JPH02154069A - Textile fablic-softening composition - Google Patents

Abstract

PURPOSE: To obtain the subject composition capable of excellently softening fabric but not increasing hydrophobic property in a rinsing cycle of the fabric by mixing a cationic softening salt with a cross-linked polysiloxane in a specific weight ratio. CONSTITUTION: This composition for softening fabric is obtained by mixing (A) a cationic softener of the formula [at least one, preferably two R groups are each a 12-30C alkyl; the other R groups are each a 1-4C alkyl, benzyl or forms a five-membered or six-membered heterocyclic ring together with a nitrogen atom; X<-> is an anion; n is 1-4] (e.g. ethyldimethylstearylammonium chloride or ditallowdimethylammonium chloride) with (B) a cross-linked polysiloxane in the weight ratio of the component A:B of 10:1 to 1:10 and further a nonionic softening auxiliary in the ratio of the auxiliary to the cationic softener of 20:1 to 1:5. The composition provides fabric with excellent softness in a rinsing cycle of a washing machine.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention This invention relates to fabric softening compositions adapted for use in the rinse cycle of automatic dishwashers. More particularly, the present invention relates to aqueous fabric softening compositions that provide improved softness and other desirable properties such as good wettability. Specifically, the invention is based on the combination of a cationic softener and a unique type of polysiloxane.

PRIOR ART AND PROBLEM TO BE SOLVED BY THE INVENTION At least one long-chain hydrochloride, such as distearyldimethylammonium chloride or a long-chain imidazolinium salt, is used to impart flexibility to fabrics during laundry rinsing. Compositions containing quaternary ammonium salts with carboxyl groups are commonly used.

For example, U.S. Patent No. 3.349.033; 3,644
,2033.946.1!5; 3,997,453;
4.013.135: and 4. See the specifications of No. 119.545 (there are many others), etc.

Although quaternary ammonium salts are salts, they are generally characterized by being water-insoluble. This is because under normal conditions the solubility in water is less than about 5% by weight. General The usual concentration used by consumers and considered to be ``typical'' is 6% by weight.

At concentrations above about 6% by weight, these cationic salts are usually present as 11% sol, and stability therefore becomes a major problem. For example, U.S. Patent No. 4,426,299, column 1, no.
See line 22. Indeed, at high concentrations of cationic salts (eg, greater than about 7% by weight), stability and viscosity become major issues. Many strategies are available to provide stable cationic base formulations at high concentrations (i.e., >6-7%) within usable and consumer-acceptable viscosity ranges (e.g., 30-500 cps). It is being See, for example, U.S. Pat. Nos. 4,442.013 and 4,661.2.
See No. 70, such highly concentrated formulations provide products of stable and acceptable viscosity, while their softening properties are essentially the same as 6-7% concentrated products. .

Cationic Softening Compositions, Particularly Cationic Softening Compositions for Use in the Rinse Cycle of Clothes Washing Machines, at Concentrations Comparable to, as well as at Lower Concentrations of, the Unmodified Formula. The idea that it would be desirable to provide cationic softening compositions that provide improved softening is not particularly new;
For example, U.S. Patent No. 4 by Wixon,
No. 000,077 discloses such a concept, in which a cationic quaternary ammonium salt softener is combined with an alcohol or alcohol ether sulfate. In addition to this, it has been shown that advantages can also be obtained in terms of increased whiteness (which is generally often adversely affected when using cationic salts).

It is also known to treat fibers or yarns and fabrics with silicone haze compositions to soften them. This point is discussed in “Colorage entitled “Silicones in the Textile Industry” - June 29
．． 1972 Dead Letter (M, J, Paid, p.
See 46 and 53) J. Additionally, U.S. Patent No. 3.968
．． 042 and 4.020,212, in which organopolysoloxanes (and primarily poly[
dimethylsiloxane]) and cationic softening surfactants (e.g. distearyldimethylammonium chloride) or traditional imidazolinium softeners (Varisoft (ν
arisoft) 475) is disclosed. Organopolysiloxanes are liquid, water-dispersible materials with a viscosity of about 10 at 77°F (25°C).
0 to about 400 cps.

