JP5097123B2 - Granular detergent composition - Google Patents

Description

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

In a detergent composition used for washing clothes such as clothes, various studies have been conventionally made to impart flexibility to the objects to be cleaned as well as a cleaning effect.
For example, a detergent composition in which smectite, a clay mineral, is blended as a fabric softening component has been proposed (see Patent Document 1).
Further, at least one 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, and C) silicone derivatives]. A cleaning composition containing various components has been proposed (see Patent Document 2).
Further, a fiber treating agent composition or a detergent composition containing water-insoluble solid particles has been proposed (see Patent Document 3).
In addition, a laundry product composition containing cationic cellulose (cationized cellulose) has been proposed (see Patent Document 4).
JP-A-1-98697 JP 2002-194391 A JP 2003-64574 A JP 2005-536618 Gazette

However, the detergent compositions described in Patent Documents 1 to 3 are still not fully satisfactory in the effect of imparting flexibility to the object to be washed.
Moreover, in the laundry product composition which mix | blended the cationized cellulose of patent document 4, although the softness | flexibility provision effect to a to-be-washed item is expressed, the malfunction which the to-be-washed object originally has falls I found it to happen.

  This invention is made | formed in view of the said situation, and makes it a subject to provide the granular detergent composition with the favorable water absorbability of a to-be-washed object while being excellent in the softness | flexibility provision effect to to-be-washed | cleaned object.

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 comprises an anionic surfactant (A), a cationized cellulose (B), and a water-insoluble and water-swellable cellulose (C).
In the granular detergent composition of this invention, it is preferable that content of the said cationized cellulose (B) is 0.1-2 mass%.
Moreover, in the granular detergent composition of this invention, it is preferable that content of the said cellulose (C) is 0.1-5 mass%.

  ADVANTAGE OF THE INVENTION According to this invention, while being excellent in the softness | flexibility provision effect to to-be-washed | cleaned object, the granular detergent composition with the favorable water absorption of to-be-washed | cleaned object can be provided.

≪Granular detergent composition≫
The granular detergent composition of the present invention comprises an anionic surfactant (A) (hereinafter referred to as component (A)), cationized cellulose (B) (hereinafter referred to as component (B)), water-insoluble and Contains water-swellable cellulose (C) (hereinafter referred to as component (C)).

<(A) component>
In the present invention, the component (A) is an anionic surfactant. By including the component (A), a cleaning effect can be obtained. Moreover, by using the combination of the component (A), the component (B) and the component (C), the effect of imparting flexibility to the object to be washed and the effect of improving the water absorption of the object to be washed are obtained at the same time as the washing effect. It is done. In particular, the combination of component (A) and component (B) improves the effect of imparting flexibility to the item to be washed.

(A) As a component, what is shown to the following (1)-(12) can be mentioned, for example.
(1) A linear or branched alkylbenzene sulfonate (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms.
(2) Alkanesulfonate having 10 to 20 carbon atoms.
(3) C10-20 α-olefin sulfonate (AOS).
(4) Alkyl sulfate or alkenyl sulfate (AS) having 10 to 20 carbon atoms.
(5) Alkyl ether sulfate having a linear or branched alkyl group having 10 to 20 carbon atoms, or an average of 0.5 to 10 moles of alkylene oxide added, or linear or branched chain having 10 to 20 carbon atoms An alkenyl ether sulfate (AES) having an alkenyl group of the following: However, the alkylene oxide is preferably any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide (EO) and propylene oxide (PO). What mixed (EO / PO = 0.1 / 9.9-9.9 / 0.1 by molar ratio) is mentioned.
(6) Alkyl phenyl ether sulfate having a linear or branched alkyl group having 10 to 20 carbon atoms, having an average of 3 to 30 moles of alkylene oxide added thereto, or a linear or branched chain having 10 to 20 carbon atoms An alkenyl phenyl ether sulfate having an alkenyl group; however, the alkylene oxide is preferably any one of alkylene oxides having 2 to 4 carbon atoms or a mixture of EO and PO (EO / PO = molar ratio). 0.1 / 9.9 to 9.9 / 0.1).
(7) Alkyl ether carboxylate having a linear or branched alkyl group having 10 to 20 carbon atoms, having an average of 0.5 to 10 moles of alkylene oxide added thereto, or a linear or branched chain having 10 to 20 carbon atoms An alkenyl ether carboxylate having a alkenyl group in the form of an alkenyl group; however, the alkylene oxide is preferably one having 2 to 4 carbon atoms or a mixture of EO and PO (molar ratio EO / PO). = 0.1 / 9.9 to 9.9 / 0.1).
(8) Alkyl polyhydric alcohol ether sulfate such as alkyl glyceryl ether sulfonic acid 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 (α-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 (soap) having 10 to 20 carbon atoms.
Said (A) component can be used as alkali metal salts, such as sodium and potassium; amine salt, ammonium salt, etc. Of these, alkali metal salts such as sodium and potassium are preferred.
Among the components (A), LAS or ABS, α-SF or MES, and soap are preferable, and LAS, MES, and an alkali metal salt of higher fatty acid (more preferably, sodium salt or potassium salt) are more preferable.

