JP2002053895A - Detergent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid detergent having an excellent washing power especially against mud stains or the like. SOLUTION: This detergent comprising (A) a cationic surfactant and (B) a nonionic surfactant in a (A)/(B) weight ratio of 0.1/99.9 to 25/75.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a cleaning agent for clothing. More specifically, the present invention relates to a cleaning agent comprising a cationic surfactant and a nonionic surfactant, which is excellent in cleaning oily dirt and mud dirt.

[0002]

2. Description of the Related Art Conventionally, in order to prevent shrinkage and texture of clothes after washing, a cationic surfactant is blended to impart flexibility, and a silicone derivative is blended to prevent shrinkage of clothes. There are known ways to do this. For example, a detergent composition comprising a nonionic surfactant as a main component and an anionic surfactant and a cationic surfactant is known.
No. 152899, JP-A-59-115498, and JP-A-62-70498.

[0003]

However, in the prior art, there is a problem that the flexibility is imparted by the cationic surfactant and the feeling is improved, but the detergency is poor.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to obtain a detergent having excellent detergency against oil stains and mud stains, and as a result, a cationic surfactant and a nonionic surfactant have been specified. The inventors have found that detergents formulated in proportions are effective for these purposes and have arrived at the present invention.
That is, the present invention contains a cationic surfactant (A) and a nonionic surfactant (B), and (A) / (B) = 0.
It is a cleaning agent having a mass ratio of 1 / 99.9 to 25/75.

The ratio (A) / (B) in the detergent of the present invention is usually 0.1 / 99.9 to 25/75, preferably 0.5 / 99.9 to 25/75.
/99.5 to 15/85, more preferably 1/99 to
It is 10/90. If the amount of (A) is less than 0.1% by mass with respect to the total amount of (A) and (B), good detergency cannot be obtained, and if it exceeds 25% by mass, detergency will be poor. .

The cationic surfactant (A) includes
And a quaternary ammonium salt type or amine salt type cationic surfactant. Examples of the quaternary ammonium salt type cationic surfactant include tertiary amines and quaternizing agents (alkyl halides such as methyl chloride, methyl bromide, ethyl chloride and benzyl chloride, dimethyl sulfate, dimethyl carbonate, ethylene oxide and the like). )
Can be used. Examples thereof include lauryltrimethylammonium chloride, didecyldimethylammonium chloride, dioctyldimethylammonium bromide, stearyltrimethylammonium bromide, lauryldimethylbenzylammonium chloride (benzalkonium chloride), and cetylpyridinium chloride. , Polyoxyethylene trimethyl ammonium chloride, stearamidoethyl diethyl methyl ammonium methosulfate, and the like.

The amine salt type cationic surfactants include:
Neutralizing primary to tertiary amines with inorganic acids (such as hydrochloric acid, nitric acid, sulfuric acid, and hydroiodic acid) or organic acids (such as acetic acid, formic acid, oxalic acid, lactic acid, gluconic acid, adipic acid, and alkyl phosphoric acid). Can be used, for example,
Examples of the primary amine salt type include aliphatic higher amines (laurylamine, stearylamine, cetylamine,
Inorganic or organic acid salts of hardened tallow amine, higher amines such as rosin amine; and higher fatty acid salts of lower amines (such as stearic acid and oleic acid). Examples of the secondary amine salt type include an inorganic acid salt or an organic acid salt such as an ethylene oxide adduct of an aliphatic amine. Examples of the tertiary amine salt type include aliphatic amines (triethylamine,
Ethyldimethylamine, N, N, N ', N'-tetramethylethylenediamine, etc., alicyclic amines (N-methylpyrrolidine, N-methylpiperidine, N-methylhexamethyleneimine, N-methylmorpholine, 1,8 -Diazabicyclo (5,4,0) -7-undecene, etc.,
Inorganic acid salt or organic acid salt of nitrogen-containing heterocyclic aromatic amine (4-dimethylaminopyridine, N-methylimidazole, 4,4'-dipyridyl, etc.); triethanolamine monostearate, stearamidoethyldiethylmethylethanolamine And tertiary amines such as inorganic or organic acid salts. One or a mixture of two or more of these can be used as the cationic surfactant (B), and preferably one or more compounds selected from the group consisting of compounds represented by formulas (1) to (4). is there.

