JPS6051506B2 - Method for producing highly dispersible dye formulations - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION French Patent No. 205,909 describes a method for producing colored molded bodies made of polymeric synthetic resins.

According to this method, water-insoluble, hydrophobic, highly polymeric synthetic resins in the form of granules, chips or powders and which do not dissolve or swell poorly in either liquid phase of a two-phase system can be mixed with each other. In a mixture of hydrophilic and organophilic solvents that dissolve together to a finite extent to form a two-phase system, the solubility in the organophilic part of the two-phase system is greater than the solubility in the hydrophilic part. The solvent is removed and the formulation thus obtained is shaped from the solution or from the melt, optionally with the addition of untreated synthetic resin.

When using synthetic resins in powder form, it is surprisingly possible to produce very concentrated dye formulations containing dye in amounts of 50% or more.

Known synthetic resins which are particularly suitable for the latter embodiment are polyamides, polyesters, but especially polypropylene and polyacrylonitrile in powder form.
The inventor has also found that a number of synthetic resins, which are actually in powder form but which, unlike the resins mentioned above, do not dissolve or swell very well in the organic part of the two-phase system, can also be used as carrier resins. I found that it can be used with good results.

It is only important that these resins are themselves insoluble in the two-phase system and are coated with the organic phase of the system in a solid state, such as a powder with a high surface area.

The process of the invention therefore offers the possibility of producing highly dispersed, concentrated liquid to solid formulations of dyes and pigments and a range of other polymeric carrier materials, which This considerably expands the scope of use of such formulations and therefore represents a major advance in technology.

The process of the present invention provides for the preparation of concentrated liquid or solid dye formulations with good dispersibility, in which (1) methylalkyl (C2-C4) forms a two-phase system in and/or with water;
) Ketone, acetylacetone, cyclohexanone, isophorone, mesityl oxide, C4-C6 alkanol, cyclohexanol, ethylene glycol ace. tate, formate ethyl ester, acetate ethyl ester, acetoacetate methyl ester, and acetoacetate ethyl ester suspended in an organic solvent.
(2) micronizing a suspension of a dye having a water solubility of less than m9/' in the presence of a mechanical grinding aid until the particle size of the suspended dye is less than 10 microns; (3) add water or the organic solvent necessary to form the two-phase system; (4) remove the mechanical grinding aid from the turbidity; (4) add the lower Alkyl cellulose ether, hydroxy-lower alkyl cellulose ether, cellulose acetate (degree of substitution 2 to 3), cellulose acetate propionate, cellulose acetate butyrate, carboxymethyl cellulose, polyacrylate, polymethacrylate, polyvinyl alcohol, polyvinyl ether of octadecyl alcohol, vinyl chloride and vinyl acetate, an acetone-soluble copolymer of acrylonitrile, vinyl chloride, and vinylidene chloride, a cyclohexanone resin, a hydrocarbon resin, an abietic acid derivative, and a salt of behenic acid. or adding a polymeric carrier that is soluble in the organic solvent but insoluble in the two-phase system; After processing,
(6) removing said solvent and (a) drying the resulting dye formulation; or (b)
This is a manufacturing method characterized by dispersion in water or an organic solvent.

Although it is possible to obtain liquid formulations by removing only a portion of the solvent used in the above operations, it is also possible to produce solid formulations so that the scope of use of these formulations is not limited by the solvent. is generally suitable.

In order to coat the polymeric carrier material as thoroughly as possible, it is important that the surface area of this carrier material is as large as possible.

However, they do not need to be so minute that they can no longer be distinguished. This is because, contrary to all similar known methods, the dye particles are not wrapped in a synthetic resin, but the polymer particles probably serve as carriers and are coated with the dye particles in a saw-like manner as much as possible ( This occurs with the help of the organic phase which forms the film). The carrier resin can be dissolved in one phase of the two-phase system.

In this case, the carrier resin precipitates out in the formation of a two-phase system, the particularly large surface of which is coated with the dye suspension. However, according to this method, the synthetic resin is usually precipitated in a gelatinous or grease-like form that is difficult to filter out. It is therefore better to introduce the pulverized synthetic resin after the formation of the two-phase system. However, it is best to combine these two possibilities.

That is, a small portion of the carrier polymer is dissolved in the solvent and the majority is introduced after the formation of the two-phase system. In this way, the former greatly increases the effective surface area and, together with the dye, is further deposited minutely on the latter, producing a powder that can be filtered out well. The particle size of the carrier particles can lie in a wide range from 1 to 500 microns, but this does not apply to dye particles.

When using the formulations according to the invention, the carrier resin is effectively brought into solution, but the dye particles are mostly present as initially divided particles. The inventor has discovered that the desired particle size of less than 10μ, preferably less than 2μ and the necessary uniform dispersion of the dye is best achieved by milling in a solvent in the presence of quartz sand, glass balls or steel balls. I learned. Mills of this type are available. Examples include burr mills or dyno mills. It should be noted that this mechanical refinement can optionally be combined with chemical treatments such as redissolution, reprecipitation or rebuilding treatments. To maintain the stability of the dye dispersion in the medium used, generally 1 to 2
A particle size of μ is sufficient.

