CN102844419B

CN102844419B - Detergent composition

Info

Publication number: CN102844419B
Application number: CN201180019178.5A
Authority: CN
Inventors: 星田善行; 小熊友一; 牧野诚
Original assignee: Lion Corp
Current assignee: Lion Corp
Priority date: 2010-04-16
Filing date: 2011-04-15
Publication date: 2015-02-04
Anticipated expiration: 2031-04-15
Also published as: JP6148008B2; JPWO2011129438A1; CN102844419A; WO2011129438A1

Abstract

Disclosed is a detergent composition which contains (A) 2.5% by mass or more but less than 40% by mass of at least one compound that is selected from among alpha-sulfofatty acid alkyl esters and salts thereof, and (B) 0.1-4% by mass (inclusive) of at least one compound that is selected from among polymer compounds having a carboxy group and a weight average molecular weight of more than 10,000 but 500,000 or less and salts of the polymer compounds. A 1% by mass aqueous solution or aqueous dispersion of the detergent composition has a pH at 25 DEG C of 5.5-9.4 (inclusive). The detergent composition exhibits excellent cleaning power and foaming performance even in cases where washing is carried out using water with high hardness, and is useful for hand washing.

Description

Detergent composition

Technical field

The present invention relates to the washing of the fibre products such as clothing, especially useful to hand washing washing detergent composition.

The Patent 2010-095382 CLAIM OF PRIORITY that the application filed an application in Japan according on April 16th, 2010, quotes its content here.

Background technology

For the detergent composition of washing clothes etc., usually allocate the anion surfactant as cleansing into.And in order to improve its cleaning force, and giving other various performance, also having allocated washing assistant into.Alkaline agent is the one in order to improve the washing assistant that cleaning force is allocated into, and consider from the viewpoint such as cleaning force and cost, alkali-metal carbonate or silicate are widely used.

The anion surfactant be widely used in the past in detergent composition is linear alkyl benzene hydrochlorate, in recent years, brings into use alpha-sulfo-fatty acid alkyl ester salt.The cleaning force of alpha-sulfo-fatty acid alkyl ester salt is excellent, in high hardness water, especially also can play height cleaning force, also have biodegradable advantage.

General, alpha-sulfo-fatty acid alkyl ester salt separately or granulation together with other tensio-active agent, after making surfactant powders, can be deployed into detergent composition together with other detergent ingredients.Such as, the water-based slip that to Patent Document 1 discloses the pH of the water-soluble salt of the alpha-sulfo-fatty acid alkyl ester containing extra fine quality ratio and zeolite, sodium sulfate be less than 10 carries out spraying dry, the spraying dry powder obtained and alkaline auxiliary lotion and binder ingredients mix and blend the method for granulation.In addition, the granular detergent composition that Patent Document 2 discloses surfactant powders and be deployed into by above-mentioned surfactant powders, described surfactant powders contains the alpha-sulfo-fatty acid alkyl ester salt of more than 40 quality % and sequestrant and/or antioxidant 0.001 ~ 0.4 quality %, and pH when it makes the 1 quality % aqueous solution is more than 7.5.

Prior art document

Patent documentation

Patent documentation 1: Japanese Patent Laid-Open 4-348196 publication

Patent documentation 2: Japanese Patent Laid-Open 10-204479 publication

Summary of the invention

Alpha-sulfo-fatty acid alkyl ester salt has above-mentioned advantage, when especially using in high hardness water, can play the cleaning force (height stability in hard water) of height, after, can estimate to be expanded and be used in the high region of bath water hardness.But, allocate the detergent composition of alpha-sulfo-fatty acid alkyl ester salt into, had the tendency that lathering property reduces, with compared with other the anion surfactant detergent composition that such as LAS allocates, bubble during washing few, and foam evanescence (foam duration is low).This lathering property has the tendency of reduction along with the water hardness raises.

Above-mentioned low whipability, with being favourable when automatic washing machine or type washing machine washing, but unfavorable when washing by hand.Namely, wash by hand the occasion of washing, when especially using washings of the same race repeatedly to wash, user tends to judge cleaning force according to the durability of the quality of bubbling and foam, and lathering property is low, probably can be considered to cleaning force also low.Therefore, this purposes requires to improve lathering property.

In view of above-mentioned aspect, even if the object of the present invention is to provide one to use high hardness water washing, also play the detergent composition useful to hand washing washing of excellent cleaning force and lathering property.

Solve the means of problem

Contriver, through extensively research, found that, by the removing especially above-mentioned alkali-metal carbonate of alkaline agent and silicate, the lathering property of alpha-sulfo-fatty acid alkyl ester salt improves.Based on this is familiar with, find through more deep research, by alpha-sulfo-fatty acid alkyl ester salt and specific macromolecular compound are combined together with specified quantitative separately, reduced the consumption of above-mentioned alkaline agent simultaneously more in the past, the pH of its 1 quality % aqueous solution is set in specified range, above-mentioned problem can be solved, complete the present invention.

In order to solve the problem, the present invention has following aspect feature.

[1] a kind of detergent composition, more than at least a kind of compound 2.5 quality % selected from alpha-sulfo-fatty acid alkyl ester and salt thereof containing (A), be less than 40 quality %, and (B) from weight-average molecular weight more than 10,000, more than at least a kind of compound 0.1 quality %, below the 4 quality % that select the macromolecular compound with carboxyl of less than 500,000 and salt thereof

The 1 quality % aqueous solution of this detergent composition or the pH of aqueous dispersions at 25 DEG C are more than 5.5 less than 9.4.

[2] according to the detergent composition recorded in [1], described detergent composition is also containing (C) more than zeolite 0.5 quality %, below 30 quality %.

[3] according to the detergent composition recorded in [1] or [2], described detergent composition is not containing the alkaline agent selected from alkali-metal carbonate and silicate.

[4] according to the detergent composition that any one in [1] ~ [3] is recorded, wherein, at least a kind of compound that described (A) selects from alpha-sulfo-fatty acid alkyl ester and salt thereof is the compound represented with following general formula (a1).

R ¹－CH(SO ₃M)－CO－O－R ²…(a1)

［ R in formula ¹alkyl or the thiazolinyl of carbonatoms 6 ~ 20, R ²be the alkyl of carbonatoms 1 ~ 6, M is hydrogen atom or gegenion.

[5] according to the detergent composition that any one in [1] ~ [4] is recorded, wherein, described (B) from weight-average molecular weight more than 10,000, at least a kind of compound selecting the macromolecular compound with carboxyl of less than 500,000 and salt thereof is at least one compound selected from poly carboxylic acid and salt thereof and carboxyl acid modified polyose and its salt.

[6] according to the detergent composition that any one in [1] ~ [5] is recorded, described detergent composition is granular.

[7] according to the detergent composition that any one in [1] ~ [6] is recorded, described detergent composition is for hand-washing washing.

Invention effect

By the present invention, a kind of detergent composition useful to hand washing washing can be provided, even if use high hardness water carries out washing also play good cleaning force and foam performance.

Embodiment

< (A) composition: at least one > selected from alpha-sulfo-fatty acid alkyl ester and salt thereof

Containing (A) composition (at least one selected from alpha-sulfo-fatty acid alkyl ester and salt thereof) in detergent composition of the present invention.

As (A) composition, be exemplified below the compound stated general formula (a1) and represent.

R ¹－CH(SO ₃M)－CO－O－R ²…(a1)

R ¹alkyl or alkenyl can be straight-chain, also can be branched.

From the viewpoint of cleaning force, R ¹carbonatoms be 6 ~ 20, preferably 8 ~ 18, more preferably 10 ~ 16.R ¹can be a kind of group, also can be the mixing of two or more group.R ²alkyl can be straight-chain, can be also branched, from the viewpoint of cleaning force, its carbonatoms be preferably 1 ~ 6, preferably 1 ~ 3, more preferably 1.

As the gegenion of M, as long as can with R ¹cH (COOR ²) SO ₃-formation water-soluble salt, citing is as basic metal, alkaline-earth metal, protonated amines and ammonium salt etc.

Basic metal, for example there are sodium and potassium etc.

Alkaline-earth metal, for example there are calcium and magnesium etc.

In protonated amines, amine can be any of primary ~ tertiary amine, and preferred the total number of carbon atoms is 1 ~ 6.Above-mentioned amine can contain hydroxyl, also can not contain, but also has the aspects such as preparation, preferably containing hydroxyl from dissolution in low temperature during cleaning.Such amine for example there are alkanolamine, the carbonatoms of above-mentioned silane alcohol base preferably 1 ~ 3.As the concrete example of alkanolamine, for example there are monoethanolamine, diethanolamine and trolamine etc.

M preferred as alkali or alkanolamine, more preferably basic metal.

(A) composition comprised in detergent composition can be a kind, also can be two or more.

Relative to the total amount of this detergent composition, in detergent composition, the content of (A) composition is more than 2.5 quality %, is less than 40 quality %, preferably more than 3 quality %, below 35 quality %, more preferably more than 5 quality %, below 30 quality %.When aforementioned proportion is more than 2.5 quality %, the effect that (A) composition brings can give full play to, and cleaning force is excellent, is less than 40 quality %, the excellences such as lathering property, easily washability.

(A) composition can be used in the material of market public sale, also can use by being recorded in International Publication the 2004-No. 111166 brochure, International Publication 2009---the material that in No. 054406 brochure, well-known manufacture method produces.Such as, obtain alpha-sulfo-fatty acid alkyl ester by sulfonated fatty acid alkyl ester, in the sulfo group alkali of above-mentioned alpha-sulfo-fatty acid alkyl ester and alpha-sulfo-fatty acid alkyl ester salt can be obtained.

The alkali that neutralization uses is corresponding with the gegenion of above-mentioned M.

Can as required in above-mentioned manufacture method, in after sulfonation and before, utilize the alcohol of methyl alcohol etc. to carry out esterification.As SO residual in resultant of reaction ₃when bimolecular adds with thing, by esterification step, this SO ₃bimolecular adds the alkoxy portion esterification with thing, facilitates SO ₃deintercalation.As a result, inhibit the generation of by product, improve the purity of alpha-sulfo-fatty acid alkyl ester in resultant of reaction.

Can as required in above-mentioned manufacture method, in above-mentioned and before operation or afterwards, for making the tone of alpha-sulfo-fatty acid alkyl ester salt more near white, the SYNTHETIC OPTICAL WHITNER of available such as hydrogen peroxide etc. carries out bleaching.