[0008]

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[0009]

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[0010]

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[0011]

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However, in the formulas (1) to (4), R ¹ , R ² and R ³ represent a hydrogen atom or an alkyl group having 1 to 24 carbon atoms,
An alkenyl group or β-hydroxyalkyl group, preferably an alkyl group or alkenyl group having 1 to 18 carbon atoms. Specifically, examples of the alkyl group include methyl, ethyl, propyl, hexyl, octyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, isoundecyl, and dodecyl. Group, isododecyl group, tridecyl group, isotridecyl group, tetradecyl group, isotetradecyl group, pentadecyl group, isopentadecyl group, hexadecyl group, isohexadecyl group, octadecyl group, isooctadecyl group, and the alkenyl group includes Examples include an octenyl group, a decenyl group, a dodecenyl group, a tetradecenyl group, a hexadecenyl group, and an octadecenyl group. Further, as the β-hydroxyalkyl group, a 2-hydroxyethyl group,
Examples thereof include a 2-hydroxypropyl group and a 2-hydroxybutyl group.

R ⁴ and R ⁵ are an alkyl group having 1 to 24 carbon atoms, a hydroxyalkyl group, a benzyl group or a compound represented by the formula:
(A ¹ O) _n -Z {Note, A ¹ is an alkylene group having 2 to 4 carbon atoms (e.g., ethylene, propylene, butylene), Z is a hydrogen atom or an acyl radical, n is from 1 to 50 integer A group represented by｝, which is preferably an integer of 5 to 30,
Preferably it is a C1-C4 alkyl group or a benzyl group. Specifically, methyl group, ethyl group, propyl group,
Examples include an isopropyl group, a butyl group, an isobutyl group, and a sec-butyl group.

R ⁶ is an alkyl group, alkenyl group or β-hydroxyalkyl group having 1 to 36 carbon atoms, preferably an alkyl group or alkenyl group having 8 to 24 carbon atoms. Specifically, in addition to the same groups as R ¹ , R ² and R ³ , eicosyl, isoeicosyl, eicosenyl and the like can be mentioned.

Y is an alkyl group having 1 to 36 carbon atoms;
Alkenyl group, β-hydroxyalkyl group, formula: R ⁴ C
A group represented by O ₂ CH ₂ — (where R ⁴ is the same as described above) or a group represented by the formula: R ⁴ OCH ₂ — (where R ⁴ is the same as described above), preferably It is an alkyl group or an alkenyl group having 1 to 18 carbon atoms. Specifically, R ¹ , R ²
And the same groups as R3.

[0016] X ^- is a counter ion, halogen ions ^(F -, Cl ^-, Br chromatography, I ^-), hydroxy ion, carbonate ion or sulfate ion and carbon having an alkyl group of 1 to 4 carbon atoms One or more anions selected from the group consisting of carboxylate ions and sulfonate ions having an alkyl group or alkenyl group of Formulas 1 to 24 are mentioned.

The compound represented by the formula (1) is, for example,
1-2 carbon atoms such as laurylamine and stearylamine
A primary amine having an alkyl group, an alkenyl group or a β-hydroxyalkyl group of 4, a dilaurylamine,
Secondary amine having an alkyl group, alkenyl group or β-hydroxyalkyl group having 1 to 24 carbon atoms such as distearylamine, or 1 to 2 carbon atoms such as trimethylamine, lauryldimethylamine and stearylamine.
And a tertiary amine having an alkyl group, an alkenyl group or a β-hydroxyalkyl group having a carbon number of 1 such as hydrochloric acid, bromic acid or iodic acid, or formic acid, acetic acid, propionic acid, lauric acid or stearic acid. ~ 24 carboxylic acid and the like.

A tertiary amine having an alkyl group having 1 to 24 carbon atoms, such as trimethylamine, lauryldimethylamine and stearylamine, having an alkyl group, an alkyl group or a β-hydroxyalkyl group can be converted to methyl chloride, benzyl chloride, dimethyl carbonate, diethyl carbonate. , An alkylating agent such as dimethyl sulfate, and the like.

Further, a primary amine having an alkyl group, an alkenyl group or a β-hydroxyalkyl group having 1 to 24 carbon atoms such as laurylamine and stearylamine, or a C1 to C24 such as dilaurylamine and distearylamine. A tertiary amine obtained by adding ethylene oxide to a secondary amine having an alkyl group, an alkenyl group or a β-hydroxyalkyl group under alkaline conditions is converted to a halogen acid such as hydrochloric acid, bromic acid or iodic acid, or formic acid, It can be obtained by a method such as neutralization with a carboxylic acid having 1 to 24 carbon atoms such as acetic acid, propionic acid, lauric acid and stearic acid.

The compound represented by the formula (2) can be obtained by heating a pyridine with an alkylating agent having 1 to 24 carbon atoms such as methyl chloride, octyl chloride, stearyl chloride, oleyl bromide, hydroxyethyl bromide under pressure. It can be obtained by reacting.

