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GB2291644A - Ultraviolet absorbing agents - Google Patents

Ultraviolet absorbing agents Download PDF

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Publication number
GB2291644A
GB2291644A GB9514407A GB9514407A GB2291644A GB 2291644 A GB2291644 A GB 2291644A GB 9514407 A GB9514407 A GB 9514407A GB 9514407 A GB9514407 A GB 9514407A GB 2291644 A GB2291644 A GB 2291644A
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Prior art keywords
formula
compound
group
textile
weight
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Granted
Application number
GB9514407A
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GB2291644B (en
GB9514407D0 (en
Inventor
Jean-Pierre Bacher
Werner Kaufmann
Dieter Reinehr
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Novartis AG
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Ciba Geigy AG
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Priority claimed from GB9414881A external-priority patent/GB9414881D0/en
Priority claimed from GB9417562A external-priority patent/GB9417562D0/en
Application filed by Ciba Geigy AG filed Critical Ciba Geigy AG
Priority to GB9514407A priority Critical patent/GB2291644B/en
Publication of GB9514407D0 publication Critical patent/GB9514407D0/en
Publication of GB2291644A publication Critical patent/GB2291644A/en
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Publication of GB2291644B publication Critical patent/GB2291644B/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C235/18—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having at least one of the singly-bound oxygen atoms further bound to a carbon atom of a six-membered aromatic ring, e.g. phenoxyacetamides
    • C07C235/20—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having at least one of the singly-bound oxygen atoms further bound to a carbon atom of a six-membered aromatic ring, e.g. phenoxyacetamides having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
    • C07C237/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C237/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C237/08—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atom of at least one of the carboxamide groups bound to an acyclic carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
    • C07D251/42—One nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
    • C07D251/42—One nitrogen atom
    • C07D251/44—One nitrogen atom with halogen atoms attached to the two other ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
    • C07D251/48—Two nitrogen atoms
    • C07D251/50—Two nitrogen atoms with a halogen atom attached to the third ring carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
    • C07D251/54—Three nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • 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
    • D06M13/10—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 oxygen
    • D06M13/12—Aldehydes; Ketones
    • 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
    • D06M13/352—Heterocyclic compounds having five-membered heterocyclic rings
    • 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
    • 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
    • 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
    • D06P1/651—Compounds without nitrogen
    • D06P1/65106—Oxygen-containing compounds
    • D06P1/65112—Compounds containing aldehyde or ketone groups
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/25—Resistance to light or sun, i.e. protection of the textile itself as well as UV shielding materials or treatment compositions therefor; Anti-yellowing treatments

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

New compounds which are useful as ultraviolet absorbing agents (UVAs) may be used for improving the sun protection factor (SPF) of textile fibre material.

