AU701586B2 - Use of hydroxybenzotriazoles for enhancing the sun protection factor of cellulosic fibre materials - Google Patents
Use of hydroxybenzotriazoles for enhancing the sun protection factor of cellulosic fibre materials Download PDFInfo
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- AU701586B2 AU701586B2 AU32945/95A AU3294595A AU701586B2 AU 701586 B2 AU701586 B2 AU 701586B2 AU 32945/95 A AU32945/95 A AU 32945/95A AU 3294595 A AU3294595 A AU 3294595A AU 701586 B2 AU701586 B2 AU 701586B2
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- naphthyl
- sulfo
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- unsubstituted
- alkyl
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/35—Heterocyclic compounds
- D06M13/355—Heterocyclic compounds having six-membered heterocyclic rings
- D06M13/358—Triazines
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/35—Heterocyclic compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
- D06P1/642—Compounds containing nitrogen
- D06P1/6426—Heterocyclic compounds
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- Textile Engineering (AREA)
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Description
S F Ref: 312068
AUSTRALIA
PATENTS ACT 1990 COMPLETE SPECIFICATION FOR A STANDARD PATENT
ORIGINAL
r r r r
D
O
a c r a Name and Address of Applicant: Actual Inventor(s): Address for Service: Invention Title: Klybeckstrasse 141 4002 Basle ct+-4tos? CS(-
SWITZERLAND
Francesco Fuso and Gerhard Reinert.
Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Wales, 2000, Australia Use of Hydroxybenzotriazoles for Enhancing the Sun Protection Factor of Cellulosic Fibre Materials Yi .A r o u r r r The following statement is a full description of this invention, including the best method of performing it known to me/us:-
.J
Use of hydroxybenzotriazoles for enhancing the sun protection factor of cellulosic fibre materials The present invention relates to the use of hydroxybenzotriazoles for enhancing the sun protection factor of cellulosic fibre materials by treating said materials with specific compounds of the class of hydroxybenzotriazoles.
It has long been common knowledge that UV radiation is harmful to the human skin and people have accordingly also been concerned to protect themselves from the effects of excessive solar radiation. The most commonly employed methods of protection are the use of a sun cream or wearing clothes. Whereas the use of sun cream virtually only comes into contention for the bare skin and is mainly applied when one is engaged in leisure pursuits or in sporting activities, the usual means of protecting the human body from solar radiation is the wearing of clothes. It has been found, however, that the wearing of an article of clothing alone, especially the white or light-coloured T-shirt worn for preference in the summer months, does not always ensure adequate sun protection.
A process for enhancing the sun protection factor of textile materials and fabrics by treating them with UV absorbers is taught in WO/94/04515. It has been found, however, that the enhancement of the sun protection factor thereby achieved does not meet the S requirements in all aspects.
Hence there is a continuing need to improve the sun protection factor of textile 20 materials.
Surprisingly, it has been found that a still greater solar protection can be achieved by treating cellulosic fabrics with specific hydroxybenzotriazoles.
SAccordingly, the invention relates to a process for enhancing the sun protection factor of cellulosic fabrics, which process comprises treating said fabrics with a 25 compound of formula So* R3\
R
1 N-A-S0 2
-Z
R2 HO N N X -B
N
N N-
I
N S-b x
-T
L'
I: I ~~Wp w :i wherein
R
1 and R 2 are each independently of the other hydrogen, C 1
-C
4 alkyl; C 1
-C
4 alkoxy; halogen; hydroxy; nitro; sulfo or carboxy;
R
3 is hydrogen; or C 1
-C
4 alkyl which is unsubstituted or substituted by C 1
-C
4 alkoxy, halogen, hydroxy, sulfo, cyano, carboxy, C 1
-C
4 alkoxycarbonyl, C 1
-C
4 alkylcarbonyloxy, carbamoyl or sulfamoyl; A is phenylene which is unsubstituted or substituted by C 1
