JP2008222919A - Granular detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a granular detergent composition excellent in flexibility-imparting effect to an object to be cleaned. <P>SOLUTION: The granular detergent composition comprises (A) an α-sulfoaliphatic acid ester salt, (B) soap and (C) a cationized cellulose, wherein the composition has (A)/(B)=25/75-95/5 of the mass ratio of the component (A) and (B). The composition preferably contains not more than 4 mass% of a linear alkylbenzene sulfonate (D). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a granular detergent composition.

From the viewpoint of saving energy and resources, in recent years, “water-saving washing” in which washing is performed with a small amount of water has become the mainstream. Along with this, the bath ratio (mass ratio of the washing liquid to the washing object) tends to decrease.
Conventionally, when washing is performed under a low bath ratio, there is a problem that the objects to be washed are easily rubbed and entangled during washing, and the objects to be washed are damaged and the texture is deteriorated.
Therefore, there is a demand for a detergent composition capable of imparting a new appearance and soft texture (flexibility) to an object to be washed even in a laundry environment with a low bath ratio.

In the detergent composition, conventionally, various studies for imparting flexibility to an object to be cleaned have been performed simultaneously with the 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).
In addition, a cleaning composition containing a compressed clay component prepared by compressing a clay component such as bentonite or montmorillonite clay has been proposed (see Patent Document 2).
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 3).
Further, a fiber treatment agent composition or a detergent composition containing water-insoluble solid particles has been proposed (see Patent Document 4).
Further, an alkaline detergent composition containing an anionic surfactant and / or nonionic surfactant, a cationic fabric softening compound, a detergent builder, and a fungal cellulase has been proposed (see Patent Document 5).

Furthermore, a detergent composition that imparts flexibility to an object to be washed by using a surfactant mainly composed of an anionic surfactant and cationized cellulose is disclosed.
Specifically, a detergent additive containing a specific cationic activator, carboxymethylcellulose (CMC) and / or polyacrylic acid, and a specific water-soluble cationic nitrogen-containing polymer (cationized cellulose) has been proposed. (See Patent Document 6).
Also, a polymer vesicle obtained by polymerizing a surfactant vesicle having a quaternary ammonium residue as a cation portion and a polymerizable anion as a counter ion, and a cationized polymer such as cationized cellulose A laundry softener composition is proposed (see Patent Document 7).

A laundry detergent composition containing a detergent surfactant, an organic or inorganic detergency builder, and a treatment agent for a modified cellulose ether fabric such as cationized cellulose that exhibits a fuzz prevention effect has been proposed (patent) Reference 8).
JP-A-1-98697 JP 2002-543270 A JP 2002-194391 A JP 2003-64574 A JP-A 61-64797 JP 54-142209 A Japanese Patent Laid-Open No. 2-113095 JP-T-2001-507396

However, the compositions described in Patent Documents 1 to 5 are still not fully satisfactory in the effect of imparting flexibility to the object to be washed.
Moreover, in the detergent composition of patent documents 6-8, although cationized cellulose is mix | blended as one of the components for giving a softness | flexibility to a to-be-washed object, in the washing environment of a low bath ratio. Further, the effect of imparting flexibility to the object to be washed is not sufficient.
Therefore, there is a demand for a detergent composition that exhibits a high flexibility-imparting effect on an object to be washed even in a laundry environment having a low bath ratio in recent years.
This invention is made | formed in view of the said situation, and makes it a subject to provide the granular detergent composition excellent in the softness | flexibility provision effect to to-be-washed | cleaned material.

As a result of intensive studies, the present inventors have found that a detergent composition containing cationized cellulose has the effect of imparting flexibility to an object to be washed by adding two specific surfactants at a specific ratio. It has been found that it is significantly improved and the present invention has been completed.
That is, the granular detergent composition of the present invention contains α-sulfo fatty acid ester salt (A), soap (B), and cationized cellulose (C), and the component (A) and the component (B). The mass ratio is (A) / (B) = 25/75 to 95/5.
In the granular detergent composition of the present invention, it is preferable that 4% by mass or less of linear alkylbenzene sulfonate (D) is contained.

  ADVANTAGE OF THE INVENTION According to this invention, the granular detergent composition excellent in the softness | flexibility provision effect to to-be-washed object can be provided.

≪Granular detergent composition≫
The granular detergent composition of the present invention comprises an α-sulfo fatty acid ester salt (A) (hereinafter referred to as component (A)), soap (B) (hereinafter referred to as component (B)), and cationized cellulose (hereinafter referred to as component (B)). C) (hereinafter referred to as component (C)).

<(A) component>
In the present invention, the component (A) is an α-sulfo fatty acid ester salt. By containing the component (A), a cleaning effect can be obtained. Moreover, the softness | flexibility provision effect to a to-be-washed object improves by combined use with (B) component.

 (A) The thing suitable as a component is illustrated below.

［式中、Ｒ^１１は炭素数８〜２０の直鎖もしくは分岐鎖状のアルキル基またはアルケニル基であり、Ｒ^１２は炭素数１〜６のアルキル基である。Ｍは対イオンを表す。］

[Wherein, R ¹¹ is a linear or branched alkyl group or alkenyl group having 8 to 20 carbon atoms, and R ¹² is an alkyl group having 1 to 6 carbon atoms. M represents a counter ion. ]

In the formula (A-1), R ¹¹ is a linear or branched alkyl group having 8 to 20 carbon atoms, or a linear or branched alkenyl group having 8 to 20 carbon atoms.
In R ¹¹ , the alkyl group or alkenyl group has 8 to 20 carbon atoms, preferably 12 to 18 carbon atoms.
R ¹² is an alkyl group having 1 to 6 carbon atoms, and may be linear or branched. In R ¹² , the number of carbon atoms is 1 to 6, and preferably 1 to 3. Specific examples include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Since the detergency is further improved, a methyl group, an ethyl group, and a propyl group are more preferable, and a methyl group is particularly preferable.
M represents a counter ion and includes, for example, alkali metal salts such as sodium and potassium; amine salts such as monoethanolamine, diethanolamine and triethanolamine; ammonium salts, among which alkali metal salts are preferred.