Description

Compounds having ultra-violet absorption properties The present invention relates to new compounds which are useful as ultraviolet absorbing agents (UVAs) and to a method of improving the sun protection factor (SPF) of textile fibre material treated with the new compounds.
It is known that light radiation of wavelengths 280-400 nm permits tanning of the epidermis. Also known is that rays of wavelengths 280-320 nm (termed UV-B*radiation), cause erythemas and skin burning which can inhibit skin tanning.
Radiation of wavelengths 320-400 nm (termed UV-A radiation) is known to induce skin tanning but can also cause skin damage, especially to sensitive skin which is exposed to sunlight for long periods. Examples of such damage include loss of skin elasticity and the appearance of wrinkles, promotion of the onset of erythemal reaction and the inducement of photo toxic or photoallergic reactions.
Any effective protection of the skin from the damaging effects of undue exposure to sunlight clearly needs to include means for absorbing both UV-A and UV-B components of sunlight before they reach the skin surface.
Traditionally, protection of exposed human skin against potential damage by the UV components in sunlight has been effected by directly applying to the skin a preparation containing a UV absorber. In areas of the world, e.g. Australia and America, which enjoy especially sunny climates, there has been a great increase in the awareness of the potential hazards of undue exposure to sunlight, compounded by fears of the consequences of alleged damage to the ozone layer. Some of the more distressing embodiments of skin damage caused by excessive, unprotected exposure to sunlight are development of melanomas or carcinomas on the skin.
One aspect of the desire to increase rhe level of skin protection against sunlight has been the consideration of additional measures, over and above the direct protection of the skin.
For example, consideration has been given to the provision of protection to skin covered by clothing and thus not directly exposed to sunlight.
Most natural and synthetic textile materials are at least partially permeable to UV components of sunlight. Accordingly, the mere wearing of clothing does not necessarily provide skin beneath the clothing with adequate protection against damage by UV radiation. Although clothing containing a deeply coloured dye and/or having a tight weave texture may provide a reasonable level of protection to skin beneath it, such clothing is not practical in hot sunny climates, from the standpoint of the personal comfort of the wearer.
There is a need, therefore, to provide protection against UV radiation for skin which lies underneath clothing, including lightweight summer clothing, which is undyed or dyed only in pale shades. Depending on the nature of the dyestuff, even skin beneath clothing dyed in some dark shades may also require protection from UV radiation.
Such lightweight summer clothing normally has a density. of of less than 200 g/m2 and has a sun protection factor rating between 1.5 and 20, depending on the type of fibre from which the clothing is manufactured.
The SPF rating of a sun protectant (sun cream or clothing) may be defined as the multiple of the time taken for the average person wearing the sun protectant to suffer sun burning under average exposure to sun. For example, if an average person would normally suffer sun burn after 30 minutes under standard exposure conditions, a sun protectant having an SPF rating of 5 would extend the period of protection from 30 minutes to 2 hours and 30 minutes. For people living in especially sunny climates, where mean sun burn times are minimal, e.g. only 15 minutes for an average fair-skinned person at the hottest time of the day, SPF ratings of at least 20 are desired for lightweight clothing.
It is already known, e.g. from WO 94/4515, that the application of specified types of UVA to a light-weighr textile materials in general can effect an increase in the SPF value of the textile so treated. The increase in SPF value achieved thereby, however, is relatively modest.
Certain new compounds have now been found which can be readily produced and which, unexpectedly, impart greatly increased SPF ratings to textile fibre materials treated with the new compounds.
Accordingly, the present invention provides a compound having the formula:
in which m is 1 or 2; A is a residue selected from those having the formulae:
in which R is phenyl, optionally substituted by 1 or 2 C1-C4alkyl groups, preferably tolyl or xylyl, or by I or 2 C1-C18alkoxy groups, or R is a group having the formula:
X is F, Cl or NHCH2OH and X1 is F, Cl. NHCH20H or a group having the formula:
-8 CO2-C1-C4aIkyI -B B --C(=O)-C,-C4alkyl
B is -O-, -NH- or -SO2-, and D is a group having one of the formulae::
CH2-C(=O) -NH( CH2OH), CH2-C(=O)-N(CH2OH)2 or -CH2CH2-OS03M in which M is hydrogen, sodium, potassium, calcium, magnesium, ammonium, mono-, di-, tri- or tetra-Cl-C4alkylammonium or ammonium that is di- or tn-substituted by a mixture of C1-C4alkyl and C1-C4hydroxyalkyl groups, preferably sodium, or, when A is a residue of formula (5) or (6), D may also be a group of formula:
B 3CO2-Cr-C4alkyl
in which B and M have their previous significance and n is 0 or 1, provided that at least one S03M group is present, or the formula:
in which X, X1 and M have their previous significance; provided that the following compounds are excluded: a) those in which A is a residue of formula (2), (3) or (4), B is -0- and D is a group of formula
CH2-C(=O)-NH(CH20H) or CH2-C(=O)-N(CH2OH)2; b) the compound 4-glycidyloxy-2-hydroxy benzophenone; and c) the compound 2-(2-hydroxy-4-glycidyloxy)-4,6-(2,4-dimethylphenyl)-1,3,5-triazine.
Preferred compounds of formula (1) include those having one of the formulae:
in which R has its previous significance and D1 is a group having the formula
CN2-C(=O)-NN(CH2OH) or CH2-C(=O)-N(CH2OH)2;
in which D1 has its previous significance;
in which D1 has its previous significance; ;
SO3M (io > B NYN xlNJJ\ N B CQ.C1-C4a!kyl SO3M (11) B or NN or X1 N)\ B -- CO-C1 -C4aIkyI SO2CH2CH2OSO3M B (12) NN X l N C02-C l-C,alkyl in which X is F or Cl and B and M have their previous significance and in which preferably X is C1, B is NH and M is Na;
in which n has its previous significance, provided that at least one group -SO3M is present, X is F or C1 and X1 is F, C1 or a group having one of the formulae::
B 9 CO2-CI-C4alkyl C(=O).C1 -C4aikyI
in which B and M have their previous significance;
in which each X is the same and is F or C1 and each X1 is the same and is F, Cl or a group having one of the formulae:
Q < 3 CO2-Cl-C4alkyl C(=Q)-C1 -C4aIkyI
in which B and M have their previous significance, or
in which M has its previous significance but is preferably Na.
The compounds of formula (1) may be produced by reacting, under known reaction conditions, a compound of formula A-(BH)m in which A, B and m have their previous significance, with m moles of a compound L-D, in which D has its previous significance and L is a leaving group or atom, preferably a halogen atom, especially a chlorine atom.
The starting materials A-(BH)m and L-D are known compounds which are readily available.
