WO2008068941A1

WO2008068941A1 - Granular detergent composition

Info

Publication number: WO2008068941A1
Application number: PCT/JP2007/067989
Authority: WO
Inventors: Noriko Yanagida; Ryo Hyodo; Hideyuki Kaneda; Naoya Tamura
Original assignee: Lion Corporation
Priority date: 2006-11-28
Filing date: 2007-09-14
Publication date: 2008-06-12
Also published as: MY165566A; JPWO2008068941A1; KR101404304B1; KR20090087886A; JP5097123B2

Abstract

Disclosed is a granular detergent composition which has an excellent effect of imparting softness to a material to be washed and can provide a good water-absorbing property to the material. The granular detergent composition comprises (A) an anionic surfactant, (B) a cationic cellulose and (C) a water-insoluble and water-swellable cellulose. In the granular detergent composition, the content of the cationic cellulose (B) is preferably 0.1 to 2 mass%. In the granular detergent composition, the content of the cellulose (C) is preferably 0.1 to 5 mass%.

Description

Specification

Granular detergent composition

Technical field

[0001] The present invention relates to a granular detergent composition. This application claims priority on November 28, 2006, based on Japanese Patent Application No. 2006-319796 filed in Japan, the contents of which are incorporated herein by reference.

[0002] For detergent compositions used for washing clothes and other items to be cleaned, various studies have been made to impart flexibility to items to be cleaned as well as cleaning effects. It has been broken.

For example, a detergent composition containing smectite, a clay mineral, as a fabric softening component has been proposed (see Patent Document 1).

Also selected from surfactants, water-insoluble water-swellable organic substances, and A) to C) [A) clay minerals and / or organically treated clay minerals, B) specific polymer compounds, C) silicone derivatives] A cleaning composition containing at least one component has been proposed! (See Patent Document 2).

In addition, a fiber treatment composition or a detergent composition containing water-insoluble solid particles has been proposed (see Patent Document 3).

In addition, laundry product compositions containing cationic cellulose (cationized cellulose) have been proposed! (See Patent Document 4).

Patent Document 1: Japanese Patent Laid-Open No. 198697

Patent Document 2: Japanese Patent Laid-Open No. 2002-194391

Patent Document 3: Japanese Patent Laid-Open No. 2003-64574

Patent Document 4: Japanese Translation of Special Publication 2005-536618

Disclosure of the invention

Problems to be solved by the invention

[0003] However, the detergent compositions described in Patent Documents !! to 3 are not yet satisfactory in terms of the effect of imparting flexibility to an object to be washed. In addition, in the laundry product composition containing the cationized cellulose described in Patent Document 4, although the effect of imparting flexibility to the washed product is exhibited, the water absorbency inherent in the washed product is reduced. It turns out that a malfunction is caused.

[0004] The present invention has been made in view of the above circumstances, and it is an object to provide a granular detergent composition that is excellent in the effect of imparting flexibility to an object to be washed and has good water absorption of the object to be washed. Means to solve the problem

[0005] As a result of intensive studies, the present inventors provide the following means in order to solve the above problems.

That is, the granular detergent composition of the present invention is characterized by containing a cation surfactant (A), cationized cellulose (B), and water-insoluble and water-swellable cellulose (C). .

In the granular detergent composition of the present invention, the content of the cationized cellulose (B) is preferably 0.;! To 2% by mass.

In the granular detergent composition of the present invention, the cellulose (C) content is preferably 0.1 to 5% by mass.

The invention's effect

[0006] According to the present invention, it is possible to provide a granular detergent composition that is excellent in the effect of imparting flexibility to an object to be cleaned and has good water absorption of the object to be cleaned.

BEST MODE FOR CARRYING OUT THE INVENTION

[0007] «Granular detergent composition»

The granular detergent composition of the present invention comprises: ayu surfactant (A) (hereinafter referred to as component (A)) and

And cationized cellulose (B) (hereinafter referred to as component (B)) and water-insoluble and water-swellable cellulose (C) (hereinafter referred to as component (C)).

[0008] <Component (A)>

In the present invention, the component (A) is an anionic surfactant. By containing the component (A), a cleaning effect can be obtained. In addition, by using a combination of component (A), component (B), and component (C), the effect of imparting flexibility to the object to be cleaned and the object to be cleaned can be achieved simultaneously with the cleaning effect. The effect of improving water absorption is obtained. In particular, the combination of component (A) and component (B) improves the effect of imparting flexibility to the item to be washed.

Examples of the component (A) include those shown in the following (1) to (; 12).

(1) Linear or branched alkylbenzene sulfonate (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms.

(2) Alkane sulfonate having 10 to 20 carbon atoms.

(3) α-olefin sulfonate (AOS) having 10 to 20 carbon atoms.

(4) Alkyl sulfate or alkenyl sulfate (AS) having 10 to 20 carbon atoms.

(5) Alkyl oxides having an average of 0.5 to 10; a monoalkylated alkyl ether sulfate having a straight chain or branched alkyl group having 10 to 20 carbon atoms or a straight chain having 10 to 20 carbon atoms. Alkenyl ether sulfate (AES) having a chain or branched chain alkenyl group; however, the alkylene oxide is preferably an alkylene oxide having 2 to 4 carbon atoms, a deviation or an ethylene oxide (EO) And a mixture of propylene oxide (PO) (molar ratio ΕΟ / ΡΟ = 0 · 1 / 9.9 to 9 · 9 / 0.1).

(6) Alkyl phenyl ether sulfate having a straight chain or branched alkyl group having 10 to 20 carbon atoms or a straight chain having 10 to 20 carbon atoms, to which 3 to 30 moles of alkylene oxide is added on average Alkenyl phenyl ether sulfate having a branched alkenyl group; however, as the alkylene oxide, preferably any one of the alkylene oxides having 2 to 4 carbon atoms, or a mixture of ΕΟ and ΡΟ (Molar ratio ΕΟ / ΡΟ = 0. 1/9. 9 to 9 · 9/0. 1).

