JPWO2010103832A1 - Perfume particles and granular detergent composition using the same - Google Patents

Abstract

A perfume particle and granular detergent composition that has a high aroma stability even during long-term storage and can impart a long-lasting aroma to the washed object after washing. A granulated product containing an encapsulated fragrance encapsulating a fragrance with a polymer compound and a neutral inorganic salt is coated with a fatty acid salt. The fatty acid salt preferably has 10 to 18 carbon atoms in the carbon chain, and the polymer compound is selected from the group consisting of polyacrylate polymer, melamine polymer and urethane polymer. It is preferable that it is at least one kind.

Description

The present invention relates to a perfume particle and a granular detergent composition using the same.
This application claims priority based on Japanese Patent Application No. 2009-059959 for which it applied to Japan on March 12, 2009, and uses the content here.

Conventionally, in order to improve the product value of a detergent composition, a perfume has been blended. One of the purposes of blending a fragrance into a detergent composition is to mask the odor of a base mainly composed of a surfactant. In addition, another object is to impart a fragrance to an object to be washed such as clothing and ensure palatability. In recent years, there has been a growing need for scents in washing, and it is desired that clothes that have been washed have a favorable aroma not only immediately after washing but also during wearing.
As a method for adding a fragrance to a detergent composition, a method of spraying a fragrance on detergent particles containing a surfactant is generally known. However, spraying the fragrance directly onto the detergent particles may come into direct contact with other components in the detergent particles, which may adversely affect the quality of the fragrance. In addition, when the fragrance is simply sprayed on the detergent particles, the fragrance of the fragrance is released at an early stage, and there is a problem that the release of the fragrance in the detergent composition itself or the object to be washed is difficult to be sustained.

  In order to solve such problems, a detergent composition has been proposed in which a perfume is supported on a porous body such as an inclusion compound or zeolite to improve the sustainability of the aroma (for example, Patent Document 1). In addition, there has been proposed a technique for controlling the release characteristics of fragrance using an encapsulated fragrance containing a fragrance using a polymer compound as a film material (for example, Patent Documents 2 and 3). Or the detergent composition which aimed at the persistence of fragrance | flavor by mix | blending inorganic salt particle | grains with detergent particle | grains is proposed (for example, patent documents 4, 5).

JP 2008-156516 A JP-T-2001-508384 Japanese National Patent Publication No. 08-506991 JP 2006-16421 A JP-A-2005-330362

However, with the conventional technology described above, although the fragrance can be imparted to the item to be washed, the fragrance persistence is not satisfactory. In addition, when the detergent composition is stored for a long period of time, there is a concern that the strength of the fragrance and the quality of the remaining fragrance will deteriorate.
Then, this invention aims at the fragrance | flavor particle | grains and granular detergent composition which have high stability of the fragrance in the preservation | save for a long period of time, and can provide the fragrance lasting for a long time with respect to the to-be-washed thing after washing.

  The fragrance particles of the present invention are characterized in that a granulated product containing an encapsulated fragrance encapsulating a fragrance with a polymer compound and a neutral inorganic salt is coated with a fatty acid salt. The fatty acid salt preferably has 10 to 18 carbon atoms in the carbon chain, and the polymer compound is selected from the group consisting of polyacrylate polymer, melamine polymer, and urethane polymer. It is preferable that it is at least one kind.

  The granular detergent composition of the present invention contains the fragrance particles.

  According to the fragrance particles of the present invention, fragrance stability during long-term storage is high, and a fragrance that lasts for a long period of time can be imparted to an object to be washed.

(Granular detergent composition)
In the granular detergent composition of the present invention, a granulated product (hereinafter referred to as (A) component) containing an encapsulated perfume encapsulating a perfume with a polymer compound and a neutral inorganic salt is a fatty acid salt (hereinafter referred to as (B) component). Perfume particles coated with a).

The form of the granular detergent composition of the present invention is a granular solid such as a powder or a granule, more preferably a powder.
Although the average particle diameter of the particle | grains of the granular detergent composition of this invention is not specifically limited, It is preferable that it is 200-1500 micrometers, and it is more preferable that it is 250-1000 micrometers. 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.

  The average particle diameter is measured using a 9-stage sieve having a mesh opening of 1680 μm, 1410 μm, 1190 μm, 1000 μm, 710 μm, 500 μm, 350 μm, 250 μm, and 149 μm, and a classification operation. In the classification operation, a small sieve sieve is stacked on a tray in the order of a large sieve sieve, and a sample of 100 g / time is placed on the top of the top 1680 μm sieve, the lid is capped, and a low-tap sieve shaker (stock) (Made by Iida Seisakusho Co., Ltd., tapping: 156 times / minute, rolling: 290 times / minute) After shaking for 10 minutes, the sample remaining on each sieve and the saucer was collected for each sieve, Measure the mass. 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 Determine the average particle size of the sample.

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, a space (storage location) required for storing the granular detergent composition can be reduced, which is advantageous. On the other hand, if it is 1.2 g / mL or less, the solubility of the granular detergent composition in water is good even after long-term storage.
In addition, the said bulk density shows the value measured according to JISK3362-1998.

  Although the water content of the granular detergent composition of the present invention is not particularly limited, it is preferably 4 to 10% by mass, more preferably 5 to 9% by mass, and further 6 to 8% by mass from the viewpoints of solubility and storage stability. preferable. In the present specification, the moisture content is a value measured with an infrared moisture meter (Kett Co., Ltd.) at a sample surface temperature of 165 ° C. for 20 minutes.

  The fluidity of the granular detergent composition of the present invention 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 in a paper container or a container with high moisture permeability such as a refillable pouch for a long period of time) is preferably 60 ° or less as an 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, when the granular detergent composition is stored, it is preferable because the usability is good, for example, the granular detergent composition can be easily taken out from the container. The repose angle 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 a granular detergent composition filled in a container flows out and a horizontal surface is measured. Specifically, the value measured using a turntable-type angle of repose measuring instrument (manufactured by Tsutsui Riken Kikai Co., Ltd.) is shown.

  As said container in the commercial product formed 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. Especially, a container that is less affected by humidity and light. It is preferable to select.

[Perfume particles]
The fragrance | flavor particle | grains of this invention coat | cover the (A) component with the (B) component. The blending amount of the fragrance particles in the granular detergent composition can be determined in consideration of the kind and blending amount of the fragrance used in the fragrance particles, the strength of the fragrance required for the granular detergent composition, and the like. For example, the fragrance particles are preferably determined in the range of 0.5 to 26% by mass in the granular detergent composition, and more preferably in the range of 0.75 to 13% by mass.

  “Coating” is not limited to the state in which the entire surface of the component (A) is covered, but it is sufficient that 70% or more of the surface area of the component (A) is covered. From the viewpoint of improving the stability of the aroma in the storage of the granular detergent composition, it is preferable that 90% or more of the surface area of the component (A) is covered, and the entire surface of the component (A) is covered. It is more preferable.

<(A) component: Granulated product containing encapsulated perfume and neutral inorganic salt in which perfume is encapsulated with polymer compound>
The component (A) includes an encapsulated fragrance (hereinafter referred to as (a1) component) encapsulating a fragrance (hereinafter referred to as (β) component) with a polymer compound (hereinafter referred to as (α) component), a neutral inorganic salt (Hereinafter referred to as component (a2)).

  The blending amount of the component (A) in the fragrance particles of the present invention can be determined in consideration of the particle size of the component (A), the particle size of the component (B), the aroma intensity required for the granular detergent composition, and the like. For example, the range of 90-99 mass% is preferable, and the range of 90-97 mass% is more preferable. This is because the component (A) can be sufficiently covered with the component (B) within the above range.

≪ (a1) component: encapsulated fragrance≫
The component (a1) is an encapsulated fragrance in which the component (α) is included in the component (α). Hereinafter, in the component (a1), a layer formed of the component (α) is referred to as a capsule wall.
The form of the component (a1) is not particularly limited, and may be solid particles, or may be a state in which the component (a1) is dispersed in water as an oil-in-water emulsion.
The particle diameter of the encapsulated flavor of component (a1) is not particularly limited. For example, in the case of a single-core structure, the average particle diameter is 0.1 to 100 μm, preferably 0.5 to 50 μm, more preferably. It is desirable to set it as 0.5-30 micrometers. When the average particle size is too small, the strength of (a1) is lowered, the capsule wall is collapsed at an early stage, and the aroma tends not to be sustained. If the average particle size is too large, the capsule wall is unlikely to collapse even if the component (a1) is adsorbed to the fiber, and the fragrance tends to be insufficiently released. The average particle diameter of the component (a1) is a value measured by a laser diffraction particle size distribution analyzer (SALD-300V, manufactured by Shimadzu Corporation). The single-core structure refers to a structure in which only one (β) component lump, which is a core substance, is present in the (a1) component.

  The thickness (wall thickness) of the capsule wall of the component (a1) is not particularly limited, but is preferably 0.01 to 5 μm, and more preferably 0.05 to 3 μm. If the wall thickness is too thin, the strength of (a1) tends to be low, the capsule wall collapses early, and the aroma tends to be difficult to sustain. When the wall thickness is too thick, even if the component (a1) is adsorbed on the fiber, the capsule wall is difficult to collapse and the fragrance tends to be insufficiently released. The thickness of the capsule wall of the component (a1) can be observed and measured with a scanning electron microscope (SEM).