The present invention also provides a method for the treatment of a textile fibre material, comprising treating the textile fibre material with 0.05 to 3.0% by weight, based on the weight of the textile fibre material, of one or more compounds having the formula (1).
The textile fibres treated according to the method of the present invention may be natural or synthetic fibres or mixtures thereof. Examples of natural fibres include vegetable fibres such as cotton, viscose, flax, rayon or linen, preferably cotton and animal fibres such as wool, mohair, cashmere, angora and silk, preferably wool. Synthetic fibres include polyester, polyamide and polyacrylonitrile fibres.
Preferably, textile fibres treated according to the method of the present invention have a density of less than 200 g/m2 and have not been previously dyed in deep shades.
Some of the compounds of formula (1) used in the method of the present invention may be only sparingly soluble in water and may need to be applied in dispersed form. For this purpose, they may be milled with an appropriate dispersant, conveniently using quartz balls and an impeller, down to a particle size of 1-2 microns.
As dispersing agents for such sparingly-soluble compounds of formula (1) there may be mentioned: - acid esters or their salts of alkylene oxide adducts, e.g., acid esters or their salts of a polyadduct of 4 to 40 moles of ethylene oxide with 1 mole of a phenol, or phosphoric acid esters of the adduct of 6 to 30 moles of ethylene oxide with 1 mole of 4-nonylphenol, 1 mole of dinonylphenol or, especially, with 1 mole of compounds which have been produced by the addition of 1 to 3 moles of styrenes on to 1 mole of phenol; - polystyrene sulphonates; - fatty acid taurides; - alkylated diphenyloxide-mono- or -di-sulphonates; - sulphonates of polycarboxylic acid esters;; - addition products of 1 to 60, preferably 2 to 30 moles of ethylene oxide and/or propylene oxide on to fatty amines, fatty amides, fatty acids or fatty alcohols, each having 8 to 22 carbon atoms, or on to tri- to hexavalent C3-C6alkanols, the addition products having been converted into an acid ester with an organic dicarboxylic acid or with an inorganic polybasic acid; - lignin sulphonates; and, in particular formaldehyde condensation products, e.g., condensation products of lignin sulphonates and/or phenol and formaldehyde; condensation products of formaldehyde with aromatic sulphonic acids, e.g., condensation products of ditolylethersuiphonates and formaldehyde; condensation products of naphthalenesulphonic acid and/or naphthol- or naphthylaminesulphonic acids and formaldehyde; condensation products of phenolsulphonic acids and/or sulphonated dihydroxydiphenylsulphone and phenols or cresols with formaldehyde and/or urea; or condensation products of diphenyloxide-disulphonic acid derivatives with formaldehyde.
Depending on the type of compound of formula (1) used, it may be beneficial toNc'arIy out the treatment in a neutral, alkaline or acidic bath. The method is usually conducted in the temperature range of from 20 to 140"C.,for example at or near to the boiling point of the aqueous bath, e.g. at about 90"C.
Solutions of the compound of formula (1), or its emulsions inorganic solvents may also be used in the method of the present invention. For example, the so-called solvent dyeing (pad thermofix application) or exhaust dyeing methods in dyeing machines may be used.
If the method of the present invention is combined with a textile treatment or finishing method, such combined treatment may be advantageously carried out using appropriate stable preparations which contain the compound of formula (1) in a concentration such that the desired SPF improvement is achieved.
In certain cases, the compound of formula (1) is made fully effective by an after-treatment. This may comprise a chemical treatment such as treatment with an acid, a thermal treatment or a combined thermal/chemical treatment.
It is often advantageous to use the compound of formula (1) in admixture with an assistant or extender such as anhydrous sodium sulfate, sodium sulfate decahydrate, sodium chloride, sodium carbonate, an alkali metal phosphate such as sodium or potassium orthophosphate, sodium or potassium pyrophosphate or sodium or potassium tripolyphosphate, or an alkali metal silicate such as sodium silicate.
In addition to the compounds of formula (1), a minor proportion of one or more adjuvants may also be employed in the method of the present invention. Examples of adjuvants include emulsifiers, perfumes, colouring dyes, opacifiers, optical whitening agents, bactericides, nonionic surfactants, fabric care ingredients, especially fabric softeners, stain release or stain repellant ingredients or water-proofing agents, anti-gelling agents such as nitrites or nitrates of alkali metals, especially sodium nitrate, and corrosion inhibitors such as sodium silicate.
The amount of each of these optional adjuvants should not exceed 1% by weight on the treated fibre.
The method of the present invention, in addition to providing protection tQ the skin, also increases the useful life of a textile article treated according to the present invention. In particular, the tear resistance and/or lightfastness of the treated textile fibre material may be improved.
Accordingly, the present invention still further provides a method of increasing the SPF rating of textile fibre material, comprising treating the textile fibre material with 0.05 to 3.0% by weight, based on the weight of the textile fibre material, of one or more compounds having the formula (1).
The present invention also provides a textile fabric produced from a fibre treated according to the method of the present invention as well as an article of clothing produced from the said fabric.
Such textile fabrics and articles of clothing produced from the said fabrics typically have an SPF rating of 20 and above whereas untreated cotton, for example, generally has an SPF rating of from 2 to 4.
The following Examples further illustrate the present invention.
Example 1
13.1 g. of 2-(2,4-dihydroxyphenyl)-4,6-diphenyl-1,3,5-triazine are stirred with 7.3 g. of potassium carbonate and 100 ml. of epichlorhydrin over 5 hours at 1 100C. After cooling the reaction mixture to 250C. and diluting it with 150 mls. of ethanol, the product which is thereby precipitated is filtered off, washed and dried in vacuum at 80"C. The compound (101) having the above structure is obtained in a yield corresponding to 88.1 % of the theoretical yield and has the following elemental analysis by weight: Analysis for C27H19N303: Req.% C 72.53; H 4.82; N 10.57 Found % C 72.3; H 4.9; N 10.4.
Example 2
Using the procedure described in Example 1, but employing 2-(2,4-dihydroxyphenyl)-4,6-di(4'-2'-ethylhexoxy)phenyl-1,3,5-triazine instead of 2-(2,4-dihydroxyphenyl)-4,6-diphenyl-1,3,5-triazine. compound (102) is obtained in a yield of 86.3 % of the theoretical and has the following elemental analysis by weight: Analysis for C40H51N305: Req.% C 73.78; H 7.86; N 6.43 Found % C 73.3; H 8.05; N 6.13.
Example 3
Using the procedure described in Example 1, but employing 2-(2,4-dihydroxyphenyl)-4 ,6-di(4'-dodecoxy)phenyl- 1,3,5 -triazine instead of 2-(2,4-dihydroxyphenyi)-4,6-diphenyl- 1,3,5-rriazine, compound (103) is obtained in a yield of 86.3 % of the theoretical and has the following elemental analysis by weight: Analysis for C48H67N305: Req.% C 75.26; H 8.82; N 5.49 Found % C 75.1; H 8.8; N 5.5.
