JPS6020422B2 - Phthalocyanine preparations stabilized against recrystallization and transformation transitions - Google Patents

Description

[Detailed description of the invention]

The present invention relates to phthalocyanine preparations which are stabilized against recrystallization and transformation transitions and which give colorations with good to high gloss. Due to their extremely small particle size, many organic pigments can only be dispersed poorly in mauve systems with great effort. Due to the high proportion of agglomerated particles, films colored with this type of preparation exhibit a low gloss. Colorants of this type currently exhibit poor flow properties. Particularly obvious examples include phthalocyanines, which pose difficulties and problems in this regard. In the past, this property was
Attempts have been made to improve this through additives and especially through preparation methods. Under the influence of the solvents contained in varnishes and printing inks and required to dissolve the binders used and to produce specific flow properties, the phthalocyanine pigments present in preparations of this type crystallize. becomes larger particles. At this time, in the Q-, y-1, 6-1 and 1-transformations of steel phthalocyanine and the Q-1 and x-transformation of phthalocyanine, a transition to a stable 31-transformation also takes place at the same time. In addition to the color density, the color tone and rheological properties of such printing inks and varnishes also change in this case. That is, a phthalocyanine derivative such as a basicly substituted copper phthalocyanine is added. A review with examples from the patent literature can be found in "Pigment Handbook" by K. Markle and H. Schafer, Volume M, pp. 157 et seq., edited by T.C. Published, New York, London, Sydney, Toronto, 1973
Hand), listed in the chapter ``Surf Ace Treatment of Organic Pigment''. The use of this additive improves, for example, the agglomeration stability of the pigment, but the dispersibility, gloss and especially the toughness become worse. Another way in which the dispersibility in particular is improved is by adding resins and polymers (e.g. British Patent No. 1144041
No., No. 1138465, No. 1139294, No. 95
7 Moth No. 4 and Specification No. 957440, U.S. Patent No. 34
92253 and 343113, Swiss Patent No. 476 Iso 6, German Patent Application Publication No. 171
9402 and 1669157, German Patent Application No. 2205171 and German Patent Application No. 2124051 and German Patent Application No. 1904432). Although preparations of this type are effective for certain applications, their use is limited due to the incompatibility or adverse influence of the varnish layer by the necessary additives. The aim of the present invention was to find a preparation of phthalocyanine pigments which contains a new class of additives and which is compatible with the media in which the additives are commonly used. At the same time, these additives should significantly improve the technical properties of the pigments or preparations, such as dispersibility, flocculation, fluidity and gloss. It is important here that the additive simultaneously prevents recrystallization and transformation transitions in the presence of aromatic solvents. This is because this can also cause defectiveness in the above sense. We have found that 'a) metal-free phthalocyanine or steel phthalocyanine as pigment and 20 to 4% by weight relative to 'b''a'
(Q) general formula (in the formula, Pc is a metal-free phthalocyanine, copper phthalocyanine, or a mixture thereof; COO-C3 ratio 1, RI is a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, a group -(C24-NH)zH or -(C36-NH)zH, R2 is a hydrogen atom 1 an alkyl group or a cyclohexyl group having ~4 carbon atoms, alk' straight or branched saturated alkylene group having from 2 to 6 carbon atoms, R means a hydrogen atom or and (8) one or more phthalocyanine derivatives each having one to two or more carbon atoms. Sulfonic acids, alkenesulfonic acids or hydroxyalkenesulfonic acids, benzenesulfonic acids, phenolsulfonic acids or naphthalenesulfonic acids, optionally with 1 or 2 alkyl groups each having 1 to 2 hard carbon atoms, or mixtures thereof It consists of
(Q):(8) containing a salt or homogeneous mixture as a stabilizer in a molar ratio of 1:1 to 1:5, and optionally {c} one or more organic liquids or It has been found that the above-mentioned drawbacks can be eliminated when using pigment preparations containing solutions of resins in organic liquids. Varnishes or printing inks colored with the preparations according to the invention give deep colorations with good to high gloss. Furthermore, the phthalocyanine pigments in the preparations and in varnishes and printing inks are stabilized against recrystallization and transformation transitions. For example, Q-steel phthalocyanine in the preparations of the invention, ie in the presence of 'b', is stable even in aromatic hydrocarbons, such as boiling benzene, and neither recrystallization nor transformation to the 31 modification occurs. Phthalocyanine pigment 'a' for the preparations of the invention
As such, metal-free phthalocyanine and phthalocyanine containing copper atoms bonded in the form of a flange compound are used. Examples include, among others: metal-free phthalocyanine in the Q-, 8- or x-modification, Q-,
Copper phthalocyanines containing no chlorine or bromine or containing on average not more than 2 chlorine or bromine atoms in the molecule, of the 8-, y-, 6- and single modifications, containing not more than 1 needle atom of chlorine and polychrome from steel phthalocyanine having 1 to 14 chlorine atoms and 15 to 2 bromine atoms in the molecule. The phthalocyanine derivative (Q) is represented by the formula 1, in which Pc is a metal-free n-valent phthalocyanine residue or an n-valent copper phthalocyanine residue, and if desired, on average per phthalocyanine. Those which may contain 1 to 2 chlorine atoms and/or 1.9 or less sulfonic acid groups are used. n means a number from 2 to 4. Constrained by manufacturing, (Q) is usually present as a mixture of two or more compounds with n on average from 2 to 4. In formula 1, X is a '1' group with a C ratio of '2-', where alk is a saturated linear or branched alkyl group having 2 to 6 carbon atoms, preferably 2 to 3 carbon atoms, and R is preferably 〈means a hydrogen atom or means a 〉, or a '3' group -CH2-CH2-COOC2day5- or -C
H2-C ratio -COO-C3 ratio- is meant. For X, in addition to the group -C Koichi, individual examples include groups represented by the following formulas. -SQ-NH-(C ratio)3-, -S02NH-(CZ)4-, S02NH-(CH2)5-, and
In addition to hydrogen atoms, the following are used as direct substituents for RI. an alkyl group having 1 to 2 carbon atoms, preferably 1 to 1 carbon atoms, or a group (C24-NH)zH or -
(C3 ratio-NH)zH (here z means an integer of 1 or 2). Examples of RI include the following: Hydrogen atom, methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, secondary butyl group, bentyl group, isobentyl group, hexyl group, isohexyl group, octyl group,
2-ethylhexyl group, nonyl group, decyl group, dodecyl group, palmityl group and stearyl group, as well as groups C2day4
-N Hiro, mC2 ratio -NH1C2 ratio1N ratio,1C3HB-
NH2 or one C3 day 61NH1C3HB-NH2. Formula 1
In, R2 means a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a cyclohexyl group. Examples of R2 include the following. Methyl group, ethyl group, propyl group, butyl group, isobutyl group, secondary butyl group, cyclohexyl group. Among these 1
Particular preference is given to alkyl radicals having up to 4 carbon atoms, such as methyl, ethyl, propyl or butyl, and cyclohexyl. Is the phthalocyanine derivative (Q) known per se?