  The blending amount of the (a1) component in the component (A) can be determined in consideration of the type and blending amount of the (β) component, the fragrance strength required for the granular detergent composition, and the like. It is preferably determined in the range of 49.5% by mass, and more preferably in the range of 22.5 to 49.5% by mass. In addition, the blending amount of the component (a1) in the granular detergent composition is preferably 0.25 to 12.5% by mass, and more preferably 0.25 to 6.25% by mass. If it is in the said range, a fragrance suitable for a granular detergent composition and a to-be-washed object can be provided.

-(Α) component: polymer compound (α) component is a polymer compound that forms, for example, a membrane-like capsule wall in an encapsulated fragrance.
As the component (α) used in the present invention, a fragrance can be stably encapsulated as a core substance. The component (α) can be determined in consideration of the type of the component (a2) and the type of the component (B), for example, polyacrylic acid-based, polyvinyl-based, polymethacrylic acid-based, melamine-based, urethane-based, etc. These synthetic polymer substances can be used, and these can be used alone or in combination of two or more.

  Examples of the monomer constituting the polyacrylic acid polymer include acrylic acid or a lower alkyl ester thereof. Examples of the monomer constituting the polyvinyl polymer include ethylene, maleic anhydride, styrene, and divinylbenzene. Examples of the monomer constituting the polymethacrylic acid polymer include methacrylic acid or a lower alkyl ester thereof. Examples of the melamine polymer include those obtained by heat curing a prepolymer composed of methylol melamine derived from melamine and formaldehyde. The urethane polymer is obtained by a condensation reaction between a polyfunctional isocyanate compound and a polyol or a polyamine compound. Examples thereof include combinations of polyphenyl isocyanate and hexamethylene diamine, toluene diisocyanate and diethylene glycol, and the like.

  The (α) component used in the present invention is preferably a polyacrylate polymer, a melamine polymer, and a urethane polymer from the viewpoint of scent sustainability (stability). Two or more kinds can be used in appropriate combination.

  The blending ratio of the component (α) in the component (a1) can be appropriately selected depending on the type of the component (α), and is preferably determined in the range of 5 to 60% by mass, for example in the range of 10 to 40% by mass. It is more preferable to determine by. If the proportion of component (α) is too low, capsule formation of component (a1) may be difficult, and if it is too large, the blending amount of component (β), which is a core substance, will be relatively low, and the desired aroma will be present. It becomes difficult to obtain.

-(Β) component: fragrance The (β) component is a fragrance constituting the core material of the encapsulated fragrance.
The fragrance used as the (β) component can be determined in consideration of the fragrance, the type of the (α) component, and the like. For example, a fragrance component or a mixture comprising a fragrance component, a solvent, a fragrance stabilizer, etc. Composition). The (β) component is preferably selected to have low reactivity with the (α) component and low water solubility.
The fragrance composition can be appropriately selected depending on the purpose, and examples thereof include a fragrance composition containing one or more fragrance components generally used in detergents, fiber finishes, and hair cosmetics. .

  Specific examples of the fragrance component include aldehydes, phenols, alcohols, ethers, esters, hydrocarbons, ketones, lactones, musks, natural fragrances, animal fragrances, and the like.

  The aldehydes are not particularly limited and can be appropriately selected depending on the purpose. For example, undecylenaldehyde, lauryl aldehyde, aldehyde C-12MNA, miracaldehyde, α-amylcinnamic aldehyde, cyclamenaldehyde, citral Citronellal, ethyl vanillin, heliotropin, anisaldehyde, α-hexylcinnamic aldehyde, octanal, ligustral, lyial, rilal, tripral, vanillin, helional and the like.

It does not specifically limit as said phenols, According to the objective, it can select suitably, For example, eugenol, isoeugenol, etc. are mentioned.
The alcohols are not particularly limited and can be appropriately selected depending on the purpose.For example, bacdanol, citronellol, dihydromyrcenol, dihydrolinalool, geraniol, linalool, nerol, sandalol, Santa Rex, Examples include terpineol, tetrahydrolinalol, and phenylethyl alcohol.

  The ethers are not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include cedula bar, glycalva, methyl eugenol, and methyl isoeugenol.

  The esters are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include cis-3-hexenyl acetate, cis-3-hexenyl propionate, cis-3-hexenyl salicylate, and p-cresate. Dil acetate, pt-butyl cyclohexyl acetate, amyl acetate, methyl dihydrojasmonate, amyl salicylate, benzyl salicylate, benzyl benzoate, benzyl acetate, cedryl acetate, citronellyl acetate, decahydro-β-naphthyl acetate, dimethylbenzyl Carvinyl acetate, Ericapropionate, ethyl acetoacetate, Erica acetate, geranyl acetate, geranyl formate, hedion, linalyl acetate, β-phenylethyl acetate Hexyl salicylate, styryl acetate, terpinyl acetate, betiberyl acetate, ot-butylcyclohexyl acetate, manzanate, allyl heptanoate, and the like.

The hydrocarbons are not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include d-limonene, α-pinene, β-pinene, and myrcene.
The ketones are not particularly limited and may be appropriately selected depending on the purpose. For example, α-ionone, β-ionone, methyl-β-naphthyl ketone, α-damascon, β-damascon, δ-damascon Cis-jasmon, methylionone, allylionone, cashmerelan, dihydrojasmon, isoea super, belt fix, isolone diforanone, coabon, rosephenone, raspberry ketone, dynascon and the like.

The lactone is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include γ-decalactone, γ-undecalactone, γ-nonalactone, γ-dodecalactone, coumarin, and ambroxan. It is done.
The musk is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include cyclopentadecanolide, ethylene brushate, galaxolide, musk ketone, tonalid, nitromusk and the like.

  The natural flavor is not particularly limited and can be appropriately selected according to the purpose. For example, orange oil, lemon oil, lime oil, petitgren oil, yuzu oil, neroli oil, bergamot oil, lavender oil, lavandin oil , Abies oil, anise oil, bay oil, bored rose oil, ylang ylang oil, citronella oil, geranium oil, peppermint oil, peppermint oil, spearmint oil, eucalyptus oil, lemongrass oil, patchouli oil, jasmine oil, rose oil, cedar oil , Essential oils such as vetiver oil, galvanum oil, oak moss oil, pine oil, camphor oil, sandalwood oil, aromatic oil, turpentine oil, clove oil, clove leaf oil, cassia oil, nutmeg oil, cananga oil, thyme oil, etc. .

The animal fragrance is not particularly limited and can be appropriately selected according to the purpose.
Such a fragrance | flavor component can be used individually by 1 type or in combination of 2 or more types as appropriate.

The (β) component of the present invention has a boiling point at room temperature of preferably less than 260 ° C., more preferably 150 ° C. or more and less than 260 ° C., from the point of freshness of the fragrance and palatability.
The boiling point of the fragrance component is, for example, “Perfume and Flavor Chemicals” Vol. I and II, Stephen Arctander, Allured Pub. Co. (1994), “Synthetic fragrance chemistry and commercial knowledge”, Motoichi Into, Chemical Industry Daily (1996), “Perfume and Flavor Materials of Natural Origin”, Stephen Arctander, Allred Pub. Co. (1994), “Encyclopedia of Fragrance”, edited by Japan Fragrance Association, Asakura Shoten (1989) and “Basic Knowledge of Fragrance and Incense”, Sangyo Tosho (1995). Quote.

The (β) component of the present invention preferably contains a fragrance component having a ClogP value of preferably 1.0 to 8.0, more preferably 3.0 to 8.0.
The ClogP value is a value representing 1-octanol / water partition coefficient = P representing the ratio of equilibrium concentrations in 1-octanol and in water in the form of logarithmic logP with respect to the base 10 for the chemical substance. The ClogP value can be obtained by f-value method (hydrophobic fragment constant method) by decomposing the chemical structure of a compound into its constituents and integrating the hydrophobic fragment constant f value possessed by each fragment (for example, Clog 3 Reference Manual Daylight Software 4.34, Albert Leo, David Weininger, Version 1, March 1994).

In general, since the fragrance is more hydrophobic as the ClogP value is larger, the fragrance composed of many fragrance components having a small ClogP value is more hydrophilic than the fragrance composed of many fragrance components having a large ClogP value. It can be said that it is a good fragrance.
Therefore, when the ClogP value is within the above range, the hydrophilic fragrance component and the hydrophobic fragrance component are combined in a well-balanced manner, so that the fragrance has a better fragrance balance and higher palatability. It is advantageous.
The ClogP value fragrance component is 30% by mass (hereinafter simply referred to as%) or more, more preferably 45% by mass or more, and still more preferably 90% by mass or more, based on the amount of the (β) component excluding the solvent. , It is desirable to contain.