(7) An alkyl ether carboxylate having a straight chain or branched chain alkyl group having 10 to 20 carbon atoms or straight chain having 10 to 20 carbon atoms, which is an average of 0.5 to 10 monoalkylated alkylene oxides. An alkenyl ether carbonate having a chain or branched alkenyl group; however, the alkylene oxide is preferably any one of alkylene oxides having 2 to 4 carbon atoms, or a mixture of ΕΟ and ΡΟ (Molar ratio ΕΟ / ΡΟ = 0.1 / 9. 9 to 9 · 9 / 0.1).

(8) Alkyl polyvalent vinylate monooleate hydrates such as alkyl glyceryl ether sulfonic acids having 10 to 20 carbon atoms. (9) C8-20 saturated or unsaturated α-sulfo fatty acid salt or methyl, ethyl or propyl ester salt thereof (a-SF or MES).

(10) Long chain monoalkyl phosphate, long chain dialkyl phosphate or long chain sesquialkyl phosphate.

(11) Polyoxyethylene monoalkyl phosphate, polyoxyethylene dialkyl phosphate or polyoxyethylene sesquialkyl phosphate.

(12) A higher fatty acid salt having 10 to 20 carbon atoms (Ishizuchi).

The component (A) can be used as an alkali metal salt such as sodium or potassium; an amine salt or an ammonium salt. Of these, alkali metal salts such as sodium and potassium are preferred.

Among the above components (A), LAS or ABS, a-SF or MES, and sarcophagus are preferable.

, LAS, MES, alkali metal salts of higher fatty acids (above, preferably sodium salt or potassium salt) are more preferable.

In the present invention, the component (A) can be used alone or in combination of two or more.

The content of the component (A) in the granular detergent composition of the present invention is preferably! To 50% by mass, more preferably 5 to 30% by mass, and more preferably 10 to 30% by mass. It is even better to be. When it is at least the lower limit of the range, the cleaning power is improved. In addition, the effect of imparting flexibility to the object to be washed is improved. On the other hand, if it is below the upper limit value, the effect of imparting flexibility to the article to be washed is sufficiently obtained.

[0011] <(B) component>

In the present invention, the component (B) is cationized cellulose. By containing the component (B), the effect of imparting flexibility to the article to be washed can be obtained. In particular, the combination of the component (B) and the component (A) improves the effect of imparting flexibility to the object to be washed.

[0012] As the component (B) in the present invention, for example, a cationic polymer obtained by reacting a cellulose raw material with a cationizing agent, and those containing a small amount of water are also preferable.

Examples of cellulose raw materials include hydroxyethyl cellulose (HEC). Examples of cationizing agents include 3-chloro-2

Monium, Glici ,: Umchloride.

In the present invention, the weight average molecular weight of the component (B) is preferably 100,000 to 2,000,000, more preferably 400,000 to 1.6 million. By being above the lower limit of the range, the effect of imparting flexibility to the object to be washed is improved. On the other hand, if it is below the upper limit value, the melting angle I · raw of component (B) itself becomes better.

In this specification, “weight average molecular weight” refers to a value obtained by analysis by gel permeation chromatography (GPC) using polyethylene glycol (PEG) as a standard substance.

[0014] The degree of cationization of the component (B) is preferably 0.3 to 1.0% by mass, more preferably 0.3 to 0.8% by mass. By being in this range, the effect of imparting flexibility to the object to be washed is improved.

However, the “degree of cationization” means the ratio (mass%) of nitrogen atoms per unit glucose ring of component (B). The nitrogen atom is derived from a cationizing agent.

The degree of cationization means that the larger the value, the stronger the cationic property of the component (B) and the higher the water solubility. Therefore, the degree of cationization is a physical property related to the adsorptivity to the object to be washed. In the present invention, when the degree of cationization is 0.3% by mass or more, a moderately strong cationic property can be obtained, and the adsorptivity to the washing object becomes better, and the flexibility to the washing object is increased. It is thought that the imparting effect is improved. On the other hand, if it is 1.0% by mass or less, the cationic strength is moderately suppressed, the water solubility does not become too high, and the adsorptivity to the object to be washed is kept good. It is considered that the effect of imparting flexibility is improved.

[0015] Suitable components (B) are exemplified below.

[0016] [Chemical 1]

… (B-1) [Wherein, -R ⁵ are each independently a hydrogen atom or a group represented by the following formula (B-1-1). 1, m and n each represent the average number of moles of ethylene oxide added. ]

[0017] [Chemical 2]

[0018] In the formula (Bl), the degree of ethylene oxide (EO) substitution per unit glucose ring is preferably 0.3 to 3.0. However, the “degree of EO substitution” means the average number of hydroxyl groups substituted with EO per glucose ring unit of the cellulose raw material (how many of the three hydroxyl groups of the glucose ring are added by EO). The maximum is 3.)

Further, the average added mole number of EO is preferably l + m + n = 0.5 to 5 · 0.

In the present invention, the component (ii) can be used alone or in combination of two or more.

In the granular detergent composition of the present invention, the content of component (ii) is preferably from 0.;! To 2% by mass, more preferably from 0.3 to 2% by mass. More preferably, it is 5 to 2% by mass. By being above the lower limit of the range, the effect of imparting flexibility to the object to be washed is improved. On the other hand, if it is below the upper limit value, the effect of imparting flexibility to the object to be washed is sufficiently obtained.

[0020] As the component (ii), specifically, Leoguard MLP, Leoguard LP (trade name; manufactured by Lion Corporation); Amerchol UCARE Polymer LR400, Amerchol UCA RE Polymer LR30M (trade name; Catal LC—100, Catinal LC—200 (above, trade name; manufactured by Toho Chemical Co., Ltd.) and the like are preferable.

[0021] <(C) component>

In the present invention, the component (C) is water-insoluble and water-swellable cellulose. By containing the component (C), the effect of improving the water absorption of the article to be washed can be obtained. In addition, the combination of the component (C) and the component (B) further improves the effect of imparting flexibility to the object to be washed. However, in this specification, “the effect of improving the water absorption of the object to be washed” refers to an effect of restoring the water absorption inherent in the object to be washed, an effect of increasing the water absorption more than the object of the object to be washed, etc. Shall be included.