-C
4 alkyl, C 1
-C
4 alkoxy, halogen or sulfo; naphthylene which is unsubstituted or substituted by Cl-C 4 alkyl, Cl-C 4 alkoxy, halogen or sulfo, or C 1
-C
12 alkylene which is unsubstituted or substituted by halogen, hydroxy, sulfato, cyano, carboxy, Cl-Csalkoxycarbonyl, C 1
-C
4 alkanoyloxy or carbamoyl, and in which the alkylene chain is interrupted from C 2 by oxygen or wherein R' is hydrogen or C 1
-C
6 alkyl, and may be branched from C 3 and R' is able to form a ring together with the alkylene chain; B is oxygen; a radical -N(R 4 wherein R 4 is hydrogen or C 1
-C
4 alkyl, or a radical S -(CH 2 )n-NH- which is attached at the triazine radical through the nitrogen atom, and in which n is 1 to 4; S X is chloro; fluoro; pyridyl which is unsubstituted or substituted by halogen, sulfo, carboxy, carbamoyl or C 1
-C
4 alkyl which is unsubstituted or substituted by hydroxy or sulfo; a radical -NR 5
R
6 wherein R 5 and R 6 are each independently of the other hydrogen,
C
1
-C
4 alkyl which is unsubstituted or substituted by Cl-C 4 alkoxy, chloro, hydroxy, sulfo, sulfato, carboxy or phenyl; phenyl which is unsubstituted or substituted by Cl-C 4 alkyl, Cl-C 4 alkoxy, halogen, sulfo or carboxy; naphthyl which is unsubstituted or substituted by
C
1
-C
4 alkyl, C 1
-C
4 alkoxy, chloro, hydroxy, sulfo or carboxy; or benzyl which is Sunsubstituted or substituted in the phenyl ring by Cl-C 4 alkyl, C 1
-C
4 alkoxy, chloro or sulfo; or a radical -OR 7 wherein R 7 is hydrogen, C 1
-C
4 alkyl which is unsubstituted or substituted by C 1
-C
4 alkoxy, chloro, hydroxy, sulfo, sulfato, carboxy or phenyl;*henyl which is unsubstituted or substituted by Cl-C 4 alkyl, Cj-C 4 alkoxy, halogen, sulfo or carboxy; naphthyl which is unsubstituted or substituted by C 1
-C
4 alkyl, C 1
-C
4 alkoxy, chloro, hydroxy, sulfo or carboxy; or benzyl which is unsubstituted or substituted in the phenyl ring by C 1
-C
4 alkyl, Cl-C 4 alkoxy, chloro or sulfo; and Z is f-haloethyl, P-sulfatoethyl, p-thiosulfatoethyl, P-phosphatoethyl, P-acetoxyethyl or vinyl A 2
,R
3 R, R 5
R
6 and R 7 defined as C 1
-C
4 alkyl are each independently of the other -c Zrr o4 -3methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.
R, and R 2 defined as G 1
-C
4 alkoxy may each independently of the other be methoxy, ethoxy, propoxy, isopropoxy, isobutoxy or tert-butoxy.
R, and R 2 defined as halogen may each independently of the other be fluoro, chioro or bromo.
R
3
R
5
R
6 and R 7 defined as Cj-C 4 alkcoxy-C 1
-C
4 alkyl are each independently of the other typically methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl or 3-ethoxypropyl.
4 R 3 defined as halo-Cl-C 4 alkyl will typically be chloromethyl, chioroethyl, 2-chloroethyl, .:2-bromoethyl, 3-chloropropyl, 3-bromopropyl, 4-chlorobutyl or 4-bromobutyl.
V4
R
3
R
5
R
6 and R 7 defined as hydroxy-Cl-C 4 alkyl will each independently of the other typically be 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, 2,3-dihydroxypropyl or 3,4-dihydroxybutyl.
R
3 R, and R 7 defined as sulfo-Cl-C 4 alkyl are each independently of the other typically sulfomethyl, 2-sulfoethyl, 3-sulfopropyl or 4-sulfobutyl.
R
3 defined as cyano-Cl-C 4 alkyl is typically cyanomethyl, 2-cyanoethyl. or 3-cyanopropyl.
R
3
R
5
R
6 and R 7 defined as carboxy-G 1
-C
4 alkyl are each independently of the other typically carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl or 1,2-dicarboxyethyl.
R
3 defined as C 1
-C
4 alkoxycarbonyl-G 1
-C
4 alkyl will typically be methoxycarbonylmethyl, ethoxycarbonylmethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 3-methoxycarbonylpropyl, 3-ethoxycarbonylpropyl, 4-methoxycarbonylbutyl or 4-ethoxycarbonylbutyl.
R
3 defined as C 1
,-C
4 alkylcarbonyloxy-C 1
-C
4 alkyl will typically be methylcarbonyloxymethyl, ethylcarbonyloxymethyl, 2-methylcarbonyloxyethyl, 2-ethylcarbonyloxyethyl, 3-methylcarbonyloxypropyl, 3-ethylcarbonyloxypropyl, -4- 4-methylcarbonyloxybutyl or 4-ethylcarbonyloxybutyl.
R
3 defined as carbamoyl-C 1
-C
4 alkyl will typically be carbamoylmethyl, 2-carbamoylethyl, 3-carbamoylpropyl or 4-carbamoylbutyl.
