JPS63161083A - Liquid detergent composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a liquid detergent composition, and more particularly, to a liquid cleaning composition containing a strong electrolytic surfactant and hydroxypropyl methyl cellulose and having excellent stability. The present invention also relates to a cleaning composition which imparts creaminess and smoothness to the foam, has good foam retention, and suppresses residual residue (stickiness) after rinsing.

[Conventional technology and its problems]

Conventionally, fatty acid alkanolamides, monoglycerides, and various ionic polymers have been used as foam modifiers for liquid detergents. However, they are not effective unless they are blended in large amounts, and if they are blended in amounts that are sufficient to produce a sufficient effect, there are problems such as a heavy or sticky feel after washing.

In addition, nonionic polymers such as polyethylene oxide,
There were problems such as poor low temperature stability among strong electrolytic surfactants.

[Means to solve the problem]

The present inventors have solved these conventional problems by creating a creamy and long-lasting foam that also suppresses stickiness after washing.In particular, with regard to hair, it eliminates tangles during hair washing and improves the quality of the foam after rinsing. We worked hard to give it a smooth feel. As a result, they found that a specific hydroxypropyl methylcellulose has excellent low-temperature stability even in the presence of a strong electrolyte surfactant, and that sufficient foam quality can be obtained with a small amount. That is, it has been found that by blending hydroxypropyl methylcellulose, a liquid detergent composition that has a fine texture and smooth foam and a smooth feel after rinsing can be obtained.

That is, the present invention comprises the following components (A) and (B) (A) of the following formula (I), (wherein the molecular terminal and R are either a hydrogen atom, a methyl group or a hydroxypropyl group) having the structural unit represented by the formula, and having a methoxy group content of 25 to 35% by weight,
The content of hydroxypropoxy groups is 5 to 15%,
The viscosity of the 2 weight aqueous solution at 20°C is 50 to 2ooo
0.1 to 2% by weight of hydroxypropyl methylcellulose, which is centipoise; (B) one or two surfactants selected from the group consisting of cationic surfactants, anionic surfactants, and amphoteric surfactants; The present invention provides a liquid detergent composition containing 2 to 50% by weight of the above as an essential component.

Hydroxypropyl methyl cellulose used as component (A) of the present invention has a structural unit represented by the above general formula (I), and preferably has an average molecular weight of 2QOOO to 7QOOO.

This hydroxypropyl methylcellulose can be synthesized by a known method, and can also be obtained as a commercially available product.

This hydroxypropyl methylcellulose is 2% by weight (
(hereinafter simply indicated as H) as an aqueous solution, and using a BM viscometer,
Viscosity is 50-40 when measured at 0°C and 30 revolutions/min.
00 centipore, <(CPS). By the way, the average molecular weight of 50CPS is about 2QOOO12000
CPS has an average molecular weight of about 7QOOO. 500
If the foam is less than PS, a sufficient foam modification effect cannot be seen, and zo
o.

If it is more than 028, the solubility will be poor.

In addition, the hydroxypropyl methylcellulose is one in which a part of the hydroxyl groups of cellulose is substituted with a methoxy group or a hydroxypropoxy group, and the content of methoxy groups is 25 to 35% in the hydroxypropyl methylcellulose.
%, preferably 27-32% The content of hydroxypropoxy groups is 5-15%, preferably 7-13%. The degree of substitution is approximately 1.5 to 2.0, that is, approximately 1.5 to 2.0 among the three hydroxyl groups contained in one unit of glucose.
are replaced. Hydroxypropyl methylcellulose outside this range has poor solubility and low-temperature stability even if the viscosity of a 2% aqueous solution at 20° C. is 50 to z000.

Among the above-mentioned hydroxypropyl methylcellulose, the most suitable one in terms of low-temperature stability and foam-modifying effect is a methoxy group content of 28 to 30%, a hydroxypropoxy group content of 7 to 12%, and a viscosity of a 2% aqueous solution at 20°C. is about 400
Hydroxypropyl methyl cellulose (Metrose 60 S H, Shin-Etsu Chemical) with an average molecular weight of about 4QOOO is exemplified.