Alternatively, it is known in principle. Their production is carried out by known methods, and in the case of the new compound (Q) also by means known per se. For example, chloromethyl (copper)-phthalocyanine and the formula (0) (in the formula R
A primary or secondary aliphatic or alicyclic amine represented by (I and R2 have the above-mentioned meanings) or a mixed aromatic-aliphatic secondary amine can be reacted. Amines of formula 0 include, for example, methylamine, dimethylamine, diethylamine, dif. Lopylamine, dibutylamine, hexylamine, cyclohexylamine, N-methylcyclohexylamine,
Octylamine. 2-ethylhexylamine, decylamine, dodecylamine, octadecylamine (stearylamine) and hexadecylamine (palmitylamine) can be used. Furthermore, in this case, the amine (0) is a saturated basic metacyclic compound having a 5-, 6-, or 7-membered ring that may have an oxygen atom, nitrogen atom, or sulfur atom as another ring member. is also suitable. An example of this type is Pi. Mention may be made of lysine, piverizine, morpholine, thiomorpholine, piperazine or N'-alkylpiverazine, such as N'-methyl- or N'-ethylpiverazine. For economic and technical as well as color reasons, alkylamines with lower alkyl groups are preferred, especially those in which each alkyl group has 1 to 4 carbon atoms. Another method for preparing compounds of formula 1 in which X is a radical -C ratio is to prepare an aminomethylene of the corresponding general formula PckH2-NH2]n, in which Pc and n have the meanings given above. The compound can be alkylated according to known methods, for example by reaction with an alkyl chloride or alkyl bromide such as methyl chloride, methyl bromide, ethyl chloride, ethyl bromide, propyl chloride, propyl bromide, butyl chloride or butyl bromide. be. The phthalocyanine derivative of formula 1 in which X is a sulfonamidoalkylene group, 1 (wherein R and alk have the above-mentioned meanings) is preferably a phthalocyanine sulfonic acid chloride represented by the formula Pc+S02CI]n and a phthalocyanine sulfonic acid chloride represented by the formula (
In these formulas, Pc, n. R, alk, RI and R2 have the above-mentioned meanings) are reacted by known means. For the production of this phthalocyanine derivative (1), the following diamines (m) are used, for example. 2-diethylaminoethylamine, 2-diethylaminoethylamine, 2-dipropylaminoethylamine, 2
-dibutylamine/ethylamine, 3-diethylaminopropylamine, 3-diethylaminopropylamine, 3
-diethylaminopropylamine, 3-cyclohexylaminopropylamine, 3-(N-methyl!N-cyclohexyl)-propylamine, 2-cyclohexylaminoethylamine, 2-(N-methyl-N-cyclohexylamino)-ethylamine, 3-hexyl Aminopropylamine, 3-octylaminopropylamine, 3-(
2-Ethylhexylamine/)-bropylamine, 3-decylaminopropylamine, 3dodecylaminopropylamine, 3-palmitylaminopropylamine, 3-stearylaminopropylamine, 2-hexylaminoethylamine, 2-octylaminoethylamine , 2-
(2-ethylhexylamino)-ethylamine, 2-decylamine/ethylamine, 2-dodecylaminoethylamine, 2-palmitylaminoethylamine, 2-stearylaminoethylamine, 2-amino-1-dimethylaminobutane, 2-amino-1-diethylamine Thylaminobutane, 2-amino-2-dibutylaminobutane, 2-amino-1-dimethylamino/hexane, 2-amino/-1-diethylami/hexane, 2-amino-1-dipropylaminohexane, 2-methyl-1-amino-3 -dimethylaminoprobane, 2-methyl-1-amino/-3-diethylaminopropane, 2-methyl-1-amino-3-dip. Pylaminopropane, 2-methyl-1-amino-3-dibutylaminopropane, 4-dimethylamino-1-aminobutane, 4-diethylamino-1-aminobutane, 4
-dibutylamino-1-aminobutane, 6-dimethylamino-1-aminohexane, 6-diethylamino-1-aminohexane, 4-diethylamino-1-methylbutylamine (1',4-dimethylamino-1-methylbutylamine-

[1', Piverazine or N-methylpiverazine. As the phthalocyanine derivative (Q), for technical and color reasons, phthalocyanine, especially copper phthalocyanine di-tetrasulfonic acid chloride (n=
2, 3 and 4) and alk is -CH4- or C3E8-
an alkylene group, R is a hydrogen atom and RI and R2 are lower alkyl groups, in particular each alkyl group having from 1 to 4 carbon atoms, or a formula m in which RI is a cyclohexyl group;