R
3 defined as sulfamoyl-Cl-C 4 alkyl will typically be sulfamoylmethyl, 2-sulfamoylethyl, 3-sulfamaoyipropyl or 4-sulfamoylbutyl.
R
5
R
6 and R 7 defined as Cl-C 4 alkylphenyl are each independently of the other typically tolyl, xylyl, mesityl, cumyl, ethylphenyl or butylphenyl.
VII R 5
R
6 and R 7 defined as Cl-G 4 alkoxyphenyl are each independently of the other typically .000 *0 methoxyphenyl, ethoxyphenyl, propoxyphenyl or butoxyphenyl.
S0* 0 0 R 5
R
6 and R 7 defined as halophenyl are each independently of the other typically chlorophenyl or bromophenyl.
000* 00 R 5
R
6 und R 7 defined as C 1
-C
4 alkoynaphthyl are each independently of the othertyial tyclnapehoptyl, ethylxnapthyl, propynpylo uynapthyl.o uoynphl
R
5
R
6 and R 7 defined as Cl-C 4 alkoynaphhyl are each independently of the otherial mtycally ethyapthyl, ethoxybnphl royatyl or but oxynapthyl
R
5
R
6 and R 7 defined as Cl-C 4 alkoybenzyl are each independently of the other typically methoybenzyl, ethybenzyl, propbenzyl or buteny.nyl R' defined as Cj-C 6 alkyl is typically methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl or hexyl.
A in the significance of CI-C 4 alkylphenylene may be exemplified by tolylene, xylylene, mesitylene, cumylen, ethylphenylene or butyiphenylene. A A in the significance of Cj-C 4 a-ikoxyphenyl may be exemplified by methoxyphenylene, ethoxyphenylene, propoxyphenylene or butoxyphenylene.
A in the significance of halophenylene may be exemplified by chlorophenylene or bromophenylene.
A in the significance of C 1
-C
4 alkylnaphthylene may be exemplified by methylnapthylene, ethylnapthylene, propylnapthylene or butylnapthylene.
A in the significance of C 1
-C
4 alkoxynaphthylene may be exemplified by methoxynapthylene, ethoxynapthylene, propoxynapthylene or butoxynapthylene.
A in the significance of C 1 -C12alkylene may be exemplified by methylene, ethylene, o propylene, tetramethylene, pentamethylene or hexamethylene.
SA in the significance of substituted phenylene may carry one or more than one of the cited substituents.
A in the significance of substituted naphthylene may carry one or more than one of the cited substituents.
Where R 5
R
6 or R 7 represent a substituted phenyl radical, said radical may be substituted S* by one or more than one of the cited substituents.
Where R 5
R
6 or R 7 represent a substituted naphthyl radical, said radical may be substituted by one or more than one of the cited substituents.
Where R 5
R
6 or R 7 represent substituted benzyl, the benzyl radical in the phenyl ring may be substituted by one or more than one of the cited substituents.
Preferred embodiments of the novel utility comprise: The use of compounds of formula wherein R 1 is hydrogen, methyl, ethyl, propyl, isopropyl, methoxy, ethoxy, chloro, hydroxy, sulfo or carboxy.
The use of compounds of formula wherein R 2 is hydrogen, methyl, ethyl, propyl, .l isopropyl, methoxy, ethoxy, chloro, hydroxy, sulfo or carboxy.
-6- The use of compounds of formula wherein X is the radical -NR 5
R
6 wherein R and R 6 are each independently of the other hydrogen; C 1
-C
4 alkyl which is unsubstituteui or substituted by Cl-C 4 alkoxy, chioro, hydroxy, sulfo, sulfato, carboxy or phenyl; phenyl which is unsubstituted or substituted by Cl-C 4 alkyl, G 1
-C
4 alkoxy, halogen, sulfo or carboxy; naphthyl which is unsubstituted or substituted by Cl-C~alkyl, Cl-G 4 alkoxy, chioro, hydroxy, sulfo or carboxy; or benzyl which is unsubstituted or substituted in the phenyl ring by Cl-C 4 alkyl, G 1
-C
4 alkoxy, chioro or sulfo.
The use of compounds of formula wherein X is the radical -NR 5
R
6 wherein R 5 is hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, P-methoxyethyl, P-hydroxyethyl, P-sulfoethyl, P-sulfatoethyl or P-carboxyethyl, and R 6 has the meaning 00 previously assigned to it.
0 0 6 o0 00 0 a The use of comojounds of formula wherein X is the radical -NR 5
R
6 wherein R 5 is o phenyl, 2-sulfophenyl, 3-sulfophenyl, 4-sulfophenyl, 2,4-disulfophenyl, Ago.. 2 -carboxyphenyl, 3-carboxyphenyl or 4-carboxyphenyl, and R 6 has the meaning previously assigned to it.
