CH676410B5 - - Google Patents

Abstract

Insecticidal aerosol compsn. comprising as active materials 2-(1-methylethoxy) phenol methylcarbamate (propoxur) silica aerogel and opt. additional known insecticides and synergists together with suitable solvents and propellan

Description

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CH 676 410G A3

Description

The progressive diffusion of washing, in washing machines, at medium-low temperature (<60 ° C), has posed many problems for detergent formulators who wish to keep the performance of the products as unaltered as possible; among these problems, the whitening power, normally developed by sodium perborate or other per-salts, undoubtedly occupies a prominent position, since, as is known, these per-salts fully perform their action, within the times set for the machine wash, only at temperatures> 80 ° C.

One of the remedies adopted so far has been the use of substances capable of "activating" the whitening capacity of per-salts at lower temperatures, therefore known as "activators"; these are substances capable of reacting stoichiometrically, in solution, with the per-salts, giving rise to peracids which have a faster oxidation kinetics than said per-salts. The introduction of these substances in washing machine detergents has actually led to an improvement in bleaching performance at medium-low temperatures; however, the increase is modest and not without drawbacks. In fact, we note that:

- the quantity of activator is limited, both for reasons of formulation space and for technical reasons (instability of the formulation) and cost; consequently, the performances are just as limited, far from the results obtainable at high temperature and often not noticeable on a practical level;

- when washing is carried out at high temperature, the activator is useless as it does not improve the already optimal performance of the perborate and is therefore wasted;

- in general the introduction of activators is accompanied by a simultaneous reduction in the perborate rates and when the detergent is used in high temperature washing there is a poorer performance.

It has now been found that these negative aspects can be overcome and other advantages are achievable if the task of bleaching at lower temperatures is entrusted to a particular additional additive, containing a softener, instead of the actual detergent.

ILLUSTRATION OF THE INVENTION

In its broadest form, the invention relates to a granular composition containing activated perborate or other equivalent activated perborate, wherein:

- the amount of perborate expressed as tetrahydrate salt is 60 to 99% (preferably 80-95%) by weight, and the amount of activator is from 0.5 to 40% (preferably 5-20%) by weight;

- at least 80% by weight of the granules has an average size between 0.05 and 1 mm;

- in addition to perborate and activator, there is a compound of formula as a softener:

R.

R1-NH- (CH2) n - N - (CH0) m - NH - R

2 m

(THE)

or:

R- C

/

N - CH,

(II)

SN - CH,

(CH2) m -0-R2

where n and m are 1, 2 or 3, where Ri, R2 and R3, equal or different from each other, represent hydrogen or an aliphatic acyl group having 10 to 20 C atoms and where R4 represents hydrogen or a group alkyl or alkenyl having 10 to 20 C atoms, the amount of softener being preferably from 1 to 10% and better still from 2 to 5% by weight.

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CH 676 410G A3

Characteristic of the above softeners is their insolubility in water, especially at alkaline pH.

Advantageously, said composition can also contain from 0.1 to 1% by weight of an optical brightener and from 0.2 to 1.5% by weight of a proteolytic enzyme.

It is known that common after-laundry softeners, consisting of cationic surfactants, are incompatible with traditional detergents used for washing; This is confirmed by the fact that the fabric softener is always and exclusively added in the last rinse, or in any case after the detergent has been completely removed. If this procedure is not followed, the softening and detergent effect will be simultaneously eliminated. The origin of this must be attributed to the charges of opposite sign brought by the ions present in the softeners (quaternary ammonium cations) and in the detergents (sulfonic anions) which, due to mutual electrostatic attraction, would give rise to insoluble and inactive adducts.

However, some research by the Applicant has led to the identification of alternative substances with fabric softening power, with a structure other than cationic surfactants, free of ionic charges and therefore compatible with traditional detergents; their solid state at room temperature and the possibility of grinding them to the desired particle size allowed their introduction into the composition according to the invention.

