JPS5823858A - Manufacture of quinacridone pigment in pigment state - 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 The present invention provides aggregated low crystallinity forms of crude quinacridones.
fnftyform) K2 After conversion, in the presence of a recoverable organic liquid, the pigment form (oigm@ntary for
m) Concerning a method of IC conversion.

The nine synthesized quinacridones, known as crude quinacridones, are generally unsuitable for use as pigments and require further processing to obtain pigment properties such as particle size, particle shape, crystalline It is well known in the industry that it is necessary to develop two structures, two strong colors, one hue, etc. The most commonly used process to convert crude quinacridones into pigmentary form is after milling (-nillinf) the crude quinacridones with large amounts of inorganic salts.

The method includes extracting the resulting crushed soybean powder.

This salt-grinding operation can produce pigments that are satisfactory for some applications.

There are two overlapping disadvantages. Firstly, it uses large amounts of salt, which severely limits the amount of pigment that can be loaded into the mill, and secondly, the salt must be disposed of.

The resulting pigment particles are often acicular, creating rheological problems in end uses such as high solids acrylic paints for automobiles.

Several attempts have been made to avoid the use of salt in grinding crude quinacridone. For example, US Patent 2,
857.400, the crude pigment is ground in a ball mill and then materialized in acetone and recovered from the acetone. In US Pat. No. 5,017,414, the crude pigment is pre-milled in a ball mill, treated with an organic liquid such as a chlorobenzene-in-water emulsion, and recovered from the emulsion. Disposal of organic liquids as well as salts poses problems.

Other methods of producing pigmentary quinacridone from crude quinacridone are shown in US Pat.

After forming it into the form of a neutral aqueous paste, it is heated to 150-500°C under pressure. Special equipment is required for heating at high temperatures and pressures.

Yet another method that eliminates the use of organic liquids (U.S. Patent No. 4.
o9n, 699), pre-milled quinacridone is aged (rip@m) in aqueous base in the presence of both cationic and nonionic surfactants. Some surfactant remains on the surface of the pigment, which can cause compatibility problems depending on the end use.

The present invention ff1ti involves converting crude quinacridone into an aggregated low crystallinity form and then grinding in the presence of an organic liquid to convert this aggregated low crystallinity quinacridone into easily dispersible pigment quinacridone. include.

The method of the present invention provides quinacridone pigments of essentially any desired particle size, and the ability to improve the rheological properties of the pigmented product with or without particle size growth inhibitors. It gives the opportunity to control one of the influencing parameters. Even small amounts of 2-7 talimidomethyl quinacridone have a significant effect on the particle size of the product produced. This particle size growth inhibitor can be incorporated during the milling step with the liquid or during the pre-milling step prior thereto.

The efficiency of the growth inhibiting action is enhanced if it is incorporated during the pre-grinding operation.

Control of particle size of quinacridone pigments in solid solution.

Pre-contact dispersion milling as described in U.S. Pat. No. 5,050.570
proeess) is difficult. This is because the process relies on ripening in dilute sulfuric acid and extraction techniques that are relatively ineffective at growing particles from the low crystallization material produced in a long and effective dispersion milling process. Additional milling cannot be used to correct this, as it would result in a product exhibiting incomplete solid solution formation.

According to the conditions of the present invention, complete solid solution is usually achieved in the particles of the final pigment product as having two different particle sizes. Do the methods of the invention incorporate a single particle size growth inhibitor?

Either modifying the organic liquid used to control the effect on the particular quinacridone used provides the necessary conditions to obtain pigments of desired particle size over a wide range of particle sizes. .

Thus, the method of the present invention provides a method for producing pigments of relatively large particle size, yet with high color intensities such as those normally exhibited by pigments of small particle size.
r@ngth), yet with excellent lightfastness [(light
t-fastness).

Another advantage of the present invention is that it avoids the need for the use of interfering surfactants in some end applications.

