FR2642084A1 - LIQUID DETERGENT COMPOSITION CONTAINING HYDROPHILIC OPTICAL AZURANT - Google Patents

Abstract

This composition is characterized in that it is practically free of conventional detergency builders, and comprises: a) up to 70% by weight of surfactants chosen from ionic, nonionic surfactants and mixtures thereof; b) from 0.01% to 2% by weight of an optical brightener of general formula: (CF DRAWING IN BOPI) in which R and R1 each represent a group -C2 H5 or -CH3 and X represents the sodium cation, the potassium cation, the ammonium cation, an amine or an alkanolamine, and c) organic and inorganic additives of known type.

Description

The present invention relates to a composition containing from 0.01% to

  2%. a hydrophilic optical brightener of general formula:

R-NH NH-R

N> NH - (Q CH-CH J NH - <(, N

N N {

@ -NH S03X 503X NH

  wherein R and R 1 are each -C = Hu or -

  It; CH. and X is the sodium cation, the potassium cation, the ammonium cation, an amine or an alkanolamine, and which is substantially free of conventional detergency builders. Said composition further comprises up to 70% of a 1; mixture of ionic and nonionic surfactants, a maximum of 3% of which may consist of

  cationic surfactants, in addition to the usual additives.

  The composition excellently solves the problem of the uniformity and brightness of the 2C9 whiteness in liquid detergents without adjuvants.

conventional detergency.

  The present invention relates to a washing liquid detergent composition, either by hand or machine, containing optical brighteners. More particularly, it relates to stable and stable isotropic liquid detergents which are substantially free of conventional additives, especially phosphorus-based inorganic builders, and which contain particularly effective optical brighteners to obtain excellent whitening effects when washing fabrics. based on cellulosic fibers, without detergent stains formation. The use of optical brighteners in detergents is well known in the prior art (see, for example, Kirk-Dthmer Encyclopedia of Chemical Technology, Vol 4, p 222). By the term "optical brighteners", hereinafter referred to for the sake of simplicity, the acronym FWA (Fluorescent Whitening Agents) means substances mixed with detergents for washing and washing machines, whether they be liquids or powders, which act by absorption of ultraviolet radiation and re-emit it at longer wavelengths corresponding to the

blue radiation of the visible spectrum.

  This phenomenon eliminates or diminishes any yellowish tint of white tissue and imparts

  brilliant in both white and colored fabrics.

  The use of said FWA is not free of drawbacks. Among them, in particular: - the formation of laundering spots on the washed fabrics due to the non-uniform distribution of the FWA on the fabric luimgme during washing; the progressive reinforcement on the tissues, after repeated washing, of stains of persistent colors,

  as a result of an accumulation of FWA in the tissue itself

  mime. The disadvantages mentioned above are particularly serious in detergents free of conventional detergency builders, such as polyphosphates, and, to a greater degree, in liquid detergents rather than

in those in powder.

  By the term "detergency builder" is meant, according to widespread use in this field, a series of substances added to the soap or surfactant compounds to facilitate the detergent action. They contribute to this goal through several mechanisms, in particular: 1) providing the necessary alkalinity to the washing medium; 2) by capturing the divalent ions, which are detrimental to both the detergency process and the brightness imparted by the FWA; 3) by keeping in suspension the dirt torn from the fibers, and thus avoiding that they are redeposited with the formation of spots; (see Kirk-Othmer, cited above, Vol 7, p 837

  et seq .; Flight. 22, p. 396 et seq.).

  In recent years, the use of conventional detergency builders based on inorganic phosphates and polyphosphates has suffered severe limitations due to the serious consequences that such compounds exert on the aquatic flora (eutrophication). The result of these limitations is that these compounds have been replaced by unusual detergency builders such as, for example, polyacrylic acid, sequestering agents and chelating organics such as the salts of EDTA, NTA, EDTMPA (ethylenediaminetetramethylenephosphonic acid), DTMPA

  (diethylenetriaminepentamethylenephosphonic acid).

  Such non-conventional detergency builders, however, do not, as discussed above, have the same positive effect that conventional adjuvants have on the homogeneous distribution of FWA in the tissues; it is therefore difficult to avoid, with this type of detergent, the formation of bleaching stains on

washed items.

  It is for these reasons that there has been a strong demand in this sector for more selectivity of FWA which can be used in detergent compositions without traditional detergency builders, without the disadvantages named above. The problem of finding suitable FWA for use in detergent compositions without conventional adjuvants has not been solved so far, particularly in

  concerning liquid detergent compositions.

