JP2000144190A - Detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a detergent composition having a high density and improved cleanability for combined stain of dirt and sebum such as stain of socks by making the composition include a specific polymer, a specified polyamine compound and a prescribed surfactant in a specific ratio. SOLUTION: This composition comprises (A) preferably 0.1-20 wt.% of a polymer composed of a structural unit of formula I (M is an alkali metal, ammonium, an alkanolamine or an alkyl) or a polymer (preferably 5,000-10,000 weight- average molecular weight) obtained by chemically modifying the end of the polymer (A), (B) 0.5-20 wt.% of a polyamide compound of formula II [R is a 1-12C alkylene, (R1O)a-R2-(OR1)b (R1 and R2 are each a 1-12C alkylene, a 3-12C hydroxyalkylene or the like; (a) and (b) are each 1-10) or the like; L is H, (R1 O)c(R2O)d-H ((c) and (d) are each 0-40) or the like; (x) is 0-100; (y) is 1-200; (w) and (z) are each 0 or 1] having 4,000-200,000 weight-average molecular weight and (c) 10-50 wt.% of a surfactant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to detergent compositions.

[0002]

2. Description of the Related Art Zeolite, crystalline silicate and the like are known as sequestering agents used in detergents for clothing. However, high-density detergents cannot improve the detergency in terms of the amount of captured Ca and the stability constant of Ca chelate. I can't hope.

[0003] Dispersants include polyacrylates,
Acrylic acid-maleic acid copolymer salts, polyethylene glycol, polyvinylpyrrolidone, carboxymethyl cellulose and the like are known, but they are still insufficient in terms of dispersing power of solid particle soil such as mud and clay.

The role of sequestering agents and dispersants for improving the washing performance has become more and more important with the increase in the density and miniaturization of detergents. In particular, composite stains of mud and sebum, such as stains on socks and the like, have become increasingly important. There is a strong demand for improved cleanability.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a high-density detergent having improved detergency, especially for a combined stain of mud and sebum, such as a sock stain.

[0006]

The present invention relates to (a) a polymer comprising a structural unit represented by the following general formula (I) or a polymer obtained by chemically modifying the terminal of the polymer:
0.1-20% by weight

[0007]

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[Wherein, M is selected from the group consisting of alkali metals, ammonium, alkanolamines and alkyl groups. (B) a polyamine compound represented by the following general formula (II) and having a weight average molecular weight of 4,000 to 200,000:
5-20% by weight

[0009]

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Wherein R is an alkylene group having 1 to 12 carbon atoms,-(R ¹ O) _a -R ^2- (OR ¹ ) _b- , -CH ₂ CH (O
R ³ ) CH ₂ — (where R ¹ and R ² are the same or different alkylene groups having 1 to 12 carbon atoms, hydroxyalkylene groups having 3 to 12 carbon atoms, and dihydroxyalkylene groups having 4 to 12 carbon atoms) , R ³ is a hydrogen atom or a carbon number 1 to
12 alkylene groups, and a and b are the same or different 1 to 10 numbers. ), L is a hydrogen atom,-(R ¹
O) _c (R ² O) _d -H (where c and d are the same or different numbers from 0 to 40, and R ¹ O and R ² O may be block polymerization or random polymerization),- (CH _{2) e} -R ⁴ (wherein, R ⁴ _{is, SO 3 M, CO 2 M} , a PO ₃ M, M is a hydrogen atom, an alkali metal, e is a number of 0 to 6. ), X is 0 to 100, y is 1 to 200, w,
z is the same or different and is 0 or 1. (C) A detergent composition containing 10 to 50% by weight of a surfactant is provided.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS [Component (a)] The component (a) of the present invention is a polymer comprising a structural unit represented by the above general formula (I) or a polymer obtained by chemically modifying the terminal of the polymer. It is united. M in the formula (I) is an alkali metal, ammonium,
Alkanolamines are alkyl groups, especially alkyl groups having 1 to 4 carbon atoms. Examples of the group for chemically modifying the terminal of the polymer include JP-B-62-3704.
The groups described in JP-A No. 4 (Kokai) No. 4, 12 column 12, lines 12 to 28 are mentioned.

