JPH0441595A - Cleaning agent composition - Google Patents

Abstract

PURPOSE:To obtain a cleaning agent compsn. having excellent cleaning and foaming power, good foam breakage, and good touch after cleaning and being less irritative to skins and hairs by compounding an anionic serfactant with a specified polyethyleneimine polymer. CONSTITUTION:A copolymer (A) with repeating units of formulas I and II (wherein R<1> is H, CH3 or C2H5; R<2> is a 4-15C alkyl, aryl or aralkyl) in a wt. ratio of formula I to formula II of 9/1 to 1/9 (polyethyleneimine polymer) and an anionic surfactant (B) (e.g. sodium mono- or di-lauryl phosphate, or sodium N-lauroylglutamate) are compounded. Even though the anionic surfactant has excellent cleaning and foaming power, there arises sometimes a problem on its being irritative to skins and hairs. It is possible by the abovedescribed combination to obtain a cleaning agent compsn. having excellent cleaning and foaming power, good foam breakage and good touch after cleaning and being less irritative to skins and hairs.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a novel detergent composition, and more particularly, it relates to a novel detergent composition that is less irritating to the skin and hair and has excellent detergency and foaming power. The present invention also relates to a new detergent composition that has good foam removal and a good feel after washing.

[Conventional technology]

Conventionally, anionic surfactants such as higher fatty acid salts and alkyl sulfates have been mainly used as bases for cleaning skin and hair because of their excellent detergency and foaming power.

[Problem to be solved by the invention]

However, although these anionic surfactants have excellent detergency and foaming power, they have the disadvantage that they may be irritating to the skin and hair.

[Means to solve the problem]

Under such circumstances, the present inventor conducted intensive research and found that if a specific polyethyleneimine polymer is used in combination with an anionic surfactant, it has excellent cleaning power and foaming power, and has good foam removal. The present invention was completed based on the discovery that a cleansing composition that has a good aftertaste and is less irritating to the skin and hair can be obtained.

That is, the present invention provides the following components (A) and (B) (A) formulas (1-1) and (I-2) c, where R' represents a hydrogen atom, a methyl group, or an ethyl group, and R2 represents It has a repeating unit represented by (I-1)/(1-
2> in a weight ratio of 9/1 to 1/9, and a copolymer (B) anionic surfactant.

In the polymer of component (A,) used in the present invention, specific examples of R2 in formula (I-2) include butyl,
Pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, tridecyl, pentadecyl, 2-methylpentyl, 2-7'pyrheptyl, phenyl, p
Examples include -methylphenyl, p-ethylphenyl, benzyl, and naphthyl groups, with those having 6 to 12 carbon atoms being particularly preferred.

Examples of the N-terminus of the polymer (A) used in the present invention include a methyl group, an ethyl group, a propyl group, a dodecyl group, etc., but a methyl group or an ethyl group is most suitable for use in the present invention. Further, examples of the C-terminus include a hydroxyl group, an acetyl group, a laurylamine group, a jetanolamine group, and the like, and a hydroxyl group or an acetyl group is preferable for use in the present invention. The molecular weight of the polymer (Δ) is not particularly limited, but is 500 to 20,000, particularly 1.
000 to 6,000 is preferred.

The structures of these copolymers include block copolymers,
Although any random copolymer can be used, block copolymers are more preferred.

Furthermore, the repeating units (r-1) and (1-2) may be combined by combining one type each of (1-1) and (I-2), or by combining one type each of (1-1) and (I-2). -2) may be used in combination of two or more types. Furthermore, when combining the repeating units (I-1) and (I-2), it is preferable that the difference in the number of carbon atoms between R' and R2 is 3 or more. Moreover, the weight ratio of the repeating units (T-1> and (1-2) constituting this copolymer (A) is 9/1 to 1
/9, but those with a ratio of 8/2 to 4/6 are optimal for use in the present invention.