In the component (β), a solvent (fragrance solvent) usually used as a fragrance composition may be blended. When a water-soluble solvent is used as the fragrance solvent, the fragrance solvent can be determined in consideration of film formation of the component (a1).
Examples of the perfume solvent include acetin (triacetin), MMB acetate (3-methoxy-3-methylbutyl acetate), sucrose diacetate hexaisobutyrate, ethylene glycol dibutyrate, hexylene glycol, dibutyl sebacate, and deltile. Extra (isopropyl myristate), methyl carbitol (diethylene glycol monomethyl ether), carbitol (diethylene glycol monoethyl ether), TEG (triethylene glycol), benzyl benzoate, propylene glycol, diethyl phthalate, tripropylene glycol, aboline (dimethyl) Phthalate), deltyl prime (isopropyl palmitate), dipropylene glycol DPG-FC (dipropylene glycol), far Sen, dioctyl adipate, tributyrin (glyceryl tributanoate), hydrolite-5 (1,2-pentanediol), propylene glycol diacetate, cetyl acetate (hexadecyl acetate), ethyl abietate, avaline (methyl abietate), Citroflex A-2 (acetyl triethyl citrate), Citroflex A-4 (tributyl acetyl citrate), Citroflex No. 2 (triethyl citrate), Citroflex No. 4 (tributyl citrate), Durafix (methyl dihydroabietate), MITD (isotridecyl myristate), polylimonene (limonene polymer), 1,3-butylene glycol and the like. The blending amount in the (β) component of these perfume solvents is preferably determined, for example, in the range of 0.1 to 50% by mass and in the range of 1 to 30% by mass in the (β) component. Is more preferable.

  In addition to the above-mentioned components, additives such as antioxidants and preservatives can be blended with the (β) component of the present invention as needed as long as the effects of the present invention are not hindered.

The blending amount of the (β) component in the (a1) component can be determined in consideration of the type of the (β) component, the fragrance strength required for the granular detergent composition, and the like, for example, 8 to 40 mass. It is preferable to determine in the range of%, and it is more preferable to determine in the range of 15-40 mass%. If it is in the said range, it is because the (a1) component will form the capsule wall of moderate intensity | strength and can release a fragrance over a long period of time.
The blending amount of the (β) component in the fragrance particles can be determined in consideration of the type of the (β) component, the fragrance strength required for the granular detergent composition, and the like, for example, 1.2 to 19. It is preferably determined in the range of 8% by mass, and more preferably determined in the range of 3.4 to 19.8% by mass. This is because, within the above range, a suitable fragrance can be released over a long period of time.
The blending amount of the (β) component in the granular detergent composition can be determined in consideration of the type of the (β) component, the fragrance strength required for the granular detergent composition, etc. It is preferable to determine in the range of 1.0 mass%, and it is more preferable to determine in the range of 0.1-0.5 mass%. If it is in the said range, it is because a granular detergent composition discharge | releases a suitable fragrance and can provide a suitable fragrance with respect to a to-be-washed object.

-Other components in the component (a1) The component (a1) includes, in addition to the components (α) and (β), an emulsifier as long as the effect of the present invention is not hindered in order to facilitate the formation of a capsule wall. , Dissolution promoters, polymerization initiators, and the like can be blended.
Examples of the emulsifier include ethylene-maleic anhydride copolymer, polystyrene sulfonate sodium salt, phenol sulfonic acid condensate, polyvinyl pyrrolidone, and surfactant.
Examples of the flavor enhancer include higher alcohol, glycerin, ethylene glycol, propylene glycol, paraffin oil, mineral oil, animal oil, vegetable oil and the like.
The polymerization initiator is not particularly limited and can be determined according to the components of the capsule wall, and examples thereof include azobisisobutyronitrile, benzoyl peroxide, N, N-dimethyl-p-toluidine, and alkyl halide.

<< (a2) component: neutral inorganic salt >>
The component (a2) of the present invention is a neutral inorganic salt. A neutral inorganic salt is a salt formed from a strong acid and a strong base, and a 1% by mass aqueous solution thereof is neither acidic nor basic. By using such component (a2), the capsule wall of component (a1) is prevented from coming into contact with an acidic or basic component, and the capsule wall can be prevented from collapsing. In addition, (a1) does not come into contact with components that easily absorb moisture, such as zeolite and silica, and therefore can prevent the capsule wall from collapsing due to moisture migration during storage. Furthermore, since the component (a2) absorbs less fragrance than a porous body such as zeolite, the fragrance of the component (a1) is likely to be released. As a result, the component (A) can release a good aroma even during long-term storage.
The component (a2) is not particularly limited, and examples thereof include metal chlorides such as lithium chloride, sodium chloride, potassium chloride, and calcium chloride, metal bromides such as lithium bromide, sodium bromide, and potassium bromide, lithium sulfate, and sulfuric acid. Examples thereof include sulfates such as sodium and potassium sulfate, and nitrates such as lithium nitrate, sodium nitrate and potassium nitrate. Of these, sodium sulfate and sodium chloride are preferred. These can be used individually by 1 type or in combination of 2 or more types.

  The component (a2) is preferably selected in consideration of the type of the (β) component and having a low adsorbing ability (fragrance adsorbing ability) of the perfume component in the (β) component. If the perfume adsorption capacity is too high, the release of the aroma of the granular detergent composition and the release of the aroma of the article to be washed are hindered, and the amount of the (β) component added is remarkably increased, which is not preferable from an economic viewpoint.

The perfume adsorption ability can be evaluated by the following means. First, 10 g of component (a2) is weighed and placed flat in a polystyrene bottle having a diameter of 24 mm. 1 g of a fragrance used as the component (β) is added to the weighed component (a2), stirred with a spoon, closed and placed (measurement sample). Similarly, 1 g of the fragrance is placed in a polystyrene bottle having a diameter of 24 mm, and the lid is closed and left standing (reference sample). One day later, the bottles of the measurement sample and the reference sample are opened, and the intensity of the fragrance of the headspace is compared by sensory evaluation, and evaluated according to the following evaluation criteria. As the component (a2), those having the following evaluation score of 4 or more are preferable.
・ Evaluation criteria 5 points: Feel the same as the standard 4 points: Feel a little weaker than the standard 3 points: Feel a little weaker than the standard 2 points: Slight aroma compared to the standard 1 point: The measurement sample is odorless

The blending amount of the component (a2) in the fragrance particles is preferably 45 to 85% by mass, more preferably 45 to 75% by mass. If it is less than the above lower limit value, it is difficult to granulate the component (A), and if it exceeds the above upper limit value, the blending amount of the component (β) becomes too small and a suitable aroma may not be obtained.
The content ratio (mass ratio) between the component (a1) and the component (a2) in the fragrance particles is preferably (a1) component / (a2) component = 1/5 to 1/1, and 1/3 to 1/1. Is more preferable, and 1/3 to 1/2 is more preferable. If it is less than the lower limit, the fragrance particles are difficult to dissolve in the washing liquid, and if the upper limit is exceeded, granulation of the component (A) becomes difficult, and the obtained component (A) is easily broken. Aroma tends to be released early.

  The amount of component (a2) in the granular detergent composition is preferably 0.25 to 62.5% by mass, more preferably 0.25 to 20.1% by mass. When the amount is less than the upper and lower limit values, the component (A) is easily broken and the fragrance is easily released at an early stage, and when the upper limit value is exceeded, the absolute amount of the cleaning components in the granular detergent composition is reduced, and the detergency There is concern that it will be damaged.

<(B) component: fatty acid salt>
The component (B) of the present invention is a fatty acid salt. The component (B) is typically represented by the following formula (I).

  RCOOM (I)

  [In the formula (I), R represents a linear or branched alkyl group or alkenyl group, and M represents at least one selected from an alkali metal, an alkaline earth metal, an amine, and an amino acid. ]

In formula (I), the number of carbon atoms of R which is a carbon chain is not particularly limited, but is preferably 10 to 18, and more preferably 12 to 18. This is because the detergency can be maintained if the carbon number is within the above range.
R may be either an alkyl group or an alkylene group, but is preferably an alkyl group.
M is an alkali metal such as sodium or potassium, an alkaline earth metal such as magnesium or calcium, ammonia, monoethanolamine, diethanolamine, triethanolamine, 2-amino-2-methylpropanol, 2-amino-2-methylpropane Amines such as diol and basic amino acids such as lysine and arginine. Among these, an alkali metal that is a divalent metal is preferable, and magnesium is more preferable.
Suitable components (B) include magnesium stearate, sodium decanoate, calcium palmitate, magnesium myristate, etc. Among them, magnesium stearate is preferred. (B) A component can be used individually by 1 type or in combination of 2 or more types.
By coating the component (A) with such a component (B), contact between the component (a1) and the detergent particles in the component (A) can be prevented, and deterioration of the component (a1) can be prevented. As a result, even during long-term storage, the fragrance can be released satisfactorily and a fragrance that lasts for a long period of time can be imparted to the item to be washed.

  The blending amount of the component (B) in the fragrance particles can be determined in consideration of the particle size of the component (A) and the like, for example, preferably 1 to 10% by mass, and more preferably 3 to 10% by mass. If it is in the said range, while fully coat | covering the surface of (A) component, while maintaining the aroma of a granular detergent composition, a highly durable aroma can be provided with respect to a to-be-washed object.

