JPH1135982A - Detergent composition for apparel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a detergent composition showing excellent detergency of skin fat and prevention of resoiling. SOLUTION: This detergent composition for apparel contains 10-40 wt.% anion surface active agent of a sulfate type (a) represented by formula I, R- O-(AO)n -SO3 M (wherein R is an alkyl group or an alkenyl group having 8-20 carbon atoms; AO is an alkyleneoxide group having 2-4 carbon atoms; M is hydrogen, an alkali metal, an alkaline earth metal, ammonium or a basic amino group; and an average molar number (n) of addition is 0-4), 2-30 wt.% polyalkyleneoxidealkylether (b) represented by formula II, R-O-(AO)m -H (wherein R and AO are the same groups as in formula I; and an average molar number m of an added alkyleneoxide is 2-6.5), 1-40 wt.% salt of N,N-bis(carboxylmethyl) serine (c) represented by formula III (wherein M is hydrogen, an alkaline metal, an alkaline earth metal, ammonium or a basic amino group; and the plural metals may be the same or different) and 10-50 wt.% alkalizing agent (d), keeping a:b in the range of 10:1-1:1 (by weight ratio).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a detergent composition for clothing having an excellent sebum detergency. In particular, the present invention relates to a detergent composition for clothing which can effectively remove stains around the mouth and the mouth, which are often problems in washing shirts and blouses.

[0002]

2. Description of the Related Art A detergent for clothing is used to remove from a washing liquid a surfactant which solubilizes stains and dissolves and disperses the fibers from the fiber into the washing liquid, and calcium and magnesium which lower the ability of the surfactant. It is composed of a sequestering agent, an alkali agent that promotes decomposition and solubilization of dirt, a polymer compound for dispersing dirt, and other cleaning builders.

[0003] The basic concept of the components to be blended in the detergent for clothing has been reached without much change so far.
Specific components have been reviewed for environmental considerations. One of them is to make the detergent phosphorus-free. In the past, phosphorus compounds such as sodium tripolyphosphate were blended in clothing detergents as sequestering agents. However, as these phosphorus compounds are concerned as one of the causes of eutrophication in lakes and marshes, crystalline sodium aluminosilicate having a specific structure (in the art, Zeolite) is a major component of sequestering agents because it has no problems with phosphate-type builders and is more stable in recent years.

[0004] On the other hand, as for the shape of the detergent, various shapes such as liquid, slurry, paste, powder or granule, tablet or rod have been proposed, and many technologies have been applied and published in each of them. Was. Among these shapes, the high bulk density of powder detergents in the late 1980's has been the mainstream of compact detergents at present because compactness greatly contributed to transportation, carrying and storage. .

[0005] Sulfate-type activators are excellent in biodegradability,
Renewable natural alcohols are also known as more environmentally preferable surfactants because they can be used as main raw materials. However, there has been a problem that the sulfate ester-type activator is inferior in detergency to oily stains as compared with linear alkylbenzene sulfate, which is a main surfactant of a clothing detergent. In order to solve this problem, Japanese Patent Application Laid-Open No. Hei 8-188793 discloses that a branched alkyl type alkyl group is used.
Japanese Patent Publication No. 509013 and Japanese Patent Publication No. 8-509014 are disclosed.

As a method for improving the detergency of oily soils, there is known a method in which a nonionic surfactant having a low HLB value is added to an anionic surfactant. For example,
Lowering of interfacial tension with triolein and hexadecane in an aqueous system in which triethylene glycol-mono-n-dodecyl ether is mixed with sodium salt of dodecyl sulfate,
Improved detergency for these components has been reported (Thompson, L., Spec Publ R Soc Chem, 118, p5
6-77, 1992). However, it is known that the detergency in actual washing is strongly affected by the hardness component in water, and the application of low HLB nonionic surfactants has not been sufficiently advanced.