[0022] In the present specification and claims, "/ water-insoluble and water-swellable cellulose" refers to cellulose having the property of absorbing water and swelling but not dissolving in water. And preferably include those having a water absorption of 1.5 times or more the mass of the cellulose.

Examples of the component (C) include powdered cellulose (cellulose powder), crystalline cell mouth, microcrystalline cellulose, and the like. Among these, powdered cellulose (a cellulose nodule) is preferable because of its good effect of improving the water absorption of the object to be washed and the effect of imparting flexibility to the object to be washed.

Among powdered cellulose (cellulose powder), those having an average fiber length of 10 to 100 111 are preferred, and those having 10 to 50 111 are more preferred. Further, those having an average fiber diameter of 10 to 50 μm are more preferable, and those having an average fiber diameter of 10 to 30 μm are more preferable.

Here, “average fiber length and average fiber diameter” means powdered cellulose, digital microscope (product name: VHX-500, manufactured by KEYENCE) and lens (product name: VH-Z100, manufactured by KEYE NCE). When the magnification is 800 and the measurement is performed, 10 fiber pieces are regarded as a cylinder for each sample.

In the present invention, the component (C) can be used alone or in combination of two or more.

The content of component (C) in the granular detergent composition of the present invention is preferably 0.;! To 5% by mass, more preferably 0.;! To 3% by mass. More preferably, the content is 3 to 1% by mass. When the content is at least the lower limit of the range, particularly 0.3% by mass or more, the water absorption of the article to be washed is improved. Further, when the content is 0.3% by mass or more, the effect of imparting flexibility to the object to be washed is also improved. On the other hand, if the amount is not more than the upper limit value, the water absorption of the article to be washed and the effect of imparting flexibility to the article to be washed can be sufficiently obtained.

[0024] Specifically, as component (C), BE600 / 10TG (average fiber length: 18 m) of powdered cellulose (cellulose powder) sold under the trade name “ARBOCEL” by Retsutenmeier Co., Ltd. , Average fiber diameter: 15 m), BE600 / 30 (average fiber length: 30 m, average fiber diameter: 18 mm), FD600 / 30 (average fiber length: 45 mm, average fiber diameter: 25 mm) , CP60 0/30 (average fiber length: 30 111, average fiber diameter: 20 111) (above, trade name) and the like are preferable.

Further, from the viewpoint of ease of handling in production, the BE600 / 10TG, the BE600 / 30, the FD600 / 30 (hereinafter, trade name), etc. can be granulated and used. For example, ARBOCEL TF30HG is a granulated version of the BE600 / 10TG (trade name).

White (trade name, Retsutenmeier Co., Ltd.) is a preferred example.

[0025] <Optional component>

In addition to the components (A) to (C), the granular detergent composition of the present invention is appropriately blended with optional components such as a detergent component that is usually used in a cleaning composition for clothing, as necessary. This force S is possible.

Specifically, for example, surfactants other than the component (A), cleaning builder, oil absorbing carrier, clay mineral, enzyme, fluorescent whitening agent, antistatic agent, surface modifier, recontamination preventing agent, particle Examples include strength-retaining agents, reducing agents, antifoaming agents, fragrances, pigments, and flexibility-imparting agents.

[0026] (Surfactant)

As surfactants other than the component (A), surfactants (nouon surfactants, cationic surfactants, amphoteric surfactants) usually used in detergent compositions can be used in combination.

Yes

Examples of nonionic surfactants include those shown below.

(1) A polyoxyalkylene alkyl ether obtained by adding an average of 3 to 30 moles, preferably 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 8 carbon atoms; Or polyoxyalkylene alkenyl ether.

Among these, preferable examples include polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, polyoxyethylene polyoxypropylene alkyl ether, and polyoxyethylene polyoxypropylene alkenyl ether. Examples of the aliphatic alcohol used here include primary alcohols and secondary alcohols, and primary alcohols are preferred. The alkyl group or alkenyl group may be linear or branched.

(2) Polyoxyethylene alkyl phenyl ether or polyoxyethylene alkyl Ninore Fennino Rete Nore.

(3) A fatty acid alkyl ester alkoxylate represented by, for example, the following general formula in which an alkylene oxide is added between ester bonds of a long-chain fatty acid alkyl ester.

(Wherein RO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms; OA represents an alkylene oxide having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms (for example, ethylene oxide, propylene N ′ represents the average number of added moles of alkylene oxide, generally 3 to 30, preferably 5 to 20. R ² represents a substituent having 1 to 3 carbon atoms. It has! /, May! / Represents a lower (1 to 4 carbon) alkyl group.

(4) Polyoxyethylene sorbitan fatty acid ester.

(5) Polyoxyethylene sorbite fatty acid ester.

(6) Polyoxyethylene fatty acid ester

(7) Polyoxyethylene hydrogenated castor oil.

(8) Glycerin fatty acid ester.

Among the nonionic surfactants mentioned above, (1) nonionic surfactants are preferred among them. The average number of alkylene oxides having 2 to 4 carbon atoms to the aliphatic alcohols having 12 to 16 carbon atoms and 16 to 16 aliphatic alcohols is 5 to 20 moles on average. Particularly preferred are added polyoxyalkylene alkyl ethers or polyoxyalkylene alkenyl ethers.

In addition, polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene alkenyl ether, polyoxyethylene polyoxypropylene alkenyl ether, fatty acid having a melting point of 50 ° C or less and HLB of 9 to 16 A fatty acid methyl ester ethoxylate in which ethylene oxide is added to the methyl ester, and a fatty acid methyl ester ethoxypropoxylate in which ethylene oxide and propylene oxide are added to the fatty acid methyl ester are preferably used.

These nonionic surfactants can be used alone or in combination of two or more.

The above "HLB" is a value obtained by Griffin's method (Yoshida, Shindo, Ogaki, Yamanaka Kyoji, "New Edition Surfactant Handbook", Kogyoshosho Co., Ltd., 1991, No. 1) (See page 234).

The above-mentioned “melting point” is a value measured by the melting point measurement method described in JIS K 0064-1992 “Method for measuring the melting point and melting range of chemical products”.

[0027] Examples of the cationic surfactant include the following.

(1) Dilong chain alkyldishort chain alkyl type quaternary ammonium salt.