Example 4
Using the procedure described in Example 1, but employing 2-(2,4-dihydroxyphenyl)-4,6-dixylyl-1,3,5 -triazine instead of 2-(2,4-dihydroxyphenyl)-4,6-diphenyl-1t3Z5-triazine} compound (104) is obtained in a yield of 85 % of the theoretical and has the fol]owing elemental analysis by weight: Analysis for C28H27N3O3: Req.% C 74.15; H 6.00 N 9.26 Found % C 74.3; H 6.2; N 9.3.
Compound (104) is known having been described in Example 6 of EP 526399.
Example 5
A) A mixture of 28.5 g. 2-(2,4-dihydroxyphenyl)-4,6-diphenyl-1 ,3,5-triazine, 9.4 g.
potassium hydroxide, 31.2 g. chloracetamide and 650 mls. ethanol is stirred at 700C. for 16 hours. After cooling, the precipitate is filtered off, washed with water and recrystallised twice from methylcellosolve.
17.5 g. of a light beige product (105a) are obtained in a yield corresponding to 52.5 % of the theoretical yield. The product has the following elemental analysis by weight: Analysis for C23H18N4O3: Req.% C 67.73; H 4.66; N 13.74 Found % C 67.9; H 4.7; N 13.6.
B) 8 g. of the compound (105a) are stirred in 250 mls. of dimethylacetamide and the mixture is rendered alkaline by the addition of 5 drops of 30 % caustic soda solution. After the addition of 20 mls. of a 36 % formalin solution, the reaction mixture is heated to 700C.
and stirred for 4 hours at this temperature. The reaction solution is poured into 1.5 litres of water and the resulting solid product is filtered off. After recrystallisation from dioxan, there are obtained 4.8 g. of a light yellow product, corresponding to a yield of 56 % of the theoretical. The product (105b) has the following elemental analysis by weight: Analysis for C27H20N404. 0.33 H2O: Req.% C 66.30; H 4.75; N 12.89 Found % C 66.3; H 4.9; N 12.7.
Example 6
Using the procedure described in Example 5, but employing 2,4-dihydroxybenzophenone instead of 2-(2,4-dihydroxyphenyl)-4,6-diphenyl. 1 ,3,5-uriazine, compound (106) is obtained in a yield of 56 % of the theoretical and has the following elemental analysis by weight: Analysis for C16H15N05.0.55 H2O: Req.% C 58.4; H 4.9; N 4.26; H20 2.99 Found % C 58.4; H 5.5; N 4.1; H20 2.99.
Example 7
6.3 g. of the compound of formula:
are dissolved in 150 mls. of water at 60 C. and treated with 10 drops of 30 % caustic soda solution. After the dropwise addition of 32.4 g. of a 37 % formaldehyde solution, and subsequent stirring at 60-650C. over 2.5 hours, 150 mls. of salt solution are added and the mixture is cooled to 10 C. The reaction mixture is filtered giving 7 g. of a solid product, corresponding to a yield of 93 % of the theoretical.
The product (107) has the following elemental analysis by weight: Analysis for C27H26N12Na2O10S2.l C2H5OH. 7.5H20: Req.% C 33.47; H 4.93; N 18.00; S 6.87; Na 4.93 Found % C33.4; H4.7; N 17.5; S 6.7; Na 5.0 Example 8
3.4 g. of cyanuric chloride are stirred in a mixture of 100 mls of acetone and 50 mls of water The mixture is chilled to -10 C. and a solution of 5.5 g. of 4-aminostilbene-2-suIfonic acid sodium salt in 50 mls of water is added over 30 minutes, followed by 10 mls of 1M sodium carbonate solution.
The resulting mixture is stirred for 2 hours at -5 to -10 C. and the solid is filtered off and dried, giving 6.8 g. of a white product corresponding to a yield of 74% of theory.
The compound (108) has the following elemental analysis by weight: Analysis for Cl7HllCl2N4NaO3S. 1.26 H2O: Req.% C 43.63; H 2.91; N 11.97; S 6.85; Cl 15.15; H2O 4.85 Found % C 43.7; H 3.0; N 12.0; S 6.8; Cl 15.0.; H20 4.85.
Example 9
Using the same procedure as in Example 8 but replacing 4-aminostilbene-2-sulfonic acid by 4-aminostilbene-2,2'-disulfonic acid disodium salt, 15.1 g. of the compound of formula (109) are obtained, corresponding to a yield of 55% of theory.
The compound (109) has the following elemental analysis by weight: Analysis for C17H10Cl2N4Na206S2. 4.63 H20: Req.% C 32.37; H 3.03; N 8.88; S 10.17; Cli 11.24; H2O 13.22 Found % C 32.4; H 3.0; N 8.9; S 10.0; Cli 11.5.; H2O 13.23.
Example 10
A) Using the procedure described in Example 8, prior to the filtration step, Compound (108) is produced as a white dispersion.
B) To this dispersion there are added 3 g. of 4-amino-ethylbenzoate, as a solid, followed by 10 mls of 1M sodium carbonate solution. The resulting pale yellow suspension is stirred for 18 hours at 250C. and the solid product is filtered off and dried, giving 8.6 g. of the white compound of formula (110), corresponding to a yield of 83% of theory.
The compound (110) has the following elemental analysis by weight: Analysis for C26H21ClN5NaOsS. 3.84 H2O. 0.14 NaCI: Req.% C 47.9; H 4.4; N 10.75; S 4.9; Cl 6.21; H2O 10.61 Found % C 47.9; H 4.4; N 10.8; S 4.8; Cl 6.5.; H2O 10.76.
Example 11
A) Using the procedure described in Example 8, prior to the filtration step, Compound (108) is produced as a white dispersion.
B) The procedure described in part B) of Example 10 is repeated except that 4-amino-ethylbenzoate is replaced by 4-amino-acetophenone. In this way, 4.8 g. of the white compound of formula (111) are produced, corresponding to a yield of 49% of theory.
The compound (111) has the following elemental analysis by weight: Analysis for CH19ClN5NaO4S. 3.96 H20. 0.16 NaCl: Req.% C 48.0; H 4.31; N 11.2; S 5.12; C1 6.59; H2O 1 1.40 Found % C 48.0; H 4.4; N 11.3; S 5.1; Cl 6.4.; H20 11.42.
Example 12
A) Using the procedure described in Example 9, prior to the filtration step, Compound (109) is produced as a dispersion.
B) The procedure in part B) of Example 10 is used for the reaction of the compound of formula (109) with 4-amino-ethylbenzoare to obtain 31.9 g. of the yellow compound (112), corresponding to a yield of 78.6% of theory.
The compound (112) has the following elemental analysis by weight: Analysis for C26H20ClN5Na2O8S2 6 H20. 0.5 NaCI: Req.% C 38.4; H 3.94; N 8.6; S 7.8; Cl 6.5; H20 13.28 Found % C 38.9; H 3.9; N 9.2; S 7.7; Cl 6.6.; H20 12.67.
Example 13
The procedure in Example 12 is repeated except that, in part B), 4-amino-acetophenone is used instead of 4-amino-ethylbenzoate. In this way, 6.3 g. of compound (113) are obtained, corresponding to a yield of 49% # of theory.
The compound (113) has the following elemental analysis by weight: Analysis for C25H18ClN5Na2O7S2. 4.61 H20.: Req.% C 41.19; H 3.76; N 9.61; S 8.80: Cl4.86; H2O 11.39 Found % C41.4; H3.8; N9.7; S 8.6; Cl 5.3.;H2O 11.39.
Example 14
The procedure in Example 12 is repeated except that, in part B), 2-amino-pyrimidine is used instead of 4-amino-ethylbenzoate. In this way, 9.2 g. of compound (114) are obtained, corresponding to a yield of 61% of theory.
The compound (114) has the following elemental analysis by weight: Analysis for C21H14ClN7Na206S2. 6 h'2O 0.33 NaCI: Req.% C 34.37; H 3.55; N 13.37; S 8.7; Cl 6.4; H2O 14.7 Found % C 34.4; H 3.6; N 13.9; S 8.5; Cl 6.3.; H20 15.1.
Example 15
The procedure in Example 12 is repeated except that, in part B), sulfanilic acid is used instead of 4-amino-ethylbenzoate. In this way, 16.9 g. of compound (115) are obtained, corresponding to a yield of 57.9% of theory.
The compound (115) has the following elemental analysis by weight: Analysis for C25H15ClN5Na3O9S3 10.67 H20. 3.5 NaCI: Req.% C 25.7; H 3.11; N 6.0; S 8.22; Cl 13.7; H20 16.45 Found % C 25.7; H 3.2; N 6.5; S 8.5; Cl 13.7.; H20 16.4.
Example 16