The synthesis of the polymer (A) used in the present invention can be carried out, for example, by 2-
It is carried out by open isomerization cationic polymerization of 2-substituted 2-oxacillin such as ethyl-2-oxacillin, and the method is described, for example, in Polym, J., 4. 87 (1973). In the case of a block copolymer, it can be obtained by sequential concave ring polymerization of two or more different 2-oxacillin monomers according to the description in JP-A-59-230027. In the case of a random copolymer, it can be obtained by ring-opening polymerization by mixing two or more different 2-oxazoline monomers and dropping them all at once or separately and simultaneously.

The anionic surfactants used in the present invention as component (B) include fatty acid, alkyl sulfate, alkyl ether carboxylic acid, polyoxyethylene alkyl ether sulfate, and phosphoric acid esters in terms of foaming properties. Preferred surfactants are surfactants such as surfactants based on surfactants, N-acyl amino acids, isethionate, and sulfosuccinic acid, and these surfactants can be used alone or in combination of two or more. Among these, phosphate ester-based, isethionate-based, and sulfosuccinic acid-based surfactants are particularly preferred because they are less irritating.

Among these components (B), fatty acid surfactants and alkyl sulfate surfactants have linear or branched saturated or unsaturated alkyl chains having 8 to 20 carbon atoms, and contain alkali metals or Those having an alkanolamine counterion are preferred.

In addition, among component (B), the alkyl ether carboxylic acid surfactant and the polyoxyethylene alkyl ether sulfate surfactant have the same alkyl chain as the above-mentioned fatty acid surfactant and alkyl sulfate surfactant. and a counter ion, and furthermore, those to which an average of 1 to 50 moles of ethylene oxide are added are preferable.

Among component (B), as a phosphate ester surfactant, for example, the following general formula (I [) or (I) R3→OCH
, CH Tsuji, 0-P-OM (I[)Z [wherein, R'', R' and R5 each have a carbon number of 8 to 1
The linear or branched chain γ alkyl in 8 represents an alkenyl group, Z and M each represent a hydrogen atom, an alkali metal, ammonium, or an alkanolamine having a hydroxyalkyl group having 2 to 3 carbon atoms, x, y, and 2 is O~1
(indicates the number of 0)].

As these compounds (I[) or (I[I), compounds with an added mole number of ethylene oxide of 0 to 3 are preferable, and in particular, those with no ethylene oxide added and with a carbon number of 12 to 3 are preferable.
Those having 14 alkyl groups are preferred. Preferred examples of these include, for example, sodium mono- or dilauryl phosphate, potassium di- or dilauryl phosphate, jetanolamine or di-lauryl phosphate, triethanolamine mono- or dilauryl phosphate, sodium mono- or simiristyl phosphate, - or potassium simiristyl phosphate, mono- or diethanolamine simiristyl phosphate, triethanolamine or triethanol similystyl phosphate, and the like.

In addition, by combining compound (II) and (I), (B)
When used as a component, the mixing ratio is (n
): (I)=10:0-5:5, especially 10:0-7
It is preferable to use the ratio of :3.

Among component (B), the N-acylamino acid surfactant has the general formula (TV) [wherein R6 represents a linear or branched alkyl or alkenyl group having 7 to 21 carbon atoms, and R7 is Represents a hydrogen atom or an alkyl or alkenyl group having 1 to 4 carbon atoms, R1
1 is a group -(CH2) pR9 (p represents an integer of 0 to 4, R9 is a hydrogen atom, a hydroxyl group, or -C00M, (M
2 is a hydrogen atom, an alkali metal or an alkanolamine)
(indicates)] Examples include compounds represented by the following.

The compound represented by the above general formula (IV) includes L form, D form,
There are two types, racemic and racemic, and either of these can be used. Preferred specific examples include N-lauroylglutamic acid, N-myristylglutamic acid, N-lauroyl-
N-methylglycine, N-lauroyl T-svaragic acid,
Examples include N-lauroylserine, alkali metal salts thereof, and alkanolamine salts.

