DE3400161A1 - Phthalocyanine compounds, their preparation and use - Google Patents

Abstract

Phthalocyanine compounds of the formula <IMAGE> in which the symbols have the meanings given in Claim 1; they can be prepared by stepwise reaction of a compound of the formula <IMAGE> with H-Q and H-Q1 and are used in particular for the dyeing of paper, but also for leather and textile material containing hydroxyl groups.

Description

PHTHALOCYANINE COMPOUNDS, THEIR PRODUCTION AND USE

The invention relates to phthalocyanine compounds with at least two basic groups different from one another.

The invention relates in particular to phthalocyanine compounds or mixtures of phthalocyanines of the formula where Pc is a metal-free or metal-containing phthalocyanine, R independently of one another is hydrogen or (1-4C) -alkyl, R1 independently of one another is a (1-6C) -alkylene or (2-6C) -alkenylene radical, Q and Q1 are a radical of the formula - NR2R3 II or e - N R4R5R6 A III, one equivalent of a cation, one equivalent of a colorless anion, m and n independently of one another a number from 0.3 to 4, p a number from 0 to 1, with the proviso that 2 - tr is m + n 6, where R2 is hydrogen, (1-12C) -alkyl, phenyl, a phenyl-substituted (1-4C) -alkyl radical, the phenyl radical being substituted by 1, 2 or 3 (1-4C) -alkyl radicals can be a (2-4C) -alkyl radical substituted by OH, a (5-8C) -cycloalkyl radical substituted by up to three (1-4C) -alkyl radicals, R3 is hydrogen, (1-12C) -alkyl or one by OH substituted (2-4C) -alkyl radical, R4 one of the meanings of R2 excluding hydrogen, R5 one of the meanings of R3 excluding hydrogen, R6 (1-12C) -alkyl, (2-4C) -hydroxyalkyl or a (1-4C) -alkyl radical substituted by phenyl denote the radicals R2 and R3 or R4 and R5 together with the N atom attached to them a 5- or 6-membered saturated heterocycle optionally containing further heteroatoms, the radicals R4, R5 and R6 together with the N atom bonded to them can form a pyri di ni ring optionally substituted by one or two (l-4C) -alkyl radicals, with the proviso that Q and Q1 are different from one another, but always simultaneously either as a radical of the formula II or a radical of the formula III.

Preferred phthalocyanine compounds or mixtures of phthalocyanine compounds correspond to the formula where Pc is a copper, cobalt, iron, zinc, aluminum or nickel, in particular copper phthalocyanine, independently of one another hydrogen or methyl, R'1 independently of one another a (1-4C) -alkylene radical or Q 'and Q'j a radical of the formula - N R'2R'3 II a or - N # R'4R'5R'6 A # III a, MH, Na, K, Li or -NH4, a non-chromophoric anion, m 'and n' denote a number from 0.3 to 3, a number from 0 to 0.7, preferably 0.3 to 0.5, with the proviso that 2 # m '+ n' is # 4, R2 is hydrogen , (1-6C) -alkyl ß-hydroxyethyl, cyclohexyl, phenyl or benzyl, R3 hydrogen, (1-6C) -alkyl or ß-hydroxyethyl, R4 one of the meanings of R2 except hydrogen, one of the meanings of R3 except hydrogen, R6 (1-4C) -alkyl, 5-hydroxyethyl or benzyl, R2 and R3 together with the N atom attached to them denote a morpholine, piperidine, pyrrolidine, piperazine or N-methyl or N-ethyl Piperazine ring, or R4, R'5 and R'6 form a pyridine, α- or ß-picoline or lutidine ring or a ring of the formula can form, in which W is the direct bond, -CH2-, -O-, -NH-, -NR7- or and R7 independently of one another denote (1-4C) -alkyl, with the proviso that Q 'and Q'1 are different from one another but at the same time denote either a radical of the formula II a or III a.

Particularly preferred phthalocyanine compounds or mixtures of phthalocyanine compounds correspond to the formula wherein CuPC is a copper phthalocyanine, R 'independently of one another -CH2-, -CH2CH2- or Q "and Q'j a radical of the formula - N R2R3 II b or - N R4R5R6 As III b, m" and n "independently of one another a number from 0.3 to 2.5 and preferably 1.0 to 1.5, with the proviso that 2.1 <m "+ n"<3, R2 is hydrogen, methyl, ethyl, n-propyl, isopropyl or butyl, R3 has one of the meanings of R4 methyl or ethyl, R5 methyl or ethyl, R6 methyl , Ethyl or benzyl, R2 and R3 ″ together with the N atom bonded to them denotes a morpholine, piperidine or piperazine ring, R4, R5 and R6 denote a pyridine, α or picoline ring or a ring of the formula can form, wherein W '-CH2-, -O-, -NH-, -N (CH3) - or mean with the proviso that Q ″ and Q'j are different from one another but at the same time mean either a radical of the formula tI b or III b.