If the dye itself is soluble in the medium used, there is no point in grinding it finer. This is because more carrier resin is required. Also, only for pigments whose particles remain unchanged, a particle size of less than 1 micron may be advantageous with respect to color density and sharpness and can be reached immediately. For example, a dye suspension in water can be milled.

However, it is better and faster to carry out this mechanical refinement by grinding in a solvent. In any case, since the solvent must be recovered by azeotropic distillation, and environmental protection is an unavoidable requirement for engineers, it is reasonable to use the water-containing organic phase of the azeotrope for grinding. Desirable and best at the same time. Dispersants are necessary in order to stabilize the dispersion, especially when milling in water. However, they must not in any case interfere with the formation of a stable two-phase system by emulsification of the organic phase. This is because this emulsification eliminates the film-forming ability of the organic phase and is no longer capable of producing a coating. In general, especially when milling in an organic phase, to avoid densification of the material to be milled,
It is therefore sufficient to dissolve a small portion of the polymeric support material in the organic phase in order to prevent mechanical refinement from being inhibited or not made possible at all.

Its dissolved amount can be 0.1-10% of the milled dye, but the mechanism of its action is not clear.
Presumably, this small amount of carrier acts as a suspending agent for the fine dye particles and thus lowers the viscosity. Increasing the amount of dissolved carrier generally has the opposite effect, that is, densification, and should be avoided. Most advantageously, carrier resins are used as suspending agents.

This is because this at least widens the range of application of the dye formulations. If this is not possible or not fully possible, it has been found advantageous to add soluble polyamides and polyureas, but especially alkylated polyvinylpyrrolidones. The latter is commercially available under the name AIltarOne. These additives can act synergistically, especially in combination with cellulose derivatives. These additives make it possible to obtain a grinding concentration of dyes of approximately 10-60%, preferably 30-50%, and thus to minimize solvent consumption. Solvents include all solvents that are finitely water-soluble and form two-phase systems. Finite water solubility is necessary to produce an optimally thick layer of organic phase on the aqueous phase that is useful for coating. Its solubility should not be less than 1 g/l, but preferably not more than 300 g/'. Among the large number of suitable solvents such as aldehydes, esters, ethers and nitriles, alcohols and ketones are preferred primarily on ecological, risk and cost grounds.

Examples of suitable ketones include methyl ethyl ketone, noacetylacetone and cyclohexanone, and examples of suitable alcohols include butanol, cyclohexanol, benzyl alcohol, phenyl glycol and hexyl glycol, and mixed esters, ethers such as ethyl glycol acetate.

The solvent is chosen primarily depending on the carrier resin.

The carrier must not be excessively swollen by the solvent even in two-phase systems, but above all it must release the absorbed solvent easily and quickly again. Suitable solvents can be easily selected by preliminary experiments. In coating the carrier resin, the ratio of water to organic phase depends primarily on the water solubility of the organic solvent, and generally 1 to 4 parts of water are used for 1 part of solvent. After the coating process, further dilution with water can be performed to completely remove the solvent. When introducing a synthetic resin carrier, it is best to stir or shake as vigorously as possible, but when diluting with water later, gentle stirring is sufficient.

Vigorous shaking damages the dye film due to friction, but this phenomenon does not occur as long as excess solvent is present as a separate phase. This is because the damaged area is recoated. Although it is optimal to carry out the above-described milling and coating operations at room temperature, higher or lower temperatures can be employed as well.

The solvent can also be removed by dilution and filtration or by steam distillation and further filtration. Unlike the insoluble carrier resins according to said patents, the coating treatment of the carriers according to the invention requires care with regard to possible deformation by solvents. Particular care is taken to remove the solvent completely. Otherwise, angulation (Ve-RhOrnllrg) and thereby poor dispersibility and other side effects may occur. It is quite surprising that carriers of the aforementioned type can be coated in this simple and safe manner.

Suitable carrier materials in the process of the invention include relatively high molecular weight salts of abietic acid, behenic acid and their reduction products as well as their metal salts! and esters with higher alcohols.

They are soluble in organic solvents but not in aqueous two-phase systems. Furthermore, low-molecular polymers of ethylene, polyvinyl chloride, copolymers of vinyl chloride and vinyl acetate, polyacrylic esters, polymethacrylic esters, mixed polymers of polyacrylonitrile, polyvinyl chloride, and polyvinylidene chloride , polyvinyl ether of octadecyl alcohol, polyvinyl isobutyl ether, alkyd resins and well organically soluble polyamides and polyurethanes.

Furthermore, mention may be made of cyclohexanone resins and hydrocarbon resins such as polyterpenes, polyinthenes, alkyl aromatic hydrocarbon resins, low molecular weight vinyl aromatic compounds and aromatic telomers with acrylonitrile. Note that particularly interesting results have been achieved using modified natural polymers such as ethers and esters of cellulose. for example,
Water-insoluble but organic-soluble ethers of cellulose such as ethyl, propyl or ethyl hydroxythyl ether, and esters such as acetylchloroacetyl and nitro compounds and mixed esters such as cellulose acetate butyrate and cellulose acetylphthalyl are mentioned. It is also possible to use water-soluble derivatives of cellulose such as methylcarboxymethyl or hydroxyethylcellulose.

