WO2001049924A2

WO2001049924A2 - A process for improving the sun protection factor of cellulosic fibre material

Info

Publication number: WO2001049924A2
Application number: PCT/EP2001/000052
Authority: WO
Inventors: Diego HÄNZI; Jean-Jacques DONZÉ; Georges Metzger; Martin Jöllenbeck
Original assignee: Ciba Spezialitaetenchemie Holding AG; Ciba SC Holding AG
Current assignee: BASF Schweiz AG
Priority date: 2000-01-07
Filing date: 2001-01-04
Publication date: 2001-07-12
Anticipated expiration: 2002-07-07
Also published as: AU2513301A; WO2001049924A3

Abstract

A process for improving the sun protection factor (SPF) of cellulosic fibre materials and blends thereof, which comprises contacting said materials with at least one compound of the formula (1), whereby R1 represents hydrogen or C1-C4alkyl; R2 represents hydrogen, c1-c4alkyl, C1-C4alkoxy, halogen or SO3M, M being hydrogen or an alkali or alkaline earth metal; X1 is chlorine, fluorine, NR3R4, OR3 or SR3, wherein R3 represents hydrogen, C1-C4alkyl or C1-C4alkoxy, which are unsubstituted or substituted by one or more SO3M, OSO3M, COOM or OH groups, C2-C4hydroxyalkoxy, C1-C4alkoxy-C1-C4alkoxy or phenyl, which is unsubstituted or substituted by one or more SO3M, COOM, OH, halogen or C1-C4alkyl groups and R4 represents hydrogen, C1-C4alkyl, C2-C4hydroxyalkoxy, C1-C4alkoxoxy-C1-C4alkoxy or phenyl, or R3 and R4, together with the nitrogen atom, form a pyrrolidine, piperidine or morpholine ring; X2 is chlorine, when X1 is chlorine, or X2 is fluorine, when X1 is, NR3R4, OR3 or SR3 and Z is a fibre reactive group, whereby the cellulosic fibre material may also be treated with a fluorescent whitening agent either before, during or after contact with the compound of formula (1).

Description

A Process for improving the Sun Protection Factor of Cellulosic Fibre Material

The present invention relates to a process for improving the sun protection factor (SPF) of cellulosic fibre materials and blends thereof, which comprises treating the cellulosic fibre materials with at least one reactive UV absorber.

The skin-damaging effect of UV radiation is well known. Protection from strong sunlight is usually sought by applying a sun cream, a composition that contains a UV absorber, directly to the skin. In particularly sunny regions, for example in Australia or America, however, the rate of skin damage due to UV radiation has recently been increasing dramatically. Accordingly, more attention is paid in these countries to protecting the skin from solar irradiation.

It has therefore been proposed that the skin should be protected not just directly, but also to reduce the UV transmissibility of the clothing and also of other sun protection articles, such as awnings or parasols. Especially cellulosic fibre materials are at least partially transparent to UV radiation, so that the mere wearing of clothing does not offer adequate protection to the skin from damage due to UV radiation. A remedy is possible here by incorporating UV absorbers into the fibre material.

However, hitherto the results achieved in respect of the protection from UV radiation in the area of cellulosic fibre materials, in particular textile materials have not been satisfactory and there therefore continues to be a need for improving the sun protection factor of these materials. Despite the fact that this is a general problem, one specific aspect has been found especially problematic. In the case of cellulosic fibre materials treated with fluorescent whitening agents (FWA's), incorporation of UV absorbers has been found to result in loss of the whitening effect, thus leading to an undesirable yellowing of the fibres.

Surprisingly, it has now been found that a particular class of UV absorber not only provides excellent sun protection factors for cellulosic fibre materials in general, but also, in combination with materials treated with FWA's, results in little or no observable reduction of the degrees of whiteness of the so-treated materials. Correspondingly, the present invention provides a process for improving the sun protection factor (SPF) of cellulosic fibre materials and blends thereof, which comprises contacting said materials with at least one compound of the formula:

whereby

R, represents hydrogen or C₁-C₄alkyl;

R₂ represents hydrogen, CrC₄alkyl, C Calkoxy, halogen or S0₃M, M being hydrogen or an alkali or alkaline earth metal;

Xi is chlorine, fluorine, NR₃R₄, OR₃ or SR₃, wherein

R₃ represents hydrogen, C₁-C₄alkyl or d-C₄alkoxy, which are unsubstituted or substituted by one or more S0₃M, OS0₃M, COOM or OH groups, C₂-C₄hydroxyalkoxy, C_r C₄alkoxy-C₁-C₄alkoxy or phenyl, which is unsubstituted or substituted by one or more S0₃M, COOM, OH, halogen or C C₄alkyl groups and

R₄ represents hydrogen, d-C₄alkyl, C₂-C₄hydroxyalkoxy, C₁-C₄alkoxoxy-C₁-C alkoxy or phenyl, or

R₃ and R₄, together with the nitrogen atom, form a pyrrolidine, piperidine or morpholine ring;

X₂ is chlorine, when Xi is chlorine, or X₂ is fluorine, when X, is, NR₃R₄, OR₃ or SR₃ and

Z is a fibre-reactive group.

