DK152512B - SULPHORIC ACID HALVESTER PREPARATIONS USED AS DISPERSIBLE IN PIGMENT PREPARATIONS FOR Aqueous FLEXOTRY COLORS AND PROCEDURES FOR ITS PREPARATION - Google Patents

Description

DK 152512 B

in

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The demands made on pigment preparations for use in aqueous flexo printing have become considerably greater due to the use of fast-moving printing machines and new developments in the binder sector. For the 5 th purpose, flowable settings with high pigment concentrations are required. Since the solids concentration in the binder used in flexo printing is approximately between 15 and 30% by weight, and at a binder-pigment blend ratio of approx. 2: 1 of the ink must be adhered to a certain viscosity range, only a small amount of liquid should be introduced via the pigment preparation. Furthermore, the pigment doughs should contain only foam-poor distribution agents, also referred to as dispersing agents, to prevent foaming of the pigmented ink, which can lead to coagulation of the pigments and to disparate pressures. In addition to the favorable foam ratio, a low intrinsic color of the dispersants is required, especially in light and brilliant tones. Despite high pigment concentrations, the dough must be fluid or pumpable in order for it to be 20 simple to handle and meet dosing requirements in practice. However, the current distribution means meet only one or the other of the above requirements. With certain lignin sulfonates, e.g. Thus, higher concentration flowable pigment doughs are produced, however, to a limited extent only because of the intrinsic color of the dispersants. Naphthalenesulfonic acid-formaldehyde-based dispersants have a poor intrinsic staining and poor foaming properties, but at high pigment concentrations they cannot be processed into flowable doughs.

Using oxalkylated alkyl phenols or their sulfating products, flowable doughs with higher pigment concentrations can be produced, but the doughs can only be used to a limited extent in aqueous flexo printing colors due to their strong foaming. The

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Based on such distribution agents, commercially available aqueous pigment doughs are predominantly used for dyeing dispersion paints for interior and exterior smears or for pigment printing on textiles. However, they do not meet the high requirements of aqueous flexo inks and are therefore not suitable for this field of application.

The problem of foaming also occurs when using the oil-soluble salts with organic amines 10 and sulfuric acid esters of oxalkylated single-chain alkyl phenols known from GB-A-1,108,410, and when using the α-sulfocarboxylic acid esters of oxalkylated novolacs, which is known from US Patent No. 3,320,212 and in which, using dicarboxylic acids, a sulfo group at the α position is attached to each carboxy group. Also, because of the foaming, the compounds described in the aforementioned patents are not suitable for use in modern flexo inks.

Surprisingly, it has been found that the problems of the known compounds can be solved by using the present sulforic acid half-ester composition which is useful as a dispersant in pigment preparations for aqueous flexo inks, especially in pigment preparations for use in aqueous flexo printing in high-speed printing machines.

The invention therefore relates to a sulfuric acid half-halter composition for use as a dispersant in pigment preparations for aqueous flexo inks, and the present invention is characterized in that it consists of a mixture of compounds of the general formula

30 I B - (0 - X) n - 0 0 - (X - 0) n - A

J-J Λ Λ

R _ * R

35 - z

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DK 152512B

wherein A represents a group of the formula -CO-CH 2 -CH-COOMe or -SO 3 Me or -CO-CH-CH 2 -COOMe, B represents a hydrogen atom and / or SO 3 Me 5 preferably a group of the meaning of A, X means an ethylene- or propylene group, R is a saturated alkyl group of 6-14 carbon atoms, Me is a hydrogen atom, an alkali metal atom or an equivalent alkaline earth metal atom, n is an integer from 2 to 25, preferably from 3 to 10, and z is a number from 1 to 9.

The invention also relates to a process for the preparation of sulphorboxylic acid ester preparations consisting of a mixture of compounds of the general formula (I), which is characterized by oxethylation or oxpropylation of multi-core alkylphenols of the formula

] "OH OH

* Ά, Ά 2o H ~ i — H-. -I (II> y: Λ *; L-i 2 where R and z have the meaning given above, react the oxethylates or oxpropylates thus obtained with maleic anhydride to the maleic acid halves and then add alkali metal or alkaline earth metal sulfites thereto.