In this invention, (A) component can be used 1 type or in mixture of 2 or more types.
The content of the component (A) is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, and 10 to 30% by mass in the granular detergent composition of the present invention. Further preferred. When it is at least the lower limit of the range, the cleaning power is improved. Moreover, the softness | flexibility provision effect to a to-be-washed object improves. On the other hand, if it is below the upper limit value, the effect of imparting flexibility to the article to be washed can be sufficiently obtained.

<(B) component>
In the present invention, the component (B) is cationized cellulose. By containing this (B) component, the softness | flexibility provision effect to a to-be-washed object is mainly acquired. In particular, the combination of the component (B) and the component (A) improves the effect of imparting flexibility to the object to be washed.

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 a polymer containing a small amount of water can be preferably cited.
Examples of the cellulose raw material include hydroxyethyl cellulose (HEC).
Examples of the cationizing agent include 3-chloro-2-hydroxypropyltrimethylammonium and glycidyltrimethylammonium chloride.

In the present invention, the weight average molecular weight of the component (B) is preferably 100,000 to 2,000,000, and more preferably 400,000 to 1,600,000. By being above the lower limit of the range, the effect of imparting flexibility to the article to be washed is improved. On the other hand, if it is below an upper limit, the solubility of (B) component itself will become more favorable.
In the present specification, “weight average molecular weight” indicates a value obtained by analyzing by gel permeation chromatography (GPC) using polyethylene glycol (PEG) as a standard substance.

The degree of cationization of the component (B) is preferably 0.3 to 1.0% by mass, and more preferably 0.3 to 0.8% by mass. By being this range, the softness | flexibility provision effect to a to-be-washed object improves.
However, the “degree of cationization” means the ratio (mass%) of nitrogen atoms per unit glucose ring of the component (B). The nitrogen atom is derived from a cationizing agent.
The cationization degree 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 is obtained, and the adsorptivity to the washing object becomes better and the flexibility to the washing object is obtained. 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.

  Suitable examples of the component (B) are shown below.

［式中、Ｒ^３〜Ｒ^５は、それぞれ独立して水素原子または下記式（Ｂ−１−１）で表される基である。ｌ、ｍ、ｎは、それぞれエチレンオキシドの平均付加モル数を示す。］

[Wherein, R ^{3 to} R ⁵ each independently represent a hydrogen atom or a group represented by the following formula (B-1-1). l, m, and n each represent the average number of moles of ethylene oxide added. ]

In the formula (B-1), the degree of ethylene oxide (EO) substitution per unit glucose ring is preferably 0.3 to 3.0. However, the “EO substitution degree” indicates 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 with EO). , A maximum of 3.)
The EO average added mole number is preferably 1 + m + n = 0.5 to 5.0.

In this invention, (B) component can be used 1 type or in mixture of 2 or more types.
In the granular detergent composition of the present invention, the content of the component (B) is preferably 0.1 to 2% by mass, more preferably 0.3 to 2% by mass, and 0.5 to 2%. More preferably, it is mass%. By being above the lower limit of the range, the effect of imparting flexibility to the article 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 can be sufficiently obtained.

  Specific examples of the component (B) include Leoguard MLP and Leoguard LP (trade name; manufactured by Lion Corporation); Amerchol UCARE Polymer LR400, Amerchol UCARE Polymer LR30M (trade name; Dow Chemical Co., Ltd.) Catalytic LC-100, Catalytic LC-200 (above, trade name; manufactured by Toho Chemical Industry Co., Ltd.) and the like are preferable.

<(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 is obtained. Further, the combination of the component (C) and the component (B) further improves the effect of imparting flexibility to the article to be washed.
However, in this specification, “the effect of improving the water absorption of the article to be washed” includes the effect of restoring the water absorption inherent in the article to be washed, the effect of increasing the water absorption beyond that originally possessed by the article to be washed, etc. Shall be.