The procedure in Example 12 is repeated except that, in part B), 2-(4-aminophenylsulfonyl)-ethylhydrogen sulfate is used instead of 4-aminoethylbenzoate. In this way, 19.5 g. of compound (116) are obtained, corresponding to a yield of 60% of theory.
The compound (116) has the following elemental analysis by weight: Analysis for C25H21ClN5Na3O12S4. 8 H20. 0.41 Na2SQ4: Req.% C 29.50; H 3.63; N 6.88; S 13.86; Cl 3.49; H2O 14.15 Found % C 29.5; H 3.50; N 7.0; S 13.7; Cl 3.7.; H2Q 14.38.
Example 17
Using the procedure described in Example 8, 18.4 g. of cyanuric chloride are stirred in a mixture of 120 mls of acetone and 100 mls of water. The mixture is chilled to -100C. and a solution of 25.4 g. of 4.4'-diaminostilbene-2,2'-disulfonic acid disodium salt in 50 mls of water is added over 30 minutes1 followed by 50 mls of 1M sodium carbonate solution.
The resulting mixture is stirred for 2 hours at -5 to -100C. and the solid is filtered off and dried, giving 24.1 g. of a white product corresponding to a yield of 67.9% of theory.
The compound (117) has the following elemental analysis by weight: Analysis for C210Cl4N8Na206S2. 5 H2O: Req.% C 30.01; H 2.51; N 14.00; S 8.01; Cl 17.62; Found % C 30.0; H 2.6; N 14.0; S 7.8; Cl 17.6..
Example 18
To the white suspension of the compound of formula (117) obtained in Example 17, prior to the filtration step, there is added 4-amino-ethylbenzoate in the manner described in Example 10.
In this way, 44.5 g. of compound (118) are obtained, corresponding to a yield of 92% of theory.
The compound (118) has the following elemental analysis by weight: Analysis for C38H30Cl2N10Na2O10S2 6.5 H2O. 1 NaCl: Req.% C 40.0; H 3.77; N 12.28; Cl 9.34; H2O 10.26 Found % C 40.0; H 3.8; N 12.3; Cl 9.2.; H20 10.0.
Example 19
Using the procedure described in Example 18 but replacing 4-amino-ethylbenzoate by 4-amino-acetophenone, 29.1 g. of compound ( 19) are obtained, corresponding to a yield of 94.6% of theory.
The compound (119) has the following elemental analysis by weight: Analysis for C36H26Cl2N10Na208S2. 16 H20. 0.6 NaCl: Req.% C 35.15; H 4.71; N 11.38; Cl 7.50; S 5.20; H2O 10.26 Found % C 35.1; H 4.8; N 11.5; Cl 7.7.; S 5.2; H2O 23.5.
Example 20
Using the procedure described in Example 18 but replacing 4-amino-ethylbenzoate by 2(4-aminophenylsulfonyl)-ethylhydrogensulfate, 46.2 g. of compound (120) are obtained, corresponding to a yield of 73.1 % of theory.
The compound (120) has the following elemental analysis by weight: Analysis for C36H30Cl2N10Na4O18S6-12.05 H2O. 18.2 NaCl: Req.% C 17.10; H 2.14; N 5.53; S 7.59; Cl 28.33; H2O 8.58 Found % C 17.1; H 2.1; N 5.6;57.5; Cl 28.6; H20 8.58.
Example 21
Using the procedure described in Example 18 but replacing 4-amino-ethylbenzoate by 4-aminopyrimidine, 16.4 g. of compound (121) are obtained, corresponding to a yield of 79% of theory.
The compound (121) has the following elemental analysis by weight: Analysis for C26H18C12N14Na206S2. 7.3 H2O. 0.7 NaCI. 1 CH3COCH3: Req.% C 33.42; H 3.75; N 18.85; Cl 9.20; S 6.15 Found % C 33.3; H 3.5; N 19.0; Cl 9.3; S 6.1.
Example 22
Using the procedure described in Example 8 but replacing 4-amino-stilbene-2-sulfonic acid sodium salt by a mixture of sulfanilic acid and 4-aminoethylbenzoate, in the required stoichiometric proportions, 41 g. of the compound of formula (122) are obtained, corresponding to a yield of 87% of theory.
The compound (122) has the following elemental analysis by weight: Analysis for Cl8HI5ClNsNaOsS. 3.67 H20: Req.% C 40.19; H 4.19; N 13.02; Cl 6.59; S 5.96; H20 12.29 Found % C 40.4; H 4.2; N 13.1; Cl 6.59; S 6.1; H20 12.3.
Example 23
Using the procedure described in Example 8 but replacing 4-amino-stilbene-2-sulfonic acid sodium salt by a mixture of sulfanilic acid and 4-aminoacetophenone, in the required stoichiometric proportions, 20.1 g. of the compound of formula (123) are obtained, corresponding to a yield of 91% of theory.
The compound (123) has the following elemental analysis by weight: Analysis for Cl7Hl3CINsNaO4S. 4 H2O. 0.25 NaCI: Req.% C 38.64; H 3.97; N 13.24; Cl 8.38; S 6.06; H20 13.62 Found % C39.1; H4.0; N 13.5; Cl 8.6; S 6.0; HXO 13.31.
Example 24
Using the procedure described in Example 8 but replacing 4-amino-stilbene-2-sulfonic acid sodium salt by a mixture of 2-(4-aminophenylsulfonyl)ethylhydrogen sulfate and 4-amino-ethylbenzoate, in the required stoichiometric proportions, 9.3 g. of the compound of formula (124) are obtained, corresponding to a yield of 73% of theory.
The compound (124) has the following elemental analysis by weight: Analysis for C20H19ClN5NaO8S2. 3.5 H20. 4.5 NaCI: Req.% C 25.40; H 2.75; N 7.41; S 6.77; H2Q 6.60 Found % C 25.4; H 2.6; N 7.4; S 6.2; H20 6.5.
Example 25
Using the procedure described in Example 8 but replacing 4-amino-stilbene-2-sulfonic acid sodium salt by a mixture of 2-amino-pyrimidine and sulfanilic acid, in the required stoichiometric proportions, 17.2 g. of the compound of formula (125) are obtained, corresponding to a yield of 86% of theory.
The compound (125) has the following elemental analysis by weight: Analysis for Cl3H9ClN7NaO3S. 4.55 H2Q: Req.% C 32.28; H 3.77; N 20.27; S 6.63; Cl 7.33; H20 16.95 Found % C 32.3; H 3.8; N 20.3; S 6.5; Cl 7.5; H2O 16.93.
Example 26
Using the procedure described in Example 8 but replacing 4-amino-stilbene-2-sulfonic acid sodium salt by a mixture of 2-(4-aminophenylsulfonyl)ethylhydrogen sulfate and 4-aminoacetophenone, in the required stoichiometric proportions, 8.9 g. of the compound of formula (126) are obtained, corresponding to a yield of 83% of theory.
The compound (126) has the following elemental analysis by weight: Analysis for C18H17ClN5NaO7S2. 3.38 H20: Req.% C 36.10; H 4.00; N 11.70; S 10.71; Cl 5.92; H20 10.17 Found % C 37.0; H 4.1; N 11.8; S 10.3; Cl5.8; H2O 10.18.
Example 27
Using the procedure described in Example 8, compound (127) is prepared and has the following elemental analysis by weight: Analysis for C20HI8ClNaO6S. 1.83 H20. 0.8 NaCI: Req.% C 41.31; H 3.78; N 9.64; S 5.51; Cl 11.00; H20 5.68 Found % C 41.3; H 3.7; N 9.6; S 5.3; Cl 11.7; H20 6.03.
Example 28
Using the procedure described in Example 8, compound (128) is prepared and has the following elemental analysis by weight: Analysis for C18H12ClNaO6S. 4 H20. 3.35 NaCI: Req.% C 29.23; H 2.71; N 7.58; S 4.33; Cl 20.9; H20 9.37 Found % C 29.2; H 2.7; N 7.6; S 4.3; Cl 17.3; H20 9.76.
Example 29
Using the procedure described in Example 18, compound (129) is prepared and has the following elemental analysis by weight: Analysis for C3sH24C12N8Na2012S2. 11.69 H20: Req.% C 38.80; H 4.06; N 9.53; S 5.45; Cl 6.03; H20 17.90 Found % C38.2; H4.0; N9.4; S5.3; Cl6.2; H2O 17.91.
Example 30
Using the procedure described in Example 18, compound (130) is prepared and has the following elemental analysis by weight: Analysis for C34H26Cl2NIoNa2Oss2 7.60 H2O: Req.% C 40.01; H 4.07; N 13.72; S 6.28; Cl 6.95; H20 13.42 Found % C 41.1; H 3.8; N 14.3; S 5.8; Cl 7.5; H20 13.41.
Examples 31 to 33 Separate samples of bleached cotton cretonne are foularded (80% liquor uptake) with an aqueous bath containing: 2 g/l 40% acetic acid 250 g/l product of Example 1, 3 or.4 to provide a concentration of 1% by weight of active ingredient on the cotton substrate.
As the product of Example 1, 3 or 4 is insoluble in water, it is added as a 5% (w/w) aqueous dispersion which is obtained by milling 5% of the product of Example I, 3 or 4 and 1% of Pluronic F 108 (polypropylene glycol containing 80% ethylene oxide) in the presence of glass beads in deionised water.