The polymer of the component (a) of the present invention desirably contains at least 50% by weight of a polymer comprising a structural unit represented by the general formula (I).

The weight average molecular weight of the polymer (a) of the present invention is from 4,000 to 75, in terms of dispersing action and solubility.
000, particularly preferably 5,000 to 10,000.

The amount of the component (a) is 0.1% in the composition in terms of capturing hardness components in the washing liquid, cleaning higher fatty acid stains, and the like.
It is 1 to 20% by weight, preferably 1 to 15% by weight, more preferably 2 to 10% by weight.

[Component (b)] The component (b) of the present invention is a polyamine compound represented by the following general formula (II).

[0016]

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[Wherein, R is an alkylene group having 1 to 12 carbon atoms,-(R ¹ O) _a -R ^2- (OR ¹ ) _b- , -CH ₂ CH (O
R ³ ) CH ₂ — (where R ¹ and R ² are the same or different alkylene groups having 1 to 12 carbon atoms, hydroxyalkylene groups having 3 to 12 carbon atoms, and dihydroxyalkylene groups having 4 to 12 carbon atoms) , R ³ is a hydrogen atom or a carbon number 1 to
12 alkylene groups, and a and b are the same or different 1 to 10 numbers. ), L is a hydrogen atom,-(R ¹
O) _c (R ² O) _d -H (where c and d are the same or different numbers from 0 to 40, and R ¹ O and R ² O may be block polymerization or random polymerization),- (CH _{2) e} -R ⁴ (wherein, R ⁴ _{is, SO 3 M, CO 2 M} , a PO ₃ M, M is a hydrogen atom, an alkali metal, e is a number of 0 to 6. ), X is 0 to 100, y is 1 to 200, w,
z is the same or different and is 0 or 1. ].

In the general formula (II), preferably, R is an ethylene group, L is-(R ¹ O) _c (R ² O) _d -H [where R ¹ is an ethylene group and R ² is propylene. Group, c is 0
40 and d are numbers of 0 to 20 (however, c + d is 1 or more), and R ¹ O and R ² O may be block polymerization or random polymerization. X is 0, y is 1 to 10, w and z are the same or different and are 0 or 1.

The dispersant of the formula (II), which is the component (b) of the present invention, is a solid dirt particle (often negatively charged).
It is presumed that nitrogen atoms are adsorbed on the surface as adsorption sites and exert a dispersing power by an action of preventing the particles from approaching each other. In other words, it is presumed that the component (b) improves the detergency because the dirt particles detached from the fibers are prevented from reattaching to the fibers by the action of the components (a) and (c). In particular, the protective action of the polymer is more effective as it is branched and spreads. Polyamine compounds having four or more active hydrogens are preferred in terms of adsorptivity to the particles, spreading of the polymer, and dispersing power. Further, from the viewpoint of dispersibility, the molecular weight is from 4,000 to 2
00,000, preferably 8,000-100,000
It is.

The amount of the component (b) is from 0.5 to
It is 20% by weight, preferably 3 to 15% by weight, more preferably 6 to 10% by weight.

[Component (c)] As the component (c), for example, at least one selected from anionic, nonionic, amphoteric, and cationic surfactants can be used. In particular, an anionic surfactant or a mixture of an anionic surfactant and a nonionic surfactant is suitable.

Examples of the anionic surfactant include:
C8-C16 alkylbenzene sulfonate, alkane sulfonate, α-olefin sulfonate, C8-C16 alcohol sulfate, polyoxyethylene alkyl ether sulfate, α-sulfofatty acid alkyl One or more selected from ester salts, and examples of the nonionic surfactant include, for example, an alkylene oxide adduct such as ethylene oxide or propylene oxide to an alcohol having 10 to 18 carbon atoms, a polyoxyalkylene addition-type fatty acid alkanolamide, and methyl. Glucamide and the like. Examples of the amphoteric surfactant include alkyl betaine and alkyl alanine, and examples of the cationic surfactant include quaternary mono-long-chain alkyl and di-long-chain alkyl ammonium salts.

