GB2205578A - Liquid detergent - Google Patents

Abstract

A transparent liquid detergent composition having a pH of 4.0 to 6.5: (a) 5 to 25 weight % of anionic surfactant of one or more kinds selected from polyoxyethylene alkylether sulfonate, alkylbenzene sulfonate, alpha - olefine sulfonate and alkane sulfonate, (b) 1 to 10 weight % of mono straight chain alkyl tertiary amine oxide, (c) 1 to 15 weight % of higher fatty acid alkanolamide (d) 0.5 to 10 weight % of polypropylene oxide adduct of polyhydric alcohol having average molecular weight of 300-4000, the molar ratio of the components (a) and (b) being 0.2 to 1 and the composition having an excellent detergency, a good forming power and an excellent stability at lower temperature.

Description

TITLE OF THE INVENTION A LIQUID DETERGENT COMPOSITION DETAILED DESCRIPTION OF THE INVENTION This invention relates to a transparent liquid detergent composition which is a weakly acidic transparent liquid detergent composition having 4.0 to 6.5 of pH, more particularly having an excellent detergent power, a good foaming power and an excellent stability at lower temperature A liquid detergent, for instance, a liquid detergent for a dinner set is required to be such powers as excellent in detergent power, foaming power, mildness to the skin, stability at low temperature, etc.In order to display such powers, the liquid detergent is required to use an anionic surfactant such as polyoxyethylene alkylether sulfate, alkylbenzene sulfonate, etc. as a main detergent basic agent is used together with a sub-surfactant such as other tertiary amine oxide, higher fatty acidic alkanol amide, etc.

For instance, although polyoxyethylene alkylether sulfate is widely used since it is an excellent detergent basic agent to the mildness to the skin, it decreases both of the detergent power and the foaming power when an added mol amount of alkylene oxide increases in order to decrease the stimulus. In order to improve such fault, such method as increasing both of the detergent power and the foaming power by using the tertiary amine oxide restraing the stimulus to the skin is disclosed in patent gazette No.

38(1963)-3264 and the same No. 38(1963)-17467.

The effect of addition of the tertiary amine oxide as a sub-surfactant is considered to be caused by the behavior in a solution thereof. In other word, the tertiary amine oxide holds the following dissociation equilibrium in the solution,

and it is known that this amine oxide acts as a non-ionic surfactant at the alkali side thereof and acts as a cat ironic surfactant at the acidic side thereof.

Further, in the case of coexistence with an anionic surfactant, for instance, polyoxyethylene alkylether sulfate, it forms the following molecular association substance to neutralize the charge of the active agent ion.

R3 R N+ OH - R4 R1O(CH2CH2O)nSO3 For this reason, the electric repulsive power between active agent moleculars which form micells decreases to facilitate the formation of the micells, while cmc decreases to increase the number of the association. As a result, the foaming occurs at a lower concentration, whereby the amount of the solubility of an oily substance increases and the detergency also increases.

In consideration of the property of the above tertiary amine oxide, when pH of the detergent composition is controlled to the acidic area, the formation of the molecular association substance of the tertiary amine oxide and the anionic surfactant is accelerated whereby the property is improved more effectively.

In the acidic area, however, since the molecular association substance is firmly formed its viscosity increases remarkably, whereby a craft point raises to deteriorate the stability at a low temperature. Further, since the system itself becomes to be hydrophobic too much, the detergency to an oily stain increases, but on the contrary the foaming power decreases remarkably, thereby damaging to an article value.

