ZA200409769B

ZA200409769B - Method for brightening textile materials

Info

Publication number: ZA200409769B
Application number: ZA200409769A
Authority: ZA
Inventors: Gerhard Wagenblast; Dieter Weber; Helmut Reichelt
Original assignee: Basf Ag
Priority date: 2002-05-03
Filing date: 2004-12-02
Publication date: 2006-06-28
Also published as: EP1504149A2; AU2003222312A1; WO2003093565A3; US20050235429A1; BR0309642A; CN1333129C; KR100973535B1; HRPK20041141B3; ATE302871T1; HRP20041141A2; BR0309642B1; DE50301054D1; ES2246470T3; AU2003222312A8; EP1504149B1; MXPA04010130A; TWI279468B; WO2003093565A2; CN1650064A; JP2005529245A

Description

PF 53500 £«.2004/79769

Brightening of textile materials

Description : The present invention relates to a process for brightening textile materials by treatment with optical brighteners in an aqueous liquor, which comprises using from 20 to 80% by weight, each percentage being based on the sum total of all brightening compounds, of the compound I

Tr ans : © \

N CHj of which up to 40 mol% can be present as cis isomer, and also from 80 to 20% by weight of at least one compound II selected from

NC

CN II m,p’

A CN

II p,o’

CN

II o,0’ NC 40 N N CN

NC

IT p,p’ 45 and also from 0 to 30% by weight of at least one compound of the general formula III

PF 53500

R

0 N 0 %e h

OMe OMe where R is selected from C4-Cijg-alkyl, in the optional presence of one or more blue or violet shading dyes from the class of the anthraquinones, azo dyes or methine dyes.

Optical brighteners are of immense economic immportance as assistants for the textile industry and for the plastics industry. Numerous compounds are known for their ability to confer a white color on textiles or plastics. However, most of these known compounds also have disadvantages. For instance, compounds of the general formula 1

Rl 1

N N R

S—v— 1

R2 0 0 R2 where for example R! and. R? may each be for example hydrogen, fluorine, chlorine, phenyl, trifluoromethyl, alkyl or numerous other radicals and where V is selected from © -CH=CH- / \

S are known from EP 0 023 026 and can be applied at low 40 temperature, but their efficiency is limited in that a lot of product is needed to achieve the desired white effect.

Also known is a process for brightening textiles by treating the textiles with distyrylbenzene compounds which are known for 45 example from CH-A 366 512, CH-A 382 709, CH-A 388 294, CH-A 389 585, CH-A 411 329, CH-A 416 078 and CH-A 465 548. EP-A 0 023 027 and EP-B2 0 030 917 and also the references cited in EP-B2 0 030

; 1 PF 53500 917 demonstrate the use of mixtures of two or more dicyanostyrylbenzene compounds for the optical brightening of polyesters.

EP 0 023 026 discloses mixtures of optical brighteners that contain from 0.05 to 0.95 part by weight of one or more compounds of the formula 2 p ved Hc H=C —( ene H-A 2p where A is a phenyl group substituted by an ortho- or para-cyano group, and also from 0.95 to 0.05 part by weight of one or more other compounds selected from a large multiplicity of other compounds. Preference is given to mixtures of 2 p,o’

NC CH=CH CH=CH

NC

2 p,o’ with compounds of the general formula 1

Rl 1

N N R

HS—v— 1

R2 0. 0 R2 where R! and R? may each be: hydrogen, fluorine, chlorine, phenyl, trifluoromethyl, C;-Cg-alkyl, alkoxy, alkylamino and numerous further radicals which are recited at page 2 lines 14-21 and V is as defined above, or with compounds of the formula 3b-4b 0 Rl 0 3b 4b iA ' PF 53500 i 4 ) where B is a functional group, R! and RZ are each as defined above, n is an integer, R3 is selected from hydrogen and

C,-Cs-alkoxy, R* is selected from C;-Cs-alkoxy groups and RS is selected from for example C;-Cg-alkyl and B is preferably a functional group, or further with compounds of the formulae 5b to 6b

RS

RY PY

~~

N= SN ; LA ~

R® 0 0 RY N R10 5b 6b where RS to R10 are each selected from various groups and V is as defined above.