The amount of the component (c) is 10 to 50% by weight in the composition in terms of detergency.

The detergent composition of the present invention contains the above (a) to
In addition to the component (c), the following components can be blended.

<Inorganic builder> Examples of the inorganic builder of the present invention include aluminosilicate and polyphosphate. Either crystalline or amorphous aluminosilicate is used, but crystalline aluminosilicate (zeolite) is preferred in terms of the ability to exchange calcium and the like. For example,
Average primary particle size represented by A-type, X-type and P-type zeolites
0.1-10 μm synthetic zeolites are preferably used. As polyphosphate, orthophosphate, metaphosphate,
Polyphosphates such as pyrophosphate, tripolyphosphate and hexametaphosphate can be used. As salt,
Alkali metal salts, especially sodium salts, are common. The composition of the inorganic builder is preferably 5 to 40% by weight, more preferably 15 to 30% by weight.

<Alkali agent>
Decomposition and solubilization of proteins and sebum components in dirt are promoted,
The cleaning effect is improved. Examples of the alkali agent include inorganic alkali metal salts such as carbonate, silicate, bicarbonate, sulfite, and sesquicarbonate. Particularly, a crystalline silicate is preferable in terms of alkali buffering ability and ability to capture a hardness component. As a crystalline silicate, the trade name “Na-SKS-6” (δ-
Powders and granules can be obtained as Na ₂ Si ₂ O ₅ ). The alkali agent is blended in the composition in an amount of 5 to 40% by weight, preferably 10 to 30% by weight.

<Enzymes> Examples of enzymes include protease, lipase, cellulase, amylase, pectinase and the like. The enzyme can be incorporated in the composition in an amount of 0.01 to 5% by weight.

<Fluorescent Dye> Examples of the fluorescent dye include 4,4'-bis- (2-sulfostyryl) -biphenyl salt, 4,4'-bis- (4-chloro-3-sulfostyryl) -biphenyl salt, One or more selected from a 2- (styrylphenyl) naphthothiazole derivative, a 4,4′-bis (triazol-2-yl) stilbene derivative, and a bis (triazinylamino) stilbene disulfonic acid derivative are added in a composition in an amount of 0.1% or more.
It can be contained at from 01 to 2% by weight.

<Other components> Organic sequestering agents such as ethylenediaminetetraacetic acid and citrate, polyacrylic acid, copolymers of acrylic acid and maleic acid, and carboxylic acids such as carboxymethylcellulose as long as the effects of the present invention are not impaired. Polymers, extenders such as sodium sulfate, dispersants or discoloration inhibitors such as polyethylene glycol, polyvinylpyrrolidone and polyvinyl alcohol, bleaching agents such as percarbonates, alkanoyloxybenzenesulfonic acid or carboxylic acid and tetraacetylethylenediamine Conventionally known components such as a bleach activator, an enzyme stabilizer such as a boron compound and sodium sulfite, an antifoaming agent such as a silicone / silica compound, an antioxidant, a bluing agent and a fragrance are used in a known blending amount. Can be blended. Of these, the amount of the bleaching agent is preferably 0.1 to 10% by weight, and the amount of the bleaching activator is preferably 0.1 to 10% by weight.

The detergent composition of the present invention is preferably a high bulk density granular detergent having a bulk density of 0.6 to 1.2 g / cm ³ .
Examples of the method for increasing the bulk density include a method of spraying nonionic surfactant onto spray-dried particles to increase the density, and a method of directly absorbing the surfactant into a powder component comprising an oil-absorbing carrier. A method of increasing the density is exemplified.