Generally, the liquid detergent composition is necessary to be controlled its viscosity to about 100 to 500 cp considering the facility of taking out it from a vessel. Further, it is required not to change its outside appearance to approximately -5 C as a standard of the stability of the liquid in winter. For this purpose, lower alcohols such as ethanol, etc., lower alkylbenzene sulfonates such as p-toleuene sulfonate, etc., glycols such as ethylene glycol, propylene glycol, etc., and urea, etc. are used as it is or as a mixture thereof. However, these hydrotrope agents is small in effect in the above weakly acidic mixture. Accordingly, much amount of mixture is required, which is not economical. Further, when these are reserved at high temperatures, these are decomposed to occur an unpleasant odor. Therefore, it is not necessarily satisfied.Furthermore, even if the decrease of the viscosity and stability at low temperature are attained, the decrease of the foaming power can not be still avoided.

From such fact, the inventors have been studied earnestly to obtain such a liquid detergent which does not decrease the foaming power even in weakly acidic areas and has a suitable viscosity and an excellent stability at low temperature. As a result, they have found that if a polypropylene oxide adduct of polyhydric alcohols having a specific molecular weight is added into a mixture of an anionic surfactant, a tertiary amine oxide and a higher fatty alcanol'amide, this compound has a suitable viscosity, an excellent stability at low temperature and further surprisingly shows a remarkable increasing effect of foaming thereby providing a sufficient foaming. Thus, this invention has completed.

Namely, this invention is to provide a transparent liquid detergent composition characterized by the following 4 components, (a) 5 to 25 weight% of anionic surfactant of one kind or more than 2 kinds selected from group of polyoxyethylene alkylether sulforate, alkylbenzene sulfonate, a-olefine sulfonate and alkane sulfonate, (b) 1 to 10 weight% of mono straight chain alkyl tertiary amine oxide, (c) 1 to 15 weight% of higher fatty acid alkanolamide (d) 0.5 to 10 weight% of polypropylene oxide adduct of polyhydric alcohol having 300 to 4000 of the average molecular weight, are comprised, and a mol ratio of component (a) and component (b) [(b)/(a)] is 0.2 to 1, and pH of the composition is 4.0 to 6.5.

To the anionic surfactant used as component (a) can be used any of the anionic surfactants of one kind or more than 2 kinds selected from the groups of polyoxyethylene alkylether sulfonate, alkylbenzene sulfonate and alkane sulfonate. However, polyoxyethylene alkylether sulfate represented by the following formula (1) is desirable in the point of mildness to the hands and skin.

R1O(CH2CH2O) n503M (1) wherein, R1 represents a straight chain or a branched alkyl group or an alkenyl group having 9 to 15 carbons, n represents 0.5 to 7 of real number in average, and M shows an alkalic metal, alkalic earth metal, ammonium group or alkanol substitution ammonium group. If the number of carbons of R1 is less than 9, the detergency is insufficient, and if more than 16, the stability at low temperature of the composition deteriorates remarkably and is not preferable. Especially, preferable number of carbons is 10 to 13. Further, when the number of adduct moles n of the ethylene oxide in the formula (1) is less than 0.5, the stimulus to the hand and skin increases and is not preferable, while if more than 8, the detergency deteriorates greately, which is not desirable. Especially, the desirable range of the number of adduct moles of ethylene oxide is 2 to 5.5.

The amount of content of the above component (a) in this invention is in the range of 5 to 25 weight%. If this content is less than 5 weight%, the detergency and the foaming power are insufficient. If it exceeds 25 weight, the stability of the composition decreases.

Especially, a preferable content is 10 to 20 weight%.

In the composition of this invention, a desirable tertiary amine oxide of mono straight chain used as the component (b) is represented by the following formula (1);

wherein R2 represents a straight chain or a branched alkyl group or an alkenyl group having 10 to 16 carbons, and R3 and R4 represent a methyl group or an ethyl group respectively. When the carbons of R2 are less than 10, the detergency of the composition is low and if exceeds 16, the stability at low temperature deteriorates remarkably, which is not preferable. This mono-straight chain tertiary amine oxide is necessary to be comprised 1 to 10 weight% in the detergent composition. If the content deviates from the range described above, its detergency decreases or the stability is damaged in the combination with the component (a).