In a preferred embodiment of the invention, the component that becomes part of the final pigment is a single quinacridone component or even a binary, ternary or quaternary solid solution. In order to avoid possible exposure of the ground powder, the pigment is ground together in a conventional ball mill with an inorganic salt of about 8 to 10 ml, such as sulfuric acid, and The material is ground into agglomerated, low-crystallization vertical material. 9. The product is highly aggregated. It doesn't look stiff, so I use sulfuric acid) Is the addition of IJum essential? stomach. The resulting ground powder is then ground in an easily recoverable organic liquid in the presence or absence of a single particle size growth inhibitor.

Any organic liquid can be used that has an effective wetting action on the pigment particles and is capable of causing these particles to grow from agglomerated, low-crystallization material into a pigment-like material. Furthermore, the organic liquid must be sufficiently volatile, either by steam distillation or by direct distillation, and must not corrode the mold and grinding parts. A wide range of organic liquids are suitable; the preferred organic liquid will vary depending on the nature of the pigment and its solubility.

Alcohols such as methanol and impropatol, ketones such as acetone and methyl ethyl ketone, hydrocarbons and carbon tetrachloride.

Chlorinated hydrocarbons such as tetrachlorethylene and 0-dichlorobenzene may be used. The choice of organic liquid will depend on the particular pigment being manufactured as well.

The cost of the organic liquid will be influenced by the ease of recovery and the risk of use. High boiling point liquids are generally
It is more difficult to recover by steam distillation and therefore more expensive. other liquids.

For example, chlorinated hydrocarbons are toxic and therefore undesirable. On the other hand, low-boiling liquids 1, such as acetone, tend to be easily flammable, but are otherwise desirable for reasons such as low cost, non-toxicity, and ease of distillation. The advantage of acetone and low-boiling alcohols is that they are miscible with water, and thus their ability to grow pigment particles can be modified by dilution with water during milling with organic liquids. It is. Dilution with water yields products with fine particle sizes.

The objects of the present invention are achieved by first converting the crude quinacridone pigment into an aggregated, low crystallinity material.

This process uses crude single or multiple raw materials in a dry state.
This can be done by grinding in a grinding rig that applies shear and abrasion to the aggregated low crystallinity product.

When the pre-pulverization used in the present invention is completely liquid-free, or when a liquid is used, 'p! The solvent that dominates the phase
) If they are present in such small quantities as pigments or resins that they retain their powder properties, and if they are pulverized in such a way that they retain their powder properties, It means to do.

As a variant, the aggregated low crystallinity quinacridone pigment can be prepared by dissolving the crude quinacridone in concentrated sulfuric acid.

It is obtained by dipping the solution into cold water.

In either case, high fK aggregated pigments with low crystallinity have a weak by ruhout coloring strength f and are of little value.

A preferred method of using unexploded uAK is to ball mill the crude quinacridone or quinacridones in the dry state in a conventional manner and then ball mill the ground powder in sufficient organic liquid to provide a fluid slurry. Including bulk crushing. The quinacridone pigments to which the present invention applies are generally quinacridones of the formula (1) or (2) or mixtures thereof; , R1, R'', R'.

Ha and r are hydrogen, fluorine, chlorine, bromine, methyl or methoxy; R1, Baa and RIG are hydrogen or chlorine; BmFi hydrogen, chlorine, bromine;

consisting essentially of nitro, an alkyl group of 1 to 5 carbon atoms, an alkoxy group of 1 to 2 carbon atoms, or benzoylamino, where m is an integer from 1 to 4; Will. Formula I.

When R1 and R1 are 1, which is relatively susceptible to significant particle growth in organic liquids such as acetone, the pigment particles become undesirably large and the product pigment becomes opaque. ), which reduces the coloring intensity.

Adding only 20 quinacridone derivatives to such pigments
By varying the weight percentage, particle size growth is sufficiently suppressed to obtain a product with attractive color properties.

9 The term 'consisting essentially' does not attempt to exclude the presence of small amounts of other substances, such as dihydroquinacridone stabilizers, but does include the presence of other substances that would impair the pigmentary properties of the quinacridone pigment. It is intended to exclude the presence of non-negligible amounts.

The length of the milling process in liquid depends on the particular quinacridone or mixture of quinacridones being treated.

It is not possible to show the variation as it varies depending on the amount fed to the mill and the type of mill used. 1. Practicing the invention by varying both milling times in order to establish the optimal time for milling a particular pigment under a given set of conditions.

