DE1694744C - Process for the production of solid base mixes for the color of synthetic polymers see - Google Patents

Description

The present invention relates to a method for the production of solid base mixes / for coloring synthetic polymers.

It is known that solid pigment base mixtures can be used to produce plastics and other polymer materials in an effective manner. A solid powder mixture of this type generally consists of a pigment color which is evenly dispersed or distributed in a plastic or polymer, the pigment concentration in the basic mixture being higher than in the finished product which has been colored with the basic mixture . In addition to those mentioned, the basic mixture can also contain other additives, for example. B. dispersants, polymerization accelerators, polymerization inhibitors, UV light absorbers. The concentrated. ³ Basic mixture is added to colored or non-colored plastic or polymer material in such an amount. d: the desired color tone results in the end product. As a result, the basic mixture must spread easily and evenly throughout the entire plastic Tiateria! distribute if they are to be useful for the stated purpose. If a solid basic mixture is to be used to color a liquid or in solution plastic or polymer material, the polymer component of the basic mixture must dissolve easily in the mass to be colored, so that the pigment

so is released and in turn evenly in the mass can distribute. Should a solid base mix for dyeing plastic or dry Polymermuterialien are used, so they must be fusible or can be easily distributed in some other way in the material to be colored. Fiin example for the latter would be the addition of a solid, colored vinyl polymer masterbatch to one solid non-colored vinyl polymer which is then extruded. The basic mix melts during extrusion and evenly colors the mass.

The most common method of making solid pigment masters is by association of pigment and polymer material, dispersion of the pigment in the polymer material through internal mixing, e.g. B. in a Banbury or Zweiwalzcnmischer or by extrusion with an extruder. The manufacturing process mentioned requires both high temperatures and considerable amounts mechanical energy. Another method is to dissolve or suspend the polymer material in a suitable solvent and subsequent addition of the pigment using a ball mill or a roller mixer?

(or other conventional devices) to achieve the desired dispersion of the pigment. On finally the solvent is evaporated from the colored base mixture, so that a solid pro product remains.

As has now been found, it is possible to use the same basic mixes in the production of to dispense with high energy input for wetting and dispensing the pigment in Jem PoWmermatcrinl Rather, it is possible through the polymer material easy mixing to color without the usual costly and tedious dispersing process devices to fall back on.

The present invention relates to a process for the preparation of solid base mixes genes for coloring synthetic polymers! with heterocyclic phthalocyanine or Azopig mcntfarbsioffen, which is characterized in that ηι, ιΐι a heterocyclic phthalocyanine or azo pigment dye in a local solvent, as it is also a lmii solvent for the polymerisation is, dispersed, mixed with the addition of an oil solution lers dissolves, ill ·. · separates insoluble constituents, in de so obtained Lösunti iL: ', Polunnisat solves. d; macl

/ α gives the solution a liquid, which with the miscible with polar solvents and at the same time for the polymer-pigment mixture a falling effect Is non-solvent and finally separates the precipitated mixture and dries.

According to a further embodiment of the method according to the invention, the polymer material is before it with the pigment dye dispersion .-cleans is dissolved in a suitable solvent. both with the polar solvent .Is also with the liquid used to precipitate is miscible. I. · the polar solvent for example dimethyl sulfoxide and that for precipitation If the liquid used is water, the following can be used Solvents can be used. ,Acetone. Methanol, L ■ lnlformamia dimethylacetaniid and of course Γ imethyl sulfoxide.

The following polymer materials can be colored with the aid of the process according to the invention: Poly: h \ lenterephthalate, Polyamides, polyacrylonitrile and mixed polymers, butadiene-acrylonitrile. Polyallyl chloride and its mixed polymers, the reactant of 1 pichlorohydrin and bisphenol-A, Reaction products from polyisocyanates and polytheres, Cellulose acetate, polyester, alkyd resins.

