid-treated products of Examples/~B and the precipitated barium sulfate and precipitated calcium carbonate of Comparative Example 1, each sample was uniformly kneaded with No. linseed oil and placed in a sample bottle ( The sample was placed in a sealed container (φ/, tmm x 3.tH), and a reviving test was conducted in a thermostatic chamber (7). As a result, for all samples, g
No reviving was observed even after 72 hours at 0°C, indicating that each of the zeolite acid-treated products (amorphous aluminosilicate) of Examples 1 to 6 had the same stability as precipitated barium sulfate and calcium carbonate. did.

[Brief explanation of drawings]

All of the drawings are electron microscope (SBM) photographs, and all of the drawings are 500x magnification, except for the Otsu diagram - 000x magnification. Figures O/J and OJ are extender pigments according to the present invention, Figures Oko and O1 are the raw zeolite before acid treatment, Figure OS is a commercially available amorphous aluminosilicate, and Figure O6 is the skeleton of the zeolite. FIG. 2 is a microscopic photograph of an acid-treated product in which the acid-treated product has been destroyed. Fig. 1, To X ++
[F] Meeting purpose ゛、゛
Figure 2 ・ Procedural amendment 6 October 2T, Showa 5 group, Mr. Commissioner of the Patent Office 1, Indication of the case Showa! S year patent application No. Kota JJ, t No. 2, Title of the invention: Extender pigment and its manufacturing method 3, Relationship with the case of the person making the amendment Patent applicant 5, Subject of the amendment (1) Detailed explanation of the invention in the specification Contents of the amendment (1) The description of the specification will be amended as follows. Hiroshi ``aooi/1oollJ r
2ootrl/1oolJ z 7 tsol/1oolJ r~tr
o resistance/10OIIJ ta ta [”J
l”nu4”Jl-Hiro “Dispersant, etc.” “Due to dispersant, etc.”/? / da
"1bbJ// issue""3713issue"/7
/II rna-xm” rNa-11J (2)
Add l-j and AJ to the box for "Na2O" in the "composition" column of "zeOlex" in Table 1 on page 23,
[Added "6.l" to Yuzu of AJ, O, J, [5to2]
JJ's Kusunoki joins λ and JJ.

Claims (1)

[Scope of Claims] / An amorphous aluminosilicate of a zeolite acid-treated product that has substantially lost the particle state of zeolite,
The oil absorption value is lθ to g. ml, Q 00 g, and the refractive index value is 8 lλ ~
An extender pigment characterized by being /jJ. , 2. The body/d pigment according to claim 1, wherein the zeolite is seven or more types selected from A-type zeolite, x-type zeolite, p-type theolite, sodalite, and analcyme. 3 Part or most of the Na and 0 components of zeolite are N
Extender pigment according to claim 0, which is a zeolite substituted with a cation other than A, in which the particle size portion of the zeolite is 7% or less with a particle size of 10 μm or more, and the particle size portion with a particle size of 6 μm or less is 5% The extender pigment according to any one of claims 1 to 3, which has a particle size distribution as described above. ! The extender pigment according to claim 7, wherein the acid-treated zeolite is coated with dense, fine, and amorphous silica or white metal hydrated oxide. 4 (J) even at low pH
A method for producing extender pigments characterized by acid treatment in a weakly acidic range up to