Resultant in above-mentioned and after operation or after bleaching process, normally solids component is the soup compound of about 50 ~ 80 quality %.Relative to above-mentioned resultant, process that is concentrated or powder can be carried out as required.Powder by kneading, the well-known comminution granulation such as extruder grain method (mediate, extruding, pulverize), stirring-granulating method or rolling comminution granulation implements.

In the alpha-sulfo-fatty acid alkyl ester salt obtained by above-mentioned manufacture method, usually except alpha-sulfo-fatty acid alkyl ester salt, also containing alpha-sulfo-fatty acid two alkali salt (the middle R of such as above-mentioned general formula (a1) ²by the salt after the displacement of the gegenion of M, hereinafter referred to as disalt).Disalt is compared with alpha-sulfo-fatty acid alkyl ester salt, although this hypofunction, still has the function of tensio-active agent.Therefore, as in the alpha-sulfo-fatty acid alkyl ester salt that aforesaid way is made, effective constituent (AI) content as tensio-active agent is that the content added up to as alpha-sulfo-fatty acid alkyl ester salt (purity) and disalt is obtained.AI content in above-mentioned alpha-sulfo-fatty acid alkyl ester salt, relative to the total mass of this alpha-sulfo-fatty acid alkyl ester salt, is preferably 10 ~ 80 quality %, more preferably 35 ~ 80 quality %, further preferred 60 ~ 70 quality %.At more than 10 quality %, manufacture efficiency and improve, below 80 quality %, handlability is strong.

In addition, in alpha-sulfo-fatty acid alkyl ester salt, except containing except alpha-sulfo-fatty acid alkyl ester salt and disalt thereof, also contain the by product of the inorganics of organism or the sodium sulfate etc. such as methyl sulfate, sulfovinic acid, propylene sulfate, rudimentary, intermediate carboxylic acid or their ester, ketone, aldehyde.These by-products contents are small, do not affect especially effect of the present invention.

< (B) composition: from weight-average molecular weight more than 10,000, less than 500,000 containing at least a kind of > selected the macromolecular compound of carboxyl and salt thereof

Detergent composition of the present invention is simultaneously containing above-mentioned (A) composition and (B) composition (from weight-average molecular weight more than 10,000, select the macromolecular compound containing carboxyl of less than 500,000 and salt thereof at least a kind).

(B) weight-average molecular weight of composition preferably more than 1.2 ten thousand, be less than 500,000, more preferably more than 1.5 ten thousand, less than 300,000, further preferably less than more than 1.5 ten thousand 10 ten thousand.When above-mentioned weight-average molecular weight is greater than 10,000, lathering property (power of spuming also has foam duration), especially foam duration is excellent.When less than 500000, the favorable solubility of detergent composition in water.

In addition in this manual, " weight-average molecular weight " represents sodium polyacrylate or polyoxyethylene glycol to use as reference material, the value obtained by gel permeation chromatography (GPC) analysis.In addition, when (B) composition is polymkeric substance or its salt of monomer (unsaturated carboxylic acid etc.) containing carboxyl, reference material is sodium polyacrylate, and when (B) composition is carboxyl acid modified polyose, reference material is polyoxyethylene glycol.

As (B) if composition use containing the macromolecular compound of carboxyl and the weight-average molecular weight of salt thereof in above-mentioned scope, be not particularly limited, suitably can select from well-known material.As the preference of above-mentioned macromolecular compound, for example there are polymkeric substance (hereinafter referred to as poly carboxylic acid) and the salt thereof of unsaturated carboxylic acid, poly-acetal carboxylic acid and the salt thereof such as metaldehyde acid (such as, Japanese Patent Laid-Open No. Sho 54-52196 publication record material), oxidation of polysaccharides class and salt thereof and carboxyl acid modified polyose and salt etc. thereof.This wherein, for making effect of the present invention more excellent, at least a kind that preferably selects from poly carboxylic acid and salt thereof and carboxyl acid modified polyose and salt thereof.

In poly carboxylic acid, as unsaturated carboxylic acid, for example there are such as vinylformic acid, methacrylic ester, hydroxyl acrylic, hydroxyl-metacrylate, maleic acid, FUMARIC ACID TECH GRADE and methylene-succinic acid etc.

The unsaturated carboxylic acid unit forming poly carboxylic acid can be a kind, also can be two or more.Here " unit " be meant to the repeating unit forming this polymkeric substance, such as acrylic acid units is the repeating unit that acrylic acid unsaturated double-bond breaks to form.

Poly carboxylic acid also can containing the monomeric unit beyond unsaturated carboxylic acid.As the monomer beyond unsaturated carboxylic acid, as long as can with the monomer of unsaturated carboxylic acid copolymerization, such as MALEIC ANHYDRIDE, acrylic acid amides, methacrylate amide, alkyl acrylate, alkyl methacrylate, vinyl alcohol, also have allyl alcohol etc.

The concrete example of poly carboxylic acid has: polyacrylic acid, polymethyl acrylic acid, poly-maleic acid, poly-hydroxyl acrylic, poly-FUMARIC ACID TECH GRADE, vinylformic acid-acid/maleic acid copolymers, acrylic acid-acrylic acid amide copolymer and vinylformic acid-allyl alcohol multipolymer etc.

As poly carboxylic acid, among above-mentioned, the poly carboxylic acid preferably containing acrylic acid units, particularly preferably polyacrylic acid (acrylic acid homopolymer), vinylformic acid-acid/maleic acid copolymers.In addition, the salt of poly carboxylic acid is not particularly limited, such as an alkali metal salt, alkali earth metal salt, protonated amine salt and ammonium salt etc.Basic metal, alkaline-earth metal and protonated amines for example there are the example identical with the example exemplified as M in above-mentioned formula (a1) respectively.

In vinylformic acid-acid/maleic acid copolymers, the ratio of maleic acid unit is higher, and cleaning force is stronger, more preferably.But when the ratio of maleic acid unit is too high, weight-average molecular weight is difficult to increase.Based on such viewpoint, in vinylformic acid-acid/maleic acid copolymers, the ratio (mol ratio) of maleic acid unit/acrylic acid units preferably 20/80 ~ 80/20, more preferably 30/70 ~ 60/40, further preferably 40/60 ~ 50/50.

Poly carboxylic acid can be used in the material of market public sale, also can use the poly carboxylic acid synthesized by well-known method.Concrete trade name, such as " ソカラ Application (registered trademark) PA40 ", " ソカラ Application (registered trademark) CP-7 ", " ソカラ Application (registered trademark) CP-9 " (above BASF Amada Co., Ltd.), " ア Network アリ Star Network (registered trademark) TL-500 ", " ア Network アリ Star Network (registered trademark) TL-400 " (Nippon Catalyst K. K.'s system), all can use well.

Oxidation of polysaccharides class is the polyose (such as-CH being imported carboxyl by oxide treatment ₂oH becomes the material of-COOH after oxidation).As polyose, citing is as Mierocrystalline cellulose, starch, amylose starch and pectin etc.

Carboxyl acid modified polyose is through and uses the modification of carboxylic acid to import the polyose of carboxyl.For the carboxylic acid of modification, for example there are the unsaturated carboxylic acid etc. such as monocarboxylic halogenide and (methyl) vinylformic acid of Mono Chloro Acetic Acid etc.

Can to illustrate material same as described above as polyose.But in order to make effect of the present invention more excellent, preferably select Mierocrystalline cellulose.

Carboxyl acid modified Mierocrystalline cellulose for example there are carboxyalkyl cellulose and salt etc. thereof.Among these, from the viewpoint of cleaning force and lathering property etc., at least a kind that preferably selects from carboxyalkyl cellulose and salt thereof.

Carboxyalkyl cellulose or its salt are that part or all of hydroxyl (with the hydroxyl of Glucopyranose ring Direct Bonding and the hydroxyl by alkylene) in cellulosic molecule becomes-O-R through etherificate ⁵-COOZ ［ R ⁵be alkylidene group, Z is hydrogen atom or gegenion ］ material.Such as, the cellulosic materials such as paper pulp, after caustic soda process, can be made into chloroacetate reaction.

R ⁵as alkylidene group, the alkylidene group of preferred straight-chain or branched, its carbonatoms preferably 1 ~ 3.Above-mentioned alkylidene group particularly preferably methylene radical, that is, carboxyalkyl cellulose is carboxymethyl cellulose particularly preferably.

For the gegenion in Z, be not particularly limited, for example there are basic metal, alkaline-earth metal, protonated amines and ammonium etc., for example there are the example identical with the example exemplified as the M in (a1) in above-mentioned formula respectively.

Carboxyl acid modified Mierocrystalline cellulose can be used in the goods of market public sale, also can to use to be synthesized by well-known method.The trade(brand)name that such as carboxymethyl cellulose is concrete, has " CMC ダイセ Le Item Number: 1105 " (ダイセ Le chemical industry Co., Ltd.) etc. to use well.

The degree of etherification of carboxyalkyl cellulose or its salt, preferably 0.2 ~ 1.3, more preferably 0.2 ~ 0.8.In addition, in the present invention, degree of etherification is meant to, in every 1 unit Glucopyranose ring, by carboxyalkyl or its salt (-R ⁵-COOZ) mean number of hydroxyl of replacing.Namely represent in 3 hydroxyls that above-mentioned Glucopyranose ring comprises have and severally to be substituted for by carboxyalkyl or its salt, be 3 to the maximum.

(B) composition comprised in detergent composition can be a kind, can be two or more.

As (B) composition, the poly carboxylic acid preferably containing acrylic acid units, more preferably vinylformic acid-acid/maleic acid copolymers.

The content of (B) composition in detergent composition, relative to the total amount of this detergent composition, at more than 0.1 quality %, below 4 quality %, preferably more than 0.3 quality %, below 3 quality %, more preferably more than 0.4 quality %, below 2.5 quality %, further preferably more than 0.5 quality %, below 2 quality %.Aforementioned proportion is more than 0.1 quality %, and lathering property is excellent, below 4 quality %, the excellences such as the solvability of detergent composition in water.

(A) ratio (mass ratio) of composition/(B) composition is preferably in the scope of 5/1 ~ 20/1, and above-mentioned ratio is preferably 5/1 ~ 10/1, within the scope of this, increase foam effect and cleaning performance all very excellent.

< (C) composition: zeolite >

Preferred detergent composition of the present invention is further containing (C) zeolite.