(2) Mono long chain alkyl tri short chain alkyl type quaternary ammonium salt.

(3) Tri long chain alkyl mono short chain alkyl type quaternary ammonium salt.

However, the above “long chain alkyl” represents an alkyl group having 12 to 26 carbon atoms, preferably 14 to 18 carbon atoms.

The “short chain alkyl” includes a substituent such as a phenyl group, a benzyl group, a hydroxy group, and a hydroxyalkyl group, and may have an ether bond between carbons. Among them, an alkyl group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms; benzyl group; a hydroxyalkyl group having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms; 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms. Polyoxyalkylene groups are preferred.

[0028] Examples of amphoteric surfactants include imidazoline-based amphoteric surfactants and amide betaine-based amphoteric surfactants. Specifically, 2-alkyl N carboxymethyl-N hydroxyethyl imidazoline betaine and lauric acid amidopropyl betaine are preferable.

[0029] (Cleaning builder)

Examples of cleaning builders include organic builders and inorganic builders. Examples of organic builders include nitrite triacetate (NTA), ethylenediaminetetraacetate (EDTA), ethylenediaminedisuccinate (EDDS), β-alanine diacetate (β-ADAA), and aspartate diacetate (ASDA). ), Methyl glycine diacetate (MGD Α), ethyl glycine diacetate (EGDA), iminodisuccinate (IDS) and other aminocarboxylates; serine diacetate, hydroxyiminodisuccinate (HIDS), hydroxyethyl Hydroxycarboxylates such as thylenediamine triacetate and dihydroxyethyldaricine; Hydroxycarboxylates such as hydroxyacetate, tartrate, citrate and dulconate; pyromellitic acid salt and benzopolycarboxylic acid Salt, cyclopentane tetracarboxylate, etc. Ether carbonates such as oxalate, oxydisuccinate, tartaric acid mono- or disuccinate; polyacrylic acid, acrylic acid-allyl alcohol copolymer, water-soluble acrylic acid maleic acid copolymer, hydroxyacrylic acid polymer, Acrylic acid polymers or copolymers such as polysaccharides and acrylic acid copolymers or their salts; polymers such as maleic acid, itaconic acid, fumaric acid, tetramethylene 1,2-dicarboxylic acid, succinic acid, and aspartic acid Copolymers or salts thereof; polysaccharides such as starch, cellulose, amylose, and pectin; polysaccharides such as carboxymethyl cellulose; non-dissociating polymers such as polyethylene glycol, polybutyl alcohol, and polybulurpyrrolidone Compounds and the like. Of these, citrate, aminocarboxylate, hydroxyaminocarboxylate, polyacrylate having a weight average molecular weight exceeding 1000, and water-soluble acrylic acid / maleic acid copolymer salt are preferable.

Examples of inorganic builders include alkaline salts such as sodium carbonate, potassium carbonate, sodium bicarbonate, sodium sesquicarbonate, sodium silicate, crystalline layered sodium silicate, and amorphous layered sodium silicate; sodium sulfate, potassium sulfate , Neutral salts such as sodium chloride and potassium chloride; orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate,)

• w 'CH 2 O (wherein M is an alkali metal atom such as sodium or potassium; X ¹ , y ¹ and w ¹ are

2

The number of moles of each component is shown. Generally, X ¹ is from 0.7 to 1.5; y ¹ is from 0.8 to 6.0, and w ¹ is an arbitrary positive number. ) Crystalline aluminosilicate represented by the general formula χ ² (Μ 0) · Α1 Ο

twenty two

• y ² (SiO ² ) -w ² (HO) (wherein M is an alkali metal atom such as sodium or potassium; x ² , y ²

3 2 2

And w ² represents the number of moles of each component, generally X ² is from 0.7 to; 1.2, y ² is from 1.6 to 2.8, w ² is 0 or any Indicates a positive number. ) Amorphous aluminosilicate represented by the general formula x ³ (NO) · NO 1 O-y ³ (SiO) · ζ ³ (Ρ O) -w ³ (HO) (where M is sodium, force Riu

2 2 3 2 2 5 2

X ³ , y ³ , z ³ and w ³ indicate the number of moles of each component, generally X ³ is a number of 0.2—1.1, y ³ is 0.2 —4. The number 0, z ³ is 0.001 — 0.8, w ³ is 0 or any positive number. ) Amorphous aluminosilicates represented by

Among them, sodium carbonate, potassium carbonate, calcium carbonate, sodium tripolyphosphate, Sodium sulfate, sodium silicate and sodium aluminosilicate are preferred.

[0031] (Enzyme)

As the enzyme, for example, protease, lipase, amylase, cellulase and the like can be used.

Specific examples of proteases include savinase, alcalase, enolase, cannase, esperaze (above, trade name; manufactured by Novozymes); API21 (trade name, Showa) Electric Works Co., Ltd.); Maxataze, Maxacal, Pyurafuetato (Purafect), Maxapem (above, trade name: manufactured by Dienencore); KAP (trade name, manufactured by Kao Corporation), JP Examples include protease K-14 and K-16 described in the 5-25492 publication.

Specific examples of lipases include commercially available lipases such as lipolase, lipolase ultra, lipex (trade name; manufactured by Novozymes), and liposome (trade name, manufactured by Showa Denko KK).

Specific examples of amylase include Termamyl, Termurare, Duramyl, Stainzyme, Promozyme 200L (trade name; manufactured by Novozymes), Maxamyl (trade name, Genencore) ), Pullulanase Amano (trade name, manufactured by Amano Pharmaceutical Co., Ltd.), DB-250, pullulanase derived from Aerobacter aerogenes ATCC9621 (the trade name; crude or crystallized product released from Seikagaku Corporation), and the like.

Specific examples of cellulase include cellzyme, carezym (trade name; manufactured by Novozymes), KAC500 (trade name, manufactured by Kao Corp.), cellulase described in claim 4 of JP-A-63-264699, and the like. Is mentioned.