Very particularly preferred phthalocyanine compounds are characterized by that Q and Q1 stand for a radical of the formula II, or that Q 'and Q; for II a or that Q "and Qj 'stand for II b.

The process for preparing the compounds or mixtures of compounds of the formula I is characterized in that 1 mol of a compound of the formula where Hal denotes a halogen atom, advantageously a chlorine, bromine or fluorine, and in particular a chlorine atom, in a first stage with m mol of a compound of the formula HQ, advantageously in water, at temperatures of 20-500 ° C., preferably 30-450 ° C. and at a pH of 9-12, preferably 10-11 in the presence of a base, advantageously an alkali hydroxide such as sodium or potassium hydroxide and in a ratio of about 1 part of a compound of the formula VI and 1 part of an amine of the formula HQ and then in a second stage with n moles of a compound of the formula H-Q1, advantageously in water and in the same solution as the 1st stage, at temperatures of 40 to 800C, preferably 50-600C and at a pH of 9- 12, preferably 10-11 in the presence of a base, advantageously an alkali hydroxide such as sodium or potassium hydroxide and in a ratio of about 1 part of a compound of the formula VI and 1 part of an amine of the formula H-Q1. The compounds of the formula VI are known, for example, from German patent specification 1.029.965, or can be prepared by methods known per se.

The amines H-Q and H-Q1 are also known or can be per se known methods are produced.

In the following formulas, Pc stands for CuPC with increasing significance; R for R '; R1 for Rj or for Q for Q 'or for Q "; Q1 for Qj or for Q'1; M for Ml; m for m 'or for m ", advantageous for 1.0-1.5; n for n', or for n", advantageous for 1.0-1.5, R2 for R2 or for R2; R3 for R3 or for R4 for Ri or for R5 for R: or for R5; R6 for R6t or for R6; R2 and R3 together for R2 and R31 or for Rz and R3 together; R4, R5 and R6 together for R4, R5 and R61 or for R4, R5 and R6 together; W for W '.

The compounds obtained can from the alkaline aqueous suspension-in which they are formed by methods known per se, are isolated.

In the compounds of the formula I, the anion AO can be replaced by others Exchange anions, e.g. with the help of an ion exchanger or by reaction with salts or acids, optionally in several stages, z.S.

via the hydroxide or via the bicarbonate or according to the German Offenlegungsschrift 2,001,748 or 2,001,816.

The anions that are customary in basic dye chemistry are used in Question, - mainly non-chromophoric anions are suitable.

Anion includes both organic and inorganic ions understand, such as halogen, such as chloride or bromide, further sulfate, bisulfate, Methyl sulfate, aminosulfonate, perchlorate, benzenesulfonate, oxalate, maleate, Acetate, propionate, lactate, succhinate, tartrate, malate, methanesulfonate or Benzoations or complex anions, such as that of zinc chloride double salts, and also the Anions of the following acids: boric acid, citric acid, glycolic acid, diglycolic acid or adipic acid or addition products of orthoboric acid with polyalcohols or cis polyols.

The new phthalocyanine derivatives obtained can be used directly as Colorants can be used or can be in the form of aqueous, e.g. stable solutions, in quaternized form and / or the corresponding salts of mineral acids or organic acids or partially internal salt form for dyeing fiber material of all kinds, of cellulose, cotton or leather, but especially of paper or Paper products are used or made of bast fibers such as hemp, flax, sissal, Jute, coconut or straw.

The dyes can also be used in the manufacture of mass-colored, sized and unsized paper can be used. You can also use it for coloring of paper can be used by the dipping process.

The dyeing of paper, leather or cellulose is carried out according to known methods Methods. The new dyes or their preparations color the wastewater in the Paper production practically not at all or only a little in terms of keeping things clean the water is particularly favorable. They are highly substantive, mottled on paper do not stain and are largely insensitive to pH. Draw the colors on paper are characterized by good lightfastness properties. Changes after prolonged exposure the tone-on-tone shade. The dyed papers are wetfast, not just against Water, but also against milk, soapy water, sodium chloride solutions, fruit juices and sweetened mineral water and because of their good alcohol resistance, also against alcoholic ones Drinks resistant; furthermore, when dyed on paper, they have good shade stability. They are readily soluble in water and the staining does not bleed.