The reaction product of the amine is preferred. Sulfonic acids (8) include alkan-, alkene and hydroxyalkene-sulfonic acids as saturated and unsaturated aliphatic sulfonic acids having 111 to 2 hard carbon atoms, and benzene, phenol- as aromatic sulfonic acids. and naphthalene sulfonic acid are used. The latter preferably have one or two hydrogen atoms replaced on the aromatic nucleus by alkyl groups having 1 to 2 carbon atoms. Examples of the sulfonic acid (8) include the following. {1} Aliphatic: methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid, octanesulfonic acid, decanesulfonic acid, dodecanesulfonic acid, tridecanesulfonic acid,
Hexadecane sulfonic acid, octadecane sulfonic acid, and also 1-alkene-1- with 8 to 2 hard carbon atoms
Sulfonic acids and 2-hydroxyalkene-1-sulfonic acids having 8 to 2 hard carbon atoms. '2' Aromatic: Benzolsulfonic acid, Q- and 8-naphthalenesulfonic acid, o- and p-toluolsulfonic acid, xylolsulfonic acid, p-tert-butylbenzenesulfonic acid, o-hydroxy mono-tertiary butylbenzenesulfone acid, p-hexylbenzolesulfonic acid, octylbenzenesulfonic acid, /nylbenzenesulfonic acid,
dodecylbenzenesulfonic acid, hexadecylbenzenesulfonic acid, octadecylbenzenesulfonic acid, o
-Hydroxy-m'm' mono-pisodecylbenzenesulfonic acid, o-hydroxynonylbenzenesulfonic acid, o-hydroxydodecylbenzenesulfonic acid, hydroxyhexadecylbenzenesulfonic acid, hydroxyoctadecylbenzenesulfonic acid, whose alkyl group is 1 to 2 monoalkyl- and alkylnaphthalene sulfonic acids having a hard carbon atom of . (8) is an aliphatic sulfonic acid having 8 to 2 carbon atoms, preferably 10 to 2N carbon atoms, or The use of benzole or naphthalene sulfonic acid, which has one or two alkyl groups and whose benzole nucleus may be substituted by a hydroxyl group, gives a particularly high gloss coloring and at the same time the pigment is susceptible to recrystallization and transformation transitions. A preparation is obtained which is stabilized against. Preferred sulfonic acids (8) for this case include:
Individual examples include the following: Dodecylbenzole sulfonic acid, dodecyl phenol sulfonic acid, didodecylphenol sulfonic acid, dodecylnaphthol sulfonic acid, nonylphenol sulfonic acid,
/Nylbenzole sulfonic acid, octadecylphenol sulfonic acid, octadecyl sulfonic acid, hexadecyl sulfonic acid, 1-tetradecene-1-sulfonic acid, 1-octadecene-1-sulfonic acid, hydroxyoctadecyl sulfonic acid. The stabilizer tb)' may optionally contain an excess of sulfonic acid (B) or an excess of (Q) (Q
) and (8) and the salt forms from (Q) and (6)
It can be used in the form of a mechanical, intimate and homogeneous mixture from. For example, it is possible to add (Q) and (8) in the desired molar ratio, for example in an organic solvent, and to obtain 'b--in solid form from the solution by evaporation and stripping off the solvent. The product thus obtained is hereinafter referred to as salt. The same results can be obtained by using as [b} an intimate and homogeneous mechanical mixture from (Q) and (8) in the corresponding molar ratios. This mixture of (Q) and (8) can be obtained, for example, by grinding or vigorous mixing in a mixing device. The molar ratio of phthalocyanine derivative (Q) to sulfonic acid (8) is from 1:1 to 1:5. Preferably, (Q) and (8) are 1:2 to 1 as 'b-
:4 containing salts or mixtures can be used. This is because an optimum stabilizing effect is achieved at the same time with good to very high gloss. The amount of stabilizing agent is usually 2 to 4% by weight, preferably 3 to 3% by weight, based on the pigment. The amount of 'b} depends on the one hand on the specific surface area of 'a';
And on the other hand it depends on how easily recrystallization and/or transformation transitions take place. That is, usually [b'
The required amount of decreases as the specific surface area of [a decreases.