The higher fatty acid alkanolamide used as the component (c) in the composition of this invention is desirable to be synthesized from a mixture of one kind or more than 2 kinds of a saturated or an unsaturated fatty acid having 10 to 18 of carbons and the alkanolamide.

As such higher fatty acid alkanolamide, for instance, palm oil fatty acid diethanolamide is included.

A higher fatty acid alkanolamide (for instance, lauric acid diethanolamide)is considered to have the following resonance constitution.

By this, the lauric acid diethanolamide has a property which combines loosely with an anionic surfactant electrostaticically. This interaction is neither so strong as that of the interaction of the anionic surfactant with the tertiary amine oxide, nor deteriorates the stability of the composition at low temperature in the acidic area like the tertiary amine oxide.

When the higher fatty acid alkanol amide is used together with the anionic surfactant and the tertiary amine oxide, this acts to restrain the formation of the molecular weight association of the anionic surfactant and the tertiary amine oxide. This causes to improve the stability as compared with the composition which only consists of the anionic surfactant and the tertiary amine oxide. For this purpose, the content of the higher fatty acid alkanolamide is preferable to be 1 to 15 weight%, preferably 2 to 8 weight%. If it is less than 1 weight%, the above effect is insufficient, but if exceeds 15 weight%, the stability deteriorates.

The component (d) of the composition of this invention is a polypropylene oxide adduct of polyhydric alcohols.

As polyhydric alcohols, dihydric.alcohols such as ethylene glycol, propylene glycol, neopentyl glycol etc., other polyhydric alcohols such as glycerin, polyglycerin, trimethylol propane, pentaerythritol, sorbitol are included as suitable ones. In these ones, polypropylene oxide adduct of ethylene glycol or glycerin are especially preferable.

These components (d) are used as it is or by mixing more than two kinds. When the component (d) is added into a weakly acidic detergent composition comprising anionic surface active agent and the tertiary amine oxide together with higher fatty acid alkanolamide, a remarkable decrease of the viscosity, the raise of the stability at low temperature and an excellent foaming effect are displayed.

However, for occurrence of the effect, the molecular weight of polypropylene oxide adduct of polyhydric alcohol is necessary to be in the range of 300 to 4,000, preferably 500 to 2,000. In case of deviating from this range, the decrease of the viscosity and the raise of the stability at low temperature are small, and the effect of the increase of the foaming does not also appear. The component (d) is 0.5 to 10 weight% in the composition, preferably 2 to 5 weight%.

In the composition of this invention, the anionic surfactant which is the component (a) and the tertiary amine oxide which the component (b) form a strong molecular association body as described above. By this, a mixing ratio of the component (a) and the component (b) in the composition influences upon the detergency of the composition greatly. In this invention, the ratio of the component (a) and the component (b) is 0.2 to 1 of molar ratio, especially 0.3 to 0.5 is preferable. If a molar ratio is less than 0.2, a sufficient detergency is not obtained even in acidic area. Further, if it exceeds 1, the stability at low temperature deteriorates remarkably, whereby free tertiary amine oxide molecules which do not form an association body with anionic surfactant in the composition increase to be cat ionized in the acidic area, whereby the stimulus to the hands and skin increases.

In this invention, pH of the composition is preferable to be in a range of 4.0 to 6.5, especially 4.0 to 6.0.

If its pH is less than 4.0, the stalbility at low temperature deteriorates to increase the stimulus to the hands and skin. Further, if its pH exceeds 6.5, the detergency becomes insufficient.

Furthermore, the composition of this invention is prevented the foaming by water insoluble substances such as abrasive, etc. Accordingly, these should not be comprised therein.

To the composition of this invention, a surfactant for a publicly known liquid detergent can be combined therein according to the necessity in a range as far as an objective performance is not damaged other than the above necessary components. As such surfactant, for instance, non ionic surfactant such as polyoxyethylene (4 to 20 of average addition moles), alkyl (C7 to C18 of straight chain or branch), ether, etc.; amphoteric surfactants such as alkylbetaine, etc., and anionic surfactants such as a-sulfo fatty acidic ester salt, Nacyl glutamate, monoalkyl phostate, etc., are included.