As soon as the polymer is in solution or in its ii -.piiinghchen state with the pigment-1 · .> ui.g is united, becomes the second stage of the invention Procedure carried out. In this ; ", | .e: th stage the PignientL.rbstofT-Polymeri. '.'. solution a liquid was added that formed a precipitate the pigment-polymer mixture causes. In all- • Jiiieinen one uses water for this purpose; However, s is also possible, any other Solvent should be used, provided that it is not from the solid pigment-polymer mixture ! (. Isable and miscible with the solvent or solvents of the pigment-polymer solution is. For example, instead of water, alcohols such as methanol or ethanol or Use aqueous mixtures of these last-mentioned substances. The pigment-polymer mixture falls ■ ilort off when using the pigment-polymer solution the precipitating solvent comes together. The solvent from the pigment-polymer solution diffuses out of 'lern precipitate into the filling liquid, so that ■. ii technically possible Single-phase solvent system and a form solid precipitate.

The pigment-polymer precipitate (basic mixture) can by filtering. Decanting to be separated from the liquid. Hs will subsequently dried in the open air or in the heat in order to remove the minor traces of liquid which are on the surface adhere to remove. The liquid phase containing the active solvent can be worked up and can be used again.

The method according to the invention is particularly special Interpretation. if polyacrylonitrile as a polymer, naterial is used. So far it has been very difficult to prepare polyacrylonitrile pigment base coats which contained a large amount of pigmented oil. With the help of the inventive Process can, however, base mixtures of Polyai'iylnitri! or a copolymer thereof . ! id Cigmeiil paint stollen in which ileι content of pigment up to / ι; W) Ciewieliispuizent .iiisniacht. It is easy to see that eiiie

5. Reduced tendency to collapse again

A base mix with the highest possible pigment content is more advantageous than a base mix with a low one Pigment content. The higher the pigment concentration in the base mix. is the smaller the amount of misery. which must be used for coloring a certain plastic. In addition, the base mixtures produced according to the invention have the following advantages:

1. Ease of solubility.

~ \ uniform particle size and distribution of the Pigment,

3. higher color strength,
-V. greater transparency of the finished product.

5.

treatment of the pigment.

So far, no procedures have become known that

so in terms of ease of use and Economics would be comparable with the method according to the invention. Daneber, is crucial Meaning that it can be used to produce basic mixtures in which the Pigmentanteii can be up to 80 percent by weight of the total mixture.

Pigments are practically insoluble in common solvents and in water. Your coloring Properties derive from their ability to reflect, refract, and diffuse light Light transmission from. Pigments that are used as dyes have a defined physical Shape and a measurable particle size. The introduction of pigments in plastics, Polymer materials and coatings generally require considerable amounts of energy. For the production dry pigment dyes it is z. B. necessary when grinding the pigment agglomerates to the desired fineness to use considerable grinding energies. The ground pigment is then used with the plastic or polymer material! mixed, so is the operation of the ball mills. Roller mixers, sand mills, in turn, require considerable ejiergy. It often happens that the pigment dyes in the polymer material again agglomerate or flocculate, precisely as a result of the extreme.1 amounts of energy that they previously received were exposed. With the introduction of the pigment dye In the Polvmermaierial in the form of a solution, the previously necessary energy supply could be avoided.

The preparation of the pigment dye solutions - the dispersion stage is, according to the invention, in one Solution tuie transformed - consists in that one

; silen pigment dye in a polar solvent such as dialkyl sulfoxide, N-alkylformamide, N-alkyl acetone amide, Ν, Ν-dialkylformamide and N, N-dialkylacetamide, in which the alkyl groups contain 1 to 10 carbon atoms, without simultaneous help a solubilizer solves. Solubilizers in the context of the present invention are acids or bases, and / was both inorganic and organic. Any acids or Bases used willow; however, it has been shown that some acids and bases in certain amounts and besomleis in connection with certain pigments deliver favorable results. For example, in principle all organic amines are as 1 ö-

suitable as an intermediary; for monoazo pigment dyes however, monoethanolamine in particular has proven to be brewable. Another useful thing organic amine is ethylindiamine. Among the usable inorganic bases include ammonium hydroxide. Potassium hydroxide and sodium hydroxide.