  In this invention, (A) component can be used 1 type or in mixture of 2 or more types.

<(B) component>
In the present invention, the component (B) is soap. By containing the component (B), a cleaning effect can be obtained. Moreover, the softness | flexibility provision effect to a to-be-washed object improves by combined use with (A) component.
(B) As a component, a C10-C20 thing is preferable and a C12-C18 thing is more preferable.
Further, it may be a saturated fatty acid salt, an unsaturated fatty acid salt, or a mixture of a saturated fatty acid salt and an unsaturated fatty acid salt.
The carbon chain in component (B) may be linear or branched, and is preferably linear. Component (B) may be a single carbon chain or a mixture of different carbon chains.
Examples of the salt include alkali metal salts and alkaline earth metal salts, alkali metal salts are preferable, and sodium salts and potassium salts are more preferable.

  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 mass ratio of the component (A) to the component (B) is (A) / (B) = 25/75 to 95/5, and 25/75 to 90/10. Preferably, it is 55/45 to 85/15, more preferably 65/35 to 80/20. When (A) / (B) is in the above range, the granular detergent composition of the present invention is excellent in the effect of imparting flexibility to the article to be washed.

  The total content of the component (A) and the component (B) is preferably 6 to 25% by mass and more preferably 10 to 20% by mass in the granular detergent composition. When it is at least the lower limit of the content, the detergency and the effect of imparting flexibility to the article to be washed are improved. If it is below the upper limit of the content, a sufficient cleaning effect can be obtained.

<(C) component>
In the present invention, the component (C) is cationized cellulose. By containing this (C) component, the softness | flexibility provision effect to a to-be-washed object is acquired.

The weight average molecular weight of the component (C) is preferably 100,000 to 2,000,000, 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 (C) component itself will become more favorable.
In addition, the weight average molecular weight of (C) component shows the value which analyzed by gel permeation chromatography (GPC) by making a standard substance into polyethyleneglycol (PEG).

The degree of cationization of the component (C) is preferably 0.4 to 1.2% by mass, and more preferably 0.4 to 0.8% by mass. By being this range, the softness | flexibility provision effect to a to-be-washed object further improves.
However, “degree of cationization” means the content (mass%) of nitrogen in the cationized cellulose molecule, and indicates the ratio of nitrogen atoms per glucose ring unit. The nitrogen atom is derived from a cationizing agent.
The degree of cationization means that the larger the value, the stronger the cationicity of the component (C) 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. When the degree of cationization is 0.4% by mass or more, the (C) component has a moderately strong cationic property, and the adsorptivity to the object to be washed becomes better. It is thought that the effect by making it contain is acquired. On the other hand, if it is 1.2% by mass or less, the cationic strength is moderately suppressed, the water solubility does not become too high, and the adsorptivity to the washing object is kept good. It is thought that the effect by containing is acquired.

  The component (C) can be produced, for example, by reacting hydroxyethyl cellulose obtained by adding ethylene oxide to cellulose and glycidyltrimethylammonium chloride as a cationizing agent.

  As a suitable component (C), a polymer compound having a repeating unit represented by the following general formula (C-1), that is, (halogen) -O- [2-hydroxy-3- (trimethylammonio) ) Propyl] hydroxyethylcellulose.

［式（Ｃ−１）中、Ｒ^３〜Ｒ^５は、それぞれ独立して水素原子または下記式（Ｃ−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。］

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

［式（Ｃ−１−１）中、Ｘはハロゲン原子を示す。］

[In the formula (C-1-1), X represents a halogen atom. ]

  In said formula (C-1-1), X shows a halogen atom, a chlorine atom, a bromine atom, a fluorine atom, an iodine atom, etc. are mentioned, A chlorine atom is preferable.

In the polymer compound represented by the formula (C-1), the degree of ethylene oxide (EO) substitution per glucose ring unit is preferably 0.3 to 3.0, and preferably 0.7 to 2.5. More preferably it is.
However, “degree of EO substitution” indicates the average number of hydroxyl groups substituted with EO per glucose ring unit of the cellulose raw material (how many OH groups are added to the three hydroxyl groups of the glucose ring). , A maximum of 3.)

  In the polymer compound represented by the formula (C-1), the average added mole number of EO per glucose ring unit is preferably 1 + m + n = 1 to 5, and in particular, the improvement of detergency, re-contamination (dirt contamination) The lower limit value is preferably 1 or more, and the upper limit value is more preferably 3 or less because the effect of suppressing (reattachment) is good.

Specific examples of the component (C) include Leogard GPS (cationization degree 1.8% by mass), Leogard GP (cationization degree 1.8% by mass), Leogard GP0 (cationization degree 1.8% by mass), and Leoguard. LP (cationization degree 1.0% by mass), Leogard KGP (cationization degree 1.8% by mass), Leoguard MGP (cationization degree 1.8% by mass), Leoguard MLP (cationization degree 0.6% by mass) [Above, product name; manufactured by Lion Chemical Co., Ltd.]; Katchinal HC-100 (cationization degree 1.0 to 2.0 mass%), Katchinal HC-200 (cationization degree 1.0 to 2.0 mass%), Katchinal LC-100 (cationization degree 0.5-1.5 mass%), kachinal LC-200 (cationization degree 0.5-1.5 mass%) [above, trade name: manufactured by Toho Chemical Industry Co., Ltd.]; UCARE P Commercial products such as oligomer LR400 (cationization degree 0.8 to 1.1% by mass), UCARE Polymer LR30M (cationization degree 0.8 to 1.1% by mass) [above, trade name: manufactured by Dow Chemical Co., Ltd.] Are mentioned as preferred.
In addition, the difference in the grade in the said commercially available thing is because the molecular weight of a cellulose, the average addition mole number of EO, a cationization degree, etc. differ.