On the other hand, zeolite is widely used as a phosphorus-free builder, but its hardness sealing mechanism is based on ion exchange, not chelate formation like phosphate. Therefore, the exchange rate is kinetically limited by the diffusion of the exchange ions in the zeolite. Therefore, there is a problem that it takes a long time for ion exchange in washing with low water temperature and short time, and the washing power is insufficient. In particular, the exchange of large Mg ions in the hydrated shell takes a very long time. Due to such performance problems of zeolites, research and development of biodegradable organic builders other than zeolites have been conducted. For example, a specific organic builder obtained by the reaction of epoxysuccinic acid or maleic acid with aspartic acid and a detergent composition containing the same are disclosed in JP-A-5-170714, and JP-A-248300 discloses a detergent composition containing a specific amount of a builder comprising hydroxyiminodisuccinic acid. Further, N, N-bis (carboxylmethyl) serine salt is superior to the organic builder in sequestering ability and biodegradability, and disclosed in Japanese Patent Application Laid-Open No. 63-267751. The formulation of serine salts as detergent builders has been suggested.

[0008]

As described above, a sulfate ester type surfactant is an environmentally desirable surfactant, but a detergent composition containing the same is a detergent composition containing an alkylbenzene sulfonate. The detergency of oily stains is still inadequate compared to that of objects, and there has been a strong demand for improving the detergency of sebum stains around the mouth and lips of shirts and blouses.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on a detergent composition for clothing to solve the above-mentioned problems, and found that a sulfate ester type anionic surfactant and a poly (meth) acrylate having a specific number of moles added. Alkylene oxide alkyl ether, N, N-bis (carboxylmethyl) serine salt and an alkaline agent, respectively, found that a detergent composition for clothing containing a specific ratio can solve the above problems,
The present invention has been completed.

That is, the present invention provides: (a) 10 to 40% by weight of a sulfate ester type anionic surfactant represented by the following general formula (I): R--O-(AO) _n --SO ₃ M (I) [In the formula, R is an alkyl group or alkenyl group having 8 to 20 carbon atoms. AO is an alkylene oxide group having 2 to 4 carbon atoms. M represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or a basic amino group, and n is a number from 0 to 4 representing an average number of moles added. (B) 2 to 30% by weight of a polyalkylene oxide alkyl ether represented by the following general formula (II), and (a): (b)
= 10: 1 to 1: 1 (weight ratio) R-O- (AO) _m -H (II) wherein R is an alkyl group or an alkenyl group having 8 to 20 carbon atoms. AO is an alkylene oxide group having 2 to 4 carbon atoms. m is a number of 2 to 6.5 representing the average number of moles of alkylene oxide added. (C) 1 to 40% by weight of N, N-bis (carboxylmethyl) serine salt represented by the following general formula (III)

[0011]

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[In the formula, M represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or a basic amino group, and a plurality of Ms may be the same or different. (D) A detergent composition for clothing containing 10 to 50% by weight of an alkali agent. Hereinafter, the components used in the present invention will be described in detail.

The sulfate type surfactant of the component (a) of the present invention is represented by the following general formula (I). During _{R-O- (AO) n -SO} 3 M (I) [wherein, R is an alkyl or alkenyl group having 8 to 20 carbon atoms. AO is an alkylene oxide group having 2 to 4 carbon atoms. M represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or a basic amino group, and n is a number from 0 to 4 representing an average number of moles added. In the general formula (I), R is an alkyl group or an alkenyl group having 8 to 20 carbon atoms.
It may be first grade or second grade. In the general formula (I), A
O is a polymer chain of an alkylene oxide having 2 to 4 carbon atoms, for example, ethylene oxide or propylene oxide, and may be a single or a random or block-added plurality of alkylene oxides.

