JP800H - Method for producing pigment grade pigments from crude pigments - Google Patents

Description

Detailed Description of the Invention This invention is a crude quinacridone or copper phthalocyanine.
Convert a crude pigment such as
This is an aqueous base solution (may contain salt)
Or basic salt solution and at least part of it
In the presence of a small amount of organic liquid present as a second phase
To a pigment form. As-synthesized, so-called crude quinacridone is generally a face
It is unsuitable for use as a pigment and must be used as a pigment.
Required properties such as particle size, grain shape, crystal structure, color strength
Must be further processed to improve the degree,
This is well known in the art. Coarse quinacridone has a face
Those who are most commonly used to change the fee structure
The method is to crush the crude quinacridone with a large amount of inorganic salt.
Then, the resulting pulverized powder is extracted. With salt
The milling method produces a satisfactory pigment for some applications.
Although manufactured, it has two major drawbacks. The first
Is a pigment that can be charged to the mill to use large amounts of salt.
The amount is greatly limited. And don't dispose of a lot of salt
That's what you have to do. And the second is the face you get
The charge is often high solid acrylic for automobiles
Rheological problems when used for final applications such as paint
The problem is to present a needle-like state. There is an attempt not to use salt for crushing crude quinacridone.
Some have been done so far. For example, US Pat. No. 285
No. 7400, a crude pigment is preliminarily powdered in a ball mill.
After crushing, homogenize in acetone and recover from acetone.
And are shown. Also, U.S. Pat. No. 3,017,414
In detail, after premilling the crude pigment in a ball mill,
Emulgio in water of water-insoluble organic liquids such as lorobenzene
And then recovered from the emulsion.
Has been. Production of quinacridone in pigment form from crude quinacridone
Another method is shown in US Pat. No. 3,287,147.
ing. This method is a paste of crude quinacridone with acid.
Product obtained by milling or ball milling in neutral water
The paste is changed to 150 ℃ -300
It is heated to ℃, and it is special for heating under high temperature and high pressure.
Another device is needed. US Pat. No. 4,024,148 describes a new crystalline state.
Of quinacridone is shown. This way
Removes quinacridone that has settled in the aqueous slurry from a large amount of water.
Water-insoluble liquid having at least one acid group and surfactant
The surfactant used is the pigment surface.
Adhere to the surface. Yet another method (US Pat. No. 4,094,699) -this one
The method does not require the use of an organic solvent, but-
Is prepared by cutting the pre-ground quinacridone in an aqueous base solution.
Aging in the presence of both onionic and nonionic surfactants.
There is a way to do it. However, in this method, some of the surfactant is
Deposition on the pigment surface, in some end-use systems
Will be a problem in terms of compatibility. The method of the present invention is based on quinacridone or copper phthalocyanine.
A crude organic pigment, such as nin, is agglomerated by a method such as preliminary crushing
The crystallinity pigment is used and the substance thus obtained is subsequently added to the salt.
Basic aqueous solution, basified aqueous salt solution or basic saline solution
Solution-eg NaHPO_Four, Na_ThreePO_Four-And the few
An organic liquid that is at least partially present as a separate and separate phase
In the presence of a small amount of body, and in the presence or absence of a surfactant
It is possible to easily pulverize the organic pigments that are agglomerated under low temperature and aggregate them.
It consists of converting to a dispersible pigment product. According to the method of the present invention, a particle size growth promoter or a growth agent is used.
With or without the use of length suppressants
To produce quinacridone pigments of all particle sizes
Which gives rise to the rheological properties of the product pigment.
Controls one of the parameters that influences
be able to. Promotion of particle size growth in the method of the present invention
To determine whether to use an agent or particle size growth inhibitor,
The characteristics of the pigment produced, especially the low crystallinity of the pigment.
Whether or not it has the property of growing particles from the state
ing. Further, according to the method of the present invention, the second phase is
By changing the type and amount of the solvent in the
You can also control Generally low
The crystallinity pigment has a pH of 7 to 14, preferably 9 to 13.5.
Small amount of organic solvent present as a separate phase in aqueous base solution
Is crushed in the presence of. Organic solvent at a given concentration
When it is dissolved in water, it is recommended to increase the concentration of the base.
Or from the solution by adding salt to the aqueous base solution
The solvent can be forced to separate. And this one
The result is that the growth of particles is promoted. For example, 75% 2,9-dichloroquinacridone and quina
The production of a solid solution consisting of 25% of clidon is the preferred solution.
When using a medium, i.e., n-pentanol, n-
The amount of pentanol used in this invention at room temperature is
N-Pentanol completely soluble in water at -22 ° C
Is 2.7% soluble in the solution-but with a base,
From the solution by adding an appropriate amount of salt or basic salt
Separates the alcohol, thereby acting on the solid solution
Growth medium can be formed. Ionic strength of the water phase
The higher the degree, the more the alcohol will separate from the solution
To do. For example, 1.2g alum in 100ml water and
2 ml of n-pentanol with 3.7% NaOH
41% of the solution separates from the solution. About twice the amount of NaOH
When the concentration is 7.3%, 68% of the alcohol is separated.
To do. In the latter case, a lithographic varnish is rubbed off.
(out) characteristics show that for some larger particle sizes
The product is obtained. In this case, the grinding is carried out at room temperature.
Grinding at higher temperatures can improve particle growth.
Expected, conversely lowering the grinding temperature reduces particle growth
Expected to do. Also, increase the crushing time to form particles.