Furthermore, derivatives such as hydroxypropylcellulose, which are soluble in water and organic solvents such as cyclohexanone, but insoluble in the two-phase system, coat very well and are therefore suitable for use in dye formulations. The dye to carrier ratio can vary widely from 1:9 to 9:1.

In most cases, a dye formulation as high as possible is desired. A proportion of 50% dye may be mentioned as a very good intermediate value. According to the method of the invention, higher 60-90%, preferably 75-85% formulations can be made in many cases in order to protect the carrier from being damaged by mechanical processing. Despite this extremely low amount of carrier, a satisfactory, especially residue-free dispersion capacity of the powder is ensured. The sparingly water-soluble or insoluble dyes used in the process of the invention include neat disperse dyes, ie, without water-soluble dispersants and fillers such as lignin sulfonates.

They generally exhibit a water solubility of about 1 to 10 Tng/'. They are as poorly soluble as possible even in the organic components of the two-phase system, and are in an exclusively dispersed form (undissolved form)
It is advantageous if it exists in Disperse dyes can be of different structures.

Examples include azo and anthraquinone derivatives, heterocyclic compounds such as triazole anthrones, quinophthalones, anthrapyridines, naphthalimides, pyrazole anthrones, diazines, acridines, acridones, and also stilbene dyes and nitro dyes. Similarly, water-insoluble metal complex dyes such as azo dyes and formadyl dyes may be mentioned.

Metals that can be used for this complexation include aluminum, nickel, copper, chromium and cobalt, and iron. The dyes can be used as metal-free intermediates or as metal complexes. Pigment dyes include inorganic pigments such as carbon black or matting agents such as titanium dioxide, and also organic matting agents such as melamine formaldehyde resins and urea formaldehyde resins, but especially polymer-soluble and insoluble organic pigments such as naphthol pigments and Mention may be made of the types of vat pigments, phthalocyanines, dioxazines, indolinones, nitro dyes, perinone dyes, quinacridone dyes as well as other polycyclic heterocycles.

Additionally, optical brighteners can also be used, preferably in conjunction with matting agents. The liquid or solid formulations produced by the method of the invention have a very wide range of uses;
This range is determined primarily by the carrier and to some extent by the dye.

Generally, this is treated with a synthetic resin, which resin can be the same as that used as the carrier. In the case of resins different from the carrier, the resins must be sufficiently compatible with each other. This limits the relatively large number of formulations containing different carriers. Disperse dyes containing water-soluble carriers such as hydroxypropyl cellulose are useful for printing and dyeing synthetic fibers from aqueous media, and corresponding formulations based on pigments are also available, sometimes with cross-binding fixatives. It is useful for printing and dyeing synthetic fibers. Disperse dyes are used in conjunction with organic soluble carriers in the solvent dyeing of synthetic fibers such as perchlorethylene, but they are particularly used in sublimation transfer printing.

Pigment dyes containing organic soluble carrier resins have wide applications not only in paper printing but also in coloring inks and lacquers. However, the area of use for the neat dyeing of synthetic materials, especially fibers, from solution or melt is particularly wide and important. Formulations similar to those described herein are known per se and have already been commercially available for some time.

They are so-called base material milling (SLlbstratma-
It is produced by the precipitation method, but especially by the so-called kneading method in the Muldenknetern.

The latter method is considered the most important technologically and the only one that is implemented on an industrial scale. This method is very expensive in terms of equipment and energy.

Furthermore, the kneading operation must be carried out in the presence of large amounts of salt and with a solvent, the recovery of which is difficult and expensive, and until now it has not been possible to recover and reuse, for example, diacetone alcohol. So much so that it remains in the experimental stage. It has already been mentioned that the carrier resin is partially severely damaged, ie chemically decomposed, by the kneading operation. Therefore, in this method, various carriers cannot be used at all, but this is not the case in the method of the present invention. Furthermore, the environmental benefits are also clear, since in the process of the invention the solvent can be separated as a 10-20% aqueous solution, azeotropically distilled and used in a recycling process. The shortcomings of these kneading methods are still known to be many and no experiments have led to products of comparable or better properties.

Solvent methods have also been attempted in a number of implementation formats, but without any technical success. See, for example, the specification of German Patent No. 1 469 621.

This patent proposes a method in which a polymer and a dye are dissolved in a solvent and then introduced into water to be gradually precipitated. As a method belonging to the same principle, U.S. Patent No. 33
No. 61705 is proposed. A method based on the same principle is proposed in US Pat. No. 3,361,705.
These two methods have the disadvantage that the dyestuffs have a particle size that is actually very fine, but of different sizes and difficult to adjust. Therefore, its reproducibility does not meet industrial requirements,
The filter value is also too low to guarantee frictionless processing. Furthermore, the so-called base material milling is described in Swiss patent number 4.
It is published in the specification of No. 550.

