DE4215394A1 - New rhodamine cpds. with polymeric anion for high light fastness - used for dyeing polyacrylonitrile fibre or in ink, electrophotographic toner for fluorescent pigment - Google Patents

Abstract

New rhodamine de4rivs. are 3,6-diamino-8-(2-carboxyphenyl) -xanthylium salts of formula (I). In (I) R1-4 = H or (substd.) 1-4C alkyl, or R2+R5 or R4 + R6 = 1,3-propylene, opt. with up to three 1-4C alkyl substit(s).; R5-8 = H or Me; R9 = H, (substd.) 1-4C alkyl or (C2H4O-)nH with n = 2 or 3, An(+) = the equiv. of an anion derived from a polymer or polycondensate contg. acid gps. (I) can be prepd. (not claimed) by dissolving the neutral dye base in e.g. water and/or lower alcohols and treatment with a polymer or polycondensate contg. acid gps.. USE/ADVANTAGE - (I) are used for dyeing polyacrylonitrile fibres, pigmenting polymers or in ink prodn. (claiemd). They are also useful in the prodn. of electrophotographic toners or fluorescent pigments and have better light fastness than commercially available rhodamines.

Description

The present invention relates to new rhodamine derivatives of Formula I.

in the
R ¹ , R ² , R ³ and R ^{4 are the} same or different and, independently of one another, are each hydrogen or optionally substituted C ₁ -C ₄ -alkyl or in each case R ² and R ⁴ or R ⁴ and R ⁶ together 1,3-propylene which can be mono- to trisubstituted by C ₁ -C ₄ alkyl,
R ⁵ , R ⁶ , R ⁷ and R ^{8 are the} same or different and are each independently hydrogen or methyl,
R ^{9 is} hydrogen, optionally substituted C ₁ -C ₄ -alkyl or a radical of the formula (C ₂ H ₄ O-) _n H, in which n is 2 or 3, and
An⊖ is the equivalent of an anion derived from a polymer or polycondensate, each of which contains acidic groups,
and their use for dyeing polyacrylonitrile fibers, for incorporation into polymers or for the production of tin.

Rhodamine dyes are known per se and belong to the Class of xanthene dyes. Examples include C.I Basic Red 1 (45-160), C.I. Basic Violet 10 (45-170) or C.I. Ba sic Violet 11 (45 175).

The known rhodamine dyes are characterized by a brilliant own color. Print or dye with these However, rhodamine dyes usually have a very high lightfastness and lose their brilliance Clouding or by reducing the fluorescence.

The object of the present invention was to create new Rhoda Provide minor derivatives that no longer have these disadvantages or only have a small amount.

Accordingly, the rhodamine derivatives mentioned at the beginning of Formula I found.

All alkyl groups occurring in the above formula I. can be straight or branched.

If substituted alkyl groups occur in the abovementioned formula I, z. B. hydroxy, C ₁ -C ₄ alkoxy, cyano or phenyl.

R ¹ , R ² , R ³ , R ⁴ and R ⁹ are e.g. B. methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, 2-hydroxyethyl, 2- or 3-hydroxypropyl, 2- or 4-hydroxybutyl, 2-methoxyethyl, 2- or 3-methoxypropyl, 2- or 4-methoxybutyl, 2-ethoxyethyl, 2- or 3-ethoxypropyl, 2- or 4-ethoxybu tyl, 2-cyanoethyl, 2- or 3-cyanopropyl, 2- or 4-cyanobutyl, benzyl or 1- or 2- phenylethyl.

R ⁹ are still z. B. 5-hydroxy-3-oxapentyl or 8-hydroxy-3,6-dioxaoctyl.

The radicals R ² and R ⁵ or R ⁴ and R ⁶ can each also mean 1,3-propylene, which can be substituted one to three times by C ₁ -C ₄ alkyl, in particular methyl. In this case, e.g. B. the following radicals come into consideration: -CH ₂ -CH ₂ -CH ₂ -, -CH (CH ₃ ) -CH ₂ -CH ₂ -, -CH (CH ₃ ) -CH ₂ -CH (CH ₃ ) - or -C (CH ₃ ) ₂ -CH ₂ -CH (CH ₃ ) -, the latter radical preferably being incorporated so that the tertiary carbon atom is adjacent to the nitrogen atom.

An⊖ is the equivalent of an anion that differs from a Po lymerisat or polycondensate derived, each acidic Contains groups.

Among acidic groups in the sense of the invention is in particular to understand the carboxylate or hydroxysulfonate group hen.

Anionic polymers can either be homopolymers or copolymers.

Suitable monomers which have acidic groups and which are the basis of the anionic polymers are, for. B. acrylic acid, methacrylic acid, maleic acid, fumaric acid, the half-ester of maleic acid or fumaric acid with lower alcohols, in particular C ₁ -C ₄ -alkanols, N- (1-hydroxysulfonyl-2-methylprop-2-yl) acrylamide, N- (1-hydroxysulfonyl-2-methyl-prop-2-yl) methacrylamide or 3-hydroxysulfonyl-2-methylprop-1-ene.

Suitable comonomers are e.g. B. acrylamide, methacrylamide, N-hydroxymethylacrylamide, 3-hydroxypropyl acrylate, 3-hydroxy propyl methacrylate, vinyl acetate, N-vinylformamide, maleic acid reanhydride or methyl vinyl ether.

The homopolymers or copolymers generally have an average lower molecular weight from 500 to 300,000, preferably 1000 to 100,000.

If An⊖ are derived from a copolymer, it points this is generally from 20 to 99% by weight preferably 50 to 95 wt .-%, of monomers with acidic groups and a proportion of 1 to 80 wt .-%, preferably 5 to 50% by weight of comonomers, in each case based on the weight of the polymer.