[0032] The method for producing the granular detergent composition of the present invention is not particularly limited and can be produced by a generally used method. Examples of cases where the granular detergent composition is in powder form include, for example, a method in which a surfactant and other raw materials are dispersed / dissolved in water and spray-dried, kneading / extrusion, stirring granulation, rolling It can be produced by a method such as granulation, compression molding, etc. after subjecting to an apparatus such as granulation, and further pulverization if necessary. [0033] The average particle size of the particles of the granular detergent composition of the present invention is not particularly limited, but is preferably 200 to 1500 mm, preferably 250 to 1000 mm. Better than mosquitoes. When the average particle size is 200 m or more, dusting is suppressed during use. On the other hand, if it is 1500 m or less, the solubility in water will be improved.

The average particle diameter of such particles is a value calculated from a particle size distribution by sieving according to the particle size test described in the Japanese Pharmacopoeia (see JP 2004-331816 A). Concrete Hakuko (granularly washed IJ yarn and product), 1680 ヽ m, 1410〃m, 1190〃m, 1000μm, 710μm, 500μm, 350μ m, 250 μm, J: and 149 μm, 9 stages | ¾ and a tray, and the classification operation is performed on the saucer from a sieve with a small opening to a sieve with a large opening. The top of the top 1680 H m sieve is topped with 100 g / g of granular detergent composition, covered with a low-tap type sieve! /, Shaker (made by Iida Seisakusho, Tapping: 156 times / Min, rolling: 290 times / min), shake for 10 minutes, collect the sample remaining on each sieve and pan, and measure the mass of the sample. When the mass frequency with each sieve is integrated, the opening of the first sieve where the integrated mass frequency is 50% or more is defined as `` aa mj, which is one step larger than a and im! /, Sieve The average value of the mass frequency from the pan to the am sieve is `` c% '', and the mass frequency on the & 111 sieve is `` (1% ''. The particle size (mass 50%) was determined and used as the average particle size of the particles.

[0034] Country average particle size Amount = 1 0 0- (= — d (logb— l.ga) x logb)) / Cd / (logb— loga))

[0035] The granular detergent composition of the present invention is excellent in the effect of imparting flexibility to the object to be washed, and has the effect that the water absorption of the object to be washed is good.

The reason why the force and the effect are obtained is estimated as follows.

According to the study by the present inventors, a conventional detergent composition containing cationized cellulose (B) in the presence of an anionic surfactant (A) is! Although the effect is manifested, it has been found that there is a problem that the water absorption inherent in the article to be washed is lowered. When the detergent composition is dissolved in water, the component (A) and the component (B) form a complex, and the complex is adsorbed on the object to be washed. As a result, when flexibility is imparted to the fibers of the object to be washed, the fiber surface is hydrophobized at the same time. Therefore, it is considered that the water absorption of the object to be washed is lowered in the conventional detergent composition.

The granular detergent composition of the present invention further contains water-insoluble and water-swellable cellulose (C) in addition to the components (A) and (B). Due to the presence of component (B), component (C) can be efficiently adsorbed between the fibers of the object to be washed even with a small amount, and component (C) is water-swellable. Therefore, the water absorption ability is good. As a result, it is considered that the effect of preventing and reducing the water absorption of the article to be washed is exhibited and the flexibility imparting effect to the article to be washed is further improved.

Therefore, it is presumed that the granular detergent composition of the present invention is excellent in the effect of imparting flexibility to the article to be washed and has the effect that the article has good water absorption.

Example

[0036] The ability to explain the present invention in more detail below using examples The present invention is not limited to these examples. “%” Means “% by mass” unless otherwise specified.

[0037] (Examples;! To 21, Comparative examples;! To 2)

The granular detergent composition of each example shown in Table 1 and Table 2 was manufactured using the components shown in Table 1 and Table 2 and the common components shown in Table 3.

In addition, the unit of the blending amount in the table indicates mass% based on the total mass of the granular detergent composition. In addition, among the components in the table, surfactants, zeolites and MA agents (metal ion scavengers) are blended in pure equivalents, and others are blended in their own form. Show. “Balance” of the amount of sodium carbonate means that the total amount is adjusted to 100% by mass.

Below, it demonstrates about the description of the component shown in the table | surface, and the manufacturing method of a granular detergent composition.

[0038] <Description of components shown in the table>.

-Ayuon surfactant (A)

MES1: α-sulfo fatty acid methyl ester having a mixing ratio of a compound having a hydrocarbon group having 14 carbon atoms and a compound having a hydrocarbon group having 16 carbon atoms in a mass ratio of 18:82 Aqueous sodium salt solution (manufactured by Lion Corporation; AI concentration = 70% by mass, the balance being unreacted fatty acid methyl ester, sodium sulfate, methyl sulfate, hydrogen peroxide, water, etc.). Here, “AI” refers to a compound contained in MES that has a function as a surfactant. MES usually contains α-sulfo fatty acid methyl ester salt, and α-sulfo fatty acid dialkali salt as a by-product. The α-sulfo fatty acid dialkali salt also has a function as a surfactant, like the α-sulfo fatty acid methyl ester salt. Therefore, the soot concentration means the total concentration of α-sulfo fatty acid methyl ester salt and α-sulfo fatty acid dialkali salt which is one of by-products.

MES2: Sodium salt aqueous solution of α-sulfo fatty acid methyl ester with a mixing ratio of the compound having a hydrocarbon group having 16 carbon atoms and the compound having a hydrocarbon group having 18 carbon atoms in a mass ratio of 80:20 (Lion ( Manufactured by Kogyo Co., Ltd .; soot concentration = 70 mass%, the balance being unreacted fatty acid methyl ester, sodium sulfate, methyl sulfate, hydrogen peroxide, water, etc.).

LAS Na: linear alkyl (10 to 14 carbon atoms) benzenesulfonic acid [manufactured by Lion Co., Ltd., Rybon LH-200 (LAS-H pure content: 96% by mass)] was prepared during the preparation of the surfactant composition. A compound neutralized with a mass% aqueous sodium hydroxide solution. The compounding amounts in Tables 1 and 2 represent values (mass%) as L AS Na.