In this invention, (C) component can be used 1 type or in mixture of 2 or more types.
The content of the component (C) in the granular detergent composition is preferably 0.1 to 3% by mass, and more preferably 0.3 to 1.5% by mass. By being above the lower limit of the content, the effect of imparting flexibility to the object to be washed is improved. On the other hand, if it is less than or equal to the upper limit value, a sufficient flexibility imparting effect to the washing object can be obtained.

  In the granular detergent composition of the present invention, the mass ratio of the total amount of the anionic surfactant to be blended and the component (C) is preferably (anionic surfactant) / (C) = 10 to 70. More preferably, it is -50, More preferably, it is 15-40. By being below the upper limit of the mass ratio, the effect of imparting flexibility to the object to be washed can be obtained satisfactorily. On the other hand, by being more than the lower limit of the mass ratio, the adhesion of white powder (powder derived from the granular detergent composition) to the washed article after washing is suppressed.

<(D) component>
In the present invention, the component (D) is a linear alkylbenzene sulfonate. When the component (D) is contained, the detergency is improved and the particles of the granular detergent composition are hardly broken and the particle shape is easily maintained. As the component (D), an alkyl group having 8 to 18 carbon atoms is preferable, and an alkyl group having 10 to 16 carbon atoms is more preferable.
Examples of the salt include alkali metal salts such as sodium and potassium; amine salts such as monoethanolamine, diethanolamine and triethanolamine; ammonium salts and the like, among which alkali metal salts are preferable.

In this invention, (D) component can be used 1 type or in mixture of 2 or more types.
As an example, a linear alkylbenzenesulfonic acid sodium salt and a linear alkylbenzenesulfonic acid potassium salt may be mixed and used.
In the granular detergent composition of the present invention, it is preferable that 4% by mass or less of linear alkylbenzene sulfonate (D) is contained. The content of the component (D) in the granular detergent composition is preferably 4% by mass or less, and more preferably 3% by mass or less. When the content is 4% by mass or less, the effect of imparting flexibility to the article to be washed is further enhanced.

<Other ingredients>
In the granular detergent composition of the present invention, in addition to the components (A) to (D), components such as a detergent component usually used in a cleaning composition for clothing and the like are appropriately blended as necessary. Can do.
Specifically, surfactants other than (A) component, (B) component and (D) component, detergency builder, fluorescent whitening agent, enzyme, enzyme stabilizer, polymers, anti-caking agent, antifoaming agent , Reducing agents, metal ion scavengers, pH adjusters, fragrances, dyes and the like.

(Surfactant)
As surfactants other than the component (A), the component (B) and the component (D), surfactants usually used in cleaning compositions (nonionic surfactants, anionic surfactants, cationic surfactants, Amphoteric surfactants) can be used in combination.

Nonionic surfactant:
Examples of nonionic surfactants include those shown below.
(1) Polyoxyalkylene alkyl ether or polyoxy obtained by adding an average of 3 to 30 moles, preferably 3 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 18 carbon atoms An alkylene 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).
[Wherein 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, Propylene oxide or the like) is an addition unit (oxyalkylene group); n ′ is the average number of moles of alkylene oxide added, and is generally 3 to 30, preferably 5 to 20. R ² represents a lower (1 to 4 carbon) alkyl group which may have a substituent having 1 to 3 carbon atoms. ]
(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”.

Anionic surfactant:
Examples of the anionic surfactant include those shown below.
(1) A branched alkylbenzene sulfonate (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 having 10 to 20 carbon atoms Alkenyl ether sulfate (AES) having a chain alkenyl group; however, the alkylene oxide is preferably any of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide (EO) and propylene oxide (PO). (Mole ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1).
(6) Alkyl phenyl ether sulfate having a linear or branched alkyl group having 10 to 20 carbon atoms, or an average 3 to 30 moles of alkylene oxide added, or a linear or branched chain having 10 to 20 carbon atoms An alkenylphenyl ether sulfate having a alkenyl group in the form of 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 in molar ratio). PO = 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, an average of 0.5 to 10 moles of alkylene oxide added, or a linear or branched chain having 10 to 20 carbon atoms Alkenyl ether carboxylate having a branched alkenyl group; however, the alkylene oxide is preferably any of alkylene oxides 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) Long chain monoalkyl phosphate, long chain dialkyl phosphate or long chain sesquialkyl phosphate.
(10) Polyoxyethylene monoalkyl phosphate, polyoxyethylene dialkyl phosphate or polyoxyethylene sesquialkyl phosphate.
The component (A) can be used as alkali metal salts such as sodium and potassium; amine salts such as monoethanolamine, diethanolamine and triethanolamine; ammonium salts and the like. Of these, alkali metal salts are preferred.
These anionic surfactants can be used singly or in appropriate combination of two or more.

Cationic surfactant:
Examples of the cationic surfactant include those shown below.
(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.

Amphoteric surfactant:
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.

(Detergency builder)
Detergency builders include inorganic builders and organic builders.

Examples of inorganic builders include alkali metal carbonates such as sodium carbonate, potassium carbonate, sodium bicarbonate, and sesquicarbonate; alkali metal sulfites such as sodium sulfite and potassium sulfite; crystalline layered sodium silicate [eg, manufactured by Clariant Japan Ltd. Crystalline alkali metal silicates such as “Na-SKS-6” (δ-Na ₂ O · 2SiO ₂ )], amorphous alkali metal silicates; sulfates such as sodium sulfate and potassium sulfate; sodium chloride Alkali metal chlorides such as potassium chloride; phosphates such as orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate, phytate; crystalline aluminosilicate, amorphous aluminosilicate , Sodium carbonate and amorphous alkali metal silicate complex (e.g., Rho ia under the trade name "NABION15"), and the like.
Among the inorganic builders, sodium carbonate, aluminosilicate, or potassium salts (potassium carbonate, potassium sulfate, etc.) or alkali metal chlorides (potassium chloride, sodium chloride, etc.) are preferred as those having the effect of improving solubility.