  The base products used in the preparation of these compositions must in fact be readily soluble or suspended in aqueous mixtures to avoid undesirable component separations upon storage of the finished product; this requirement strongly limits the number of compounds that can be used as FWA in the intended applications and

  therefore complicates the task of the researcher.

  The chemical compounds known and most often used in the art as FWA to enhance the whiteness and brightness of the cellulosic tissues subjected to washing, are essentially the salts, and in particular the sodium salts, of the following acids (next to each acid name is the registration number under which the corresponding sodium salt is classified by the Chemical Abstract Society = CAS): biphenyl-4,4'-bis (styryl-2-sulphonic acid)

(CAS NO: 27344-41-8) (I)

  4,4'-bis [t4-anilino-6- (N-methyl-N-2-) - acid

  hydroxyethyl) amino-1,3,5-triazin-2-yl] aminoastilbène-

2,2'-disul fonic

(CAS N: 13863-31-5) CII)

  4,4'-bis [(4-anilino-6-morpholino-1,3,5-triazin-2-) -acetate

  yl) amino2stilbène-2,2'-disulfonic

(CAS N: 16090-02-1) (III)

  4,4'-bis [(4,6-dianilino-1,3,5-triazin-2-) -acetic acid

  yl) amino] stilbene-2,2'-disulfonic

(CAS N: 133-66-4) - CIV)

  4,4'-bisE (4-anilino-6-morpholino-1,3,5-triazin-2-) -acetate

yl) aminoastilbene-2-sulphonic

(CAS N: 102269-58-9) (CV)

  4-C2H-naphtho [1,2-d] triazol-2-yl) stilbene-2- acid

sulfonic

(CAS N: 6416-68-8) (VI)

  The salts of acids (I), (II) and (III) are well soluble in water, unlike the salts of acids (IV), (V) and (VI) which are only slightly. These correspond to some of the FWAs described in the

  prior art documents cited in the following.

  All the compounds described above have, in any case, disadvantages for use in liquid detergent compositions. In particular: the salts of the acid (I) fail to impart a sufficiently high degree of whiteness at the average temperatures, and they also have an excessive cost because of their chemical structure; the salts of the acid (II) tend to accumulate in the tissues, thus giving rise, after a series of washes, to a persistent greenish tint; - Salts of the acid (III), which are among those most used in industrial practice, show a tendency to turn into a yellow amorphous form, thus causing undesirable color changes in the liquid detergent compositions; - finally, the salts of the acids (IV), (V) and (VI) do not, under any circumstances, confer to the washed fabrics

  a white hue sufficiently intense and brilliant.

  In the known liquid detergent compositions of the prior art, the disadvantages described above have been eliminated in a first step and, as indicated above, with the aid of conventional detergency builders (see, for example, US Pat. GB-A-2028365 which uses organic phosphates). More recently, however, it has been proposed (cf., for example, European Patent Applications EP-A-167205 and EP-A-237119) liquid detergent compositions without conventional additives and containing FWA whose characteristics have been selected to have: - low solubility in water; a low affinity vis-à-vis the cellulosic fibers; a high hydrophobicity; in such a way that their affixing action to the fabric of the FWA is disadvantaged and that their uniformity of

distribution is therefore improved.

  The FWA used for this purpose are those of the acids indicated above under the references CIV), (V) and (VI); the results obtained with the compositions

  detergents described in patent applications EP-A-

  167205 and EP-A-237119, however, are rather unsatisfactory. If, on the one hand, the disadvantage of the formation of bleaching spots has been avoided, on the other hand the level of whiteness obtained is much poorer, because of the intrinsic characteristics of the FWAs used, and in any case not at all satisfactory with respect to the results obtained with liquid detergents containing conventional detergency

with powdered detergents.

  The object of the present invention is therefore ultimately to provide a liquid detergent composition comprising an optical brightener but devoid of, or substantially free from conventional detergency builders, and which is completely free from the disadvantages mentioned above, which suffer the

  known liquid detergent compositions of this type.