In this process, the carrier polymer and dye are sand milled in an inert solvent that cannot dissolve or swell the dye and polymer. This method has many drawbacks. That is, the synthetic resin cannot be ground in large quantities or is not fine enough to be vacuum separated from the sand. Also, by the time the dye dispersion reaches the required fine particle size, the polymer is often so severe that it is no longer completely soluble in the medium used (i.e. it has decomposed much more significantly than in the case of kneading). receive damage. Therefore,
This substrate milling method is a successor to the kneading method, and the unsatisfactory results of the former can be attributed to the latter's inheriting of the kneading method, which is itself undesirable. The method of the present invention and the formulations made by the method have a number of important advantages over these known methods and products.

Thus, according to the invention, the dye dispersion can be milled and then passed through a microfilter, for example a KunOfilter with a pore size of 10 μm. Therefore, the formulation is not at all a heterogeneous material containing even raw materials as is often unavoidable in the case of kneading methods. Furthermore, the carrier resin is not mechanically treated, as already mentioned, and therefore is not damaged.

This is the reason why formulations with low amounts of carrier and high percentages are obtained. Furthermore, the homogeneous dispersibility of the formulation is particularly good, which accounts for the very good filter values and results in high operating safety and low interference during production.

This article describes the developments to date in the field of dye compound manufacturing. When considered, the common feature is that one always strives to achieve fine dye particles and then wraps them in a thin protective covering of finer synthetic resin particles to prevent them from agglomerating and coarsening.

In the case of the method of the invention, the decisive progress in the invention.

Ayumu's goal lies in completely breaking down this conventional concept and implementing it in the exact opposite way. That is, in the present invention, on the contrary, synthetic resin particles are used as the core (and) carrier, and these are coated with a thin, as homogeneous layer of dye particles. It is quite surprising that this method generally yields redispersible formulations.

However, by this method the decisive advances mentioned above have been realized and the quantitative proportions of the formulations have been improved. In other words, when dye particles are wrapped in synthetic resin, compared to when the synthetic resin is used as a carrier and this is wrapped in dye particles,
It was revealed all at once that a large amount of synthetic resin would be used. At least the noteworthy basis lies in the fact that the high percentage formulations according to the invention are easier and better produced than by known methods. Next, the present invention will be explained in more detail with reference to Examples.

In these examples, parts mean parts by weight. "A dye nodule of the formula Example 1 is rubbed with 1 (4) parts of quartz sand in part A of cyclohexanone until the particle size of the dispersion is less than 10 microns, essentially 1 to 5 microns. crush.

After filtering off the sand, 100 parts of water was added thereto, and two drops of ethyl cellulose in powdered water were introduced with vigorous stirring. After uniformly distributing the carrier polymer, it is diluted with water with gentle agitation and stirred until a flowable and easily filterable condition is produced. This is filtered off with suction and the yellow powder obtained is dried. This compound lol
part, ethanol (branch) part and methyl ethyl ketone 5 (2 parts)
) in a 5% solution of ethylcellulose (
Stir and disperse within the company.

The paper is printed with this printing ink, which is combined with a polyester fabric and kept in a press at 2100C for 0 seconds.
A bright, fast, yellow transfer print is thus obtained. Equally good results can be obtained if ethyl hydroxyethyl cellulose, cellulose acetate butyrate, polymethacrylic acid esters or hydroxypropyl cellulose are used instead of ethyl cellulose.

EXAMPLE 2 A dye cut of the formula is dispersed in a solution of 2 parts of ethyl cellulose in 58 parts of cyclohexanone and ground in a sand mill until the particle size is essentially 1-2 microns.

After separating the sand, this dispersion is mixed with a dispersion of 8 parts of micronized ethyl cellulose in 1 (1) part of water with thorough stirring.

After homogenization, a further 400 parts of water are added to this, stirred for 1 hour, filtered and the formulation thus obtained in the form of granules is dried in vacuo. This blue powder exhibits similarly good properties as the formulation described in Example 1.

Processing in the same manner, except that the dyes described in Example 1 are used instead of the dyes mentioned above, give yellow formulations with similarly good properties.

With both formulations, fast prints are obtained by the method described in Example 1.

Example 3 A dye of the formula 5C8 is dispersed in a 2% solution of ethylcellulose in n-butanol and milled in a sand mill until the particle size of the dispersion is less than 10 microns.

Separate the sand, add 1 (1) part of water and stir in 11.5 parts of pulverized ethyl cellulose. After homogenizing this, 9(1) parts of water are slowly added and the mixture is stirred until it is in a form that can be easily filtered.

It is then filtered, washed with water and vacuum dried at 70'C. The red powder thus obtained can be dispersed very well in printing inks consisting of ethanol, methyl ethyl ketone and ethyl cellulose. Similarly good results can be obtained by using methyl ethyl ketone instead of n-butanol.

Similarly good formulations are also obtained using cellulose acetate butyrate or polymethacrylic acid ethyl ester in place of ethylcellulose.

Example 4 Dye 2 (2) of the formula is milled in a solution of 5 parts of ethylcellulose in 75 parts of cyclohexanone until the particle size is less than 5 microns.

After separation of the sand used for milling, one (1) part of water is added to the dispersion with vigorous stirring. After adding another 9 parts of water, stir gently until a well filterable form is produced, filter and dry. The formulation thus obtained produces fast blue prints on polyamide and polyester fibers by the method described in Example 1.

Isophorone, mesityl oxide, methyl isobutyl ketone, n-pentanol, n instead of cyclohexanone
- Equally good results are obtained using hexanol or cyclohexanol.