00 0 6 The use of compounds of formula wherein X is the radical -NRSR 6 wherein R 5 is goufo1nphhl toufo1nphhl A-uf--ahhl -sulfo-1-naphthyl, 7-sulfo-1-naphthyl, 8-sulfo-1-naphthyl, 1-sulfo-2-naphthyl, 0*0# -sulfo-2-naphthyl, 6-sulfo-2-naphthyl, 7-sulfo-2-naphthyl, 8-sulfo-2-naphthyl, 6-sul,7-diahy,7sulfo-2-naphthyl, 6,8-disulfo2-naphthyl 4,8-disulfo-2-naphthyl, 4,7-disulfo-2-naphthyl, 3,8-disulfo-2-naphthyl, 4,6-disulfo-2-naphthyl, 3,7-disulfo-2-naphthyl, 3,6-disulfo-2-naphthyl, 4,6-tisulfo--naphthyl, 2,7-risulfo-2-naphthyl, 3,6,8-trisulo-1-nphthyl 4,6,8-trisulfo-2-naphthyl, 1,4,7-trisulfo-2-naphthylo 3,6,8-trisulfo--naphthyl, adR a the significance previously assigned to it.
The use of compounds of formula wherein X is the radical -NR 5
R
6 wherein R 5 is benzyl, 2-sulfobenzyl, 3-sulfobenzyl or 4-sulfobenzyl, and R 6 has the meaning previously assigned to it.
The use of compounds of formula wherein X is the radical -NR 5
R
6 wherein R 6 is hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, P-methoxyethyl,j -7- P-hydroxyethyl, P-sulfoethyl, P-sulfatoethyl or P-carboxyethyl, and R 5 has the meanings and preferred meanings previously assigned to it.
The use of compounds of formula wherein X is the radical -NR 5
R
6 wherein R 6 is phenyl, 2-sulfophenyl, 3-sulfophenyl, 4-sulfophenyl, 2,4-disulfophenyl, 2-carboxyphenyl, 3-carboxyphenyl or 4-carboxyphenyl, and R 5 has the meanings and preferred meanings previously assigned to it.
()The use of compounds of formula wherein X is the radical -NR 5
R
6 wherein R 6 is 2-sulfo-1-naphthyl, 3-sulfo-1-naphthyl, 4-sulfo-1-naphthyl, 5-sulfo-1-naphthyl, feac, 0 6-sulfo-1-naphthyl, 7-sulfo-1-naphthyl, 8-sulfo-1-naphthyl, 1-sulfo-2-naphthyl, 5-sulfo-2-naphthyl, 6-Sulfo-2-naphthyl, 7-sulfo-2-naphthyl, 8-sulfo-2-naphthyl, a 1,5-disulfo-2-naphthyl, 5,7-disulfo-2-naphthyl, 6,8-disulfo-2-naphthyl, 4,8-disulfo-2-naphthyl, 4,7-disulfo-2-naphthyl, 3,8-disulfo-2-naphthyl, 4,6-disulfo-2-naphthyl, 3,7-disulfo-2-naphthyl, 3,6-disulfo-2-naphthyl, 4,6,8-trisulfo-1-naphthyl, 2,4,7-trisulfo-1-naphthyl, 3,6,8-trisulfo-1-naphthyl, 4,6,8-trisulfo-2-naphthyl, 1,5,7-trisulfo-2-naphthyl or 3,6,8-trisulfo-2-naphthyl, and R 5 has the meanings and preferred meanings previously assigned to it.
The use of compounds of formula wherein X is the radical -NR 5
R
6 wherein R 6 is benzyl, 2-sulfobenzyl, 3-sulfobenzyl or 4-sulfobenzyl, and R 5 has the meanings and preferred meanings previously assigned to it.
The use of compounds of formula wherein X is the radical -NR 5
R
6 wherein one of the substituents R 5 and R 6 is G 1
-G
4 alkyl which is unsubstituted or substituted by Cl-C 4 alkoxy, chloro, hydroxy, sulfo, sulfato, carboxy or phenyl; phenyl which is unsubstituted or substituted by C 1
-C
4 alkyl, Cl-C 4 alkoxy, halogen, sulfo or carboxy; naphthyl which is unsubstituted or substituted by CI-C 4 alkyl, C 1
-C
4 alkoxy, chloro, hydroxy, sulfo or carboxy; or benzyl which is unsubstituted or substituted in the phenyl ring Cl-C 4 alkyl, Cl-G 4 alkoxy, chloro or sulfo, and the other substituent R 5 or R 6 is hydrogen, methyl or ethyl.