In the present specification and claims, “water-insoluble and water-swellable cellulose” is cellulose that has the property of absorbing water and swelling but not dissolving in water, preferably the mass of the cellulose. Including those having a water absorption of 1.5 times or more.
Examples of the component (C) include powdered cellulose (cellulose powder), crystalline cellulose, microcrystalline cellulose, and the like. Among these, powdered cellulose (cellulose powder) is preferable because the effect of improving the water absorption of the article to be washed and the effect of imparting flexibility to the article to be washed are good.
Among powdered cellulose (cellulose powder), those having an average fiber length of 10 to 100 μm are preferable, and those having 10 to 50 μm are more preferable. Moreover, what has an average fiber diameter of 10-50 micrometers is preferable, and what is 10-30 micrometers is more preferable.
Here, “average fiber length and average fiber diameter” are obtained by using powdered cellulose with a digital microscope (product name: VHX-500, manufactured by KEYENCE) and a lens (product name: VH-Z100, manufactured by KEYENCE). When the measurement is performed at a magnification of 800 times, values calculated by regarding 10 pieces of fiber as a cylinder for each sample are shown.

In this invention, (C) component can be used 1 type or in mixture of 2 or more types.
The content of the component (C) is preferably 0.1 to 5% by mass, more preferably 0.1 to 3% by mass in the granular detergent composition of the present invention, and 0.3 to 1 More preferably, it is mass%. When the amount 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. Moreover, the softness | flexibility provision effect to a to-be-washed object improves by being 0.3 mass% or more. On the other hand, if it is below 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.

Specifically, as component (C), BE600 / 10TG (average fiber length: 18 μm, average fiber diameter: 15 μm) of powdered cellulose (cellulose powder) sold under the trade name “ARBOCEL” from Rettenmeier Co., Ltd. ), BE600 / 30 (average fiber length: 30 μm, average fiber diameter: 18 μm), FD600 / 30 (average fiber length: 45 μm, average fiber diameter: 25 μm), CP600 / 30 (average fiber length: 30 μm, average fiber diameter: 20 μm) (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 (or above, trade name) and the like can be granulated and used. For example, ARBOCEL TF30HG White (trade name, Rettenmeyer Co., Ltd.) is a preferred example of the granulated BE600 / 10TG (trade name).

<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 detergent composition for clothing. be able to.
Specifically, for example, surfactants other than the component (A), cleaning builders, oil-absorbing carriers, clay minerals, enzymes, fluorescent whitening agents, antistatic agents, surface modifiers, anti-contamination agents, particle strength Examples include a holding agent, a reducing agent, an antifoaming agent, a fragrance, a pigment, and a flexibility-imparting agent.

(Surfactant)
As surfactants other than the component (A), surfactants (nonionic surfactants, cationic surfactants, amphoteric surfactants) usually used in detergent compositions can be used in combination.
Examples of nonionic surfactants include those shown below.
(1) A polyoxyalkylene alkyl ether obtained by adding an average of 3 to 30 mol, preferably 5 to 20 mol, of an alkylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms 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 alkenyl phenyl ether.
(3) Fatty acid alkyl ester alkoxylates represented by, for example, the following general formula (I) in which alkylene oxide is added between ester bonds of long-chain fatty acid alkyl esters.
R ¹ CO (OA) _{n ′} OR ² (I)
(In the formula, R ¹ CO 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, N ′ represents the average number of moles of alkylene oxide added, and is generally 3 to 30, preferably 5 to 20. R ² represents a substituent having 1 to 3 carbon atoms. (The lower (C1-C4) alkyl group which may have is shown.)
(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 above nonionic surfactants, the nonionic surfactant (1) is preferable, and among these, an average of 5 to 20 moles of alkylene oxide having 2 to 4 carbon atoms was added to an aliphatic alcohol having 12 to 16 carbon atoms. Polyoxyalkylene alkyl ether or polyoxyalkylene alkenyl ether is particularly preferred.
Also, polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene alkenyl ether, polyoxyethylene polyoxypropylene alkenyl ether, fatty acid methyl ester and ethylene having a melting point of 50 ° C. or less and HLB of 9 to 16 A fatty acid methyl ester ethoxylate to which an oxide is added, a fatty acid methyl ester ethoxypropoxylate in which ethylene oxide and propylene oxide are added to a fatty acid methyl ester, and the like are preferably used.
These nonionic surfactants can be used singly or in appropriate combination of two or more.
The above-mentioned “HLB” is a value determined by the Griffin method (Yoshida, Shindo, Ogaki, Yamanaka, edited by “New Edition Surfactant Handbook”, Kogyoshosho, 1991, p. 234) reference).
The “melting point” is a value measured by the melting point measurement method described in JIS K 0064-1992 “Measuring method of melting point and melting range of chemical product”.