The compound represented by the formula (3) is obtained by heating and condensing a fatty acid having 1 to 36 carbon atoms such as lauric acid and stearic acid with triethanolamine to form an ester-type tertiary amine. And a method of reacting the above-mentioned tertiary amine of the ester type by heating methyl chloride, dimethyl carbonate and dimethyl sulfate under pressure.

The compound represented by the formula (4) is, for example, an amide-type tertiary amide obtained by subjecting a fatty acid having 1 to 36 carbon atoms such as lauric acid and stearic acid to heat condensation with N, N-diethylethylenediamine. It can be obtained by a method of neutralizing a tertiary amine with an acid such as hydrochloric acid or acetic acid, or a method of reacting the amide-type tertiary amine by heating methyl chloride, dimethyl carbonate, or dimethyl sulfate under pressure. In order to make the counter ion X ⁻ in the formulas (1) to (4) a hydroxy ion, a compound in which X ⁻ is a halogen ion is formed,
It can be obtained by adding silver hydroxide thereto and heating.

The HLB of (A) is usually from 10 to 25, preferably from 12 to 24, and more preferably from 15 to 22, from the viewpoint of detergency. When it is in the range of 10 to 25, the detergency becomes better. Here, HLB is an HLB (Hydrophile-Lipophile) calculated by summing numerical values indicating organicity and inorganicity (Oda, Teramura, "Synthesis and Application of Surfactants", page 501, Maki Shoten).
Balance).

Examples of the nonionic surfactant (B) include an alkylene oxide addition type nonionic surfactant (b-1) and a polyhydric alcohol type nonionic surfactant (b-2). Examples of (b-1) include a higher alcohol (8 to 18 carbon atoms) alkylene (2 to 4 carbon atoms) oxide (1 to 30 moles added per active hydrogen) adduct, and an alkyl (1 to 12 carbon atoms) ) Phenol ethylene oxide (1 to 30 moles added per active hydrogen)
Adducts, fatty acids (8-18 carbon atoms), ethylene oxide (1-30 additional moles per active hydrogen) adduct,
Polypropylene glycol (molecular weight 200-4000)
Ethylene oxide (1 to 50 additional moles per active hydrogen) adduct and polyoxyethylene (1 to 30 additional moles per active hydrogen) alkyl (1 carbon atom)
-20) allyl ether, sorbitan monolaurate ethylene oxide (addition mole number 1-30) adduct, sorbitan monooleate ethylene oxide (addition mole number 1)
~ 30) Multivalent (2 to 8 or more) such as adducts
Fatty acids of alcohols (C2-30) (C8-2)
4) Ester ethylene oxide adducts (addition moles per active hydrogen of 1 to 30) and the like. (B
Examples of -2) include polyvalent (2 to 8 or more) such as glycerin monostearate, glycerin monooleate, sorbitan monolaurate, and sorbitan monooleate.
Fatty acids of alcohols (C2-30) (C8-2)
4) Esters, fatty acid alkanolamides such as lauric acid monoethanolamide, lauric acid diethanolamide and the like.

Of these, preferred is (b-1), and particularly preferred is a compound represented by the following general formula (5). _{RO - [(C 2 H 4} O) n / (A 2 O) m] - (C 2 H 4 O) q - (A 2 O) r -H (5)

In the above general formula (1), R is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, preferably an aliphatic hydrocarbon group having 10 to 18 carbon atoms. 8 to 1 carbon atoms
When the ratio is in the range of 8, better cleaning power can be obtained. Specifically, an octyl group, a 2-ethylhexyl group, a decyl group,
Saturated aliphatic hydrocarbon groups such as lauryl group, myristyl group, palmityl group, stearyl group, 1,1-dimethyloctyl group; octenyl group, decenyl group, dodecenyl group, tridecenyl group, pentadecenyl group, oleyl group, linoleyl group, etc. Unsaturated aliphatic hydrocarbon group (alkenyl group,
Alkadienyl group, alkatrienyl group and alkapolyenyl group); and cyclic aliphatic carbon groups such as ethylcyclohexyl group, propylcyclohexyl group, octylcyclohexyl group and nonylcyclohexyl group.
These aliphatic carbon groups may be linear or branched.