(in) The use of compounds of formula wherein A is phenylene which is unsubstituted or substituted by Cj-C 4 alkyl, C 1
-C
4 alkoxy, halogen or sulfo.
The use of compounds of formula wherein A is the group -(CH 2 )a,-NH-(CH 2 -8wheren a is an integer from 1 to 6 and b is an integer from 1 to 6.
The use of compounds of formula wherein Z is the radical -CH 2
CH
2
OSO
3
H.
The use of compounds of formula wherein X is pyridyl, 3-methylpyridyl, 3-p-hydroxyethylpyridyl, 4-p-sulfoethylpyridyl, 4-chloropyridyl, 3-sulfopyridyl, 2-carboxypyridyl, 3,5-dicarboxypyridyl or 2-carbamoylpyridyl, 3-carbamoylpyridyl, 4-carbamoylpyridyl, preferably 3-carboxypyridyl and 4-carboxypyridyl.
The use of compounds of formula whrein B is oxygen or -NH-.
The compounds of formula and the preparation thereof are disclosed, inter alia, in JP 8 Kokai Hei 3-239757 and JP Kokai Hei 3-241069.
Cellulosic fibre materials typically include the natural cellulose fibres such as cotton, linen S. and hemp, as well as cellulose and regercrated cellulose. The compounds of formula (1) are also suitable for treating hydroxyl group-containing fibres that are components of fibre S blends, typically blends of cotton with polyester or polyamide fibres. Preferred fibre materials are those having a density of 30 to 200 g/m 2 Cotton is the preferred cellulosic 0:o. fibre material. The fibre materials referred to may be in different forms of presentation, including filaments or yarns or woven or knitted fabrics.
The compounds of formula can be applied to the fibre material and fixed thereon by different means commonly employed in the textile industry, preferably in the form of aqueous solutions. They are suitable for pad dyeing or, preferably, for the exhaust process.
The exhaust process is carried out in the temperature range from 50 to 120 0
C,
conveniently from 50 to 70 0 C, in the presence of an acid acceptor such as sodium carbonate, sodium hydrogencarbonate, sodium formate, potassium carbonate, sodium silicate, sodium trichloroacetate or sodium triphosphate, in the absence or presence of a neutral salt such as sodium sulfate or sodium chloride.
The liquor ratio in the exhaust process can be chosen over a wide range, for e: mple from 1:3 to 1:200, preferably from 1:10 to 1:40.
The compounds of formula are used in the practice of this invention typically in an -9amount of 0.005 to 10 by weight, preferably 0.05 to 2 by weight, based on the fibre material.
The application of the compounds of formula to the fibre material can be made in a separate treatment bath or in the dyebath, before, during or after dyeing.
The treatment bath or dyebath may also contain other conventional assistants such as wetting agents, deaerators and antifoams or penetration enhancers.
The cellulosic fabrics treated with the compounds of formula are distinguished by a very high sun protection factor. The sun protection factor is defined as the quotient of harmful UV radiation without sun protection and harmful UV radiation with sun 0, protection. Accordingly, a sun protection factor is also an indicator of the permeability of the untreated fabric and the fabric treated with the hydroxybenzotriazoles used in the practice of this invention to UV radiation.
The calculation of the sun protection factor of textile materials can be made, inter alia, by the method of B. L. Diffey und J. Robson in J. Soc. Cosmet. Chem. 40, 127-133 (May/June 1989).
0 0 The invention is illustrated by the following Examples in which parts and percentages are by weight, unless otherwise indicated. The relationship of parts by weight to parts by volume is the same as that of the kilogram to the litre.
Example 1: A 100 g sample of bleached cotton tricot is treated at 60*C for 20 minutes in a jet dyeing machine.
The liquor contains 1 g of the compound of formula
SO
3 H HO
C
N N S0 HN NCHCHOSO (100) HN -1 .N SO 2
CH
2
CH
2
OS
3
H
1% Ir~-~d c lar and 75 g of sodium sulfate.
To the liquor are then added 30 g of sodium carbonate and the cotton tricot is treated at for another 60 minutes. The fabric is then removed from the liquor, washed repeatedly with cold, warm and hot water and dried.
The treated cotton tricot material has an excellent sun protection factor.
Example 2: Tne procedure of Example 2 is repeated, but replacing 1 g of the compound of formula (100) with 0.75 g of the compound of formula C0 2
H
N
*pow 0009 060* 09 9 0000 a 00 *r o ,9 99 40 999 9 9, 0 b9 9 (101), giving cotton tricot material which likewise has an excellent sun protection factor.