Now, the content of (C) composition in detergent composition, relative to the total amount of this detergent composition, preferably more than 0.5 quality %, below 30 quality %.(C) composition containing such ratio, can improve lathering property (latherability and foam duration).

The content of above-mentioned (C) composition, relative to the total amount of this detergent composition, preferably more than 5 quality %, below 330 quality %, more preferably more than 8 quality %, below 30 quality %.

Zeolite is the aluminium silicate salt of crystallographic, and for example there are type A zeolite, X-type zeolite, y-type zeolite and P type zeolite etc., these can use as (C) composition.As (C) composition, from the viewpoint of cleaning performance, preferred type A zeolite.

(C) median size of composition, preferably 2 ~ 10 μm, more preferably 3 ~ 8 μm.Median size is more than 2 μm, and cleaning performance is good, and more than 10 μm then cleaning performance is low.

In addition, " median size " in this specification sheets is the value (quality 50% footpath) measured by following measuring method.When median size is more than 149 μm, use median size measuring method (1), when median size is below 149 μm, use median size measuring method (2).

(measuring method (1) of median size)

First, to measuring object (sample), use mesh to be that 9 grades of sieves of 1680 μm, 1410 μm, 1190 μm, 1000 μm, 710 μm, 500 μm, 350 μm, 250 μm and 149 μm carry out progressive operation with pallet.Progressive operation is carried out as follows, pallet stacks according to the order being sieved to the large sieve of mesh little from mesh, 100g sample is put into from the sieve of 1680 μm of topmost, cover lid, is arranged on Ro-Tap (Co., Ltd.'s meal field makes made, bounces number of times: 156 beats/min, rotation: 290 beats/min), temperature 25 DEG C, after vibrating 10 minutes under the atmospheric condition of relative humidity 40%, for each sieve mesh, sample residual on respective sieve and pallet is reclaimed.

The classification sample of each particle diameter of 1410 ~ 1680 μm (on 1410 μm), 1190 ~ 1410 μm (on 1190 μm), 1000 ~ 1190 μm (on 1000 μm), 1000 ~ 710 μm (on 710 μm), 500 ~ 710 μm (on 500 μm), 350 ~ 500 μm (on 350 μm), 250 ~ 350 μm (on 250 μm), 149 ~ 250 μm (on 149 μm), pallet ~ 149 μm (through 149 μm) can be obtained by repeating such operation, and calculate quality frequency (%).

The mesh of the initial sieve of calculated quality frequency more than 50% is set to a μm, the mesh of the sieve than a μm of large one-level is set to b μm, the integration of the quality frequency of the sieve from pallet to a μm is set to c%, and the quality frequency on the sieve of a μm is set to d%, average particulate diameter (quality 50% footpath) can be obtained by following formula.

[several 1]

Averaged particles footpath (quality 50% footpath)=10 ^{[50-{c-d/ (log b-log is x log b} a)]/d/ (log b-log is a) }}

(measuring method (2) of median size)

Laser diffraction/diffuse transmission type particle size distribution device is used to measure.Condition determination is the damp process that hole field makes the LA-920 that institute's (strain) makes, and measures temperature: normal temperature, dispersion medium: ion exchanged water, speed of circulation: 8, churning time: 5 minutes, ultrasonic intensity: 7, relative refractive index (water): 1.20.

(C) composition comprised in detergent composition can be a kind, also can be two or more.

The content of (C) composition in detergent composition, relative to the total amount of this detergent composition, preferably at more than 0.5 quality %, below 30 quality %, preferably more than 1 quality %, below 27 quality %, more preferably more than 2 quality %, below 25 quality %.Aforementioned proportion is when discontented 0.5 quality %, and the effect that (C) composition brings can not be not fully exerted, and on the other hand, more than 30 quality %, may cause lathering property and cleaning force deficiency.

< (D) composition: higher alcohols >

Preferred detergent composition of the present invention is further containing higher alcohols, and latherability can improve further thus.

In the present invention, " higher alcohols " is the alcohol of carbonatoms 10 ~ 16, (D) composition carbonatoms more preferably 12 ~ 14.

(D) composition can be 1 yuan of alcohol, also can be polyvalent alcohol, preferably 1 yuan of alcohol.

The alkyl forming the alcohol of (D) composition can be straight-chain, branched or ring-type, preferred straight-chain or branched, most preferably straight-chain.In addition, above-mentioned alkyl can be saturated, also can be undersaturated, preferably saturated.

(D) composition contained in detergent composition can be a kind, also can be two or more.

(D) composition can be used in the goods of market public sale, also can to use to be synthesized by well-known method.Commercially available product concrete example has, コノ mono-Le 20P (trade(brand)name, New Japan Chem Co., Ltd's system, straight chain type C12 higher alcohols (lauryl alcohol)), ダイヤ De one Le 13 (trade(brand)name, Mitsubishi chemical Co., Ltd's system, C13 higher alcohols (the material (2-methyl body) containing branched carbon chain, straight chain type body is 49%)), CO-1270 (trade(brand)name, P & G Chemicals society system, (higher alcohols of carbonatoms 12 is 68-74 quality % to straight chain type C12/14 higher alcohols, the higher alcohols of carbonatoms 14 is 24-30 quality %)), コノ mono-Le 1495 (trade(brand)name, New Japan Chem Co., Ltd's system, straight chain type C14 higher alcohols (tetradecyl alcohol)) etc.

The content of (D) composition in detergent composition, relative to the total amount of this detergent composition, preferably at more than 0.1 quality %, below 2 quality %, more preferably more than 0.2 quality %, below 1.5 quality %, further preferably more than 0.3 quality %, below 0.7 quality %.Aforementioned proportion is when more than 0.1 quality %, and the effect that (D) composition brings can give full play to, and easy washability may be caused during more than 2 quality % inadequate.

(D) ratio (mass ratio) of composition/tensio-active agent (A+E+F), the amount preferably in 1/15 ~ 1/100 scope, more preferably 1/40 ~ 1/30, in this scope, foam enhancing effect and cleaning performance are all very excellent.

< (E) composition: the anion surfactant > beyond (A) composition

Detergent composition of the present invention, as required, also can contain (E) composition (anion surfactant beyond above-mentioned (A) composition).

As the anion surfactant beyond (A) composition, as long as the material used in washing composition is just not particularly limited in the past, various anion surfactants can be used.

As anion surfactant, such as, following material can be enumerated.

(1) straight chain type of the alkyl containing carbonatoms 8 ~ 18 or containing the alkyl benzene sulphonate (ABS) (LAS or ABS) of side chain and salt thereof.Consider from cleaning performance viewpoint, the carbonatoms of alkyl particularly preferably 10 ~ 14.

(2) alkylsulphonic acid of carbonatoms 10 ~ 20 and salt thereof.

(3) the alpha-olefin sulfonic acid (AOS) of carbonatoms 10 ~ 20 and salt thereof.

(4) alkyl-sulphate of carbonatoms 10 ~ 20 or thiazolinyl sulfuric acid (AS) and salt thereof.Also have lathering property from the viewpoint of cleaning performance, particularly preferably the carbonatoms of alkyl or thiazolinyl is 10 ~ 14.

(5) any one in the average addition oxirane of 0.5 ~ 10 mole of carbonatoms 2 ~ 4, or the straight chain with carbonatoms 10 ~ 20 of oxyethane and propylene oxide (mol ratio EO/PO=0.1/9.9 ~ 9.9/0.1) or alkyl (or thiazolinyl) ether sulfuric acid (AES) of containg branched alkyl radical (or thiazolinyl) and salt thereof.

(6) any one in the average addition oxirane of 3 ~ 30 moles of carbonatomss 2 ~ 4, or the straight chain with carbonatoms 10 ~ 20 of oxyethane and propylene oxide (mol ratio EO/PO=0.1/9.9 ~ 9.9/0.1) or alkyl (or thiazolinyl) the phenyl ether sulfuric acid of containg branched alkyl radical (or thiazolinyl) and salt thereof.

(7) any one in the average addition oxirane of 0.5 ~ 10 mole of carbonatoms 2 ~ 4, or the straight chain with carbonatoms 10 ~ 20 of oxyethane and propylene oxide (mol ratio EO/PO=0.1/9.9 ~ 9.9/0.1) or alkyl (or thiazolinyl) the ether carboxylic acid of containg branched alkyl radical (or thiazolinyl) and salt thereof.

(8) the alkyl polyols ether sulfuric acid that the alkyl glycerol ether sulfonic acid of carbonatoms 10 ~ 20 is such and salt thereof.

(9) long-chain monoalkyl, two dialkyl group or trialkyl phosphate and salt thereof.

(10) polyoxyethylene monoalkyl, two dialkyl group or trialkylphosphate salts.

(11) higher fatty acid of carbonatoms 10 ~ 20 and salt (soap) thereof.

In these tensio-active agents, the form of salt is not particularly limited, such as, have the examples such as an alkali metal salt, alkali earth metal salt, protonated amine salt and ammonium salt.Basic metal, alkaline-earth metal and protonated amines for example there are the example identical with the example exemplified as the M in above-mentioned formula (a1) respectively, wherein preferred as alkali salt.

(E) composition can be used alone a kind, also can two or more also use.Wherein, consider from raising lathering property and the viewpoint such as formulation, preferably comprise at least one chosen from LAS and AS, more preferably containing LAS.

The content of the composition (E) in detergent composition, as long as in the scope harmless to effect of the present invention, be not particularly limited, from the viewpoint of cleaning performance and lathering property, ratio (mass ratio) amount preferably in the scope of 10/0 ~ 1/9 of (A) composition/(E) composition.Aforementioned proportion preferably 8/2 ~ 2/8, more preferably 5/5 ~ 1/2.

The total amount of (A) composition in detergent composition and (E) composition, relative to the total amount of this detergent composition, at more than 2.5 quality %, preferably more than 2.5 quality %, below 45 quality %, more preferably more than 3.0 quality %, below 42 quality %, further preferably more than 5 quality %, below 40 quality %.When aforementioned proportion is less than 2.5 quality %, cleaning force may be made inadequate, aforementioned proportion, more than 45 quality %, may make lathering property or easy washability etc. not.

< (F) composition: the tensio-active agent > beyond anion surfactant

Detergent composition of the present invention can contain (F) composition (tensio-active agent beyond anion surfactant) as required.As (F) composition, be not particularly limited, suitably can select from the well-known tensio-active agents such as nonionogenic tenside, cats product and amphoterics.

［ nonionogenic tenside ］

As nonionogenic tenside, as long as the material used in washing composition is just not particularly limited in the past, various nonionogenic tensides can be used.