British Patent No. 1,549.180 discloses a combination of a cationic salt and a silicone, in which the silicone is used as a waterproofing agent, an ironing aid, an antistatic agent,
In addition to the previously known benefits such as soil release agents and soil release agents, it also provides the benefit of softening. The silicone used here is a siloxane having a viscosity of "at least 100 centistokes to a maximum of 8000 centistokes at 25°C. The wood patent seems to limit siloxanes with a viscosity of 8000 centistokes or less. However, siloxanes of higher viscosities (e.g. up to 170,000 centistokes) are also disclosed; however, the data indicate that optimal performance is obtained in the range of 3,000 to 8,000 cs (Example 1). Substantially similar disclosures are made in other foreign patents, such as French Patent No. 2.318,268, which corresponds to British Patent No. 1.549.180.

The Shikajigi French patent also includes additional examples showing that "high viscosity silicones are excellent softeners."

Further, U.S. Pat.
ff) discloses a composition comprising a quaternary ammonium salt and a polysiloxane to impart properties.

The specific viscosity given for polysiloxane is 25°
It is 10,0OOcs at C. None of the prior art in the laundry softener field discloses crosslinked polysiloxanes.

Cationic softeners, mixtures of cationic softeners, mixtures of cationic softeners and anionic softeners (e.g. alcohol sulfates or alcohol ether sulfates), and/or crosslinking with nonionic softeners (e.g. fatty alcohols or fatty acid esters) It has been found that improved softening compositions can be obtained by combining with polysiloxanes. Polysiloxanes may be liquid, semi-solid, or solid. The viscosity of Borinloxane liquid is about 100cs~
The viscosity may be in any range from several hundred cs to several thousand cs to tens of thousands of as much as it becomes impossible to measure. Preferred polysiloxane viscosities are from about 10,000 cs (25°C) to maximum elastomeric type viscosities (i.e. non-measurable viscosities).

Using the compositions of the present invention, fabrics are obtained which not only have excellent flexibility but also have improved wettability.

As is well known, the use of cationic softeners tends to produce fabrics with some degree of water resistance, ie, these softeners tend to render the fabrics somewhat hydrophobic. Silicone (i.e. polysiloxane) as disclosed in GB 1.549.180
is also believed to increase the hydrophobicity of the fabric. Notwithstanding such disclosures and considerations, the compositions of the present invention not only provide improved and superior softening to fabrics, particularly during the rinse cycle of a washing machine, but also increase the hydrophobicity of the fabrics. It has been found that there is no need to cause In fact, the fabrics obtained using the compositions of the present invention exhibit improved wettability.As most people know, the complaint against cationic fabric softeners is that
In particular, towels softened using cationic fabric softeners do not absorb water as well as pristine or untreated towels.
That's the point. The comfort factor is often directly related to the ability to absorb moisture, which is why there are complaints about synthetic materials. Thus, for example, nylon fabrics have a lower ability to absorb sweat than cotton, so they are often less comfortable to wear in hot climates, a problem that is exacerbated when these synthetic materials are softened with cationic fabric softeners. I will do it.

(Means for Solving the Problems) Cationic softeners useful in the present invention have the following general formula [wherein at least one, preferably two R groups (for example, R (!: R+) are 12 is an aliphatic group having ~30 carbon atoms and the other R7J (e.g. There are all kinds of quaternary ammonium compounds represented by R, l (e.g. R2 and pz).
The nitrogen atom and/or one or more other heteroatoms (preferably nitrogen atoms) may be taken together to form a 5- or 6-membered heterocycle, where X- is, for example, a halogen ion, a sulfate ion. , methyl sulfate ion, nitrate ion, acetate ion, phosphate ion, benzoate ion, and oleate ion. The symbol "a" represents the ionic valence of the anion and therefore the number of quaternary ammonium cation moieties attached to it.Thus, for the sulfate anion, dimethylethyllauryl ammonium chloride, dimethylmethylethyl laurylcetylammonium chloride (
dimethyl-methyl-1aur
yl-cety! ammonium II chlorid
e), propyl myristyl ammonium chloride (prop
yl myristyl ammonium chlo
ride).