Stone wall: 12 to 18 carbon atoms; sodium fatty acid (made by Lion Co., Ltd., pure: 67% by mass, titer: 40 to 45); fatty acid composition: 12.11.7% by mass, 14 4 wt%, C16 29. 2 wt%, C18F0 (stearic acid) 0.7 wt%, C18F1 (Orein acid) 56.8 wt%, C1 8F2 (Reno one Honoré acid) 1.2 weight ^_0/0; molecular weight : 289).

'Cationized cellulose (B)

Cationized cellulose AX: hydroxy E chill cellulose (manufactured by Sumitomo Seika Chemicals Co., Ltd., trade name: AX 15, 1 mass ^_0/0 solution viscosity (25 ° C): 15000~30000mPa ' s) in 30 g (100 parts by weight), isopropyl alcohol 300 g (1000 parts by mass) of a mixed solvent in which / water (mass ratio) = 85/15 and 5 g (16.5 parts by mass) of a 25% by mass aqueous sodium hydroxide solution were further added and mixed. Next, the mixture was stirred and mixed for 30 minutes, and 150 g (500 parts by mass) of the supernatant of the mixed solvent was extracted.

Then, the temperature is raised to 50 ° C and glycidyltrimethylammonium as a cationizing agent. Mouth Ride (Sakamoto Yakuhin Kogyo, trade name: SY-GTA80, effective concentration: 73 mass% aqueous solution) 3 g (10 parts by mass) was added and reacted for 3 hours. Thereafter, a 10% by mass isopropyl alcohol hydrochloride solution was added to adjust the pH to 6 to obtain a cationized cellulose slurry.

Then, after spin-drying and drying (70 to 80 ° C.), cationized cellulose AX (weight average molecular weight: 1.6 million, cationization degree: 0.6 mass%, solid content: 91 mass%) was obtained. .

[0040] Cationized cellulose LF: Hydroxyethyl cellulose (product name: LF, manufactured by Sumitomo Seika)

15, 1% by weight aqueous solution viscosity (25 ° C): 700 ~; 1300mPa's) 30g (100 parts by mass) mixed solvent 300g (1000% by mass) isopropyl alcohol / water (mass ratio) = 85/15 Part) and a 25 mass% sodium hydroxide aqueous solution 4.5 g (15 parts by mass) were further added and mixed. Next, the mixture was stirred and mixed for 30 minutes, and 150 g (500 parts by mass) of the supernatant of the mixed solvent was extracted. Then, the temperature was raised to 50 ° C, and 4 g (13 parts by mass) of glycidyl trimethyl ammonium chloride (made by Sakamoto Pharmaceutical Co., Ltd., trade name: SY-GTA80, effective concentration: 73% by mass aqueous solution) was added as a cationizing agent. And reacted for 3 hours. Thereafter, a 10% by mass isopropyl alcohol hydrochloride solution was added to adjust the pH to 6 to obtain a cationized cellulose slurry.

Then, after centrifugal dehydration and drying (70 to 80 ° C.), cationized cellulose LF (weight average molecular weight: 900,000, cationization degree: 0.6 mass%, solid content: 91 mass%) was obtained. .

[0041] 'Cenorelose (C)

Cellulose powder A: ARBOCEL BE600 / 30 (trade name, manufactured by Retsutenmeier; average fiber length 30, 1 m, average fiber diameter 18, 1 m).

Cellulose powder B: ARBOCEL TF—30HG White (trade name, manufactured by Lettuce Meyer); Cellulose powder A is granulated to a particle size of 0.4 to 1.25 mm.

Cellulose powder C: ARBOCEL FD600 / 30 (trade name, manufactured by Retsutenmeier; average fiber length 40 Hm, average fiber diameter 25 m).

[0042] · Optional ingredients

Nonionic surfactant: ECOROL26 (trade name, manufactured by ECOGREEN; alcohol having 12 to 16 carbon atoms; an alcohol having an alkyl group of 16) average 15 mol of ethylene oxide adduct (pure 90 mass)

%).

Zeolite: A-type zeolite · Shilton B (trade name, manufactured by Mizusawa Chemical Co., Ltd .; pure content: 80% by mass). MA agent: Acrylic acid / maleic anhydride copolymer sodium salt (trade name: Aqualic TL 400, manufactured by Nippon Shokubai Co., Ltd .; pure 40% by weight aqueous solution).

Tripolyphosphate Na: sodium tripolyphosphate (manufactured by Mitsui Chemicals, Inc.).

Silicate Na: Powdered sodium silicate No. 2 (manufactured by Nippon Chemical Industry Co., Ltd.).

Sulfurous acid Na: anhydrous sodium sulfite (manufactured by Shinshu Chemical Co., Ltd.).

Sodium sulfate: neutral anhydrous sodium sulfate (manufactured by Nippon Chemical Industry Co., Ltd.).

Carbonic acid K: Potassium carbonate (powder) (manufactured by Asahi Glass Co., Ltd .; average particle size 490 ^ 111, bulk density 1 · 30 g / cm 3).

Sodium carbonate: granular ash (Asahi Glass Co., Ltd., average particle diameter 32 (^ 111, bulk density 1.07 g / cm ³ ) Carbonic acid Ca: Charcoal Cal M400 (Asahi Deposit Co., Ltd.).

Fluorescent agent: Chinopearl CBS—X (trade name, Ciba Specialty Chemicals) / Chinopar AMS—GX (trade name, Ciba Specialty Chemicals) = 3/1 (mass ratio) mixture. Coated sodium carbonate particles: Prepared in the following first to third steps, 85% by weight of sodium carbonate, 3% by weight of sodium salt of acrylic acid / maleic anhydride copolymer, 7% by weight of lauric acid, water, and the rest Surface-treated inorganic particles.

(First step)

Sodium carbonate was introduced into a professional shear mixer (Ohira Yokai Co., Ltd.) equipped with a blade-shaped shovel and clearance between the shovel walls of 5 mm (filling rate: 30% by volume), and stirring was started at 150 rpm. (Chopper rotation speed: 1015 rpm, blade tip speed (peripheral speed): 6.9 m / s). Ten seconds after the start of stirring, an aqueous solution of acrylic acid / maleic anhydride copolymer sodium salt was sprayed for 180 seconds with a pressure nozzle (flat nozzle) having a spray angle of 115 degrees to perform granulation-coating operation.