As nonionogenic tenside, such as, following material can be enumerated.

(1) polyoxyalkylene alkyl (or thiazolinyl) ether that the oxirane of the carbonatoms 2 ~ 4 of average addition 3 ~ 30 moles, preferably 4 ~ 20 moles, more preferably 5 ~ 17 moles obtains on the fatty alcohol of carbonatoms 10 ~ 18, preferably 12 ~ 14.

Wherein, desirably polyxyethylated (or thiazolinyl) ether and polyoxyethylene polyoxypropylene alkyl (or thiazolinyl) ether.

Fatty alcohol used herein, for example there are primary alconol or secondary alcohol.In addition, this alkyl can contain side chain.Fatty alcohol is preferably primary alconol.

(2) polyxyethylated (or thiazolinyl) phenyl ether.

(3) the addition fatty acid alkyl ester alcoxylates of oxirane between the ester bond of long-chain fat acid alkyl ester.

(4) polyoxyethylene sorbitan fatty acid ester.

(5) Polyoxyethylene Sorbitol Fatty Acid Esters.

(6) polyoxyethylene fatty acid ester.

(7) polyoxyethylene hydrogenated castor oil.

(8) glycerol fatty acid ester.

(9) fatty acid alkyl amide.

(10) polyoxyethylene alkyl amine.

(11) alkyl glycoside.

(12) alkyl amine oxide.

As the fatty acid alkyl ester alcoxylates of above-mentioned (3), for example there are the compound represented by following formula (3-1).

R ⁹CO(OA) _ｎOR ¹⁰…(3－1)

In formula (3-1), R ⁹cO represents carbonatoms 6 ~ 22, is preferably the fatty acid residue of 8 ~ 18.

OA represents carbonatoms 2 ~ 4, is preferably the oxirane addition unit of 2 ~ 3, is preferably oxyethane, propylene oxide.When n is more than 2, the OA of more than 2 in formula each other can be identical, also can be different.

N represents the average addition mole number of oxirane, is generally 3 ~ 30, is preferably 5 ~ 20.

R ¹⁰represent hydrogen atom or the alkyl that substituent carbonatoms is 1 ~ 3 can be had.

These nonionogenic tensides can be used alone a kind, also can two or more also use, wherein, from the viewpoint of cleaning force and manufacturing etc., at least a kind that preferably selects from polyoxyalkylene alkyl (or thiazolinyl) ether of (1) and the fatty acid alkyl ester alcoxylates of (3).Wherein, preference is, Voranol EP 2001, polyoxyethylene alkene ether, polyoxyethylene polyoxy-propylene, polyoxyethylene polyoxypropylene alkene ether, the fatty acid methyl ester ethoxylate that addition of ethylene oxide obtains on fatty acid methyl ester, and the ethoxylated propoxylated thing of the fatty acid methyl ester that addition propylene oxide, oxyethane obtain on fatty acid methyl ester.

The fusing point of nonionogenic tenside is preferably less than 50 DEG C, more preferably below 40 DEG C.

Here fusing point is the value that the melting point determination by recording in JIS K0064-1992 " fusing point of chemical preparations and fusion range measuring method " determines.

In addition, the HLB of nonionogenic tenside preferably 7 ~ 16, more preferably 8 ~ 14.

HLB is the value (referring to Jitian, entering in rattan, great Yuan, mountain to compile in collaboration with, " new edition tensio-active agent handbook ", industrial books Co., Ltd., the 234th page in 1991) of being tried to achieve by Griffin method.

［ cats product ］

As cats product, as long as the material used in washing composition is just not particularly limited in the past, various cats products can be used.

As cats product, such as, single two or the trialkyl positively charged ion with 1 to 3 long-chain (being preferably carbonatoms more than 8) alkyl can be used.Particularly preferably contain the cats product of 1 ~ 2 ester group and 1 ~ 2 long chain hydrocarbon groups in molecule.

As the concrete example of cats product, there is the single-long-chain alkyl trimethyl ammonium chloride of chain alkyl or the thiazolinyl with 1 carbonatoms 8 ~ 22, there are the chain alkyl of two carbonatomss 8 ~ 22 or two long chain alkyl dimethyl ammonium chlorides of thiazolinyl, there is the chain alkyl of 3 carbonatomss 8 ~ 22 or the tri-long-chain alkyl ammonio methacrylate of thiazolinyl, there is the chain alkyl of 1 carbonatoms 8 ~ 22 or the N-acyloxy ethyl-N of thiazolinyl, N-dimethyl-N-hydroxy ethyl ammonium chloride, and there is the chain alkyl of 2 carbonatomss 8 ~ 22 or the N of thiazolinyl, N-diacyl oxygen base ethyl-N, N-alkyl dimethyl ammonium chloride etc.

［ amphoterics ］

As amphoterics, as long as the material used in washing composition is just not particularly limited in the past, various amphotericses can be used.

As amphoterics, the sultaine and carboxybetaine such as with 1 or 2 long-chain (preferred carbonatoms is more than 8) alkyl can be used.

This long chain hydrocarbon groups can contain ester group, amide group or ether, and in addition, long chain hydrocarbon groups can be 1 chain, also can be 2 chains.In addition, in long chain hydrocarbon groups, the ratio etc. of the cis body/trans body of the saturation type/ratio of unsaturated type, the distribution of carbon chain length and unsaturated group is not particularly limited.In addition, long chain hydrocarbon groups can be derived by the lipid acid of the manufacture raw material as above-mentioned cats product or fatty acid methyl ester.As the concrete example of amphoterics, for example there are N, N-bis-trimethylammonium-N-ammonium methyl sulfovinate, N, N-bis-trimethyl-glycine of trimethylammonium-N-ammonium methyl Eufin and so on; N-acyl group oxygen ethyl-N hydroxyethyl-N-ammonium methyl betaines; N-acylamidopropoyl-N, N-dimethyl ammonium betaine class and N-acylamidopropoyl-N, N'-dimethyl-N'-beta-hydroxy propyl ammonium trimethyl-glycine etc.

Above-mentioned amphoterics can comprise the quaternized product of this nitrogen-atoms, as the alkanolamine of raw material, the amido betaine of its corrective or its quaternaries etc.

(F) composition can be used alone any a kind, also can two or more also use.

In above-mentioned, consider from cleaning performance excellence, (F) composition is preferably containing nonionogenic tenside.(F) component content in detergent composition, can consider that (A) composition and (E) component content suitably set.The total amount of above-mentioned (A) composition, (E) composition and this (F) composition, relative to the total amount of this detergent composition, preferably at more than 5 quality %, the amount of below 45 quality %, preferably more than 6 quality %, the amount of below 43 quality %, more preferably more than 7 quality %, the amount below 42 quality.When aforementioned proportion is more than 5 quality, cleaning force can improve, and more than 45 quality %, then easily washability worsens.

In addition, (F) composition relative to (A) composition and (E) composition total amount allocate into than (mass ratio), preferably total amount/(F) composition=10/0 ~ 4/1 of (A) composition and (E) composition, from the viewpoint of lathering property, preferably 50/1 ~ 4/1 scope in.

Other composition > of <

Detergent composition of the present invention, in the scope of its effect harmless, can contain other the composition beyond mentioned component (A) ~ (F).To other above-mentioned compositions, be not particularly limited, can suitably select from the various additives in the past allocating detergent composition into as required.Such additive, for example there are such as washing assistant, spices, pigment, white dyes, enzyme, enzyme stabilizers, other polymer class, anti-caking agent, reductive agent, metal ion capturing agent, pH adjusting agent etc., SYNTHETIC OPTICAL WHITNER, bleach-activating agent, bleaching catalyst, UV light absorber and clay mineral etc.Concrete example is shown hereinafter.

［ washing assistant ］

Washing assistant, be substantially divided into alkaline agent, other inorganic builders and a few class of organic washing-assisting detergent, these can be used alone one, also can two or more appropriately combined use.

This specification sheets also has in these claims, and " alkaline agent " is meant to the pH that can improve detergent solution, has the composition of certain pH shock absorption.

As alkaline agent, for example there are alkali-metal carbonate or supercarbonate, alkalimetal silicate also has amine etc.As the concrete example of alkali-metal carbonate, for example there are sodium carbonate, salt of wormwood, sodium potassium carbonate, sodium sesquicarbonate and sodium bicarbonate etc.

As the concrete example of alkali-metal supercarbonate, there are sodium bicarbonate, saleratus etc.

As the concrete example of alkali-metal silicate, there are water glass, lamina sodium silicate, Starso and sodium metasilicate (オ Le ソケイ acid) etc.

As the concrete example of amine, for example there are monoethanolamine, diethanolamine and trolamine etc.

Alkaline agent can be used alone a kind, also can two or more appropriately combined use.

But in the present invention, alkali-metal carbonate and silicate, can bring detrimentally affect to lathering property, so the combined amount being selected from the alkaline agent of alkali-metal carbonate and silicate is more few better, particularly preferably not containing above-mentioned alkaline agent.

Above-mentioned inorganic builders, as long as in the past for all using in the cleansing composition of clothing, be not particularly limited, such as, for example there are the phosphoric acid salt of amorphousness aluminium silicate salt, orthophosphoric acid salt, pyrophosphate salt, tri-polyphosphate, metaphosphate, hexametaphosphate, phytate etc. and the complex body of crystalline silicate and carbonate and amorphous alkaline silicate.

The form of salt is not particularly limited, if any examples such as an alkali metal salt, alkali earth metal salt, protonated amine salt and ammonium salts.Basic metal, alkaline-earth metal and protonated amines for example there are respectively with as the M in above-mentioned formula (a1) for the identical each example of example, wherein preferred as alkali salt.

These inorganic builders can independent a kind of use, also can two or more also use.

As above-mentioned organic washing-assisting detergent, for example there are the aminocarboxylate of such as nitrilotriacetic acid(NTA) salt, edetate, Beta-alanine diacetin, aspartic acid diacetin, MDGA salt, iminodisuccinic acid etc.; Hydroxyaminocarboxylic acids's salt of Serine diacetate, oxyimino disuccinate, hydroxyethyl ethylene diamine triacetate and dihydroxyethylglycin salt etc.; The hydroxycarboxylate of glycolate, tartrate, Citrate trianion and gluconate etc.; Pyromellitic acid salt, the ring carboxylate salts such as benzo polycarboxylate and pentamethylene tetracarboxylic acid hydrochlorate; The ether carboxylates such as carboxymethyl group tartronate, carboxyl methoxy succinate, oxo succinate and tartrate monobutane diacid salt or tartrate two succinate; And the polymkeric substance etc. containing carboxyl of weight-average molecular weight less than 10,000.Above-mentioned polymkeric substance, except weight-average molecular weight less than 10,000, also has such as same with above-mentioned (A) composition material.