It can also be increased in length. Particle size also depends on base concentration
Remains constant and simply changes the amount of organic solvent used.
Can be increased. That is, 1.2 g
2,9-Dichloroquinacridone containing sodium sulfate
/ Quinacridone (75/25) pigment 12g and water 95ml
And milling with 50% NaOH aqueous solution 7.7 g,
When 1 ml of n-pentanol was used,
Generation of smaller particle size than when using 2 ml
Give things. Then, 4 ml of n-pentanol was used.
In some cases, the decrease in tinctorial strength was observed.
The particle size increases to the extent that it can be seen. Preferred n-
The amount of pentanol is 1-2 ml. n-pentanol
The product with very small particle size
It usually has very poor dispersibility and rheology.
Indicates As pointed out earlier, the amount of alcohol present
If kept constant, the amount of base used also depends on the particle size.
Influences. Ie used in said system
The amount of alcohol used is 2 ml, and the amount of 50% NaOH aqueous solution is
When squeezed to 3.9 g, the particle size decreases
Let's do it. Double 50% NaOH aqueous solution to 15.4g
And a significant effect on the color strength of the rubout test.
Particle size increases without reverberation. Required Yes
The amount of machine liquid is generally determined by increasing the ionic strength of the aqueous phase.
Decrease, or by increasing the pH of the aqueous phase.
Needed to produce pigments with optimal strength and rheology
The combination of various ionic strength, pH and the amount of organic liquid is suitable for various pigments.
Each is different and must be decided on a case-by-case basis.
No During the crushing process, the acid attacked the metal crusher, resulting in crushing.
In order to prevent hydrogen from being generated in the
Done in. However, when using a water-soluble solvent
Is the amount of alcohol that the ionic strength of the medium separates from the solution
To decide. Therefore, some of the bases are similar ions
Even if replaced with strong neutral salt, it is the same in the scraping test
A product can be obtained which shows such a result. This aqueous powder
Crushing can be done only in the presence of organic liquid and aqueous base solution.
it can. Preferred base aqueous solution is alkali metal water
Aqueous solutions of oxides, especially NaOH and KOH
preferable. Alternatively, this aqueous grind was made basic
Brine solution-basified by addition of eg NaOH
It can also be carried out in a solution of aluminum sulfate or NaCl.
it can. Alternatively, this water-based crushing may be performed with Na_TwoHPO_Four
Or Na_ThreePO_FourIt can also be performed in a basic solution such as
it can. n-Pentanol partially dissolves in the medium during milling
Therefore, it is believed that it acts as both a solvent medium and a dispersant.
2,9-dichloroquinacridone, this and quina
Solid solution with clidone or 2,9-dimethylquinacry
Manufactures pigments such as dong and solid solution of quinacridone
It is not necessary to use the surfactants normally required to do this. Surfactants can be used during milling if required
However, depending on the characteristics of the activator and the pigment, the activator is
It accelerates or interferes with the pigment aging process. Pigments
0.5-10% by weight of cetyltrimethyl, based on
Quaternary ammonium salts such as ammonium chloride, preferred
Such as benzyltributylammonium chloride
Like quinacridone and especially before dissolving the salt completely in water.
When used with the 75/25 solid solution described in 1.
The length is considerably increased. On the other hand, dodecylbenzene sulfo
A surfactant such as acid or its amine salt
Additives such as talimidomethylquinacridone are small
Slows particle size growth and forms a transparent product.
Shows a great effect on. Condensation product of nonylphenol and ethylene oxide
If a small amount of nonionic surfactant like
Can enhance the growth of particles. This phenomenon is
90% 2,9-dimethylquinacridone and 1 quinacridone
Solid solution consisting of 0% and quinacridone 60% and 2,9
-Produce a solid solution consisting of 40% dichloroquinacridone
It was seen when doing. The use of surfactants is not essential. Because
Water consisting of 1/8 inch (0.00032m) balls
The crushing medium used in the crushing process is pigment and water-based
With enough friction to form an intimate mixture with the aqueous phase
This is because it gives mixing. If desired from an end-use perspective, surface active
Agents may be used. In many universal applications, the interface
Pigments without activators would be desirable. Of this invention
The method is suitable for producing such pigments. 2-
If you use a small amount of phthalimidomethylquinacridone,
The particle size of the resulting product is greatly affected.
It This particle size growth inhibitor can be used even in the liquid grinding process.
It can also be added in the preliminary crushing step before that.
The effect of suppressing growth is higher when added in the preliminary crushing step.
This results in a small particle size and no surfactant
The product can be produced. Quinacridone solid solution pigment particle size control
In the prior art shown in US Pat. No. 3,030,370.
It is difficult with some dispersion grinding methods. Because the preceding technique
In surgery, control of particle size in dilute sulfuric acid
Depending on the aging and extraction process of the
Low crystallinity product produced in an effective dispersion grinding process
Because the effect of growing particles from the quality is relatively small
It It is not possible to make the grinding incomplete to adjust this.
I can't come. Because incomplete crushing results in incomplete solid solution composition
It forms the indicated product. Under the conditions of this invention,
The final pigment product odor with various particle size levels.
Complete solid solution is achieved. The method of the present invention uses particles
Organic liquid to which a size growth inhibitor is added or used
Effects of inhibitors on quinacridone used by adjusting the body
By controlling the fruit, a wide range of particle support
To obtain the desired particle size pigment over
It can also be changed to. Therefore, this invention
According to the method, high tinctorial strength-this
Is generally a feature of small particle size pigments.