From this multiplicity of embodiments, Table 2 demonstrates by way of example what are essentially mixtures of 2 p,o0‘ or other isomers with 3c §)

N— CHj oO ] ..3c and with the following derivatives of 4 b.1l and 4 b.2:

H5C N en {coos Ha 0 4 b.1

H,C N N CHj 40 ene 4 0 o~N 4 b.2 45 The brighteners thus defined are applied by various methods and provide good CIE whiteness.

: PF 53500

EP-A 0 023 028 claims mixtures containing from 0.05 to 0.95 part by weight of a mixture consisting of from 20 to 100% by weight of 2 p,o’

NC

2 p,o’ and from 0 to 80% by weight each of the compounds 2 p,p‘ and 2 0,0’ - = CN 2 p,p’

CN

CH=C (ens J

NC

2 o,0’ and also from 0.05 to 0.95 part by weight of one or more derivatives of the formulae la and 3a to 6a, useful as optical brighteners, la and 3a ‘to 6a being defined essentially similarly to EP-A 0 023 026.

DE-A 197 32 109 demonstrates the optical brightening of polyamide or polyurethane by mixtures of derivatives of compounds of type la

Rl

A A 1

S—x— a 0) 0 R2 40 where R! and R2 are independently H or C;-Cg-alkyl, A is selected from N and CH and X is selected from

: PF 53500 a ° -CH=CH- /\

S and also from stilbenyl, styryl or imidazolyl, with one or more isomers of 2 or one of the numerous derivatives of 4

NC

— ee

CN

2

R3

N

\ = — CH=CH B 6]

R4 4 or numerous further derivatives, for example with 5 b (see above). By way of example, mixtures are demonstrated inter alia (Examples 19-21) of 1 a.l with 4 b.1

H3C N N CH, 0 0 1 a.l

HC N

\ CH=CH COOCH3; 0 4 b.1 40 The mixtures exhibit a synergistic effect with regard to CIE whiteness and also good lightfastness.

EP-A 0 321 393 describes the use of compounds of type 1 b,

. , PF 53500

H—c H=C i— 1b 0 0] where D is a C;-Cg-alkyl group, and compounds of the formula 2 in brightener dispersions. The compounds of type 1 b or 2 are disclosed either by themselves or as specific mixtures, referred to in the cited reference as mixtures 1 to 6 (pages 6-8). In EP-A 0 321 393 it is stated at page 9 line 18 that it is essential to the invention that the mixture contain a copolymer of 2-vinylpyrrolidone with 3-vinylpropionic acid.

In EP-A 0 682 145 the lightfastness of textiles is improved by treating them with formulations containing a fluorescent UV absorber which absorbs at a wavelength of from 280 to 400 nm and is selected from 4,4'-bistriazinylaminostilbene-2,2‘-disulfonic acids, 4,4‘'-diphenylstilbenes, 4,4*-distyrylbiphenyls, 4-phenyl-4‘-benzoxazylstilbenes, stilbenylnaphthotriazoles, 4-styrylstilbenes, coumarins, pyrazolines, naphthalimides, triazinylpyrenes, 2-styrylbenzoxazole or 2-styrylnaphthoxazole derivatives, benzimidazolebenzofurans, oxanilide derivatives and bisbenzoxazol-2-yl and bisbenzimidazol-2-yl derivatives, for example of the formulae 1 c¢ or 1 d (claim 8),

R14 14

N N R

H—x—

R14 6 0 R14 | lc

R17 rl

N N pa

N

\ /

R15 R16 1d 40 where each R14 is independently hydrogen or C;-Cyq-alkyl or tert-butyl or -C(CHs3)2-phenyl or CO0-C;-C4-alkyl

[1 1) ) PF 53500

RY and R!®* are the same or different and selected from H, C,-C,- each RY is the same or different and selected from H and SO;

X is selected from / \) -CH=CH-

JN ; and X! is selected from [/\ -CH=CH- oO

However, lightfastness improvement is usually governed by other factors than play a part in the optical brightening of textiles.

A bright white is of immense economic importance in relation to a very wide variety of products, for example in relation to textiles and in relation to shaped plastics articles. The above- demonstrated numerous mixtures, especially the mixtures demonstrated in the examples of EP-A 0 023 026 and EP-A 0 023 028 and also EP-A 0 682 145, exhibit a white which is frequently not sufficiently bright for demanding customers. Moreover, further performance characteristics have room for improvement. Finally, it is desirable for economic reasons for brighteners to be more efficient in that less brightener is needed to achieve the same or a greater effect.