Examples include sitalodimethylammonium chloride and corresponding methosulfate and acetate. As an imidazolinium compound, the general formula (■) is shown. Typical compounds of the above formula I include ethyldimethylstearylammonium chloride, cetyldimethylbenzylammonium chloride, dimethyldistearylammonium chloride, benzyldimethylstearylammonium chloride, and benzyl bromide. dimethylstearylammonium,
Trimethylstearylammonium chloride, trimethylcetylammonium bromide, diethyl distearyl ammonium chloride, diethyl octyl stearyl ammonium chloride (in the formula, each R4 group is independently hydrogen or CI to C4
iRs is an alkyl group, preferably hydrogen, is an aliphatic group, preferably a C8-C1 alkyl or acyloxyalkyl, more preferably CIj-Ctt
R4 is an aliphatic group, preferably 01-C4 alkyl, more preferably methyl or ethyl; a and b are 0 or l, and a+b
iRt with =1 is selected as R3, which may be the same or different, or lower alkyl of 01-C1, such as haloalkyl, hydroxyalkyl, aminoalkyl, alkylaminoalkyl, acylaminoalkyl, etc. May be IIA alkyl; and χ
- is an expression! A more preferred compound of formula 0 is a compound represented by formula II (which is the same anion as in the case of formula II) (
a) [wherein Rs+ R&+ (a) and (b) are as defined for formula ) or C3-C4 alkyl), representative compounds of Formula 0 and Ila include 2-hebcudecyl-1-methyl-1-oleylamidoethyl-imidazolinium ethosulfate, 2-
Heptadecyl-1-methyl 1-(2-stearoylamido)ethyl-imidazolinium sulfate, 2-heptadecyl-I-methyl-I-(2-stearoylamido)ethyl imidazolinium chloride, 2-coco-1-
(2-hydroxyethyl)-1-hensyl-imidazolinium chloride, 2-coco-■-(hydroquinethyl)-1-(4-chlorobutyl)-imidazolinium chloride, 2-coco-1-(2- hydroxyethyl)-1
-Octadecenyl-imidapurinium chloride, 2-
tall oil fatty acid -1-(2-hydroxyethyl)-1-hensyl-imidazolinium chloride, 2-tall oil fatty acid -(2-hydroxyethyl)-1-(4-chlorobutyl)imidapurinium chloride, 2-heptadecenyl-1-(2-hydroxyethyl)-1-(4-chlorobutyl)-imidazolinium chloride, 2-heptadecenyl-1-(2-hydroxyethyl)-1-benzyl-imidapurinium chloride, and 2-hebucdecyl-1-(hydroxyethyl)-1-octadecyl-imidazolinium ethyl sulfate.

The following formula ■ [In the formula, the R group is a C9° to C5° aliphatic group (preferably alkyl or alkenyl) or RO-(C11,)
, −(In this case, R represents the same meaning as above, and C3゜~
C1° aliphatic group, preferably alkyl or alkenyl)
is hydrogen, C, ~C4 alkyl or hydroxyalkyl; i is an integer from 2 to 6 and mζ is an integer from 1 to 5; and X is as defined for formula (A)). Preferred compounds are those in which R is C+Z to C+S and R is lower alkyl (particularly methyl).

Examples of compounds of 2m include N-taloyl-N N
N',N'-tetramethyl-1,3-pronogundiammonium-dimethosulfate, N-chloroyl-N
,N',N'-1-methyl-1,3-pronodiaammonium-dimethosulfate,N-Olay J-retoN,N',N',N'-pentamethyl-1,3-pronodia Ammonium-dimethosulfate, N-talo-yl-N,N,N',N',N'-bencmethyl-1,3-propanediammonium-dimethosulfate, N-stearyl-N,N,N', N',N'-pentamethyl-1,3-propanediammonium-dimethosulfate, and N-stearyloxypropyl-N
,N'.