Examples of the cationic surfactant include the following.
(1) Dilong chain alkyl dishort 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; a benzyl group; a hydroxyalkyl group having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms; a polyalkyl having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms. Oxyalkylene groups are preferred.

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

(Washing builder)
Examples of cleaning builders include organic builders and inorganic builders.
Examples of the organic builder include nitrilotriacetate (NTA), ethylenediaminetetraacetate (EDTA), ethylenediaminedisuccinate (EDDS), β-alanine diacetate (β-ADAA), aspartate diacetate (ASDA), Aminocarboxylates such as methyl glycine diacetate (MGDA), ethyl glycine diacetate (EGDA), iminodisuccinate (IDS); serine diacetate, hydroxyiminodisuccinate (HIDS), hydroxyethylethylenediaminetriacetic acid Salts, hydroxyaminocarboxylates such as dihydroxyethylglycine salt; hydroxycarboxylates such as hydroxyacetate, tartrate, citrate, gluconate; pyromellitic acid salt, benzopolycarboxylate, cyclopentanetetracarboxylic acid Cycloates such as acid salts Carboxylic acid salt; ether carboxylate such as carboxymethyl tartronate, carboxymethyloxysuccinate, oxydisuccinate, tartaric acid mono- or disuccinate; polyacrylic acid, acrylic acid-allyl alcohol copolymer, water-soluble acrylic acid- Acrylic acid polymers or copolymers such as maleic acid copolymer, hydroxyacrylic acid polymer, polysaccharide-acrylic acid copolymer or salts thereof; maleic acid, itaconic acid, fumaric acid, tetramethylene 1,2- Polymers or copolymers of dicarboxylic acid, succinic acid, aspartic acid and the like or salts thereof; polysaccharide oxides such as starch, cellulose, amylose and pectin; polysaccharides such as carboxymethylcellulose; polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone etc Undissociated polymeric 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, chloride Neutral salts such as sodium and potassium chloride; phosphates such as orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate, phytate; general formula x ¹ (M ₂ O) · Al ₂ O ₂ · y ¹ (SiO ₂ ) · w ¹ (H ₂ O) (wherein M is an alkali metal atom such as sodium or potassium; x ¹ , y ¹ and w ¹ represent the number of moles of each component; In general, x ¹ is a number of 0.7 to 1.5, y ¹ is a number of 0.8 to 6.0, and w ¹ is an arbitrary positive number. Salts; formula _{^{x 2 (M 2 O) ·}} Al 2 O 3 · y 2 (SiO 2) · w 2 (H 2 O) ( alkali metal atom in the formula, M like sodium, ^{potassium; x} 2, y ² and w ² indicate the number of moles of each component, generally x ² is a number from 0.7 to 1.2, y ² is a number from 1.6 to 2.8, and w ² is 0 or arbitrary Amorphous aluminosilicate represented by general formula x ³ (N ₂ O) · Al ₂ O ₃ · y ³ (SiO ₂ ) · z ³ (P ₂ O ₅ ) · w ³ (H ₂ O) (wherein M is an alkali metal atom such as sodium or potassium; x ³ , y ³ , z ³ and w ³ represent the number of moles of each component, generally x ³ is 0.2 the number of to 1.1, ^{y 3} is the number of 0.2 to 4.0, ^{z 3} is 0.001 to 0.8, ^{amorphous w 3} is expressed by.) indicating 0 or any positive number Al Nokei acid salts.
Of these, sodium carbonate, potassium carbonate, calcium carbonate, sodium tripolyphosphate, sodium sulfate, sodium silicate, and sodium aluminosilicate are preferable.

(enzyme)
As the enzyme, for example, protease, lipase, amylase, cellulase and the like can be used.
Specific examples of the protease include savinase, alcalase, evalase, cannase, esperase (trade name; manufactured by Novozymes); API21 (trade name, Showa Denko ( Maxatase, Maxacal, Purefect, Maxapem (above, trade name; manufactured by Genencor); KAP (trade name, manufactured by Kao Corporation), Japanese Patent Laid-Open No. 5- And protease K-14 and K-16 described in Japanese Patent No. 25492.
Specific examples of the lipase 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, Duramil, Steinzyme, 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 ATCC 9621 (above, trade name; crude or crystallized product released from Seikagaku Corporation), and the like.
Specific examples of cellulase include cellzyme, carezyme (trade name; manufactured by Novozymes), KAC500 (trade name, manufactured by Kao Corp.), cellulase according to claim 4 of JP-A 63-264699, and the like. Is mentioned.