Further, other arbitrary components used for ordinary liquid detergent compositions, for instance, lower alcohols such as ethanol, etc., lower alkylbenzene sulfonate such as p-toleuene sulfonate, etc.; glycols such as ethylen glycol, propyren glycol, etc.; hydrotrope agent such as urea, etc.; pH buffer solution such as citric acid, malic acid, etc.; organic or inorganic builders, preventive agent for hand irritation, enzyme, protein derivative, coloring agent, perfume, preservative, etc. can be combined therein.

The transparent liquid detergent composition of this invention has an excellent detergency, a rich foaming power and a suitable viscosity and further is excellent in the stability at low temperature. Accordingly; it is useful as the detergent for kitchen, especially the detergent for table wares.

EXAMPLES Then, this invention will be described more in details by examples. However, this invention is not defined by the examples.

Example 1 Compositions shown in Table 1 are prepared and the detergency, foaming power, viscosity, stability at low temperature of each composition are investigated. The measurement and the evaluation of the performances of various kinds of the detergent compositions in each example are performed as follows.

Test Method (detergency) After adding 0.1 weight% of Sudan II (red pigment) as an indicator to a beef tallow, 5 g of this is coated to a porcelain dish (25 cm in diameter). Then, the dish is rubbed to wash with a sponge saturated with detergent and water. The detergency is shown by the numbers of dishes which are cleaned to a condition of no existence of the remained beef tallow to be removed from the dish.

(foaming power) A foaming power is determined when 0.1 weight% of butter sold on the market as a stained component is added to the detergent solution having 0.5 weight% of detergent concentration. A measuring method is performed by adding the above detergent solution containing the butter therein into a glass cylinder having 5 cm in diameter, rotatively stirring for 5 minutes, and then determing the height of foaming after stop.

(viscosity) Each composition is put into a viscosity beaker held at 20"C and determined by a B type viscosity meter (rotor No. 3. If the viscosity exceeds 2,000 cp, rotor No. 4 is used; 60 rpm).

(Stability at low temperature) The evaluation is performed after preserving the examples for 10 days in a thermostatic chamber at -5 C.

Evaluation Content o : no change A : slightly opaque x : separation or precipitation Example 2 Compositions shown in Table 2 are prepared, and the detergency, foaming power, viscosity, and stability at low temperature of each composition are investigated.

Example 3 Compositions shown in Table 3 are prepared, and the detergency, foaming power, viscosity, and stability at low temperature of each composition are investigated. Table 1