The foularding is conducted at either alkaline pH (pH adjusted to 10-11 with soda) or at acidic pH (pH adjusted to 4-4.5 with acetic acid). Drying of the treated cotton samples is effected at 800C. for two minutes, followed by thermofixing for one minute at 1700C.
The Sun Protection Factor (SPF) is determined by measurement of the UV light transmitted through the swatch, using a double grating spectrophotometer fitted with an Ulbricht bowl. Calculation of SPF is conducted as described by B.L.Diffey and J.Robson in J. Soc. Cosm. Chem. 40(1989), pp. 1 j0-]31.
In order to evaluate the wash fastness of the treated cotton samples, respective samples are washed once, five times or ten times in an aqueous bath containing 7g/1 of a standard ECE detergent having the composition (weight %): 8.0% Sodium alkylbenzene sulfonate 2.9% Tallow alcohol-tetradecane-ethylene glycol ether (14 mols EO) 3.5% Sodium soap 43.8% Sodium tripolyphosphate 7.5% Sodium silicate 1.9% Magnesium silicate 1.2% Carboxymethyl cellulose 0.2% EDTA 21.2% Sodium sulfate Water to 100%.
Each wash is conducted at 600C. for 15 minutes at a liquor ratio of 1:10.
The results obtained are set out in the following Table 1.
Table 1
Treatment SPF Example Test UVA alkaline/ number of washes acidic none one five ten - none (control) acidic 4.2 4.2 31 cpd. of Ex.1 alkaline 41 47 31 35 alkaline 46 53 53 51 32 cpd. of Ex.4 acidic 42 42 60 59 33 cpd. of Ex.3 acidic 38 - - 44 Example 34 Separate samples of bleached cotton cretonne are foularded (80% liquor uptake) with an aqueous bath containing: 2 g/l 40% acetic acid 12.5 g/l product of Example 2 to provide a concentration of 1% by weight of active ingredient on the cotton substrate.
As the product of Example 2 is insoluble in water, it is added as a 100% (w/w) aqueous dispersion which is obtained by milling 100% of the product of Example 2 and 1% of Pluronic F 108 in the presence of glass beads in deionised water.
The remaining procedure is as described in Examples 31 to 33.
The results obtained are set out in the following Table 2.
Table 2
Treatment SPF Example Test UVA alkaline! number of washes acidic none one five ten - none (control) acidic 5.4 5.4 5.1 4.9 34 cpd. of Ex.2 acidic 30 38 34 37 Example 35 Separate samples of bleached cotton cretonne are foularded (80% liquor uptake) with an aqueous bath containing: 15 g/l MgC12 250 g/l product of Example 5b to provide a concentration of 1% by weight of active ingredient on the cotton substrate.
As the product of Example 5b is insoluble in water, it is added as a 5% (w/w) aqueous dispersion which is obtained by milling 5% of the product of Example 5b and 1% of Pluronic F 108 in the presence of glass beads in deionised water.
The remaining procedure is as described in Examples 31 to 33.
The results obtained are set out in the following Table 3.
Table 3
Treatment SPF Example Test UVA alkaline number of washes acidic none one five ten - none (control) acidic 5.4 5.4 5.1 4.9 35 cpd. of Ex.5b slightly acidic 36 32 27 21 Examples 36 and 37 Separate samples of bleached cotton cretonne are foularded (80% liquor uptake) with an aqueous bath containing: 5 gIl Ml4Cl 250 gll product of Example Sb or 6 to provide a concentration of 1% by weight of active ingredient (product of Example Sb) or 0.2% by weight of active ingredient (product of Example 6), each based on the cotton substrate.
As the product of Example 5b or 6 is insoluble in water, it is added as a 5% (w/w) aqueous dispersion which is obtained by milling 5% of the product of Example Sb or 6 and 1% of Pluronic F 108 in the presence of glass beads in deionised water.
The remaining procedure is as described in Examples 31 to 33.
The results obtained are set out in the following Table 4.
Table 4
Treatment SPF Example Test UVA alkaline/ number of washes acidic none one five ten - none (control) slightly acidic 5.4 5.4 5.1 4.9 36 cpd. of Ex.5b slightly acidic 37 35 47 55 37 cpd. of Ex.6 slightly acidic 17 23 18 19 Example 38 Separate samples of bleached cotton cretonne are foularded (80% liquor uptake) with an aqueous bath containing: 5 g/l MgCl2 250 gZl product of Example 7 to provide a concentration of 0. 1% or 0.5% by weight of active ingredient on the cotton substrate.
As the product of Example 7 is insoluble in water, it is added as a 5% (w/w) aqueous dispersion which is obtained by milling 5% of the product of Example 7 and 1% of Pluronic F 108 in the presence of glass beads in deionised water.
The remaining procedure is as described in Examples 31 to 33.
The results obtained are set out in the following Table 5.
Table 5
Treatment SPF Concn. number of washes Example Test UVA alkaline/ FWA acidic none one five ten - none (control) - acidic 4.1 4.1 4.1 4.2 0.1% 10 15 12 12 38 cpd. of Ex.7 slightly acidic 0.5% 23 26 27 27 Examples 39 to 51 Separate samples of bleached cotton cretonne are foularded (80% liquor uptake) with an aqueous bath containing: 10 g/l Na2SO4 50 g/l product of relevant Example to provide a concentration of 0.1 % or 0.7% by weight of active ingredient on the cotton substrate.
As the products of the relevant Examples are insoluble in water, they are added as a 5% (w/w) aqueous dispersion which is obtained bv milling 5% of the product of the relevant Example and 1% of Piuronic F 108 in the presence of glass beads in deionised water.
The remaining procedure is as described in Examples 31 to 33.
The results obtained are set out in the following Table 6.
Table 6
Treatment SPF Concn.
Example Test UVA FWA @@@@@@ acidic none one five ten - none (control) - neutral 7 5 5 6 39 cpd. of Ex.8 0.2% neutral 34 22 29 29 40 cpd. of Ex.10 0.1% neutral 29 31 22 19 41 cpd. of Ex.23 0.2% neutral 41 22 16 13 42 cpd. of Ex.11 0.1% neutral 39 36 22 23 43 cpd. of Ex.19 0.2% neutral 26 40 36 29 44 cpd. of Ex.21 0.1% neutral 21 19 13 11 45 cpd. of Ex.26 0.2% neutral 18 14 9 12 46 cpd. of Ex.29 0.2% neutral 30 34 31 28 47 cpd. of Ex.30 0.2% neutral 38 23 22 20 48 cpd. of Ex.17 0.2% neutral 18 13 7 15 49 cpd. of Ex.18 0.2% neutral 29 36 21 19 50 cpd. of Ex.20 0.2% neutral 28 32 31 28 51 cpd. of Ex.22 0.2% neural 20 13 8 7 Examples 52 to 55 Separate samples of bleached cotton cretonne are foularded (80% liquor uptake) with an aqueous bath containing: 4 g/l NaHCO3H 50 g/l urea 50 g/l product of relevant Example to provide a concentration of 0.2% by weight of active ingredient on the cotton substrate.
As the products of the relevant Examples are insoluble in water, they are added as a 5% (w/w) aqueous dispersion which is obtained by milling 5% of the product of the relevant Example and 1% of Pluronic F 108 in the presence of glass beads in deionised water.
The remaining procedure is as described in Examples 31 to 33 except that the thermofixing is conducted for 2 minutes at 1300C.
The results obtained are set out in the following Table 7.
Table 7
Concn. SPF Example Test UVA number of washes UVA none one five ten - none (control) - 7 5 5 4 52 cpd.ofEx.17 0.2% 28 15 15 24 53 cpd. of Ex.18 0 2% 45 49 45 34 54 cpd. of Ex.20 0.2% 33 35 36 48 55 cpd. of Ex.6 0.2% 29 27 26 21 The results in the Tables 1 to 7 denlonstr;lte the substantial increase in the SPF values of cotton samples treated according to the present invention and that cotton samples treated according to the present invention are fast to washing.