Among the components (B) used in Honhatsu, the isethionate surfactant has the general formula (V)R” -C00C
A compound represented by H2CH2SO,M, (V) [wherein RIQ represents an alkyl or alkenyl group having 7 to 21 carbon atoms, and M3 represents a cationic group derived from a hydrogen atom, an alkali metal or an alkanolamine] can be mentioned.

In the compound represented by the above general formula (V), R”-
Examples of the fatty acid group represented by COO- include lauric acid group, myristic acid group, oleic acid group, coconut oil fatty acid group, etc., and counter cations represented by M3 include potassium, sodium, triethanolamine, gelatin, etc. Examples include tanolamine, monoethanolamine, and the like.

Among the components (B) used in the present invention, the sulfosuccinic acid surfactant has the general formula (VI) or (■) R''-C-CH-C)12-COOM.

SO, M4 (VI) R”-C-CH, -CH-(1:OOM,
(■) 303M.

[In the formula, RI I is R12O-(-CH, C820- or R13CONHf CH2CH20-)-, (R'' is a straight or branched alkyl or alkenyl group having 8 to 22 carbon atoms, and R13 is a straight-chain or branched alkyl or alkenyl group having 7 to 21 carbon atoms. represents a linear or branched alkyl or alkenyl group, and q is 0 to 20
), and M4 represents a hydrogen atom or a cation that forms a water-soluble salt selected from alkali metals, alkaline earth metals, ammonium, and organic ammonium respectively] or an ethoxylate thereof or sulfosuccinates derived from higher fatty acid amides.

Among the compounds represented by formula (VI) or (■) above, the sulfosuccinate ester of a higher alcohol or its ethoxylate is a sulfosuccinate ester of a secondary alcohol ethoxylate having 11 to 13 carbon atoms.
Sodium salt (for example, Nippon Shokubai Kagaku Kogyo, Softanol MES-3, 5, 7°9, 12; each number indicates the average number of added moles of ethylene oxide (8 units)),
Lauryl alcohol or lauryl alcohol ethoxylate ([EO=3.6.9.12> disodium salt of sulfosuccinate, carbon number 12-15 Synthesis 1
Examples include disodium salts of sulfosuccinates of alcohols and their ethoxylates (EO=2 to 4). In addition, sulfosuccinic acid esters derived from higher fatty acid amides include lauric acid polyethylene glycol (
BO=1.2) disodium salt of sulfosuccinate ester of amide, polyethylene glycol oleate (lE
O=1.2) Disodium salt of sulfosuccinate ester of amide, coconut oil fatty acid polyethylene glycol (HD
Sodium salts of sulfosuccinic acid esters of = 4 and the like can be mentioned.

The amounts of the above-mentioned components (A) and (B) in the cleaning composition of the present invention vary depending on the dosage form of the cleaning composition, but in total, for example, the liquid cleaning agent contains about 1 to 30% by weight. Appropriate amounts are about 10 to 50% by weight for gel-like detergents, and about 20 to 80% by weight for solid detergents. In addition, the blending ratio of component (A) and component (B) is (A):
(B)-10: 1 to 1:100 is preferred, especially (
It is preferable that A):(B)=5:1 to 5:5.

The cleaning composition of the present invention can also contain other commonly used surfactants in addition to the above-mentioned essential components.

In addition, the cleansing composition of the present invention may contain conventional additives for skin or hair cleansers, such as alcohols such as ethanol, anionic polymers, nonionic polymers, cationic polymers, etc. Viscosity modifiers and conditioning agents: moisturizing ingredients such as chrycerol and sorbitol; organic or inorganic powders with scrubbing effects;
Other preservatives, ultraviolet absorbers, bactericidal agents, fragrances, pigments, and the like may be added to the extent that they do not impair the effects of the present invention.