Long-lasting and excellent lightfastness-this is generally a large grain
Relatively large, which also shows the characteristic of child-sized pigments
Pigments with a large particle size can be produced. Another advantage of this invention is that the surfactant is
Use surfactants if known to cause harm.
The point is that you can avoid it. Insoluble in water or separated from solution by salting out and separated
It forms a phase and from the low crystallinity state to pigment gray
Any that can grow particles into a substance
Organic liquids can also be used. Completely or completely in water
Mostly insoluble solvents can also be used, but in this case
For this purpose, it is effective to add a surfactant. For example,
2,9-dichloroquinacridone / 75 of quinacridone /
When using o-dichlorobenzene for 25 solid solutions
In this case, a product having a weak coloring strength is obtained,
Lithographic printing varnish (litho
Sufficient strength for scraping test of (graphic varnish)
A product having the formula n-hexano
, Cyclohexanol, cyclohexanone, 2-pen
Use another solvent such as Tanone and n-octyl alcohol
Have very good strength, but n-pe
The product obtained when ntanol was used under the same conditions
Pigment product with smaller particle size compared to
It Of course, all of these solvents are, for example, unsubstituted
It is easy to grow like Nacridone itself and is relatively more soluble.
Larger pigment particles when used with easy-to-understand ingredients
Will grow to size. In a preferred embodiment of this invention, the final pigment constitutes
The raw material ingredients-whether this is a single quinacridone ingredient
Whether it is a 2, 3 or 4 solid solution
-Explosion of mill powder generated in a normal ball mill.
About 8-10% inorganic salt based on pigment to avoid
-E.g. sodium sulphate-co-milled and agglomerated
Use low crystallinity material. Highly aggregated product dust
If it doesn't look like, it ’s not necessary to add sodium sulfate.
There is no. The term "pre-milling" in this invention refers to the complete liquid.
Not be present at all, or if the phase-dominant solvent (phase d
irecting solvent) or a liquid such as a surfactant
If a small amount of these or pigments have powder characteristics,
It means to grind in the presence of a sustainable amount. Alternatively, the agglomerated low crystallinity quinacridone pigment is
Dissolve the crude quinacridone in concentrated sulfuric acid and then add this solution to cold water.
It can also be obtained by introducing it inside. Which way
Even though the resulting low crystallinity highly aggregated face
The material has a weak coloring power as determined by a scraping test,
There is no value. The preferred method for use in this invention is to first use a crude
Dry the nacridone or the crude quinacridone mixture by a conventional method.
After pulverizing in a ball mill,
Diluted base solution, basified salt solution
Rui is a particle size growth promoter in basic salt solution
Ball milling with or without growth inhibitors
There is a way to do it. The small amount of solvent used was crushed
Prior to or during acid extraction, which is usually done later
Must be easily removed by steam distillation and properly disposed of.
Collected if necessary. If the second crush is omitted
The solvent was removed after the mixture was simply refluxed and acidified
In some cases, even if a surfactant is present, 2,9-
Dichloroquinacridone / Quinacridone 75/25 solid solution
The mass tone of the body becomes dark and the coloring power is good.
This is because the product is not matured sufficiently. The organic liquid used in this invention is preferably an acid extraction operation.
At the same time, it has sufficient performance to be completely removed by steam.
There must be. And during this acid extraction operation, crushing
Sometimes the metal bound to the pigment dissolves in hot dilute sulfuric acid.
Also, organic liquids do not corrode mills and grinding elements and
Must be chemically stable in aqueous base. A
Like rucol, ketone, hydrocarbon, chlorinated hydrocarbon, etc.
A wide variety of solvents are suitable. The solvent used individually
It will depend on the nature of the pigment and especially on its solubility.
Cheaper and less toxic solvents are preferred. Organic used
The amount of liquid is relatively about 5 to 25% by weight based on the pigment.
Due to the small volume, this separated, separate non-aqueous phase is
It is generally not economical to recover for use.
The solvent can simply be distilled and condensed to drip. The preferred pigment for use in this invention is quinacridone.
It The quinacridone pigment to which the present invention is applicable is generally
The following formula I Or formula II 15-fold with quinacridone represented by
Up to 5% by weight, preferably up to 5% by weight of formula IIIThe odor in the above formula consisting essentially of quinacridone
And R¹, R^Two, R^Three, R^Four, R⁵And R⁶Is hydrogen,
R, which is fluorine, chlorine, bromine, methyl or methoxy⁷, R
⁹And R^TenIs hydrogen or chlorine, R⁸Is hydrogen, chlorine, bromine,
Nitro, alkyl group having 1 to 5 carbon atoms, 1 carbon atom
Or an alkoxy group of 2 or benzoylamino. Change
Is an integer of 1 to 4. R¹And R^TwoWhere H is H
Quinacridone of I-this is, for example, a diluted base
Particle growth in a mixture of aqueous solution and n-pentanol
Is undesirably easy to occur-if pigment particles are used
Are undesirably large, resulting in a pigment product
It will be opaque and the color strength will be reduced.
To such a pigment, 1.0 weight of the quinacridone derivative of formula III is added.
Particle size growth can be achieved by adding a small amount such as
Sufficiently restrained and attractive wear in metallic finish
A product with color characteristics can be obtained. The term "consisting essentially of" means dihydroquinac
Other such as redone or anilinoacridone stabilizer etc.