  This purpose has been achieved by the Applicant through a discovery made during his own research, discovered which is the object of the present invention. The Applicant has indeed found, quite surprisingly compared to the teachings of the prior art, that the brighteners o.ptiques of general formula: R-NHi NH-R

N> E> - SUI- CHC-C, N

/ --- NN

<Do S03X So3X NH

  in which R and Rx each represent a group -

  CmH0 or -CH3 and X represents the sodium cation, the potassium cation, the ammonium cation, an amine or an alkanolamine, and in particular the water-soluble salts of the acids of formulas:

  4,4'-bis (4-anilino-6-ethylamino-1,3,5-triazin-2-) acid

  yl) amino-] stilbene-2,2'-disulfonic acid (CAS Nz 24565-13-7 of the sodium salt of the acid) (VII)

  4,4'-bis (4-anilino-6-methylamino-1,3,5-triazin-2-) -acetate

  yl) amino] stilbene-2,2'-disulfonic acid (CAS N: 35632-99-6.de acid) (VIII) already known for a long time and experienced with little success in the field of detergent powder compositions, however, they are particularly effective when used in liquid detergent compositions, which are clear and transparent, or opaque because of the presence of bodies uniformly distributed therein, even in the almost complete absence of conventional detergency builders, such as that

phosphates and polyphosphates.

  FWA derived from acids of formula (VII) and (VIII), although having physical characteristics diametrically opposed to those chosen in the prior art - and this while being well soluble in water, so particularly hydrophilic, and manifesting furthermore, excellent affinity for cellulosic fibers - give the washed fabrics a high whiteness and a complete absence of laundering stains when incorporated in a liquid detergent composition according to the present invention; the whitened fabric also has a particularly bright and pleasant appearance. It is considered that such an unpredictable effect, even in the absence of the auxiliary effect of classical adjuvants, is due, without this explanation being able to limit in any way the invention, to the self-leveling power of the FWA of the present invention which allows their uniform distribution 2S on the fabric, even when their distribution

initial is not homogeneous.

  The object of the present invention is therefore achieved, on the basis of the above mentioned discovery, by a liquid detergent composition, for hand washes and the machine, characterized in that it is practically devoid of adjuvants of conventional detergents, and comprises: a) up to 70%. by weight of surfactants

  selected from ionic surfactants,

  ionic and their mixtures; b) from 0.01% to 2% by weight of an optical brightener of the general formula: R-Ni NH-R

R-NE N 1

N> NilH-N CH = CH- --.NH- N

N N N

O: N X SO3X

  in which R and RP each represent a group -

  C = H = or -CH3 and X represents the sodium cation, the potassium cation, the ammonium cation, an amine or an alkanolamine, and c) organic and inorganic additives of known type. We will now better describe the invention in detail with the aid of some examples of detergent compositions containing the FWA of the present invention, and comparative examples of detergent compositions containing the FWA of the prior art. In the examples which follow, the 2 'sodium salts of the acids of formula (VII) and (VIII) are compared with those of the acids of formula I, II, III, IV, using the same weight proportions as for the various products. of the market, which correspond roughly to the proportions of the specific extinctions measured at the wavelength 349 nm, corresponding to the maximum absorption in the UV, according to the following table:

  -_______________________________________

Compounds: El

I 502

I I 520

III 1024

IV 361

V 441

VI 513

Example 1

  0.1% by weight of the sodium salt of the acid (VII) is added to a liquid detergent composition having the following composition: Water 44.7 g dodecylbenzene sulphonic acid 4.0 g sodium lauryl ether sulphate 4, 0 g Triethylamine Laurylsulfate 4.0 g Ethoxylated natural alcohol ethoxylate Cmo-Cim (9 moles ethylene oxide) 20.0 g Polyglycol CPM 400) 20.0 g Triethanolamine 2.3 g The mixture is stirred until the mixture is stirred. the FWA is completely dissolved. Then, with the mixture obtained, a washing bath at a concentration of g / l is prepared. EMPA / 302 dirty cotton cloth pieces measuring 10 × 10 cm were subjected to 10 successive washing cycles in a Linitest machine with a weight ratio of 1/10 relative to the bath described.

  and at temperatures of 30 and 60 C.

  The degree of whiteness of the tissues after 2, 5 and 10 washes is evaluated by means of an Elrepho Zeiss reflection spectrophotometer and the relative value (W) expressed according to the Berger formula for the degree of whiteness. The results of these measurements and the measurements of successive examples 2 and 3 as well as comparative examples A, B, C and D are represented in FIG.

table 1.

  The cotton pieces are further subjected to a visual examination in ultraviolet light, after washing, for a

  evaluation of uniformity of whiteness.

  :: The results of this evaluation appear

also in Table 1.

Example 2

  0.9% is added to the detergent composition of Example 1. of a 20% solution in the diethylene glycol of the

  sodium salt of the acid of formula (VII).

