JP2008156565A - Additive particle for washing, method for producing the same, and detergent for clothes containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an additive particle for washing preventing functional substances from running off at the time of production or washing, adhering the functional substances effectively on the clothes and improving sustained release effects thereof, to provide a method for producing the same and a detergent for clothes including the same. <P>SOLUTION: This additive particle for washing clothes contains a component(a): at least one functional substance selected from among a perfume component, a deodorant, a repellent, a UV absorber, an antimicrobial agent, a bactricide, a softener and an antisoil redeposition agent, a component(b): a silica particle, a component(c): a fiber-adsorbing substance comprising at least one selected from among a clay mineral, cellulose, cationized cellulose and a cationic surfactant, with an adsorption rate of 20% or more. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

 The present invention relates to laundry additive particles suitably added to, for example, clothes detergents used for washing clothes and fibers, a method for producing the same, and clothes detergents including the same.

In recent years, laundry detergents are required to have other functions in addition to the strength of detergency. For example, there is a high demand for the persistence of the scent after washing, the whiteness and flexibility after washing, and the like. In addition, if washing is performed using a detergent imparted with repellent properties, an insect repellent effect can be expected by wearing clothes.
However, a functional substance having such a function tends to flow out during washing, and it is difficult to maintain its effect.

Therefore, methods for impregnating a porous substance with a functional substance have been examined as a technique for enhancing the retention and sustained release effect of the functional substance.
For example, Patent Document 1 describes a method for producing a moisture-resistant composition in which particles of an inorganic carrier material and a substance such as a fragrance are emulsified, and the emulsion is spray-dried and granulated.
Patent Document 2 discloses a method in which hydrophobic modified silica is dispersed in oil (perfume) and then emulsified in an aqueous polymer, the emulsion is sprayed, and the sprayed emulsion is dehydrated to form encapsulated oil particles. Are listed.
Patent Document 3 describes a detergent composition to which porous inorganic carrier particles that have absorbed a fragrance are added.
Patent Document 4 discloses a sustained-release fragrance composition in which a film layer is formed with a film-forming polymer on the entire surface of solid particles obtained by granulating an inert carrier powder adsorbed with a fragrance using a binder solution. The manufacturing method of the thing is described.
Patent Document 5 discloses a liquid or liquefiable active ingredient, a water-insoluble solid support component, a water-soluble and / or water-dispersible encapsulating substance, one or more auxiliary ingredients, acrylamide and dimethylaminoethyl. Described is a method of making a detergent auxiliary composition comprising a surface adhesion enhancing cationic polymer such as a copolymer of acrylate with methyl chloride quaternary salt (DMA3-MeCl) by spray drying.
Japanese National Patent Publication No. 8-506991 Special table 2003-505537 gazette JP-A-5-209188 Japanese Examined Patent Publication No. 62-29056 JP-T-2006-523729

However, in the methods described in Patent Documents 1 and 2, since spray drying is performed, it is necessary to apply heat to some extent. However, since the fragrance and the like have a low boiling point, the fragrance flows out during the production of granules and particles. A large drying device and a large amount of drying energy were required. Further, since spray drying is performed after emulsification, the process is likely to be complicated, and it is difficult to optimize the emulsifier and the like, and thus the production cost is high.
In the detergent composition described in Patent Document 3, since a fragrance is only impregnated with a porous material having a specific pore size, it is difficult to suppress the outflow of components such as fragrance, which is likely to occur when washing is easy, and washing is completed. It was difficult to keep the ingredients until time.
In the method described in Patent Document 4, it is difficult for the scent to be maintained even in the clothes after washing.
In the method described in Patent Document 5, since it is produced by spray drying, there is a problem that the use of a low boiling point component that is easily volatilized and a component that is easily deteriorated or modified by heat is restricted.

  The present invention has been made in view of the above circumstances, prevents the outflow of a functional substance at the time of manufacture or washing, effectively adheres the functional substance to clothing, and improves the sustained release effect. Another object of the present invention is to provide laundry additive particles, a method for producing the same, and a laundry detergent containing the same.

  As a result of intensive studies, the present inventors have focused on the fact that particles having improved retention of the functional substance can be obtained by impregnating the functional substance with silica particles that are porous carriers. And in low boiling functional materials, such as a fragrance | flavor, it discovered that the particle | grains which suppress the outflow in water and show high retainability by using the porous support | carrier which processed the surface hydrophobically are obtained. Furthermore, by including the fiber-adsorbing substance together with the silica particles impregnated with the functional substance, the functional substance is retained in the particles even after rinsing and washing, and the particles containing the functional substance are changed to clothing ( The present invention has been completed by finding that it adheres to (fiber) and brings about a very excellent effect on clothing, and the durability of the effect (sustained release effect) is increased.