Suitable polycondensates which have acidic groups are for example, polycondensates based on formaldehyde and Napthalene sulfonic acids, formaldehyde and naphthalene and Me thylnaphthalenesulfonic acids or formaldehyde and phenolsul  fonic acids. The molar ratio formaldehyde: aromatics is usually at 1: 2 to 2: 1.

The polycondensates generally have a medium molecule lar weight from 500 to 300000, preferably 800 to 70000, on.

Depending on the molecular weight, the anions have Polymer or polycondensate base usually 10 to 2000 acidic groups in the molecule. In the Re the rhodium amine cation is not the only counter ion. Much can do more than further counterions e.g. B. still protons or Sodium or potassium ions will be present, with protons are to be emphasized.

In general, about 0.1 to 80% of the acidic groups in the Anion based on polymer or polycondensate is rhodamine cation as a counter ion.

Preferred are rhodamine derivatives of the formula I in which R ₁ , R ² , R ³ , R ⁴ and R ⁹ independently of one another are hydrogen or C ₁ -C ₄ alkyl.

Rhodamine derivatives of the formula Ia are also preferred

in which R ¹ , R ⁸ and R ⁹ each independently represent hydrogen or C ₁ -C ₄ alkyl, in particular methyl or ethyl, and An⊖ has the abovementioned meaning.

The new rhodamine derivatives of the formula I are advantageous when you get the neutral dye base that is in the Lactone form or in a quinoid form or those of Formula II

obeyed, in which R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each have the abovementioned meaning, in a suitable solvent, for. As water, lower alcohols, such as methanol, ethanol, propanol or isopropanol, or mixtures of these solvents, solves and risat with acidic polyme or polycondensate. It is advantageous to use an excess of polymer or polycondensate. Based on 1 mol of rhodamine dye, 1 to 500, preferably 4 to 300 molar equivalents of polymer or polycondensate are generally used. After a subsequent stirring phase of 0.25 to 24 hours at a temperature of 10 to 50 ° C., the new rhodamine derivatives of the formula I have been formed and can be used in this form or, if appropriate, after removal of the solvent.

The rhodamine derivatives according to the invention are particularly suitable partial way for dyeing polyacrylonitrile fibers Incorporation in polymers or for the production of inks. They can also be used in the production of toners for the Electrophotography or in the manufacture of fluorescence sence pigments are used.

They are characterized by improved light fastness compared to conventional rhodamines.  

The following examples are intended to explain the invention in more detail tern.

General manufacturing and measuring instructions

A solution of 1.0 g neutral dye base in 300 ml was water with 50.0 g of an anionic polymer or Po Lykondensats added and stirred at 20 ° C for 12 hours.

The resulting reaction mixture is with a wire doctor applied to a glass slide and in a spectrometer measured the absorption. The thickness of the film becomes like this chosen that a transmis in the absorption maximum of the films sion is obtained from 10 to 25%.

These layers are included in a Hanau Sun Tester exposed to a 1500 watt xenon lamp. After a certain period of time the increase in transmission would be spectrometric detected.

Within a not too large interval of the transmis sion increase (e.g. from approx. 15% to approx. 40%) Slope of the best-fit line determined by the measuring points, the numerical value obtained is the measure of the light fastness.

The numerical value given in table 3 has the dimension: Transmission increase in percent per hour exposure time.

The following neutral dye bases were used.  

Table 1

The following polymers / polycondensates were used.

Table 2

In Table 3 below are those after the above Lightfastness values measured by the new Rhodaminde method derivatives listed.  

Table 3

Table 4 shows the light fastness values of Rhodamine dyes with common counterions or the ent speaking neutral dye base.

Table 4

Claims (7)

1. Rhodamine derivatives of the formula I. in the
R ¹ , R ² , R ³ and R ^{4 are} identical or different and, independently of one another, are each hydrogen or optionally substituted C ₁ -C ₄ -alkyl or in each case R ² and R ⁵ or R ⁴ and R ⁶ together 1.3- Propylene, which can be monosubstituted to trisubstituted by C ₁ -C ₄ alkyl,
R ⁵ , R ⁶ , R ⁷ and R ^{8 are} identical or different and, independently of one another, are each hydrogen or methyl,
R ^{9 is} hydrogen, optionally substituted C ₁ -C ₄ -alkyl or a radical of the formula (C ₂ H ₄ O-) _n H, in which n is 2 or 3, and
An⊖ is the equivalent of an anion derived from a polymer or polycondensate, each containing acidic groups. 2. Rhodamine derivatives according to claim 1, characterized net that the acid groups in the anion carboxylate or Hydroxysulfonate groups are.   3. Rhodamine derivatives according to claim 1, characterized net that the average molecular weight of the anion that is derived from a polymer or polycondensate, 500 to 300,000. 4. Rhodamine derivatives according to claim 1, characterized net that An⊖ means the equivalent of an anion that is derived from a homo- or copolymer. 5. Rhodamine derivatives according to claim 1, characterized in that R ¹ , R ² , R ³ , R ⁴ and R ⁹ each independently represent hydrogen or C ₁ -C ₄ alkyl. 6. Rhodamine derivatives according to claim 1, which of the formula Ia obey in which R ¹ , R ⁸ and R ⁹ each independently represent hydrogen or C ₁ -C ₄ alkyl and An⊖ has the meaning mentioned in claim 1. 7. Use of the rhodamine derivatives according to claim 1 for Dyeing of polyacrylonitrile fibers, for incorporation in Polymers or for the production of inks.