As the aluminosilicate, either crystalline or amorphous (amorphous) can be used, and crystalline aluminosilicate is preferable from the viewpoint of cation exchange ability.
As the crystalline aluminosilicate, A-type, X-type, Y-type, P-type zeolite and the like can be suitably blended, and the average primary particle size is preferably 0.1 to 10 μm. The content of the crystalline aluminosilicate in the granular detergent composition is preferably 1 to 40% by mass, particularly preferably 2 to 30% by mass from the viewpoint of powder physical properties such as cleaning performance and fluidity.
When mix | blending potassium carbonate, the content is from a point of the effect of a solubility improvement, Preferably it is 1-15 mass% in a granular detergent composition, More preferably, it is 2-12 mass%, More preferably, it is 5-5. 12% by mass.
When blending an alkali metal chloride, the content thereof is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, and still more preferably, in the granular detergent composition in terms of the effect of improving solubility. It is 3-7 mass%.
When blending the crystalline alkali metal silicate, the content thereof is preferably 0.5 to 40% by mass, more preferably 1 to 25% by mass, and further preferably from the viewpoint of cleaning performance in the granular detergent composition. Is 3 to 20% by weight, particularly preferably 5 to 15% by weight.

Examples of the organic builder include aminocarboxylates such as nitrilotriacetate, ethylenediaminetetraacetate, β-alanine diacetate, aspartate diacetate, methylglycine diacetate, and iminodisuccinate; serine diacetate, hydroxyiminodia Hydroxyaminocarboxylates such as succinate, hydroxyethylethylenediamine triacetate, dihydroxyethylglycine; Hydroxycarboxylates such as hydroxyacetate, tartrate, citrate, gluconate; pyromellitic acid salt, benzoate Cyclocarboxylates such as polycarboxylates, cyclopentanetetracarboxylates; ether carboxylates such as carboxymethyltaltronate, carboxymethyloxysuccinate, oxydisuccinate, tartaric acid mono- or disuccinate; Salt of acrylic acid-allyl alcohol copolymer, salt of acrylic acid-maleic acid copolymer, salt of polyacetal carboxylic acid such as polyglyoxylic acid; hydroxyacrylic acid polymer, polysaccharide-acrylic acid copolymer Salt of acrylic acid polymer or copolymer such as polymer; salt of polymer or copolymer such as maleic acid, itaconic acid, fumaric acid, tetramethylene 1,2-dicarboxylic acid, succinic acid, aspartic acid; starch, Examples thereof include polysaccharide oxides such as cellulose, amylose and pectin, and polysaccharide derivatives such as carboxymethylcellulose.
Among the organic builders, citrate, aminocarboxylate, hydroxyaminocarboxylate, polyacrylate, salt of acrylic acid-maleic acid copolymer, and salt of polyacetal carboxylic acid are preferable. In particular, hydroxyiminodisuccinate, salt of acrylic acid-maleic acid copolymer having a weight average molecular weight of 1000 to 80000, polyacrylate, polyglyoxyl having a weight average molecular weight of 800 to 1000000 (preferably 5000 to 200000) Polyacetal carboxylates such as acids (for example, those described in JP-A-54-52196) are preferred.
As for content of an organic builder, 1-20 mass% is preferable in a granular detergent composition, More preferably, it is 1-10 mass%, Most preferably, it is 2-5 mass%.

The said detergency builder can be used individually by 1 type or in combination of 2 or more types as appropriate.
Among the above detergency builders, the detergency and stain dispersibility in the washing liquid are improved, so that citrate, aminocarboxylate, hydroxyaminocarboxylate, polyacrylate, acrylic acid-maleic acid It is preferable to use an organic builder such as a polymer salt or a polyacetal carboxylic acid salt in combination with an inorganic builder such as zeolite.
The content of the detergency builder in the granular detergent composition is preferably 10 to 80% by mass and more preferably 20 to 75% by mass from the viewpoint of imparting sufficient cleaning performance.

(Fluorescent brightener)
Examples of the optical brightener include 4,4′-bis- (2-sulfostyryl) -biphenyl salt, 4,4′-bis- (4-chloro-3-sulfostyryl) -biphenyl salt, and 2- (styryl). Phenyl) naphthothiazole derivatives, 4,4′-bis (triazol-2-yl) stilbene derivatives, bis- (triazinylaminostilbene) disulfonic acid derivatives, and the like.
The above-mentioned optical brighteners can be used alone or in combination of two or more.
The content of the fluorescent brightening agent in the granular detergent composition is preferably 0.001 to 1% by mass.
Specific examples of commercially available products include Whiteex SA, Whitex SKC (trade name; manufactured by Sumitomo Chemical Co., Ltd.); Chino Pearl AMS-GX, Chino Pearl DBS-X, Chino Pearl CBS-X (above, trade name; Ciba). -Specialty Chemicals); Lemonite CBUS-3B (above, trade name: manufactured by Khyati Chemicals) and the like are preferable. Of these, Tinopearl CBS-X and Tinopearl AMS-GX are more preferable.

(enzyme)
Enzymes are classified according to the reactivity of the enzyme, and include hydrolases, oxidoreductases, lyases, transferases, and isomerases, and any of them can be applied in the present invention.
Of these, protease, esterase, lipase, nuclease, cellulase, amylase, pectinase and the like are preferable.

Specific examples of the protease include pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, sptilisin, papain, promeline, carboxypeptidase A or B, aminopeptidase, aspergillopeptidase A or B, and the like.
As commercial products, sabinase, alcalase, cannase, everase, deozyme (above, trade name: manufactured by Novozymes); API21 (trade name, manufactured by Showa Denko KK); Maxacar, Maxapem (above, trade name: manufactured by Genencor) ); Protease K-14 or K-16 (protease described in JP-A-5-25492) and the like.