That is, the laundry additive particles of the present invention are characterized by containing the components shown in the following (a) to (c).
(A) Component: At least one functional substance selected from a fragrance component, a deodorant, a repellent, an ultraviolet absorber, an antibacterial agent, a bactericidal agent, a softening agent, and a recontamination preventive agent.
(B) Component: Silica particles.
(C) Component: A fiber-adsorbing substance composed of at least one selected from clay minerals, cellulose, cationized cellulose, and cationic surfactants, and having an adsorption rate on cotton cloth of 20% or more.

Here, in 100% by mass of the laundry additive particles, the content of the component (a) is 5 to 70% by mass, the content of the component (b) is 5 to 80% by mass, and the component (c) The content is preferably 5 to 80% by mass.
The component (a) is preferably a fragrance component.
Furthermore, it is preferable that the component (b) exhibits hydrophobicity.
Moreover, the detergent for clothes of this invention contains the said additive particle | grains for washing.

Moreover, the manufacturing method of the additive particle for laundry of this invention mixes the following (a) component and the following (b) component, and prepares the powder mixture which (a) component impregnated to (b) component. And a granulation step of compacting the powder mixture together with the following component (c).
(A) Component: At least one functional substance selected from a fragrance component, a deodorant, a repellent, an ultraviolet absorber, an antibacterial agent, a bactericidal agent, a softening agent, and a recontamination preventive agent.
(B) Component: Silica particles.
(C) Component: A fiber-adsorbing substance composed of at least one selected from clay minerals, cellulose, cationized cellulose, and cationic surfactants, and having an adsorption rate on cotton cloth of 20% or more.

According to the present invention, washing additive particles that prevent the outflow of a functional substance at the time of production or washing, effectively attach the functional substance to clothing, and improve the sustained release effect, and the production thereof Methods and clothing detergents comprising the same can be provided.
Furthermore, according to the present invention, it is possible to produce additive particles for laundry containing a high concentration of functional substance, and since it is not necessary to treat at high temperature during production, the outflow of the functional substance can be suppressed, and a high effect can be obtained. Can be expressed.

Hereinafter, the present invention will be described in detail.
The laundry additive particles of the present invention contain a functional substance, silica particles, and a fiber adsorbing substance.

[Laundry additive particles]
<(A) Component: Functional substance>
As a functional substance, at least 1 sort (s) chosen from a fragrance | flavor component, a deodorant, a repellent, an ultraviolet absorber, an antibacterial agent, a disinfectant, a softening agent, and a recontamination prevention agent is used. Among these, a fragrance component is preferable.
The content of the functional substance is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and further preferably 30 to 50% by mass in 100% by mass of the additive particles for laundry. When the lower limit value of the content of the functional substance is less than the above value, the sustained release effect is lowered, and the active ingredients in the laundry additive particles are reduced. On the other hand, when the upper limit of the content is higher than the above value, the functional substance tends to flow out in water, and the retention property is lowered.

(Fragrance ingredient)
As perfume ingredients, ethers such as aliphatic ethers, aromatic ethers, oxides such as aliphatic oxides and terpene oxides, acetals, ketals, phenols, phenol ethers, fatty acids, terpene carboxylic acids, Synthetic fragrances such as hydrogenated aromatic carboxylic acids, acids such as aromatic carboxylic acids, acid amides, nitromusks, nitriles, amines, pyridines, quinolines, pyrroles, indoles, etc. One kind or two or more kinds of blended fragrances including natural fragrances, natural fragrances and / or synthetic fragrances can be mixed and used. For example, in 1996, Motoichi Into, published by Chemical Industry Daily, “Synthetic Fragrance Chemistry and Product Knowledge”, 1969 MONTCLAIR, N. J. et al. Fragrances described in “Perfume and Flavor Chemicals” by STEFEN Arctander can be used.