Moreover, among the surfactants of component (B), the following are exemplified as anionic surfactants.

(I) A linear or branched alkylbenzene sulfonate having an alkyl group having an average carbon number of 10 to 16.

(2) Contains a linear or branched alkyl group or alkenyl group with an average of 10 to 20 carbon atoms, with an average of 0.5 to 20 carbon atoms per molecule.
8 moles of ethylene oxide, propylene oxide,
Butylene oxide, ethylene oxide and propylene oxide in a ratio of 0.1/9,9-9.9/0.1 or ethylene oxide and butylene oxide in a ratio of 0.1/9.9-9,9/0.1 Alkyl or alkenyl ether sulfate added in ratio.

(3) An alkyl or alkenyl sulfate having an alkyl group or alkenyl group having an average carbon number of 10 to 20.

(A) Olefin sulfonate having an average of 10 to 20 carbon atoms in one molecule.

(5) Alkanesulfonate having an average of 10 to 20 carbon atoms in one molecule.

(6) A saturated or unsaturated fatty acid salt having an average of 10 to 24 carbon atoms in one molecule.

(7) It has an alkyl group or alkenyl group with an average carbon number of 10 to 20, and an average of 0.5 to 8 moles of ethylene oxide, propylene oxide, butylene oxide, ethylene oxide and propylene oxide in 0.1 / molecule per molecule. 9.9-9.9/0.1 ratio or ethylene oxide and butylene oxide 0.1
/9.9 to 9.9/0.1 alkyl or alkenyl ether carboxylate.

(8) α-sulfo fatty acid salt or ester represented by the following formula.

Ry-CHC(hY 03Z (wherein Y is an alkyl group having 1 to 3 carbon atoms or a counter ion, 2
is the counterion. R7 represents an alkyl group or alkenyl group having 10 to 20 carbon atoms. ) (9) An amino acid type surfactant represented by the following general formula.

9 RIG (wherein R8 is an alkyl group or alkenyl group having 8 to 24 carbon atoms, Rg is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, RIG is an amino acid residue, and X is an alkali metal or alkaline earth (Indicates a metal ion.) (In the formula, R8, R9 and X have the above-mentioned taste, and nl
represents an integer from 1 to 5. ) In formula C, Rs and X have the meanings described above, and ml is 1 to
Indicates an integer of 8. ) R11RIO (wherein R8, RIo and X have the above meanings,
R11 represents a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, or a hydroxyalkyl group. )9 RIO (wherein R9, RIO and X have the meanings described above, R
12 represents a β-hydroxyalkyl group or a β-hydroxyalkenyl group having 6 to 28 carbon atoms. ) RIG (In the formula, RIOs R+2 and (I0) Phosphate surfactant (I) Alkyl (or alkenyl) acidic phosphate ester (R80) H2-P-+OH)H2 (wherein R8 has the above meaning, H2 and Mari are n
Indicates a number where 3+膓=3 and n2=1 to 2. )(n)
Alkyl (or alkenyl) phosphate ester OR.

Rs OP -ORs (wherein, R8 has the meaning described above) (iiD
Alkyl (or alkenyl) phosphate ester salt (Rao)R3-P→OM)H3 (wherein R8 has the above meaning, M is sodium,
Potassium, calcium, R3 and simple, n3 + 膓 = 3
, n3=1 to 3) Examples of the zwitterionic surfactants include the following.