A need exists to provide - a process for brightening textile materials which provides a particularly bright white coupled with improved efficiency and otherwise likewise improved performance characteristics; - formulations for a process for brightening textile materials and

AMENDED SHEET r .

PF 53500 - uses for the new formulations.

We have found that this need is fulfilled by the process defined at the beginning.

Textile materials for the purposes of the present invention include fibers, slivers, yarns, threads, wovens, knits, nonwovens and garments composed for example of polyester or polyester blends. The textile materials are preferably composed of synthetic polyesters or of blends containing from 45 to 90% by weight of polyester.

Brightening or optically brightening compounds for the purposes of the present invention are fluorescent compounds which are capable of absorbing in the range from 280 to 400 nm and of emitting at a higher wavelength. Examples include compounds from the class of the stilbenes, distyrylbenzenes, diphenyldistyryls, triazinyls, benzoxazoles, bisbenzoxazoles, bisbenzoxazolylthiophenes, bisbenzoxazolylnaphthalenes, pyrenes, coumarins and naphthaleneperidicarboximides. Brightening or optically brightening compounds shall refer especially to brightening or optically brightening compounds of the formulae I,

IT and III. Weight percentages shall hereinafter be based on the sum total of the brightening compounds, unless expressly stated otherwise.

The term “aqueous liquors” as used herein also comprehends liquors which, as well as water as main constituent, contain up to 40% by volume of one or more further solvents, for example alcohols such as ethanol. The pH of the liquors used according to the present invention is preferably in the range from 3 to 12 and more preferably in the range from 3 to 8.

The processed defined at the beginning is embodied by treating textile materials with from 20 to 80% and preferably from 20 to 70% by weight and more preferably from 30 to 50% by weight of the compound of the formula I

H,C N

TL Ye

AAS Gt \ .

CH,

AMENDED SHEET

, , PF 53500 of which up to 40 mol% may be in the form of the corresponding cis isomer, and also from 80 to 20% by weight of at least one of the compounds II

NC

CN IT m,p’

CN

ONO

IT p,o’

CN

NC

ITI o,0’

CN

N\ \

NC

III

CC

OMe OMe where R is selected from C4-Cj;p-alkyl, for example n-butyl, 40 iso-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isocamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, n-octyl, 2-ethylhexyl, n-nonyl and n-decyl; preference is given to n-butyl and 2-ethylhexyl.

, PF 53500 ’ It is preferable, as well as from 20 to 80% by weight of the compound I, to use: from 0 to 30% by weight of a compound of the general formula III and from 20 to 70% by weight each of at least one of the compounds II p,0‘ or m,p’.

Particular preference is given to using from 20 to 70% by weight of the compound II p,o’ and from 10 to 50% by weight of the _ 10 compound m,p’ as well as from 20 to 70% by weight of the compound I and from 0 to 30% by weight of a compound of the general formula III.

Another particularly preferred embodiment, as well as from 30 to 50% by weight of compound I and from 0 to 30% by weight of a compound of the general formula III, utilizes from 30 to 60% by weight of the compound II p,0’, from 10 to 30% by weight of the compound II o,0’ and optionally from 10 to 50% by weight of the compound m,p‘.

The compound I is synthesized for example as described in

US 2,842,545, US 2,875,089 or US 3,147,253. For the purposes of the present invention, the definition of I also comprehends such isomer mixtures as contain from 0.2 to 40 mol% and preferably fromn 0.7 to 20 mol% of cis isomer. The fraction of cis isomer is determined by spectroscopic or chromatographic methods familiar to one skilled in the art, see for example J. Chromat. 1967, 27 (2), 413-22.

The dicyanostyryl compounds II p,o‘, II m,p‘, II p,p‘’ and II 0,0’ are used in the form of their trans isomers. They customarily contain from 0.01 to 10 and preferably from 0.1 to 5 mol% of isomers having at least one cis double bond, the fraction of cis isomers being determined by spectroscopic methods known to one skilled in the art. They are readily obtainable from terephthaldicarboxaldehyde and the corresponding cyanobenzyl 40 phosphorylides by a twofold Wittig reaction.