  Here, main fragrance names are shown below. Eugenol, geraniol, bacdanol, dipropylene glycol, linalool, phenylethyl alcohol, 9-decen-1-ol, citronellol, isoeugenol, cedrol, cis-3-hexenol, nerol, terpineol, borneol, cis-3-hexenyl salicylate, Dibutylhydroxytoluene, methylatrate, manzanate, fluitate, pt-butylcyclohexyl acetate, menthol, tetrahydrolinalol, dimethylbenzylcarbinol, geranyl acetate, citronellyl acetate, phenylethyl acetate, methyl dihydrojasmonate, benzyl acetate, Linalyl acetate, terpinyl acetate, acetyl cedrene, p-tert-butylcyclohexyl acetate Tate, 2-tert-butylcyclohexyl acetate, methylanthranilate, dimethylbenzylcarvinyl acetate, nonanal, decanal, undecanal, 2-methylundecanal, anisaldehyde, heliotropin, hexylcinnamic aldehyde, lyial, lyral, Vanillin, ethyl vanillin, muscone, cyclohexadecenone, musk ketone, tonalide, yonon, methyl ionone, β-methylnaphthyl ketone, cacimelan, α, β, γ-damascone, limonene, pinene, myrcene, caryophyllene, cyclopentadecanolide, γ -Decalactone, γ-undecalactone, coumarin, galaxolide, ambroxan, cedolyl methyl ether, farenal, indole, benzyl alcohol, benzyl salicyle , Para tertiary butyl cyclohexanol, ortho tertiary butyl cyclohexanol, cinnamic alcohol, phenoxyethanol, dihydrolinalol, myrsenol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, 3-octanol, 1-octen-3-ol , 9-decenol, trans-2-cis-6-nonadienol, farnesol, nerolidol, bisabolol, patchoulialcohol, vetiverol, p-tertiary butylcyclohexanol, ambrinol, 1- (2-t-butylcyclohexyloxy) -2 -Butanol, dihydromyrsenol, dimethol, dimyrcetol, fenthyl alcohol, hexyl salicylate, hydrotropic alcohol , Mayol, methyl salicylate, mugol, nopyr alcohol, nerol, oxyphenylone, lavandulol, sandaroa, sandera, santarex, bramanol, polysantol, evanol, dimethylbenzyl carbinol, tetrahydromegol, tetrahydro Geraniol, thymol, carvacrol, paramethylanisole, belt fix, tonalid, allyl amyl glycolate, allyl cyclohexane propionate, amyl valerate, amyl salicylate, isoamyl acetate, isoamyl salicylate, acetyl eugenol, benzyl salicylate, bergamyl acetate , Bornyl acetate, Butyl butyrate, Benzyl formate, Cedryl acetate, Citronellyl forme , Cyclaset, cyclaprop, cinnamyl acetate, flutate, phenylethylphenyl acetate, geranyl formate, cis-3-hexenyl acetate, hexyl salicylate, isobornyl acetate, isononyl acetate, jasmar, menthyl acetate, methyl Salicylate, nopyrucetate, nerylacetate, methylphenylacetate, neobergamate, ethyl-2-methylpentanoate, styralyl acetate, styralylpropionate, tetrahydrolinalyl acetate, tetrahydrogeranylacetate , Beldox, cis-3-hexenal, trans-2-hexenal, heptanal, octanal, adxal, amylcinnamic aldehyde, benzaldehyde , Synamic aldehyde, citral, citrusal, citronellal, cyclamenaldehyde, p-ethyl-2,2-dimethylhydrocinnamaldehyde, 3- (pt-butylphenyl) -propylaldehyde, cuminaldehyde, dupical, helional aldehyde, hyacinthaldehyde , Hydroxycitronellal, isocyclocitral, ligustral, mugealdehyde, miracaldehyde, tripral, 4-tricyclodecylidenebutanal, trimethylcyclohexene methylbutanal, safranal, perilaldehyde, α-methylenecitronellal, undecylenaldehyde , Dimethyloctanal, trimethylundecenal, trans-2-nonenal, acetophenone, rosephenone, carvone, ceres Tolyd, cis jasmon, caron, dihydro jasmon, diphenyl oxide, coabon, methyl lavender ketone, raspberry ketone, civeton, cyclopentadecanone, oxahexadecen-2-one, olibon, oxyphenylon, traseolide, acetyl cedrene, methyl lavender ketone , Isocyclemon, iron, α-dynascon, isodamascon, damacenone, neron, 3,3-dimethylcyclohexylmethylketone, p-tertiary-butylcyclohexanone, cycloten, trimethylcyclopentanone, hexylcyclopentanone, maltol, ethyl maltol, sotron, 2,5-dimethyl-4-hydroxy-3 (2H) -furanone, terpinene, ferrandrene, p-cymene, farnesene, 3-ca , Terpinolene, camphene, sabinene, bisabolen, cedrene, guaien, diphenyl, diphenylmethane, ambret lid, n-butylphthalide, propylidenephthalide, butylidenephthalide, δ-hexalactone, δ-octalactone, δ-nonalactone, δ -2-decenolactone, δ-undecalactone, δ-dodecalactone, δ-tetradecalactone, lactoscatone, γ-hexalactone, γ-octalactone, γ-nonalactone, whiskey lactone, angelica lactone, γ-dodecalactone, γ Jasmolactone, jasmine lactone, cis jasmon lactone, cyclohexyl lactone, ε-decalactone, ε-dodecalactone, ethyl 2-methylbutyrate, allyl heptanoate, ethylene dodecandioate, gala Solide, cyclohexadecanolide, 10-oxahexadecanolide, 11-oxahexadecanolide, 12-oxahexadecanolide, ethylene brushate, 14-methyl-hexadecenolide, 14-methyl-hexadecanolide, Ocymene epoxide, paracresyl methyl ether, rose oxide, cinnamylnitrile, cuminylnitrile, quinoline, isoquinoline, p-methylquinoline, 6-isopropylquinoline, isobutylquinoline, yarayara, acetic acid, heptanoic acid, octanoic acid, decanoic acid, Gellanic acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, benzoic acid, phenylacetic acid, cinnamic acid, hydrocinnamic acid, vanillic acid, anise oil, bay oil, boadrose oil, cananga oil, cardamom oil, Cassia oil, Cedarwood oil, Orange oil, Mandarin oil, Tangerine oil, Basil oil, Nutmeg oil, Citronella oil, Clove oil, Coriander oil, Elemi oil, Eucalyptus oil, Fennel oil, Galvanum oil, Geranium oil, Hiba oil, coconut oil , Jasmine oil, Lavandin oil, Lavender oil, Lemon oil, Lemongrass oil, Lime oil, Neroli oil, Oak moss oil, Ocotia oil, Patchouli oil, Peppermint oil, Perilla oil, Petit glen oil, Pine oil, Rose oil, Rosemary oil , Camphor oil, good oil, clary sage oil, sandalwood oil, spearmint oil, spike lavender oil, star anise oil, thyme oil, tonka bean tincture, turpentine oil, vanilla bean tincture, vetiver oil, ylang ylang oil, grapefruit oil, Yuzu oil, benzoin, Peruvian balsam, truva Sam, tuberose oil, Musukuchinki, Kas thorium tincture, civet tincture, ambergris tincture. Moreover, diethyl phthalate, benzyl benzoate, isopropyl myristate, hercorin, isopentane, orange terpene and the like can be used as a perfume solvent or a retention agent, but are not limited thereto.