Excludes that the substance is present as a minor component
Other substances reduce the pigment properties of quinacridone pigments
When it is present in such a large amount, it is excluded. It is not possible to limit the time of the liquid grinding process. why
If so, the quinacridone or quina that the grinding time is processed
Clidon mixture, mill loading and use
It depends on the type of mill. Under given conditions
To determine the optimum time to grind a pigment in
In order to achieve this, the present invention can be carried out using two different grinding times.
A sample of the final product that is
A method of comparing with the quasi-sample is suggested. Commercial size
Sano mill generally requires at least 4 to 6 hours.
It may extend to 12-24 hours or even longer
I can't. Laboratory scale or semi-utility scale mill
Then, much longer time is required. Liquid grinding is general
Should be performed at 10 ° C to 60 ° C, and 20 ° C to 50 ° C.
Is preferred. After the milling operation, the pigment slurry is diluted with water to a pH of 1-1.
After being made acidic, it is heated and dissolved by steam distillation.
The medium is distilled off and the grinding medium is used during dry and wet grinding operations.
Dissolves the metal that is grated from the body. Of this extraction process
After that, the pigment is separated by filtration, washed and dried. The quinacridone pigment produced by the conventional method is often used.
It has a needle-like shape, but it is manufactured by this invention.
The pigment particles formed have a platelet-like shape. This invention
The quinacridone pigment produced by the method of
If surface treatment such as that shown in
It has a plate-like shape and particle size
In order to be able to
More desirable than Don pigments. Made by the method of this invention
The pigments produced are better than conventional quinacridone pigments
Has excellent rheological properties. This was developed for automobiles
High Solid Content Thermosetting Acrylic Enamel Solid Colorant
It is best understood when used as (solid color). Servant
This is because most of the quinacridone pigments from the past have high viscosity.
While it cannot be practically used in these systems, this
The quinacridone pigments produced according to the invention are in these systems
Can be used. The products of this invention also have normal heat.
Good rheological properties even in curable and thermoplastic systems
Shows sex. So far, solid color enamel solid color (solid colo
2,9-dichloroquinacry satisfactory for use as r)
To obtain a solid solution with Don pigment or its quinacridone
And was difficult. According to the present invention, 2,9-dichloro
75% / 25% solid solution of loquinacridone and quinacridone
Body, corresponding 90/10 solid solution or 100% dichlor
Made of roquinacridone for new high solids enamel
However, it is easy to produce a satisfactory pigment. For various systems
2,9-dimethylquinacridone face that is attractive to be present
A solid solution or a solid solution of it with quinacridone
You can In addition, other useful solid solution combinations
You can also make it. Smaller particle size with particle size growth inhibitors
The product of, thermosetting enamel or thermoplastic
Appropriately dispersed in a car topcoat made of lacquer
For excellent strength and geometrical isomerism--usually two ton
e) Effects or called flip-flops
It is possible to obtain finishing paints with and. Characteristics of the latter
Is a peculiar aesthetic value, and changes in color depth depending on the viewing angle
And it often appears as a change in hue.
This effect is a flat pane covered with a metallic finish
Slowly rotate the panel from a vertical angle to an obtuse angle.
It can be observed. See if this two-color effect increases
Color depth when the angle is changed from vertical to either direction
Will increase. In the presence of 2-phthalimidomethylquinacridone
The product particles aged to show a greater dichroic effect
Has less light scattering when dispersed properly and enhances the two-color effect.
Smaller pigments with smaller particle size
It is. The odor of the pigment produced by the method of the present invention
That a larger two-color effect is achieved by
Pigments do not use pigment growth inhibitors or
Particles that are sufficiently smaller than the product when used without
The size of the X-ray
It is also confirmed by measurement. Aluminum quinacridone sulfonate treated with
The product of the invention of is in a thermosetting acrylic enamel system?
Has a good two-color effect and is therefore aesthetically pleasing and rheological
It is also a pigment with good characteristics. In the following examples, all "parts" are by weight.
It Example I In this example, the liquid grinding process was performed using two sodium hydroxide.
With and without quaternary ammonium salt
Do both if not, dichloroquinacridone /
It is for producing a quinacridone solid solution. Approximately 1/2 inch in diameter (0.
0127m), 1/2 inch long (0.0127m)
Scale cylinder "Cyl-Pebs" 1000 parts, 4 inches
(0.1 m) nail "twenty penny" 100 parts, rough
30 parts of 2,9-dichloroquinacridone, crude quinacridone
Charge 10 parts and 4 parts of anhydrous sodium sulfate. The mill
48 hours 55 at 40 rpm, which is about 74% of the critical speed
Rotate at ~ 60 ° C. “Critical speed” means
The force that exceeds the gravity causes the grinding element to stay on the outer wall of the mill.
Means a card. Open the mill and fill the contents with “Cyl-Pebs”
And the nail is separated and removed through a screen
You Next, a part of the obtained mill powder (0.029 parts)
Made of steel with a diameter of 1/8 inch (0.0032 m)
Ball 1.32 parts, water 0.20 parts, 50% NaOH aqueous solution
Contains 0.034 parts and 0.0036 parts of n-pentanol
Charge into a laboratory scale ball mill. This Mi
The rotor is rotated for 72 hours at about 74% of the critical speed. That
After that, the contents of the mill are separated from the steel balls by a disc.