  Although the compounding quantity of (B) component in a granular detergent composition is not specifically limited, 0.005-7.5 mass% is preferable and 0.005-2.68 mass% is more preferable. When it is less than the above lower limit, it is difficult to obtain a suitable fragrance of the granular detergent composition itself, and the fragrance imparted to the article to be washed tends to be insufficient. When the above upper limit is exceeded, there is a concern that the cleaning power of the granular detergent composition is reduced.

[Optional ingredients of granular detergent composition]
In addition to the fragrance particles, various detergents, builders and the like and fragrances other than the (β) component can be blended as detergent components in the granular detergent composition. Such detergent components can be blended as surfactant-containing particles granulated separately from the perfume particles.

<Surfactant>
When a granular detergent composition contains the following surfactant, 10-30 mass% is preferable and, as for the total amount of surfactant, 15-30 mass% is more preferable.

≪Anionic surfactant≫
(1) A methyl, ethyl or propyl ester (α-SF or MES) salt of a saturated or unsaturated α-sulfo fatty acid having 8 to 20 carbon atoms.
(2) Alkali metal salts or alkaline earth metal salts of higher fatty acids having an average number of carbon atoms of 10 to 20 fatty acids.
(3) A linear or branched alkylbenzene sulfonate (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms.
(4) Alkane sulfonate having 10 to 20 carbon atoms.
(5) α-olefin sulfonate (AOS) having 10 to 20 carbon atoms.
(6) C10-20 alkyl sulfate or alkenyl sulfate (AS).
(7) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) with an average of 0.5 Alkyl (or alkenyl) ether sulfate (AES) having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added by 10 mol.
(8) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) on average 3 to 30 An alkyl (or alkenyl) phenyl ether sulfate having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added in a mole form.
(9) Any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) with an average of 0.5 An alkyl (or alkenyl) ether carboxylate having 10 to 20 moles of a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms.
(10) Alkyl polyhydric alcohol ether sulfates such as alkyl glyceryl ether sulfonic acids having 10 to 20 carbon atoms.
(11) Long chain monoalkyl, dialkyl or sesquialkyl phosphate.
(12) Polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphate.
These anionic surfactants can be used as alkali metal salts such as sodium and potassium, amine salts and ammonium salts. These anionic surfactants may be used as a mixture.

≪Nonionic surfactant≫
Examples of nonionic surfactants include the following.
(1) Polyoxyalkylene alkyl (or alkenyl) obtained by adding an average of 3 to 30 moles, preferably 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms Ether Among these, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferable. Examples of the aliphatic alcohol used here include primary alcohols and secondary alcohols. The alkyl group may have a branched chain. As the aliphatic alcohol, a primary alcohol is preferable.
(2) Polyoxyethylene alkyl (or alkenyl) phenyl ether (3) Fatty acid alkyl ester alkoxylate represented by the following general formula (II) in which alkylene oxide is added between ester bonds of long-chain fatty acid alkyl ester

R ¹ CO (OA) _n OR ² (II)

[In Formula (II), R ¹ CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms, and OA represents 2 to 4 carbon atoms such as ethylene oxide and propylene oxide, preferably 2 to 2 carbon atoms. 3 represents an alkylene oxide addition unit, and n represents the average number of moles of alkylene oxide added, generally 3 to 30, preferably 5 to 20. R ² represents an optionally substituted lower (1-4 carbon atoms) 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 above-described nonionic surfactant (1) is preferable, and an average of 5 to 20 moles of an alkylene oxide having 2 to 4 carbon atoms is added to an aliphatic alcohol having 12 to 16 carbon atoms. Polyoxyalkylene alkyl (or alkenyl) ether is preferred. A polyoxyethylene alkyl (or alkenyl) ether having a melting point of 50 ° C. or less and an HLB of 9 to 16, a polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether, a fatty acid methyl ester ethoxylate obtained by adding ethylene oxide to a fatty acid methyl ester, A fatty acid methyl ester ethoxypropoxylate obtained by adding ethylene oxide and propylene oxide to a fatty acid methyl ester is preferably used. Moreover, these nonionic surfactants can be used individually by 1 type or in combination of 2 or more types as appropriate.
The HLB of the nonionic surfactant in the present invention is a value determined by the Griffin method (Yoshida, Shindo, Ogaki, Yamanaka, edited by “New Edition Surfactant Handbook”, Kogyoshosho Co., Ltd., 1991). , Page 234).
The melting point in the present invention is a value measured by a melting point measurement method described in JIS K0064-1992 “Method for measuring melting point and melting range of chemical product”.

≪Cationic surfactant≫
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.

≪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 the inorganic builder 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 (for example, manufactured by Clariant Japan Ltd.) Trade name "Na-SKS-6" (δ-Na ₂ O · 2SiO ₂ ) and other crystalline alkali metal silicates; 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 composites (eg Rhodia) Such as NABION15 (trade name)), 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 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 mass average particle diameter is preferably 0.1 to 10 μm. The blending amount of the crystalline aluminosilicate in the granular detergent composition is preferably 10 to 40% by mass, and particularly preferably 2 to 30% by mass from the viewpoint of powder properties such as cleaning performance and fluidity.

  When potassium carbonate is blended, the blending amount thereof is preferably 1 to 15% by mass, more preferably 2 to 12% by mass, and further preferably 5 to 5% in the granular detergent composition from the viewpoint of the effect of improving solubility. 12% by mass.

  When the alkali metal chloride is blended, the blending amount thereof is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, and still more preferably, in the granular detergent composition from the viewpoint of improving the solubility. It is 3-7 mass%.

  When blending the crystalline alkali metal silicate, the blending amount is preferably 0.5 to 40% by mass, more preferably 1 to 25% by mass, and still more preferably from the viewpoint of cleaning performance in the granular detergent composition. Is 3 to 20% by mass, particularly preferably 5 to 15% by mass.

  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 and cyclopentanetetracarboxylates; ether carboxylates such as carboxymethyltaltronate, carboxymethyloxysuccinate, oxydisuccinate, tartaric acid mono- or disuccinate; poly Crylate, acrylic acid-allyl alcohol copolymer salt, acrylic acid-maleic acid copolymer salt, polyacetal carboxylic acid salt 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 and hydroxymethylcellulose.

  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 1000-80000, polyacrylate, acrylic acid-maleic acid copolymer having a weight average molecular weight of 1000-80000 Salts, polyacrylates, polyacetal carboxylates such as polyglyoxylic acid having a weight average molecular weight of 800 to 1000000 (preferably 5000 to 200000) (for example, those described in JP-A-54-52196), polysaccharides Derivatives are preferred.

  As the polysaccharide derivative, carboxymethylcellulose represented by the following formula (III) or a salt thereof (hereinafter sometimes referred to as CMC) is preferable.

[R ^{3 to} R ⁵ in Formula (III) each independently represent a hydrogen atom, a carboxymethyl group (CH ₂ COOH), or a salt thereof. m represents a repeating unit. ]

  Examples of the salt of carboxymethyl cellulose include alkali metal salts such as sodium and potassium, ammonium salts, and the like, and a mixture of these salts may be used. Of the above, carboxymethylcellulose sodium salt is preferred.

  Preferable examples of CMC include an anionic water-soluble and water-insoluble cellulose ether obtained by reacting monochloroacetic acid after treating pulp with caustic soda as a raw material.

The weight average molecular weight of CMC is 100,000 or more, preferably 300,000 or more, more preferably 800,000 or more. As an upper limit, Preferably it is 1200000 or less, More preferably, it is 1000000 or less. If the weight average molecular weight of CMC is not less than the above lower limit, the effect of preventing recontamination can be remarkably improved. On the other hand, if the weight average molecular weight of CMC is not more than the above upper limit value, the solubility in the washing liquid will be good. The weight average molecular weight of CMC can be measured by gel filtration chromatography (GPC) -differential refractive index detector (RI) system, eluent: 0.1 M NaNO ₃ , flow rate: 1 mL / min, sample : 0.02 to 0.3% by mass, Solvent: 0.1 M NaNO ₃ , Injection amount: Meaning a value calculated by calculating the weight average molecular weight as a numerical value in terms of PEG under the operating conditions of 200 μL. For the above measurement, for example, a liquid feed pump: Shodex DS-4 (manufactured by Showa Denko KK), a degasser: ERC3115 (manufactured by ERC KK), a column: Shodex SB-806MHQ (manufactured by Showa Denko KK) ), A differential refractive index detector: Shodex RI-71 (manufactured by Showa Denko KK) and the like can be used.

  The degree of etherification of CMC is preferably 0.2 to 1.3, more preferably 0.2 to 0.8. In the present invention, the degree of etherification refers to the average number of hydroxyl groups substituted with a carboxymethyl group or a salt thereof per glucose ring unit (of the three hydroxyl groups of the glucose ring, how many are carboxymethyl groups or It indicates whether or not it has been replaced by a salt, and is a maximum of 3).

  The average particle diameter of CMC is preferably 10 to 1500 μm, more preferably 10 to 500 μm, and still more preferably 10 to 100 μm. When the average particle diameter is in such a range, it is preferable in terms of solubility and solidification. The average particle size of CMC can be calculated from the particle size distribution by sieving, as in the granular detergent composition.