[0031]

EXAMPLES Example 1 (1) Preparation of High Bulk Density Granular Detergent Composition Compound (1), Compound (2), a part of zeolite, LAS, AE, AM at the blending amount (% by weight) shown in Table 1 No. 2, sodium silicate, sodium carbonate, fluorescent dye (4, 4 '
-Bis- (2-sulfostyryl) -biphenyl salt) and sodium sulfate, a 60% by weight solids aqueous slurry was prepared and spray-dried. The obtained particles were put into a high-speed mixer (manufactured by Fukae Kogyo Co., Ltd.), and a part of zeolite and a crystalline silicate (A) were added thereto. Was gradually dropped to perform granulation. Thirty seconds before the end of granulation, the remainder of the zeolite was added.
The obtained granulated particles and the enzyme were mixed in a V blender to prepare a high-density granular detergent composition (Product 1 of the present invention) (average particle size: 450 μm, bulk density: 780 g / L). For other products of the present invention and comparative products, high-density granular detergent compositions were prepared according to the above-mentioned scheme at the mixing ratios shown in Table 1.

(2) Performance Evaluation <Detergency Test> (1) Preparation of Sebum-Stained Cloth The preparation of the stained cloth was carried out by printing an artificially contaminated liquid having the following composition on the cloth using a gravure roll coater. (Gravure roll cell capacity 58 cm ³ / m ² , coating speed 1.
0 m / min, drying temperature 100 ° C., drying time 1 minute, using cotton cloth 2003 cloth (manufactured by Tanika Shoten)).

The composition of the artificially contaminated liquid was 0.4% by weight of lauric acid, 3.1% by weight of myristic acid, and 2.% by weight of pentadecanoic acid.
3% by weight, 6.2% by weight of palmitic acid, 0.4% by weight of heptadecanoic acid, 1.6% by weight of stearic acid, 7.8% by weight of oleic acid, 13.1% by weight of triolein, n-hexadecyl palmitate 2 0.2% by weight, squalene 6.5
% By weight, egg white lecithin liquid crystal material 1.9% by weight, Kanuma red clay 8.1% by weight, and carbon black 0.01% by weight.

(2) Preparation of Soiled Soil Cloth The soiled cloth was prepared by drying Kanuma Horticultural Akadama Soil at 120 ° C. for 4 hours and then pulverizing, and drying a 150 mesh (100 μm) pass at 120 ° C. for 2 hours. , About 150 g was dispersed in 1 liter of perchrene and brought into contact with a cloth of width # 2003 (see JP-A-55-26473).

(3) Cleaning conditions and evaluation method 10 cm × 10 cm
5 pieces of the above-mentioned contaminated cloth, and 100
Washed at rpm. The washing conditions were as follows: washing time: 10 minutes, detergent concentration: 0.067% by weight, water hardness: 4 ° DH, water temperature: 20 ° C., rinsing; tap water for 5 minutes. The cleaning rate (%) is 550 n of the original cloth before and after the cleaning and the contaminated cloth before and after the cleaning.
The reflectance at m was measured by a self-recording colorimeter (manufactured by Shimadzu Corporation) and determined by the following equation.

[0036]

(Equation 2)

[0037]

[Table 1]