In the particles prepared in the first step, if the water content with respect to the total amount of the particles exceeds 10% by mass, the device is dried by introducing hot air to adjust the water content to 10% by mass or less. did.

(Second process)

Subsequently, while continuing stirring in a professional-share-one mixer, lauric acid was sprayed for 180 seconds with a pressure nozzle (full cone nozzle) with a spray angle of 60 degrees, and coating operation was performed. And Subsequently, stirring was continued for 30 seconds to obtain particles.

(3rd process)

Next, the obtained particles are packed into a fluidized bed (Product name: Glatt—POWREX, Model No. FD—WRT-20, manufactured by Baurex Co., Ltd.), and after filling, 15 ° C wind (air) is fluidized into the fluidized bed. The particles were cooled down to \ 20 ° C.

The air velocity in the fluidized bed was adjusted in the range of 0.2-10. Om / s while confirming the fluidization state.

Yes

The obtained particles were classified using a sieve having an opening of 2000 m to obtain surface-treated inorganic particles (coated Na carbonate particles) passing through the sieve having an opening of 2000 m.

[0044] Lauric acid: manufactured by NOF Corporation, trade name: NAA-122; melting point 43 ° C.

Perfume: Perfume composition A shown in [Table 11] to [Table 18].

Enzyme 1: Sabinase 12T (Novozymes) / LIPEX100T (Novozymes) / Sinzym 12T (Novozymes) = 5/1/4 (mass ratio) mixture.

Enzyme 2: Dezyme 12T (Novozymes)

According to the composition shown in Tables 1 to 3, a surfactant-containing particle is prepared by the preparation method shown below, and the granular detergent composition of each example shown in Table 1 and Table 2 using the surfactant-containing particle. The thing was manufactured.

[0046] [Examples;! To 19, Comparative Examples 1 and 2]

(Preparation of surfactant-containing particles)

First, water was placed in a jacketed mixing tank equipped with a stirring device, and the temperature was adjusted to 60 ° C. To this, a surfactant containing component (A) (excluding MES and nonionic surfactant) was added and stirred for 10 minutes. Subsequently, MA agent, sodium sulfate, and fluorescent agent were added. Further, after stirring for 10 minutes, a part of zeolite (2.0% by mass equivalent (to surfactant-containing particles, the same shall apply hereinafter) for addition during kneading, 3.2% by mass equivalent of grinding aid And 1.5 mass% equivalent of each surface coating zeolite)), Na carbonate, K carbonate and Na sulfite were added respectively. Furthermore, after stirring for 20 minutes to prepare a slurry for spray drying with a moisture content of 38% by mass, the amount of air is adjusted using a countercurrent spray drying tower at a hot air temperature of 280 ° C. Control was obtained to obtain spray-dried particles having a water content of 5% by mass.

On the other hand, a part of nonionic surfactant (25% by mass with respect to MES) is added to an aqueous slurry of MES obtained by sulfonating and neutralizing the fatty acid ester of the raw material (water concentration 25% by mass). Then, the mixture was concentrated under reduced pressure with a thin-film dryer until the water content became 11% by mass to obtain a mixed concentrate of MES and nonionic surfactant.

The above-mentioned spray-dried particles, the above mixed concentrate, 2.0% by mass of zeolite, 0.5% by mass of the remaining nonionic surfactant and water except for spray addition were added to a continuous kneader (Kurimoto Co., Ltd.). KRC-S4 type), and kneaded under conditions of a kneading capacity of 120 kg / hr and a temperature of 60 ° C. to obtain a surfactant-containing kneaded product. This surfactant-containing kneaded product was cut with a cutter while extruding it with a pelleter double (Fuji Padal Co., Ltd., EXDFJS-1100 type) equipped with a die with a hole diameter of 10 mm. 5 m / s) and a molded product containing a pellet-like surfactant having a length of about 5 to 30 mm was obtained.

Next, particulate zeolite (average particle size 180 m) as a grinding aid was added to the obtained pellet-shaped surfactant-containing molded product, and an amount equivalent to 3.2% by mass was added, and cold air (10 ° C, 15 m / m) was added. s) Using Fitzmill (DKA-3, manufactured by Hosokawa Micron Co., Ltd.) arranged in three stages in series under the coexistence, crushed (screen hole diameter: 1st stage / 2nd stage / 3rd stage = 12mm / 6mm / 3mm, Number of rotations: 1st stage / 2nd stage / 3rd stage 4700rpm) Finally, with a horizontal cylindrical rolling mixer (cylinder diameter 585mm, cylinder length 490mm, container 131.7L drum inner wall surface with inner wall surface clearance 20mm, height 45mm baffle plate) In addition, under the conditions of a filling rate of 30 volume%, a rotational speed of 22 rpm, and 25 ° C., 1.5 mass% of an equivalent amount of finely divided zeolite is added, and 0.5 mass% of an equivalent amount of Nouon surfactant and fragrance are sprayed, Rolled for 1 minute and surface-modified to prepare surfactant-containing particles.

(Manufacture of granular detergent composition)

Using a horizontal cylindrical rolling mixer (with a cylinder diameter of 585 mm, a cylinder length of 490 mm, a container 131.7 L inner wall with two baffle plates with a clearance of 20 mm and a height of 45 mm from the inner wall) 5 components such as cationized cellulose (B), cellulose powder (C), coated sodium carbonate particles, surfactant-containing particles, and enzyme under the conditions of 30% by volume, 22 rpm, and 25 ° C. Mixing for a minute, the granular detergent composition of each example was manufactured. [0048] [Example 20]

(Preparation of surfactant-containing particles)

First, water and sodium hydroxide for neutralizing linear alkylbenzene sulfonic acid were added in an equimolar amount to the amount of linear alkylbenzene sulfonic acid added to a jacketed mixing tank equipped with a stirrer. The temperature was adjusted to 60 ° C, linear alkylbenzenesulfonic acid was added, and the mixture was stirred for 10 minutes. Subsequently, sodium tripolyphosphate, MA agent, sodium sulfate, and fluorescent agent were added.