Example 5 The blue dye described in Example 2 was mixed with 2 (1) parts of quartz sand in a solution of 1 part of ethyl cellulose in 100 parts of methyl ethyl ketone and 50 parts of water to form a fine dispersion with a particle size of 10 microns or less. Grind until .

The sand is then separated, stirred in with 9 parts of pulverized ethylcellulose, diluted with 400 parts of water, filtered off with suction and dried. A blue powder with good properties similar to those described in Example 2 is thus obtained. Example 6 Two parts of the dye described in Example 5 were added to two parts of sand in one part of cyclohexanone and one part of hydroxypropylcellulose was added.
) until the particle size is less than 10 microns.

The sand is then separated, 200 parts of water are added to it, 29 parts of hydroxypropylcellulose in powder form are added, stirred, diluted with 200 parts of water, the precipitate is filtered off and dried. Part of the formulation thus obtained is dispersed in part a of water with stirring. A paper tape is impregnated with this dispersion on a foulard and allowed to dry. This paper is combined with a polyamide fabric and heated in a press at 190° C. for 3 hours. A fast blue dyeing is thus obtained. EXAMPLE 7 The dyestuff described in Example 5 is ground between two pods in a water seal with the addition of 1 part of hydroxypropyl cellulose and 2 (4) parts of quartz sand.

Separate the sand and add cyclohexanone (1) to this dispersion.
Add part. Micronized ethyl cellulose is introduced into this 2-phase 8 system while stirring vigorously. After homogenizing the mixture, the solvent is distilled off as an azeotrope in vacuo and the formulation thus formed is filtered off and dried. This formulation can be used to produce blue prints by the method described in Example 1.

Example 8 A dye loading part of the formula is ground in cyclohexanone part A with 1 (1) part of quartz sand until the particle size of the dispersion is 1 to 5 microns.

Separate the quartz sand, add 100 parts of water and add part of ethylhydroxyethylcellulose with vigorous stirring.

It is then diluted with water with gentle stirring until a well filterable form is produced, filtered off with suction and dried. Two parts of this formulation are dispersed in one (1) part of perchlorethylene at room temperature and diluted to 10 parts. After adding 0.5 part of Persamide 962, the dispersion is heated under reflux for 3 minutes and filtered hot through a paper filter. There is no residue left at all. In this dispersion 1 (4) polyester threads
The sections are stained under reflux for 3 times.

A fast yellow dyeing is thus obtained. 1 as a dye
-By using amino-2-oxyethoxy-4-hydroxyanthraquinone. An equally good formulation is obtained which produces a red dyeing.

Example 9 9 parts of carbon black are dispersed in m parts of cyclohexanone and sand milled to a particle size of essentially . Grind to 1 micron or less.

Separate the sand and add 3 parts of ethylcellulose and stir. To this is added 1 (1) part of water and 27 parts of micronized ethylcellulose are introduced with stirring. While stirring, further dilute with 50(2) of water, filter by suction, and dry. This formulation can be well dispersed in a printing ink consisting of 45 parts of ethanol, 45 parts of methyl ethyl ketone, 8 parts of ethyl cellulose and 2 parts of Hoechst wax PA-520, which produces a deep black print on paper. give.

・Example 10 200 parts of quartz sand was added to a solution of 1 part of hydroxypropylsenolose dissolved in 4 parts of cyclohexanone to 50 parts of 2,2''-dimethoxydibenzanthrone until the particle size became essentially 1 μm or less. and grind it.

After separating the sand, this dispersion is stirred into a solution of 100 parts of hydroxypropylulose in 91 parts of water. The extremely fine whitish green dispersion thus obtained is diluted to 5 parts and then divided into 2 parts. Spray drying one of them produces a light powder with good dispersibility. Dilute the other side with 7 parts of water to make a total volume of 100 α. Noodle fabrics are also impregnated with foulard in this dispersion and squeezed to a liquid absorption of 70%.

After drying this with hot air, it is passed through another foulard containing an aqueous solution of sodium hydroxide Hakube and sodium dithionite Shunbu dissolved in water 1e, and then boiled for 60 seconds. The dyeing thus obtained is finished by oxidation, washing with water, neutralization, soaping, and drying using conventional methods. This produces a uniform, very bright green staining. Similarly good results can be obtained by using carboxymethylcellulose or polyvinyl alcohol instead of hydroxypropylcellulose.

Example 11 Fifteen parts of chlorinated copper phthalocyanine are ground in a mixture of 84 parts of methyl ethyl ketone and 1 part of ethyl cellulose with the addition of 1 (1) part of quartz sand until the particle size is essentially below 1 micron.

Filter off the sand, add 1 (1) part of water, and add 1 part of ethyl cellulose.
Add 4 parts of water, stir and after thorough homogenization add 4 parts of water.
Dilute with 0CB. The powder is filtered off, dried and ground. Next, repeat the above operation. That is,
After separating the sand, this dispersion was treated with ethyl cellulose 14
Dissolve one part, filter through a pressure filter, slowly add one (1) part of water with stirring, remove the methyl ethyl ketone by steam distillation, filter off with suction and dry. The formulation thus obtained can be processed by the method described in Example 1 to be converted into a printing ink and to produce a deep, clear green shade on paper.