Example 3: The procedure of Example 2 is repeated, but replacing the compound of formula (100) with the same amount of the compound of formula HN S02CH 2
CH
2
OSO
3
H
/-0 (102), N2 YT\
N
Cl giving cotton tricot material which likewise has an excellent sun protection factor.
Claims (21)
1. A process for enhancing the sun protection factor of cellulosic fabrics, which process comprises treating said fabrics with a compound of the formula RI R 3 N-A-S0 2 -Z R2 HO N N B 4 N N N x (0, wherein R 1 and R 2 are each independently or the other hydrogen, C 1 -C 4 alkyl; C 1 C 4 alkoxy; halogen; hydroxy; nitro; sulfo or carboxy; R 3 is hydrogen; or C 1 -C 4 alkyl which is unsubstituted or substituted by C1-C 4 alkoxy, halogen, hydroxy, sulfo, cyano, carboxy, Cl-C 4 alkoxycarbonyl, C 1 -C 4 alkylcarbonyloxy, carbamoyl or sulfamoyl; A is phenylene which is unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen or sulfo, naphthylene which is unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen or sulfo, or C 1 -C 12 alkylene which is unsubstituted or substituted by halogen, hydroxy, sulfato, cyano, carboxy, C 1 -C 5 alkoxycarbonyl, C 1 -C 4 alkanoyloxy or carbamoyl, and in which the alkylene chain is interrupted from C 2 by oxygen or wherein R' is hydrogen or C 1 -C 6 alkyl, and may be branched from C 3 and R' is able to is form a ring together with the alkylene chain; B is oxygen; a radical -N(R 4 wherein R 4 is hydrogen or C 1 -C 4 alkyl, or a radical -(CH 2 1 -NI-H- which is attached at the triazine radical through the nitrogen atom, and in which n is 1 to 4; X is chloro; fluoro; pyridyl which is unsubstituted or substituted by halogen, sulfo, carboxy, carbamoyl or C 1 -C 4 alkyl 0which is unsubstituted or substituted by hydroxy or sulfo; a radical -NR 5 R 6 wherein R; and R6 are each independently of the other hydrogen, C 1 -C 4 alkyl, which is unsubstituted or substituted by C1-C4alkoxy, chloro, hydroxy, sulfo, sulfato, carboxy or phenyl; phenyl which is unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, sulfo or carboxy; naphthyl which is unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, chloro, hydroxy, sulfo or carboxy; or benzyl which is unsubsiituted or substituted in the phenyl ring by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, chloro or sulfo; or a radical -OR 7 wherein R 7 is hydrogen C 1 -C 4 alkyl which is unsubstituted or substituted by CI-C 4 alkoxy, chloro, hydroxy, sulfo, sulfato, carboxy or phenyl; phenyl which is unsubstituted or substituted by CI-C 4 alkyl, C 1 -C 4 alkoxy, halogen, sulfo or carboxy; naphthyl which is unsubstituted or substituted by C-C 4 alkyl, C 1 -C 4 alkoxy, chloro, hydroxy, sulfo or carboxy; or benzyl which is unsubstituted or substituted in the phenyl ring by Cj-C 4 alkyl, C 1 -C 4 alkoxy, chloro or sulfo; and Z is P haloethyl, P-sulfatoethyl, P-thiosulfatoethyl, P-phosphatoethyl, p-acetoxyethyl or vinyl.
2. The process according to claim 1, wherein R 1 is hydrogen, methyl, ethyl, propyl, isopropyl, methoxy, ethoxy, chloro, hydroxy, sulfo or carboxy. IN:\.IBA]26207:TLT 12
3. The process according to either claim 1 or claim 2, wherein R 2 is hydrogen, methyl, ethyl, propyl, isopropyl, methoxy, ethoxy, chioro, hydroxy, sulfo or carboxy.
4. The process according to any one of claims 1 to 3, wherein X is the radical NR
5 R 6 wherein R 5 and R 6 are each independently of the other hydrogen; CI-C 4 alkyl which is unsubstituted or substituted by C 1 -C 4 alkoxy, chloro, hydroxy, sulfo, sulfato, carboxy or phenyl; phenyl which is unsubstituted or substituted by Cl-C 4 alkyl, C 1 C 4 alkoxy, halogen, sulfo or carboxy; naphthyl which is unsubstituted or substituted by Cl-C 4 alkyl, Ci-C 4 alkoxy, chloro, hydroxy, sulfo or carboxy; or benzyl which is unsubstituted or substituted in the phenyl ring by CI-C 4 alkyl, Cl-C 4 alkoxy, chloro or sulfo. The process according to claim 4, wherein R 5 is hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, j3-methoxyethyl, j3-hydroxyethyl, P3- sulfoethyl, P-sulfatoethyl or P-carboxyethyl.