N1-tris(3-hydroxypropyl) - 1.3
-Furopane diammonium dimethosulfate, etc.

The polysiloxane used in the present invention has the following structural units: °M' units "D" units °T' single (stand) structural units [wherein R is alkyl (especially lower (01-C4) alkyl)], substituted alkyl (e.g. alkoxy, amino,
rf by halogen etc. substituted alkyl), aralkyl (e.g., benzyl), etc.; the preferred R group is methyl; the "M" unit increases the number of structural units from 0 to about 10% (
For example, 0%. It is generally represented by a rope-like structure consisting of 2%, 5%). "D" units account for about 20 to about 95% of the number of units, and "T" units account for about 2 to about 80% of the number of units.

The preferred range is 0 to 5% of “gate” units;
units is about 40 to about 80%; and "T" units are about 10 to about 60%. The most preferred range is 0 to 5% or less "H" units (e.g., 1%, 2%, or 3%);
60-80% D"units; and about 20-80% "T" units
approximately 40%, m. n. and p are respectively “i
", °D". and “↑” is an integer representing the relative content of units. Expressed as a ratio when there is a “−” median, (
nap)/- ranges from about 100:l to 10:1 (preferably from about 100+1 to 20:I), and if no units are present, the ratio n/p ranges from about 49=1 to 1: 4(
It is preferably about 4:1 to 1:1.5).

Compositions of the invention are readily made at typical 6-8% active ingredient levels. It has been found that higher levels of active ingredients can be used according to prior art methods, and as previously shown, active ingredients of up to 60% level can also be used. However, despite the level of active ingredients, the key point in obtaining the maximum benefits of the present invention is the weight ratio of cationic softener to polysiloxane. The weight ratio of cationic softener to polysiloxane ranges from about 100:1 to about 1:10; a preferred weight ratio is about 15:1 to 1:1O; a more preferred weight ratio is 1:1-1. more preferable weight ratio is 5:
1 to l:5; sat, 2:l, i:t, 1
Very good results are obtained at weight ratios of :2 and 1:5.

Regarding the viscosity, it is about 10,000-400. 0
A viscosity of 0.00 cps (e.g. 60.000 cps) gives very good results for softening;
, 000, viscosity up to OOOcρS and higher viscosity are also the same. Of particular interest are elastomeric products with so-called infinite viscosity. These products are not only excellent softeners, but also provide wetting properties that are superior to those provided by low viscosity materials.

In addition to cationic softeners, alcohol sulfates (e.g. softener adjuvants, or e.g. CI4-C1M alcohol sulfates); alcohol ether sulfates (e.g. CIA-C11 alcohols with 2 or 3 or 4 moles of ethylene oxide added); sodium paraffins (e.g. CI&~Cps);
) sulfonates; nonionic substances such as paraffins, fatty acid ester glycol and glyceryl esters, and fatty alcohols (e.g. CI&~C1, alcohols); and higher (C, ~C2°, e.g. stearic)
Ethoxylated fatty amine salts of fatty acids and the like may also be added. These adjuvants have a weight ratio of cationic softener to adjuvant of about 20:1! :5 (preferably about 15=1 to I:1
, more preferably used at lO:I~3;l. The present composition may contain opaque additives (e.g. resin emulsions), sequestering agents, viscosity modifiers such as inorganic salts (i.e. sodium nitrate, sodium chloride, calcium chloride, etc.), and solubilizers (e.g. hydrotropes). It may also contain the usual adjuvants such as.

Particularly preferred additional components are high molecular weight alcohols, especially C
e = C3° fatty alcohol (generally n-dodenyl alcohol, n-tetradecyl alcohol, oxotrizotyl alcohol, n-hexadecyl alcohol,
n-octadecyl alcohol, eicosyl alcohol, etc.) and fatty alcohol mixtures of synthetic alcohols and natural alcohols (e.g. stearyl alcohol). The preferred weight ratio of cationic softener to fatty alcohol is 6
:1 to 2.1, more preferably 5:1 to 3:l, and most preferably 4.5:I to 3.5:I (e.g. 4:
1).