In the practice of the process according to the present invention, it may be advantageous to add one or more blue or violet shading dyes. Useful shading dyes generally belong to the 45 class of disperse dyes and vat dyes. These are customary

A PF 53500 designations. The Colour Index lists such dyes for example as

Disperse Blue or Disperse Violet or Vat Blue or Vat Violet. ) Blue dyes from the class of the anthraquinones, azo dyes or methine dyes are particularly suitable.

Dyes from the class of the anthraquinones conform for example to the formulae A 1 to A 4 0 OH 0 HN 3 NH o — 52 0 NH, 23 . 24 .- 0 HN 5 ’ CLC | a 7° z6 0 HN 74 0) NH 2 _H s— — s0,— 0) OH A 4 45 where

Claims

PF 53500 We claim:-

1. A process for brightening textile materials by treatment with optical brighteners in an aqueous liquor, which comprises using from 20 to 80% by weight, each percentage being based on the sum total of all brightening compounds, of the compound I Tr NP © \ N CH3 of which up to 40 mol% can be present as cis isomer, and also from 80 to 20% by weight of at least one compound II selected from NC CN II m,p’ : ) © II p,o’ CN II o,0' NC 40 NC ITI p,p’ 45 and also from 0 to 30% by weight of at least one compound of the general formula III

. . PF 53500 R 0] N 0] IIT OMe OMe where R is selected from C4-Cj p-alkyl, in the optional presence of one or more blue or violet shading dyes from the class of the anthraquinones, azo dyes or methine dyes.

2. BA process as claimed in claim 1, wherein from 20 to 70% by weight of the compound II p,0’ is used as well as from 20 to 80% by weight of the compound I and from 0 to 30% by weight of a compound of the general formula III.

3. A process as claimed in claim 1 or 2, wherein from 20 to 70% by weight of the compound II m,p’ is used as well as from 20 to 80% by weight of the compound I and from 0 to 30% by weight of a compound of the general formula III.

4. A process as claimed in claim 1, wherein from 20 to 70% by weight of the compound II p,o’ and from 10 to 50% by weight of the compound II m,p’ are used as well as from 20 to 70% by weight of the compound I and from 0 to 30% by weight of a compound of the general formula III.

5. A process as claimed in claim I, wherein from 30 to 60% by weight of the compound II p,o’ and from 10 to 30% by weight of the compound II o,0’ are used as well as from 30 to 60% by weight of the compound I and from 0 to 30% by weight of a compound of the general formula IIT. 40 6. A process as claimed in claim 1, wherein from 20 to 60% by weight of the compound II p,o’, from 10 to 50% by weight of the compound II m,p’ and from 10 to 30% by weight of the compound II 0,0’ are used as well as from 20 to 50% by weight of the compound I and from 0 to 30% by weight of a compound 45 of the general formula III.

2 PS PF 53500 .

7. A process as claimed in any one of the preceding claims, wherein R is 2-ethylhexyl in the compound III.

8. A process as claimed in any one of the preceding claims, wherein from 0.5 to 200% by weight, based on the sum total of all brightening compounds, is additionally used of one or more dispersants.

8S. A process as claimed in any one of the preceding claims, wherein the textile material is polyester.

10. A process as claimed in any one of the preceding claims, wherein the textile material is a blend containing from 45 to 90% by weight of polyester.

11. Formulations comprising from 20 to 80% by weight, each percentage being based on the sum total of all brightening compounds, of the compound I, from 20 to 70% by weight of at least one compound II, from 0 to 30% by weight of at least one compound of the formula III and also in each case optionally one or more blue or violet shading dyes from the class of the anthraquinones, azo dyes, methine dyes, violanthrones or indanthrones, one or more dispersants, water and further additives.

12. The use of formulations as claimed in claim 11 for brightening textile materials.

13. A process according to the invention for brightening textile materials, substantially as hereinbefore described or exemplified.

14. A process for brightening textile materials including any new and inventive integer or combination of integers, substantially as herein described.

15. Formulations as claimed in claim 11, substantially as hereinbefore described or exemplified. AMENDED SHEET

? w Cp PF 53500

16. Formulations according to the invention including any new and inventive integer or combination of integers, substantially as herein described.

17. The use of formulations as claimed in claim 12, substantially as hereinbefore described or exemplified.

18. The sue of formulations including any new and inventive integer or combination of integers, substantially as herein described. AMENDED SHEET