Specific examples of the esterase include gastric lipase, buncreatic lipase, plant lipase, phospholipase, cholinesterase, phosphotase and the like.
Specific examples of the lipase include commercially available lipases such as lipolase, Lipex (trade name; manufactured by Novozymes), and liposum (trade name, manufactured by Showa Denko KK).
Examples of cellulases include commercially available cellzymes (trade names, manufactured by Novozymes); alkaline cellulase K, alkaline cellulase K-344, alkaline cellulase K-534, alkaline cellulase K-539, alkaline cellulase K-577, alkaline cellulase K- 425, alkaline cellulase K-521, alkaline cellulase K-580, alkaline cellulase K-588, alkaline cellulase K-597, alkaline cellulase K-522, CMCase I, CMCase II, alkaline cellulase E-II, and alkaline cellulase E -III (cellulase described in JP-A-63-264699) and the like.
Examples of amylase include commercially available Termamyl and Duramil (manufactured by Novozymes).

The said enzyme can be used individually by 1 type or in combination of 2 or more types as appropriate.
In addition, it is preferable to use the enzyme granulated as separate stable particles in a state of being dry blended with detergent dough (particles).

(Enzyme stabilizer)
As the enzyme stabilizer, for example, calcium salt, magnesium salt, polyol, formic acid, boron compound and the like can be blended. Of these, sodium tetraborate, calcium chloride and the like are preferable.
An enzyme stabilizer can be used individually by 1 type or in combination of 2 or more types as appropriate.
As for content of the enzyme stabilizer in a granular detergent composition, 0.05-2 mass% is preferable.

(Polymers)
In the granular detergent composition of the present invention, as a binder or a powder physical property modifier used when densifying the granular detergent composition particles, or for imparting a recontamination preventing effect on hydrophobic fine particles (dirt). , Blending polyethylene glycol having an average molecular weight of 200 to 200,000, a salt of acrylic acid and / or maleic acid polymer having a weight average molecular weight of 1,000 to 100,000, a cellulose derivative such as polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl methyl cellulose (HPMC), etc. Can do.
In addition, a copolymer of a repeating unit derived from terephthalic acid and a repeating unit derived from ethylene glycol and / or propylene glycol, a terpolymer, or the like can be blended as a soil release agent.
Further, polyvinyl pyrrolidone or the like can be blended in order to impart an effect of preventing color transfer.
Among the above polymers, HPMC is preferable and HPMC having a weight average molecular weight of 20,000 or more is more preferable from the viewpoint of imparting flexibility to an object to be washed and preventing recontamination.
Such polymers can be used singly or in appropriate combination of two or more.
As for content of the said polymers in a granular detergent composition, 0.05-5 mass% is preferable.

(Anti-caking agent)
As the anti-caking agent, paratoluenesulfonate, xylenesulfonate, acetate, sulfosuccinate, talc, fine powder silica, clay, magnesium oxide and the like can be blended.

(Defoamer)
Examples of the antifoaming agent include conventionally known ones such as silicone / silica-based ones. Moreover, you may use this antifoamer as an antifoamer granulated material obtained by the following manufacturing method.
[Method for producing antifoam granulated product]
First, 100 g of maltodextrin (trade name, manufactured by Nissho Chemical Co., Ltd .; enzyme-modified dextrin) is added with 20 g of silicone (compound type, product name: PS Antifoam, manufactured by Dow Corning) as an antifoam component and mixed. To obtain a homogeneous mixture. Next, after mixing 50 mass% of the obtained homogeneous mixture, polyethylene glycol (PEG-6000, melting point 58 ° C.) 25 mass%, and neutral anhydrous sodium sulfate 25 mass% at 70-80 ° C., an extrusion granulator ( Granulate by model EXKS-1, manufactured by Fuji Paudal Co., Ltd. to obtain a defoamer granulated product (see JP-A-3-186307).

(Reducing agent)
Examples of the reducing agent include sodium sulfite and potassium sulfite.

(Metal ion scavenger)
The metal ion scavenger captures trace metal ions and the like in tap water and has an effect of suppressing the adsorption of metal ions to the fiber (object to be washed).
As metal ion scavengers, in addition to those included in the detergency builder, aminopolyacetic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, glycolethylenediaminehexaacetic acid; 1-hydroxyethane-1,1-diphosphonic acid (HEDP) -H), ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, hydroxyethane-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic Acid, hydroxymethanephosphonic acid, ethylenediaminetetra (methylenephosphonic acid), nitrilotri (methylenephosphonic acid), 2-hydroxyethyliminodi (methylenephosphonic acid), hexamethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) ) Organic phosphonic acid Conductor or a salt thereof; diglycolic acid, citric acid, tartaric acid, oxalic acid, organic acids or salts thereof such as gluconic acid and the like.
The said metal ion trapping agent can be used individually by 1 type or in combination of 2 or more types as appropriate.
The content of the metal ion scavenger in the granular detergent composition is preferably 0.1 to 5% by mass, more preferably 0.5 to 3% by mass. If it is 0.1 mass% or more, the effect which capture | acquires the metal ion in tap water will improve. On the other hand, if it is 5 mass% or less, the effect of capturing metal ions is sufficiently obtained.

(PH adjuster)
The pH of the granular detergent composition of the present invention is not particularly limited, but from the viewpoint of cleaning performance, the pH in a 1% by mass aqueous solution of the granular detergent composition is preferably 8 or more, and the 1 mass It is more preferable that pH in a 9% aqueous solution is 9-11. When the pH is 8 or more, the cleaning effect is easily exhibited.
As a technique for controlling the pH of the granular detergent composition, the pH is usually adjusted with an alkaline agent. In addition to the alkaline agent described in the detergency builder, monoethanolamine, diethanolamine, triethanolamine, etc. Examples include alkanolamine, sodium hydroxide, potassium hydroxide and the like.
Specifically, for example, from the viewpoint of solubility in water and alkalinity, NABION15 (trade name, Rhodia Co., Ltd.), which is a mixture of sodium carbonate, sodium silicate, and water at a ratio of 55/29/16 (mass ratio). Are preferably used.
Moreover, in order to prevent that the pH of a granular detergent composition becomes high too much, it can also adjust to the said pH range using an acid etc.
Examples of the acid include the metal ion scavenger, alkali metal dihydrogen phosphates such as potassium dihydrogen phosphate, lactic acid, succinic acid, malic acid, gluconic acid, or polycarboxylic acids thereof, citric acid, sodium hydrogen carbonate. , Sulfuric acid, hydrochloric acid and the like can be used.
Further, it is possible to use a buffering agent for preventing a decrease in pH due to an acid component derived from fiber dirt during washing.
The said pH adjuster can be used individually by 1 type or in combination of 2 or more types as appropriate.