Suitable starting materials of the general formula (II) are multi-core alkyl phenols (novolacs) as obtained by acidic condensation of monoalkyl phenols, e.g. octyl, nonyl, dodecylphenol or mixtures thereof with formaldehyde in the molar ratio of 2: 1 - 10: 9. The formaldehyde can be used as an aqueous solution or as paraformaldehyde. As catalysts, mineral acids such as sulfuric acid, phosphoric acid or preferably hydrochloric acid due to its light volatility can be used at a concentration of from 0.1 to 5% by weight. Con- 4

DK 152512B

C

densification is carried out under nitrogen at temperatures of from 20 to 150 ° C, preferably 80-130 ° C. The water present after the condensation must be distilled off, finally under reduced pressure (<50 mm Hg), until the water content of the resin is less than 0.3%.

These novolaks are more or less brittle, clear, in large blocks of yellow-brown colored resins. They consist of mixtures of multicore, methylene bridges linked to methylphenol cores. The composition is, above all, of the relationship between alkyl phenol and formaldehyde.

The oxalkylation of both the mono-core and the multi-core alkyl phenols occurs with alkylene oxides, e.g. 1,2-propylene oxide or preferably with ethylene oxide, by known methods, preferably with alkali metal hydroxides or alkoxides as catalysts, at 100-200 ° C, preferably at 140-170 ° C.

The amount of alkylene oxide is adjusted so that for each phenolic hydroxyl group, between 2 and 25 moles of alkylene oxide are introduced.

Suitable as alkali metal hydroxides are potassium hydroxide or preferably sodium hydroxide, such as alkali metal oxides. sodium methylate or ethylate, and the concentration should preferably be 0.05-1.0% by weight, calculated on the phenol at the beginning of oxalkylation. The oxalkylation can be carried out without pressure or in pressure vessels with propylene oxide or preferably ethylene oxide or mixtures of both, the alkylene oxide being supplied in gaseous or liquid form.

The reaction of the oxalkylates thus prepared with maleic anhydride to the maleic acid esters is effected by mixing the components and stirring at 20-100 ° C, preferably 40-80 ° C, in the presence of alkali metal hydroxides whose concentration should be 0.05-1 , 0% by weight, based on the total mixture. Since maleic anhydride tends to sublimate, it is advantageous to operate in pressure vessels having a pressure of 0.2-1.0 ato nitrogen or air and to provide vigorous mixing because the molten maleic acid

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anhydride at the beginning of the reaction is poorly miscible with the oxalkylates. The amount of maleic anhydride can be adjusted so that all the oxalkylate-hydroxyl end groups or just a portion thereof, but at least one, is reacted.

The conversion of these maleic acid half-ester compounds to the corresponding sulfuric acid halvesters occurs after the addition of aqueous solutions of sulfites or hydrogen sulfites. For each maleic acid half ester group, 1.0-1.5, preferably 1.05-1.1 mole, calculated as sulfuric acid, is used in the form of alkali metal or alkaline earth metal sulfites or bisulfites or pyrosulfites. The sulfites are particularly suitable here because of the disalts of the sulfuric acid halves.

The amount of water added may be 50-85% by weight, based on the total solution or mixture, and is dependent on the solubility of the sulfuric acid half salts and the viscosity of the solutions. The reaction temperatures are at 20-100 ° C, preferably 40-80 ° C. The 15-50% aqueous solutions thus prepared can be used directly. However, the water can also be removed from these solutions, e.g. by spray drying ,, before further application.

Because of their low foaming propensity and poor intrinsic color, the sulfuric acid half-ester preparations thus prepared are excellent as distribution agents in the preparation of highly pigmented and flowable pigment preparations used in aqueous flexo printing.

The pigment preparations are prepared in a known manner by dispersing the pigments, e.g. azopigments, azopigments with lacquer properties, triphenylmethane pigments, thioindigopigments, perylenetetracarboxylic pigments, dioxazine pigments, quinacridone pigments or other phthalocyanine pigments,

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eg. a mother-of-pearl or double-knit kneader.