On the other hand, pigment forms or modifications that are significantly prone to phase transitions and/or recrystallization require higher loadings of 'b'. Thus, in the case of halogen-free Q-transformer copper phthalocyanines, an addition of 5 to 10% by weight, preferably 8 to 1% by weight of [b} is required to obtain optimal stabilization against transformation transitions. shall be. In the case of copper phthalocyanines in the 8-, y-, 6- and mono-modifications, the amount of 'b} added for this purpose is preferably 3 to 5% by weight relative to [a}'. Optimal gloss is 20-3% by weight of 'b' to 'a'
obtained using a preparation containing. 'b} in the preparation
The proportion can be increased to more than 4% by weight. However, the addition of such large amounts no longer results in benefits such as further increasing the gloss or further increasing the stabilization against transformation transitions or recrystallization. As organic liquids 'c', which optionally contain one or more resins in solution, those customary for the production of printing inks, colored varnishes and pigment pastes are used. Examples are aromatic hydrocarbons such as benzole, toluol, ethylbenzole and xylol, halogenated hydrocarbons such as chlorobenzole, alcohols such as methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, secondary butanol and tertiary butanol. butanol, glycols such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol and monoalkyl ethers having 1 to 4 carbon atoms in the alkyl group,
Polyglycols such as polyethylene glycol and polypropylene glycol, diacetone alcohol, benzyl alcohol, phenol substituted phenols, naphthols and substituted naphthols, cresols, xylenol, ketoso such as acetone, methyl ethyl ketone, methyl isobutyl ketoso, acetophenone and cyclohexanone, carboxylic acids esters such as acetic acid, propionic acid, glycolic acid or lactic acid with aliphatic alcohols or glycols having 1 to 5 carbon atoms, carboxylic acid amides such as dimethylformamide and N-methylpyrrolidone and mixtures of these liquids. be. The resin contained in the organic solvent may be natural, semi-synthetic and/or synthetic. Examples of this type include natural resins such as rosin, copal, dammar and shellac, semi-synthetic resins such as oligomeric and polymeric rosins, esters using mono- or polyhydric aliphatic alcohols and/or phenols. modified rosin, calcium, zinc or magnesium salts of rosin (so-called resinates), cellulose esters, cellulose ethers and rubber derivatives, synthetic resins such as maleic resins, phenolic resins, urea-formaldehyde resins, melamine resins, aldehydes. Resins and ketone resins, polyester resins, polymeric resins such as polyacrylate resins, polyvinyl acetate, polystyrene, polyisobutylene, polyamide resins, epoxy resins and silicone resins or mixtures of various resins. The preparations according to the invention can be produced in the form of powder or liquid preparations. To produce a powdered preparation, the following procedure can be carried out. The salt [b' prepared beforehand from (Q) and (8) is added in solid form to the pigment {a' and the powder is homogenized in a grinding device such as a ball mill or an edge runner or an intensive mixing device. However, you can also operate as follows. A preparation is first prepared in water or preferably in an organic liquid which can be easily removed, from which a powder preparation is then obtained by evaporation, mist drying or freeze drying. For the industrial production of powdered mixtures, the first-mentioned method is preferred. A liquid preparation can be produced, for example, as follows. 'a} and [b) etc. in organic liquids that can be easily removed,
or the suspensions from {a), (Q) and (8), on porcelain,
The milled bodies of glass, sand or steel are dispersed and homogenized in a dispersing device, such as a ball mill, a rope mill or a sand mill. Liquid preparations can also be produced by similar means, without removal of the organic liquid. When components 'a} and (b' in 'c' are used at relatively high concentrations, or when a viscous resin solution is used as [c}, dispersion can be carried out in a kneader or mixer. Advantageously, (Q) and (8) are first reacted, preferably in an organic liquid, to form 'b}, and then 'b' is incorporated into [a',
Preferably, it is incorporated in the presence of an organic liquid or resin solution. Incorporation and homogenization are carried out in suitable dispersion equipment, such as kneaders, ball mills, sand mills or net-and-pole mills. You can also operate as follows. The pigment or crude pigment is first suspended in an organic liquid or resin solution [c] and then the pigment (Q) is added in the form of a pre-prepared salt or mechanical mixture or as a component (Q).
and (B) separately into the suspension, and the resulting mixture is then dispersed by entrainment and mixing. For the industrial production of the liquid preparations according to the invention, the two operating methods mentioned below are particularly advantageous and are therefore recommended. The preparations according to the invention can also contain other auxiliaries, such as dispersion stabilizers or other auxiliaries commonly used for the particular application. Preparations intended for the production of analog printing inks can contain, in addition to the resin used as binder, the customary auxiliary substances for printing inks, such as anti-smearing agents or drying agents. Provided that these auxiliaries are finely dispersed, they have no or virtually no effect on gloss. This also applies to the specification for recrystallization and transformation transitions. The liquid and powder preparations of the invention do not differ in quality. Both forms can be mixed and processed equally well in varnishes or printing inks, in organic liquids or in resin solutions. Printing inks that come into consideration here include those containing binders and pigments in pure organic matter, as well as those containing binders and pigments in the form of aqueous dispersions. Furthermore, the solid mixtures are suitable for coloring synthetic resins. For mixing in pulverulent preparations, a simple concentration using a high-speed dissolver is often sufficient. This is because the pigments contained in powdered preparations can be easily dispersed in systems containing solvents. Pasty preparations can, of course, be incorporated more easily into many organic media. Since the powder preparation according to the invention contains virtually no substances that are incompatible with the system to which the pigment is to be added,
Unlike the liquid preparation of the present invention, it can be widely used. Organic pigments milled without the addition of tb' generally have poor pigment properties. The additive of the present invention unexpectedly does not cause the above-mentioned deterioration. The powdered preparations thus described have, as an advantage over conventional pigments, a relatively small apparent volume. This means that the filling volume is small and less dust is generated during processing. The pigmentations, prints and coatings obtained with the preparations according to the invention have good color properties similar to pigments [a}. Thus, the coloration unexpectedly exhibits high optical stability, overlay resistance, solvent resistance and bleed-through resistance similar to that of the base pigment 'a'. On the other hand, the colorations obtained with the preparations according to the invention are clearly superior in gloss and color brightness to those obtained with pure pigment 'a1 alone. Furthermore, the friction fading properties of the varnish are improved. After being dispersed in a solvent-containing binder, the pigment preparations of the present invention are essentially more finely dispersed than previous pigments. This can be confirmed using disc centrifugal bag counterfeiting (the measurement method is described by J. Fraser in "Pigment. Handbook", Volume M, p. 53, edited by T.C. Patton, John Wiley & Sons). Publishers, New York, London, Sydney, Kent, 1973). For example, after a dispersion period of 20 minutes in toluene intaglio varnish, 50% of the material is 0.0
In contrast, good common pigments have a particle size of 0.140 mm or less. What is noteworthy is the very good chromatic properties of intaglio printing inks containing in particular toluene. In general, a significant deterioration in fluidity is observed as the particle size decreases (Böhhausel, M.H.