In the present invention, the sulfate ester type surfactant (a) is incorporated in the composition in an amount of 10 to 40% by weight. Ten
If the amount is less than 40% by weight, sufficient washing performance cannot be obtained, and if the amount exceeds 40% by weight, the solubility of the detergent is impaired. The alkyl group in the general formula (I) can be used for both straight and branched chains. As the branched chain, a secondary alkyl group or a Guerbet type is preferable. These have good properties in terms of cleaning performance, biodegradability, solubility of detergent particles, and suitability for production. However, the presence of a multiple branch point tends to reduce the biodegradability, or lowers the crystallinity, which may hinder the powdering of the detergent. Care must be taken when using it.

The polyalkylene oxide alkyl ether of the component (b) of the present invention is represented by the following general formula (II). R-O- (AO) _m -H wherein R is an alkyl group or an alkenyl group having 8 to 20 carbon atoms. AO is an alkylene oxide group having 2 to 4 carbon atoms. m is a number of 2 to 6.5 representing the average number of moles of alkylene oxide added. As the alkylene oxide (AO), ethylene oxide and propylene oxide may be used alone or in combination. The average number of moles of AO added is 2
6.5, preferably 3-6. If the amount is less than 2 mol, not only does the re-contamination preventive property against soot stains decrease, but also the detergency of sebum decreases. This tendency is particularly remarkable when the hardness is high. On the other hand, when the amount exceeds 6.5 mol, the oily soil cleaning property is undesirably reduced.

In the present invention, the component (b) contains 2
It is important that the weight ratio of the component (a) to the component (b) is (a) :( b) = 10: 1 to 1: 1. If the component (b) is less than 1/10 the component (a), the effect of adding the component (b) cannot be obtained, and if it exceeds 1: 1, the ability to prevent re-contamination of soot stains decreases. In particular, when the component (b) having an average addition mole number of the alkylene oxide of about 2 to 4 mol is blended or when the propylene oxide adduct is blended, it is better to increase the ratio of the component (a). Can be

The N, N-bis (carboxylmethyl) serine salt of the component (c) of the present invention is represented by the following general formula (III).

[0018]

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[Wherein, M represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or a basic amino group, and a plurality of Ms may be the same or different. In the present invention, the component (c) is 1 to 40% by weight in the composition,
Preferably, the content is 3 to 30% by weight. If it is less than 1% by weight, a sufficient cleaning effect cannot be obtained, and if it exceeds 40% by weight, it becomes difficult to produce a detergent.

As the alkali agent of the component (d), an alkali agent conventionally known in the detergent field can be used. In particular, in the present invention, the maximum pH of an aqueous solution or dispersion having a concentration of 0.1% by weight is 10 or more (20 ° C.), and 5 ml or more of 0.1N HCl aqueous solution is required to adjust 1 liter of the aqueous solution or dispersion to pH 9. An alkali agent comprising the compound described above is more preferable in terms of cleaning performance. Examples thereof include alkali metal carbonates such as sodium carbonate, which are collectively referred to as dense ash and light ash, and amorphous alkali metal silicates such as JIS Nos. 1, 2 and 3. Crystalline silicates, especially those described in JP-A-60-227895, have an exchange ability with calcium ions in addition to an alkali buffering ability, and are particularly preferred base materials. As the crystalline silicate, JP-A No.
The crystalline silicate described in JP-A-7-89712 is also preferred.

The crystalline silicate used in the present invention has excellent alkali ability and is distinguished from crystalline aluminosilicate. The crystalline silicate used in the present invention preferably has a maximum pH of 11 or more as defined above.
Particularly preferred as crystalline silicates are those having the following composition. _{x (M 2 O) · y} (SiO 2) · z (Me m O n) · w (H 2 O) (IV) wherein, M is Group Ia elements of the periodic table (particularly preferably K and / Or Na), and Me is an element of group IIa of the periodic table, IIb
One or a combination of two or more selected from group III elements, group IIIa elements, group IVa elements or group VIII elements (preferably Mg,
Ca), y / x = 0.5-2.6, z / x = 0.01-0.9
, W = 0 to 20, and n / m = 0.5 to 2.0. The production method of the crystalline silicate represented by the general formula (IV) can be referred to JP-A-7-89712.