It is recommended that samples of the produced product be compared with standard samples exhibiting the desired Chongqing pigment quality.

Normally, commercial scale mills require a minimum of 4 to 6 hours of grinding, but this may be extended to a longer period of time, such as 12 to 18 hours. For laboratory-scale or intermediate-scale mills, considerable time is required. Generally grinding in liquid #i10~60℃, preferably Fi20~
Performed at 50°C.

Following the milling operation, the quinacridone pigment is usually extracted in a hot dilute acid, such as 15-sulfuric acid, to remove any metals that may have been introduced into the pigment during milling. Following the extraction process, the pigment is dried.

While normally produced quinacridone pigments are often needle-like in shape,9 the pigment particles produced by the present invention are generally plate-like in shape. The quinacridone pigments produced by the method of the present invention are better dispersible than conventional quinacridone pigments due to their laminar shape and controllability of their tabular shape and particle size.

Pigments produced by the method of the invention have improved rheological properties compared to previous quinacridone pigments. This is most evident in the dark color stylings of new vinolid thermoset acrylic paints developed for automotive applications. Although most conventional quinacridone pigments could not be practically used in these systems due to their high viscosity, the quinacridone pigments prepared according to the present invention are suitable for these systems. 2゜made Muyu, Ya customary. , □
, exhibit improved rheological properties in thermoplastic and thermoplastic systems.

Hitherto, it has been difficult to obtain a satisfactory solid solution of 2,9-dichloroquinacridone pigment for hybrid coatings with quinacridone. By implementing the present invention.

Satisfactory pigments of solid solutions of 75-2,9-dichloroquinacridone and 25-quinacridone or Filoo-dichloroquinacridone are readily prepared for use in new hybrid coatings. Solid solutions of attractive 2,9-dimethylquinacridone pigments with quinacridone can be prepared in a similar manner.

The use of particle growth inhibitors has resulted in products with fine particle sizes and increased strength when properly dispersed in either thermosetting paints or thermoplastic lacquers for automotive topcoats. and geometric isomerism←r＊ona@t
rle m*som@r1gm) (generally called m' two-tone 1 effect book flip-full flip) effect is obtained. This latter property is particularly relevant for anchorage value and is manifested as a change in color depth and sometimes hue depending on the viewing angle. Observed by slow rotation to an obtuse angle.As the two-tone increases, the color deepens as the viewing angle changes from vertical to either direction.Product aged in the presence of 2-phthalimidomethylquinacridone The larger one-two-tone I effect is observed in particles due to the creation of pigments with smaller particle sizes, which when properly dispersed exhibit less light scattering and an increased one-two-tone I effect.

1 two-tone l achieved with pigments produced by this method
The higher the value of 1, the more effective they are at producing small particle sizes, even in products containing only small amounts of growth inhibitors, as confirmed by X-ray measurements. Have water ice.

The products obtained by treatment with aluminum quinacridone sulfonates give pigments with a large one-tone I and a corresponding artistic appearance in thermosetting acrylic coating systems, as well as significantly improved rheological properties. .

In the following examples, all parts represent parts by weight.

Example ■ Two laboratory-scale ball mills each have a diameter of 1.2 mm.
1500 parts of 7cW1 (1/2 inch) steel balls.

Charge 150 parts of roofing nails, 45 parts of 2,9-dimethylquinacridone, 5 parts of quinacridone, and 5 parts of anhydrous sodium sulfate. The mill is operated at one critical speed f' (critical succession means that the centrifugal force overcomes the gravity and the grinding media (ffrindlng@l
The mill is rotated for 96 hours at a speed of about 74 degrees K (am@nts) held against the outside wall of the mill. Open the mill, take out the contents and pass through a sieve to remove the steel balls and nails.

Next, the obtained powder (12 parts) was added to a diameter of 5.2 m (1/8
It contained 600 parts of steel shot (inch) and 79 parts of acetone. Charge each of four laboratory scale ball mills. The mill is run for 72 hours at about 74-degrees of its critical speed. Remove the contents of the mill and sieve to remove the steel shot, wash the shot with acetone, and sieve to collect all the pigment slurry. Steam is passed through the slurry until a temperature of 95°C is reached. Acetone is completely removed by holding at Ilf at 95° C. for 10 minutes. The slurry is cooled to 85°C, and 1.04 parts of 55-thiosulfuric acid aqueous solution is added thereto. Hold the slurry at 80-85°C for 1 hour.