  The manufacturing method of the granular detergent composition of this invention is not restrict | limited in particular, It can manufacture with the manufacturing method generally used. Examples of the case where the granular detergent composition is in powder form include, for example, a method of dispersing and dissolving a surfactant and other raw materials in water, spray drying, kneading / extrusion, stirring granulation, rolling It can be manufactured by a method of subjecting it to granulation or the like, subjecting it to kneading, granulation, compression molding or the like, and further pulverizing as necessary.

The average particle diameter of the particles of the granular detergent composition of the present invention is not particularly limited, and is preferably 200 to 1500 μm, more preferably 250 to 1000 μm. When the average particle size is 200 μm or more, dusting is suppressed during use. On the other hand, the solubility to water improves that it is 1500 micrometers or less.
The average particle diameter of such particles indicates a value calculated from the particle size distribution by sieving according to the particle size test described in the Japanese Pharmacopoeia (see JP 2004-331816 A).
Specifically, the granular detergent composition is classified using a 9-stage sieve having openings of 1680 μm, 1410 μm, 1190 μm, 1000 μm, 710 μm, 500 μm, 350 μm, 250 μm, and 149 μm, and a tray. In the classification operation, a sieve with a small opening is stacked in the order of a sieve with a large opening, and a granular detergent composition of 100 g / time is placed on the top of the top 1680 μm sieve, and the lid is covered, and a low-tap type sieve is shaken. Mounted on a machine (made by Iida Seisakusho, tapping: 156 times / minute, rolling: 290 times / minute), vibrated for 10 minutes, and then collected each sieve and the sample remaining on the pan for each sieve. To measure the mass of the sample. Then, when the mass frequency of the tray and each sieve is integrated, the opening of the first sieve where the integrated mass frequency is 50% or more is “a μm”, and the opening of the sieve that is one step larger than a μm is “ bμm ”, the integrated value of the mass frequency from the pan to the aμm sieve is“ c% ”, and the mass frequency on the aμm sieve is“ d% ”, and the average particle size (mass 50%) is The average particle diameter of the particles was determined.

The granular detergent composition of the present invention is excellent in the effect of imparting flexibility to an object to be cleaned, and has an effect that the water absorption of the object to be cleaned is good.
The reason why such an effect can be obtained is estimated as follows.
According to the study by the present inventors, in the conventional detergent composition in which the cationized cellulose (B) is blended in the presence of the anionic surfactant (A), the effect of imparting flexibility to the object to be washed is expressed. It turned out that the malfunction which the water absorption which a to-be-washed object originally has falls arises.
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, flexibility is imparted to the fibers of the article to be washed, and at the same time, the fiber surface is hydrophobized. Therefore, in the conventional detergent composition, it is considered that the water absorption of the article to be washed decreases.
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). The component (C) can be efficiently adsorbed between the fibers of the washing object even in a small amount due to the presence of the component (B), and the component (C) is water-swellable. The water absorption ability is good. Thereby, 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 speculated that the granular detergent composition of the present invention is excellent in the effect of imparting flexibility to the object to be washed and also has the effect that the water absorption of the object to be washed is good.

  Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. “%” Means “% by mass” unless otherwise specified.

(Examples 1-21, Comparative Examples 1-2)
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 compounding quantity in a table | surface shows the mass% on the basis of the total mass of a granular detergent composition. In addition, among the components in the table, surfactant, zeolite and MA agent (metal ion scavenger) indicate the compounding amount in terms of pure component, and others indicate the compounding amount as it is (as it is). “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.

<Description of components shown in the table>.
・ Anionic surfactant (A)
MES1: An aqueous solution of a sodium salt of an 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 (lion ( AI concentration = 70 mass%, balance is unreacted fatty acid methyl ester, sodium sulfate, methyl sulfate, hydrogen peroxide, water, etc.).
Here, “AI” indicates a compound having a function as a surfactant contained in MES. MES usually contains α-sulfo fatty acid dialkali salt as a by-product in addition to α-sulfo fatty acid methyl ester salt. The α-sulfo fatty acid dialkali salt also has a function as a surfactant, like the α-sulfo fatty acid methyl ester salt. Therefore, AI 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 having a mixing ratio of a compound having a hydrocarbon group having 16 carbon atoms and a compound having a hydrocarbon group having 18 carbon atoms in a mass ratio of 80:20 (lion ( AI concentration = 70 mass%, balance is 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., Rypon LH-200 (LAS-H pure content: 96 mass%)] was added at the time of preparation of the surfactant composition. A compound neutralized with a mass% aqueous sodium hydroxide solution. The compounding amounts in Tables 1 and 2 indicate values (mass%) as LAS-Na.
Soap: Fatty acid sodium having 12 to 18 carbon atoms (manufactured by Lion Corporation, pure content: 67% by mass, titer: 40 to 45 ° C .; fatty acid composition: C12 11.7% by mass, C14 0.4% by mass, C16 29 2% by mass, C18F0 (stearic acid) 0.7% by mass, C18F1 (oleic acid) 56.8% by mass, C18F2 (linoleic acid) 1.2% by mass; molecular weight: 289).