  Such CMCs are sold under the trade name “CMC Daicel” by Daicel Chemical Industries, Ltd. 1110, 1120, 1130, 1140, 1160, 1180, 1190, 1220, 1240, 1260, 1280, 1290, 1380. 2200, 2260, 2280, 2450, 2340, etc., and Sun, such as F10LC, F600LC, F1400LC, F10MC, F150MC, F350HC, F1400MC, F1400MG, etc., sold by Nippon Paper Chemical Co., Ltd. under the trade name “Sunrose” Rose F series, Sunrose A series such as A02SH, A20SH, A200SH, SLD-F1 (above, trade name), Serogen (trade name) F-BSH-6, F- sold by Daiichi Kogyo Seiyaku Co., Ltd. 6HS9 And the like. Among the above, CMC Daicel 1130, 1180, 1190, Sunrose F1400LC, F1400MC, Sunrose SLD-F1, and Serogen F-6HS9 are particularly preferable. CMC can be used individually by 1 type or in combination of 2 or more types.

  1-20 mass% is preferable in a granular detergent composition, as for the compounding quantity of an organic builder, More preferably, it is 1-10 mass%, More 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 a salt of a polymer, a salt of polyacetal carboxylic acid, an organic builder such as carboxymethyl cellulose and hydroxymethyl cellulose, and an inorganic builder such as zeolite. There are various grades of detergency builders available on the market, but these grades do not limit the use of the present invention. For example, impurities mixed in the production of the commercial product and quality stability It may contain a storage stabilizer and an antioxidant added for the purpose of conversion.

  The blending amount of the detergency builder in the granular detergent composition is preferably 10 to 80% by mass, 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.
As for the compounding quantity of the optical brightener in a granular detergent composition, 0.001-1 mass% is preferable.

  Commercially available fluorescent brighteners include Whiteex SA, Whiteex SKC (trade name) manufactured by Sumitomo Chemical Co., Ltd .; Chino Pearl AMS-GX, Chino Pearl DBS-X, Chino Pearl CBS- manufactured by Ciba Japan Co., Ltd. X (above, trade name); Lemonite CBUS-3B (trade name) manufactured by Khyati Chemicals and the like are preferable. Of these, chinopearl CBS-X and chinopearl AMS-GX are more preferable.

<Enzyme>
Enzymes include hydrolases, oxidoreductases, lyases, transferases, and isomerases when classified according to the reactivity of the enzyme.
Of these, protease, esterase, lipase, nuclease, cellulase, amylase, pectinase and the like are preferable.

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.
Commercially available products include sabinase, alcalase, cannase, everase, deozyme (trade name; manufactured by Novozymes); API21 (trade name, manufactured by Showa Denko KK); Maxacal, Maxapem (all, trade name: manufactured by Genencor) Protease K-14 or K-16 (protease described in JP-A-5-25492) and the like.

Examples of the esterase include gastric lipase, buncreatic lipase, plant lipase, phospholipase, cholinesterase, phosphotase and the like.
Examples of the lipase include commercially available lipases such as lipolase, Lipex (above, trade name: manufactured by Novozymes), and liposum (trade name, manufactured by Showa Denko KK).
Examples of cellulases include commercially available cellzymes (trade name, manufactured by Novozymes); alkaline cellulase K, alkaline cellulase K-344, alkaline cellulase K-534, alkaline cellulase K-539, alkaline cellulase K-577, and 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 (the cellulase described in JP-A-63-264699) and the like.
Examples of amylase include commercially available products such as 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.
It is preferable that the enzyme is granulated as separately stable particles and used in a state of being dry blended with the detergent dough (particles).

<Enzyme stabilizer>
As an enzyme stabilizer, calcium salt, magnesium salt, a polyol, formic acid, a boron compound etc. can be mix | blended, for example. 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 the compounding quantity 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 surfactant-containing particles, or to impart a recontamination preventing effect on hydrophobic fine particles (dirt). , Polyethylene glycol having a weight average molecular weight of 200 to 200,000, acrylic acid and / or maleic acid polymer salt having a weight average molecular weight of 1,000 to 100,000, cellulose derivatives such as polyvinyl alcohol, carboxymethylcellulose, hydroxypropylmethylcellulose (HPMC), etc. be able to.
Further, as a soil release agent, 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.
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 the compounding quantity 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.

<Antifoaming agent>
Examples of the antifoaming agent include silicone / silica-based ones. Moreover, you may use this antifoamer as the following antifoamer granulated material.
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, 50% by mass of the obtained homogeneous mixture, 25% by mass of polyethylene glycol (PEG-6000, melting point: 58 ° C.), and 25% by mass of sodium sulfate were mixed at 70 to 80 ° C., and then an extrusion granulator (model EXKS). -1, manufactured by Fuji Powder 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, glycolethylenediaminehexacetic 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 for the compounding quantity of the metal ion scavenger in a granular detergent composition, 0.1-5 mass% is preferable, More preferably, it is 0.5-3 mass%. If it is in the said range, the effect which capture | acquires the metal ion in tap water will improve.

<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 described above. 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 alkali agent. In addition to the alkali agent described in the detergency builder, monoethanolamine, diethanolamine, triethanolamine, and the like. Examples include alkanolamine, sodium hydroxide, potassium hydroxide and the like. For example, from the viewpoint of solubility in water and alkalinity, NABION15 (trade name, manufactured by Rhodia), which is a mixture of sodium carbonate, sodium silicate, and water at a ratio of 55/29/16 (mass ratio) is used. Is preferred.
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.

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

[Method for producing granular detergent composition]
<(A1) Component Production Method>
The production method of the component (a1) hinders the effects of the present invention as long as the component (β) is a core substance, the component (α) is a capsule wall, and the component (α) can be included in the component (β). As long as it is not, a known method can be used. For example, an interfacial polymerization method, an in-situ polymerization method, etc. are mentioned, and can be determined according to the type of the component (α).
Especially, when using a urethane type polymer as ((alpha)) component, an interfacial polymerization method is preferable. Specifically, an emulsifier aqueous solution having an arbitrary concentration is prepared in one container, and a fragrance solution of the (β) component and the polyisocyanate compound is prepared in another container. Next, the aqueous emulsifier solution and the perfume solution are stirred at high speed with a high speed stirrer to prepare an oil-in-water (O / W) type emulsion. Next, an encapsulated fragrance dispersion in which the component (a1), which is an encapsulated fragrance, is dispersed in water by adding an aqueous polyamine solution having an arbitrary concentration, stirring for an arbitrary time at room temperature, and reacting to cure the capsule wall. Obtainable.

  Further, for example, when a melamine polymer is used as the (α) component, an in-situ polymerization method is preferable, and a method of forming the capsule wall from the outside of the core substance is preferable. Specifically, in a container equipped with a stirrer, the (β) component is dispersed in water and stirred under an arbitrary temperature condition to prepare a fragrance dispersion in which the (β) component has an arbitrary particle size. Apart from the fragrance dispersion, for example, melamine and formaldehyde are subjected to condensation polymerization at an arbitrary temperature to prepare a water-soluble prepolymer. And the said prepolymer is added to a fragrance | flavor dispersion liquid, and the condensation fragrance | flavor dispersion liquid which (a1) component disperse | distributed to water can be obtained by carrying out the condensation polymerization further under arbitrary temperature conditions.

The dispersion concentration of the (β) component in the fragrance dispersion liquid is not limited, but is preferably determined in the range of 10 to 40% by mass, for example. Although the temperature which prepares a fragrance | flavor dispersion liquid is not specifically limited, For example, it is preferable to determine in 60-80 degreeC.
The mixing ratio of melamine and formaldehyde in the preparation of the prepolymer is preferably determined in the range of melamine / formaldehyde (mass ratio) = 3/1 to 6/1, for example. Although the temperature which prepares a prepolymer is not specifically limited, For example, it is preferable to determine in 60-80 degreeC. Although the reaction time in prepolymer preparation is not specifically limited, It is preferable to determine in the range for 5 to 20 minutes.
The pH in the condensation polymerization performed by adding the prepolymer to the fragrance dispersion can be determined in the range of 2 to 5, for example. For pH adjustment, for example, an acid such as citric acid, sulfuric acid, hydrochloric acid or the like can be selected. Although the reaction conditions in the condensation polymerization performed by adding the prepolymer to the fragrance dispersion are not particularly limited, for example, the reaction temperature is preferably determined in the range of 60 to 80 ° C. The reaction time is not particularly limited, but is preferably determined in the range of 3 to 6 hours.
An emulsifier can be added to the fragrance dispersion liquid as necessary.

  For example, when a polyacrylic acid polymer or polymethacrylic acid polymer is used as the component (α), an in-situ polymerization method in which the capsule wall is formed from the core material side is preferable. For example, a mixture dispersion in which monomers such as ethyl acrylate and ethyl methacrylate, a polymerization initiator, and a (β) component are dispersed in water and stirred with a stirrer, and the (β) component is adjusted to an arbitrary particle size. Obtain a liquid. An encapsulated fragrance dispersion in which the component (a1) is dispersed in water can be obtained by polymerizing the component (β) under an arbitrary temperature condition while introducing nitrogen gas into the mixed dispersion.