The new dyes can also be modified with anionic groups Dyeing, padding or printing polyamide or polyester textiles.

In the following examples the parts mean parts by weight which Percent weight percent; the temperatures are given in degrees Celsius.

Example 1 28 parts (1/30 mol) of a mixture consisting of bis- and tris- (chloroacetylamidomethyl) copper phthalocyanines (m + n = 2.5) are made into a paste with 300 parts of water; the pH value is adjusted to 7-8 with an approximately 30% sodium hydroxide solution. To this end, 2.84 parts (1/30 mol) of piperidine are added with stirring and at 20-30 °. The whole is gradually warmed to 40-43 ° and the pH is kept between 10.5 and 11.0 by adding dropwise 4.5 parts (1/30 mol) of a 30% sodium hydroxide solution. The reaction is complete as soon as the pH remains constant at this value. The dye obtained or the dye mixture of the formula is completely soluble in acetic acid (40-45%). Now 10 parts (1/10 mol) of dibutylamine are added to the reaction mixture, then the whole thing is again stirred at 55-60 "until the pH value is 10.5-11-0 / 20 mol) of 30% sodium hydroxide solution remains constant.

The dye or dye mixture corresponds to the formula It dissolves in dilute lactic acid or acetic acid with a brilliant blue color. The paper dyeings show remarkable wet fastness properties.

The wastewater is colorless. The lightfastness is excellent.

B e i s p i e 1 2 Instead of the 28 parts used in Example 1 Bis- and tris- (chloroacetylamidomethyl) copper phthalocyanines with m + n = 2.5 26.6 parts of a mixture of bis- and tris- (chloroacetylamidomethyl) copper phthalocyanines used with m + n = 2.1. A dye with good solubility in dilute vinegar or lactic acid and good coloring properties are also obtained.

The structure of other dyes is shown in the following table. They can be prepared according to the information in Example 1 and correspond to the formula wherein A, B, m and n have the meanings given in the columns.

As the anion A #, those listed in the description are suitable.

Table 1 AA m B n No: j 3 -N (C2H5) 2 1 -N (CH2CH2CH2CH3) 2 1.5 4 -N (CH2CH2CH3) 2 1 do. 1.4 , CH3 5 -N (CH / CH) 2 1 do. 1.4 6 do. 1 -N 3 1.4 7 -N g 1 -N (CH2CH2CH3) 2 1.4 8 do. 1 -N (CH2CH2CH2CH3) 2 1.3 9 ß 1 -7 3 1.3 10 do. 0.3 do. 2 The dyes of Examples 3-10 dye paper with brilliant blue shades with good fastness properties, in particular wet fastness properties.

B e i 5 p i e 1 11 21 parts (1/40 mol) of a mixture of bis and Tris (chloroacetylamidomethyl) copper phthalocyanines (m + n = 2.5) are used in 350 Parts of water are stirred in and adjusted to pH with a 30% strength sodium hydroxide solution posed from 7-8. Then 3.3 parts (1/40 mol) of a 45% trimethylamine solution are added and gradually warms the whole thing up to 32-420.

The pH is increased by the dropwise addition of 3.4 parts (1/40 mol) of 30% Sodium hydroxide solution kept at 10-10.5. Then 6 parts (3/40 mol) of pyridine added, the temperature increased to 55-60 ° and by adding dropwise about 5.1 parts Sodium hydroxide solution kept the pH at 10.5-11.

After stirring for 3 hours, the dye is filtered off, washed neutral and salt-free with water and dried. The dye of the formula dissolves in dilute acetic or lactic acid with a blue color. The paper dyeings show particularly good wet fastness properties.

COLOR REGULATION A 70 parts are chemically bleached in a Hollander Sulphite cellulose (made from softwood) and 30 parts chemically bleached sulphite cellulose (made of birch wood) ground in 2000 parts of water.

0.2 parts of that described in Example 1 are sprinkled onto this mass Dye. After a mixing time of 20 minutes, paper is made from this mass. The absorbent paper obtained in this way is colored blue. The sewage is practically colorless.