Open on the lean. Wash the balls with water (about 0.4 parts). Substance
Collect all pigments as a slurry. This basicity
Dilute sulfuric acid is added to the slurry to neutralize NaOH and
Acidify to about 1.3-1.5. In this slurry
Steam is passed until the temperature reaches 87-93 ° C, which
The alcohol is distilled off and the temperature is raised to 87-93 ° C for 1 hour.
Keep for a while. Next add 0.006 parts of alum
Quinacridone monosulfonic acid 0.0011 parts aqueous slurry
Add Lee over 30 minutes. This allows the pigment surface to
About 4.3% aluminum quinacridone monosulfonic acid
Deposit salt. Heat to 87-93 ° C for another 30 minutes
Continuing the process, the product is isolated by heating and the acid is gone with warm water.
Wash until dry. 0.026 parts of pigment recovered
It The product obtained is somewhat larger than the commercially available product.
However, its rheological properties are better than expected.
Really excellent. Even in the high-solids type enamel system,
The products usually have attractive rheological properties, unlike
Show. Test this car finish paint routinely
And a wider particle size distribution with a smaller particle size
Compared with the product that has this high solid content enamel mill base
Is about 1/10 of the yield stress (dyne /
cm²And a 3.6-fold decrease in viscosity. This
The beneficial properties of solid red for automotive topcoat finishes
It is especially important to form. Use the same mill powder as above but reduce the NaOH concentration by about 50%.
Reduce (0.21 parts water and 50% NaOH aqueous solution 0.0
(I used 17 parts)
Grinded in the same aqueous medium by the method described previously,
Very rheologically superior to products of the same composition
(Millbase viscosity is 2.6 times lower) but higher base concentration
Rheologically inferior to the product obtained at below
A small particle size product is obtained. Aqueous grinding under lower base concentration, water and hexylene green
Add tributylbenzylammonium chloride to the mixture with caul.
0.002 parts of a solution prepared by dissolving 44.4% of loride
All we have to do is change to the previously mentioned method
So, again, the particle size is so large that the stone
When performing a rubout test on a plate printing varnish
Masstone gives a brighter product. High solidity
In mold enamel this product is of similar composition on the market
It has a mill base viscosity that is about 41 times lower than that of
Shows a prominent millbase rheology. Example II This example illustrates the agglomeration performed prior to the liquid grinding process.
Of alternative methods for producing low crystallinity quinacridone
Is. In 552 parts of concentrated sulfuric acid stirred at a temperature of 30 ° C or less
To 37.5 parts of crude 2,9-dichloroquinacridone and crude
Add 12.5 parts quinacridone. The substance is completely in solution
100% while maintaining the temperature below 30 ℃
Add 184 parts of sulfuric acid. Material dissolves after stirring for 15 minutes
It The resulting solution was stirred for 30 minutes and stirred for 2000 parts.
Slowly add to water in 30 minutes and form during this time
Keep the slurry at 0-10 ° C. Have a product
Isolate, wash with water until acid-free and dry. 48.5 copies
A dry product of is obtained. The product was prepared in the original water / pentanol shown in Example I.
Ball mill with the same concentration and make it with the attrition mill method
Exactly the same product as the product obtained from the low crystallinity precursor
Masston produced a pigment close to that of tint. Liquid powder
The product before grinding is weaker and even colorier than the final pigment
There wasn't. Example III In this example, the ionic strength of the aqueous solution is the alcohol content.
It shows the effect of separation and pigment growth on particles. Millpau made according to the method described in Example I
13.2 inch diameter (0.0032
m) steel ball 600 parts, water 95 parts, 50% NaOH
Containing 7.7 parts of aqueous solution and 1.63 parts of n-pentanol
Charge into a laboratory scale ball mill (A). Already
In one similar experiment, mill contents were tested at critical speeds.
Anhydrous sodium sulfate before spinning at about 74% for 72 hours
Add 4.54 parts more (B). And on the third mill
Then, reduce the amount of water to 90 parts and add 50% NaOH aqueous solution.
Was increased to 15.4 parts (C). The three mills were carried out in the manner described in Example I.
It was Although C and B have different NaOH concentrations,
Both mass tone and tint scrubbing test
Show similar results to each other. On the other hand, A is Masstone
Is darker, which is the smaller particle size of the product
It is shown that. This is because the presence of sodium sulfate is B
Bring the total ionic strength of the aqueous solution close to the C level, and
It is believed that it produced a product with various coloring properties. one
Direction A is crushed in a medium with a half ionic strength, so n-
Pentanol only separates little from aqueous solutions, so
Products of darker mass tone with smaller particle size
It seems to be a waste. Example IV This example shows an example using another alcohol.
It n-amyl alcohol was added to (A) 1-hexanol 1.
63 parts or (B) cyclohexanol 1.92 parts
Otherwise, all the same as shown in Example III-A.
Pigment A using mill powder, milling conditions and treatment method
B was obtained. These pigments A and B have sufficient coloring strength and both
Are similar to each other in tint and mass tone
It was Furthermore, both were crushed in the presence of n-pentanol.
The mass tone is much higher than the corresponding product
It was dark. n-Pentanol grows particles of this pigment
More effective as a medium. Example V This example is an example using a substantially water-insoluble organic solvent.
is there. n-Pentanol was added to 0.0057 parts of o-dichloroben
Replace with Zen, and use nonionic surfactant (p-noni
Condensation product of luphenol and ethylene oxide)
Example except that 0.0013 parts was added
Same as described in I (for higher base concentration)
The product using powder, milling and processing conditions
Obtained. This product is comparable to the product described in Example I.