The cleaning composition of the present invention can be manufactured according to a conventional method and can be in any form such as solid, paste, or liquid.
It can be used as a variety of cleaning agents for hair, skin, clothing, tableware, etc., but it is particularly effective as a cleaning agent for skin and hair such as facial cleansers, shampoos, and body shampoos.

〔Effect of the invention〕

The detergent composition of the present invention has excellent detergency and foaming power, has good foam removal, has a moist and good feel after washing, and is extremely useful as it has little irritation to the skin and hair.

〔Example〕

Hereinafter, the present invention will be explained in more detail by showing synthesis examples of the polymer according to the present invention and examples of the present invention, but the present invention is not limited to these examples.

Synthesis Example 1 After purging a 51-hole flask with a thermometer, dropping funnel, and stirrer with dry nitrogen, 300 m of acetonitrile was added to the 51-hole flask at room temperature. ! , 93.10 g (0,500 mol) of methyl tosylate were charged. Stirring was started, and the temperature of the system was raised in an oil bath. Under reflux, 375 g (2,215 mol) of 2-hebutyl-2-oxacillin was added to 2
The mixture was added dropwise over a period of time, and was further refluxed for 24 hours to carry out polymerization (the above is the first step).

Then 876.5 g of 2-methyl-2-oxazoline (
A mixture of 10.30 mol) and 800 rn1 of acetonitrile was added dropwise over 2 hours, and the mixture was refluxed for an additional 24 hours to carry out polymerization (second step). After cooling, reprecipitation was performed with 20β isopropyl ether, and the mixture was heated at 80°C for 48 hours.
The polymer was vacuum dried.

The composition ratio of the obtained block copolymer was measured using a proton NMR device (solvent double hydrogen ratio chloroform), and the molecular weight was measured using a vapor pressure osmometer (solvent: chloroform).

The results are shown in Table 1.

Synthesis Example 2 Methyl tosylate 119.2 as the first step of polymerization
g (0,64 mol), 640 g (3,78 mol) of 2-hebutyl-2-oxazoline, 400 g of acetonitrile
rnl, as the second step of polymerization, using 960 g (11.3 mol) of 2-methyl-2-oxazoline and 500 ml of acetonitrile as reaction reagents, polymerization was carried out using the same reaction apparatus and reaction conditions as in Synthesis Example 1. Refined.

Table 1 shows the results of measuring the composition ratio and molecular weight of the block copolymer in the same manner as in Synthesis Example 1.

Synthesis Example 3 Methyl tosylate 92.56 as the first step of polymerization
g (0.50 mol), 2-ethyl-2-year-old xacillin 870.0 g (8.78 mol), acetonitrile 5
00mf, 2-undecyl- as the second step of polymerization
Using 373.2 g (1.66 mol) of 2-oxazoline and 100 rnl of acetonitrile as reaction reagents, polymerization was carried out using the same reaction apparatus and reaction conditions as in Synthesis Example 1, and purification was carried out under the same conditions.

Table 1 shows the results of measuring the composition ratio and molecular weight of the block copolymer in the same manner as in Synthesis Example 1.

Synthesis Example 4 Methyl tosylate 186.2 as the first step of polymerization
g (1,00 mol), 2-phenyl-2-oxazoline 500. Og (3.28 mol), acetonitrile 300 ml. 2-ethyl-2 as the second step of polymerization
Using 500.0 g (5.05 mol) of xacillin and 600 g of cetonitrile as reaction reagents, polymerization was carried out using the same reaction apparatus and reaction conditions as in Synthesis Example 1, and purification was carried out under the same conditions.

Table 1 shows the results of measuring the composition ratio and molecular weight of the block copolymer in the same manner as in Synthesis Example 1.

Margin below Synthesis examples 5 to 9 -(I-2) in the same manner as in Synthesis Example 1.

A block polymer was synthesized.

Table 2 shows the list.