Further, a crystalline silicate having the following composition can also be preferably used. M ₂ O · x ′ (SiO ₂ ) · y ′ (H ₂ O) (V) wherein M represents an alkali metal (particularly preferably K and / or Na), x ′ = 1.5 to 2.6, y '= 0 to 20 (particularly preferably substantially 0). The crystalline silicate of the general formula (V) is disclosed in JP-A-60-227895, Phys. Chem. Glasses. 7, 127-138 (1966), and Z. Kristall.
ogr., 129, p396-p404 (1969). Also, the product name “Na-SKS-6” from Hoechst (δ-Na2Si2O5)
As powders and granules.

In the present invention, the crystalline silicate is blended preferably in an amount of 1 to 30% by weight, particularly preferably 3 to 25% by weight, whereby a more excellent detergency can be obtained.

Other alkaline agents include sodium sesquicarbonate and sodium hydrogen carbonate.
Phosphates such as tripolyphosphate also act as alkaline agents. In the present invention, the alkali agent as the component (d) is blended in the composition at 10 to 50% by weight. If it is less than 10% by weight, the cleaning properties of oily stains are insufficient. If the amount exceeds 50% by weight, the re-contamination preventing property of the particle soil is reduced, which is not preferable.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION The detergent composition of the present invention comprises the above (a)
In addition to the essential components (b), (c) and (d), other optional components as described below can be contained.

As the anionic surfactant other than the component (a), a linear alkyl benzene sulfonate having a carbon chain length of 10 to 18, an α-sulfofatty acid ester salt and the like can be used in combination. Amino acid surfactants and N-acyl amino acid surfactants can be used as amphoteric surfactants, and fatty acid alkanolamides can be used as nonionic surfactants other than the component (b). In a small amount, a cationic surfactant can be used in combination. Quaternary ammonium salts and the like can be used as the cationic surfactant.

In particular, the detergent composition for clothing of the present invention comprises:
It is preferable to blend an unsaturated carboxylic acid-based polymer having a weight average molecular weight of 1,000 to 150,000 as the component (e).
The component (e) has a function of sequestering metal ions, a function of dispersing solid particle dirt from clothes into a washing bath, and a function of preventing the particles from reattaching (recontamination) to clothes.
Specifically, a copolymer represented by the following formula (VI) or /
And a carboxylic acid-based polymer such as a homopolymer represented by the formula (VII). The copolymer is generally a random polymerization.

[0028]

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Wherein Z is an olefin having 1 to 8 carbon atoms;
Maleic acid (anhydride) such as acrylic acid, methacrylic acid, itaconic acid, methallyl sulfonic acid, or a salt of a copolymer of maleic anhydride and a monomer copolymerizable with maleate, and m is a weight average molecular weight of the copolymer. 1000-1500
The value indicates 00. M is _{Na, K, NH 4, H} . )

[0030]

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(In the formula, P is a monomer capable of being homopolymerized, and examples thereof include acrylic acid, methacrylic acid, and maleic acid. M ′ is a homopolymer having a weight average molecular weight of 1,000 to
It is a value indicating 150000. Homopolymers are Na, K,
It has become a salt such as NH _4. ) Acrylic acid among these carboxylic acid polymer - salts of maleic acid copolymers and polyacrylate (Na, K, NH ₄₎ has particularly excellent. The weight average molecular weight is suitably from 1,000 to 80,000. The carboxylic acid-based polymer as the component (e) can be easily obtained by polymerizing an unsaturated organic carboxylic acid or an organic polycarboxylic acid. Component (e) is incorporated in the composition in an amount of 0.5 to 5% by weight, preferably 1 to 4% by weight. If the content is less than 0.5% by weight, a sufficient effect cannot be obtained, and if it exceeds 5% by weight, the solubility of the detergent is undesirably reduced.