Is Masstone darker and tint stronger than anything?
It was. The method of this example reduces the relatively small particle size.
Moisture, producing a sufficiently strong pigment. Example VI In this example, a liquid pulverization process is performed by using two different quaternary annes.
Method with or without monium salt
And 2-phthalimidomethylquinacrid in liquid pulverization process
2,9-dichloroquinac
It is for producing a redone pigment. The same semi-practical scale ball mill used in Example I
And the same grinding media used in Example I, 2,9-di
40 parts of chlorocunaclidone and 4 parts of sodium sulfate
Charge, grind as described in Example I, and remove.
It was A part (0.12 parts) of the mill powder thus obtained
Steel ball with a diameter of 1/8 inch (0.0032m) 5.
29 parts, water 0.84 part, 50% NaOH aqueous solution 0.14
Scale containing 0.01 part of n-pentanol and 0.014 part of n-pentanol
It was charged into the ball mill. Then steer the mill contents
Open the ball on the screen to hold the ball, and put the ball in water (about 1.8
Part) to collect substantially all the pigment as a slurry.
I have Dilute sulfuric acid is added to the stirred slurry to neutralize the base and
The pH was adjusted to about 1.3-1.5. Opened the resulting slurry
Heat with steam in a beaker to raise the temperature to 87-93 ° C.
The temperature of the germ was kept for 1 hour. Next alum 0.02 parts
Quinacridone monosulfonic acid 0.0044
A portion of the aqueous slurry was added over 30 minutes. Furthermore
Continue heating at 87-93 ° C for 1 hour before overheating the product.
The extract was washed with warm water and dried until free of acid.
0.12 parts of pigment are recovered. The obtained product is excellent in high-solid content enamel system.
Showing rheology. For high-solid type heat-curing system for automobiles
Tested at the same time, but the same color but quinacrid on the market
Compared to products of different composition and particle size.
Rubase is 5 times higher with 11.6 parts lower yield stress
Shows a decrease in viscosity. This makes high gloss clear (disti
Enables solid red with nctness). 44.4 of tributylbenzyl ammonium chloride
% Water / hexylene glycol mixture solution 0.0079 parts
Repeat the above-mentioned aqueous crushing by changing
The slurry was then processed as above to isolate the product. stone
As a result of a scrubbing test in a plate printing varnish, the mast
Somewhat brighter (larger particle size) formation
The thing was obtained. In high solids enamel this product is
Good rheology, ie tetraalkylammonium
Using the same product made in the absence of halide,
Rheology with a 7.5 times lower millbase viscosity than namel
Indicates This tetraalkylammonium chloride
Is a particularly attractive grain growth promoter. Because this
Are completely dissolved in water and washed off from the pigment surface.
This may interfere with the subsequent end use of the pigment.
Because there is no. However, particle size growth effect
Can also be used by using other quaternary ammonium salts
Was shown. An amount of selenium equivalent to 3.3% based on the pigment
Chilltrimethylammonium chloride in water / organic liquid
Other than this example with the only difference being that the milling process is used.
By performing the method described in
To obtain products with increased opacity
It was On the contrary, a small amount of 2% of 2-phthalate based on the pigment
Water / organic liquid powder using imidomethylquinacridone
After the crushing process, the lithographic printing varnish was scraped off.
Test results show very dark mass tone (smaller particle size
Product) was obtained. Raw of this smaller particle size
The product is larger and has higher value for car finishing
Suitable for metallic finish paints with excellent two-color effect. Example VII This example shows 2,9-dichloroquina on a semi-practical scale.
Production of 90% / 10% solid solution of Clidone / Quinacridone
To do. Scale ball 97 with a diameter of 1/8 inch (0.0032m)
Example VI into a semi-practical scale ball mill containing 5 parts
Pre-milling method described (with 2,9-dichloro in mill)
The point is to insert 36 parts quinacridone and 4 parts quinacridone.
20 parts of mill powder made by changing the case), water
107 parts, 30% NaOH aqueous solution 56 parts, n-pentano
562 parts and benzyltributylammonium chloride
Ride's 40% water / hexylene glycol mixture solution
0.45 part was charged. Rotate the mill at 40 rpm for 38 hours
did. The internal temperature of the mill was 30 to 32 ° C. Open this mill and squeeze the contents into a steel ball
I took it out. Wash the ball with water and practically all
The pigment was collected as a slurry. Add dilute sulfuric acid to the obtained basic slurry to remove NaOH.
It was then acidified to a pH of about 1.3-1.5. By steam
Heat the slurry to 87-93 ° C to drive off the alcohol.
The product was then alum as described in Example I.
And quinacridone monosulfonic acid slurry,
Approximately 4.3% aluminum quinacridone sulfonate on the surface
Deposited. This slurry is about 30 minutes 87-93 ℃
The pigment was isolated by filtration, washed and dried. This pigment has improved rheology in high solids enamel
Characteristic and excellent image as solid red for automobile finishing
It exhibits high gloss and distinctness. Example VIII This example illustrates the use of a ketone as the organic solvent phase.
You 2,9-Dichloro prepared by the method described in Example VI
Further grind loquinacridone mill powder as follows:
It was 13.2 parts of the mill powder were added to a diameter of 1/8 inch (0.