Compound (1): a polymer comprising a structural unit represented by the general formula (I) (weight average molecular weight: 10,000
0, M is sodium) Compound (2): a polyamine compound represented by the general formula (II) and having a weight average molecular weight of 70,000 [R is an ethylene group, L is-(R ¹ O) _c (R ² O ) _d -H (R ¹ is an ethylene group,
R ² is a propylene group, c / d = 1/4, and R ¹ O and R
² O is block polymerization), x is 0, y is 1, z is 1, and w is 0. ] · Compound (3): weight-average molecular weight of 16,000 of the polyamine compound represented by the general formula (II) [wherein R is an ethylene group, L is _{^{- (R 1 O) c (}} R 2 O) d -H ( R ¹ is an ethylene group,
R ² is a propylene group, c / d = 1/4, and R ¹ O and R
² O is block polymerization), x is 0, y is 4, z is 1, and w is 0. LAS: linear alkyl (C ₁₂ ) benzenesulfonic acid sodium salt SFE: α-sulfo fatty acid methyl ester sodium salt AS: alkyl (C ₁₂ ) sulfate sodium salt AE: polyoxyethylene (6 mol) alkyl (C ₁₂ ) ether ・ LB: alkyl (C ₁₂ ) dimethyl betaine ・ MG: methylalkyl (C ₁₂ ) glucamide ・ AM: sodium salt of maleic acrylate (molar ratio 7/3) copolymer, average molecular weight 70000 ・ zeolite: M ₂ O ・ Al ₂ O ₃・ 2SiO ₂・ 2H
₂ O, average particle size 2 μm, ion exchange capacity 290 CaC
O ₃ mg / g Crystalline silicate (A): M ₂ O 1.8 SiO ₂ 0.0
2M'0 (where M: Na, K, K / Na = 0.0
3, M ′ = Ca, Mg, Mg / Ca = 0.01), ion exchange capacity 224 CaCO ₃ mg / g, average particle size 12
μm Crystalline silicate (B): M ₂ O.2SiO ₂ , ion exchange capacity 224 CaCO ₃ mg / g, average particle diameter 30 μ
m, trade name SKS (manufactured by Hoechst-Tokuyama Co., Ltd.) ・ FA: sodium salt of higher (C ₁₁ ) fatty acid ・ PEG: polyethylene glycol having an average molecular weight of 7000 ・ Common components: 0.5% by weight of fluorescent dye and 2.0% by weight of enzyme
And Glauber's salt, and the total amount of Glauber's salt was adjusted to 100% by weight. The enzyme is a protease [Sabinase 1
2.0T type W (manufactured by Novo Nordisk)],
Lipase [Lipolase 100T (manufactured by Novo Nordisk)], cellulase [KAC500G (manufactured by Kao Corporation)], and amylase [Termamyl 60T (manufactured by Novo Nordisk)] are mixed at a ratio of 2: 1: 1: 1. .

[0039]

According to the present invention, a high-molecular polymer (component (a)) having a high hardness component blocking power and a polyamine compound (component (b)) having a dispersing power to solid soil particles such as clay are provided.
By using a high detergency detergent composition containing
The cleaning effect on composite stains in which oil stains and solid stains have been difficult to clean so far, such as sock stains, is improved.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Hideji Takata 1334 Minato, Wakayama-shi, Wakayama Prefecture F-term in Kao Corporation Research Institute 4H003 AB19 AB21 AB27 AC08 AD04 BA09 DA01 EA15 EA16 EA28 EB07 EB13 EB32 EB36 EB38 EC01 EC02 FA04

Claims (1)

[Claims] (A) A polymer comprising a structural unit represented by the following general formula (I) or a polymer obtained by chemically modifying the terminal of the polymer: 0.1 to 20% by weight [Wherein, M is selected from the group consisting of alkali metals, ammonium, alkanolamines and alkyl groups. (B) a polyamine compound represented by the following general formula (II) and having a weight average molecular weight of 4,000 to 200,000:
5 to 20% by weight Wherein R is an alkylene group having 1 to 12 carbon atoms,-(R
¹ O) _a -R ^2- (OR ¹ ) _b- , -CH ₂ CH (OR ³ ) CH _2-
(Where R ¹ and R ² are the same or different and have 1 to 1 carbon atoms)
An alkylene group having 2 carbon atoms, a hydroxyalkylene group having 3 to 12 carbon atoms, a dihydroxyalkylene group having 4 to 12 carbon atoms, R ³ is a hydrogen atom or an alkylene group having 1 to 12 carbon atoms, and a and b are the same. Or 1 to 10 different numbers. ) And L is a hydrogen atom,-(R ¹ O) _c (R ² O) _d
-H (wherein, c, d is the number of the same or different 0 to 40, R ¹ O and R ² O may be a random polymerization in block _{polymerization.), - (CH 2)} e -R 4 ( Where R ⁴ is S
O ₃ M, CO ₂ M, and PO ₃ M, where M is a hydrogen atom or an alkali metal, and e is a number from 0 to 6. ) And x
Is 0 to 100, y is 1 to 200, w and z are the same or different and are 0 or 1. (C) A detergent composition containing 10 to 50% by weight of a surfactant.