Claims (33)

Claims
1. A compound having the formula:
in which m is 1 or 2; A is a residue selected from those having the formulae:
in which R is phenyl, optionally substituted by 1 or
2 C1-C4alkyl groups, or by 1 or 2 C1-C18alkoxy groups, or R is a group having the formula:
X is F, Cl or NHCH20H and X1 is F, CI, NHCH20H or a group having the formula:
CO2-C1C4aJkyI Q < G(=O)-Cl-C4aikyi
B is -O-, -NH- or -S02-; and D is a group having one of the formulae::
CH2-C(=O)-NH(CH2OH), CH2-C(=O)-N(CH2OH)2 or CH2CH2-OSO3M in which M is hydrogen, sodium, potassium, calcium, magnesium, ammonium, mono-, di-, tri- or tetra-C1-Caalkylammonium or ammonium that is di- or tn-substituted by a mixture of Cl-C4alkyl and C1-C4hydroxyalkyl groups, or, when A is a residue of formula (5) or (6), D may also be a group of formula:
CO2-C1-C4atkyt
in which B and M have their previous significance and n is 0 or 1, provided that at least one SO3M group is present, or the formula:
in which X, X1 and M have their previous significance; provided that the following compounds are excluded: a) those in which A is a residue of formula (2), (3) or (4), B is -0- and D is a group of formula
CH2-C(=O)-NH(CH2OH) or CH2-C(=O)-N(CH2OH)2; b) the compound 4-glycidyloxy-2-hydroxy benzophenone; and c) the compound 2-(2-hydroxy-4-glycidyloxy)-4,6-(2,4-dimethylphenyl)-1,3,5-ttiazine 2. A compound according to claim 1 in which R is tolyl or xylyl.
3. A compound according to claim 1 or 2 in which M is sodium.
4. A compound according to claim 1 in which the compound of formula (I) has the formula:
in which R is as defined in claim 1 and Dl is a group having the formula
CH2-C(=O)-NH(CH2OH) or CH2-C(=O)-N(CH2OH)2.
5. A compound according to claim 1 in which the compound of formula (1) has the formula:
in which D1 is as defined in claim 4.
6. A compound according to claim 1 in which the compound of formula (1) has the formula:
in which D1 is as defined in claim 4.
7. A compound according to claim 1 in which the compound of formula (1) has the formula:
SO3M $ (10) x N;N X/; N \ B 4 C02-C, -C,aikyl in which X is F or Cl and B and M are each as defined in claim 1.
8. A compound according to claim 1 in which the compound of formula (1) has the formula:
SOaM (1 1) B NN X /; N )\ B CO-C1-CaIkyI in which X is F or Cl and B and M are each as defined in claim 1.
9. A compound according to claim l in which the compound of formula (1) has the formula:
SO2CH2CH2OSQM (12) B NYN X /; N COz-C,-C,alky) in which X is F or Cl and B and M are each as defined in claim 1.
10. A compound according to any of claims 7 to 9 in which X is Cl, B is NH and M is Na.
11. A compound according to claim l in which the compound of formula (1) has the formula:
in which M and n are as defined in claim 1, provided that at least one S03M group is present, X is F or Cl and X1 is F, Cl or a group having one of the formulae:
BM C02-C1-C4aIkyI B < C(=O)-C1-C4alkyl
in which B and M are each as defined in claim 1.
12. A compound according to claim 11 in which X is Cl, B is NH and M is Na.
13. A compound according to claim 1 in which the compound of formula (1) has the formula:
in which each X is the same and is F or Cl and each Xl is the same and is F, Cl or a group having the formula:
C02-C1-C4aIkyI C(=O)-C 1C4aIkyI
in which B and Mare each as defined in claim l.
14. A compound according to claim 13 in which each X is Cl, B is NH and M is Na.
15. A compound according to claim 1 in which the compound of formula (1) has the formula:
in which M is as defined in claim 1.
16. A compound according to claim 15 in which M is Na.
17. A process for the production of a compound of formula (1) comprising reacting a compound of formula A-(BH)m in which A, B and m are as defined in claim 1, with m moles of a compound L-D, in which D is as defined in claim 1 and L is a leaving group or atom.
18. A process according to claim 17 in which L is a halogen atom.
19. A process according to claim 18 in which L is a chlorine atom.
20. A method for the treatment of a textile fibre material, comprising treating the textile fibre material with 0.05 to 3.0% by weight, based on the weight of the textile fibre material, of one or more compounds having the formula (1) as defined in claim 1.
21. A method according ro claim 20 in which the textile fibres treated are cotton, viscose, flax, rayon, linen, wool, mohair, cashmere, angora, silk, polyester, polyamide or polyacrylonitrile fibres.
22. A method according to claim 21 in which the textile fibres treated are cotton fibres.
23. A method according to any of claims 20 ro 22 in which the textile fibres treated have a density of less than 200 g/m2 and have not been previously dyed in deep shades.
24. A method according to any of claims 20 to 23 in which the compound of formula (1) is only sparingly soluble in water and is applied in dispersed form.
25. A method according to any of claims 20 to 24 in which, in addition to the compound of formula (1), a minor proportion of one or more adjuvants is also employed.
26. A method according to claim 25 in which the adjuvants are emulsifiers, perfumes, colouring dyes, opacifiers, optical whitening agents, bactericides, nonionic surfactants, fabric care ingredients, anti-gelling agents or corrosion inhibitors.
27. A method according to claim 26 in which the amount of each of the adjuvants does not exceed 1% by weight on the treated fibre.
28. A method of increasing the SPF rating of textile fibre material, comprising treating the textile fibre material with 0.05 to 3.0% by weight, based on the weight of the textile fibre material, of one or more compounds having the formula (1) as defined in claim 1.
29. A method according to claim 28 whereby the tear resistance and/or lightfastness of the treated textile fibre material are also improved.
30. A textile fabric produced from a fibre treated according to a method as claimed in any of claims 20 to 29.
31. An article of clothing produced from a textile fabric according to claim 30.
32. A compound according to claim 1 substantially as hereinbefore described with reference to any one of the foregoing Examples.
33. A method according to claim 20 substantially as hereinbefore described with reference to any one of Examples 31 to 55.
GB9514407A 1994-07-23 1995-07-14 Compounds having ultra-violet absorption properties Expired - Fee Related GB2291644B (en)