0032m) steel ball 600 parts, water 90 parts, 50%
NaOH aqueous solution 15.4 parts, 2-pentanone 3.24 parts
And nonionic surfactant Igepal CO-970 (nonylphene
0.6 part of a condensation product of a norl and ethylene oxide
Charged into a laboratory scale ball mill containing. The resulting slurry was treated as in Example I and scraped off.
Results of crushing test Grinding in the presence of n-pentanol
Much the same masstone as the pigment of Example I, especially tint
12.2 parts of pigment having exactly the same t) are obtained. Example IX This example shows, with and without surfactant,
Manufacture of 9-dimethylquinacridone / quinacridone solid solution
To do. Approximately 1/2 inch in diameter in a semi-practical scale ball mill
(0.0127 m) 1/2 inch long (0.0127 m)
m) Steel cylinder "Cyl-Pebs" 1000 parts, 4 in
100 parts of "twenty penny" nail (0.1 m), rough
36 parts of 2,9-dimethylquinacridone, crude quinacridone
Charge 4 parts and 4 parts of anhydrous sodium sulfate and add 55
Rotated at ~ 60 ° C, 40 rpm for 48 hours. Open the mill
Screen for "Cyl-Pebs" and nails
Taken out through. Next, a part (0.29 part) of the obtained mill powder was directly added.
Steel ball with a diameter of 1/8 inch (0.0032m) 10.
57 parts, water 1.98 parts, 50% NaOH aqueous solution 0.34
Parts, dodecylbenzene sulfonic acid isopropylamine salt
(Surfactant) 0.01 part and n-pentanol 0.0
A laboratory scale mill containing 36 parts was charged. The mill
In the mill, it rotates at about 75% of its critical speed for 72 hours.
The contents were opened on a screen holding steel balls. Suchi
Wash the ball with water and collect all diluted slurries from the mill
It was The total slurry volume was about 3 liters. In an open beaker
At this time, add 33% sulfuric acid to this slurry to adjust the pH.
Adjusted to 1.3-1.5. Then steam in this slurry
The temperature was raised to 87-93 ° C through this and maintained at this temperature for 1 hour.
During this period, the alcohol was distilled off by steam during this period. Next
Then add 2-88 parts of water to 0.088 parts of this hot slurry.
0.0079 parts of talimidomethylquinacridone suspended
The resulting slurry was added and stirred for 1 hour at 87-93 ° C.
I kept the heat. The product is separated by filtration and warm water free of acid
It was washed and dried, and a part was dried at 80 ° C. 0.26 in all
Some pigment was recovered. The product is more transparent and commercially available 2,
9-Dimethylquinacridone Magenta with a color similar to
Zenta-colored pigment, very quickly in industrial alkyd systems
Exhibits rheological properties. Moreover, this product is an excellent product.
Good workability and good for ordinary universal colorant systems
Shows coloring properties. Is the surface active agent dodecylbenzene sulfonic acid itself?
The same result can be obtained. However, the interface
When performed without activator, it is somewhat opaque (opaqu
e) but the tint is similar to larger particle size
The product of is obtained. This was obtained without using a surfactant.
The product of is extremely rare in the usual thermosetting enamel system for automobiles.
Shows good performance. Example X This example uses an orange solid solution quinacridone pigment.
It is manufactured. 1/2 inch diameter in laboratory scale ball mill
(0.0127 m) steel ball 1500 parts, roux
150 parts of roofing nail, coarse gamma
21 parts of clidon, 1 part of crude 4,11-dichloroquinacridone
4.5 parts, crude quinacridone 9.5 parts, 6,13-dihydride
5.0 parts roquinacridone and 5.0 anhydrous sodium sulfate
Section and load the mill at about 75% of the critical speed for 96 hours
It rotated. Open the mill and put the contents into balls and nails.
Taken out through the screen to fasten. 1 part of the obtained mill powder (13.2 parts)
/ 8 inch (0.0032m) steel ball 600 parts,
95 parts of water, 7.7 parts of 50% NaOH aqueous solution and n-pen
Laboratory scale ball mill containing 1.63 parts of tanol
Insert the mill into the mill and run the mill at about 74% of its critical speed.
It rotated for 72 hours. Fasten steel balls to mill contents
On the screen and wash the balls with water (about 200 parts).
Thus, substantially all of the pigment was collected as a slurry. e
The resulting slurry with 4.3% aluminum quinacridone
As described in Example I, including treatment with luphonate
By the method, 11.8 parts of orange pigment was obtained. The pigment obtained is similar with regard to X-ray pattern and color.
It was comparable to the commercial product with the composition of. But Masston is larger
It was brighter as a result of the threshold particle size. In the liquid crushing process, 2-phthalimide
When 3% of tilquinacridone is used,
A product with a stone depth was obtained. Example XI This example shows a transparent quinacridone /
Made 60/40 solid solution of 2,9-dichloroquinacridone
It is to build. 30 parts crude gamma quinacridone, 2,9-dichloroquina crude
20 parts of clidon and 5 parts of anhydrous sodium sulfate were used as examples.
Co-milled with the mill and milling method described in X. The resulting mill powder was then pigmented in a ground mixture and
2% by weight of 2-phthalimidomethylquinacridone
All others are described in Example X, with the only changes being made.
Crushed in dilute aqueous base solution in the presence of n-pentanol
did. In order to suppress the growth suppression effect, the less active suppression
Or 4% by weight based on the pigment
Nonionic surfactants such as Igepal CO-970
You can also add. Actual treatment method and surface treatment
The procedure was as described in Example I. The resulting pigment is odorless in the latest high solids content enamel system.