Collect the product by washing with water and washing with water until the acid is gone.

Drying at 80°C yields 43.2 parts of pigment. When tested by friction in lithographic varnish, this product outperforms commercially available 2,9-dimethylquinacridone.
However, it is ton @ + blocky color tone).

At least 1o-larger in colored intensity.

After adding 104 parts of sulfuric acid aqueous solution of 33-, the temperature was lowered to 80
This example is repeated except that the mixture is held at ~8.5 DEG C. for half an hour, then 15 parts of 2-7 talimidomethylquinacridone are added as an aqueous dispersion and heating is continued at 80 DEG-85 DEG C. for an additional half hour. The product is collected in an oven, washed with water until the acid is removed, and dried at 80°C. This product shows particularly good rheological properties and very good coloring properties when tested in thermosetting automotive paints. The prepared kneaded base material for automobiles (mN1 hase) has a Ford cup viscosity of 54 seconds, but the Ford cup viscosity of commercially available 2,9-dimethylquinacridone #144 to 61 seconds. This has obvious benefits in terms of handling of the kneaded base material and in the finishing of the final automobile.

Example ■ This example shows the effect on particle size of splitting the addition of K-12-7-tomethyl quinacridone by adding it in part during the co-milling step with acetone.

Medium M1 work scale cv hole Jze 4 le 1Cyl-P
@bs'.

1000 cylinders made of steel, approximately 1/2 inch in diameter and 1/2 inch in length.

'twenty penny', i.e. 10clL (
100 parts of 4-inch nails, 40 parts of 2,9-dimethylquinacridone, and 4 parts of anhydrous sulfuric acid. Mill at aOrpm (approximately 74 inches of critical speed) for 48 hours.

Rotate at 55-60°C. Open the mill, take out the contents, and remove the 'Cyl-P@bs' and nails with a sieve.

Then, a portion (0,029 parts) of the obtained powder powder, 3
．． 2■ (1/8 inch) diameter steel shotgun 1.52II
S, 2-7 talimidomethylquinacridone 0,0002
6 parts and 0.17 parts of acetone.

Load into two laboratory-scale ball mills. The mill is run for 72 hours at about 74-degrees of its critical speed.

Remove the contents of the mill onto a sieve to remove the steel pellets.

Wash the shot with acetone 1 to ensure that essentially all the pigment is collected as a slurry. Steam is passed through the slurry until Temperature 1 reaches 95°C. Warm to 95℃ for 10
The acetone is completely removed after holding for 1 minute. The slurry was cooled to 85°C, and 110 parts of 35% sulfur beak was added to it.
I can do it. After holding the slurry at 80-85°C for half an hour,
-7 Talibidomethylquinacridone 0. OOtl 5
Process in two parts.

Continue heating at 80-85°C for an additional half hour. The product is collected in a furnace, washed with water until the acid is removed, and then transferred at 80°C. When tested by rubbing in a lithographic varnish, this product has a dark color (very small particle size) as usual for masstones, but it contains all of the 2-7 thalimidomethyl quinacridone extracted from the extract. It was added and processed. Similar products and tones are actually the same intensity.

The small particle size of the product Fi1's two-tone properties gives it a sandy, metal-like finish, making it highly valued for automotive finishes.

Example■ This example has remarkable rheological properties.

2. The production of a solid solution pigment of 9-dicycloquinacridone is illustrated.

In three laboratory scale containers, 1500 parts of 2 inch diameter steel balls, 150 parts of roofing nails, and 57.5 parts of crude 2,9-dichloroquinacridone.