Other builders include sequestering agents such as crystalline aluminosilicate, which is a zeolite; organic sequestering agents such as ethylenediaminetetraacetic acid (EDTA) and citrate; extenders such as sodium sulfate; Dispersants or color transfer inhibitors (PVP) such as pyrrolidone (PVP) and polyvinyl alcohol (PVA), carboxymethyl cellulose, bleaching agents such as sodium percarbonate, and the like, as described in JP-A-6-316700, and tetraacetylethylenediamine (TAED). Bleach activators, enzymes such as proteases, cellulases, amylases and lipases, enzyme stabilizers such as boron compounds and sodium sulfite, biphenyl-type and stilbene-type fluorescent dyes, defoamers such as silicone / silica, antioxidants , Bluing agents, fragrances, etc. Can be formulated ingredients in a known amount. Specifically as the above components, JP-A-8-2180
No. 93 can be used.

As the production method, a conventionally known production method can be used, and the production conditions are easily selected by those skilled in the art under appropriate conditions according to the composition.

[0034]

According to the present invention, a detergent composition having excellent detergency against sebum stains of clothing can be obtained.

[0035]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

Example 1 Various detergent compositions were prepared according to the formulations shown in Tables 2 and 3, and the following evaluations were made. The results are shown in Tables 2 and 3.

<Evaluation Method for Sebum Detergency> Preparation of Model Sebum / Carbon Soil Contaminated Fabric A model contaminated liquid having the composition shown in Table 1 below was prepared.

[0038]

[Table 1]

1 kg of the above composition was dissolved and dispersed in 80 liters of perchrene, and the T / C blended plain woven fabric (polyester / cotton =
65/35) is immersed to attach dirt, and the perclene is dried and removed.

Washing conditions and evaluation method The above prepared 10 cm
Five artificially stained cloths of 10 cm were put and washed at 100 rpm with a tergotometer. The washing conditions are as follows. Washing conditions Washing time 10 minutes Detergent concentration 0.067% Water hardness 3 水 DH Water temperature 20 ° C Rinse with tap water 5 minutes Washing power is the self-recording colorimeter (550nm reflectance of the original fabric before and after washing). The cleaning rate (%) was determined by the following equation, and the average value of the five sheets was shown as the cleaning power.

[0041]

(Equation 1)

<Test Method for Preventing Soot Soil Recontamination> A cotton white cloth (gold cloth 2003 cloth) was cut into a piece of 10 cm × 10 cm to make a set of five pieces. 0.25 g of carbon was added to 1 liter of the aqueous detergent solution for evaluation, and a test was carried out with a tart gometer under the following conditions. Cleaning conditions Cleaning time 10 minutes Detergent concentration 0.067% Water hardness 3 ゜ DH water temperature 20 ° C Rinsing 5 minutes in tap water The re-contamination prevention performance is the reflection at 550nm of the original cloth (white cloth) before cleaning and the contaminated cloth after testing. The rate was measured with a self-recording colorimeter (manufactured by Shimadzu Corporation), and the recontamination prevention rate was determined by the following equation.

[0043]

(Equation 2)

[0044]

[Table 2]

[0045]

[Table 3]

(Note) The symbols in the table have the following meanings. · AS1: Mitsubishi Chemical (Co., Ltd.) Dobanol 25 (C ₁₂ ~C
₁₅ ) Sodium sulfate sodium salt of AS) AS2: Secondary alkyl sulfate salt represented by the following structure (alkyl carbon number of raw material α-olefin 16/14 = 7)
/ 3 derived from the mixture. Compounds of m = 0 and n = 13 and m = 1 and n = 12 in the following formula are 70% in total, m
= 0 and n = 11 and m = 1 and n = 10 in total
30%)

[0047]