Of the acids, mineral acids, and among these, in turn, HCI and H., SO _{4, have} proven to be the most useful; in some cases, however, organic acids can also be used.

The choice of an acidic or basic solubilizer depends on the pigment. which is to be made soluble. With the help of basic i .ösunesvermiukr it is stored in front of alkm Monoazo. Disazo-. Azonaphtol- and Phthalocv uninpigmeuifarbsioffe. make heterocyclic pigments soluble in general. Dur.h acidic solubilizers Above all, metallized pigment dyes can be made soluble.

The fact of the dissolution of the pigment is clearly evident. Yellow azo pigment dyes for example, if they are slurried or dispersed in the dimethyl sulfoxide, retain their bright yellow tones. while the mix is opaque. After adding an amine, the mixture changes its color to deep brown-red and becomes transparent. By dissolving, unmet illized red dyes either become even darker Red. purple or blue or \ change to lighter Shades of orange. Green PhathalocyaniiVarbstofU change turn blue and become brighter. Ap'hraquinone dye Tc and heterocyclic dye Tc behave differently, but also here generally change color.

The pigment dye solutions are prepared as follows: a large excess of the pigment dye is dissolved in a polar solvent such as e.g. ü. Dimethyl sulfoxide. slurried the selected solution. Depending on the case, an acid or a rabbit is added until no more pigment sticks dissolve. The excess of unreacted pigment is removed so that a clear fillrate remains in which the pigment is dissolved. As soon as the solubilities of the selected substances are known, clear solutions can be produced in one operation by mixing the appropriate amounts of the components.

Among the pillar solvents that are recommended be used, sinu the stalk polar like Ljiicthylsullovid. Dimcthviaeetamid and Dimethvlformamul most suitable. In addition, any other polar solvents can also be used provided that they betrenciuie Polymernlatenal are able to solve uiid moreover In addition, it is completely miscible with the liquid used for the precipitation - generally water are.

Hei application as described above Working method let see clear pigment oil solutions Iu-Istellen, in iL.u'n the amount of the Pignient stain up to 20 weight piozeni eggs in total mix matters.

The so heirestellu, ¹ clear solutions are then in the manner described beieits further to the (η imdmiscluin "cn ν eiarbcitel.

The iiachfnlgi iulv'11 examples serve to further I iläulenmi: ili'i I ι li'idiiin ¹ .

B e i s ρ i e I 1

A large excess of de-monoazo dye is placed in a beaker which contains 100 ml of dimethyl sulfide Hansa Yellow K) -G. To the obtained slurry is added, with stirring, Monoethanolamine. until the optimum solubility of the pigment is reached; then it never will !. '

ίο removed pigment. The filtrate consists of 3.0 "Vo solubilized pigment and 97 ⁰ Zn solvent, which in turn is composed of 81.5 ¹ Vo dimethyl sulfoxide and 18.5 ⁰ O monoethanolamine. The pigment solution is mixed with a dimethyl

sul ^f 'Mdlösuna, united, which contains an equivalent menu', of polyacrylonitrile.

The 50/50 mixture of pigment and polyene: pour thinly into a grölten vein while stirring shot of water. As soon as the mixture touches the water, the pigment and polymer come together fancy, so that there is an endless, colored art Forms strand or thread in the water. Since the solvents in the Pigmcnt-Polymcr solution with are miscible with water, they diffuse into it so that the colored Kur.ststoffsirang solvent-free remains behind. To neutralize tki as Solubilizer used one adds a base out! Add a calibrated amount of acid. The entire pigment-polymer solution is converted into a solid strand the latter is removed from the water-solvent mixture and mixed with fresh Washed with water to remove the last traces of adhering solvent and dissolved salts. The strand is then rinsed with methanol.

so that the moisture adhering to the surface at low temperatures. /.B. 50 to 70 -C. removed in an oven. The basic mixture thus obtained is made up of 5I) ⁰ Zn PigmenifarbsioiT and 5O ° / o Polynermaterial. The basic mixture is incorporated into a large volume of colorless polyacrylonitrile, so that the base product is a uniformly yellow colored polyacrylonitrile.