(Fragrance)
The fragrance | flavor in this invention is a mixture (fragrance | flavor composition) which consists of a fragrance | flavor component, a solvent, a fragrance | flavor stabilizer, etc.
As such a fragrance, for example, those described in JP-A Nos. 2002-146399 and 2003-89800 can be used.
0.001-2 mass% is preferable and, as for content of the fragrance | flavor in a granular detergent composition, 0.01-1 mass% is more preferable.

(Dye)
In the present invention, various dyes such as dyes and pigments can be used to improve the appearance of the granular detergent composition. Of these, pigments are preferable from the viewpoint of storage stability, and those having oxidation resistance are particularly preferable.
Examples of such a dye include oxides, and preferable examples include titanium oxide, iron oxide, copper phthalocyanine, cobalt phthalocyanine, ultramarine blue, bitumen, cyanine blue, and cyanine green.

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. For example, the surfactant and other raw materials are dispersed / dissolved in water and spray-dried, and are used for kneading / extrusion, stirring granulation, tumbling granulation, etc. Etc., and can be produced by a method such as pulverization if necessary.
The blending method of the component (C) is not particularly limited, and is a method of premixing when preparing a slurry for spray drying together with an alkali agent or a detergency builder. And a method in which the component (C) is post-mixed (mixed with surfactant-containing particles and the like) in the form of powder.

The form of the granular detergent composition of the present invention is a solid such as a powder or granule, more preferably a powder.
The bulk density of the granular detergent composition is preferably 0.3 g / mL or more, more preferably 0.5 to 1.2 g / mL, and still more preferably 0.6 to 1.1 g / mL. When the bulk density is 0.3 g / mL or more, the space (storage location) required for storing the granular detergent composition can be reduced, which is advantageous. On the other hand, when it is 1.2 g / mL or less, the solubility of the granular detergent composition in water becomes good even after long-term storage.
In addition, the said bulk density shows the value measured according to JISK3362-1998.

  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, the lower limit is more preferably 250 μm or more, further preferably 280 μm or more, and 300 μm or more. Particularly preferred. The upper limit is more preferably 1000 μm or less, and even more preferably 700 μm or less. When the average particle diameter is 200 μm or more, generation of dust is difficult to occur, and dusting is suppressed during use. On the other hand, the solubility to water improves that it is 1500 micrometers or less.

The average particle size of the particles of the granular detergent composition is classified into the following classification operations 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. The value obtained by performing is shown.
In this classification operation, a sieve with a small mesh size is stacked on a tray in the order of a sieve with a large mesh size, and a granular detergent composition of 100 g / times is placed on the top of the top 1680 μm sieve, and the lid is covered and a low-tap type sieve. Mounted on a shaker (manufactured by Iida Seisakusho Co., Ltd., tapping: 156 times / minute, rolling: 290 times / minute), vibrated for 10 minutes, and then collected each sieve and the sample remaining on the tray for each sieve. Thus, the mass of the sample is measured.
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 diameter (mass 50%) is The average particle size of the granular detergent composition was determined.

The fluidity of the granular detergent composition is preferably 60 ° or less, more preferably 50 ° or less as an angle of repose.
In addition, the fluidity of the granular detergent composition after storage (when stored for a long time in a paper container or a highly permeable container such as a refillable pouch) is preferably 60 ° or less as the angle of repose. More preferably, it is not more than 0 °.
When the angle of repose is 60 ° or less, the handleability of the granular detergent composition particles tends to be good. In addition, the case after storage is preferable because the granular detergent composition can be easily taken out from the container and the usability is good.
The angle of repose can be measured by a repose angle measurement method based on a so-called discharge method in which an angle formed between a slip surface formed when granular detergent composition particles filled in a container flow out and a horizontal plane is measured. Specifically, the value measured using a turntable type angle of repose measuring instrument (manufactured by Tsutsui Rika Kikai Co., Ltd.) is shown.

  As the container in the commercial product obtained by filling the granular detergent composition of the present invention into a container, it can be selected in consideration of ease of use, stability, etc., and in particular, a container that is less affected by humidity and light. It is preferable to select.

The method of using the granular detergent composition of the present invention is not particularly limited, and the article to be washed is washed by putting it in a washing machine so that the solution is preferably 0.02 to 0.5% by mass. Method: A method of immersing the article to be washed in a 0.02 to 2% by mass solution is preferable. In particular, it can be suitably used for a method of putting in a washing machine and washing for 5 to 20 minutes.
The items to be washed by the granular detergent composition of the present invention are not particularly limited, and normal detergent compositions such as clothes, cloths, sheets, curtains and other textiles are to be washed. The same thing as a to-be-washed object is mentioned.

The granular detergent composition of the present invention has an effect of being excellent in the effect of imparting flexibility to an object to be washed. The reason why such an effect can be obtained is estimated as follows.
In the detergent composition containing an anionic surfactant and cationized cellulose (C), when the detergent composition is dissolved in water, the anionic surfactant and the component (C) form a complex, By adsorbing the composite to the object to be cleaned, flexibility is imparted to the fibers of the object to be cleaned.
The present inventors have found that when the component constituting the complex and the mixing ratio of the component are changed, the expression of the effect of imparting flexibility to the object to be washed changes greatly.
In the present invention, α-sulfo fatty acid ester salt (A) and soap (B) are used as anionic surfactants, and (A) component and (B) component are used in combination at a specific mass ratio, so that (A ) Since the adsorptivity of the complex composed of the component (B) and the component (C) to the object to be washed is remarkably increased, or the structure of the adsorbing film more suitable for the expression of flexibility is obtained. It is presumed that the effect of imparting flexibility to the object to be washed is significantly improved.