5 parts of crude r-quinacridone and 5 parts of anhydrous sodium sulfate
The tube is rotated for 96 hours at a speed of about 75 degrees below the critical speed. Sieve the steel balls and nails to remove the bottom and collect the dried pulverized powder.
4,800 parts of 2M (8 inch per part) steel shot, 120 parts of the above-mentioned pulverized powder, and 790 parts of acetone were charged. the mill at its critical speed of about 7
Rotate at 5-0 speed for 72 hours. Remove the contents of the mill onto a sieve to remove the steel pellets. Acetone is added to clean the steel shot to capture essentially all the pigment slurry from the barrel. Steam is passed through the slurry until fIAllj is 95°C. After holding the temperature t-95"CK for 10 minutes, the acetone is completely removed and the steam is stopped. The slurry is cooled to 85°C and it is
Add 1 part and 24 parts of Meigen to slurry 'IP80~85
Heat for half an hour at ℃. It is then treated with an aqueous slurry containing 5 parts of quinacridone monosulfonic acid for half an hour to precipitate 47 parts of aluminum quinacridone sulfonate onto the surface of the pigment. Continue heating at 80-85°C for another half hour. Isolate the product under conditions.

Wash with hot water until acid is removed. 150 parts of pigment are recovered.

The particle size of this product is slightly larger than that of the reprinted equivalent product, but
Its rheological properties are better than expected. The product exhibits exceptionally attractive rheological properties, making it particularly suitable for binder paint systems.

Smaller particle size product K with wide particle size distribution
In comparison, when tested as a kneaded base material for automotive binder and thermosetting paints, 7 this kneaded base material shows a 43-fold reduction in viscosity.

The advantage of this is the dark red mold (5t) for top coating of automobiles.
yllt+g 5olid reds) K: Particularly important.

Example ■ This Example Fi describes an alternative method of obtaining aggregated low crystallinity quinacridone before milling in an organic liquid.

Add 552 parts of concentrated sulfuric acid to 552 parts of concentrated sulfuric acid while stirring at a temperature lower than 50°C.
Add 575 parts of crude 2,9-dichloroquinacridone and 125 parts of crude quinacridone. Since this material did not go into solution, 184 parts of 100% sulfuric acid was kept at a temperature below 50°C. Add by size.

After stirring for 15 minutes, all materials went into solution.

The resulting solution was gradually added to a mixture of 2000 parts of water and ice over a period of 1.5 hours with stirring, during which time the resulting slurry was maintained at 0-10<0>C. Isolate the product in a furnace, wash it with water until the acid is gone, and dry it. 485 parts of dry product are obtained.

When this product is ball milled in acetone essentially as in Example 1a, the product obtained is in fact equivalent to the product obtained in Example 2. The product before milling in acetone was not as intensely colored as the final product, and was less distinct.

Example V This example illustrates the effect of 2-7 talimidomethyl quinacridone on the particle size of the product described in Example IITK.

Dry milling is carried out exactly as described in Example tn.

The resulting ground powder is ground in acetone in the presence of 2-phthalimidomethylquinacridone as follows.

In a laboratory scale mill, 600 parts of 5.2'o+ (1/8 inch) steel balls, 13.2 parts of the ground powder of Example ■, 2-7
Add 0.24 parts of talimidomethylquinacridone and 79 parts of acetone. The mill is run for 72 hours at a speed of about 75-degrees of its critical speed. Acetone is distilled off with steam,
The product is extracted with dilute aqueous sulfuric acid and treated with 43% alhi-umquinacridone sulfonate as described in Example ITJ. 12 parts of pigment are recovered. Comparing the degree of fK reduction with the product of Example (2) in lithographic varnish, the masstone is clearly darker and therefore has a smaller particle size, but the color strength is comparable to the product of Example (2).

Example 2 This example describes the production of a solid solution pigment of Fi2, 9-dimethylquinacridone.

Laboratory Scale Mill K 1500 parts 1/2 inch diameter steel balls, 150 parts roofing nails, 5751 parts crude gamma-quinacridone. Charge 125 parts of crude 2,9-dimethylquinacridone and 5 parts of anhydrous sodium sulfate. This last one is added as an exposure suppressant to the ground powder;
It can be excluded when working on a laboratory scale.

The mill is run for 96 hours at about 75 degrees below its critical speed. Separate the steel balls and nails with a sieve and collect the dry crushed powder.