The following examples 2 to 13 apply

the procedure described in Example 1 above, in each case with modification of individual conditions on. The deviations from the procedure according to Example I are listed below.

Example 2

The polyacrylonitrile is not dissolved in dimethyl sulfoxide before it is combined with the pigment solution.

B e i s ρ 1 e I 3

Diniethylacctamide is used in place of Dimethyl sulfoxide.

B e i s ρ i e I 4

Dimethylformamide is used instead of dimethyl sulfoxide

Example 5

One uses p-Azo: iaphlholrot in place of the Monoazofathsuilles Hansagelb K) -Il. The pigment solution consists of 7 ″ ″ pigment and ¹ ″ 3 ″ ″ solvent, which in turn consists of 74.3 ″ ″ dimethyl sulfoxide and 25.7 ″ monolamine.

1 i 694 744

7 8

Example ₍ , solvent; the lef-.tere was composed of ⁽ > 7.5 '*, <i

dimethyl sulfoxide and 2.5 ¹ Vn sulfuric acid / usaii-

Chlorinated p-A / onaphlholrut is given to SU'llc ili: s men. Use an acid as a solubilizer

Monoazo dyes * Hansauelli 10-G used. That was, was: \ ii'chloscnd as much base was added.

pigment solution provided as an intermediate product; lie- 5 dal. '; complete neutralization occurred,

consists of 3.7% pigment and 3% solvent. The results obtained when applying the

which in turn from S (S ₁ O ⁰ Ai dimethyl sulfoxide and Examples 2 to 13 described procedures

14.0 ° / o consists of monoethanolamine. targets correspond to those of Example 1.

B c i s ρ i e I 7

¹⁰ Example 14

One uses in place of the monoazo dyes *

Hansagelb K) -G the monoazo dye litholrubin- The test arrangements according to Examples 5

Red. The pigment to 13 produced as an intermediate product were repeated once more, however

solution consists of 4.4% pigment and 95.6% lo-ditncthylacetamide or dimethylformamide instead

solvent, which in turn was made up of 84.6% dimethyl 15 of dimethyl sulfoxide. One received

sulfoxide and 15.4% monoethanolamine. good results in all cases.

Example 8

• "Example 15 Instead of the monoazo dye *

Hansa Yellow 10-G Azonaphthol B.O.N. Brown. The as ao man worked again as indicated in Example 1,

The pigment solution produced as an intermediate is used, however, successively in place of di-

from 15.9% pigment and 84.1% solvent, the meth ·, uulfoxid the following solvents: in turn from 99.0% dimethyl sulfoxide and

Composed of 1.0% monoethanolamine. Methylformamide

_J5 dibutylformamide

Example 9 methyl acetamide

Instead of the monoazo dye, * Dibuty is used! acetamide

Hansagelb K) -G the diazofarbstolT Benzidinclb OT Dibutylsulfoxid

and alcoholic KOH instead of monoethanol- w, ^y j *. ,, ·,

amine. The pigment produced as an intermediate is methyl-dccylsulfoxide

solution consisted of 7.4% pigment and 92.6% Lö- Dioctylformam.d

solvent. which in turn consists of 97.5% dimethyl nonylformamide

sulfoxide and 2.5% KOH. 'Dihexylacetam.d

Dccylacetamide

B e 1 s ρ 1 e 1 K) 35 Good results were obtained in all cases. Instead of the monoazo dyes * Hansagelb K) -G

became a heterocyclic * pigment, namely China Example 16 cridon red and alcoholic KOH used instead of monoethanolamine. As an intermediate product, the procedure according to Example 1 is reproduced Pigment solution contained 8.0% pigment 40 holt; instead of polyacrylonitrile, however, CeIIuunef 92.0% solvent: the solvent used continued loose acetate. Corresponding information is obtained from 95.0% dimethyl sulfoxide and 5.0% potassium results. With the obtained basic mixture can hydroxide together. a large amount of colorless cellulose acetate

_,. . . .. be dyed evenly.