Example 12 4,4″-diamino-1,1″-dianthraquinonyl part in cyclohexanone part with diameter 171
77! 200 parts of silica spheres are added and milled until the particle size is still visible to the naked eye and is no larger than 1 micron.

Next, the silica spheres are separated. Acetyl cellulose with addition of 300 parts of water and micronized (degree of substitution 2.5)
Add part (9) and stir. Tournique Event (H)
After thoroughly mixing with a stirrer, slowly add water to dilute to 10 (1) parts in total. Stir further until it forms a form that can be filtered well.
Filter and dry. The powder thus obtained can be stirred in acetone to form a very fine dispersion. This can be used to spin dye acetylcellulose from an acetone solution. Similarly good results can be obtained using triacetylcellulose powder. This formulation can be very finely dispersed in methylene chloride or chloroform and used for neat solution dyeing of triacetylcellulose.
Powders of copolymers of vinyl chloride and vinyl acetate likewise give formulations which can be dispersed very well in methylene chloride and which can be used for solution dyeing of polyvinyl chloride fibers.

Additionally, acetone-soluble copolymers of acrylonitrile, vinyl chloride, and vinylidene chloride can be very well dispersed in acetone and can be used in formulations for spin-dying modified acrylonitrile fibers and acetylcellulose fibers. You can get things. In the latter case, n-butanol is used instead of cyclohexanone. Example 1
3 Parts of dye (9) of the formula are ground in m parts of cyclohexanone with the addition of 2 (1) parts of quartz sand until the particle size is less than 2 microns.

The sand is filtered off, 100 parts of water is added, and the pulverized abietic acid ester mixture is added and stirred. After thorough mixing, the mixture is further diluted with 5 parts of water. After standing overnight, the suspension is filtered and the resulting powder is dried. It can be dispersed very well in aromatic solvents and can be used for pigmenting textile colors and textile inks.

Polyval ester (P
Similarly good results can be obtained using Olypaleester. Also, if cellulose acetate butyrate is substituted for abietic acid ester, a formulation is obtained which can be very finely dispersed in ketones and alcohols and which can be used for the production of colored lacquers. Additionally, good results have been obtained using carbon black, indigo, quinacridone and copper phthalocyanine.

Example 14 One (1) part of carbon black is ground in a cyclohexanone chamber with the addition of 1 (1) part of quartz sand until the particle size is less than 1 micron.

The sand was then separated, and into this dispersion was added (1) part of magnesium behenate, stirred, to this was added 100 parts of water with vigorous stirring, diluted with 50 parts of water, filtered and thus obtained. Let the black powder dry. 2 parts of this powder are added to 8 parts of a 10% solution of low polymer polyethylene in cyclohexanone and 100 parts of polypropylene granules are uniformly mixed therein. Slowly add the water to this while stirring thoroughly. Further dilute with 1 (1) part of water, decantate and dry. If this is melted and spun,
A clean and homogeneous black polypropylene fiber is obtained.

Equally good results are obtained on polyamide fibers. The use of chlorinated phthalocyanines produces a fast green dye.

Example 15 Two parts of the dyestuff of formula 8 are ground in part A of cyclohexanone with 1 part polyvinyl ether of octadecyl alcohol and 20 parts of quartz sand until the particle size of the dispersion is essentially no greater than 5 microns.

Separate the sand, add 2 parts of water and Antalon ■220
Add a micronized mixture of 4 parts (alkylated polyvinylpyrrolidone, molecular weight 8600) and 15 parts polyvinyl ether of octadecyl alcohol. After thorough stirring, an additional 600 parts of water is added to this and the precipitated powder is filtered off and dried. The blue powder thus obtained allows it to be well distributed in tetrachlorethylene and is as described in Example 8. A fastening blue dyeing is produced on polyester fibers by the method of Example 16: A solution of 1 part of ethyl cellulose in 2 parts of sec-butanol saturated with water. Add sand to the solution and grind until the particle size is 1 micron or less.

Separate the sand, add w parts of water, add 9 parts of ethyl cellulose, stir, dilute with plenty of water with gentle stirring until a granular, easily filterable form is produced, filter.
Wash, dry, and scrape. The formulation thus obtained can be dispersed well in paper printing inks based on ethylcellulose and produces transparent yellow prints.

Similarly good results are obtained using tertiary butanol instead of sec-butanol.

Preferred yellow formulations are also obtained in a similar manner using dyes of the formula:

Using the dye of the formula, a very fast reddish brown color is obtained.

formula A yellowish red color is obtained using the dye represented by

Similarly good formulations are obtained by the same method but using ethyl glycol acetate instead of butanol.

Example 17 1,4-diamino-2,3-dichloroanthraquinone 1
The urabe is ground in a sand mill in the presence of 1 part ethyl cellulose in 300 parts sec-butanol saturated with water until the particle size is less than 2 microns.