(U) Sulfonic acid type amphoteric surfactant (I) RBCONH-R13-N"-Rts-
SO3- (wherein R11 has the meaning described above, R1
3 is an alkylene group having 1 to 4 carbon atoms, and R14 is an alkylene group having 1 to 4 carbon atoms.
-5 alkyl group, and R15 represents an alkylene group or hydroxyalkylene group having 1 to 4 carbon atoms. ) (I) R@-N"-Rts-803- (wherein Rs and R15 have the above-mentioned meanings, Rla,
R1? each represents an alkyl group or an alkenyl group having 8 to 24 carbon atoms or 1 to 5 carbon atoms. ) (C2H40)n4H In the formula, R11 and R15 have the above meanings, and H4
represents an integer from 1 to 20. ) (I2) Betaine type amphoteric surfactant represented by the following general formula (I) Rls -N'' -R2O-COO-1 In the formula, R18 is an alkyl group having 8 to 24 carbon atoms, an alkenyl group, β-hydroxy R19 is an alkyl group or β-hydroxyalkenyl group, R19 is an alkyl group having 1 to 4 carbon atoms, Rg
o represents an alkylene group or a hydroxyalkylene group having 1 to 6 carbon atoms. ) (C,H40)n4H 1 In the formula, RIJl, R40 and H4 have the above-mentioned meanings. ) (lti) Rts -N+-Rzo -COO-(
In the formula, Rlg and R20 have the meanings described above, and lhl
represents a carboxyalkyl group or a hydroxyalkyl group. ) (I3) Alkylamine oxide represented by the following formula.

Rts R? -N-4Q In formula 1, R7 has the meaning described above, and R23 and R24 each represent an alkyl group having 1 to 3 carbon atoms. ) Furthermore, the following are exemplified as cationic surfactants.

(I4) A cationic surfactant represented by the following formula.

In formula C, at least one of R28% Ro, R27, and R28 represents an alkyl group or alkenyl group having 8 to 24 carbon atoms, the others represent an alkyl group having 1 to 5 carbon atoms, and X'' represents a halogen atom. . ) (wherein, Rzs, R26, R2
γ and X'' have the above meanings.) (In the formula, 'Rzs, R16, X' and R4 have the above meanings, and R28 represents an alkylene group having 2 to 3 carbon atoms. Among the surfactants that are the detergent base, particularly preferred are (2) polyoxyethylene alkyl sulfate salt (average number of added moles of 2 to 4), and (9) &I 2
amide amino acid type surfactants, particularly their alkali metal salts such as their sodium salts.

In other words, the alkali metal salts of these anionic surfactants, especially their sodium salts, are among the most preferred as liquid detergent bases, but because they are strong electrolytes, they do not allow foaming of nonionic polymers such as polyederene oxide. Even if it was added as a modifier, it would salt out, and no foam-modifying effect could be obtained, making it impossible to mix stably. However, hydroxypropyl methylcellulose, which is the component (A) of the present invention, can be used not only in liquid detergents based on weak electrolytes such as alkanolamine salts of anionic surfactants, but also in liquid detergents based on strong electrolytes such as those described above. It can also be incorporated into liquid detergents and has an excellent foam-modifying effect.

The cleaning composition of the present invention can be prepared by blending the component (A) in an amount of 0.1 to 2% (hereinafter simply referred to as "C") and the component (B) in an amount of 2 to 50% according to a conventional method. prepared.

In addition to the above-mentioned essential ingredients, the cleaning composition of the present invention contains solubilizers such as propylene glycol, glycerin, and urea, which are used as ingredients in known cleaning compositions, ethanol, inorganic salts, higher alcohols, and polypropylene. A viscosity modifier such as acrylic acid, other fragrances, pigments, ultraviolet absorbers, antioxidants, anti-dandruff agents, bactericidal agents, preservatives, etc. can also be blended.

〔Effect of the invention〕

The cleaning composition of the present invention has both excellent cleaning properties due to the strong electrolyte and excellent foaming properties due to the hydroxypropyl methylcellulose. Therefore, it can be particularly advantageously used as shampoo, skin cleansing agent, dishwashing agent, etc.

〔Example〕

The present invention will be explained in more detail with reference to Examples below. In addition, in the following experiment, the liquid cleaning agent was evaluated as follows. In addition, the amounts of the ingredients are all shown in weight it% of the effective content.

(I) Solubility, low-temperature stability: A liquid detergent composition is prepared by a conventional method, and the state of the liquid immediately after preparation is judged according to the following criteria, and it is determined as "solubility" and -5.
The condition when stored at ℃ for 1 day was determined in the same manner and indicated as "low temperature stability".