1) l, - type and below margin synthesis examples 10 to 11 According to synthesis example 1, -(I-2)yo--(T-1),,-(I-2),,
, -type block copolymers were synthesized.

Table 3 shows the list.

Below are margin synthesis examples 12 to 13. According to synthesis example 1, using a mixture of two types of
A random copolymer was synthesized by performing a polymerization reaction in steps.

Table 4 shows the list.

Test Example 1 The various polymers obtained in Synthesis Examples 1 to 4 were made into 1% aqueous solutions, and polyoxyethylene (30 mol) lauryl ether was used as a control to determine the water solubility (cloud point), surface tension, foam stability, and A comparison was made regarding solubilization ability and skin irritation. Table 5 shows the results.
Shown below.

Below are the margins Measurement conditions Book 1 Surface tension: Wilhelmy method, 30℃ book 2 Foam stability: *3 Solubilization ability Relative value when the amount of Nisdan ■ solubilized (determined from the absorbance at 500 nm) is set to Synthesis Example 1 as 100 Book 4 Skin irritation 2 For 10 women, each prepared aqueous solution 8
Perform continuous washes for 15 minutes using rnl. After 24 hours, the condition of the washed area (left side of the forearm) was observed with the naked eye, and rough skin was determined as a rough skin score according to the following criteria, and the average value was determined.

Test Example 2 The polymers obtained in Synthesis Examples 5 to 13 were made into 1% aqueous solutions, and the surface tension, foam stability, and solubilization ability were compared in the same manner as in Test Example 1. The results are shown in Table 6.

Margin Example 1 Cleaning compositions having the compositions shown in Table 7 below were prepared, and each cleaning composition was used to wash by hand. Sensory evaluation was performed on the sense of discomfort such as dryness when washing the face with lukewarm water for 1 minute each for 1 week. The results are shown in Table 7.

<Evaluation criteria> Refreshing feeling after washing: ◎ Very good ○ Good △ Average × Bad irritation feeling: ◎ Not at all ○ Almost never △ Somewhat × Yes As is clear from the results in Table 7, the cleaning of the present invention The agent composition had an excellent feel after washing and was not irritating.

Further, all of the cleaning compositions of the present invention had good foam removal properties.

Furthermore, in the products 1 and 3 of the present invention, Production Example 2 was used as a polymer.
-13, similar results were obtained.

Example 2 Liquid facial cleanser: Polymer 10 (wt%) Sodium monolauryl phosphate 35 Sodium lauroyl sarcosinate 7 Mupropylene glycol 5 Fragrance Appropriate amount Water 1:
Product obtained in Synthesis Example 1 Total 2: Product obtained in Synthesis Example 1 Example 3 Anti-dandruff shampoo: Polymer 08 (wt%) Ethyl alcohol fragrance, appropriate amount of pigment Total 4: Product obtained in Synthesis Example 1 The above-mentioned light detergent had extremely low irritation to the skin and had good detergency.

Example 5 Bathroom cleaner polymer *5 4 (wt%) total
100 pieces 3: Synthesis example 1
The anti-dandruff shampoo obtained above had extremely low irritation to the skin and also had good anti-dandruff effects.

Example 4 Light detergent: Polymer 1!L (wt%) Citric acid total 1.00 Efficiently removes adhering soap scum.

that's all Ethyl alcohol 8 Fragrances Appropriate amount Water Remaining amount

Claims (1)

[Claims] 1. The following components (A) and (B) (A) Formulas ( I -1) and ( I -2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ( I -1) ▲ Mathematical formulas , chemical formulas, tables, etc.▼(I-2) [In the formula, R^1 represents a hydrogen atom, methyl group, or ethyl group, and R^2 represents an alkyl group, aryl group, or aralkyl group having 4 to 15 carbon atoms. It has a repeating unit expressed as (I −1)/(I
-2) A cleaning composition comprising a copolymer (B) anionic surfactant in a weight ratio of 9/1 to 1/9.