The sand is separated and a dispersion of 33 parts of ethyl cellulose in 66 parts of water is added to this dispersion and stirred. It is further diluted with water to a total of 2000 parts, passed through a perforated disc mill (LOchschei anti-Nmuhle), filtered and the formulation thus obtained is dried. If this is used according to the method described in Example 1, fast violet dyeings and prints are obtained. Similarly good results are obtained using propylcellulose or cellulose acetate propionate instead of ethylcellulose. Examples 1, 2, 3 and 4
Similarly good formulations are obtained using the dyes described in .

Example 18 A solution of 10 parts of chlorinated copper phthalocyanine and 2 parts of vinyl chloride polymer (commercially available under the trade name Rhodapaca) dissolved in 398 parts of ethyl glycol acetate saturated with water, 4 parts of It is ground in a sand mill until the particle size, which is still visible to the naked eye, is less than 1 micron.

Separate the sand and add to this pigment dispersion a dispersion of 98 parts of Lodapass AX in 100 parts of water, stir until uniformly mixed, and then dilute with 20(1) parts of water. The mother liquor is filtered off with suction, 10 parts of water are added, stirred again and the mixture is stirred until it is in a form that is sufficiently filterable. Then suction filter and dry. The powder thus obtained can be very finely dispersed in acetone and used for solution dyeing of polyvinyl chloride. It should be noted that similarly good blue colors are obtained using copper phthalocyanine and very well dispersing black colors are obtained using carbon black.

Furthermore, equally good results can be obtained by replacing ethyl glycol acetate with methyl acetoacetate, ethyl acetoacetate, ethyl formate, ethyl acetate or acetylacetone.

Example 19 30 parts of carbon black (Printex 300) were prepared using a glass pole in a solution of 0.6 parts of ethyl cellulose dissolved in m parts of sec-butanol saturated with water.
Grind until no macroscopic particles larger than microns are present.

Separate the glass poles and stir into this dispersion a dispersion of 29.4 parts of ethyl cellulose in ω parts of water, stir until uniformly mixed, and dilute with more water to make a total of 50C5. Filter this and dry the black powder obtained.

This can be used for paper printing according to the method described in Example 10. Example 2
0 parts of thioindigo are ground in tertiary butanol with 0.3 parts of ethyl cellulose using 100 parts of glass pole and 5 parts of rock salt.

This is diluted with 150 parts of water, the glass pole is separated, w parts of ethyl cellulose are added, further diluted with 35C8 of water, filtered, washed and dried. The formulation thus obtained is suitable for printing according to the method described in Example 1.
Example 21 3(1) parts of the dye described in Example 4 are mixed with 697 parts of water-saturated sec.
part and grind until the particle size is 1 to 3 microns (
This is achieved after milling for about 6 hours in a Dynomill of type KDLl5).

Silica spheres were separated from this dispersion and the pore size was 1.
Filter through a 0 micron Kunofilter. One part of the dye paste thus obtained is thoroughly mixed with 9.7 parts of an abietic acid derivative (commercially available under the trade name Stybelite Resin), and further a part of water is added and stirred. After 5 minutes, slowly pour in 4 parts of water, stir for 1 hour, filter, wash and dry.

In this way, a blue powdered powder is obtained. Add 3.75 parts of this blue powder to 66.25 parts of ethyl cellulose, isopropanol and petroleum benzene (boiling point 110-140°C).
Add to the textile ink consisting of a 50% mixture of and stir.

In this way, a stable printing 2 ink that can be printed on paper is obtained. 3 circles 2 at 210℃ on polyester fabric
Intermittent transfer printing produces a fast blue print. Equally good formulations can be obtained if equal parts of the following commercially available products are used in place of the above abietic acid derivatives. Textile ink is obtained.

Example 22 4 parts of N,N''-diethyldipyrazole anthronyl are added to 80 to 10 parts of an aqueous bath containing 2% sodium hydroxide and 2% sodium hydrosulfite.
Build at 90 degrees Celsius.

This is cooled and the crystallized leuco form is filtered off, washed and dried. A yellowish-red powder is thus obtained. This is ground in 1 part of sec-butanol saturated with water with 10 parts of ethyl cellulose and 4 parts of quartz sand until the particle size is 1 micron or less. After separating the grinding aid, add cellulose acetate propionate, which is soluble in alcohol, stir, mix with 10 parts of water, and add 5 parts of water (10 parts).
) dilute with 1 part. This is filtered and the blue-red powder obtained is dried. Add this powdered powder into 9 parts of denatured ethanol and stir.

A glass fiber fabric is impregnated in this solution, wrung to a weight gain of 50% and dried in a sealed chamber with hot air trapping the evaporated alcohol. A uniformly red-dyed fabric is thus obtained which is resistant to sunlight and washing.

Similar results are obtained on pomegranate and polyester fabrics.

Similarly good results can be obtained by carrying out the same procedure, except that instead of building up the above dye, water is poured in from a 10% sulfuric acid solution to reprecipitate it.

Although the present invention has been described in detail above, specific examples of the configuration of the present invention can be summarized as follows.

(1) A method as claimed in the preceding claims for producing a solid dye formulation.

(2) The method according to claim 1 or item (1) above, wherein the method is micronized in an organic solvent with limited water solubility that is mixed with or saturated with water.

(3) A method as claimed in the preceding claims or in the preceding paragraph (1) or (2), in which a ketone or alcohol having a solubility in water of at least 1% and as much as 30% at room temperature is used as the organic solvent.