These organic washing-assisting detergents can independent a kind of use, also can two or more also use.

As washing assistant, especially preferred above-mentioned inorganic builders, wherein from the viewpoint of cleaning performance, preferably phosphate, more preferably tri-polyphosphate.

In detergent composition, the amount in the scope of preferred (C) composition/tripolyphosphate=19/1 ~ 1/19 of the content of tripolyphosphate and the ratio (mass ratio) of above-mentioned (C) composition, preferably 3/1 ~ 1/9, be more preferably 13/7 ~ 3/17.

The content of the above-mentioned washing assistant in detergent composition, relative to the total amount of this detergent composition, preferably more than 5 quality %, below 25 quality %; More preferably more than 6 quality %, below 20 quality %.The content of above-mentioned washing assistant is more than the lower value of above-mentioned scope, and lathering property etc. can improve, and in addition, more than higher limit, the solvability of detergent composition in water can worsen.

［ spices ］

As spices, be not particularly limited, the fragrance component or flavor compositions recorded in such as Japanese Patent Laid-Open 2002-146399 publication or Japanese Patent Laid-Open 2003-89800 publication can be used.

In addition, the mixture that is made up of fragrance component, solvent and perfume stable agent etc. of flavor compositions.

As spices, can be used alone one, also can be two or more suitable combinationally using.

When allocating spices in cleansing composition into, this combined amount relative to the total amount of cleansing composition, preferably 0.001 ~ 10 quality %, more preferably 0.01 ~ 5 quality %.

［ pigment ］

In order to make the outward appearance of detergent composition good, allocate various pigment into.

As pigment, any dyestuff and pigment can be used.From the viewpoint of storage stability, it is desirable to pigment, especially preferred oxides etc. have the compound of scale resistance.As these compounds, for example there are titanium oxide, ferric oxide, copper phthalocyanine, cobalt phthalocyanine, ultramarine, Prussian blue, phthalocyanine blue and flower cyanines green etc.

As pigment, can be used alone a kind, also can two or more appropriately combined use.

［ white dyes ］

As white dyes, such as 4,4 '-bis--(2-sulfostyryl)-biphenyl salt, 4,4 '-bis--(the chloro-3-sulfostyryl of 4-)-biphenyl salt, 2-(styryl phenyl) naphthothiazoles derivative, 4, the 4 '-white dyes of bis-(triazole-2-base) stilbene derivative and two-(Triazinylaminostilbedisulphonic) disulfonic acid derivatives etc.

As the white dyes in market public sale, such as WHITEX (registered trademark) SA, WHITEX (registered trademark) SKC (is trade(brand)name above; Sumitomo Chemical Co's system), チノパ mono-Le (registered trademark) AMS-GX, チノパ mono-Le (registered trademark) DBS-x, チノパ mono-Le (registered trademark) CBS-x (above trade(brand)name; チバスペシヤ Le テイケミカ Le ズ society system), Lemonite CBUS-3B (above, trade(brand)name; Khyati Chemicals society system) etc., wherein, preferred チノパ mono-Le (registered trademark) CBS-x, チノパ mono-Le (registered trademark) AMS-GX.

As white dyes, can be used alone a kind, also can two or more appropriately combined use.

The combined amount of white dyes, relative to the total amount of cleaning combination, preferably at more than 0.001 quality %, below 1 quality %.

［ enzyme ］

As enzyme, classify from the reactivity of enzyme, for example there are hydrolase, redox enzymes, lyase, transferase and isomerase etc., be all applicable to the present invention.Wherein, optimization protein lytic enzyme, esterase, lipase, nuclease, cellulase, amylase and polygalacturonase etc.

As proteolytic ferment, for example there are the lucky Luo Liang PEPA A of stomach en-, trypsinase, Chymotrypsin, collagenase, M-Zyme, elastoser, subtilisin, papoid, Carboxypeptidase A or B, aminopeptidase and Ah or B.As at market public sale proteolytic ferment, サ PVC Na one ゼ (registered trademark), ア Le カラ mono-ゼ (registered trademark), カ Application Na one ゼ (registered trademark), エバラ mono-ゼ (registered trademark), デオザイ system (registered trademark) (above trade(brand)name; ノボザイ system ズ society system); API21 (trade(brand)name; Showa Denko K. K's system); マ Network サカ Le, マ Network サペ system (above trade(brand)name; ジエネ Application コア society system); Proteolytic ferment K-14 or K-16 (proteolytic ferment recorded in Japanese Patent Laid-Open 5-25492 publication) etc.

As esterase, there are gastric lipase enzyme, steapsase, vegetation fat enzyme, phosphatide enzyme, cholinesterase enzyme, phosphoric acid ester enzyme.

As lipase, for example there are リ Port ラ mono-ゼ (registered trademark), ライペ Star Network ス (registered trademark) (above trade(brand)name; ノボザイ system ズ society system), リ Port サ system (trade(brand)name; Showa Denko K. K's system) etc. in the example such as lipase of market public sale.

As cellulase, セ Le ザイ system (trade(brand)name; ノボザイ system ズ society system); Soda cellulose enzyme K, soda cellulose enzyme K-344, soda cellulose enzyme K-534, soda cellulose enzyme K-539, soda cellulose enzyme K-577, soda cellulose enzyme K-425, soda cellulose enzyme K-521, soda cellulose enzyme K-580, soda cellulose enzyme K-588, soda cellulose enzyme K-597, soda cellulose enzyme K-522, CMC-AZE I, CMC-AZE II, soda cellulose enzyme E-II and soda cellulose enzyme E-III (more than, Japanese Patent Laid-Open No. Sho 63-264699 publication record cellulase) etc.

As amylase, citing is as in ステイ Application ザイ system (registered trademark), タ mono-マミ Le (registered trademark) of market public sale, デユラミ Le (registered trademark) (above trade(brand)name; ノボザイ system ズ society system) etc.

Above-mentioned enzyme can be used alone a kind, also can two or more appropriately combined use.

In addition, enzyme is preferably a granulated into stable particle in addition, to use with the state of detergent raw material (particle) dry mixed.

The combined amount of enzyme in detergent composition, relative to the total amount of cleansing composition, preferably more than 0.05 quality %, below 5 quality %.

［ enzyme stabilizers ］

As enzyme stabilizers, calcium salt, magnesium salts, polyvalent alcohol, formic acid can be used, go back organic boron compound etc.Wherein, preferably 4 Sodium Tetraboratees or calcium chloride etc.

As enzyme stabilizers, can be used alone one, also can be two or more suitable combinationally using.

The combined amount of enzyme stabilizers, relative to the total amount of cleansing composition, preferably more than 0.05 quality %, below 2 quality %.

［ other polymer class ］

Prevent from, by the performance again polluted of hydrophobic particulate, can polyoxyethylene glycol and polyvinyl alcohol etc. being allocated into give further, as tackiness agent when making the above-mentioned particle densification containing tensio-active agent or powder property agent.

In addition, as spot deintercalation agent, the multipolymer or terpolymer etc. of terephthalic acid and ethylene glycol and/or propylene glycol units can be allocated into.

In addition, in order to give the effect preventing colour contamination into, Polyvinylpyrolidone (PVP) etc. can be allocated.

In above-mentioned each example, preferred polyoxyethylene glycol.Its molecular-weight average preferably 200 ~ 200,000, more preferably 1500 ~ 7000.The molecular value of polyoxyethylene glycol is here measured by GPC.

Above-mentioned polymkeric substance, can use independent one, also can be two or more suitable combinationally using.

When allocating above-mentioned polymer class in cleansing composition into, its combined amount relative to the total amount of cleansing composition, preferably at more than 0.05 quality %, below 5 quality %.

［ anti-caking agent ］

As anti-caking agent, for example there are such as tosilate, xylenesulfonate, acetate, sulfosuccinate, talcum, fine silica, clay and magnesium oxide etc.

Anti-caking agent can be used alone a kind, also can two or more appropriately combined use.

［ reductive agent ］

As reductive agent, for example there are S-WAT and potassium sulfite etc.

［ metal ion capturing agent ］

Metal ion capturing agent, can catch the trace metal ion etc. in tap water, has and suppresses the effect of adsorption of metal ions on fiber (cleaned material).

The metal ion capturing agent of detergent composition can be allocated into, removing be included in above-mentioned washing assistant those, for example there are ethylenediamine tetraacetic acid (EDTA), nitrilotriacetic acid(NTA) and ethylene glycol ethyl ethers two amino polyacetic acid class of hexaacetic acid etc.; 1-hydroxyl ethane-1; 1-di 2 ethylhexyl phosphonic acid (HEDP-H), ethane-1; 1-di 2 ethylhexyl phosphonic acid, ethane-1; 1; 2-tri methylene phosphonic acid, hydroxyl ethane-1; 1; 2-tri methylene phosphonic acid, ethane-1; the organic phospho acid derivative of 2-dicarboxyl-1,2-di 2 ethylhexyl phosphonic acid, hydroxy methane phosphonic acids, EDTMP, nitrilo three (methylene phosphonic acid), 2-hydroxyethyl imino-diacetic (methylene phosphonic acid), hexamethylene-diamine four (methylene phosphonic acid) and diethylene triamine penta(methylene phosphonic acid) etc. or its salt; The organic acid of diglycollic acid, tartrate, oxalic acid and gluconic acid etc. or its salt etc.

Above-mentioned metal ion capturing agent can be used alone a kind, also can two or more appropriately combined use.

The content of the metal ion capturing agent in detergent composition, must use in the scope not damaging its performance.

［ pH adjusting agent ］

Detergent composition of the present invention, as described later, because the aqueous solution of solid constituent concentration 1 quality % or aqueous dispersions are 25 DEG C time, pH more than 5.5, less than 9.4, in order to obtain the pH of above-mentioned expectation, as required, pH adjusting agent can be allocated into.But, when only containing above-mentioned each composition, and when pH is expected value, might not need to allocate pH adjusting agent into.