  With the mixture obtained, the washing is carried out according to the methods, the proportions by weight and

  the concentrations indicated in Example 1.

Example 3

  To the detergent composition of the example is added

  1 0.18% of the sodium salt of the acid of formula (VIII).

  With the mixture obtained, the washing is carried out according to the methods, the proportions by weight and

  the concentrations indicated in Example 1.

  Comparative Example A To the detergent composition of the example is added

  0.10% of the sodium salt of the acid of formula CI).

  With the mixture obtained, the washing is carried out according to the methods, the proportions by weight and

  the concentrations indicated in Example 1.

  Comparative Example B To the detergent composition of the example is added

  1 0.25% of the sodium salt of the acid of formula CII).

  With the mixture obtained, the washing is carried out according to the methods, the proportions by weight and

  the concentrations indicated in Example 1.

  Comparative Example C The exemplary detergent composition is added

  0.20%. sodium salt of the acid of formula (III).

  With the mixture obtained, the washing is carried out according to the methods, the proportions by weight and

  the concentrations indicated in Example 1.

  Comparative Example D To the detergent composition of Example i is added

  0.175% of the sodium salt of the acid of formula CIV).

  With the mixture obtained, the washing is carried out according to the methods, the proportions by weight and

  the concentrations indicated in Example 1.

FXIE M1I -I [XE MI'I I EXEMPll: I

  2 lava lav. IV. 2 1, Iv. 'Iv. Il) lIv. 2 lava 1.Iv. I.Iv.

  w (30 '() 159 /,) 17t, 7.89, 159; 110 I 119 158, 8 170.0 178.5 C) 161.0 171, 7 18 r, 1 161.1 112.2 H t, 1 160.5 170.8 179.3 uni form evaluation, blue-heat unl shape., bleteatri utni form, bluishness vi suelle w A Il C 1)

  2 lava 5 lava. 10 lo. 2 lava 5 lava. 10 lo. 2 lava 5 lava. 10 lo. 2 lava 5 lava. 10 lo.

  óO-o) 156.1 162.1 171.4 1159.1 169.7 118.3 157.8 169.3 178 148.2 153.4 l165.1 w60C> 156.3 163.2 168.0 16 (0.0 170.3 119.2 159, H 17107 180.1 151.2 157.4 169.0 0% one size fits all, pink stained, stained blue, blue plain, neutral VIs uel _ _ _ _ _ _ _ _ _ _ ._ _ ___

Example 4

  The sodium salt of the acid of formula (VII) is added at a rate of 0.18% by weight to a liquid detergent composition having the following composition: Water 38.3 g Dodecylbenzenesulfonic acid 3.0 g Lauryl ether sulphate sodium 3.0 g Triethylamine Laurylsulfate 3.0 g Synthetic alcohol ethoxylate Clo-Ci = i (9 moles of ethylene oxide 20.0 g Sodium soap 10.0 g Triethanolamine 1.7 g The mixture is mixed until the FWA is completely dissolved, then a washing bath at the concentration of g / l is prepared with the resultant mixture, and EMFA / 302 dirty cotton fabric pieces of dimensions 10 × 10 cm 2 are subjected. 10 successive washing cycles in a Linitest machine with a 1/10 weight ratio to the described bath

  and at temperatures of 30 and 60 C.

  The degree of whiteness of the tissues after 2, 5 and 10 washes is evaluated by means of an Elrepho Zeiss reflection spectrophotometer and the relative value (W) expressed according to the Berger formula for the degree of whiteness. The results of these measurements and measurements of successive examples 5 and 6 as well as comparative examples E; F, G and H are represented in the

table 2.

  The cotton pieces are further subjected to a visual examination after washing, in ultraviolet light, for a

  evaluation of uniformity of whiteness.

  The results of this evaluation are

also in Table 2.

Example 5

  0.9% of a 20% solution in the diethylene glycol of Example 4 is added to the detergent composition of Example 4.

  sodium salt of the acid of formula (VII).

  With the mixture obtained, the washing is carried out according to the methods, the proportions by weight and

  the concentrations indicated in Example 4.

1C Example 6

  To the detergent composition of Example 4 is added

  0.18% of the sodium salt of the acid of formula (VIII).

  With the mixture obtained, the washing is carried out according to the methods, the proportions by weight and

  the concentrations indicated in Example 4.