COLOR REGULATION B 0.5 parts of the dye from Example 1 are used dissolved in 100 parts of hot water and cooled to room temperature. This solution add 100 parts of chemically bleached sulfite cellulose, and 2000 parts Water was ground in a dutchman. Mixing takes place after 15 minutes the gluing.

Paper made from this material has a blue color Medium intensity shade with good wet fastness properties.

COLOR REGULATION C An absorbent paper web made of unsized paper is drawn through a dye solution of the following composition at 40-50 °: 0.5 part of the dye from 1; 0.5 parts starch and 99.0 parts water. The excess Dye solution is squeezed out through two rollers. The dried paper web is dyed blue and with good fastness properties.

The same good paper colorations are obtained if one in the above Dyeing instructions A, B and C equivalent amounts of a liquid preparation or adding a granulate preparation.

COLOR REGULATION D 2 parts of the dye according to Example 1 are used dissolved in 4000 parts of softened water at 400. Bring 100 parts pre-wetted Cotton fabric into the bath and heat the bath to boiling temperature for 30 minutes.

The bath is kept at boiling temperature for 1 hour and replaced with time at time the evaporated water. The dye is then taken out of the liquor, rinsed with water and dried. The dye is absorbed practically quantitatively the fiber on; the dye bath is practically colorless. A blue color is obtained with good lightfastness and good wetfastness.

COLOR REGULATION E 100 parts freshly tanned and neutralized Chrome grain leather are in a liquor of 250 parts of water of 550 and 1 part of the dye prepared according to Example 1 (as an acid addition salt) for 30 Min.

Fulled in the barrel and in the same bath with 2 parts of an anionic Treated fat liquor based on sulfonated oil for a further 30 minutes.

The leathers are dried and finished in the usual way. Man receives leather of any color in blue tones.

Other low-affinity, vegetable retanned leathers can also be used be colored by known methods.

The dyes of the other examples can also be used in an analogous manner be dyed according to the dyeing instructions A - E.

Claims (8)

PHTHALOCYANINE COMPOUNDS, THEIR PRODUCTION AND USE 1. Phthalocyanine compounds or mixtures of phthalocyanines of the formula wherein Pc is a metal-free or metal-containing phthalocyanine, R independently of one another hydrogen or (1-4C) -alkyl, R1 independently of one another a (1-6C) -alkylene or (2-6C) -alkenylene radical, Q and Q1 a radical of Formula -NR2R3 II or -NR4R5R6 A (3 III, one equivalent of a cation, one equivalent of a colorless anion, m and n independently of one another a number from 0.3 to 4, p a number from 0 to 1, with the proviso that 2 # m + n # 6, where R2 is hydrogen, (l-12C) -alkyl, phenyl, a phenyl-substituted (l-4C) -alkyl radical, the phenyl radical being substituted by 1,2 or 3 (l-4C) - Alkyl radicals can be substituted, a (2-4C) -alkyl radical substituted by OH, a (5-8C) -cycloalkyl radical substituted by up to three (1-4C) -alkyl radicals, R3 is hydrogen, (1-12C) -alkyl or a (2-4C) -alkyl radical substituted by OH, R4 one of the meanings of R2 except hydrogen, R5 one of the meanings of R3 except hydrogen, R6 (1-12C) -alkyl, (2-4C) -hydroxyalkyl or a (1-4C) -alkyl radical substituted by phenyl denote the radicals R2 and R3 or R4 and R5 together with the N atom attached to them a 5- or 6-membered saturated heterocycle optionally containing further heteroatoms, the radicals R4, R5 and R6 together with the N atom bonded to them can form a pyridinium ring optionally substituted by one or two (l-4C) -alkyl radicals, with the proviso that Q and Q1 are different from one another, but always simultaneously either a radical of the formula II or mean a radical of the formula III. 2. Process for the preparation of the compounds or mixtures of compounds of the formula I, characterized in that 1 mol of a compound of the formula wherein Hal denotes a halogen atom, first with m moles of a compound of the formula H - Q and then with n moles of a compound of the formula H - Q1 in the presence of a base. 3. Use of the compounds according to claim 1 for dyeing or printing of paper or leather. 4. Use of the compounds according to claim 1 for dyeing, padding or printing on natural or regenerated cellulose. 5. Use of the compounds according to claim 1 for dyeing, padding or printing on bast fibers such as hemp, flax, sissal, jute, coconut or straw. 6. The according to claim 3 dyed or printed paper or leather. 7. The textile material dyed, padded or printed according to claim 4. 8. The dyed, padded or printed according to claim 5 Bast fibers.