As shown by the results shown in the examples, machine washes carried out with normal commercial detergents, to which the compositions according to the invention are added, containing fabric softener, lead not only to the improvement of the whitening effect but also to a very soft laundry . This means that the softeners according to the invention not only do not interact negatively with the surfactants of the detergent, but resist rinses, remaining firmly anchored to the fibers. If the new compositions, containing the softener, are used alone, that is in the absence of detergent, the softening effect is even more pronounced. The use of a bleaching composition containing activators, and therefore specifically designed for bleaching at medium-low temperature, separated from the detergent and to be added to the latter before washing, offers the following advantages:

- possibility to dose the activator as desired according to the desired result and limitation of use only in cases where it is actually necessary to obtain an effective bleaching at lower temperature;

- no waste in high temperature washes, because in this case the additive is not necessary and you can avoid using it, and the possibility of using the additive also on its own, when a detergent effect is not required, with a consequent saving of the latter.

In addition, such an additive can also find a useful application in other washing methods, such as for example in hand laundry, where up to now the bleaching is carried out only occasionally, and only on white fabrics, with hypochlorite. Without going into the merits of the numerous defects related to hypochlorite, it is sufficient to underline that the bleaching with hypochlorite is, for known reasons, subsequent to a previous washing phase by common surfactant-based detergents, separated from the bleaching phase by an abundant rinsing, while the use of the additive with activator does not require any additional phase to that of cleaning. The use of bleaching additives in washing laundry is nothing new; for a long time and on the market, for example, pure perborate (or percarbonate), to be added to detergent both in machine and normal washing, but in critical temperature conditions its effectiveness is negligible, as also highlighted by examples below, which illustrate the invention without however limiting its scope in any way.

METHODS COMMON TO EXAMPLES 11. 2. 3. 4. 5. 8.

Of fundamental importance for the stability, homogeneity and performance of the product are some chemical-physical characteristics of the components, such as particle size, specific weight, frangibility, moisture content, etc. By way of example, we report below these characteristics for some of the components used, referring to the specific examples for the description of the minor components. Frangibility is determined according to the European Laboratory Standard Practice Instructions Nr. 7/17050 of 19 June 1971.

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CH 676 410G A3

Sodium perborate particle size (PBS)

residue on% mesh (by weight)

0.80 mm

3.8

0.40 mm

54.3

0.20 mm

89.9

0.16 mm

96.3

Titre in active oxygen = 10.3%

Specific apparent weight = 0.77 g / cm

frangibility:

Original particle size fraction

Final fraction below the minimum level

0.4 mm <0 <0.8 mm

13.2% by weight (<0.4 mm)

Particle size of the activator (tetraacetyl-ethylenediamine)

residue on mesh of

% (by weight)

1.7 mm

1

1.0 mm

10

0.600 mm

66

0.355mm

94

0.125mm

99

Specific apparent weight = 0.55 g / cm3; Activator titer (TAED) = 93%; Moisture = 1.5% by weight;

frangibility:

Original particle size fraction Final fraction below the minimum level 0.4 mm <0 <0.8 mm 22.2% by weight (<0.4 mm) 0> 0.8 mm 32.2% by weight (<0.8 mm)

The granules of the activator used (TAED) are the result of an agglomeration carried out on the smallest particles of the compound, initially in the form of a powder; considering the importance of the size of the particles constituting the granules, for the purpose of their dissolution rate in the washing bath, and therefore of the consequent activating effect on the perborate, we report here below the particle size distribution:

residue on mesh of

% by weight

0.355mm

7

0.125mm

57

0.062mm

81

Considering the stoichiometry characteristics according to which the peroperated / TAED (or other activator) interaction takes place, and therefore the activation of the PBS, the maximum equivalent useful ratio between PBS and TAED and the 1: 1 ratio (as is known , each TAED molecule is able to react with two PBS molecules) which corresponds, in weight terms, to a mixture containing 60% of PBS and 40% of TAED. Lower but equally useful results can still be obtained even with a higher PBS / TAED ratio, i.e. in the absence of TAED. The best cost / performance ratio, not binding for the purposes of the invention, was obtained for a PBS / TAED = 90/10 weight mixture, hereinafter referred to as "PRODUCT".