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AS3: sodium polyoxyethylene tetradecyl ether sulfate sodium salt, average addition mole number of ethylene oxide n = 1.0 LAS: alkyl benzene sulfonic acid “Alken L (carbon number of alkyl chain 10 to 10) manufactured by Nisseki Detergent Co., Ltd. 14) 48%
Those that have been neutralized with NaOH · fatty acid salt: tallow derived fatty soda · AE-1: Nonidet _{S-3 (. C 12,} C 13 as the average of 3 moles of EO alcohol manufactured by Mitsubishi Chemical (Co.)) · AE- 2: Polyethylene oxide alkyl ether (carbon chain length C ₁₂ , average number of moles of added ethylene oxide 5.
5) · AE-3: Nonidet S-7 (C _12, C ₁₃ that the average 7 moles of EO alcohol, Mitsubishi Chemical Co., Ltd.) · AE-4: polyethylene oxide alkyl ether (carbon chain length C ₁₂ , Average number of moles of ethylene oxide added 1
2) ・ Crystalline silicate: SKS-6 (δ-Na ₂ Si ₂ O ₅ , crystalline layered silicate, average particle diameter 20 μm, manufactured by Hoechst Tokuyama Co., Ltd.) ・ Amorphous silicate: JIS No. 2 sodium silicate ・ Dense grains Ash: sodium carbonate ・ Zeolite: 4A zeolite, average particle size 3 μm ・ APC: N, N-bis (carboxymethyl) serine trisodium salt ・ AA-MA: Sokaran CP5 (acrylic acid-maleic acid copolymer, average molecular weight 70000) PEG: polyethylene glycol, average molecular weight 600
0 ・ Fluorescent dye: Tinopearl CBS (Ciba-Geigy)
And Whitetex SA (manufactured by Sumitomo Chemical Co., Ltd.) in the same weight ratio.・ Fragrance: Uses the flavor composition described in Examples of JP-A-8-239700. ・ Enzyme: Sabinase 12.0T type-W (protease, manufactured by Novo Nordisk), Lipolase 100T (lipase, manufactured by Novo Nordisk), Termamyl 60T (Amylase, manufactured by Novo Nordisk) and KAC500 (alkali cellulase, manufactured by Kao Corporation) in a weight ratio of 2: 1: 1: 1.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification symbol FI C11D 3:33 3:08 3:10 3:37) (72) Inventor Tomoki Yanagisawa 1334 Minato, Wakayama-shi, Wakayama Pref. In-house (72) Inventor Sachiko Kamioka 1334 Minato, Wakayama-shi, Wakayama Pref.

Claims (3)

[Claims] (A) A sulfate ester type anionic surfactant represented by the following general formula (I): 10 to 40% by weight R-O- (AO) _n -SO ₃ M (I) R is an alkyl or alkenyl group having 8 to 20 carbon atoms. AO is an alkylene oxide group having 2 to 4 carbon atoms. M represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or a basic amino group, and n is a number from 0 to 4 representing an average number of moles added. (B) 2 to 30% by weight of a polyalkylene oxide alkyl ether represented by the following general formula (II), and (a): (b)
= 10: 1 to 1: 1 (weight ratio) R-O- (AO) _m -H (II) wherein R is an alkyl group or an alkenyl group having 8 to 20 carbon atoms. AO is an alkylene oxide group having 2 to 4 carbon atoms. m is a number of 2 to 6.5 representing the average number of moles of alkylene oxide added. (C) 1 to 40% by weight of N, N-bis (carboxylmethyl) serine salt represented by the following general formula (III): [Wherein, M represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium or a basic amino group,
M may be the same or different. (D) A detergent composition for clothing containing 10 to 50% by weight of an alkali agent. (2) The component (e) further comprises a weight average molecular weight of 1000
0.5 to 50000 unsaturated carboxylic acid polymer
The detergent composition for clothing according to claim 1, which is contained by weight. 3. The detergent composition for clothing according to claim 1, wherein m in the general formula (II) of the component (b) is 3 to 5.