The concentration of the (β) component in the mixed dispersion is not particularly limited and is preferably determined in the range of 10 to 40% by mass, for example. The concentration of the monomer in the mixed dispersion is not particularly limited, and for example, it is preferably determined in the range of 5 to 30% by mass with respect to the (β) component. The concentration of the polymerization initiator in the mixed dispersion is preferably determined in the range of 0.1 to 5% by mass with respect to the monomer.
The temperature condition for adjusting the particle diameter of the (β) component is not particularly limited, and is preferably determined in the range of 20 to 70 ° C, for example.
Although the polymerization conditions for the (β) component are not particularly limited, for example, the polymerization temperature is preferably determined in the range of 60 to 80 ° C. The polymerization time of the (β) component is not particularly limited, but is preferably determined in the range of 3 to 6 hours.

<Method for producing perfume particles>
In the method for producing the fragrance particles, the component (a1) and the component (a2) are granulated to prepare the component (A) (granulation step), and the obtained component (A) is coated with the component (B). (Coating process).
A known granulation method can be used for the granulation step. For example, by adding the component (a2) to the mixing means and spraying the component (a1) onto the component (a2) while flowing the component (a2), the granulated product of the component (a1) and the component (a2) (A) component which is can be obtained.
A known coating method can be used for the coating step. For example, while the component (A) obtained in the granulation step is fluidized by a mixing means, the component (B) is added, and the surface of the component (A) is coated with the component (B) to obtain fragrance particles. be able to.

  The mixing means is not particularly limited, and examples thereof include a granulating apparatus such as a rolling granulator and a stirring granulator, a mixing apparatus such as a horizontal cylindrical rolling mixer, a vertical mixer and a horizontal mixer.

  Although the temperature in a granulation process is not specifically limited, For example, 5-40 degreeC is preferable and 20-30 degreeC is more preferable. This is because, within the above range, the capsule wall of the component (a1) can be prevented from collapsing, and excess fluid can be removed to maintain fluidity.

  Although the temperature in a coating process is not specifically limited, For example, 5-40 degreeC is preferable and 20-30 degreeC is more preferable. This is because, within the above range, the capsule wall of the component (a1) can be prevented from collapsing, and aggregation of the fragrance particles can be prevented to maintain fluidity.

<Method for producing granular detergent composition>
The granular detergent composition of the present invention can be obtained by powder mixing fragrance particles and surfactant-containing particles.
The production method of the surfactant-containing particles is not particularly limited, and a known production method can be used. For example, surfactants other than fragrance particles and other detergent components are dispersed / dissolved in water and spray-dried, and are used for devices such as kneading / extrusion, stirring granulation, rolling granulation, etc. It can be produced by a method of granulating, compression molding, etc., and further pulverizing if necessary.
A known method can be used as the method of powder mixing, and examples thereof include a method of mixing using a powder mixing apparatus such as a ribbon mixer.

[how to use]
The method of using the granular detergent composition of the present invention is not particularly limited, and the washing object 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 article to be washed by the granular detergent composition of the present invention is not particularly limited, and for example, the article to be washed by a normal detergent composition, such as textile products such as clothes, cloths, sheets, and curtains. The same thing as washing is mentioned.

As described above, since the encapsulated fragrance contains the fragrance with a polymer compound, the fragrance component does not come into direct contact with other detergent components (especially surfactants). For this reason, it can prevent that a fragrance | flavor component changes in quality and a fragrance deteriorates.
When the capsule wall is in contact with the surfactant or alkali in the detergent composition for a long time, the capsule wall is broken and the (β) component is gradually released. However, since the granulated product of the encapsulated perfume and the neutral inorganic salt is coated with the fatty acid salt, the perfume particle of the present invention can exist stably in the granular detergent composition without breaking the capsule wall. As a result, the granular detergent composition containing the fragrance particles maintains the fragrance even during long-term storage. In addition, since the capsule wall does not break and the component (a1) adheres to the article to be washed, the aroma imparted to the article to be washed is maintained for a long period of time.

  Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. In addition, in the compounding amount of an Example and a comparative example, unless there is particular notice, "%" represents the mass%.

(Raw materials used)
The raw materials used in Tables 4 to 7 are shown below.
[(A2) component: neutral inorganic salt]
・ Sodium sulfate: neutral anhydrous sodium sulfate (manufactured by Nippon Chemical Industry Co., Ltd.)
・ Sodium chloride: Special reagent grade
[(A2) ′ component: Comparative component of component (a2) ・ Sodium carbonate: granular ash (average particle size 320 μm, bulk density 1.07 g / mL, manufactured by Asahi Glass Co., Ltd.)
・ Powdered cellulose: ARBOCEL BE600 / 10TG (trade name, manufactured by Rettenmeier)
・ Zeolite: Shilton B (trade name, A-type zeolite, manufactured by Mizusawa Chemical Co., Ltd .; pure content 80% by mass)
Bentonite: Landrosil PR414 (trade name, manufactured by Zudchemi)
・ Acid clay: Mizuka Ace (trade name, Mizusawa Chemical Co., Ltd.)
・ Zinc oxide: Fine zinc oxide (Hanamotojo Chemical Co., Ltd.)

[(B) component: fatty acid salt]
・ Magnesium stearate: (Nippon Yushi Co., Ltd.)
・ Sodium decanoate: (Sigma Aldrich Japan Co., Ltd.)
[(B) ′ component: component to be compared with component (B)]
・ Zeolite: Type A zeolite (trade name: Shilton B, manufactured by Mizusawa Chemical Co., Ltd .; pure content: 80% by mass)

[Components in surfactant-containing particles]
Α-sulfo fatty acid methyl ester sodium salt (MES) mixed concentrate:
The MES mixed concentrate was prepared by the method described below. In Table 4, the compounding amount of MES indicates the pure content of MES in the MES mixed concentrate.
<Sulfonation step>
Methyl palmitate (product name: Pastel M-16, manufactured by Lion Corporation) and methyl stearate (product name: Pastel M-180, manufactured by Lion Corporation) were mixed at 80:20 (mass ratio). Further, by performing hydrogenation treatment by a conventional method, the iodine value was reduced to 0.2 and purified to obtain a purified fatty acid methyl ester. This purified fatty acid methyl ester was flowed in a thin film reactor using SO ₃ gas diluted to 7% with dehumidified air, with a reaction molar ratio (SO ₃ / saturated fatty acid ester) = 1.18 and a reaction temperature of 80 ° C. Sulfonation under conditions gave a sulfonated product.

<Aging process>
The resulting sulfonated product was introduced into a loop ripening tube with a double tube jacket having an average residence time of 20 minutes. Three loop type ripening tubes were connected in succession, and the average residence time was 60 minutes. In order to maintain sufficient agitation and constant temperature, the sulfonated product is allowed to flow through a loop aging tube at a linear speed of 0.16 m / s, and the aging reaction is controlled at 78 to 82 ° C. to complete the sulfonation. α-sulfo fatty acid methyl ester was obtained.

<Esterification and bleaching process>
After introducing 20 parts by mass of methanol (industrial grade, moisture 500 ppm or less, manufactured by Sumitomo Chemical Co., Ltd.) with respect to 100 parts by mass of the obtained α-sulfo fatty acid methyl ester, this mixture and 35% hydrogen peroxide (35% 5.7 parts by mass of industrial hydrogen peroxide (industrial grade, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was introduced into a continuous loop reactor equipped with a mixing mixer and a heat exchanger for bleaching, and α-sulfo fatty acid methyl ester A bleached product was obtained.

<Neutralization process>
Next, with respect to 125 parts by mass of the bleached product of α-sulfo fatty acid methyl ester, 28 parts by mass of a 48% NaOH aqueous solution (caustic soda manufactured by Daiso Corporation: industrial grade), 25 parts by mass of a nonionic surfactant, 69 parts by mass of water, 24 parts by mass of methanol (Sumitomo Chemical Co., Ltd. methanol: industrial grade) and 5 parts by mass of LAS-H (Lypon LH-200 (pure content 96%), manufactured by Lion Corporation) are continuously supplied to the neutralization line. did.
The neutralization method employs the neutralization method described in JP-A-2001-64248, so that a 48% NaOH aqueous solution can be quantitatively fed between the premixer and the neutralization mixer so that it can be neutralized continuously. I made it. And the neutralized product (α-sulfo fatty acid methyl ester sodium salt = MES) of α-sulfo fatty acid methyl ester that has been neutralized in advance, and the bleach-treated product of α-sulfo fatty acid methyl ester, After thoroughly mixing with a premixer, it was mixed with a 48% NaOH aqueous solution to obtain a neutralized product.

<Concentration process>
Using the above neutralized product as a raw material surfactant aqueous solution, recycling flash evaporation described in JP-A No. 2004-210807 is performed, lower alcohol is removed and concentrated, and a MES concentrated mixture (MES62 with a moisture content of 10.8%) is obtained. %, LAS-Na 3.5%, nonionic surfactant 16.8%).