In the preparation of the kneader, the pigments are introduced by introducing the pigments into the aqueous solution of the sulphuric acid half-ester composition which is already placed in the kneading apparatus, optionally with the addition of small amounts of other dispersing agents, and kneading by tough consistency. After finishing, the desired color strength and consistency are diluted by the addition of ethylene glycol and water. Using a bead mill, the pigments are homogenized by stirring to a dough in a mixture of the above-described aqueous dispersant, ethylene glycol and water, and optionally small amounts of other dispersants. This pumpable suspension is then generally milled in a continuous quartz bead mill with a diameter of 1-3 mm, possibly several times, for the desired distribution. Then the desired color strength can be adjusted with water or ethylene glycol. The ratio of dispersant to pigment powder can be varied within wide limits and is generally from 0.1 to 0.2 parts by weight by weight of dispersant. 1 part dry pigment powder.

Example

Preparation of Sulphoric Acid Half -ester Preparations of Oxalkylated Multi-Core Alkyl Phenols.

A) Novolak preparation z + 1 mole of alkylphenol and Z mole of formaldehyde are mixed at room temperature and stirred for 4 hours at 95 -106 ° C under reflux after addition of 0.55% by weight of concentrated HCl (wf. 1.18), calculated on alkylphenol. . The water is then distilled off, finally under reduced pressure, at approx. 20-2 mm Hg.

b) Oxalkylation and sulphoric acid half ester preparation Preparation 1 mol of novolac is oxalkylated with 0.2% by weight NaOH, calculated on 35 novolac, at 140-170 ° C with n (z + 1) mol of ethylene oxide and

DK 152512B

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7 is esterified at 50-80 ° C with stirring with z + 1 or fewer moles of maleic anhydride. After dilution with water, stir at 40-80 ° C and for 15-120 minutes 1.05-1.1 moles of sodium sulfite as aqueous solution and stir for 1 hour after the mixture has become clear water soluble. . The amount of water added can be between 50 and 85% by weight of the final solution.

In this process, the substances are prepared in the table below.

10 15 20 25 30 35

g DK 152512 B

n

0 O

ti) tMH N fO Ol cm M 0 ** * * - * · cd r * g ot ro 01 2

β I

0) tn ri oo O 'ί * +) <D + J * *> * »* · m β (D in LD H ri φΗφβ σοηησι> Λ> -1 Η Η + {id J) r- Ο Ο Ο j * β I ^ - ν>.

0)> £ 1 + J vorirli — 1

51 »S {ί (TiririO

[>) il tJ tH i — I H

ω __J ____-___- ·

£ 00 CM ri H

ri r> LO LO H

φ O CM CM H

H m in in an in id M Q - * *> *>

S - β Η Η Η H

<D

5-1 * ΰ

> From-H

ω 5-i β Ti Η Η> i 0 οι ro> ί οι

0) Λ S

Η β Η rd Π3 S ___ I — 1 -, ---— ~ 0)

-Q I

id β Εη Ο) «—t τ3, _ι> i-rl ΓΓ Ν ID ΟΙ ^ .β X! g Η m -Ρ Ο ”Η! Β Ν ι 'Η, i4. · —I — ι Ο Ή Η ι — 1 n) æ / Λ \ s

3 ° - (9) L

> ^ - · 'Ρη ----- ο β ω ηι tn æ β U. ΓΟ Η Η ΓΟ 00 id I-4--1 § Κ / ΐ \ ° ° {Ο0 3 \ / · «β β s:: σι U_ ιΰ β id · ft β Η cm η -i 8 β β ft

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In the examples below, the preparation of pigment preparations for aqueous flexo printing inks based on sulphuric acid halves preparations is described as distribution agents.

EXAMPLE 1 125 parts by weight of the azofar vest fabric prepared by coupling diazotized 3,3 '- dichlorobenzidine on acetacetic anilide (Pigment Yellow 12, Color Index No. 21090) was kneaded hard for approx. 1 hour with 54 parts by weight of a 35 wt.% Aqueous solution of sulfuric acid half ester preparation # 2 in the table in a double trough kneading apparatus. After finishing the distribution, dilute 60 parts by weight of ethylene glycol and 11 parts by weight of water. The 55% by weight thin liquid pigment composition can be adjusted in each ratio with aqueous 15 flexo printing variants, e.g. saponified shellacs, saponified polyvinyl acetates, and by simple stirring to a flexo color.