This does not mean that this mixture offers the highest performance (obtainable only with the stoichiometric ratio), but rather that it is able to develop the highest increases in whitening effect at the lowest cost.

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CH676 410G A3

Example 1

High and medium temperature bleaching tests in the washing machine were carried out by adding the "product" to common "heavy-duty" detergents; the washing modes were as follows: WASHING MACHINE: REX SL 228 T by the ZANUSSI company PROGRAM AT 60 ° C = Program E of the washing machine PROGRAM AT 90 ° C = Program C of the washing machine DETERGENT DOSAGE = 150 g / wash «PRODUCT» DOSAGE = 40 g / wash LINEN: 3 Kg. of white cotton tea towels for washing

TESTS: 2 pieces 10 x 10 cm of EMPA 114 cotton, standardly stained with red wine at the EMPA Institute in St. Gallen (Switzerland), for each wash.

PROCEDURE: At the end of the washing program, the specimens were dried and ironed; subsequently the degree of bleaching was determined by reflectometry. The data in Table 1 are expressed in terms of% of bleaching, understood as:

A ^ x 100, where:

C-B

A = degree of whiteness (%) of the washed specimen;

B = degree of whiteness (%) of the specimen before washing;

C = whiteness degree (%) of the completely bleached specimen.

The whiteness degrees were measured with Elrepho Zeiss reflectometer assuming MgO = 100% whiteness and using the filter N ° 6 (X = 464 nm). The results showed that the addition of only perborate at 60 ° C leads to very modest increases in the cleaning power and that the addition of the "product" leads, instead, to 60 ° C, to a higher increase; the bleaching degree is also higher than that obtainable with an excellent commercial detergent containing activator (Bio Presto). Even at 90 ° C the addition of the "product" leads to higher bleaching levels, especially with respect to the detergent with activator (Bio Presto) and the use of the "product" leads to bleaching increases that are more marked the lower the whitening capacity of the detergent alone (see tests with DIXAN and with Sole Bianco).

Table 1

Proven formula Washing program at:

60 ° C 90 ° C

Dixan (Henkel) 63 90 Dlxan (Henkel) + PBS 65 94 Dixan (Henkel) + «product» 70 95 Sole Bianco (Panigal) 53 -Sole Bianco + «product» 69 -Bio soon with TAED (Lever) 68 85

Example 2

Bleaching tests, tending to reproduce the conditions of a hand wash, were conducted in the following ways. In one liter of hot water at 50 ° C, 5 g of a heavy-duty handwashing detergent (Bio Presto, handwashed by Lever) was dissolved and then 4 g of "product"; they then introduced (for each wash) 2 pieces of the stained cotton of the example 1, and left to cool to rest, stirring occasionally. At the end, the specimens, rinsed and ironed, were subjected to bleaching degree measurement , as described in example 1. The data are collected in Table 2; it can be observed that the effect of the detergent alone is very poor, that the addition of PBS significantly improves the bleaching results and that the addition of the «product »However leads to significantly higher values, especially for shorter washes.

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CH 676410G A3

Table 2

Bleaching duration (%)

of washing only detergent detergent + PBS

detergent + «product»

1 hour

23

45

64

2 hours

23

49.5

67

4 hours

23

57

74

8 hours

23

60

76.5

Example 3

A further improvement of the whitening power of the "product" was obtained by adding it with optical bleaching agents which, as is known, are able, in suitable conditions, to give greater brilliance to colored fabrics and a more dazzling white sensation to non-colored ones. Following the procedure described in Example 2, as regards conditions, methods and dosages (washing duration = 4 hours), hand laundry tests were performed, using both the «product» alone and the «product as bleaching agents. »Added with various optical bleaches; the tests were conducted on white cotton specimens, free of optical bleaches. At the end of the test, the specimens, rinsed, dried and ironed, were subjected to measurement of the degree of whiteness according to the color coordinate method, known as Tristimulus, using the X, Y, Z filters and processing the numerical data according to the standards of the same method. A crucial condition is that the optical bleach is specific for low temperature washing and that it resists oxidizing chemical agents; without limiting the scope of the invention, a 4-4'-distyrylbiphenyl derivative, produced by Ciba-Geigy and marketed as TINOPAL CBS-X, was chosen as an example, having the following particle size:

