DE2023530A1 - Pre-treated pigment and process for its manufacture - Google Patents

Description

PATENTANWÄLTE 69 HEIDELBERG, Gaisbergstrasse 3

Telephone: (06221) 25335 - Telegram address: ULLPATENT Our! Eichen: Ö22 * f

Kemisk Vaerk Kgfee A / S, 01by Lyng, DK-46OO Kifee, Dänemar k

Pretreated pigment_and_making process.

It is known to pretreat pigments in various ways in order to facilitate their distribution in binders can be achieved, for example in those used for paints and varnishes, in printing ink bases and in plastics be used. The binders used in this context or carriers are described below as film-forming, water-resistant pigment binders, for example are incompatible with viscous liquids such as those used for spinning. As examples of the Materials used in this context for such a pretreatment are long-chain amines, for example primary, to mention secondary or tertiary amines, which are combined with polyoxyethyl or polyoxypropyl groups can. Such amines can also be derived from cyclic hydrocarbons, terpenes, and the like. The pre-treatment consists in a treatment by which the pigment particles coated or incorporated into the amine in question.

The present invention involves making pretreated Pigments on the subject, which have the particular advantage that with the help of binders from such pigments produced films, such as color films or prints, achieve a color intensity, a gloss and a transparency

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that of films of the same composition exceeds, in which the pigments used do not appear are pretreated this way. So it is the object of the invention, the so-called optical properties of the film or the layer in which the pretreated pigment is used. This task is solved and the purpose of the invention is achieved in that pretreated pigments are produced, the particles of which are coated with an organic amide or which are incorporated into this amide, which is compatible with the film-forming, water-resistant Binders. Such amides include those of the fatty acids including long-chain fatty acids, which can be substituted on the nitrogen atom by one or two lower alkyl groups. According to a preferred Embodiment of the invention, the pigment is characterized by an amide of the following formula:

R ¹ (CONR ² R ⁵ ) _n ,

in which R is an aliphatic hydrocarbon radical with 1 to 6 carbon atoms and the valence η and the hydrocarbon radical in the event that it is aliphatic, saturated or unsaturated, straight-chain or branched, dimerized or polymerized, or represent a cyclic or alicyclic hydrocarbon radical can, including aromatic or polycyclic hydrocarbons, including terpenic hydrocarbons, and the hydrocarbon can be substituted by hydroxyl, nitro, halogen or COOR ^ groups, where R is a hydrocarbon group or hydrogen or in which either R ² or R ^ or both groups the formula

- (R ⁵ o) _m H.

belong in the R ^ methylene, ethylene or propylene and m represents an integer from 1 to 20 while the other of these groups is hydrogen or alkyl.

For a more detailed explanation of the expression "compatible", as it is used in connection with the paints and varnishes or printing inks «it should be mentioned that the aforementioned Means must be able to be homogeneous in the formed water-insoluble To be recorded film and in the context of a complete incorporation of the pigment particles to with whom it is matched in this film. It has been found that by pretreating a pigment with such an amide, the clarity, intensity and Transparency of color increases. As an example of the film-forming, water-resistant pigment binders that Such binders are to be used advantageously in connection with the pretreated pigment mention which of drying oils, dimerized, trimerized or polymerized drying oils, resins including alkyds and acrylic resins, copal resin, nitrocellulose, Shellac, phenolic resins, polyamides, epoxy compounds exist or contain such, all of which are expedient used in conjunction with solvents or extenders such as turpentine oil, turpentine oil substitute, and others Hydrocarbons, ethers, esters, ethanol, propanol, acetone, dioxane or chlorinated hydrocarbons. Naturally such extenders or solvents should be mixed with water be miscible, provided the film formed is anhydrous or water-resistant after the evaporation of the streak agent or solvent. It is also in use Pretreated pigments as described above of importance that the strength and resistance to mechanical or previous influences remain unchanged or become greater in the case of a corresponding film in which a pigment was used that was not pretreated in this way is.

As a pretreatment agent, for example, can be mentioned the amides of fatty acids, such as capron, lauric, Stearic and palmitic acid amides, amides of corresponding un- ' saturated fatty acids such as oleic acid amide or linoleic and

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Linolenic acid amide, amides of mixtures of such fatty or unsaturated acids, amidated polycarboxylic acids, for example Azelaic acid diamide, resin acid amide, corresponding amides, which are substituted on the amide hydrogen by alkyl or Acyloxy groups and benzamide.

The proportion of the pretreatment agent according to the invention can vary between about 2 to 150 # of the incorporated pigment. The most appropriate ratio depends heavily on the type of pigment. Ks must be taken into account in this context that the use of a large amount of amide is not necessary and is a disadvantage for W the intensity of the color, which is increased compared to films in which the pigment content is relative to the amount of the not pretreated Pigments is calculated. This is a consequence of the fact that the amide is compatible with and forms part of the binder. The amount of pretreatment agent is therefore by no means critical and, in case of doubt, a sufficient amount should be chosen.