The examples described below are intended to explain the present invention in more detail, but the present invention is not limited thereto. Unless otherwise specified, parts are parts by weight.

Actual difference A softening composition consisting of the following components was prepared.

X- Ditalodimethylammonium chloride 3.6CI4-C
Ill fatty alcohol 0.9 siloxane (
Crosslinked X2-7589) 0.5 viscosity is 180
Compared to cps' substantially straight borynloxane, the use of this product resulted in a terry cloth towel with excellent flexibility and also improved towel wetting properties.

Six times hard using 110ml per wash over 8 repetitions.
Softening evaluation tests can be performed using cotton terry cloth towels or using terry cloth towels in a standard washing machine according to conventional laboratory procedures. Wettability was determined by dipping a portion of a thin piece of treated cloth into water and measuring the height to which water was wicked up.

Use the following cationic softeners, and also use DTDMMC (
The procedure of Example 1 was repeated with different amounts of 3.6%).

Part (- (a) DTDM^c
(4,0%) (b) [)TD? lAC(3
,2%) (C) Dimethyl distearyl
(3,6%) ammonium methosulfate (d) 2-hebutodecyl-1= (3,6%
) Methyl-1-olylamidoLllyl imidazolinium ethosulfate lFi [II cab ~ auto, Example 1 and Examples 1 and Example n Each of (a) to II (e) was repeated.

8. Xatecyl alcohol octadecyl alcohol glyceryl monostearate CI6~Clll fatty alcohol - (- (0.9%) (0.9%) (0.9%) (1.2%) Actual picture I/V X2-7589 cross-linked Porinlow F-san instead of Tomozu no Nao Sada (Si PI445E-Walker Chemical Co,
(Walker Chemical Co.) )Example except that polydimethyl-xane was used! , a similar composition was prepared. Although this composition has an excellent softening effect, the wettability is significantly inferior to that of Example I.

In the suction test, the suction height of the test sample of Example 1 was 44.8 tara, while the suction height of the test sample of this example was 35.8 tara. It was dmm.

A difference of 3 and 5 mm in the test results is considered to be quite large.

The removal of fatty alcohols and Example 0 (a
) and It (b), the level of cationic softener was increased to 30%.
repeated. Good results were obtained.

(4 other people)

Claims (1)

[Claims] 1. A fabric softening composition comprising (A) a cationic softening salt, and (B) a crosslinked polysiloxane. 2. The weight ratio of (A) and (B) is about 100:1 to about 1:1
2. The fabric softening composition according to claim 1, which has a molecular weight of 0. 3. The nonionic softening aid is prepared in such a way that the weight ratio of the cationic softening salt to the nonionic softening aid is 20:1.
3. The fabric softening composition according to claim 2, wherein the composition is comprised in a ratio of 1:5 to 1:5. 4. The fabric softening composition of claim 2, wherein the weight ratio of (A) and (B) ranges from about 5:1 to 1:1. 5. The fabric softening composition of claim 3, wherein the weight ratio of (A) and (B) ranges from about 5:1 to 1:1. 6. The fabric softening composition according to claim 2, 4, or 5, wherein the cationic softener is a quaternary ammonium compound. 7. The quaternary ammonium compound has the general formula (a) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, at least one, preferably two, of the R groups are C_
has an alkyl moiety of 1_2 to C_3_0, the other R group is a lower alkyl or benzyl of C_1 to C_4, or forms a 5- or 6-membered heterocycle with the nitrogen atom, and X^- is an anion; and n is an integer of 1 to 4), the fabric softening composition according to claim 4. 8. Cationic softener (Q), crosslinked polysiloxane (S
), and nonionic softening adjuvant (E), Q:S:
A fabric softening composition comprising E in a range of 100:1:5 to 1:10:1. 9. Claims 1, 2, 3, 4, in the water of the rinse cycle.
9. A method of treating laundry to soften it in the rinse cycle of a clothes washer, the method comprising the step of adding a fabric softening composition according to Item 5 or 8.