LAS-H: linear alkyl (C10-14) benzenesulfonic acid (Lypon LH-200, 96% pure, manufactured by Lion Corporation)
LAS salt: A compound obtained by neutralizing LAS-H with 48% sodium hydroxide aqueous solution and a compound neutralized with 48% aqueous potassium hydroxide instead of neutralizing with sodium hydroxide in a mass ratio of 1: 2 mixed. The compounding quantity of the LAS salt in Table 4 shows the value (mass%) as these mixtures.
Soap: Fatty acid sodium having 12 to 18 carbon atoms (manufactured by Lion Corporation, pure content: 67%, titer: 40 to 45 ° C .; fatty acid composition: C12 11.7%, C14 0.4%, C16 29.2% C18F0 (stearic acid) 0.7%, C18F1 (oleic acid) 56.8%, C18F2 (linoleic acid) 1.2%; molecular weight: 289).
Nonionic surfactant: ECOROL 26 (trade name, manufactured by ECOGREN, alcohol having an alkyl group having 12 to 16 carbon atoms) average 15 mol of ethylene oxide adduct (pure 90%).
Enzyme: Sabinase 12T (Novozymes) / LIPEX100T (Novozymes) / Stainzyme 12GTS (Novozymes) Cellzyme 0.7T (Novozymes) = 4/1/4/1 (mass ratio) mixture.
MA agent: acrylic acid / maleic anhydride copolymer sodium salt (trade name: Aqualic TL-400, manufactured by Nippon Shokubai Co., Ltd .; pure 40% aqueous solution).
・ Zeolite: Shilton B (trade name, A-type zeolite, made by Mizusawa Chemical Co., Ltd .; 80% pure)
-Sodium sulfite: anhydrous sodium sulfite (manufactured by Shinshu Chemical Co., Ltd.).
・ Sodium sulfate: neutral anhydrous sodium sulfate (manufactured by Nippon Chemical Industry Co., Ltd.)
Sodium carbonate: granular ash (average particle size 320 μm, bulk density 1.07 g / mL, manufactured by Asahi Glass Co., Ltd.)
Potassium carbonate: potassium carbonate (powder) (average particle size 490 μm, bulk density 1.30 g / mL, manufactured by Asahi Glass Co., Ltd.)
-Brightening agent: Chinopearl CBS-X (Ciba Specialty Chemicals) / Chinopearl AMS-GX (Ciba Specialty Chemicals) = 3/1 (mass ratio) mixture.
-Dye: Ultramarine (Ultramarine Blue, manufactured by Dainichi Seika Kogyo Co., Ltd.)

(Production Example 1) Preparation of encapsulated fragrance A Encapsulated fragrance A was prepared as follows. The encapsulated fragrance A has a capsule wall formed of a urethane-based polymer compound.
In a 300 mL beaker, 200 g of ion-exchanged water and 5 g of polystyrene sulfonate sodium salt having an average molecular weight of 16,000 (trade name: Politi PS-1900, manufactured by Lion Corporation) were added as an emulsifier and dissolved to obtain an aqueous emulsifier solution. In another 100 mL beaker, 55 g of the fragrance composition β1 shown in Table 1 and 8 g of polyphenyl isocyanate (trade name: PAPI-135, manufactured by Dow Chemical Co., Ltd.) were added and mixed to obtain a fragrance solution.
Next, an aqueous emulsifier solution and a fragrance solution were placed in a 500 mL beaker, and stirred at 3000 rpm for 5 minutes with a homomixer to prepare an O / W type emulsion A. Next, 75 g of a 40% hexamethylenediamine aqueous solution is added to this O / W emulsion A, and the capsule wall is reacted and cured by stirring at 400 rpm for 2 hours at room temperature. Liquid A was obtained. The encapsulated fragrance dispersion A thus obtained was measured with a laser diffraction particle size distribution analyzer (SALD-300V, manufactured by Shimadzu Corporation). As a result, the average particle size of the encapsulated fragrance A was about 5 μm. Moreover, the content rate of the fragrance | flavor composition (beta) 1 in the obtained encapsulated fragrance | flavor A was about 16%.

(Production Example 2) Preparation of encapsulated fragrance B Encapsulated fragrance B was prepared as follows. The encapsulated fragrance B has a capsule wall formed of a melamine polymer compound.
Sodium salt of ethylene-maleic anhydride copolymer (trade names: A-C573A, 573P, manufactured by Honeywell) and polystyrene sulfonate sodium salt having an average molecular weight of 16,000 as an emulsifier (trade name: Polyty PS-1900, 150 g of the fragrance composition β2 shown in Table 2 was added to 300 g of an aqueous solution containing 5% of each (Lion) and stirred with a homomixer at a speed of 2,500 rpm to prepare an O / W emulsion B. Separately, 30 g of melamine (Tokyo Kasei Kogyo Co., Ltd.), 100 g of 35% formaldehyde aqueous solution and 350 g of water were added with sodium hydroxide to adjust the pH to about 9, followed by stirring at 80 ° C. for 30 minutes, and methylolmelamine An aqueous solution was prepared. This methylolmelamine aqueous solution was added to the O / W emulsion B and stirred at 70 ° C. for about 2 hours to harden the capsule wall to obtain an encapsulated fragrance dispersion B in which the encapsulated fragrance B was dispersed. As a result of measuring the particle diameter of the encapsulated fragrance B in the same manner as the encapsulated fragrance aqueous solution A, the average particle diameter was about 4 μm. Moreover, the content rate of the fragrance | flavor composition (beta) 2 in the obtained encapsulated fragrance | flavor B was about 16%.

(Production Example 3) Preparation of encapsulated fragrance C Encapsulated fragrance C was prepared as follows. In the encapsulated fragrance C, a capsule wall is formed of an acrylic ester polymer compound. As an emulsifier, 6 g of phenolsulfonic acid formaldehyde condensate (Belcotan N, manufactured by Nippon Seimitsu Chemical Co., Ltd.), 8 g of polyvinyl pyrrolidone (Tokyo Chemical Industry Co., Ltd.) having a K value of 90, 236 g of paraffin oil (Pure Chemical Co., Ltd.), 160 g of fragrance composition β3, 45.3 g of methyl methacrylate (Tokyo Chemical Industry Co., Ltd.), 39.7 g of diethylaminoethyl methacrylate (Tokyo Chemical Industry Co., Ltd.), 0.63 g of azobisisobutyronitrile (Tokyo Chemical Industry Co., Ltd.) And dimethyl-2,2′-azobisisobutyrate (Tokyo Kasei Kogyo Co., Ltd.) (0.92 g) was dispersed in 512 g of water using a high-speed toothed disk mill at room temperature and 4500 rpm for 20 minutes. Mold emulsion C was prepared. The O / W type emulsion C was a stable O / W type emulsion C having a particle diameter of 2 to 15 μm. The O / W emulsion C was heated to 60 ° C. with stirring with a horseshoe stirrer and stirred for 1.5 hours. Next, the O / W type emulsion C was increased to 65 ° C. in 20 minutes and stirred at this temperature for 4 hours. Thereafter, the O / W emulsion C was cooled to room temperature while stirring to obtain an encapsulated fragrance dispersion C in which the encapsulated fragrance C was dispersed. As a result of measuring the particle diameter of the encapsulated fragrance C with a laser diffraction particle size distribution analyzer, the particle diameter was 2 to 15 μm, and the average particle diameter was about 4 μm. Moreover, the content rate of the fragrance | flavor composition (beta) 3 in the obtained encapsulated fragrance | flavor C was about 16%.

(Examples 1-17)
[Step A]
Surfactant-containing particles were produced according to the formulations shown in Tables 4-6. Water was put into a jacketed mixing tank equipped with a stirrer, and the temperature was adjusted to 60 ° C. To this, a part of the LAS salt (excluding the amount brought in from the MES-containing composition obtained in the following step B) and soap were added and stirred for 10 minutes. Subsequently, the MA agent was added. After further stirring for 10 minutes, a part of the zeolite (2.0% equivalent for addition during kneading, 5.0% equivalent for grinding aid, 1.5% equivalent for surface coating was removed). Balance), sodium carbonate, potassium carbonate, sodium sulfate. The slurry was further stirred for 20 minutes to prepare a slurry for spray drying having a moisture content of 38%. The slurry for spray drying was spray dried using a countercurrent spray drying tower at a hot air temperature of 280 ° C. to obtain spray dried particles having an average particle size of 320 μm, a bulk density of 0.30 g / mL, and a water content of 5%.

[Step B]
Spray dried particles obtained in step (A), MES mixed concentrate, 2.0% type A zeolite, remaining nonionic surfactant excluding 0.3% equivalent for spray addition, fluorescent brightener and water Was added to a continuous kneader (KRC-S4 type, manufactured by Kurimoto Steel Co., Ltd.), kneaded under the conditions of a kneading capacity of 120 kg / hr and a temperature of 60 ° C., and a mixture of 6% water containing a surfactant was obtained. Obtained. The mixture obtained in the step (B) was cut with a cutter while extruding it using a pelleter double (EXDFJS-100 type, manufactured by Fuji Powder Co., Ltd.) equipped with a die having a hole diameter of 10 mm (cutter peripheral speed was 5 m / m). s) A pellet having a length of about 5 to 30 mm was obtained.