In the production of the pretreated pigment, a process is used which is characterized by that the pigment powder is first mixed with a suspension, a solution, a melt or a powder of the pretreatment agent is mixed, or by the fact that a solution or suspension of the pigment with a solution, suspension or Melt of the pretreatment agent is mixed, after which the mixture is filtered, dried and, if necessary, in more arbitrary Sequence is cooled and the mixture is then ground in two ways.

In this way it is meaningless and by nature of the pigment and the pretreatment agent depends on whether the pigment of the pretreatment agent in suspended} or dissolved State or whether © s is used in the molten state. If both components are used in a solid, powdery state, it is necessary to add a small amount of a solvent.

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Apply solvent to one of the components to ensure sufficient adhesion and penetration of the pretreatment agent reach. It is particularly worth mentioning that pigments are produced by coupling or with the help of some other precipitation reaction do not need to be isolated from the suspension obtained by the precipitation.

According to the circumstances, the pretreated pigment becomes obtained in moist form, in which case it must conveniently be dried after filtration, or in molten form, in which case it must be cooled. The direct process product can also be in the form of a solid or plastic mass are obtained, which is conveniently ground after cooling, or it can be in shape such a mass or in the form of coarse grains for incorporation used in the agent in question.

Examples

1.) 95 parts of acetoacetylaminobenzene were dissolved in 2,000 parts of water with 21 parts of sodium hydroxide. After adding 250 parts of crystalline sodium acetate and 400 parts of ice, dilute hydrochloric acid was slowly added with gentle stirring to reprecipitate the dissolved compound. Finally, 18 parts of stearic acid amide in 18 parts of glacial acetic acid were added with continuous stirring. A tetrazo compound was added to the coupling component thus prepared in the course of about 1 1/2 hours at 15 ° C., the tetrazo compound being prepared in the usual manner from 63 parts of 4,4'-diamino - ^^ '- dichlorodiphenyl. After the coupling had ended, the suspension was heated to about 80 ° C., filtered, washed and dried. Yield: 174 parts of 90 % purity pigment.

When testing this pigment as a component of an ordinary nitrocellulose-based printing ink for packaging material was found to be the intensity of the color

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ORIGINAL INSPECTED

has increased by 20 % and that the gloss and transparency have improved significantly compared to a corresponding printing ink made from the same pigment without pretreatment with stearic acid amide.

2.) A 3.0 # aqueous solution of a pigment called "CIPigment Yellow 14", containing 100 parts of this pigment; 8 parts of molten monoethanolamide were added to the tallow fatty acid with stirring at? 0 ° C. After stirring for 2 hours, the precipitate was filtered off, washed and dried. Yield: 108 parts or 92.7 % pigment.

When this pigment was tested in an alcoholic shellac solution, a considerable improvement in the Gloss and clarity found compared to the same pigment under the same conditions, however without pretreatment according to the invention.

3.) 100 parts of "C.I.Pigment Yellow 13" were carefully mixed with the help of a rapidly rotating stirrer in 225 parts of extraction gasoline, in which 18 parts Azelic acid diamide were dissolved. Yield: 118 parts of 84.8 tiger pigment.

After the solvent had evaporated, the pigment obtained was tested as a component of a typical printing ink. It was found that the color intensity was improved by 20% and that the gloss was higher than that obtained with a corresponding printing ink from the same pigment, but without treatment according to the invention.

4.) In a paste mixer, 1,000 parts of a plate cooler with 28 % color pigment in the form of the preparation "CIPigment Red 17" were filled. 35 parts of caproic acid amide dissolved in 40 parts of £ xtr & ktionsb3BSin were added. The whole thing was at about 50 ° C until completely homogeneous

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nity mixed over the course of about 2 hours, whereupon the The mass was emptied and dried. Yield: 15-16 parts an 88.7% pigment.

When this pigment was tested as a component of an ordinary folyamide-based printing ink, it was found that the color strength was improved by about 10% and that the gloss and transparency were improved in comparison with a printing ink produced under the same conditions from the same pigment, but without Had improved treatment according to the invention.

5.) 200 parts of ¹¹ C. I * Pigment Orange 34 "and 180 parts of monoethanolamide of a dimerized fatty acid were placed in a knotting device. During the kneading process, small amounts of a volatile solvent, such as ethanol, were added to improve the contact between the pigment powder and the treatment agent The solvent was finally completely evaporated. In the course of 2 to 3 hours, the contents changed to a homogeneous plastic mass. After cooling and crushing the product, the amount of which amounted to 380 parts of a 52.7% pigment, this passed through Incorporation in a polyamide varnish was found to have improved the color strength by about 25% , matt and that the gloss and transparency had improved significantly compared to the same pigment which was not treated according to the invention.