・Honitzhimann's "Falbe Ten Lac" Volume 77, 10
9, p. 1971). In contrast, in the case of the present invention, this effect is essentially reduced, and in parallel there is a substantial deagglomeration of the dispersion. The additive according to the invention has the further advantage that small amounts are required to prevent crystallization and transformation transitions. The shade of the pigments of the various modifications is thereby only slightly influenced. Therefore, the interesting reddish steel phthalocyanines (Q-, 6-1 and 1-modifications) and phthalocyanines (Q-1 modification) can be brought into processable form in auburn agents containing aromatic solvents. The preparations according to the invention can also be incorporated into and processed in synthetic resins such as PVC and polyethylene at the temperatures commonly employed. The invention is further illustrated by the following examples. Parts and percentages in the examples refer to weight, and parts by volume have a relationship of k9 to parts by weight. Example 1 'a} Copper phthalocyanine 2 of the 8-modification in pigment form is combined with 2.5 parts of tris-diethylamine/methylene-copper phthalocyanine and 2 dodecylbenzole sulfonic acids.
．． 75 parts of toluene together with 5 parts are dispersed over 2 hours in a closed container in a shaking device (Red Devil) with a glass bulb (diameter 3 winds) of 10 cough volume parts. A liquid paste of low viscosity is obtained which is eminently suitable for pigmenting printing inks. Preparation of the 'b' printing ink 8 parts of the solid material of the preparation according to Example 1 and 4 were mixed with 35% Toluor-Albertol varnish 92
The mixture was dispersed for 2 minutes using a toothed disk dispersion machine. The rheological properties of this ink are shown in Table 1. The color properties of the colors produced using this ink are summarized in Table 2. [c - Comparative experiment against this {
Prepare the preparation as in a- except that in (cl) no 'b' is added, in (c2) only (Q) is added and in (c3) only (3) is added. The results obtained with these preparations are shown in the table below for comparison. Examples 2-4 Example 1 was operated similarly, but the ratio of tris-jethylaminomethylene-steel phthalocyanine to dodecylbenzole sulfonic acid was changed to 1:1.5 mol in Example 2;
1:2 mol in Example 3 and 1:4 in Example 4.
The amount is 5 moles. The rheological properties and color properties of the toluene intaglio printing ink produced from these are shown in Tables 1, 2, and 3. The test was conducted in the same manner as in Example 1'b}. Table 1 1) Tris-methylene jethylaminosteel phthalocyanine in PSn 2) DBS engineered dodecylbenzole sulfonic acid 3
) Measured at an angle of 450 using a Gardner multi-gloss meter with standard black glass as 100%. 4) At the flow limit. And the final viscosity knife is “Rheology” by Jen Casson.
・Of Dishaas Systems,” pages 84-104,
According to the method described in C. C. Mill, ed., Pergamon Publishers, New York, 1959. Table 2 1) PSn
= Tris-methylene dithylamino copper phthalocyanine 2
) DBS = Dodecylbenzole sulfonic acid 3) DI
According to N6164 (standard light type 0), in T and S 0.04 units are clearly distinguished by a color expert, and in S a larger number means higher purity. Table 3: 1) See DIM 53206 and V. Bartel, "Einführung in Die Korngleisenmestechnique", Springer Verlag, 1960. 2) 5Z: Particle size at which 50% of the particle material has a value larger or smaller than this value. 3) Log standard distribution. Examples 5 to 23 Working as in Example 1, but using the same amount of the phthalocyanine derivatives listed in Table 4 instead of the tris-jethylaminomethylene-copper phthalocyanine, liquid preparations were likewise obtained. , which is practically similar in its color properties to the paste obtained according to Example 1. I DIN 53206 and V. Bartel, Einfjürnung in D. Korngle-Semestechnik Haspringer I., 196, 196. 2.