As pH adjusting agent, for example there are as above-mentioned washing assistant for example alkaline agent (such as the alkanolamine of monoethanolamine, diethanolamine and trolamine etc.), other also have the basic cpd of sodium hydroxide and potassium hydroxide etc.; The acidic cpd of the basic metal dihydrogen phosphate of above-mentioned metal ion capturing agent, potassium primary phosphate etc., lactic acid, succsinic acid, oxysuccinic acid, gluconic acid, sulfuric acid, hydrochloric acid, citric acid and linear alkyl benzene acid etc.In addition, in order to prevent the sour composition of the fiber spot when cleaning from making pH reduce, pH buffer reagent can be used.These pH adjusting agents, can be used alone one, also can two or more appropriately combined use.

<pH>

Detergent composition of the present invention, pH at its 1 quality % aqueous solution or aqueous dispersions (this detergent composition of 1g is dissolved or is dispersed in the material obtained in 99g water) 25 DEG C is more than 5.5, less than 9.4, preferably 6.0 ~ 9.2, more preferably 6.5 ~ 9.1.Above-mentioned pH is more than 5.5, and cleaning force is good, and in addition, below 9.4, lathering property is good, and during hand wash laundry, washing lotion is soft without wound to skin.

The present invention, being meant to of " pH at the 1 quality % aqueous solution or aqueous dispersions (this detergent composition of 1g is dissolved or is dispersed in the material obtained in the water of 99g) 25 DEG C being more than 5.5; less than 9.4 ", the temperature of 25 DEG C is as benchmark, and the pH of the 1 quality % aqueous solution or aqueous dispersions (this detergent composition of 1g is dissolved or is dispersed in the material obtained in the water of 99g) is in above-mentioned scope.Namely, when preparing in the above-mentioned aqueous solution or the temperature of aqueous dispersions beyond 25 DEG C, according to the above-mentioned pH scope of this temperature correction, the above-mentioned aqueous solution within the scope of this pH correction or aqueous dispersions are also contained in scope of the present invention.

In other words, if when certain temperature, pH is not more than 5.5, the scope of less than 9.4, but when being benchmark with 25 DEG C, pH is modified to more than 5.5, and the aqueous solution in the scope of less than 9.4 or aqueous dispersions are included within scope of the present invention.

The form of detergent composition of the present invention can be the solid state such as granular (powder and particle), tablet, coal briquette shape, sheet, strip, and also can be liquid, ideal state be solid, preferred particulates shape.

When the form of detergent composition of the present invention is granular, the median size of detergent composition preferably 200 ~ 1500 μm, more preferably 300 ~ 800 μm, preferably 400 ~ 700 μm further.Median size, more than lower value, can suppress the powder that wafts during use, time below higher limit, and favorable solubility in water.

In addition, the bulk density of said detergent composition, preferably 0.3 ~ 1.5g/cm ³, more preferably 0.4 ~ 1.0g/cm ³, in addition, bulk density is the value measured by JIS3362:1998.

In addition, when detergent composition is granular, amount of moisture is preferably less than 10.0 quality %.

The manufacture method of detergent composition of the present invention is not particularly limited, and according to the form of the detergent composition that will manufacture, can manufacture according to usual method.

Such as, manufacture method when detergent composition is granular, for example there are the slip first preparing and comprise detergent raw material again by its spray-dired method; The method of granulation is carried out by comminution granulation (knead, extrude, pulverize), stirring-granulating method or the rolling comminution granulation spray-dired powder and detergent raw material kneaded, extrudes; And the manufacture method etc. of powder shaped detergent raw material mechanically mixing (powder mixing).These methods, can be used alone any a kind, also can two or more use appropriately combined.

From the viewpoint of production efficiency, allocate in the composition of detergent composition, preferably at least (A) composition is after making powder shaped separately, mixes with other powder shaped detergent raw material.

As the example of preferred manufacture method, such as, for example there are:

Part or all of detergent raw material beyond (A) composition is mixed equably together with water, be prepared into slip, above-mentioned slip spraying dry, by the method that (A) composition of the spray dried particle obtained, powder shaped mixes with residue detergent raw material (powdery) powder.

Mixing (A) composition beyond composition part or all, carry out granulation by stirring-granulating method, broken comminution granulation (knead, extrude, pulverize) or rolling comminution granulation, the granules obtained is carried out with (A) composition of powder shaped, remaining raw material (powdery) method that powder mixes; And

Use each composition of powder shaped, they are carried out the method for powder mixing.

In each method, after powder mixing, the operation (C) composition, nonionogenic tenside, spices or pigment etc. are coated on the surface of particle can be carried out further.

When detergent composition is tablet, granular detergent composition obtained above, by producing with tabletting machine.

When detergent composition is liquid, the allotment that is mixed with water as required of above-mentioned each composition is made.

The detergent composition of the invention described above, even if use high hardness water to wash, also can play excellent cleaning force and lathering property.Therefore, washing can use in high hardness water (such as 10 ° of DH).In addition, because there is high lathering property, for hand washing washing time be useful.In addition, by the pH of 1% aqueous solution or aqueous dispersions in above-mentioned scope, when washing by hand washing, washing lotion is gentle to skin, is also useful to hand washing washing viewed from this point.

By (A) composition and (B) composition are combined, even if especially in high hardness water, also height cleaning performance and lathering property can be played, its reason we think (A) even if composition be also not easy under high rigidity separate out and carry out work as promoting agent, there is high level of cleanliness performance, in addition, (B) composition makes the film of the bubble of generation stablize, and enhances the persistence of foam.

Further, we think (C) composition, when foam film exists, can reduce liquid drainage speed, can improve foam duration by foam stabilising effect.

In addition, (D) composition can improve latherability by stable foam film.

In addition, also found (E) composition such with LAS or AS and the used time, had good whipability when washing by hand, cloth is also more soft and smooth.

The washing object of detergent composition of the present invention, identical with the washing object (washings) of general detergent composition, citing is as fiber products such as clothing, napkin, sheet and curtain.

Use the washing methods of detergent composition of the present invention, be not particularly limited, use well-known washing methods all passable.Concrete example, as detergent composition is dropped in water, washs washings in above-mentioned water (washings).Input amount now, according to the combined amount of (A) composition and other tensio-active agent, have difference, usually, the concentration of detergent composition in washings, when when washing by hand washing being 0.1 ~ 10 quality % (preferably 0.2 ~ 1 quality %), use washing machine, preferably 0.01 ~ 2 quality % (preferably 0.02 ~ 1 quality %).During washing washings, no matter be hand washing, or can with washing machine (two slot type washing machines, automatic washing machine and tumbling-box washing machine etc.).From the viewpoint of validity of the present invention, preferably as water poured into the hand washing washing of dissolving detergent composition cleaning clothes in bucket.

Embodiment

To the present invention, by showing that embodiment is specifically described further, but the present invention is not limited to these embodiments.

In the present embodiment, " % ", without specified otherwise, represents " quality % ".

The measuring method used in following each example and raw material will show below.

［ measuring method ］

〔pH〕

PH measures according to JISZ8802-1984, uses the pH meter measuring device (HM-30S) of DKK-TOA Co., Ltd. to measure the pH value of various detergent composition 1% solution (25 DEG C).

(measuring the weight-average molecular weight of the macromolecular compound containing carboxyl)

Macromolecular compound weight-average molecular weight containing carboxyl, by using the gel permeation chromatography of polyoxyethylene glycol as reference material.

(measuring method of median size)

First, to measuring object (sample), be that the sieve of 9 grades of 1680 μm, 1410 μm, 1190 μm, 1000 μm, 710 μm, 500 μm, 350 μm, 250 μm and 149 μm and pallet carry out progressive operation with mesh.Progressive operation is carried out as follows, pallet stacks with the order being sieved to the large sieve of mesh that mesh is little, 100g sample is put into from the sieve of 1680 μm of topmost, cover lid, be arranged on Ro-Tap (manufactured by the making of Co., Ltd.'s meal field, bouncing number of times: 156 beats/min, rotation: 290 beats/min), temperature 25 DEG C, after vibrating 10 minutes under the atmospheric condition of relative humidity 40%, for each sieve mesh, sample residual on respective sieve and pallet is reclaimed.

[several 2]

(measuring method of moisture content)

Moisture content uses kett (MOISTURE PETERMINATION balance FD-600) to measure, and sample size is 5g, and the changes in weight of 140 DEG C of heating after 20 minutes is amount of moisture.

［ raw material ］

(raw material of alpha-sulfo-fatty acid methyl ester (salt) (below, being designated as MES))

Uniphat A60: trade(brand)name " パステ Le-M-16 " Lion Corporation's system.

Methyl stearate: trade(brand)name " パステ Le-M-180 " Lion Corporation's system.

Methyl alcohol: industrial level below moisture 500ppm, Sumitomo Chemical Company Ltd's system.

35% hydrogen peroxide: 35% industrial hydrogen peroxide, Mitsubishi Gas Chemical Co., Ltd. system.

Sodium hydroxide: caustic soda, industrial level, Co., Ltd.'s system.

(anion surfactant (removing (A) composition))

Sodium lauryl sulfate (being designated as AS-Na below): trade(brand)name " SLS ", PEPMACO MANUFACTURING CORPORATION system.

Linear alkyl benzene acid sodium (being designated as LAS-Na below): when preparing the slip of spraying dry or granulation time NaOH in and linear alkyl (carbonatoms 10 ~ 14) Phenylsulfonic acid (being designated as LAS-H below) (trade(brand)name " ライ Port Application LH-200 ", Lion Corporation's system, purity 96%) material that obtains.The quality % of what the amount of allocating in table 1 ~ 3 represented is LAS-Na.

(nonionogenic tenside)

Voranol EP 2001 (being designated as AE below): average 9 moles of the ethylene oxide of the alcohol (trade(brand)name " CO-1214 ", P & G Chemicals system) of the alkyl containing carbonatoms 12 ~ 16 adds adult (purity 90%, Lion Corporation's system).

(zeolite, other washing assistant)

Zeolite: type A zeolite, trade(brand)name " zeolite Na-4A ", THAI SILICATE Chemicals system.

Tripoly phosphate sodium STPP (being designated as STPP below): Central Glass Co., Ltd. system.

Sodium carbonate: granular soda ash, Asahi Glass Co., Ltd's system.

Water glass: the mixture of the mass ratio 46:54 of No. 2, water glass No. 1/water glass, Nippon Chemical Ind's system.

Sodium sulfate: neutral thenardite, Nippon Chemical Ind's system.