In the general formula (5), A ² is an alkylene group having 3 or 4 carbon atoms, and n is 0 or an integer of 1 to 12, preferably 1 to 10. Also, q is 1 to
It is an integer of 16 and preferably 2-12. n is 0
Or, when q is in the range of 1 to 8, and q is in the range of 1 to 16, more excellent detergency can be obtained. Also, m
Is 0 or an integer of 1 to 6, preferably 1 to 4. R is 0 or an integer of 1 to 15, preferably 1 to 8. When m is in the range of 0 or 1 to 6, and when r is in the range of 0 or 1 to 15, the fluidity of the detergent is further improved. Also, (m + n + q)
Is an integer of 1 to 30, preferably 6 to 20. (M
+ N + q) in the range of 1 to 30 can provide a better detergency. Also, (n + q) / (m + n + q + r)
Is 0.5 to 1.0, preferably 0.7 to 0.9.
It is. When the content is in the range of 0.5 to 1.0, more excellent detergency can be obtained.

Among the compounds represented by the general formula (5), the aliphatic alcohol (a1) is substituted with the alkylene oxide (b1).
And the weight average molecular weight (M
w) and the number average molecular weight (Mn) by GPC (Mw).
/ Mn) satisfies the following relational expression (6) or (7), and the distribution constant c obtained from the following general expression (8) is 1.
Compounds having 0 or less are particularly preferred. Mw / Mn ≦ 0.030Ln (v) +1.010 (where v <10) (6) Mw / Mn ≦ −0.026Ln (v) +1.139 (where v ≧ 10) (7) In (2) and (3), v represents the average number of moles of the alkylene oxide (b1) added per mole of the aliphatic alcohol (a1). Also, Ln
(V) shows the natural logarithm of v. Aliphatic alcohol (a
As 1), an alcohol having an aliphatic hydrocarbon group having 8 to 18 carbon atoms can be used. a1 is preferably an alcohol having an aliphatic hydrocarbon group having 10 to 18 carbon atoms. Specifically, the alcohol having an aliphatic hydrocarbon group exemplified in the description of R in the general formula (5) can be given.
Further, as the alkylene oxide (b1), ethylene oxide, propylene oxide and butylene oxide can be used, and any addition form of single, random, block or a combination thereof may be used.

C = (v + n ₀ / n ₀₀ −1) / [Ln (n ₀₀ / n ₀ ) + n ₀ / n ₀₀ −1] (8) where v is the expression (3) Alternatively, as in (4), n ₀₀ represents the number of moles of the aliphatic alcohol (a1) used in the reaction, and n ₀ represents the number of moles of the unreacted aliphatic alcohol (a1). More preferably, c is 1.0 or less. When c is 2.0 or less, the content of the unreacted aliphatic alcohol becomes extremely small, and more favorable surface activity can be obtained.

The above-mentioned alkylene oxide addition type nonionic surfactant (b-1) can be produced by using a usual alkylene oxide addition reaction.
It can be produced by adding ethylene oxide, propylene oxide, and butylene oxide to alcohol at 200 ° C. by a specific addition method. For example, blocks higher alcohol having 8 to 18 carbon atoms, an alkali (e.g., KOH) or an acid (e.g., BF _3, etc.) under a nitrogen atmosphere was added a catalyst, is random addition of a mixture of ethylene oxide and propylene oxide, then ethylene oxide And then block addition of propylene oxide.

As the aliphatic hydrocarbon alcohol having 8 to 18 carbon atoms, a saturated or unsaturated primary, secondary or tertiary alcohol can be used. Of these, preferred are saturated aliphatic primary alcohols. 10-18 carbon atoms
Is preferred. One or two aliphatic hydrocarbon alcohols
Any mixture of more than one species may be used.

Specific examples of the saturated aliphatic primary alcohol include decyl alcohol, lauryl alcohol, stearyl alcohol, and alcohol synthesized using a Ziegler catalyst [for example, ALFOL 1214 (CON)
DEA), alcohols produced by oxo synthesis [for example, Dovanol 23, 25, 45 (Mitsubishi Yuka), tridecanol (Kyowa Hakko), oxocol 1213, 1215, 1415 (Nissan Chemical) , Diamond Doll 115-L, 115H, 135 (manufactured by Mitsubishi Chemical Corporation)]. As the saturated aliphatic secondary alcohol, those obtained by an oxidation method using n-paraffin as a raw material, Oil Chemistry, Vol. 21, No. 5, pp. 233 to 242 (1.
972). Examples of unsaturated aliphatic alcohols include oleyl alcohol, alcohols obtained by a reduction method [for example, trade names: Hicoll 40, 60 (manufactured by Kyowa Yushi), Angecol 50A]
(Manufactured by Shin Nippon Rika)].