Further, in the granular detergent composition of the present invention, when 4% by mass or less of the linear alkylbenzene sulfonate (D) is contained, the detergency is improved and detergent particles that are not easily broken are easily formed. The effect is obtained.
Moreover, in the granular detergent composition of this invention, the softness | flexibility provision effect to a to-be-washed object will further increase if content of (D) component shall be 4 mass% or less. The reason why such an effect can be obtained is assumed as follows. When the content of the component (D) in the composite is 4% by mass or less, a composite having good adsorptivity to the object to be washed is formed, or a more suitable adsorbent film for expressing flexibility. Since the structure is obtained, it is presumed that the effect of imparting flexibility to the object to be washed is further enhanced.

Moreover, according to the granular detergent composition of this invention, the high softness | flexibility provision effect to to-be-washed | cleaned material is acquired, without using another softness | flexibility provision component together.
Moreover, the granular detergent composition of the present invention is suitable as a detergent composition used for washing in a laundry environment having a low bath ratio.

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

(Examples 1-14, Comparative Examples 1-3)
The granular detergent composition of each example shown in Table 1 was manufactured using the components shown in Table 1 and the common components shown in Table 2.
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, anionic surfactants, nonionic surfactants, zeolites and MA agents are blended amounts in terms of pure components, and the others are blended amounts as they are (as they are). “Balance” of the amount of sodium carbonate means that the total amount is adjusted to 100% by mass.
(A) / (B) (mass ratio) shows the value which represented the compounding ratio of (A) component and (B) component by mass ratio.
"Comparative example 1" is an example in which the component (A) is not blended and contains the component (B) and the component (C), and is a comparative control in the evaluation of the effect of imparting flexibility to the object to be washed.
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)
(A-1) MES: Sodium salt of 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 solution (manufactured by Lion Co., Ltd .; AI concentration = 70 mass%, the 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.

(A-2) MES: Sodium salt 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 Aqueous solution (manufactured by Lion Co., Ltd .; AI concentration = 70 mass%, the balance being unreacted fatty acid methyl ester, sodium sulfate, methyl sulfate, hydrogen peroxide, water, etc.).
“AI” is the same as described above.

・ Soap (B)
Soap: Fatty acid sodium having 12 to 18 carbon atoms (manufactured by Lion Corporation, pure content: 67% by mass, titer: 40-45 ° C .; fatty acid composition: C12 (lauric acid) 11.7% by mass, C14 (myristic acid) 0.4 mass%, C16 (palmitic acid) 29.2 mass%, C18F0 (stearic acid) 0.7 mass%, C18F1 (oleic acid) 56.8 mass%, C18F2 (linoleic acid) 1.2 mass%; Molecular weight: 289).

・ Linear alkylbenzene sulfonate (D)
LAS: linear alkyl (10 to 14 carbon atoms) benzenesulfonic acid [manufactured by Lion Co., Ltd., Rypon LH-200 (LAS-H pure content 96% by mass)], 48 masses at the time of preparing the surfactant composition A mixture of a compound neutralized with an aqueous sodium hydroxide solution and a compound neutralized with an aqueous 48 mass% potassium hydroxide solution in a mass ratio of 2: 1. The compounding quantity in a table | surface shows the value (mass%) as these mixtures.

・ Cationized cellulose (C)
(C-1) Cationized cellulose LF: Hydroxyethyl cellulose (manufactured by Sumitomo Seika, trade name: LF-15, 1% by mass aqueous solution viscosity (25 ° C.): 700 to 1300 mPa · s) 30 g (100 parts by mass) with isopropyl 300 g (1000 parts by mass) of a mixed solvent with alcohol / water (mass ratio) = 85/15 and 4.5 g (15 parts by mass) of a 25% by mass aqueous sodium hydroxide solution 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 4 g (13 parts by mass) of glycidyltrimethylammonium chloride (manufactured by Sakamoto Pharmaceutical Co., Ltd., trade name: SY-GTA80, aqueous solution having an effective concentration of 73% by mass) 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 LF (weight average molecular weight: 900,000, cationization degree: 0.6 mass%, solid content: 91 mass%).

(C-2) Cationized cellulose AX: Hydroxyethyl cellulose (manufactured by Sumitomo Seika, trade name: AX-15, 1% by mass aqueous solution viscosity (25 ° C.): 15000-30000 mPa · s) 30 g (100 parts by mass) and isopropyl 300 g (1000 parts by mass) of a mixed solvent with alcohol / water (mass ratio) = 85/15 and 5 g (16.5 parts by mass) of a 25% by mass aqueous sodium hydroxide solution 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 Yakuhin Kogyo, trade name: SY-GTA80, aqueous solution having an effective concentration of 73% by mass) 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%).

・ Other ingredients (common ingredients)
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).
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 ).
Fluorescent agent: Chinopearl CBS-X (trade name, Ciba Specialty Chemicals) / Chinopearl AMS-GX (trade name, Ciba Specialty Chemicals) = 3/1 (mass ratio) mixture.
Perfume: Perfume composition A shown in JP-A-2002-146399 [Table 11] to [Table 18].
Enzyme: Sabinase 12T (Novozymes) / LIPEX100T (Novozymes) / Stainzyme 12T (Novozymes) = 5/4 (mass ratio).

<Method for producing granular detergent composition>
According to the composition shown in Tables 1 and 2, surfactant-containing particles were prepared by the preparation method shown below, and the granular detergent compositions of the respective examples shown in Table 1 were produced using the surfactant-containing particles.