Composition 0. This invention ompara ive examp e 5: 1 m o x r polyoxyethylene-3-dodecyiether 20 17 15 5 5 10 30 10 15 5 10 Q I (UO mooX pio S -o N v N i N o X o o x Sodium dodecyl.benzene sul fona te o 10 rd I X mclly, aOObQ tx-sodium define I N P? e o (average molecular weight X p l o H t7 o v I a o ur ur o O Sodium sulfonate 0 01 pr m h molecular weight l o cb I I mo ooX/ d tv CD v 1 < 1 5 4 7 2 2 2 7 0.5 2 2 7 O m \o aD 3 13 o D X O < Uk Nmma)mo moO tD o o a: un o I *1(diol type *2) 3 4 4 3 3 3 4 4 0.1 12 3 Water Residue { I vi I o E: I Or ratio | ] 0.46 0.43 0.86 0.22 0.21 0.25 0.43 U7 H H , o q) > (controlled suitably by 6.0 6,0 5.5 .5.5 m X N o o acid or sodium I u, N H (num1r of > v n o v e 13 20 5 8 13 13 Rcu 1 . cz, o I power (mm) 95 95 92 90 91 96 95 '25 30 50 60 I ON (cp, 20"C) 150 100 200 180 110 100 1800 50 800 30 130( I \o I at low temperature ) 0 0 0 0 0 0 X 0 x x e 3 j J J H o I o s to X z I n c N W) n vz o o rn H 04 r u X S r E > , n I ~ v v X X l c X < o . < l I ux C t78 O O O > s h 4D 1 O O H I C t ~ H O l C O u Q) wI G) X ~ n X WI Ck l ID C 1 3 D 3 C O O O E ~ X n Ul > A .0 1-' h tJ GU l : > , N X h 9 E Ç > X h D / ~ c e o X ~ v : E o l W e) X ~ c 1 ~ X ~ ux S ^ E N 3 t o o c ~ u U > > O ~ xn = E o H X > % tu al o) Q fi :J O D C k ffi l o t) 2) H .H ~ a) u D I > * e) ~ O e O E X ~ o ~ r 3 ~ I &commat; < r E v E .< ,, , < o o > * o I 4 O O O U - r ' h X U C > > I X ak v z E O z < U U c JJ : l X n r > H H O v C h O > < 9 I ç E :: E < e E r > - o o o m c uz ~ I O : O ~ n v U o v h U v O -~ $ L -~ u < O O Q X E N c aç ~ r c E > E3 s > t > f O v Y v w ul n C} o: o &commat; X o X o e N e o = U c o -H D O uz 3 v ffi w c N *1 The number represents an average moleculer weight of the compound.

*2 PO adducts whose sterting material is ethylen glycol.

Table 2

Composition No. This ,o rs t r 13 14 15 a Q 18 19 20 21 22 I o 01 1 o I a c N I OCOX m polynxyethylene-4-dodecylether l 20 10 10 10 20 20 20 10 10 0) I Q)O C n m Yr I 0 O yl O 0 Sociiutn dodecylbenzene > 1 10 10 10 10 10 u I 0 nl I L1 I v ae dimetbylamine oxide o 3 3 2 oo 3 2 2 a N I C7 0\43 E I a) a'cid diethanolamide o m 5 oo o o o vo o X N 3 m ,cy, 'C n ~ kl ((Ii()1 type *2) 5 5 5 3 3 3 5 5 5 3 3 O CN O OCCC > O C N C rn c: v O n C C C Water rs dije I d" o c ani e moO Molar ratio t(a)/(b)] 0.30 0.30 I RS ~ G U'1 E Id" o fi (controlled suitably by sulfric 4.0 c rs 4.0 n I v O t) ~ O O acid or I c > I o C I v O itimbtir of c3irhs m c 111 1 13 m: n o 10 O V) N I F1 N .~i l ~ I I n o m I oo 003 I Ln N O 21 at low temperature O O O lll X 0 0 0 ~I I'S t r1 V 0t H Z I C O C I ~, h O I h C W ~ I O V L1 1 a) la : ~ O I X vLI r O > s ~C C / &verbar; ~ t1 r O a: v E sr ~ X W C .~ U O / , ux O E > > s U / C fG + ~ .1 0 C C &commat; H ~ n X L' l xJ c CH c L X X o E / > , N E U > X > o E 3 I av ,o : X = ~ o j C o o ~ ~ H ~ O o fi > Qss O 5 3 X D P ~ H o o > s o í C O O O O 4 V 4 ul O C > > I s c v xn U w D $ v / c E c E > u c v : c va ~ I c ~ o : u . < ) v tJ v - o - E u ^ &commat; h o ~ t O E U n . o r H v ~ e , ul fa t U o o o U P X o o Ps o -d t 3 = Co X C L > tl *1 The number represents an average molecular weight of the compound.

*2 PO adducts whose starting material is ethylen glycol.