(macromolecular compound containing carboxyl)

High molecular polymer 1: the sodium salt of pulverous vinylformic acid/acid/maleic acid copolymers, trade(brand)name " ソカラ Application (registered trademark) CP-7Granules NL ", weight-average molecular weight 50000, BASF Amada Co., Ltd. system.

High molecular polymer 2: the sodium salt of vinylformic acid/acid/maleic acid copolymers, trade(brand)name " ア Network アリ Star Network (registered trademark) TL-500 ", weight-average molecular weight 15000, Nippon Shokubai Co., Ltd's system.

High molecular polymer 3: sodium polyacrylate, trade(brand)name " ソカラ Application (registered trademark) PA-40 ", weight-average molecular weight 15000, BASF Amada Co., Ltd..

High molecular polymer 4: sodium polyacrylate, trade(brand)name " ソカラ Application (registered trademark) PA-25 ", weight-average molecular weight 4000, BASF Amada Co., Ltd..

High molecular polymer 5: Xylo-Mucine, trade(brand)name " CMC ", Item Number: 1105, weight-average molecular weight 60000, degree of etherification 0.6 ~ 0.8, Daicel chemical industry Co., Ltd. system.

Other composition > of <

Higher alcohols: the alcohol mixture of the alkyl containing carbonatoms 12 ~ 16, trade(brand)name " CO-1214 ", P & G Chemicals system.

CBS: white dyes, trade(brand)name " チノパ mono-Le (registered trademark) CBS-X ", チバスペシヤ Le テイケミカ Le ズ society system.

AMS: white dyes, trade(brand)name " チノパ mono-Le (registered trademark) AMS-GX ", チバスペシヤ Le テイケミカ Le ズ society system.

Enzyme: the mixture of proteolytic ferment (サ PVC Na one ゼ (registered trademark) 12T)/amylase (ステイ Application ザイ system (registered trademark) 12T)/lipase (LIPEX (registered trademark) 100T)/cellulase (セ Le Network リ mono-Application 4500T)/glucuroide (マ Application Na ウエイ 4.0T) (more than, be all novozymes Amada Co., Ltd. system)=6/2/2/1/4 (mass ratio).

Spices: the flavor compositions A that Japanese Patent Laid-Open 2002-146399 publication ［ table 11 ］ ~ ［ table 18 ］ represents.

Pigment: ultramarine, Dainichiseika Color Chem's system, Ultramarine Blue.

The manufacture > of < Production Example 1:MES detergent use particle

(1. the manufacture of pulpous state MES)

Fatty acid methyl ester blends (Uniphat A60 (trade(brand)name " パステ Le M-16 ", Lion Corporation's system) and methyl stearate (trade(brand)name " パステ Le M-180 ", Lion Corporation's system) mixture that is pre-mixed with the mass ratio of 9:1) the 330kg capacity that injects band stirrer is the reaction unit of 1KL, limit is stirred, while the anhydrous sodium sulphate as colouring inhibitor is knocked down by 5 quality % relative to above-mentioned fatty acid methyl ester blends.Then, under continuing stirring, at temperature of reaction 80 DEG C, the SO becoming 4 capacity % with nitrogen dilution ₃gas (sulfonation gas) 110kg (being 1.2 times moles relative to above-mentioned fatty acid methyl ester blends) is blown into constant speed for 3 hours consuming time, simultaneously bubbling, and continues to remain on 80 DEG C and carry out maturation 30 minutes.

Then, the methyl alcohol 14kg supplied as lower alcohol carries out esterification, and esterification temperature is 80 DEG C, and the maturation time is 30 minutes.

Then, from reaction unit, taking out carboxylate, utilize pipeline stirrer, neutralizing continuously by adding the equivalent of sodium hydroxide aqueous solution.

Afterwards, this corrective is injected SYNTHETIC OPTICAL WHITNER mixing duct, supply is scaled 35% hydrogen peroxide of 1% with purity relative to anionic surfactant concentration (the total concentration of alpha-sulfo-fatty acid methyl ester sodium salt (MES-Na) and alpha-sulfo-fatty acid disodium salt (di-Na salt)), and mix, remain in 80 DEG C and bleach, thus obtain the MES of pulpous state.

(2.MES slurry concentrated)

MES slurry obtained above, imports to it vacuum film evaporating machine (thermal conductive surface: 0.5m being about 11m/s rotation with rotating speed 1,060rpm, tip speed with the speed of 35kg/h ²the internal diameter of the treating part of tubular: 205mm, thermal conductive surface and the gap as the blade tip of scraping blade: 3mm, trade(brand)name " エ Network セバ (registered trademark) ", god's steel パンテツク Co., Ltd. system) in, concentrate under the condition of inwall Heating temperature (temperature of thermal conductive surface) 135 DEG C, vacuum tightness (pressure in handling part) 0.007 ~ 0.014MPa.

The temperature of the enriched material obtained is 115 DEG C, and moisture content is 2.5%.

(manufacture of 3.MES solid matter)

By the concentrated MES slurry obtained, continuously with the speed of 222kg/h to banded water cooler (NR3-Lo. water cooler) supply of double belt dropping into gap between belt pulley and be adjusted to Japanese ベ Le テイ Application グ Co., Ltd. of 2mm, cooling.Tape movement speed is now 6m/s, in addition the flow of water coolant is upper band side 1500L/h (flows down at the band back side in a counter-current configuration and cool), lower band side 1800L/h (spray to the band back side and cool), the temperature of cooling water of supply is 20 DEG C.Discharge the thing sheet containing tensio-active agent that obtains discharging paying genus masher of arranging near belt pulley from cooling zone to grind with the rotating speed of 200rpm, obtain the MES solid matter of the sheet of 25 DEG C.

(manufacture of 4.MES detergent use particle)

The MES solid matter of the sheet obtained (temperature is 25 DEG C); from spiral squeezing type tablets press (Co., Ltd.'s system; エ Network スト Le one De オ mono-ミ Star Network スエ Network スト Le one De, オ mono-ミ Star Network ス De EM-6 type; speed of mainshaft 70rpm) material pouring inlet, supply continuously with the speed of 100kg/h.Rotating screw axle afterwards, makes first and second oar rotate with 100rpm, mixing MES solid matter, extrudes simultaneously, can obtain the MES solid matter of strip from the hole of the 3rd orifice plate.

After this strip material is at room temperature cooled to 30 DEG C, with zeolite (among aftermentioned embodiment and comparative example, when using the MES detergent use particle not allocating zeolite composition into, do not add) together, put into pulverizer (Gang Tian Jinggong Co., Ltd system, high speed disintegrator ND-10 with the speed of 1kg/min, rotating speed of flail 840rpm, in net φ 4mm, break into pieces, obtain the MES detergent use particle of median size 500 μm.

The MES detergent granules obtained has following proterties.

When allocating zeolite into: MES purity 86.6%, zeolite 4%, moisture 3.4%, sodium sulfate 2.2%, methyl sulfate 3.8%.

When not allocating zeolite into: MES purity 91.1%, moisture 2.5%, sodium sulfate 2.4%, methyl sulfate 4.0%.

< embodiment 1 ~ 14,16, comparative example 1 ~ 4>

By following manufacture method A, produce the granular detergent composition of the composition (%) shown in table 1 ~ 2.In table 1 ~ 2, " Bal " of sodium sulfate represents equal amount (making the total amount of this granular detergent composition be the amount of 100%).

［ the manufacture method A of granular detergent composition: spraying dry ］

First, inject water toward being equipped with in the tempering tank with well of whipping appts, adjusting its temperature is 50 DEG C.

Add sodium sulfate, white dyes (CBS inward, AMS), stir 10 minutes, then, add anion surfactant (LAS-Na (LAS-H neutralizes the material obtained through NaOH), AS-Na), after washing assistant (STPP, sodium carbonate and water glass), higher alcohols and high molecular polymer 1 ~ 5, stir 10 minutes, add the powders A type zeolite of a part.Stir 30 minutes further afterwards, prepare the slip of spraying dry.The temperature of the spraying dry slip obtained is 50 DEG C.This spraying dry slip is spraying dry in the reverse-flow spray drying unit possessing press atomization nozzle, obtains spray dried particle.

The spray dried particle obtained and a part of powders A type zeolite, enzyme (proteolytic ferment, amylase, lipase, cellulase and glucuroide) mix in V agitator, add MES detergent use particle again, spray perfume and nonionogenic tenside (AE), in order to make a spray dried particle part painted, on rotary conveyor, conveying (the spray dried particle layer height 30mm on rotary conveyor is continued with the speed of 0.5m/s, layer width 300mm), 20 quality % aqueous dispersions of pigment are sprayed at its surface, obtain the granular detergent composition of amount of moisture 6%.

1% aqueous solution of the granular detergent composition prepared, measures its pH, and this result shows in table 1 ~ 2.

< embodiment 15, comparative example 5 >

By following manufacture method B, produce the granular detergent composition of the composition (%) shown in table 2.In table 2, " Bal " of sodium sulfate represents equal amount (making the total amount of this granular detergent composition be the amount of 100%).

［ the manufacture method B of granular detergent composition: powder mixes ］

FS-1200 homogenizer/the tablets press using the industry of dark river to manufacture, manufactures washing composition according to the composition shown in table 2 by following step.

A part for STPP, sodium sulfate, white dyes (CBS and AMS) and zeolite is passed through stirrer, at stirrer speed 100rpm, under the condition of guillotine cutter speed 2000rpm, dry mixed 60 second, add water (0.375 quality % a great deal of), with identical stirrer speed and guillotine cutter speed operation 90 seconds in stirrer.Utilize the cooling jacket passing into water that temperature is maintained less than 50 DEG C.

Stirrer is added with high molecular polymer 1 using as the water (1.4 quality % a great deal of) of tackiness agent, nonionogenic tenside (AE), at stirrer speed 100rpm, under the condition of guillotine cutter speed 2000rpm, spheroidizing process 180 second.Utilize the cooling jacket passing into water that temperature is maintained less than 50 DEG C.The resultant obtained through this step is granular solids.Stop the guillotine cutter of stirrer, in stirrer, stirred for 120 seconds with speed 90rpm, add enzyme and MES detergent use particle simultaneously, then add zeolite (2 quality % a great deal of) and carry out surface modification, spices is sprayed, obtains the particle containing tensio-active agent.In order to painted for a part for the particle containing tensio-active agent obtained, use the method same with manufacture method A, 20 quality % aqueous dispersions sprayings of pigment, obtain the granular detergent composition that amount of moisture is adjusted to 4%.