6. The process according to claim 4, wherein R 6 is hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, P-methoxyethyl, P-hydroxyethyl, P3-4 sulfoethyl, f-sulfatoethyl or f-carboxyethyl.
7. The process according to claim 4, wherein R 5 is phenyl, 2-sulfophenyl, 3- sulfophenyl, 4-sulfophenyl, 2,4-disulfophenyl, 2,5-disulfophenyl, 2-carboxyphenyl, 3- carboxyphenyl or 4-carboxyphenyl. 20
8. The process according to claim 4, wherein R 6 is phenyl, 2-sulfophenyl, 3- sulfophenyl, 4-sulfophenyl, 2,4-disulfophenyl, 2,5-disulfophenyl, 2-carboxyphenyl, 3- :0"9 carboxyphenyl or 4-carboxyphenyl.
9. The process according to claim 4, wherein R 5 is 2-sulfo-1-naphthyl, 3-sulfo-1- "000 naphthyl, 4-sulfo-1-naphthyl, 5-sulfo-1-naphthyl, 6-sulfo-1-naphthyl, 7-sulfo-1-naphthyl, 8-sulfo-1-naphthyl, 1-sulfo-2-naphthyl, 5-sulfo-2-naphthyl, 6-sulfo-2-naphthyl, 7-sulfo-2- 00 naphthyl, 8-sulfo-2-naphthyl, 1,5-disulfo-2-naphthyl, 5,7-disulfo-2-naphthyl, 6,8-disulfo- 0: 2-naphthyl, 4,8-disulfo-2-naphthyl, 4,7-disulfo-2-naphthyl, 3, 8-disulfo-2-naphthyl, 4,6- *disulfo-2-naphthyl, 3 ,7-disulfo-2-naphthyl, 3 ,6-disulfo-2-naphthyl, 4,6, 8-trisulfo-1 0000naphthyl, 2,4, 7-trisulfo-1-naphthyl, 3,6, 8-trisulfo- 1-naphthyl, 4,6, 8-trisulfo-2-naphthyl, 0 30 1,5,7-trisulfo-2-naphthyl or 3,6,8-trisulfo-2-naphthyl.
The process according to claim 4, wherein R 6 is 2-sulfo-1-naplithyl, 3-sulfo-1- naphthyl, 4-sulfo-1-naphthyl, 5-sulfo-1-naphthyl, 6-sulfo- 1-naphthyl, 7-sulfo-1-naphthyl, 8-sulfo-1-naphthyl, 1-sulfo-2-naphthyl, 5-sulfo-2-naphthyl, 6-sulfo-2-naphthyl, 7-sulfo-2- naphthyl, 8-sulfo-2-naphthyl, 1 ,5-disulfo-2-naphthyl, 5 ,7-disulfo-2-naphthyl, 6, 8-disulfo- 2-naphthyl, 4,8-disulfo-2-naphthyl, 4,7-disulfo-2-naphthyl, 3, 8-disulfo-2-naphthyl, 4,6- disulfo-2-naphthyl, 3, 7-disulfo-2-naphthyl, 3 ,6-disulfo-2-naphthyl, 4,6, 8-trisulfo-l- naphthyl, 2,4,7-trisulfo-l-naphthyl, 3,6, 8-trisulfo-1-naphthyl, 4,6, 8-trisulfo-2-naphthyl, ,7-trisulfo-2-naphthyl or 3,6, 8-trisulfo-2-naphthyl.
11. The process according to claim 4, wherein R 5 is beuzyl, 2-sulfobenzyl, 3- 1 R~t 1 sulfobenzyl or 4-sulfobenzyl, IN:%LIBA]26207T-T 13
12. The process according to claim 4, wherein R 6 is benzyl, 2-sulfobenzyl, 3- sulfobenzyl or 4-sulfobenzyl.
13. The process according to claim 4, wherein one of the substituents R 5 and R 6 is C 1 -C 4 alkyl which is unsubstituted or substituted by C 1 -C 4 alkoxy, chloro, hydroxy, sulfo, sulfato, carboxy or phenyl; phenyl which is unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, sulfo or carboxy, naphthyl which is unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, chloro, hydroxy, sulfo or carboxy; or benzyl which is unsubstituted or substituted in the phenyl ring C 1 -C 4 alkyl, C 1 -C 4 alkoxy, chloro or sulfo, and the other substituent R 5 or R 6 is hydrogen, methyl or ethyl.
14. The process according to any one of claims 1 to 13, wherein A is phenylene which is unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen or sulfo.