A fibre-reactive group is to be understood as meaning such a group which is capable of reacting with the hydroxyl groups of the cellulosic fibre or with the amino groups of polyamide fibre materials to form covalent chemical bonds. Many such reactive groups are known, in particular from the chemistry of the so-called "reactive dyes". However, within the scope of the present invention, preferred fibre-reactive groups Z are those in which Z is a radical of the formula:

-S0₂-Y (2),

-S0₂NH-Y (3), -NHC0(CH₂)₃S0₂-Y (4),

-CONH(CH₂)₂S0₂-Y (5) or

-NHCO-Y (6),

Y representing vinyl, β-sulphatoethyl, . β-thiosulphatoethyl, β-phosphatoethyl, β-acyloxyethyl or β-haloethyl, especially those in which Z is a radical of formula (2) and Y represents - CH₂CH₂OS0₃M, M being as defined previously.

Within the scope of compounds of formula (1 ), the groups R , and R₂ preferably represent hydrogen and a further preferred embodiment is represented by formula (1), wherein Xi and X₂both represent chlorine or X₁ represents NR₃R₄ and X₂ represents fluorine, R₃ and R₄ being as previously defined.

Most preferably, the reactive UV absorber utilized in the process of the invention is of the formula

Within the definition of the substituents in compound (1 ), Cι-C₄alkyl may be methyl, ethyl, n- or isopropyl or n-, sec- or t-butyl, C₁-C₄alkoxy may be methoxy, ethoxy, n- or isopropoxy or n-, sec- or t-butoxy, C₂-C₄-hydroxyalkyl may be hydroxyethyl, hydroxypropyl or hydroxybutyl, whilst halogen may be fluorine, chlorine, bromine or iodine, preferably chlorine and M is Na, K, Ca or Mg, preferably Na.

The quantities of compound (1) to be applied to the cellulosic material according to the process of the invention may vary over a wide range. However, when used in amounts of between 0.5 and 10% by weight, based on the weight of the fibre material, useful effects may be obtained. Preferably, however, the amount of the compound of formula (1) used is from 3 to 10% and especially from 4 to 7% by weight, based on the weight of the fibre material. Cellulosic fibre materials are to be understood as meaning, for example, the natural cellulose fibre, such as cotton, linen and hemp, and also cellulose pulp and regenerated cellulose. The process of the invention is also suitable for treating hydroxyl-containing fibres present in blend fabrics, for example, blends of cotton with polyester fibres or polyamide fibres.

The fibre materials used have a density of between 30 and 200g/m², preferably between 100 and 150g/m², the porosity of the material lying in the range of 0.1 to 3%, preferably 0.1 to 1.5%.

Preferably, the cellulosic fibre material used is cotton or a cotton blend.

The fibres mentioned may be present in various forms, for example, as staple or yarns or as wovens or knits.

A further aspect of the invention, as previously mentioned, is to provide excellent sun protection factors for cellulosic fibre materials in combination with fluorescent whitening agents (FWA's), whereby little or no observable reduction of the degrees of whiteness of the so-treated materials results.

For this purpose, application of the UV absorber (1) may be performed before, during or after treatment of the material with the FWA.

Any FWA suitable for whitening cellulosic fibre materials may be applied for this purpose. However, suitable FWA's are, in general, those derived from triazinylaminostilbenes, naphtho- or v-triazolylamino stilbenes, distyryl biphenyls, diphenyl pyrazolines, benzoxazoles, coumarin or carbostyryl compounds, whereby these derivatives preferably contain sulphonic acid groups.

Specific examples of suitable FWA's are:

whereby the invention is not to be regarded as being restricted solely to the use of these FWA's.

The application of the UV absorbers and also, when desired, the FWA's, can take place by an exhaust or continuous process. In the exhaust process the liquor ratio can be chosen within a wide range, for example, from 3:1 to 200:1 , preferably from 10:1 to 40:1. It is advantageous to operate at a temperature of 20 to 120°C, preferably 40 to 110°C, advantageously in the presence of acid-binding agents, for example, sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium formate, potassium carbonate, sodium silicate, sodium trichloroacetate or sodium triphosphate, in the presence or absence of neutral salts, for example, sodium sulphate or sodium chloride.