As a method for producing a compound satisfying the above formula (6) or (7) and having a distribution constant c of 1.0 or less obtained from the above formula (8), a general catalyst (lithium, sodium, A method of adding an alkylene oxide to an aliphatic alcohol using a catalyst capable of narrowing the molecular weight distribution as compared with an alkali metal hydroxide or carbonate such as potassium or cesium, or a basic catalyst such as an amine compound A method of adding 1 to 3 mol of an alkylene oxide to an aliphatic alcohol using a general catalyst, removing unreacted alcohol by distillation or the like, and then adding the alkylene oxide using a general catalyst. The preferred production method. Examples of the catalyst for narrowing the molecular weight distribution include a calcined magnesium oxide-containing compound (Japanese Patent Application Laid-Open No. 1-164437), a calcined hydrotalcite (Japanese Patent Application Laid-Open No. 2-71841), and a perchlorate (US Pat. No. 4,112). 231),
Examples include catalysts selected from perhalic acid (salt), sulfuric acid (salt), nitric acid (salt), and divalent or trivalent metal alcoholates.

The content of (A) in the detergent in the present invention is usually 0.01 to 20% by mass, preferably 0.1 to 15% by mass, more preferably 0 to 15% by mass, based on the total mass of the detergent. 0.5 to 10% by mass.

The content of (B) is usually from 10 to 95% by mass, preferably from 20 to 95% by mass, based on the total mass of the detergent.
It is 80% by mass, more preferably 30 to 60% by mass. Of the content of (B), preferably, the content of the compound represented by the general formula (5) is 8 based on the content of (B).
5% by mass or more, particularly preferably, a compound represented by the general formula (5) that satisfies the relational expressions (6) and (7) and the distribution constant c obtained from the general formula (8) is 1.0 or less. The content of a certain compound is 85% by mass or more based on the content of (B).

The water content is usually 2 to 80% by mass, preferably 10 to 60% by mass, based on the total mass of the detergent. In addition, if necessary, other components besides (A), (B) and water may be added in an amount of 0% based on the total mass of the detergent.
-50% by mass.

Other components include anionic surfactants ｛alkyl (1 to 20 carbon atoms) ether sulfate,
0 to 15% by mass of sulfated or carboxymethylated product of an ethylene oxide adduct (1 to 30 moles of addition) of an aliphatic (C1 to C20) alcohol, builder (polyvalent carboxylate, caustic soda, soda) Ash, ammonia, alkali builders such as triethanolamine and sodium tripolyphosphate, chelating agents such as EDTA and NTA) in an amount of 0 to 10% by mass, a fluorescent agent, a bleaching agent, a softener, an enzyme, a disinfectant, a fragrance, and a coloring agent. 0 to 5% by mass, hydrophilic solvent (methanol, ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, etc.)
0 to 20% by mass of an antifoaming agent (a silicone-based antifoaming agent or a polyoxyalkylene-based antifoaming agent, a mineral oil-based antifoaming agent, etc.)
0-5 mass% can be contained. The form of the detergent may be liquid or solid (powder, granule, block, etc.), and is preferably liquid.

The cleaning agent of the present invention is particularly useful for cleaning natural fibers, synthetic fibers, and blended and woven fibers thereof. Natural fibers include cotton, hemp, wool and the like, and synthetic fibers include regenerated cellulose fibers such as rayon and acetate, and synthetic fibers such as polyester, polyamide fiber, acrylic and spandex. These blended and interwoven fibers include cotton and hemp and other fibers (such as wool, polyester, polyamide, and acrylic), wool and other fibers (such as polyester, polyamide, and acrylic), and polyester fiber and other fibers (such as rayon, Acetate, polyamide, acrylic, spandex, etc.), polyamide fibers and other fibers (rayon, acetate, acrylic, spandex, etc.).

The cleaning agent of the present invention is usually 0.001 g / L.
Used at concentrations ranging from 〜5 g / L.

The bath ratio is not particularly limited, but is usually 1: 4 to
The ratio is 1:40, preferably 1: 6 to 1:30.

The washing temperature can be arbitrarily selected depending on the type of the fiber to be applied, but is usually 5 to 80 ° C., preferably 20 to 50 ° C.

The detergent of the present invention can be used not only as a detergent for clothes, but also as an industrial detergent, for example, a refining agent for textiles, a soaping agent and the like.

In the case of washing using the detergent of the present invention, the washing method is not particularly limited.
In washing machines and industrial use, it can be used for batch processing by a liquid jet dyeing machine, continuous processing by a continuous refining device, and the like. Among them, it is suitable as a detergent for washing using a washing machine of a type that causes less damage to the laundry such as a centrifugal washing type. The centrifugal washing method is a novel washing method in which a water flow is created by "centrifugal force" by rotating the tub itself of the washing machine, and dirt is removed by the force of water passing through the laundry. For example,
Matsushita Electric Industrial Co., Ltd. "Centrifugal washing machine NA-800
P ".