O: Transparent and uniform.

Δ: Slightly opaque or with a small amount of precipitate.

×: A large amount of precipitation or phase separation was observed.

(2) Smoothness of foam, creaminess, stickiness after rinsing: 30? Moisten the hair with 40℃ water and add 202℃ of water. Next, the above liquid cleaning composition 1? A control shampoo (without hydroxypropyl methylcellulose in each experiment) was used to cleanse and evaluate the sudsiness, creaminess, and non-stickiness after rinsing.
A sensory evaluation was conducted in comparison with

Evaluation details O: Clearly superior to the control shampoo.

Δ: Slightly better than the control shampoo.

×: Same as control shampoo.

Example 1 A liquid cleaning composition shown in Table 1 was prepared according to a conventional method,
Its solubility and low temperature stability were evaluated.

The results of this are also shown in the same table. In addition, in the composition of Table 1, hydroxypropyl methyl cellulose accounts for 2% of the total.
The viscosity of the water bath liquid at 20°C is about 400 (average molecular weight about 4QOOO).

(I) Milanor C2M Conc (manufactured by Milanor); (9
) Gv) In the formula, R13CO=coconut fatty acid residue, t
= 1, X = NaO) (2) methoxy group 29%, hydroxypropoxy group 8°5% (3) 28%,
Section 60 (A) l 21.5%,
8% (5) 1 29% (Hydroxypropoxy group free) (6) Ceropond 45,000
A (B P Company); 25°C, viscosity of 10% aqueous solution 500
0PS (average molecular weight approximately 2,700) (7) Shin-Etsu I (PC, EFG (Shin-Etsu Chemical): 25°C,
Viscosity of 1% aqueous solution: 1500 (average molecular weight approximately 2.000) Example 2 Liquid detergent compositions (shampoos) were prepared using hydroxypropyl methylcellulose of various viscosities, and their solubility and foam strength were evaluated. .

The results are shown in Table 2. The methoxy group content and hydroxypropoxy content of the hydroxypropyl methylcellulose used were 29% and 9.9%, respectively.
It is 5%.

(Composition) Polyoxyethylene (3) Sodium lauryl sulfate 1
5-hydroxypropyl methylcellulose (Table 2)
0.5 Lauric acid diethanolamide 3 Ion exchange water Remainder Table 2 Comparative product 5 5 (aooo) OX
16 to (Ia00o) Ox invention product 3 50 (2QOOO) OOl
4 100 (000 to 2) ○ Ol5
200 (33ooo) ○ C16400
(AQOOO) O○-7600 (5QOOO
) OOl8 800 (000 to 5)
○ 0I91,500 (000 to 6)
OOl10 2.000 ('7QOOO)
OO comparison product 7 4,000 (80,000)
Viscosity (CPS) and average molecular weight (in parentheses) of a 2% aqueous solution at 20°C.

Example 3 A liquid detergent composition (shampoo) having the composition shown in Table 3 was prepared, and its performance was sensory evaluated.

The results are also shown in the same table.

The viscosity of a 2% aqueous solution of hydroxypropyl methylcellulose at 20°C is 4000PS (average molecular weight 4QOO
O), the methoxy group content is 28 to 30%, and the hydroxypropoxy group content is 7 to 12%.

that's all

Claims (1)

[Claims] 1. The following components (A) and (B) (A) The following formula (I), ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, the molecule terminal and R are hydrogen atom, methyl group or hydroxypropyl group), and the content of methoxy groups is 2
5 to 35% by weight, the content of hydroxypropoxy groups is 5
0.1 to 2% by weight of hydroxypropyl methylcellulose whose 2% by weight aqueous solution has a viscosity of 50 to 2,000 centipoise at 20°C, (B) a cationic surfactant, an anionic surfactant; A liquid cleaning composition containing as an essential component 2 to 50% by weight of one or more surfactants selected from the group consisting of surfactants and amphoteric surfactants.