3.2 m (1/8 inch) in a laboratory scale ball mill
600 parts of steel pellets having a diameter of , 15.2 parts of the above-mentioned pulverized powder and 79 parts of acetone were charged. The mill has a critical speed of about 7
Rotate at a speed of 5- for 72 hours.

The contents of the mill are taken out onto a sieve to separate out the steel shot.

The steel shot is cleaned with acetone to collect essentially all the pigment slurry from the mill. Steam is passed through the slurry to reach a temperature of 95°C. After keeping the temperature at 95° C. for 10 minutes, the acetone is completely removed □ and the water vapor is stopped. The slurry was cooled to 85°C, and a 35-thiosulfuric acid aqueous solution
1 part acidic VC.

The product is kept at about 85° C. for 1 hour and then isolated, washed with water and dried.

This product is a complete solid with a relatively large particle size, exhibits remarkable thermal stability in high density polyethylene, and has the same composition but dispersion milling technology (dl@persion m
The thermal stability is clearly higher than that of the product manufactured using the latest technology.
(500°F), but exhibits better thermal stability at 16°C (600°F).

Example 2 In this example, a solid solution of quinacridone 2,9-dichloroquinacridone containing quinacridone as a main component was produced. Figure 3 shows the effect of changing particle size when introducing 2-7 tallytomethylquinacridone during milling in acetone.

Laboratory scale mil Kt27cIIL (1/2 inch)
1,500 parts of steel balls with a diameter of
Charge 2.5 parts and 5 parts of anhydrous sodium sulfate. The mill is run for 96 hours at about 75 degrees of its critical speed. Separate the steel balls and nails with a sieve.

Collect the dry ground powder.

Diameter 5.2w5 (1/8
600 parts of steel shot (inch), 13.2 parts of the above ground powder
79 parts of acetone and 0.48 parts of 2-7 taloid methyl quinacridone first and 0.2 parts second.
Prepare 4 parts. The mill is run for 72 hours at a speed of about 75-degrees of its critical speed. The contents of the mill are passed through a sieve to separate the steel shot.

The steel shot is washed with acetone to collect essentially all the pigment slurry from the mill. Steam is passed through the slurry to reach a temperature of 95°C. All the acetone was removed by keeping the temperature at 95°C for 10 minutes.

Stop steam. Cool the slurry to 85°C.

Acidic Kl was added with 261 parts of a 53-thiosulfuric acid aqueous solution and kept at 85°C for 1 hour. It is then treated with an aqueous slurry containing 0.5 parts of quinacridone monosulfonic acid for half an hour to coat 45% on the surface of the pigment.
of aluminum quinacridone sulfonate. Continue heating at 80-85°C for another half hour. The product is isolated by filtration, washed acid-free with hot water and dried.

Got it here. The product containing 4 ml of 2-7 talimidomethyl quinacridone had significantly smaller particle size than the product containing 9.2 ml of 2-7 thalimidomethyl quinacridone. Their color strength in thermosetting acrylic paints is essentially the same, but they differ in their 12-tone effect in metallic finishes, which is similar to that of products containing 4-2-phthalimidomethylquinacridone. The two-tone color is larger and therefore presents a more attractive appearance. Furthermore, this latter product exhibits substantially better rheological properties in thermosetting coating systems when compared to commercial products of similar color and one-tone I effect.

Example In this example, during the production of a solid solution of quinacridone 2,9-dimethylquinacridone, introducing 2-7thalimidomethylquinacridone during the grinding operation in acetone changes the particle size according to K. Explain the effect of

Dry pre-milling is carried out as reported in Example ■, but in the one case the 2-phthalicidomethylquinacridone, based on the charge pigment, and in the other case its additive, Fi4-, in acetone. Add to the grinding process. All other steps are carried out as described in Example 1, except that the addition causes precipitation of approximately 4.5-aluminum quinacridone sulfonate on the pigment surface.

Got it here. 4- Products containing additives.

The particle size is considerably smaller than the product containing additives 2-1, and the latter has a smaller particle size than the product without additives. Lithographic varnishes and thermosetting acrylic paints are essentially the same in strength, but differ in color tone in bulk. The darker the mass tone, the more desirable the product is for use in metal-like automotive finishes.