Table 3

la fi H polyoxyethylene-4-dodecylether sulfonate 15 b 15 n o o 4 15 15 Ix I in noo I 2 2 2 'VI 00 Palm oil fatty diethanolamide 6 t O m I M ri I Y m N O X (d | type z z v It) 3 k P4tD *1(diol type < PPG20OO type *3) " 2 ,o I 3 CD *1(triol type n O m \1 ~1 l N &commat; o o O O PO adduct of sorbitol (3000*1) 0 CU v, NrlO\O PO adduct of o tH S e N On y, N \0 z1 4 C y I N cl q\ Water ín < I o > In f t n v O O Molar ratio | N 0.27 0.27 0.27 0.27 0.27 0.27 0.27 0.27 ml I " Pli (controlled stiitably by | 5.5 m 5.5 5.5 5.5 o m o O acid or sodium hydroxide) I 0 FCI,,, (number of dishes) I m 13 13 In o o Iruv, rl I I ol at low ternporature 0. 0 0 0 0 O &verbar; h O p I ,C < U . S 0 st ~ tH El A3 t'3 * on uX G} Cl O 0 < h o O 0 h C ≈ n a E J 0 .4J > ws = v l v X H ^ n rn ,-t n h Ô ,AJ l I O O rs &num; * O S : 0 h l O I C nt * tl 4J C t e X > < > ~ ~ X W X í s C S O t' PS S O z ~ U O o E v ,t ffi > > S D " rt r h ç l > ; ep ffi > fi fi 4 t st ~ A3 h ~ v l s la - > v E o v s - > O E o l V , r V ~ ,-t -1 h C U. ,C Ct E cs 3 l a) > ~ 0 0 h 0 a) e E o l : > . s > t o ~t *,-t v ul m ~ 5 E : l x v v O -i h h ) ~ C h t;N l O &commat; v -t tO v v W tu W ~ Pts O U V l : E ,AJ 5 ~ ~ o o 3 3 ~ íO 4D ~ -~t uz ~ ~ ~ < -t o O :s O I a * V V V H V v , O C > > I a&num;s c I ~ * o o u * w V c v v I ,~ < o o o D ::) o v c s O cs í E > - O o o O O ss ct A3 0 O O %1 = [n ta A3 X O W1 h U v 0 s u E < n .^ t U es Q ,";t ~ ) E o ~ ffi A3 A3 ~ O t C ; < ~ fi o X c O o o e a, ffi v ffi o o o tS n o o o o &commat;d v (St u) ct X n z N N ffi 3 s ffi X vt *1 The number represents an average molecular weight of the compound.

*2 PO adducts whose starting material is ethylen glycol.

*3 PO adducts whose sterting material is glycerine.

Claims (4)

1. A transparent liquid detergent composition characterized by comprising the following 4 components (a) to (d), having 0.2 to 1 of molar ration [(b)/(a)] of the component (a) and the component (b), and having 4.0 to 6.5 of pH of the composition; (a) 5 to 25 weight% of anionic surfactant of one kind or more than tow kinds selected from groups of polyoxyethylene alkylether sulfate, alkylbenzene sulfonate, a-olefine sulfonate and alkane sulfonate.

(b) 1 to 10 weight% of mono straight chain alkyl tertiary amine oxide, (c) 1 to 15 weight% of higher fatty acid alkanolamide, (d) 0.5 to 10 weight% of polypropylene oxide adduct of polyhydric alcohols having 300 to 4,000 of an average molecular weight.

2. A transparent liquid detergent composition according to claim 1 wherein the component (a) is a polyoxyethylene alkylether sulfate represented by the following formula (1) R1O(CH2CH2O)nSO3M (1) wherein R1 represents a straight chain or a branched alkyl group or alkenyl group, n is a real number having a value of 0.5 to 7 in average and M is an alkali metal, an alkali earth metal, ammonium group or alkanol substitution anmonium group.

3. A transparent liquid detergent composition according to claim 1 wherein polypropylene oxide adduct of a polyhydric alcohol is polypropylene oxide adduct of ethylene glycol or glycerine.

4. Transparent liquid detergent compositions substantially as described in the Examples.