[0044]

EXAMPLES The present invention will be described in detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. Hereinafter, parts and% indicate parts by mass and% by mass, respectively. The conditions for measuring the molecular weight of the nonionic surfactant (B) by GPC are as follows. <Measurement conditions of GPC> Model: HLC-8120 (manufactured by Tosoh Corporation) Column TSK gel SuperH4000 TSK gel SuperH3000 TSK gel SuperH2000 (both manufactured by Tosoh Corporation) Column temperature: 40 ° C. Detector: RI solvent: tetrahydrofuran Flow rate: 0 0.6 ml / min Sample concentration: 0.25% Injection volume: 10 μl Standard: Polyoxyethylene glycol (manufactured by Tosoh Corporation; TSK STANDARD POLYETHYLENE OXIDE) Data processor: SC-8020 (manufactured by Tosoh Corporation)

The gas chromatography (hereinafter abbreviated as GC) measurement conditions used for measuring the concentration of the unreacted aliphatic alcohol of the nonionic surfactant are as follows. <GC measurement conditions> Model: Gas chromatograph GC-14B (manufactured by Shimadzu Corporation) Detector: FID column: Glass column (inner diameter = about 3 mm, length = about 2 m) Column filler: silicone GE SE-30 5% column Temperature: Increased from 90 ° C to 280 ° C. Heating rate = 4 ° C / min Carrier gas: Nitrogen Sample: 50% acetone solution Injection volume: 1 μl Quantitation: Use an aliphatic alcohol having 2 or 3 fewer carbon atoms than the aliphatic alcohol used as the internal standard substance Quantified.

Examples 1 to 10 By reacting octylamine with methyl chloride, a cationic surfactant (c1, in the formula (1), R ¹ = R ² = R
^{3 = H, R 4 = C} 8 H 17, X - = Cl -, HLB: 11.
9) was obtained. Cationic surfactant (c1), nonionic surfactant (B) shown in Table 2, citric acid, triethanolamine, propylene glycol, alcalase 2.5
Using L and water, detergents were prepared in the amounts shown in Table 3.

Examples 11 to 12 By reacting dimethyl stearylamine with dimethyl carbonate, a cationic surfactant (c2; in the formula (6), R ¹ =
^{_{C 18 H 37, R 2 =}} R 3 = R 4 = CH 3, X - = CH 3 CO 3 -,
HLB: 9.1) was obtained. Cationic surfactant (c2)
And a nonionic surfactant (B) shown in Table 2, citric acid,
Using triethanolamine, propylene glycol, 2.5 L of alcalase and water, detergents were prepared in the amounts shown in Table 4.

Examples 13 to 17 By reacting octyl chloride with pyridine, a cationic surfactant (c3, in the formula (2), Y = C ₈ H ₁₇ , X ⁻
= Cl ^-, HLB: 19.4) was obtained. Using the cationic surfactant (c3), the nonionic surfactant (B) shown in Table 2, citric acid, triethanolamine, propylene glycol, 2.5 L of alcalase and water in the amounts shown in Table 4 A cleaning agent was made.

Examples 18 to 21 After caprylic acid was reacted with triethanolamine, dimethyl carbonate was reacted to obtain a cationic surfactant (c4, in the formula (3), R ⁵ = CH ₃ , R ⁶ = C ₇ H _15, ^X - = C
H3CO3 ^-, HLB: 20.0) was obtained. Formulation shown in Table 4 or Table 5 using cationic surfactant (c4), nonionic surfactant (B) shown in Table 2, citric acid, triethanolamine, propylene glycol, 2.5 L of alcalase and water The detergent was made by volume.

Examples 22 to 24 Reaction of dilaurylmethylamine with methyl chloride
And a cationic surfactant (c5, in the formula (1), R¹
= R^Two= C₁₂H₂₇, R^Three= R^Four= CH_Three, X^-= Cl ^-, HL
B: 9.6). Table with cationic surfactant (c5)
2. Nonionic surfactant (B) described in 2, citric acid, trie
Tanolamine, propylene glycol, alcalase
Washing with 2.5 L and water at the compounding amount shown in Table 7
A preparation was made.