In comparison with existing commercial quinacridone pigments with similar color,
Provide a mill base that exhibits a viscosity reduction of about 3 times overall. Example XII This example produces a beta quinacridone pigment product.
It is something. 50 parts crude beta-quinacridone and 5 parts anhydrous sodium sulfate
Was milled for 72 hours on the mill described in Example X. The mill powder obtained was mixed with 4% by weight of 2 in the grinding mixture.
-Only adding phthalimidomethylquinacridone
Alternatively, all other n-as described in Example X
Trituration in dilute aqueous base in the presence of pentanol. The mill contents were prepared in a manner similar to that described in Example X.
Leak out and adjust the aqueous slurry to pH 1.3-1.5 with dilute sulfuric acid
After that, steam is passed through the stirred slurry to bring the temperature to 87-
Raised to 93 ° C. Keep this slurry at this temperature for 2 hours
The product was then isolated by filtration and freed from acid with warm water.
Washed until Violet powder dried at 80 ° C
Got The tint from the rubout test is
Strong and masstone produces commercial beta-quinacridone
It was brighter than anything. Example XIII This example demonstrates the preparation of a gamma quinacridone pigment product.
It is something. Gamma quinacridone 50 parts, anhydrous sodium sulfate 5 parts and
And dimethylformamide 2 as phase control solvent
Parts for 40 hours using the mill described in Example X
did. The mill powder obtained was processed as described in Example XII.
In addition, n-pentanol and 2-phthalimidomethylquina
Trituration in dilute aqueous base in the presence of clidone. And extract
It was carried out as described in the published Example XII. This gamma quinacridone when added to a lithographic printing varnish
Pigments are tinted compared to commercial gamma quinacridone products
(tint) is stronger, mass tone is more opaque
que). Example XIV This example illustrates the addition of a semi-chlorinated copper phthalocyanine pigment.
It is manufactured. 4-chlorophthalic acid and phthalic anhydride were converted into urea and chloride.
Crude containing 4.5 wt% chlorine obtained by reacting with 1 copper
Commercial scale with semi-chlorinated copper phthalocyanine without additives
It was pre-ground with. 12 parts of the obtained mill powder is ⅛ inch in diameter
(0.0032m) steel ball 600 parts, water 95 parts,
50% NaOH aqueous solution 7.7 parts, dodecylbenzenesulfate
0.48 parts of isopropylamine sulfonate and n-penta
In a laboratory scale ball mill containing 1.63 parts of knoll
Load the mill into the mill and run the mill at about 74% of its critical speed.
Crushed for 72 hours. After separating the slurry from the steel balls, the material was tested in Example XI.
Processed as described in I. The product obtained was found to have masstone and
Almost the same as commercial pigment in both tint and tint
It showed a bad result.

Claims (1)

Claims: 1. A solution obtained by dissolving a crude pigment in concentrated sulfuric acid is poured into water to precipitate a composition having a low crystallinity. Or the liquid is completely absent or if liquids such as phase controlling solvents or surfactants are used, these are present in small amounts or in amounts sufficient to maintain the powder properties of the pigment to give crude pigment. After conversion of the crude pigment precursor into agglomerated pigments of low crystallinity by pre-milling; (b) the obtained low crystallinity pigments having a pH of 7-14,
And 5 to 25% by weight, based on the pigment, of alcohols having 4 to 8 carbon atoms, ketones having 5 to 8 carbon atoms and halogenated aromatic compounds having 6 to 8 carbon atoms. Milling in water containing an organic liquid to give a two-phase system; and then (c) recovering the pigment grade product from the crude pigment precursor to the finished copper phthalocyanine pigment or Or A quinacridone or a plurality of quinacridones represented by A method for producing a finished pigment consisting essentially of a solid solution or mixture with quinacridone represented by: However, in the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶
Represents hydrogen, fluorine, chlorine, bromine, methyl or methoxy, R ⁷ , R ⁹ and R ¹⁰ represent hydrogen or chlorine, R
⁸ represents hydrogen, chlorine, bromine, nitro, alkyl having 1 to 5 carbon atoms, alkoxy having 1 to 2 carbon atoms or benzoylamino, and m represents an integer of 1 to 4. 2. A process according to claim 1 in which the agglomerated pigment of low crystallinity is prepared by grinding the crude pigment in the complete absence of liquid. 3. A method according to claim 1 wherein the water has a pH of 9 to 13.5. 4. The method according to claim 1, wherein the organic liquid is pentanol. 5. A process according to claim 1 wherein the quinacridone consists essentially of 2,9-dimethylquinacridone and up to 5% by weight of phthalimidomethylquinacridone. 6. A process according to claim 1 wherein the quinacridone consists essentially of 2,9-dichloroquinacridone and up to 5% by weight of phthalimidomethylquinacridone. 7. A process according to claim 1 wherein the quinacridone is a solid solution consisting essentially of 2,9 dimethylquinacridone, quinacridone and up to 5% by weight of phthalimidomethylquinacridone. 8. A process according to claim 1, wherein the quinacridone is prepared in the presence of 0.5 to 10% by weight, based on quinacridone, of benzyltributylammonium chloride. 9. A process according to claim 1 wherein the quinacridone is a solid solution consisting essentially of 2,9-dichloroquinacridone, quinacridone and up to 5% by weight of phthalimidomethylquinacridone.