Example 2 20 200 parts by weight of a Cu-phthalocyanine pigment (Pigment

Blue 15, Color Index no. 74160) knead cool for approx. 3 hours with 100 parts by weight of a 30% by weight aqueous solution of sulphuric acid half ester preparation in the table in a double-trough kneader with the addition of 10 parts by weight of di-25-naphthoylmethane disulfonate. By subsequent dilution with 80 parts by weight of ethylene glycol and 10 parts by weight of water, a flowable dough with 50% by weight pigment is obtained.

EXAMPLE 3 57 57 parts by weight of an azo pigment with lacquer properties (Pigment Red 53, Color Index No. 15585 Lake) are milled in 27 parts by weight of a 35% aqueous solution of sulphuric acid halide preparation # 2, 20 parts by weight of ethylene glycol and 38.5 parts by weight of water for 2 hours in a 1 liter laboratory bead mill during the addition of approx. 600 parts by weight of silica-quartzite beads (2-3 mm

DK 152512B

10 o in diameter) as grinding bodies. Upon completion of grinding, the grinding bodies are extracted over a sieve and a pourable pigment dispersion having a pigment content of 40% by weight is obtained.

Example 4 When dispersing 312 parts by weight of Pigment Red 14 (Color Index No. 12380) with 102 parts by weight of a 40% by weight aqueous solution of sulphuric acid half ester preparation # 3 with the addition of 6 parts by weight of dinaphthoylmethane disulfonate 10 as set forth in Example 1 and then diluting with 120 parts by weight of ethylene glycol and 60 parts by weight of water to a pigment content of 52% by weight, a flowable, foam-poor pigment composition suitable for the production of flexo inks is obtained.

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Example 5 75 parts by weight of the pigment obtained by mixing coupling of diazotized 3,3'-dichlorobenzidine to acetate-acetic anilide and acetate-acetic acid p-anisidide in a ratio of 9: 1, was eluted with 40.5 parts by weight of a 35% by weight aqueous solution of sulfuric acid half ester preparation # 4 in the table for about 1 hour. 2 hours in a double trough kneading machine. After finishing finely, 30 parts by weight of ethylene glycol and 4.5 parts by weight of water are diluted and a flowable dough containing 50% by weight pigment is obtained.

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Claims (3)

1. Sulfuric acid half ester composition for use as a dispersant in pigment preparations for aqueous flexo printing inks, characterized in that it consists of a mixture of compounds of the general formula ~ B - (0 - X) - 0 Ί 0 - (X - 0) - A. J is a group of the formula -CO-CH 2 -CH-COOMe or SO 3 Me -CO-CH-Cl 2 -COOMe, B represents a hydrogen atom and / or preferably-SO 3 Me a group having the meaning of A, X means an ethylene or 20 propylene group, R means a saturated alkyl group having 6-14 carbon atoms, Me means a hydrogen atom, an alkali metal atom or an equivalent alkaline earth metal atom, n is a number from 2 to 25, and z is a number from 1 to 9. A process for preparing a sulfuric acid half-ester composition according to claim 1, and comprising a mixture of compounds of the general formula "B - (O - X) n - 0 0 - (X - 0) n - A 30 1 1 HJ- --- jiV-CH2 ---- fj- ^ j (I) W vr R _ z R 35 O DK 152512 B where A means a group of the formula -CO-C ^ -CH-COOMe or SO3Me -CO-CH -C 2 -COOMe, B means a hydrogen atom and / or for zone 5, preferably a group with the meaning of A, X means an ethylene or propylene group, R means a saturated alkyl group of 6-14 carbon atoms, Me means a hydrogen atom, an alkali metal atom or an equivalent alkaline earth metal atom, n is a number from 2 to 25, and z is a number from 1 to 9, characterized by oxethylating or oxpropylating multi-core alkyl phenols of the formula OH Ί OH Ar Å H - fr 4 - «2 - fr (II) / Αχν * \ R _ z R where R and z have the meaning given above, the 20 thus obtained oxethylates or oxpropylates with maleic anhydride react to the maleic halves and add the alkali metal - or alkaline earth metal sulphites for these. 25 30 35