Example IJ * ^fc

45

Example 17 was used instead of the monoazo dye Hansacelb 10-G a red monoazo dye and

Ethylenediamine instead of monoethanolamine. The man works as indicated in Example 1,

pigment solution produced as an intermediate product, however, uses cellulose acetate instead of poly-

contains 8.1% pigment and 91.9% solvent, wel- 50 acrylonitrile and dissolves the polymer in acetone instead

this in turn consists of 84.6% dimethyl sulfoxide and dimethyl sulfoxide. One also gets in this

15.4% ethylenediamine composed. Case good results. The basic mixture obtained:

. . ., can be used to dye a large amount of colorless

Example _ Cellulose acetates can be used.

Instead of the monoazo dye * Hansa Yellow 10-G 55

Plithalocyanine green was used instead of Example 18 Ethylenediamine was used for monoethanolamine.

The pigment solution produced as an intermediate product is repeated as in Example 1

contained 4.5% pigment and 95.5% solvent; give, but changes the weight ratio

the latter was composed of 69.0% dimethyl sulfoxide 60 from pigment to polymer, so that one reason

and 31.0% ethylene diamine combined. Mixtures with the following weight ratios

_. . , ,, from pigment to polymer gets: B c 1 s ρ 1 e i 13

Instead of the monoazo dyes Hansagelb K) -G

a metallized 2-B red magnet was used: 65 sulfuric acid was used in place of monohanolamine. The one produced as an intermediate product Pimnentlösi.ng contained 11.75% pigment and 88.25%

pigment polymer 20th 80 4 (1 60 60 40 80 20th

Ho is pi c I 14 I'nlvathvlenkrephthalat

I'uiyamid

Niiiii repeated again in Examples 1 to ί> Huladicn-Ai-rylnilr'l-Mischpnlymcr

^ esehihiertiM) working methods, veiwendoi however; tn IVlwhr, lirhlorid

Place of l'olyaeryhiitril the following 'olymcrmal- 5

Good hearing results are obtained in all cases.

Claims (7)

Patent claims: ! Process for the preparation of solid base mixes for dyeing rynlhetic Polymers with heterocyclic phthalocyanine or azo pigment dyes, thereby characterized in that one has a heterocyclic Phthalocyanine or azopigmeni dye in a polar solvent, which at the same time is also a solvent for the polymer. dispersed. with the addition of a loyalty mediator dissolves, separates the insoluble constituents, the polymer in the so-called novel solution dissolves, then / u gives the solution a liquid which is miscible with the polar solvent and at the same time for the rYl> .ner pigment mixture is a falling non-solvent and finally separates the precipitated mixture and dries. 2. The method according to claim 1, characterized in that one is used as the polar solvent Dialkyl sulfoxides, N-alkylformamides, N-alkylacetamides. Ν, Ν-dialkylformamides or N, N-dia'kylacetamide, in which the alkyl groups have 1 to 10 carbon atoms is used. 3. The method according to claim 1 or 2, characterized in that the polymer material dissolved in a solvent that is compatible with the polar solvent and is miscible with the liquid used for precipitation, the pigment color profile solution add / t 4. Verfaiiren according to claim 1, 2 or 3, characterized characterized in that a heterocyclic monoazo, disazo, Azdiaphthol or phthalocyanine dyes and a base is used as a solubilizer. 5. The method according to claim 1, 2 or 3, characterized in that one is used as the pigment dye metallized azo dye and as a solvent uses an acid. ft. Method according to one of Claims 1 to 5, characterized in that the PoIvv.e; sat is a homo- or copolymer of acrylonitrile in an amount of from 20 to 80 percent by weight, and the pigment in an amount from 50 to 20 percent by weight, based on the total mixture, is used. 7. The method according to claim 6, characterized in that that the pigment is based in an amount of 50 to 75 percent by weight on the total mix.