・ Cationized cellulose (B)
Cationized cellulose AX: Hydroxyethyl cellulose (manufactured by Sumitomo Seika, trade name: AX-15, 1% by weight aqueous solution viscosity (25 ° C.): 15000-30000 mPa · s) 30 g (100 parts by mass), isopropyl alcohol / water (mass) Ratio) = 85/15 mixed solvent 300 g (1000 parts by mass) and 25 mass% sodium hydroxide aqueous solution 5 g (16.5 parts by mass) were 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.
Thereafter, the temperature is raised to 50 ° C., and 3 g (10 parts by mass) of glycidyltrimethylammonium chloride (manufactured by Sakamoto Pharmaceutical Co., Ltd., trade name: SY-GTA80, effective concentration: 73% by mass aqueous solution) is added as a cationizing agent for 3 hours. Reacted. Thereafter, a 10% by mass isopropyl alcohol hydrochloride solution was added to adjust the pH to 6 to obtain a cationized cellulose slurry.
And it spin-dehydrated and passed through drying (70-80 degreeC), and obtained cationized cellulose AX (weight average molecular weight: 1.6 million, cationization degree: 0.6 mass%, solid content: 91 mass%).

Cationized cellulose LF: hydroxyethyl cellulose (manufactured by Sumitomo Seika, trade name: LF-15, 1% by weight aqueous solution viscosity (25 ° C.): 700 to 1300 mPa · s) 30 g (100 parts by mass), isopropyl alcohol / water (mass) Ratio) = 85/15 mixed solvent 300 g (1000 parts by mass) and 25 mass% sodium hydroxide aqueous solution 4.5 g (15 parts by mass) were 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.
Thereafter, the temperature was raised to 50 ° C., and 4 g (13 parts by mass) of glycidyltrimethylammonium chloride (manufactured by Sakamoto Pharmaceutical Co., Ltd., trade name: SY-GTA80, effective concentration: 73 mass% aqueous solution) was added as a cationizing agent for 3 hours. Reacted. Thereafter, a 10% by mass isopropyl alcohol hydrochloride solution was added to adjust the pH to 6 to obtain a cationized cellulose slurry.
And it spin-dehydrated and passed through drying (70-80 degreeC), and obtained cationized cellulose LF (weight average molecular weight: 900,000, cationization degree: 0.6 mass%, solid content: 91 mass%).

・ Cellulose (C)
Cellulose powder A: ARBOCEL BE600 / 30 (trade name, manufactured by Rettenmeier; average fiber length 30 μm, average fiber diameter 18 μm).
Cellulose powder B: ARBOCEL TF-30HG White (trade name, manufactured by Rettenmeier; granulated cellulose powder A to a particle size of 0.4 to 1.25 mm).
Cellulose powder C: ARBOCEL FD600 / 30 (trade name, manufactured by Rettenmeier; average fiber length 40 μm, average fiber diameter 25 μm).

-Optional component Nonionic surfactant: ECOROL26 (trade name, manufactured by ECOGREN; alcohol having an alkyl group having 12 to 16 carbon atoms) an average of 15 moles of ethylene oxide adduct (pure content: 90% by 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: tripolyphosphate soda (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) (Asahi Glass Co., Ltd .; average particle size 490 μm, bulk density 1.30 g / cm ³ ).
Na carbonate: granular ash (manufactured by Asahi Glass Co., Ltd., average particle size 320 μm, 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) / Chinopearl AMS-GX (trade name, Ciba Specialty Chemicals) = 3/1 (mass ratio) mixture.