6.) 2 ropes of coconut fatty acid monoethanolamide, dissolved in 4 parts of ethanol, were added with stirring to a 1.8% aqueous suspension of iron "CIPigment Violet 3 ^M , containing 100 parts of the pigment. The suspension was filtered, washed and dried. Yield : 102 parts 98 £ lge £ Pigeent.

When testing this pigment in nitrocellulose lacquer it was

an improved quality compared to a corresponding one "found untreated pigment.

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7 ·) Ss 22.2 parts of 1-chloro ^ -methyl - ^ - aminobenzene-5-sulfonic acid were diazotized in a known manner and diluted to 400 parts with ice water. Excess nitric acid was removed with the aid of a small amount of sulfamic acid. 15.2 parts of 2-hydroxynaphthalene, dissolved in 250 parts of water, and 4.3 parts of sodium hydroxide were added with vigorous stirring. After coupling was complete at a moderately alkaline pH, 5 parts of resin acid monoethanolamide, dissolved in 10 parts of methanol, together with 20 parts of BaClg, 2H ₂ O were added. The suspension was heated to about 80 ° C. and held at this temperature until the characteristic change in color, accompanied by the metallization, had appeared. The pigment was then filtered, washed and dried. When this pigment was tested in nitrocellulose lacquer, it was found that the gloss and transparency were improved compared to the same pigment without treatment according to the invention.

8.) There were 11 parts of molten coconut fatty acid dimethylamide with vigorous stirring of a 1.7 ^ strength aqueous Suspension of "C.I. Pigment Blue 15" containing 100 parts of the pigment was added. After further stirring for a few hours the suspension was filtered, washed and dried. Yield: 110 parts of a 90.8% pigment.

^w When testing this pigment as part of a printing ink based on phenolic resin was found that the dispersion substantially improved and the gloss higher was- ". when obtained under the same conditions with the same pigment that was not treated according to the invention.

9 ·) 100 parts of carbon black and 50 parts of oleic acid dipolyoxyethylene amide were introduced into a kneading device »

During the knocking process, the T @ ap @ ratiir was about 70 ° C and during the first part of the crust process small amounts of ethanol or a similar volatile solvent to improve the mixture of the Pigraant powder and

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of the treatment agent added. In the course of about 2 Hours the content had changed to a homogeneous mass, which was then removed and refrigerated. Yield: 150 parts of a 66.7% pigment.

This product was tested as a component of a printing ink based on nitrocellulose for packaging material purposes. It showed a much higher gloss, transparency and blackness than the untreated carbon black under corresponding ones Conditions.

■ 10.) In a vessel with a fast-running stirrer 8 parts of stearic acid diethanolamide in 500 parts of water ' emulsified at 70 ° C. With vigorous stirring, 50 parts Soot suspended in here with batch addition over the course of about half an hour. After another hour With stirring, the suspension was filtered and dried. Yield: 57 parts of an 87.8 # pigment.

Testing of this product showed essentially the same results as those given under Example 9.

11.) 100 parts of titanium white of the rutile type were made with the help introduced a rapidly rotating stirrer into a solution of 5 parts of benzamide and 80 parts of extraction gasoline.

After the solvent had evaporated, 105 parts of a 95, ^2- point pigment being obtained, this pigment was tested against untreated titanium white in a nitrocellulose-based printing ink. It was found that the pigment according to the invention exhibited a better gloss without any problems.

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Claims (4)

- ίο - claims 1.) Pretreated pigment for use in film-forming, water-resistant pigment binders, characterized in that the particles are coated in or incorporated into an amide compatible with such binders. 2.) pigment according to claim 1, characterized in that the amide has the formula R ¹ (CONR ² R ⁵ ) _n has, in which R ^{1 is} a hydrocarbon radical with 1 to 6 carbon atoms and a valence η and the hydrocarbon radical is saturated or unsaturated, straight-chain or branched, dimerized or polymerized or cyclic, including aromatic or polycyclic including terpenic, and is conveniently characterized by hy- Yy is substituted hydroxyl, nitro », halogen or COOR groups, where R ^{4 is} a hydrocarbon group or hydrogen or either R ² or R ^ or both groups with the formula - (R ⁵ O) _1n H represent and R. Methylene, ethylene or propylene and m is an integer from 1 to 20, while the other of these groups is hydrogen or alkyl. 3.) pigment according to claim 1 and 2, characterized in that the amount of pretreatment agent is between about 2 % and 150 %, based on the dry, untreated pigment. 4.) Process for the production of the product according to claim 1 to 5, characterized in that zianSchst a pigment powder with a suspension, solution or Selmelze 109849 / 1S12 202353G a powder of the pretreatment agent or a solution or suspension of the pigment mixed with a solution, suspension or melt of the pretreatment agent
is, whereupon the mixture is filtered and, if necessary, dried and cooled in any order and finally ground appropriately. 109849/1512