In the continuous process, the liquor add-on is advantageously 40-700, preferably 40-500, % by weight. The fibre material is then subjected to a heat treatment process to fix the applied UV absorbers. This fixing can also be effected by the cold batching method.

The heat treatment preferably takes the form of a steaming process in a steamer with ordinary or superheated steam at a temperature of 98 to 105°C for, for example,1 -7, preferably 1 -5 minutes. The fixing of the UV absorber by the cold batching process can be effected by storing the impregnated and preferably rolled-up material at room temperature (15 to 30°C) for 3 to 24 hours, for example, the cold batching time being known to depend on the UV absorber.

On completion of the application process and fixation, the treated materials are conventionally rinsed, soaped, for example, for 20 minutes at 90°C with a solution containing 1g/l. of calcined sodium carbonate, and dried.

The treatment bath may optionally contain other customary auxiliaries, for example, levelling, wetting deaerating and antifoaming agents, penetration accelerants or crease resisting agents.

The cellulose fibre materials treated by the process of the present invention possess high sun protection factors. The sun protection factor is defined as the ratio of the harmful dose of UV energy on protected skin to the harmful dose of UV energy on unprotected skin. Accordingly, a sun protection factor is also a measure of the transmissivity of fibre materials untreated and of those treated with reactive UV absorbers described in this invention. The sun protection factor can be determined, for example, by the method described by B.L.Diffey and J.Robson in J.Soc.Cosmet.Chem., 40, 127-133 (1989).

The UV absorbers of formula (1) are known or may be prepared by known methods.

The examples which follow illustrate the invention; parts and percentages are by weight unless otherwise stated.

Example 1

Four samples each of 10g. of a pre-washed cellulose fabric having a weight of 140g/m² and a porosity of 0.9% are treated in an AHIBA® dyeing machine at a liquor ratio of 1 :20 in four different liquors.

Liquor 1 contains 5g/l. of a commercial crease inhibitor (Cibafluid C™), 30g/l Glauber's salt, 15g/l. calcined sodium carbonate and 2ml/l. 30% sodium hydroxide solution

Liquor 2 corresponds to Liquor 1 , but additionally contains 3% of the UV absorber of formula (7), based on the weight of the fabric.

Liquor 3 corresponds to Liquor 1 , but additionally contains 5% of the UV absorber of formula (7), based on the weight of the fabric.

Liquor 4 corresponds to Liquor 1 , but additionally contains 10% of the UV absorber of formula (7), based on the weight of the fabric.

The fabric samples are added to the application liquor containing crease inhibitor and Glauber's salt, which is previously heated to 60°C. After 5 minutes the UV absorber, previously emulsified in 15ml. of the appropriate liquor, is added at pH 7. After 20 minutes 15g/l. of calcined sodium carbonate is added in 3 portions of 5g/l over 15 minutes followed, after 50 minutes, by 2ml/l of 30% sodium hydroxide solution. Following a total application time of 60 minutes, the samples are removed, rinsed in the overflow for 10 minutes at 70°C, then for a further 10 minutes at 50°C and, finally neutralised with acetic acid and dried at room temperature. The determined sun protection factors of the four specimens are depicted in Table 1 : Table 1

The above results clearly demonstrate the substantial improvement in sun protection factor attained by the use of compound (7).

Example 2

Four samples each of 10g. of a pre-bleached (hydrogen peroxide) cotton- poplin fabric hhaavviinngg aa wweeiigghhtt ooff 111100gg//mm²² aanndd aa ppoorroossiittyy ooff 00..44--00..55%% i are treated in a ZELTEX® dyeing machine at a liquor ratio of 1 :30 in four different liquors.

Liquor 1 contains 30g/l. Glauber's salt, 15g/l. calcined sodium carbonate and 0.8g/l. 36°Be sodium hydroxide solution.

Liαuor 2 corresponds to Liquor 1 , but additionally contains 1% of the UV absorber of formula (7), based on the weight of the fabric.

Liquor 3 corresponds to Liquor 1 , but additionally contains 2.5% of the UV absorber of formula (7), based on the weight of the fabric.

Liquor 4 corresponds to Liquor 1 , but additionally contains 5% of the UV absorber of formula (7), based on the weight of the fabric.