(4) The method according to the above claims or the above items (1) to (3), in which methyl ethyl ketone, cyclohexanone, acetylacetone, butanol, cyclohexanol, phenyl glycol, ethyl glycol acetate or hexyl glycol is used as the organic solvent.

(5) an organic substance acting as a suspending agent in the organic phase and in an amount of not more than 20% with respect to the carrier material used and not increasing the viscosity of the dispersion (this substance may be the same as or in phase with the carrier material mentioned above); soluble in the organic phase, but insoluble in the two-phase system). The method described in (4).

(6) The method described in the preceding item (5) using cellulose ether or cellulose ester as the organic substance. (7) The method according to the preceding item (5), in which alkylated polyvinylpyrrolidone having a molecular weight of at least 5,000 and at most 30,000 is used as the organic substance. (8) The method according to the claims or items (1) to (7) above, in which cellulose ether or cellulose ester is used as the polymer carrier. (9) The method described in the preceding item (8) using cellulose ether or cellulose ester which is insoluble in water.

(11) Use of a water-insoluble synthetic substance, preferably a metal salt or ester of a resin acid, having a molecular weight of at least 350 as a carrier;
The method described in. (11) The method according to the claims or items (1) to (10) above, in which a pure disperse dye or a water-insoluble metal complex dye is used as the dye.

(12) The scope of the above-mentioned claims or the preceding clause (
1) The method described in (11). (13) The method described in the claims or the preceding paragraphs (1) to (10), wherein an organic or inorganic pigment insoluble in water and the polymer is used as the dye.
(10) The method according to the preceding claims or the preceding paragraphs (1) to (10) using inorganic or organic matting agents and/or optical brighteners as dyes.

An additional related original invention (Japanese Patent Application No. 45-106374) discloses that water-insoluble hydrophobic polymeric synthetic resins in the form of solids, particularly granules or powders, are soluble in each other only to a finite extent and are in a two-phase system. In a mixture of hydrophilic and organophilic solvents forming a dye or optical the solvent is removed, the synthetic resin thus treated is dried and it is removed from its molten state or the solvent, optionally with the addition of an untreated polymeric fully synthetic resin. A process for producing a colored molded article made of a polymeric synthetic resin, which method comprises molding a colored article from a solution dissolved in a polymeric synthetic resin.

In contrast, the present invention provides for a suspension of a sparingly water-soluble or insoluble dye suspended in water and/or in an organic solvent which is finitely water-soluble and forms a two-phase system. mechanically micronized to a particle size of at most 10μ and preferably at most 2μ in the presence of a suspending agent, preferably soluble in the organic portion of the milling medium, and then the After removing the mechanical grinding aid, add water or a finitely water-soluble organic solvent as necessary to form a two-phase system, and thus, after forming the two-phase system, add this dye suspension to water or a finitely water-soluble organic solvent. The dye-containing organic phase is mixed with at least one polymeric carrier that is soluble in the aqueous organic solvent but insoluble in the two-phase system, and the carrier suspension thus obtained is mixed with at least one polymeric carrier that is soluble in the aqueous organic solvent but insoluble in the two-phase system. well-dispersible dyes, characterized in that they are treated until homogeneously distributed on the surface of The invention relates to a process for producing a concentrated liquid or solid dye formulation, and satisfies the requirements for an additional patent as provided in Article 31, Item 1 of the Patent Law over the original invention.

Claims (1)

Claims: 1. A process for preparing a concentrated liquid or solid dye formulation with good dispersibility, comprising: (1) a methylalkyl (C_2-C_4) ketone forming a two-phase system in and/or with water; , acetylacetone, cyclohexanone, isophorone, tantyl oxide, C_4-C_6 alkanol,
about 10 mg suspended in an organic solvent selected from the group consisting of cyclohexanol, ethylene glycol acetate, ethyl formate, ethyl acetate, methyl acetoacetate, and ethyl acetoacetate.
(2) micronizing a suspension of a dye having a water solubility of less than /l in the presence of a mechanical grinding aid until the particle size of the suspended dye is less than 10 microns; (3) adding water or the organic solvent necessary to form the two-phase system; and (4) adding the lower alkyl cellulose ether before or after forming the two-phase system. , hydroxy-lower alkyl-cellulose ether,
Cellulose acetate (degree of substitution 2 to 3), cellulose acetate propionate, cellulose acetate butyrate, carboxymethyl cellulose, polyacrylate, polymethacrylate, polyvinyl alcohol, polyvinyl ether of octadecyl alcohol, copolymer of vinyl chloride and vinyl acetate,
An acetone-soluble copolymer of acrylonitrile, vinyl chloride, and vinylidene chloride, a cyclohexanone resin, a hydrocarbon resin, an abietic acid derivative, and a salt of behenic acid, which is soluble in water or the organic solvent. adding an insoluble polymeric carrier to the two-phase system;
(5) treating the carrier suspension until said dye-containing organic phase is uniformly distributed on the surface of said polymeric carrier; (6) removing said solvent; and (a) drying the dye formulation or (b)
A manufacturing method characterized by dispersion in water or an organic solvent.