Coated Na carbonate particles: prepared in the first to third steps shown below, from 85% by mass of sodium carbonate, 3% by mass of sodium salt of acrylic acid / maleic anhydride copolymer, 7% by mass of lauric acid, water, and the rest Surface-treated inorganic particles.
(First step)
Sodium carbonate was charged into a plow shear mixer (Daihei Kiko Co., Ltd.) equipped with a blade-shaped shovel and a clearance between the shovel and the wall surface of 5 mm (filling rate: 30% by volume), and stirring was started at a main shaft of 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 sodium salt of acrylic acid / maleic anhydride copolymer was sprayed for 180 seconds with a pressure nozzle (flat nozzle) having a spray angle of 115 degrees to perform granulation / coating operation.
In addition, in the particle | grains prepared at the 1st process, when the moisture content with respect to this particle | grain whole quantity exceeds 10 mass%, hot air is introduce | transduced into the said apparatus and it dries, and the moisture content is adjusted to 10 mass% or less. did.
(Second step)
Subsequently, lauric acid was sprayed and added for 180 seconds with a pressure nozzle (full cone nozzle) having a spray angle of 60 degrees, while continuing the stirring of the Proshear mixer. Subsequently, stirring was continued for 30 seconds to obtain particles.
(Third step)
Next, the obtained particles are packed into a fluidized bed (product name: Glatt-POWREX, model number FD-WRT-20, manufactured by Paulex Co., Ltd.), and after filling, 15 ° C. wind (air) is placed in the fluidized bed. The particles were cooled to 20 ° C., and particles were cooled.
The air velocity in the fluidized bed was adjusted in the range of 0.2 to 10.0 m / s while confirming the fluidized state.
The obtained particles were classified using a sieve having an opening of 2000 μm to obtain surface-treated inorganic particles (coated Na carbonate particles) passing through a sieve having an opening of 2000 μm.

Lauric acid: manufactured by NOF Corporation, trade name: NAA-122; melting point 43 ° C.
Perfume: Perfume composition A shown in JP-A-2002-146399 [Table 11] to [Table 18].
Enzyme 1: Sabinase 12T (Novozymes) / LIPEX100T (Novozymes) / Stainzyme 12T (Novozymes) = 5/4 (mass ratio).
Enzyme 2: Deozyme 12T (manufactured by Novozymes)

<Method for producing granular detergent composition>
According to the composition shown in Tables 1-3, surfactant-containing particles are prepared by the preparation method shown below, and the granular detergent composition of each example shown in Tables 1 and 2 using the surfactant-containing particles. Manufactured.

[Examples 1 to 19, Comparative Examples 1 and 2]
(Preparation of surfactant-containing particles)
First, water was put into 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 (for surfactant-containing particles, hereinafter the same)) for addition during kneading, 3.2% by mass equivalent of grinding aid And 1.5 wt% of each surface coating zeolite was removed.), 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 water 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. Particles were obtained.
On the other hand, a part of the nonionic surfactant (25% by mass relative to MES) is added to the aqueous slurry of MES obtained by sulfonating and neutralizing the fatty acid ester of the raw material (water concentration 25% by mass), The mixture was concentrated under reduced pressure with a thin-film dryer until the water content was 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 mass% equivalent amount of zeolite, 0.5 mass% equivalent amount of the remaining nonionic surfactant and water except for spray addition were added to a continuous kneader (Kurimoto Co., Ltd.). (Kakosho, KRC-S4 type) was 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 Paudal Co., Ltd., EXDFJS-100 type) equipped with a die with a hole diameter of 10 mm (cutter peripheral speed was 5 m). / S), a pellet-shaped surfactant-containing molded product having a length of about 5 to 30 mm was obtained.
Next, 3.2% by mass of particulate zeolite (average particle size: 180 μm) as a grinding aid is added to the obtained pellet-shaped surfactant-containing molded product, and coexisting with cold air (10 ° C., 15 m / s) Below, it grind | pulverized using the Fitzmill (Hosokawa Micron Co., Ltd. product, DKA-3) arrange | positioned in series 3 steps (screen hole diameter: 1st stage / 2nd stage / 3rd stage = 12mm / 6mm / 3mm, Number of rotations: 1st stage / 2nd stage / 3rd stage is 4700 rpm) Finally, with a horizontal cylindrical rolling mixer (with a cylinder diameter of 585 mm, a cylinder length of 490 mm, a drum inner wall surface of the container 131.7 L, a clearance between the inner wall surface of 20 mm, and a height of 45 mm baffle plates) Add 1.5% by weight of finely divided zeolite under the conditions of a filling rate of 30% by volume, a rotational speed of 22 rpm, and 25 ° C., and spray for 0.5% by weight of nonionic surfactant and fragrance for 1 minute. And surface modified to prepare surfactant-containing particles.

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

[Example 20]
(Preparation of surfactant-containing particles)
First, water and sodium hydroxide for neutralizing linear alkylbenzene sulfonic acid were added in an equimolar amount with respect 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.
Further, after stirring for 10 minutes, Na carbonate, Na silicate, sodium sulfite and Ca carbonate were added. Furthermore, after stirring for 20 minutes to prepare a slurry for spray drying with a water 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. Particles were obtained.
Surfactant-containing particles were prepared by mixing the spray-dried particles with an A-type zeolite fine powder equivalent to 2.0% by mass as the final composition.