(Examples 1-5, 7-12, 14)
[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. (B) component and (D) component were added to this, and it stirred for 10 minutes. Subsequently, MA agent, sodium sulfate, and fluorescent agent were added (this addition step is referred to as “raw material input 1”). Further, after stirring for 10 minutes, a part of the zeolite (0.5% by mass equivalent (to the surfactant-containing particles, the same shall apply hereinafter) for addition during the kneading, 5.0% by mass equivalent of the grinding aid And 2.1 wt% of each zeolite for surface coating equivalent to the surface coating were removed.), Na carbonate, K carbonate, and Na sulfite were added respectively. Furthermore, after stirring for 20 minutes to prepare a slurry for spray drying having a moisture content of 38% by mass, the slurry is spray dried using a countercurrent spray drying tower at a hot air temperature of 280 ° C. Dry particles were obtained.
On the other hand, an aqueous slurry (moisture concentration of 25% by mass) of the component (A) obtained by sulfonating and neutralizing the starting fatty acid ester is a part of the nonionic surfactant (25% by mass with respect to MES). %) And 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, 1.0 mass% equivalent amount of the remaining nonionic surfactant and water except for spray addition were added to a continuous kneader (Kurimoto Co., Ltd.). (Made by Kakosho, KRC-S4 type) (this charging stage is referred to as “raw material charging 2”), kneaded under conditions of a kneading capacity of 120 kg / hr and a temperature of 60 ° C., and kneaded with surfactant I got a thing. 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 mass of finely divided zeolite under the conditions of a filling rate of 30% by volume, a rotation speed of 22 rpm and 25 ° C., and spray for 1.0% by mass of nonionic surfactant and fragrance for 1 minute. And surface modified to prepare surfactant-containing particles.

[Production of granular detergent composition]
Filled using a horizontal cylindrical rolling mixer (with a cylinder diameter of 585 mm, a cylinder length of 490 mm, a drum internal wall surface of the container 131.7L and two baffle plates with a clearance of 20 mm from the internal wall surface and a height of 45 mm) (C-1) Cationized cellulose LF, surfactant-containing particles, and components such as enzymes were mixed 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 6)
In the production method of Example 7, a granular detergent composition was produced in the same manner as in the production method of Example 7, except that the component (D) was not blended.

(Example 13)
In the production method of Example 1, in the raw material charging 3, in place of (C-1) cationized cellulose LF, (C-2) cationized cellulose AX was added and mixed. A granular detergent composition was produced in the same manner as the production method.

(Comparative Example 1)
In the production method of Example 1, the granular detergent composition was produced in the same manner as in the production method of Example 1, except that the component (A) was not blended and the amount of the component (B) was 16% by mass. .

(Comparative Example 2)
In the production method of Example 1, the granular detergent composition was produced in the same manner as in the production method of Example 1, except that the component (B) was not blended and the amount of the component (A) was 16% by mass. .

(Comparative Example 3)
In the production method of Example 1, the granular detergent composition is the same as the production method of Example 1 except that the component (C) [(C-1) cationized cellulose LF] is not blended in the raw material charging 3. Manufactured.

<Method for evaluating the effect of imparting flexibility to the object to be washed>
[Preprocessing]
1kg of polyester jersey (obtained from Dyeing Materials Co., Ltd., Tanigami Shoten), two-tank washing machine (product name: CW-C30A1-H1 type, manufactured by Mitsubishi Electric Corporation), using tap water at 50 ° C A commercially available detergent top (manufactured by Lion Co., Ltd.) was washed at a standard use concentration (20 g of detergent top with respect to 30 L of tap water, ie 667 ppm) and 30 times the bath ratio. After the dehydration operation was repeated twice, the rinsing / dehydration operation of “Rinse with running water for 15 minutes and then dehydrate for 5 minutes” was repeated five times. It was used for.
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 treatment]
A mini fully automatic washing machine (product name: JW-Z23A, manufactured by Haier) is used as a washing machine, and 12 L of tap water with a water temperature of 28 ° C. is stored in the tank of the mini fully automatic washing machine. After dissolving 13.3 g of the detergent composition, add a total of 800 g of clothing (3 cotton towels, 4 BVD skin shirts, 1 polyester jersey (60 cm x 30 cm)) and wash in the standard course And dried indoors.

Using a cotton towel after drying, the effect of imparting flexibility to the object to be washed was evaluated as follows using Comparative Example 1 as a comparative control.
Regarding the softness of the cotton towel, a pair of comparison between the cotton towel washed with the granular detergent composition of each of the above examples and the cotton towel washed with the granular detergent composition of Comparative Example 1 It was done by a person.
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 were given to the slightly more flexible cotton towel, and -1 point was given to the slightly lesser cotton towel; And the total score of 10 persons was calculated | required and the softness | flexibility provision effect to the cotton towel was evaluated based on the following evaluation criteria. The results are shown in Table 1.
(Evaluation criteria)
A: The total score of 10 people was 17 to 20 points.
A: The total score of 10 people was 13 to 16 points.
A: The total score of 10 people was 9 to 12 points.
(Triangle | delta): The total score of 10 people was 5-8 points.
X: The total score of 10 people was -4 to 4 points.
Xx: The total score of 10 people was -5 points or less.

As is clear from the results in Table 1, the granular detergent compositions of Examples 1 to 14 according to the present invention are more suitable for washing objects than the granular detergent composition of Comparative Example 1 containing the component (C). It was confirmed that the effect of imparting flexibility was excellent.
Moreover, from Examples 6-10, it has confirmed that the softness | flexibility provision effect to a to-be-washed object further improved because content of a linear alkylbenzenesulfonate (D) is 4 mass% or less.

Claims (2)

α-sulfo fatty acid ester salt (A), soap (B), and cationized cellulose (C),
The granular detergent composition, wherein the mass ratio of the component (A) to the component (B) is (A) / (B) = 25/75 to 95/5.   The granular detergent composition of Claim 1 in which 4 mass% or less linear alkylbenzene sulfonate (D) contains.