Example ■ This example illustrates the effect of 2-phthalimidomethylquinacridone introduced during the dry milling operation. Dry milling is carried out as described in Example 2, except that in addition to the other ingredients, 1.5 parts of 2-phthalimidomethylquinacridone is also charged to the mill before dry milling. The trim and surface treatment were exactly the same as in Example 2. This product was manufactured in Example ①. It is essentially the same as the product containing 4-2-7 talitomethylquinacridone.

Example X This example describes the production of a golden solid solution pigment consisting primarily of quinacridonequinone.

The conditions for milling 43.7 parts of quinacridone quinone, 63 parts of anilinoacridone, 0.1 part of quinacridone, and 5 parts of anhydrous sodium sulfate using the mill and grinding media of Example (2) were as reported in Example (2). Seconds. The resulting ground powder is ground in acetone and purified as reported in Example ■, but the resulting product is kept at 11 in the pressed mass and then the salt is precipitated onto the pigment dispersed in water. Expand the volume with 5-basic nickel carbonate in a similar manner. The resulting solid solution product was colored in gold and acid immersed under high speed stirring as described in U.S. Patent Application No. 153,208, filed May 27, 1980.

It is very compatible with the automotive acrylic paint produced by Minato et al. using the same ingredients.

Example 0 C This example describes the preparation of an orange solid solution quinacridone pigment.

Using the mill and grinding procedure described in Example ■.

21 parts of r-nacritone, 145 parts of 4,11-dichloroquinacridone, and 95 parts of quinacridonequinone.

6. Mix and grind 50 parts of 15-dihydroquinacridone and 5 parts of anhydrous sodium sulfate. The dry grinding conditions used were as reported in Example ①.

The resulting pulverized powder is pulverized in acetone and purified by the method shown in Example 1 with the addition of treatment with nium quinacridone sulfonic acid.

Although this product is comparable in x-ray and color to reprint grade products of similar composition, Masstone is lighter in color as a result of the larger grain size.

When 5-2-7 talimidomethyl quinacridone, on a total pigment basis, is included in the grinding process in acetate/medium, it skews well toward the commercial grade product in mass tone depth, but
A product is obtained in which the viscosity of the dispersion in a thermosetting acrylic paint is improved.

EXAMPLE

Using the nine mill and milling operations described in Example VIK.

Part of crude r-quinacridone SO, 20 parts of crude 2,9-dimethylquinacridone, and 5 parts of anhydrous sodium sulfate are mixed and ground. The resulting pulverized powder is divided into 5 parts and separated into 5 parts.
Grind in organic liquid as described in Example VIK. 1st
In implementation (m), acetone was used as the organic liquid, and the second
In the fifth implementation (b), methanol is used as the organic liquid, and in the fifth implementation (e), Improlzonol is used as the organic liquid. Purification and surface treatment were as described in Example ①. 9. The particle size of the obtained product is different. (c) has the smallest particle size and is therefore dark in color and the most transparent. Product 11 (b) Fi particle size is intermediate, product (a) #i particle size is largest, lightest color and paper masonry is the most opaque. In color tone all three products are essentially the same. Therefore, two products with nine different particle sizes can be made by changing the organic liquid in the second grinding step.

Example xm In this example, for the particle size of the product described in Example x■. Describe the effects of water used in combination with water-miscible organic liquids.

Using the pulverized powder produced in the dry pulverization process of Example ①.

(d) 100-acetone (・) 78.54 acetone + 21.5-water (f) 50-
Grinding in an organic liquid is carried out using acetone + 50 - water (g) 100 units of propatool (h) 50 - units of propatool + 50 - water according to the procedure of Example (2).

Purification and surface treatment are the same as those described in Example ①.

The resulting pigment was rub tested in two lithographic varnishes and is very similar to what can be expected in some automotive finishes. The mass tone is slightly darker and more transparent than the product (el), and the product (f)
) The product (s) is slightly darker than the product (d). Product (h) Fi is slightly darker in color than Product (f) and (gl).In this way, in the grinding process in an organic liquid, when the organic liquid is diluted with water, the particle size can be controlled by K. Can be done.