Measure the pH of 1% aqueous solution of the granular detergent composition prepared, this result is displayed in Table 2.

In addition, only have embodiment 13 and comparative example 4, when manufacturing detergent composition, the amount of the sodium hydroxide used as neutralizing agent by adjustment, makes 1% aqueous solution pH of this granular detergent composition consistent with the pH in table.

For the granular detergent composition of the embodiment 1 ~ 16 obtained and comparative example 1 ~ 5, carry out following evaluation.This result is recorded in the lump in table 1 ~ 2.

[evaluation method]

(evaluation of latherability during hand washing washing)

Prepare cask washing (internal diameter , degree of depth 10cm), add the water 3L of adjusted hardness and temperature wherein.For water hardness, first calcium chloride 2 hydrate 262.5g is dissolved in the ion exchanged water of 10L and makes 1000 ° of DH hard water, then according to hardness ion exchanged water dilution adjustment (1 ° of DH=10mg (calcium oxide)/L (water)) of table 1 ~ 2, the temperature of above-mentioned water is 30 DEG C.

In above-mentioned water, granular detergent composition is added container by the amount (concentration of granular detergent composition is according to the washing composition usage quantity (g/L) shown in table 1 ~ 2) of defined, stirred for 30 seconds with hand.Then, cotton flesh shirt is immersed in relatively that it is in the dirt oil of the following composition of 0.1 % by weight, it can be used as test cloth, 1 this test cloth (about 150g) is put into container, and both hands hold above-mentioned test cloth, and front and back wash 20 times by rubbing with the hands, wash by hand 1 minute.

Then, the test cloth that squeezing is washed, measures the foam height of wash water picture with the test tube with Standard line.Measure 3 places, get the mean value of foam height.Using the foam high (mm) after the cleaning of a slice test cloth as latherability value, above-mentioned foam is high is qualified at more than 35mm.

In addition, high for the foam determined, its ratio high relative to the foam of comparative example 1 (foam any one of embodiment 1 ~ 16 and comparative example 1 ~ 5 is high/foam of comparative example 1 is high × 100) is calculated, and its result is recorded in table 1 ~ 2 in the lump as foam enhancing rate (%).

(evaluation of foam duration during hand washing washing)

In the evaluation of above-mentioned latherability when washing by hand washing, be replaced with new test cloth at every turn, repeatedly carry out the operation washing by hand test cloth, as terminal when the foam height after cleaning is 3mm, now, assess foam duration with the sheet number of cleaned test cloth.In addition, washing test cloth more than 8, foam duration is qualified.

(dirt oil composition)

Oleic acid: 45%

Triolein: 25%

Cholesterol acid ester: 19.5%

Whiteruss: 4%

Squalene: 4%

Cholesterol: 2.5%

(evaluation of cleaning performance)

Assist cloth (not having the cloth of spot) in artificial dirt, soak into latter made artificial dirt cloth (washing scientific institution system) oiling, be cut into the material of 5 × 5cm as pollution cloth.Use Terg-O-tometer (UNITED STATES TESTING society system) as washing test device.

The washing composition usage quantity (g/L) that the concentration of modulation granular detergent composition and the water hardness show respectively in table 1 ~ 2 also has the washings 900mL (temperature 30 DEG C) of hardness (° DH).

Above-mentioned washings, above-mentioned pollution cloth 10 and clean looped fabric are put into washing test device, and bath raio is 30 times, washing 10 minutes under 120rpm, the condition of 30 DEG C.Then, move in double-cylinder type washing machine (Mitsubishi Electric's (strain) makes, Item Number: CW-C30A1-H), dewater after 1 minute, wash 3 minutes in tap water (15 DEG C, 4 ゜ DH) 30L, air-dry.

For the pollution cloth after unwashed pollution cloth and cleaning, measure reflectivity (name of product: SE200 type) respectively with the colour-difference meter of Japanese electricity Se society, calculate cleaning rate by following formula.

Cleaning rate (%)=(K/S of the pollution cloth after the K/S-cleaning of the pollution cloth before cleaning)/(K/S-of the pollution cloth before cleaning does not have the K/S of the cloth of spot) × 100

In formula, K/S=(1-R/100) ²/ (2R/100), R are reflectivity (%) ］

Calculate the cleaning rate (%) that 10 are polluted cloth, the detergent composition of this mean value more than 75% is qualified.

[table 1]

[table 2]

As shown in table 1 ~ 2, the granular detergent composition of embodiment 1 ~ 16, in whole evaluations of latherability, foam duration and cleaning performance, higher than acceptance line (latherability (foam is high) more than 35mm, foam duration more than 8, and cleaning rate more than 75%).Especially allocate in the embodiment 1 of zeolite, with except not allocating zeolite into, other forms compared with identical embodiment 3, latherability, foam duration and cleaning performance are all higher.In the contrast of embodiment 4 and 5, also can confirm there is same result.In addition, allocate the embodiment 10 of higher alcohols into, and in addition form with it compared with identical embodiment 1, latherability improves.

On the other hand, the pH of 1% aqueous solution is 11.1 respectively, the comparative example 1,2 of 10.9 and allocate the comparative example 5 that weight-average molecular weight is the comparative example 3 of the high molecular polymer 4 of 4000, the combined amount of high molecular polymer 1 is 5 quality % into, although each example cleaning performance is good, latherability, foam duration are all defective.In addition, the pH of 1% aqueous solution is the comparative example 4 of 4.8, and whole evaluations of latherability, foam duration and cleaning performance are all defective.

< embodiment 17 ~ 23, comparative example 6 ~ 8>

By following manufacture method C, produce the granular detergent composition of the composition (%) represented in table 3.In table 3, " Bal " of sodium sulfate, represents equal amount (making the total amount of this granular detergent composition be the amount of 100%).

［ the manufacture method C of granular detergent composition: stirring-granulating ］

LAS-Na, STPP, sodium sulfate, white dyes, water glass, higher alcohols, high molecular polymer 1 ~ 3 and 5, and a part for zeolite is dissolved or disperses in water, after preparing the slip of moisture 38 quality %, use reverse-flow spray-drying tower, under the condition of hot blast temperature 300 DEG C, spraying dry obtains spray dried particle.

The spray dried particle obtained, drop into and sickle shaped shovel is installed, (Co., Ltd. マ Star ボ mono-makes for Luo Dige (loedige) stirrer that gap between shovel-wall is 5mm, M20 type) (filling ratio 50 volume %), start the stirring of main shaft 200rpm, knife mill 200rpm.Dropped into nonionogenic tenside (AE) at these 2 minutes consuming time, then stir 5 minutes, drop into a part (1 quality % a great deal of) for powders A type zeolite, stir 2 minutes, obtain thus containing surfactant particles.

The particle containing tensio-active agent obtained, a part (2 quality % a great deal of) for powders A type zeolite, enzyme and MES detergent granules mix in V agitator, spices is sprayed, in order to painted containing the part of surfactant particles what obtain, use the method same with manufacture method A 20 quality % aqueous dispersions sprayings of pigment, obtain the granular detergent composition that amount of moisture is set in 7%.

Measure the pH of 1% aqueous solution of the granular detergent composition prepared.This result is displayed in Table 3.

For the granular detergent composition obtained, carry out evaluation (latherability, foam duration and cleaning performance) similarly to Example 1.Just, when evaluating foam enhancing rate (%) of latherability, not obtain relative to comparative example 1, but high relative to the foam of comparative example 6, this result is recorded in table 3 in the lump.

[table 3]

As shown in table 3, the granular detergent composition of embodiment 17 ~ 23, in whole evaluations of latherability, foam duration and cleaning performance, higher than acceptance line (latherability (foam is high) more than 35mm, foam duration more than 8, and cleaning rate more than 75%).Especially allocating in the embodiment 17 of zeolite, comparing with in addition forming with it identical embodiment 18, latherability, foam duration and cleaning all increase.In addition, allocating the embodiment 23 of higher alcohols into, comparing with in addition forming with it identical embodiment 16, latherability improves.

On the other hand, the pH value of 1% aqueous solution is the comparative example 6 of 10.5, although cleaning performance is good, latherability and foam duration are all defective.In addition, do not allocate the comparative example 7 of high molecular polymer into, latherability, foam duration and cleaning performance are all defective.In addition, do not allocate MES into, but allocate the comparative example 8 of LAS-Na replacement into, although latherability and foam duration are well, cleaning performance is defective, is not suitable for using high hardness water washing.

Utilizability in industry

Detergent composition of the present invention is, when namely using high hardness water washing, also can play excellent cleaning force and lathering property, may be used for the washing composition hand-washing washing.

Claims

1. a detergent composition,

More than the compound 2.5 quality % represented containing (A) following general formula (a1), be less than 40 quality %,

R ¹－CH(SO ₃M)－CO－O－R ²…(a1)

In formula, R ¹for alkyl or the thiazolinyl of carbonatoms 10 ~ 16, R ²for the alkyl of carbonatoms 1, M is basic metal,

And

(B) from weight-average molecular weight more than 10,000, the polyacrylic acid of less than 100,000 and salt, acid-co-maleic acid and salt thereof, and more than at least one compound 0.1 quality %, below the 4 quality % that select in carboxymethyl cellulose and salt thereof,

2. detergent composition according to claim 1, described detergent composition is also containing (C) more than zeolite 0.5 quality %, below 30 quality %.

3. detergent composition according to claim 1, described detergent composition is not containing the alkaline agent selected from alkali-metal carbonate and silicate.

4. detergent composition according to claim 1, described detergent composition is granular.

5. detergent composition according to claim 1, wherein, the mass ratio of (A) composition/(B) composition is 5/1 ~ 20/1.

6. detergent composition according to claim 1, described detergent composition is further containing the anion surfactant (E) beyond (A) composition.

7. detergent composition according to claim 6, described detergent composition is further containing the tensio-active agent (F) beyond anion surfactant.

8. detergent composition according to claim 7, the alcohol (D) of described detergent composition further containing carbonatoms 10-16.

9. detergent composition according to claim 6, wherein, the mass ratio of (A) composition/(E) composition is 10/0 ~ 1/9.

10. detergent composition according to claim 7, wherein, (A) composition is 10/0 ~ 4/1 with total amount/(F) composition of (E) composition.

11. detergent composition according to claim 8, wherein, the mass ratio of (D) composition/tensio-active agent (A+E+F) is 1/15 ~ 1/100.

12. detergent composition recorded according to any one in claim 1 ~ 11, described detergent composition is for hand-washing washing.