residue on mesh of

%

0.315 mm

0.8

0.100 mm

77.2

0.050 mm

97.6

The bleach was introduced into the "product" by mixing; the results are collected in Table 3, from which it can be seen that the treatment with the «product» alone increases the whiteness of the fabric in a purely marginal way and that the addition of small quantities of the optical brightener, on the other hand, improves considerably.

Table 3

mode

Degree of white (Tristimulus)

Without any additives

123

With the addition of the «product»

126

With added product + Tinopal CBS-X (0.05%) *

145

With the addition of the «product» + Tinopal CBS-X (0.1%) *

152

With the addition of the «product» + Tinopal CBS-X (0.2%) *

156

*% by weight with respect to the «product».

Example 4 (Tests in washing machine with optical bleach)

The tests were carried out using the «product» with the addition of Tinopal CBS-X as the bleaching agent, also with Tinopal DMS-X, more suitable for high temperature washing, following the procedure described in Example 1, with the following variants :

WASHING MACHINE = CANDY P 9.71 PROGRAM AT 60 ° C = washing machine program 4 PROVINI = as in example 3

DETERMINATION OF THE DEGREE OF WHITE = as in example 3.

Data and results are in Table 4; as can be seen, in the low temperature conditions of the tests, the presence of an optical bleach suitable for high temperatures not only does not improve the result, but slightly reduces the performance of the specific optical bleach for low temperature.

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CH 676410G A3

Table 4

Degree of white

MODE '

(Tristimulus)

"product" + TINOPAL CBS-X (0.1%) *

160

"product» + riN0PAL CBS "X (0'U) *

153

(TINOPAL DMS-X (0.5%) *

"product" * jTIN0PAL CBS ~ X *

154

(TINOPAL DMS-X (0.3%) *

. "(TINOPAL CBS-X (0,03S} *" product + J

149

[TIHOPAL DMS-X (0.15%) *

*% by weight with respect to the "product".

Example 5

Components with a softening effect on the washed fabric were added to the "product" of Example 1; this additional feature makes the invention a completely new whitening additive which does not find similar results in other products on the market. The added fabric softener (hereafter indicated by the letter A) had a structure of the type:

RI-NH (CH2) 2 -NH - (CH2) 2-NH2

where Ri = aliphatic acyl group with 18 atoms C.

The fabric softening tests were carried out by washing white cotton terry towels from a single production stock in a CANDY P 9.71 washing machine at 60 ° C (program 4) (1 towel + 3 kg of white cotton tea towels as ballast for each wash), using a commercial detergent (Sole Bianco from Panigal) at a dosage of 150 g / wash, added with 40 g of «product» with fabric softener. At the end of the washing program, the test towels were dried, ironed and examined manually for their softness.

For comparison, washing was also carried out with the same detergent but without "product"; at the last rinse a commercial softener (Coccolino concentrate from Lever) was added to the prescribed doses (20 g / wash).

To define the degree of softness of the treated specimen, an arbitrary score was established from 0 to 10 where 10 represents the effect of the traditional fabric softener and zero is the situation of the towel before the test.

To guarantee a uniform and significant starting condition of the specimens, all new towels

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CH 676 410G A3

they were previously washed at least 10 consecutive times in a high temperature washing machine with a heavy-duty detergent.