Example 2 This example describes the preparation of pigmentally unsubstituted medium nacridone.

50 parts of γ-quinacridone and 50 parts of mono-β-quinacridone are both milled for 96 hours using the mill and grinding media of Example 1.

The pulverized powder thus produced is pulverized together with an organic liquid by the procedure described in Example ①, and purified in accordance with the report of the same Example.

(,) 13.2 parts of (b) (, 1152 parts of (a) + 2-7 thalimidomethylquinacridone (P) 1! 1.2 parts of (a) + 41 phthalimidomethyl quinacridone (q) 152 parts - (r) 15.2 parts -+2- 7-talimidomethyl quinacridone (s) 1 part 2 parts -1,4- 7-talindomethyl quinacridone product (n) # (o) and (plHα - Quinacridone.

When tested by friction in lithographic ink, the product (tl)
exhibits very light mass tones and weak tones. The product (ol F! Masstone is darker in color).

In this respect it is as warm as pigmented products. Product (q) Fi product (・) is darker in second mass tone.

Products (q), (F, l and (s)#- are slightly α-
β-quinacridone including quinacridone. Product (q
) The H mass tone is very bright and the Sho9 tone is weak.

Product (r) is substantially more intense in tone, has a slightly darker mass tone, and is about as dark as the commercial product. The product (-) is much darker in mass tone than the product of comparable color strength (rl, but slightly yellow due to the large amount of crystallographic impurities in the α-quinacridone).

Patent Applicant: E.I. du Bon d'Aunemur & Company

Claims (1)

[Claims] A quinacridone of the formula,! and mixtures thereof, and quinacridones of the formula up to 15% by weight in which R1, y, Ha,
R4, R1 and V are hydrogen, fluorine, chlorine, bromine, methyl or methoxy: Rt, B* and R1
11 is hydrogen or chlorine; and Ha is hydrogen, chlorine, bromine, nitro, or an alkyl group of 1 to 5 carbon atoms. From a crude quinacridone consisting essentially of an alkoxy group of 1 to 2 carbon atoms, an alkoxy group of 1 to 2 carbon atoms, and m being an integer of 1 to 4, the crude quinacridone has a low crystallinity. After conversion to the aggregate form, the quinacridone with low crystallinity is milled in an organic liquid effective to improve the crystallinity of the quinacridone particles.
) L, and then the pigmentary product is recovered. A method of producing quinacridone of pigmentary quality. 2. The method according to claim 1. The above aggregate nine low crystallinity quinacridone compositions. After the crude Nacridone was treated with concentrated sulfuric acid KII*. A method prepared by mixing the solution into water to precipitate the assembled low crystallinity quinacridone composition. 3.4! A method according to claim 1. The aggregated low-crystalline quinacridone is obtained by dry ball-milling the crude quinacridone mixture produced by Honshiki Co., Ltd.
lm() is the method of producing a book. 4%% The method according to claim 3. A method in which the liquid is a lower alcohol or ketone containing up to an equal amount of water. 5. The method according to claim 4. The method wherein the organic liquid is acetone. & A method according to claim 5. A method in which the quinacridone is 2,9-dimethylquinacridone and up to 5% by weight of 7-thallimidomethylquinacridone. 7. The method according to claim 5. A method in which the quinacridone consists essentially of 2,9-dichloroquinacridone, including up to 5 weight percent of 7-thallimidomethylquinacridone. 8. The method according to claim 5. □ A method in which the quinacridone is a solid solution consisting essentially of 2,9-dichloroquinacridone, quinacridone and up to 5 parts by weight of phthalimidomethylquinacridone. 9% The method according to claim 5. The quinacridone is quinacridone in 2,9-dimedel,
A solid solution process consisting essentially of quinacridone and up to 5 wt. of 7-thallimidomethylquinacridone. 1α The method according to claim 5. A method wherein the quinacridone is a solid solution consisting essentially of quinacridone, dihydroquinacridone, 4.11-dichloroquinacridone and quinacridonequinone. 11% The method according to claim 5. A method wherein the quinacridone is a solid solution consisting essentially of dP nacridonequinone and anilinoacridone.