The process according to any one of claims 1 to 13, wherein A is the group (CH 2 )a-NH-(CH 2 wherein a is an integer from 1 to 6 and b is an integer from 1 to 6.
16. The process according to any one of claims 1 to 15, where Z is the radical -CH 2 CH 2 OSO 3 H.
17. The process according to any one of claims 1 to 3, wherein X is pyridyl, 3- methylpyridyl, 3-P-hydroxyethylpyridyl, 4-p-sulfoethylpyridyl, 4-chloropyridyl, 3- sulfopyridyl, 2-carboxypyridyl, 3,5-dicarboxypyridyl or 2-carbamoylpyridyl, 3- carbamoylpyridyl, 4-carbamoylpyridyl, preferably 3-carboxypyridyl and 4- 20 carboxypyridyl. j oo'.
18. The process according to any one of claims 1 to 3, wherein B is oxygen or NH-.
19. The process according to claim 1, wherein R 1 is hydrogen or sulfo, R 2 is hydrogen, R 3 is hydrogen or ethyl, A is phenyl, B is -NH- or -CH 2 X is chloro, A 25 is a direct bond and Z is the radical -CH 2 CH 2 OSO 3 H. I
20. The process according to any one of claims 1 to 19, wherein the cellulosic fibre material is cotton. S21. A process for enhancing the sun protection factor of cellulosic fabrics, substantially as hereinbefore described with reference to any one of the Examples. 30 22. Cellulosic fabrics treated by the process of any one of claims 1 to
21. Dated 9 December, 1998 Ciba Specialty Chemicals Holding Inc. Patent Attorneys for the Applicant/Nominated Person S135 SPRUSON FERGUSON Use of Hydroxybenzotriazoles for Enhancing the Sun Protection Factor of Celullosic Fibre Materials Abstract The invention relates to the use of the compound of formula R1 R3 N-A-SO 2 -Z R2HO N for enhancing the sun protection factor of cellulosic fibre materials; wherein R 1 and R 2 are each H, alkyl; alkoxy; halogen; OH; nitro; sulfo or carboxy; R 3 is H; or unsubstituted or substituted alkyl; A is unsubstituted or substituted phenylene; unsubstituted or substituted naphthylene, or unsubstituted or substituted alkylene, and in which the 10 alkylene chain is interrupted from C 2 by O or wherein R' is hydrogen or alkyl, and may be branched from C 3 and R' is able to form a ring together with the alkylene chain; B is O; -N(R 4 wherein R 4 is H or alkyl, or -(CH 2 )n-NH- which is attached at the s triazine radical through the N atom, and in which n is 1 to 4; X is Cl; F; unsubstituted or substituted pyridyl; -NR 5 R 6 wherein R 5 and R 6 are each H, unsubstituted or substituted alkyl; unsubstituted or substituted phenyl; unsubstituted or substituted naphthyl; or unsubstituted or substituted benzyl; or -OR 7 wherein R 7 is H, unsubstituted or substituted alkyl; unsubstituted or substituted phenyl; unsubstituted or substituted naphthyl; or unsubstituted or substituted benzyl; and Z is P-haloethyl, 3-sulfatoethyl, t t [p-thiosulfatoethyl, p-phosphatoethyl, -acetoxyethyl or vinyl. C e
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH295294 | 1994-09-29 | ||
| CH2952/94-1 | 1994-09-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU3294595A AU3294595A (en) | 1996-04-18 |
| AU701586B2 true AU701586B2 (en) | 1999-02-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU32945/95A Ceased AU701586B2 (en) | 1994-09-29 | 1995-09-28 | Use of hydroxybenzotriazoles for enhancing the sun protection factor of cellulosic fibre materials |
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| AU (1) | AU701586B2 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03239759A (en) * | 1990-02-17 | 1991-10-25 | Nippon Paint Co Ltd | Metallized paper for label and coating composition used for producing the same |
| JPH03241069A (en) * | 1990-02-15 | 1991-10-28 | Sumitomo Chem Co Ltd | Hydroxybenzotriazole compound and dyed fiber material, containing the same fixed thereto and fast to perspiration and light |
-
1995
- 1995-09-28 AU AU32945/95A patent/AU701586B2/en not_active Ceased
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03241069A (en) * | 1990-02-15 | 1991-10-28 | Sumitomo Chem Co Ltd | Hydroxybenzotriazole compound and dyed fiber material, containing the same fixed thereto and fast to perspiration and light |
| JPH03239759A (en) * | 1990-02-17 | 1991-10-25 | Nippon Paint Co Ltd | Metallized paper for label and coating composition used for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| AU3294595A (en) | 1996-04-18 |
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