Dz: Particle size at which 50% of the particle material has a value greater or less than this value. 3 Logarithmic machine distribution. Table 4 0uPc dicopper phthalocyanine Pc The production of the metal-free phthalocyanine toluol intaglio printing varnish and the coloring with this varnish are carried out analogously to Example 1 {b}. Evaluation is also performed in the same manner as in Example 1. A specific gloss improvement is obtained as a distinct feature. The measurement results are shown in Table 5. Table 5 Draw-down gloss value Example 24 [a'B- Steel phthalocyanine 2 anchors, tris-jethylaminomethylethane 2.5 parts of steel phthalocyanine and 2.5 parts of dodecylbenzole sulfonic acid in 75 parts of toluene. Then, the mixture is dispersed for 2 hours in an Azusa-type ball mill. A liquid base of low viscosity is obtained, which is very well suited for pigmenting varnishes and printing inks, in particular toluol intaglio printing inks and polyamide intaglio printing inks. 'b - Comparative Experiment' Proceeding as in 'a', but without the addition of dodecylbenzenesulfonic acid, results in a highly viscous and non-flowing paste, which can only be removed from the condenser container after further addition of toluene. I can do it. Examples 25-38 The same machine as Example 24 is operated, except that instead of dodecylbenzole sulfonic acid, the sulfonic acids listed in Table 6 below are added in the amounts indicated in the table. A paste is obtained having the rheological properties shown in column 5 of the table. Using the obtained paste, a colored article is produced in the same manner as in Example 1 {b--, and the gloss value of this coloring is measured (see Example 1 for the measuring method). Table 6 Example 39 23 parts of a mixture from Q- and 8-copper phthalocyanines, 7 parts of a mixture from tetra- and trisujethylaminomethylene-copper phthalocyanines (n=3.2), 50% resin in toluene A mixture of 2 parts of zinc acid solution, 11 parts of 2,4-bis-dodecylbenzole sulfonic acid and the resulting ink smear inhibitor, sold under the name Colorol, 1 part of the base 2$ A liquid concentrate is obtained by dispersing one part in three parts of toluene in a mill. By simple incorporation into a suitable binder solution, ready-to-use, multicolored printing inks are obtained which are eminently suitable, for example, for toluene intaglio printing or polyamide intaglio printing. The prints (pigments) obtained with this printing ink are distinguished by a high gloss, high tonal purity and very good flow properties. Practically equally good results can be obtained by using other resins instead of zinc resinate, such as calcium resinate, rosin or dimerized rosin. Example 40 {a} Preparation of salts from (Q) and (8): ~41 containing on average 3.9 solid basic residues
0 parts and dodecylbenzole sulfonic acid (molar ratio approx. 1
:3) is mixed in a kneader at 80 qo, salt formation taking place. After lining, the salt can be crushed into powder. 'b' Pigment Preparation: [a}' 4 parts of the salt thus obtained are dispersed together with 16 parts of 8-copper phthalocyanine in 80 parts of toluene in a mill. A liquid preparation of low viscosity is obtained, which is eminently suitable for coloring printing inks and varnishes. Example 41 8 parts of Q1 steel phthalocyanine in pigmented form and 2 $ parts of the salt obtained according to Example 40a are kneaded in a Sigma bran mixer with the addition of 4 parts of propanol. The solvent is vaporized off in a kneader and the bulky preparation obtained is crushed in a sieve mill (mill with two discs rotating in opposite directions and having steel convex plates). Grind into powder. The preparations obtained can be used in general, for example in solvent-containing printing inks or varnishes. This preparation can be incorporated into printing inks or varnishes by means of a dissolver. The colorations obtained with this printing ink or varnish are clearly superior in quality to those obtained with state-of-the-art pigments. Example 42 Proceed as in Example 41, except that instead of salt, the corresponding base ingredient is on average 3.
A jethylaminomethylene-steel phthalocyanine with an n of 5 and Star IJ sulfonic acid are used. The preparation obtained has properties similar to those obtained according to Example 41. Example 43 Same procedure as Example 41, but using B-Steel phthalocyanine instead of Q-Steel phthalocyanine. Example 44 Crude steel phthalocyanine (phthalodinitrile and chlorinated steel (1
) prepared in nitrobenzole in the presence of ammonia are ground dry in a ball mill with 25 parts of the salt obtained according to Example 40a at 105 mm for 5 field hours. Then 6 parts of clay available commercially under the name Penton 35 are added and the mixture is homogenized. A pigment preparation is obtained which exhibits very good dispersibility and very good flow properties, especially in intaglio printing varnishes containing toluene. Prints obtained with this type of ink have a high degree of gloss. Example 45 75 parts of Q-steel phthalocyanine are homogenized dry in a mixer with 25 parts of the salt obtained according to Example 40a}. The preparations thus obtained are stable in organic liquids such as benzol, toluol or xylol. The transition to the 81 metamorphosis does not occur even on prolonged contact with this liquid. This product can therefore be used in particular in the field of printing inks and varnishes for rotary intaglio printing, for example for illustrated newspapers. Examples 46-50 Pigment preparations were prepared as in Example 45, except that Q
Pigments shown in Table 7 are used in place of Ikko phthalocyanine. Table 7 1 Contains 15% chlorine and 46% bromine. Example 51(a) One part of (on average n=3) is reacted with 1.5 parts of dodecylbenzole sulfonic acid (molar ratio about 1:3) in an aqueous suspension at 50 oo to form the salt. The resulting dye salt is separated by filtration and dried.