Another term of comparison was introduced in the experimentation using a new detergent for washing machine recently put on the market, with softening power, that is the "Dynamo 2 with softener" of the Colgate-Palmolive firm. The tests were carried out by adding the above softener to the "product", from the following particle size:

residue on mesh of

%

0.500 mm

7.2

0,315

38.8

0.100 mm

81.6

0.050 mm

94.6

The results, shown in Table 5, show that by using the «product» suitably added with the fabric softeners object of the invention, it is possible to obtain, in the washing phase alone, without any additional operations, softness results (as well as bleaching) comparable with those of a commercial cationic fabric softener (especially when in the washing bath the concentration of A and the Coccolino cationic are similar, as in test 7) and clearly higher than those of a detergent with a fabric softener.

Table 5

Test number

Products used

Degree of softness

1

None (blank test)

0

2

White Sun + Coccolino

10

3

Sole Bianco + («product» + 1% A) (*)

2

4

Sole Bianco + («product» + 2% A) (*)

6

5

Sole Bianco + («product» + 3% A) (*)

7

6

Sole Bianco + («product» + 4% A) (*)

8

7

Sole Bianco + («product» + 5% A) (*)

8

8

Dynamo 2 with fabric softener

2

(*)% by weight, referred to the "product".

Example 6

This test was performed in the presence of a proteolytic enzyme, in granular form, having the following particle size distribution:

residue on mesh of

%

0.8 mm

8.2

0.5 mm

98.6

0.2mm

100

The whitening formulation had the following weight composition (composition I):

Sodium perborate tetrahydrate 90 parts

TAED (93% of title) 10 parts

Optical brightener Tinopal CBS-X 0.2 parts

Proteolytic enzyme (Esperase from Novo Enzymes) 1 parts

The results are shown in Table 6 and refer to 60 ° C tests carried out in the washing machine as per example 1 (program E), adding to 150 g of commercial detergent for heavy-duty washing machine (Sole Bianco of the Panigal company), 40 g of said whitening formulation. In addition to 3 kg of ballast, consisting of white cotton tea towels (for each wash), 10 x 10 cm cotton specimens were introduced

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CH676 410G A3

soiled in a standard way at the EMPA institute in St. Gallen (CH) with various types of soils, as listed in Table 6. For comparison, a series of washes was carried out by adding the whitening composition previously defined as "product" to Sole Bianco.

The data that express the percentages of detergency or bleaching, calculated as described in example 1, show that the addition of a bleaching additive, designed for low temperature, as is the "product", significantly improves the performance of the sole detergent not only on oxidizable dirt such as red wine but, surprisingly, also on dirt traditionally considered non-oxidable such as, for example, blood or cocoa. They also demonstrate that the enrichment of the "product" with the appropriate components described leads to even higher and more complete results.

Table 6

Type of dirt

Bleach (%) Only detergent

Cleaner + «product»

Detergent + composition (I)

White cotton

87

88

89

not soiled

EMPA 101

46

48

48.5

(shirt collar type)

blood

52

54

57

cocoa

49

52

56

Red wine

53

69

70

Example 7

The storage stability of the whitening composition object of the present invention is higher than that of detergent formulations for washing machines containing activators and also that of detergent formulations that do not contain them, although for the whitening composition the stability conditions are more critical due to the more frequent contact between persale and activator; the stability was determined by following the residual titre of the formulations for about 30 days, introduced in boxes for detergents of the E2 format (500 g of powder per box), then sealed and kept in a thermohygrostatic oven at 40 ° C and at 55% of relative humidity. The weight composition of the bleaching additive tested was the following (composition II):

sodium perborate tetrahydrate

90 parts

TAED (93% of title)

10 parts fabric softener (compound A of example 5)

5 parts Tinopal CBS-X optical bleach

0.25 parts proteolytic enzyme

0.5 parts

The stability data, expressed as a percentage of residual perborate compared to the initial one, are collected in Table 7.