The fabric samples are added to the application liquor containing the Glauber's salt, which is previously heated to 60°C. After 15 minutes the UV absorber is added (except for Liquor 1) at pH 7. After 30 minutes 15g/l. of calcined sodium carbonate is added in 3 portions of 5g/l over 15 minutes followed, after 15 minutes, by 0.8g/l. of 36°Be sodium hydroxide solution. Following a total application time of 70 minutes, the samples are removed, rinsed in the overflow for 10 minutes at 70°C, then for a further 10 minutes at 50°C and, finally neutralised with acetic acid.

Subsequently, the samples prepared above are treated with an optical whitening either by the exhaust process or by padding as follows:

a) the samples are treated with 0.13% of FWA (9) and with 3g/L. of stabilized sodium dithionite by the exhaust process at 95°C for 60 minutes, the liquor ratio being 1 :30.

b) the samples are subjected to a reductive bleach with 3g/l. of stabilized sodium dithionite for 60 minutes at 95°C and a liquor ratio of 1 :30 and, subsequently treated with 3.6g L. of FWA (8) by the padding process, the picik-up being 65%, and dried at 70°C.

The degrees of whiteness, determined according to the method of Ganz, and the sun protection factors, according to AS/NZS 4399/1996, of the samples are then measured, the results being summarized in Table 2 below:

Table 2

The above results clearly demonstrate the substantial improvement in sun protection factor attained by the use of compound (7), whilst the degree of whiteness of the treated fabrics is not dramatically reduced.

Claims

1. A process for improving the sun protection factor (SPF) of cellulosic fibre materials and blends thereof, which comprises contacting said materials with at least one compound of the formula:

whereby

R_T represents hydrogen or Cι-C₄alkyl;

R₂ represents hydrogen, Cι-C₄alkyl, C C₄alkoxy, halogen or S0₃M, M being hydrogen or an alkali or alkaline earth metal; X, is chlorine, fluorine, NR₃R₄, OR₃ or SR₃, wherein R₃ represents hydrogen, C C₄alkyl or d-C₄alkoxy, which are unsubstituted or substituted by one or more S0₃M, OS0₃M, COOM or OH groups, C₂-C₄hydroxyalkoxy, d-dalkoxy-d-

C₄alkoxy or phenyl, which is unsubstituted or substituted by one or more S0₃M, COOM,

OH, halogen or C₁-C₄alkyl groups and R₄ represents hydrogen, d-C₄alkyl, C₂-C₄hydroxyalkoxy, d-dalkoxoxy-d-dalkoxy or phenyl, or R₃ and R₄, together with the nitrogen atom, form a pyrrolidine, piperidine or morpholine ring; X₂ is chlorine, when X, is chlorine, or X₂ is fluorine, when X_t is, NR₃R₄₎ OR₃ or SR₃ and Z is a fibre reactive group.

2. A process according to claim 1 wherein, in the compound of formula (1), the fibre reactive group Z is a radical of the formula:

-S0₂-Y (2),

-S0₂NH-Y (3),

-NHCO(CH₂)₃S0₂-Y (4),

-CONH(CH₂)₂S0₂-Y (5) or -NHCO-Y (6),

Y representing vinyl, β-sulphatoethyl, . β-thiosulphatoethyl, β-phosphatoethyl, β-acyloxyethyl or β-haloethyl

3. A process according to claim 2, in which the fibre reactive group Z is a radical of formula (2) and Y represents -CH₂CH₂OS0₃M, M being as defined in claim 1.

4. A process according to any one of claims 1 to 3, in which, in the compound of formula (1 ), R, and R₂ represent hydrogen.

5. A process according to any one of the preceding claims, in which, in the compound of formula (1 ), X! and X₂ both represent chlorine or Xi represents NR₃R₄and X₂ represents fluorine, R₃ and R₄ being as defined in claim 1.

6. A process according to claim 1 , in which the compound of formula (1 ) is:

7. A process according to claim 1 , wherein the amount of the compound of formula (1) used is from 0.5 to 10% by weight, based on the weight of the fibre material.

8. A process according to claim 1 , wherein the amount of the compound of formula (1) used is from 3 to 10% by weight, based on the weight of the fibre material.

9. A process according to claim 1 , wherein the amount of the compound of formula (1) used is from 4 to 7% by weight, based on the weight of the fibre material.

10. A process according to claim 1 , wherein the cellulosic fibre materials used have a density of between 30 and 200g/m², preferably between 100 and 150g/m².

11. A process according to claim 1 , wherein the cellulosic fibre materials used have a porosity of between 0.1 and 3%, preferably between 0.1 and 1.5%.

12. A process according to claim 1 , wherein the cellulosic fibre material used is cotton or a cotton blend.

13. A process according to any one of the previous claims, whereby the cellulosic fibre material is treated with a fluorescent whitening agent either before, during or after contact with the compound of formula (1).