[b-12.5 parts of salt 'a' and 37 parts of crude steel phthalocyanine
．． Knead with 55 parts of ethylene glycol for 1 field hour with 5 parts of rock salt and 30 parts of rock salt. Subsequently, rock salt and ethylene glycol are eluted using water. The dried pigment preparations have very good dispersibility in solvent-containing printing inks and varnishes. The colorations obtained with this preparation exhibit a high degree of gloss. Compared to preparations containing only basic copper phthalocyanine derivatives,
The former exhibits very good overlay properties without exhibiting any bleeding in printing inks and varnishes. The inks and varnishes also exhibit very good flowability. Examples 52-58'a} Salts are prepared analogously to Example 51 {a' from the phthalocyanine derivatives listed in Table 8 and dodecylphenol sulfonic acid. The molar ratio of phthalocyanine derivative to sulfonic acid is 1:3. 'b) A preparation is prepared analogously to Example 51 (b) from 12.5 parts of the salt obtained by 'a} and crude steel phthalocyanine. Table 8 Examples 59-6
5 Crude steel phthalocyanine (phthalodinitrile and chlorinated steel (1
) obtained in nitrobenzole in the presence of ammonia) in an average of 3. A mixture of diethylamide/methylene-copper phthalocyaniso containing needle-hard methylene groups and the sulfonic acids listed in Table 9 below (molar ratio of phthalocyanine derivative to sulfonic acid is 1:3)
．． 2) Mill with 25 parts in a ball mill for 5 q hours. Then 6 parts of clay are added and the mixture is homogenized. The resulting preparation gives, for example, a high gloss print after mixing with a toluol intaglio printing varnish (Albertol-KP670) using Red Delbi. The pigment content of the printing ink is 8% based on the printing ink. Table 9 shows the gloss of this printing ink scraped onto a film from cellulose acetate in comparison to a commercially available copper phthalocyanine pigment. Table 9 Example 66 Example 40' Preparation of salt from 'a' (Q) and (8)
a}. However, the molar ratio of phthalocyanine derivative to dodecylbenzenesulfonic acid is 1:4. A preparation is prepared in the same manner as in Example 44 from 'b' crude steel phthalocyanine 8 branches and the salt obtained from [a'. The preparation obtained has almost as good properties as those according to Example 44. It is particularly suitable for coloring printing inks and varnishes containing aromatics. Example 67 Performed from 6 $ parts of 8-copper phthalocyanine pigment and 9 parts of a salt from tris-methylene diethylaminosteel phthalocyanine (n=3.5) and dodecylbenzole sulfonic acid (molar ratio 1:2). A preparation is prepared analogously to Example 40b' in an aqueous suspension with the addition of 3 parts of surface-active substance in a sand mill. The pigment is separated in an oven, washed with water and dried. This preparation is particularly suitable for melamine brightening varnishes and intaglio printing inks and is distinguished by a high gloss and high purity. Example 4 parts of a single-transformed steel phthalocyanine are suspended in 80 parts of ethanol. The suspension is brought to boiling temperature, then 2 parts of the reaction product described under 'b) are added to the ethanolic suspension and the mixture is kept under reflux for 2 hours. The pigment is then monochromated by direct suction furnace filtration. The suspension in ethanol can also be worked up by adding 800 parts of water to remove the ethanol. The pigment is isolated from the aqueous suspension by filtration. In both cases, finely divided, transformation-stable copper phthalocyanine pigments of the 8-1 modification are obtained, which do not transform into the 8-1 modification even after boiling in benzene for 8 hours. The starting product is treated in a similar manner, but without the addition of additives, at 0.0% in boiling benzene. A steel phthalocyanine that transforms to the B-transformation within an hour is obtained. 'b- Stabilizer: Tris-jethylaminomethylene-
One part of copper phthalocyanine is reacted with one part of dodecylbenzole sulfonic acid (molar ratio 1:3) in a mirror mill at 80 minutes. After the kneaded material is mixed, it is pulverized. Example 69 45 parts of tri-copper phthalocyanine in pigment form was mixed with 5 parts of tris-jethylaminomethylene-steel phthalocyanine and p-tert-butylphenol sulfonic acid (molar ratio 1:3).
) and dry mix with the mixture from ). The resulting preparation is stable to recrystallization in the following solvents. Benzol with a boiling point or lower, toluol with a temperature of 65°C or lower, and butanol with 11 of ○ or lower. The resulting preparation exhibits the same properties as the starting pigment, such as exudation properties, light properties, etc. In contrast, the pigments used as starting materials crystallize under the conditions mentioned, which leads to their quality being poor. Examples 70 to 72 The procedure was as in Example 69, except that trisujethylami/methylene-
A mixture of copper phthalocyanine and dodecylbenzole sulfonic acid is used as stabilizing agent. Table 10 The preparation obtained has similar advantageous properties to that according to Example 69. Example 73 47.5 parts of sea steel phthalocyanine was also prepared from trisujethylaminomethylene-steel phthalocyanine and dodecylbenzole sulfonic acid in a molar ratio of 1:3 (see example illustration 'b') Salt 2.5 Boil at boiling temperature for 4 hours in 50% ethanol with water. The preparation is then washed with ethanol and dried (60 qo). The resulting preparation is stable in aromatic solvents such as benzol or toluene at temperatures below 70 qo. No transition to 31 metamorphosis takes place. This preparation can be easily dispersed in resin solutions used for printing inks or for the production of varnishes. The prints or coatings obtained have very good toughness, such as overlay toughness, soap resistance and solvent resistance. On the other hand, the Y-steel phthalocyanine used as starting material transforms into the 8-form in the abovementioned solvent, with simultaneous recrystallization taking place. Example 74 Q-steel phthalocyanine in pigment form (bound by sulfuric acid swelling) 15 bases were mixed with salt from ethane sulfonic acid and tris-methylene dietylamino steel phthalocyanine (molar ratio 3:1) in a Sigma kneader. Along with 15 parts,
Knead for 2 hours at room temperature using 75 parts of isopanol. The isopanol is then removed by washing with water and the pigment is dried. The preparations obtained are transformationally stable in printing inks containing solvents, especially aromatic solvents, in contrast to the case of untreated pigments. Also, no transition to the 81 metamorphosis occurs even after storage for several days at 50:00 in a varnish binder. Example 75 Proceed as in Example 74, except that instead of the Q-copper phthalocyanine pigment, a 6-modified pigment is used. A highly reddish, solvent-resistant pigment preparation is obtained, which is particularly suitable for varnishes and pigmented inks. Example
76 Proceed as in Example 74, but instead of steel phthalocyanine, a metal-free phthalocyanine pigment of the Q-modification is used. Pigment preparations are obtained which are stable against recrystallization at temperatures below 80° C. in organic solvents. In the absence of additives, a transition to the 8-transformation occurs. Examples 77-93 7 parts of the copper phthalocyanine pigment listed in Table 11, tris-jethylaminomethylene-steel phthalocyanine (Q) and the sulfonic acid (8 parts) listed in the table in the molar ratios shown in the table.