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GB9417562A GB9417562D0 (en) 1994-09-01 1994-09-01 Compounds and their use
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2316401A (en) * 1996-08-17 1998-02-25 Ciba Geigy Ag Triazine U.V.absorbing and fluorescent whitening agents
DE19735900A1 (en) * 1997-08-19 1999-02-25 Beiersdorf Ag Photoprotective combinations
DE19735901A1 (en) * 1997-08-19 1999-02-25 Beiersdorf Ag Cosmetic or dermatological light stabilizers, which contain solid-state UV filter substances and polymeric UV filter substances based on silicone
US5939379A (en) * 1996-08-17 1999-08-17 Ciba Specialty Chemicals Corporation Triazine derivatives and their use
WO1999050379A1 (en) * 1998-04-01 1999-10-07 Unilever Plc Sunscreens and compositions containing them

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115745917B (en) * 2022-11-07 2024-01-30 宁波家联科技股份有限公司 Long-acting ultraviolet absorber and preparation method and application thereof

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Publication number Priority date Publication date Assignee Title
WO1994004515A1 (en) * 1992-08-12 1994-03-03 Sandoz Ltd Method of increasing the spf rating and compounds suitable for increasing the spf rating of fibre or fabric

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994004515A1 (en) * 1992-08-12 1994-03-03 Sandoz Ltd Method of increasing the spf rating and compounds suitable for increasing the spf rating of fibre or fabric

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2316401A (en) * 1996-08-17 1998-02-25 Ciba Geigy Ag Triazine U.V.absorbing and fluorescent whitening agents
US5939379A (en) * 1996-08-17 1999-08-17 Ciba Specialty Chemicals Corporation Triazine derivatives and their use
DE19735900A1 (en) * 1997-08-19 1999-02-25 Beiersdorf Ag Photoprotective combinations
DE19735901A1 (en) * 1997-08-19 1999-02-25 Beiersdorf Ag Cosmetic or dermatological light stabilizers, which contain solid-state UV filter substances and polymeric UV filter substances based on silicone
WO1999050379A1 (en) * 1998-04-01 1999-10-07 Unilever Plc Sunscreens and compositions containing them

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GB9514407D0 (en) 1995-09-13

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