Furthermore, after stirring for 10 minutes, sodium carbonate, sodium silicate, sodium sulfite and calcium carbonate were added. Furthermore, after stirring for 20 minutes to prepare a slurry for spray drying with a moisture content of 38% by mass, the amount of air is adjusted using a counter-current spray drying tower at a hot air temperature of 280 ° C to achieve a spray with a moisture content of 5% by mass. Dry particles were obtained.

Surfactant-containing particles were prepared by mixing 2.0% by mass of A-type zeolite fine powder as a final composition with the above spray-dried particles.

[0049] (Production of granular detergent composition)

Using a horizontal cylindrical rolling mixer (with a cylinder diameter of 585 mm, a cylinder length of 490 mm, a container 131.7 L inner wall with two baffle plates with a clearance of 20 mm and a height of 45 mm from the inner wall) Mixing components such as cationized cellulose (B), cellulose powder (C), surfactant-containing particles, enzyme, and fragrance for 5 minutes under the conditions of a filling rate of 30% by volume, a rotational speed of 22 rpm, and 25 ° C. The granular detergent composition of each example was manufactured.

[0050] [Example 21]

(Preparation of surfactant-containing particles)

Surfactant particles were prepared in exactly the same manner as in Example 3, except that the cationized cellulose (B) was added to the continuous kneader together with the spray-dried particles and the surfactant mixture concentrate.

(Manufacture of granular detergent composition)

A granular detergent composition was produced in the same manner as in Example 3, except that the power of adding cationized cellulose B was not used.

[0051] <Evaluation> The granular detergent composition obtained in each example was evaluated for the softness-imparting effect and water absorbability shown below.

[0052] [Sample preparation]

(Preprocessing)

Polyester jersey (Dyeing Materials Co., Ltd.) lkg, two-tank washing machine (Product name: CW—C30A 1-H, manufactured by Mitsubishi Electric Corporation), using 50 ° C tap water, commercially available Detergent Totsu

1

(Lion Co., Ltd.) was used at the standard concentration (30g of tap water, detergent top 20g, ie 6767ppm) and 30 times the bath ratio. After repeating the above twice, the rinsing and dehydration operation of “rinse under running water for 15 minutes and then dehydrate for 5 minutes” was repeated 5 times, and then pretreated by hanging at room temperature.

The same pretreatment was applied to 1 kg of cotton towel (manufactured by Toshinsha Co., Ltd., 220 mm border soft FT) 1 kg and B.V.D skin shirt (round neck short sleeve T-shirt, product number G0134TS).

[0053] (Cleaning treatment)

Using a fully automatic electric washing machine (product name: JW—Z23A, manufactured by Haier) as a washing machine, and using a normal course of the fully automatic electric washing machine, tap water with a water temperature of 20 ° C, one polyester jersey (38 g / sheet), 2 cotton towels (71 g / sheet), 3 BV D skin shirts (140 g / sheet) (total 600 g) (hereinafter collectively referred to as “clothes”) The bath ratio is 20 times (low water level: 12U and the granular detergent composition concentration in each case is 833ppm (10g of granular detergent composition for 12L of tap water). After that, it was hung and dried at room temperature.

[0054] [Evaluation of flexibility imparting effect]

The cotton towel was softened! /, And the cotton detergent was washed with the granular detergent composition of each of the above examples, and the standard detergent composition (granularity of Comparative Example 1) instead of the granular detergent composition of each example. A pair of comparisons with a cotton towel that had been subjected to the above-described washing treatment by removing the cationized cellulose AX from the detergent composition was conducted by 10 specialist panelists.

The evaluation is that if there is a clear difference in flexibility between a pair of cotton towels to be compared, give a high flexibility, +2 points for the cotton towel, low! /, 2 points for the cotton towel; If there is a slight difference, the flexibility is slightly higher, the cotton tannole will be + 1 point, slightly lower! /, The one will be given 1 point; If there was no difference, they were given 0 points. Then, the total score of 10 people was obtained, and the flexibility imparting effect was evaluated based on the following criteria! The results are shown in Tables 1 and 2.

(Evaluation criteria)

◎◎: 16-20 points.

: 11 ~; 15 points.

○: 6 to 10 points.

Δ: 1 to 5 points.

X: 0 points or less.

[0055] [Evaluation of water absorption]

JIS L 1907 (Water absorption test method for textile products) 7. 1. In accordance with the bi-rec method, a cotton towel that has been cleaned with the granular detergent composition of each of the above examples is cut into 200 mm x 15 mm and From one end to 5 mm, it was immersed in pure water (20 ° C soil 2 ° C) colored with a pigment (trade name: Sumilight Supra Turquoise Blue G, manufactured by Sumitomo Chemical Co., Ltd.). At this time, the height of the water (water absorption length, unit: mm) rising to 10 minutes for the cut cotton towel section was measured.

Then, the average value of the 10 measurements was obtained, and the water absorption of the cotton towel was evaluated based on the following criteria. The results are shown in Tables 1 and 2.

(Evaluation criteria)

○: 95 mm or more.

Δ: 90 mm or more and less than 95 mm.

X: Less than 90mm.

[0056] [Table 1]

686.90 / .00Zdf / X3d VZ 6890 / 800Z OAV

[0058] [Table 3]

[0059] As is clear from the results of Tables 1 and 2, the granular detergent compositions of Examples:! To 18 according to the present invention are excellent in the effect of imparting flexibility to the object to be cleaned, and the object to be cleaned. The ability to absorb water is good.

On the other hand, the granular detergent composition of Comparative Example 1 lacking cellulose (C) has poor water absorption, and Comparative Example 2 lacking cationized cellulose (B) has a low flexibility-imparting effect on the object to be washed. It could be confirmed.

Industrial applicability

[0060] According to the present invention, it is possible to provide a granular detergent composition that is excellent in the effect of imparting flexibility to an object to be cleaned and has good water absorption of the object to be cleaned.

Claims

The scope of the claims

[1] A granular detergent composition characterized by comprising a ayu surfactant (A), a cationized cellulose (B), and a water-insoluble and water-swellable cellulose (C).

[2] The granular detergent composition according to claim 1, wherein the content of the cationized cellulose (B) is 0.

[3] The granular detergent composition according to claim 1 or 2, wherein the content of the cellulose (C) is 0.;