  Comparative Example E To the detergent composition of Example 4 is added

  0.10% of the sodium salt of the acid of formula CI).

  With the mixture obtained, the washing is carried out according to the modalities, the proportions by weight and

  the concentrations indicated in Example 4.

  Comparative Example F To the detergent composition of Example 4 is added

  0.25% of the sodium salt of the acid of formula CII).

  With the mixture obtained, the washing is carried out according to the methods, the proportions by weight and

  the concentrations indicated in Example 4.

  Comparative Example G To the detergent composition of Example 4 is added

  0.20% of the sodium salt of the acid of formula (III).

  With the mixture obtained, the washing is carried out according to the methods, the proportions by weight and

  the concentrations indicated in Example 4.

  Comparative Example H To the detergent composition of Example 4 is added

  0.175% of the sodium salt of the acid of formula (IV).

  With the mixture obtained, the washing is carried out according to the methods, the proportions by weight and

  the concentrations indicated in Example 4.

  Atli t.AII N 't XtP [! I I4 XI MFI, XtHI' t6;

  2 wash .5 wash. 10lav. 2 la. v. the Iav. 2 lava LaIV.10lav.

  (30WC) 157.8 169.5 178.0 15 /, 9 169.7 178.2 157.5 169.3 177.0

  w 6o0c) 160.1 171.3 179.9 16o. (11_, 4 _? __, _ 159.3 169.2 178.1

  _ _ _ _ _ _ _ _ _ _ _ _ _ _ - - - - - - -... -...-, -..-. - - - - - - _ _ _ _ I _ _ _ _ _ _ _ _ _

  The evaluation is of a form, (i) the uniform, bluish visual, the form, the blueness of a blue elm. F C I! _ ,, __, ____ __.......................

  ................. l .._._......... ____ "_ .. DTD: 2 wash 5 wash 10 wash 2 wash (5 mL) 10 mL, 2 mL, 5 mL, 10 mL, 2 mL, 5 mL, 10 mL of water.

l lay. ___a y! 0 a. there.

  (30 ° C) S54.8 160.2 17 () 5 1S7.6 168.1 176.0 I56.5 167.1 176.4 145.1 149.7 162.8

5460th 169.2 19 0 4 5 152.2 165.3

- [_.1 --- r.

  t (60'C) 155.2 161.3 171.7 158.5 170.5 178, 158.3 169.6 179.1 145 days

6. 9. 1 I .__ 152

  ruddy valuation roe stain, v-erdatre stained blue8tre uniform, neutral O visual the C__

  From the above description and the

  From the results of the examples given, it can be appreciated exactly how the liquid detergent compositions of the present invention have fully achieved the intended purpose, by obtaining a particularly satisfactory degree of whiteness of the washed parts and completely free of bleaching stains. This positive result is achieved by the use, in said detergent compositions, of FWA consisting of the water-soluble salts of general formula described above. These FWAs actually have, when incorporated into the liquid detergent compositions, even virtually free of conventional detergency builders, the following advantages over known FWAs: a) they are perfectly compatible with them without giving rise to separation phase or precipitation; (b) they spread evenly over the fabric giving rise to a whiteness of great intensity and a pleasant and brilliant appearance; c) they do not accumulate in the tissues and therefore do not cause green tint in the tissues themselves, as a result of repeated washing; d) they can be easily incorporated into detergent formulations, as they are readily soluble in most of the solvents in said formulations, such as, for example, ethylene glycol, diethylene glycol, propylene glycol, their monoesters with lower alcohols, low molecular weight polyglycols

molecular, or their mixtures.

Claims (3)

  A liquid detergent composition for hand and machine washes, characterized in that it is substantially free of conventional detergency builders, and comprises: a) up to 70% by weight of surfactants   selected from ionic tehsioactive agents,   ionic and their mixtures; b) from 0.01% to 2% by weight of an optical brightener of general formula: NN N H / w NE-_ xH v CHi-CH - \ _ -.I-'ON N / NH-- N NCe-NE --- 5 tOX SO X NB NH--   in which R and R1 each represent a group -   C2Hs or -CH3 and X represents the sodium cation, the potassium cation, the ammonium cation, an amine or an alkanolamine, and c) organic and inorganic type of additives. 2. Liquid detergent composition according to claim 1, characterized in that R- and R 1 are both -C = He and X is sodium cation.   3. Liquid detergent composition according to one of   claims 1 or 2, characterized in that said   surfactants contain up to 3%. agents ationic surfactants. cationic surfactants.