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

[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.
(Production of granular detergent composition)
A granular detergent composition was produced in the same manner as in Example 3 except that cationized cellulose B was not blended.

<Evaluation>
For the obtained granular detergent composition of each example, the softness-imparting effect and water absorption evaluation described below were performed.

[Sample preparation]
(Preprocessing)
A 1 kg polyester jersey (Dyeing Materials Co., Ltd.), a two-tank washing machine (product name: CW-C30A1-H _{1 type} , manufactured by Mitsubishi Electric Corporation), using 50 ° C. tap water, a commercially available detergent The top (manufactured by Lion Co., Ltd.) was washed and dehydrated at the standard usage concentration (detergent top 20g for 30L of tap water, ie, 667ppm) and the bath ratio 30 times. After repeating twice, the rinsing / dehydration operation of “rinsing with running water for 15 minutes and then dewatering for 5 minutes” was repeated 5 times, and then pretreatment was carried out by hanging at room temperature.
1 kg of cotton towel (Toshinsha Co., Ltd., 220cm border soft FT) V. The same pretreatment was applied to 1 kg of D skin shirt (round neck short sleeve T-shirt, product number G0134TS).

(Cleaning process)
Using a fully automatic electric washing machine (product name: JW-Z23A, manufactured by Haier) as a washing machine, using a tap water with a water temperature of 20 ° C. according to the normal course of the fully automatic electric washing machine, one polyester jersey ( 38 g / sheet), 2 cotton towels (71 g / sheet), B. V. D skin shirt 3 sheets (140 g / sheet) (total 600 g) (hereinafter collectively referred to as “fabrics”), bath ratio 20 times (low water level: 12 L) and granular detergent composition of each example The fabric was washed at the concentration of 833 ppm (10 g of granular detergent composition with respect to 12 L of tap water) by treating the cloth in the same bath. Then, it was hung and dried at room temperature.

[Evaluation of the effect of imparting flexibility]
Regarding the softness of the cotton towel, a cotton towel subjected to the washing treatment with the granular detergent composition of each of the above examples, and a standard detergent composition (from the granular detergent composition of Comparative Example 1 to the cation) 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 was performed by 10 professional panelists.
The evaluation is that if there is a clear difference in flexibility between the pair of cotton towels to be compared, give +2 points to the cotton towel with higher flexibility and -2 points to the lower cotton towel; +1 points for the slightly more flexible cotton towel and -1 point for the slightly lesser cotton towel; And the total score of 10 persons was calculated | required and the softness | flexibility provision effect was evaluated based on the following reference | standard. The results are shown in Tables 1 and 2.
(Evaluation criteria)
A: 16-20 points.
A: 11-15 points.
○: 6 to 10 points.
Δ: 1 to 5 points.
X: 0 points or less.

[Evaluation of water absorption]
In accordance with JIS L 1907 (Textile Water Absorption Test Method) 7.1.2 A cotton towel that has been washed with the granular detergent composition of each of the above examples is cut into 200 mm × 15 mm according to the Bilek method, From one end to 5 mm, it was immersed in pure water (20 ° C. ± 2 ° C.) colored with a pigment (trade name: Sumilight Supra Turquoise Blue G, manufactured by Sumitomo Chemical Co., Ltd.). At this time, the height (water absorption length, unit: mm) of rising water for 10 minutes was measured for the cut cotton towel section.
And the average value of this measurement 10 times was calculated | required and the water absorption of the cotton towel was evaluated based on the following reference | standard. 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 90 mm.

As is clear from the results of Tables 1 and 2, the granular detergent compositions of Examples 1 to 18 according to the present invention are excellent in the effect of imparting flexibility to the object to be washed and have good water absorption of the object to be washed. It was confirmed that.
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) can be confirmed to have a low flexibility-imparting effect on the object to be washed. It was.

  ADVANTAGE OF THE INVENTION According to this invention, while being excellent in the softness | flexibility provision effect to to-be-washed | cleaned object, the granular detergent composition with the favorable water absorption of to-be-washed | cleaned object can be provided.

Claims (3)

  A granular detergent composition comprising an anionic surfactant (A), a cationized cellulose (B), and a water-insoluble and water-swellable cellulose (C).   The granular detergent composition according to claim 1, wherein the content of the cationized cellulose (B) is 0.1 to 2% by mass.   The granular detergent composition according to claim 1 or 2, wherein a content of the cellulose (C) is 0.1 to 5% by mass.