) is intimately mixed for 1 hour in a kneader with the addition of 35 parts of a mixture of 75% water and 25% ethanol. The kneaded material is diluted with water and washed in a furnace. After drying, a transformationally stable pigment preparation is obtained which does not recrystallize even on prolonged contact with aromatic hydrocarbons such as benzole, toluol or chlorobenzole at temperatures below 65 qo. Table 11 ouPoi Copper Phthalocyanine Pc 3 Metal-Free Phthalonanine Example 5 parts of metal-free crude phthalocyanine were prepared from tris-methylene ethylamine/steel phthalocyanine and dodecylbenzole sulfonic acid (molar ratio 1:1.7). 4 parts of salt and 40 parts of rock salt were added and ground in a dry state for 1 hour. Subsequently, the rock salt is removed by boiling extraction with water, and the pigment is dried in an oven. gives a monomorphic phthalocyanine preparation, which, contrary to the case of the untreated product,
It is stable against transformation transitions in varnishes and printing inks containing aromatic substances, giving turquoise colorations.
Example 95 90 parts of crude steel phthalocyanine are mixed with 97 parts of 65% sulfuric acid and 9 parts of a salt from tris-methylene jethylaminosteel phthalocyaniso and dodecylbenzole sulfonic acid (molar ratio 1:3) and kept at room temperature for 1 hour. worship at the rope. This mixture is diluted with 575 parts of water and at the resulting temperature 0. Insect time rope worship. more water 3
After dilution with 0.00 base, the pigment is placed in an oven, washed to remove the acid, and dried. It is suitable for pigmenting varnishes and printing inks and gives a strikingly reddish-blue coloration with very good consistency. Examples 96 to 114 The modified pseudophthalocyanine pigment or phthalocyanine pigment 5 Kyoto shown in the twelfth coin was mixed with phthalocyanine transferor D and dodecylbenzole sulfonic acid (8
) (the molar ratio of D:(3) represents the first tail length of 1) in a dry state. The pigment preparations thus obtained are stable against recrystallization in organic solvents and at common processing temperatures. They are therefore particularly suitable for pigmenting varnishes and printing inks. Other benefits include common additives (e.g., K. Markle and H. Sheifer, "Surf Eighth Treatment of Organic Pigmentation Handbook, Vol. 15 et seq., edited by T.C. Patton, John Wiley) and Sons Publishing, New York, London, Sydney, Toronto, 1973).In varnishes, for example, the overlay properties are significantly improved (D) and (8). No defects occur due to the addition of .No leakage of solvents, acids or alkali is observed in packaging printing.Table 12 ○ uPc = Copper phthalocyanine Pc Phthalocyanine Example 115 8 - Metamorphosis of crude steel phthalocyanine 4 Base part with 4 parts of a salt from tris-methylene amino steel phthalocyanine and dodecylbenzole sulfonic acid in a molar ratio of 1:3,
Grind dry in a ball mill for 5 field hours at 35°C. A pigment preparation containing the pigment in the Q-modification is obtained. This preparation is suitable for pigmenting varnishes and printing inks. Example 116 The procedure is as in Example 115, except that the copper phthalocyanine is replaced by metal-free crude steel phthalocyanine of the 31-transformation.

Claims (1)

[Claims] 1. General formula ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ (Formula Pc is an n-valent residue of metal-free phthalocyanine, copper phthalocyanine, or a mixture thereof, -CH_2-
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ X is the group -CH_2-CH_2-COO-C_2H_4- or -
CH_2-CH_2-COO-C_3H_6-, R^1
is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a group -(C_2H_4-NH)zH or (C_3H_9
-NH)zH, R^2 is a hydrogen atom, an alkyl group or cyclohexyl group having 1 to 4 carbon atoms, alk is a linear or branched saturated alkylene group having 2 to 6 carbon atoms, R means a hydrogen atom or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ means ▲There are mathematical formulas, chemical formulas, tables, etc.▼, n is a number from 2 to 4, and z is an integer of 1 or 2 ) and one or more phthalocyanine derivatives (α) represented by 1 to 20 carbon atoms each, and an alkanesulfonic acid, alkenesulfonic acid or hydroxyalkenesulfonic acid, each having 1 to 20 carbon atoms, if desired.
benzenesulfonic acid, phenolsulfonic acid or naphthalenesulfonic acid or a mixture thereof (β) having one or two alkyl groups having 0 carbon atoms, and the molar ratio of (α):(β) is 1:1 to 1:5 of a salt or homogeneous mixture (b) as a stabilizer and optionally one or more organic liquids or a solution of the resin in an organic liquid (c). contains. A phthalocyanine preparation stabilized against recrystallization and transformation transitions, giving a coloration with good gloss. 2 (α)
and (β) or a homogeneous mixture (b) of 10 to 40% by weight based on (a), where (β) is 8 to 18% by weight.
alkanesulfonic acids or alkenesulfonic acids with 6 to 20 carbon atoms, respectively
Preparation according to claim 1, characterized in that it is benzenesulfonic acid, phenolsulfonic acid or naphthalenesulfonic acid or a mixture of these sulfonic acids with one or two alkyl groups. 3. Preparation according to claim 1, characterized in that it contains from 2 to 10% by weight of (b) relative to (a).