[Step C]
Fitzmill (DKA-3, Hosokawa Micron Co., Ltd.) was added to the resulting pellets in an amount equivalent to 5.0% A-type zeolite as a grinding aid and arranged in series in the presence of cold air (10 ° C., 15 m / s). (Screen hole diameter: 1st stage / 2nd stage / 3rd stage = 12 mm / 6 mm / 3 mm, rotational speed: 1st stage / 2nd stage / 3rd stage are all 4700 rpm) A pulverized product containing a surfactant was obtained.
Filling rate using 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 and two baffle plates with a clearance of 20 mm from the inner wall surface and a height of 45 mm) Under the conditions of 30% by volume, 22 rpm, and 25 ° C., 1.5% equivalent amount of zeolite was added to the pulverized product and rolled for 1 minute while spraying 0.3% equivalent amount of nonionic surfactant, Granulated particles were obtained.
In order to color a part of the obtained granulated particles, the granulated particles were transferred by a belt conveyor at a speed of 0.5 m / s (the surfactant-containing particle layer on the belt conveyor had a height of 30 mm, a layer The surface was sprayed with 0.1% of a 20% aqueous dispersion of pigment on the surface to obtain surfactant-containing particles.

According to the composition shown in Tables 4 to 6, the component (a2) is charged into a small pulverizer (model: SK-M, manufactured by Kyoritsu Riko Co., Ltd.), and the component (a1) is gradually charged over 5 minutes while stirring. Then, stirring was further continued for 3 minutes to obtain a granulated product. The granulated product was dried for 1 day and then passed through a sieve (JIS-Z8801) having an opening of 850 μm. The portion that did not pass through the sieve was pulverized by Trio Blender (manufactured by Trio Science), passed through a sieve having an aperture of 850 μm, and passed through the sieve. After all the granulated material was passed through the sieve in this way, the component (B) was added to the granulated material, and thoroughly mixed with a table grinder to obtain perfume particles (step D).
The obtained perfume particles, surfactant-containing particles, sodium sulfite, and an enzyme were mixed with a horizontal cylindrical rolling mixer (cylinder diameter 585 mm, cylinder length 490 mm, inner wall surface on drum inner wall surface of container 131.7 L). And having a baffle plate with a clearance of 20 mm and a height of 45 mm) and rolling for 1 minute under the conditions of a filling rate of 30 vol%, a rotation speed of 22 rpm, and 25 ° C. to obtain a granular detergent composition (above) Step E).
About the obtained granular detergent composition, residual fragrance property and fragrance property were evaluated.

(Comparative Examples 1-6)
In accordance with the formulation of Tables 6-7, except that the component (a2) added in step D was changed to the component (a2) ′, the example was the same as in Example 1, except that sodium sulfate was added instead of sodium sulfate. In the same manner as in Example 1, a granular detergent composition was obtained. About the obtained granular detergent composition, residual fragrance property and fragrance property were evaluated.

(Comparative Example 7)
A granular detergent composition was obtained in the same manner as in Example 1 except that the component (B) added in Step D was changed to the component (B) ′ according to the formulation in Table 7. About the obtained granular detergent composition, residual fragrance property and fragrance property were evaluated.

(Comparative Example 8)
According to the composition of Table 7, a granular detergent composition was obtained in the same manner as in Example 1 except that the component (B) was not added in Step D. About the obtained granular detergent composition, residual fragrance property and fragrance property were evaluated.

(Comparative Examples 9-11)
According to the composition of Table 7, a granular detergent composition was obtained in the same manner as in Example 1 except that the enzyme and sodium sulfite were mixed while spraying the component (a1) on the surfactant-containing particles without providing the step D. It was. About the obtained granular detergent composition, residual fragrance property and fragrance property were evaluated.

(Evaluation test)
[Long-term storage method of detergent]
Using paper consisting of three layers of coated cardboard (basis weight: 350 g / m ² ), wax sand paper (basis weight: 30 g / m ² ), and kraft pulp paper (basis weight: 70 g / m ² ) from the outside, A box having a length of 15 cm, a width of 9.3 cm, and a height of 18.5 cm was produced. In this box, 1.0 kg of granular detergent composition is placed, stored in a constant temperature and humidity chamber of 45 ° C., 85% RH for 8 hours and 25 ° C., 65% RH for 16 hours for 28 days, and then allowed to stand at room temperature for 24 hours. Set as a long-term storage sample.
Using paper consisting of three layers of coated cardboard (basis weight: 350 g / m ² ), wax sand paper (basis weight: 30 g / m ² ), and kraft pulp paper (basis weight: 70 g / m ² ) from the outside, A box having a length of 15 cm, a width of 9.3 cm, and a height of 18.5 cm was produced. In this box, 1.0 kg of the granular detergent composition was placed and allowed to stand at room temperature for 24 hours to be used as a reference sample.

[Test method]
<Pretreatment>
Store 50 ° C tap water in a two-tank washing machine (product name: CW-C30A1-H1 type, manufactured by Mitsubishi Electric Corporation), and use a commercially available detergent top (made by Lion Corporation) at a standard concentration (30L tap water). In contrast, detergent top 20 g, ie 667 mg / L) was added to the water. After putting 1kg of cotton towel (220mm border soft FT, manufactured by Toshin Co., Ltd.) into the washing machine and repeating the washing and dehydrating operations of "washing for 15 minutes and then dehydrating for 5 minutes" twice at a bath ratio of 30 times, The rinsing / dehydration operation of “15 minutes of running water rinsing and 5 minutes of dehydration” was repeated 5 times. Thereafter, the cotton towel was pretreated by hanging and drying at room temperature.
B. V. The same pretreatment was applied to 1 kg of D skin shirt (round neck short sleeve T-shirt, product number G0134TS).

<Cleaning process>
Cotton towel 2 pre-treated using a fully automatic electric washing machine (product name: JW-Z23A, made by Haier) as a washing machine and using tap water with a water temperature of 20 ° C. according to the normal course of the fully automatic electric washing machine Sheet (71 g / sheet), pretreated B. V. D skin shirts (140 g / sheet) (total 562 g, hereinafter collectively referred to as “fabrics”) 21 times the bath ratio (low water level: 12 L) and the granular detergent composition of each example The cloth was treated in the same bath at a concentration of 833 mg / L (10 g of granular detergent composition with respect to 12 L of tap water). Then, it was hung and dried at room temperature.

[Evaluation of residual fragrance]
The residual fragrance property was evaluated by comparing the cotton towel washed with the granular detergent composition of the reference sample in each example and the cotton towel washed with the granular detergent composition of the long-term storage sample. The sample was washed with a reference sample or a long-term storage sample, and after 3 days of drying, a sensory test was performed according to the following evaluation criteria by five professional panelists. The average score of five professional panelists was calculated, and the evaluation was classified into five grades A to E.

[Evaluation of fragrance]
The fragrance property was evaluated by comparing the cotton towel washed with the granular detergent composition of the reference sample of each example described above and each cotton towel washed with the granular detergent composition after long-term storage sump. The sample was washed with a reference sample or a long-term storage sample, cut into 10 × 10 cm 3 days after drying, and the cut towels were rubbed together three times, and then subjected to a sensory test according to the following evaluation criteria by five professional panelists. The average score of five professional panelists was calculated, and the evaluation was classified into five grades A to E.

<Evaluation criteria>
Acceleration test of granular detergent composition in each case 5 points: equivalent to reference sample 4 points: slightly weaker than reference sample 3 points: slightly weaker than reference sample 2 points: reference sample 1 point: very weak compared to the reference sample

<Evaluation classification>
The average of the five professional panelists and the following classifications.
A: 4.6 to 5 points B: 3.6 to less than 4.6 points C: 2.6 to less than 3.6 points D: 1.6 to less than 2.6 points E: 1.6 points Less than

As shown in Tables 4 to 7, in the granular detergent compositions of Examples 1 to 17 in which the fragrance particles of the present invention were blended, the evaluation classification of the remaining fragrance and the fragrance was C or B.
On the other hand, in Comparative Examples 1 to 6 using the component (a2) ′ instead of the component (a2), the evaluation classification of residual fragrance and fragrance was D or E. In Comparative Example 8 which was not covered with the component (B), the evaluation classification of the remaining fragrance and the fragrance was D. In Comparative Example 7 using zeolite instead of (B) component, and Comparative Examples 9 to 11 in which (a1) component was directly sprayed on the surfactant-containing particles, the evaluation classification of residual fragrance and fragrance were both E. Met.
From the above results, it is possible to improve the fragrance and fragrance after long-term storage by granulating an encapsulated fragrance and a neutral inorganic salt and further using the fragrance particles whose surface is coated with a fatty acid salt. I understood.

  The fragrance particles of the present invention have high fragrance stability during long-term storage and can impart a fragrance that lasts for a long time to the object to be washed. .

Claims (4)

  A perfume particle, wherein a granulated product containing an encapsulated perfume encapsulating a perfume with a polymer compound and a neutral inorganic salt is coated with a fatty acid salt.   The perfume particle according to claim 1, wherein the fatty acid salt has 10 to 18 carbon atoms in the carbon chain.   The fragrance according to claim 1 or 2, wherein the polymer compound is at least one selected from the group consisting of a polyacrylate polymer, a melamine polymer, and a urethane polymer. particle.   The granular detergent composition containing the fragrance | flavor particle | grains of any one of Claims 1-3.