Table 7

Formulations Storage time (days)

7

14

21

28

Bleaching composition (II)

98.7

97.8

91.9

85

Dixan (Henkel)

94.5

85.3

78.2

74.2

Bio Presto with TAED (Lever)

95

94

80

71.7

Example 8

The importance of the particle size of the individual components of the whitening composition object of the invention is highlighted by the values in Table 8, which refer to results obtained in initial hand washing tests at 50 ° C, according to the procedure of Example 2, on specimens soiled with red wine, using two blends of sodium perborate tetrahydrate and TAED with the same composition as bleaching agents

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CH 676 410G A3

percentage / PBS = 90%; TAED (93% titer) = 10% / e with the same purity of the components, but different for the particle size of the PBS.

residue on mesh of

PBS in composition A PBS in composition B

0.80 mm

3.8%

86.0%

0.40 mm

54.3%

98.5%

0.20 mm

89.9%

99.6%

0.16 mm

96.3%

99.7%

Table 8

Duration of washing

Bleach (%)

(Hours)

Bleaching composition A

Bleaching composition B

1

64

54.5

2

67

57.5

4

74

59

8

76.5

67

Example 9 (Tests on lanaì.

The composition of the invention can also be used as a bleaching agent for woolen fabrics to replace the known products on the market based on dithionite. Compared to the latter, an activated perborate composition offers the following advantages:

- absence of bad smells during treatment and applicability even on colored garments;

- compatibility with all types of traditional detergents;

- no need, therefore, for additional and separate washing phases.

As regards the elimination of the yellowing of the wool, due to the resurfacing of the original color of the fiber after the washing, one can, in fact, obtain similar results to the products based on dithionite.

The results obtained on white virgin wool specimens for treatment with the following activated perborate bleaching composition (composition III) are shown below (Table 9):

sodium perborate tetrahydrate 90 parts by weight

TAED (93% titer) 10 parts by weight

Optical brightener (Tinopal SWN concentrate) 0.5 parts by weight

The grain size of the concentrated Tinopal SWN is the following:

residue on mesh of

%

0.500 mm

0.5

0.315 mm

4.5

0.100 mm

38

0.050 mm

86

Table 9

Whiteness formulation (%)

Composition (III)

71.9

The reported results were obtained in hand-washing washing tests with an initial temperature of 40 ° C on wool pieces of 20 x 5 cm, having an initial whiteness degree of 68, immersed in a liter of solu-

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tion containing 4 g of composition (ili). For the determination of the degree of whiteness (%) on the rinsed and dried pieces, the method of Example 1 was followed.

Claims (8)

claims 1. Granular composition, containing activated perborate, in which: - the amount of perborate, expressed as tetrahydrate salt, is from 60 to 99% by weight, the amount of activating agent being from 0.5 to 40% by weight; - at least 80% by weight of the granules has an average size between 0.05 and 1 mm; - in addition to perborate and activator, there is a compound of formula as a softener: R1-NH- (CH2) n-N- (CH2) in-NH2 where n and m are 1,2 or 3 and where Ri and R3, equal 0 different from each other, representing hydrogen or an aliphatic acyl group, having from 10 to 20 atoms C. 2. Composition according to claim 1, wherein the amount of fabric softener is from 1 to 10% by weight. 3. Composition according to claim 1, containing from 0.1 to 3% by weight of an optical brightener suitable for temperatures of 60 ° C. 4. Composition according to claim 1, containing 0.2 to 1.5% by weight of a proteolytic enzyme. 5. Composition according to claim 1, wherein: a) the amount of perborate as tetrahydrate is from 80 to 95% by weight and the amount of activator is from 5 to 20% by weight; b) the amount of fabric softener is 2 to 5% by weight and the fabric softener formula is as follows: RI-NH- (CH2) 2-NH- (CH2) 2-NH2 -Ri = aliphatic acyl group having 16-18 C atoms; c) there is an optical brightener, in an amount from 0.1 to 1% by weight. d) a proteolytic enzyme is present, in an amount from 0.2 to 1.5% by weight. Use of the composition according to claim 1, for washing white or colored textile materials, at temperatures equal to or lower than 60 ° C, the washing being carried out in the presence of a detergent based on surfactants and builders. Use according to claim 6, wherein the textile materials are cotton or other cellulosic fiber fabrics, or mixed fabrics containing cellulosic fibers. Use according to claim 6, wherein the textile materials are wool fabrics or mixed fabrics containing wool. 12