Examples 25 to 30 Triethylamine was reacted with diethyl sulfate to prepare a cationic surfactant (c6; in the formula (6), R ¹ = R ² = R ^3).
= R ⁴ = C ₂ H ₅ , X ⁻ = C ₂ H ₅ SO ₄ ⁻ , HLB: 25.
0) was obtained. Cationic surfactant (c6) and nonionic surfactant (B) described in Table 2, citric acid, triethanolamine, propylene glycol, 2.5 L of alcalase
And water were used to prepare detergents in the amounts shown in Table 5.

Examples 27 to 28 Ethyl chloride was reacted with pyridine to form a cationic surfactant (c7, in the formula (2), Y = C ₂ H ₅ , X ⁻ =
Cl ^-, HLB: 36.0) was obtained. Washing using the cationic surfactant (c7), the nonionic surfactant (B) shown in Table 2, citric acid, triethanolamine, propylene glycol, 2.5 L of alcalase and water at the compounding amounts shown in Table 5 A preparation was made.

Examples 29 to 30 After stearic acid was reacted with N, N-diethylethylenediamine, dimethylsulfuric acid was reacted to obtain a cationic surfactant (c8, in the formula (4), R ⁵ = CH ₃ , R ⁶ = C
₁₇ H ₃₅ , X ⁻ ＣＨCH ₃ SO ₄ ⁻ , HLB: 14.8). A cationic surfactant (c8) and a nonionic surfactant (B) described in Table 2, citric acid, triethanolamine,
Detergents were prepared using propylene glycol, 2.5 L of Alcalase and water in the amounts shown in Table 5.

Comparative Examples 1 to 5 Using a nonionic surfactant shown in Table 2, citric acid, triethanolamine, propylene glycol, 2.5 L of alcalase and water, and sodium dodecylbenzenesulfonate or sodium dodecylether sulfate were used. Thus, detergents were prepared in the amounts shown in Table 7.

Comparative Examples 6 to 10 Using the nonionic surfactants listed in Table 2, the same cationic surfactants as in Example 1, citric acid, triethanolamine, propylene glycol, alcalase 2.5 L and water A detergent was prepared in the amount described in No. 6.

Tables 1 and 2 show the structures of the nonionic surfactants used in the examples and comparative examples. EO represents an oxyethylene group, PO represents an oxypropylene group,
EO / PO indicates random addition, and EO-PO indicates block addition. Mw / Mn is a measured value by GPC, a calculated value calculated from the relational expression (6) or (7), a distribution constant c
Indicates a value obtained by measuring the amount of unreacted alcohol by GC and calculating from the relational expression (8).

[0057]

[Table 1]

[0058]

[Table 2]

The detergents prepared in Examples 1 to 30 and Comparative Examples 1 to 10 were tested for detergency, foaming power and the like. The results are shown in Tables 3 to 6. The test method is as follows.

[0060]

[Table 3]

[0061]

[Table 4]

[0062]

[Table 5]

[0063]

[Table 6]

<Detergency Test> The detergency was measured using a centrifugal washing machine “NA-F800P” manufactured by Matsushita Electric Industrial Co., Ltd.
Artificially contaminated cloth (cotton knit) is made up of 50L of water, bath ratio 30 times,
Washing was performed for 10 minutes under the conditions of a detergent usage of 25 g and a water temperature of 25 ° C. Then, rinsing was performed twice for 3 minutes, and the detergency was calculated and evaluated by the following formula. Detergency _{(%) = {(R W} -R S) / (R I -R S)} × 10
0 In addition, R _I is the reflectivity of the clean cloth, R _W is the reflectance of the cleaning cloth, R
_S indicates the reflectance of the stained cloth, and the reflectance at 540 nm was measured using a multi-source spectrophotometer (manufactured by Suga Test Instruments). The artificially stained cloth used was a wet artificially stained cloth (540, manufactured by Washing Science Association, Japan) having the soil composition shown in Table 8.
The reflectance in nm is 40 ± 5%).

[0065]

[Table 7]

As evaluation criteria, ◎ indicates a detergency of 40% or more, ○ indicates a detergency of 32% or more and less than 40%, Δ indicates a detergency of 20% or more and less than 32%, and x indicates a detergency of less than 20%.

<Foaming power test> Using 1.5 L of a 0.1% aqueous solution of a detergent, a foaming power at 25 ° C. with a high-pressure jet type liquid foaming tester (manufactured by Tsujii Dyeing Machinery Co., Ltd.) Was evaluated.

As evaluation criteria, those having a bubbling height of 20 mm or less were represented by ○, those of 20 to 50 mm were represented by Δ, and those of 50 mm or more were represented by x.

[0069]

The cleaning agent of the present invention has an effect of being excellent in washing of clothes, especially oil stains and mud stains, and low foaming. Further, the cleaning agent of the present invention exerts an extremely excellent effect as a cleaning agent for a washing machine of a type that causes less damage to laundry, particularly for a centrifugal type washing machine.

Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court II (Reference) C11D 1/62 C11D 1/62 1/722 1/722 (72) Inventor Hiroshi Itayama Hitotsubashi Nohonmachi, Higashiyama-ku, Kyoto-shi, Kyoto 11-1 Sanyo Kasei Kogyo Co., Ltd. (72) Inventor Yumi Kawasaki 11-11 1 Sanyo Kasei Kogyo Co., Ltd. (72) Inventor Yasuhito Shiratsuka Higashiyama-ku, Kyoto, Kyoto 11F, No.1, Hitotsubashi No.1 F-term (reference) in Sanyo Chemical Industry Co., Ltd. 4H003 AC08 AC23 AE02 AE03 AE05 AE06 AE08 AE10 DA01 DB01 DB02 EB04 EB08 EC02 ED02 FA21 4J005 AA12 BB02

Claims (5)

[Claims] 1. A composition comprising a cationic surfactant (A) and a nonionic surfactant (B), wherein (A) / (B) = 0.1 / 9.
A cleaning agent having a mass ratio of 9.9 to 25/75. 2. The cleaning agent according to claim 1, wherein the HLB of (A) is 10 to 25. 3. The cleaning agent according to claim 1, wherein (A) is at least one compound selected from the group consisting of compounds represented by the following general formulas (1) to (4). Embedded image Embedded image Embedded image Embedded image However, in the formulas (1) to (4), R ¹ , R ² and R ³ are a hydrogen atom or an alkyl group, alkenyl group or β-hydroxyalkyl group having 1 to 24 carbon atoms, and R ⁴ and R ⁵ are carbon atoms. 1
24 alkyl group, hydroxyalkyl group, benzyl group, or the formula :-( A ¹ O) _n -Z (Note, A ¹ is 2 carbon atoms
4, an alkylene group, Z is a hydrogen atom or an acyl group, and n is 1
Is an integer of ５０50. ), R ⁶ has 1 carbon atom
To 36 alkyl groups, alkenyl groups or β-hydroxyalkyl groups, Y is an alkyl group having 1 to 36 carbon atoms, alkenyl group, β-hydroxyalkyl group, formula: R ⁴ CO ₂ CH
A group represented by _2- (where R ⁴ is the same as described above) or a formula: R ⁴ OCH ₂ — (where R ⁴ is the same as described above)
And a counter ion X ⁻ is a halogen ion, a hydroxy ion, a carbonate ion or a sulfate ion having an alkyl group having 1 to 4 carbon atoms, and a carboxylic acid having an alkyl group or an alkenyl group having 1 to 24 carbon atoms. One or more anions selected from the group consisting of acid ions and sulfonate ions. 4. The cleaning agent according to claim 1, wherein (B) is a compound represented by the following general formula (5). Formula _{RO - [(C 2 H 4} O) n · (A 2 O) m] - (C 2 H 4 O) q - (A 2 O) r -H (1) { wherein, R is the number of carbon atoms 8-18 aliphatic hydrocarbon groups, A ²
Is an alkylene group having 3 or 4 carbon atoms, and n is 0 or 1
12 is an integer, m is 0 or an integer of 1 to 6, q is 1 to 16
And r is 0 or an integer of 1 to 15, (m + n + q)
Represents an integer of 1 to 30, and (n + q) / (m + n + q + r) represents 0.5 to 1.0. [(C ₂ H ₄ O) _n · (A
² O) _m ] indicates random addition or block addition. ｝ 5. The cleaning agent according to claim 4, wherein (B) is a compound produced by adding an alkylene oxide (b1) to an aliphatic alcohol (a1) and satisfying the following. The ratio of weight average molecular weight (Mw) to number average molecular weight (Mn): Mw / Mn satisfies the following relational expression (6) or (7). Mw / Mn ≦ 0.030Ln (v) +1.010 (where v <10) (6) Mw / Mn ≦ −0.026Ln (v) +1.139 (where v ≧ 10) (7) v indicates the average number of moles of the alkylene oxide (b1) added per mole of the aliphatic alcohol (a1).分布 The distribution constant c obtained from the following equation (5) is 1.0 or less. c = (v + n ₀ / n ₀₀ -1) / [Ln (n ₀₀ / n ₀ ) + n ₀ / n ₀₀ -1] (8) where v is the same as the expression (3) or (4), n ₀₀ Represents the number of moles of the aliphatic alcohol (a1) used in the reaction, and n ₀ represents the number of moles of the unreacted aliphatic alcohol (a1). ｝