(Deodorants)
The deodorant is not particularly limited as long as it is a substance that masks the generated bad odor. Specifically, Ogon, Asenyaku, Sage, Cha, Rosemary, Fennel, Thyme, Nutmeg, Pepper, Turmeric, Vanilla, Paprika, Yokuinin, Psycho, Kiso, Suhou, Curren, John Love, Oxalis, Dokudami, Tsuga, Ginkgo , Black pine, larch, red pine, giraffe, holly mushroom, lilac, hornbill, Japanese cypress, hornbill, forsythia, chestnut, alder, pear, pomegranate, fig, mainspring, sardine, cypress, plantain, mugwort, sagebrush, red-billed sardine, red-billed sword The extract etc. which are extracted with a solvent etc. from fern, a porcupine, Koba no ash, sweet potato (sucrose), etc. are mentioned.
These deodorizers may be used alone or in combination of two or more.

(Repellent)
The repellent is a drug generally used for repelling insects such as pests, and utilizes the property that insects avoid and avoid the smell and taste.
The repellent component is preferably a natural material extract from the viewpoint of safety. Specifically, jasmon, dihydrojasmon, methyl jasmonate, methyl dihydrojasmonate, methyl eugenol, isoeugenol, amyl salicylate, isoamyl salicylate, hexyl salicylate, cis-3-hexenyl salicylate, benzyl salicylate, L-menton, L- Carvone, benzaldehyde, benzyl alcohol, 2-phenylethyl alcohol, 2-phenoxyethanol, α-amyl cinnamaldehyde, cinnamon alcohol, cinnamaldehyde, ethyl cinnamate, propyl cinnamate, isopropyl cinnamate, cinnamyl acetate, amyl benzoate, benzoic acid Isoamyl, hexyl benzoate, cis-3-hexenyl benzoate, heptyl benzoate, octyl benzoate, farnesol, nerolidol, fetol, tetrahydro Nalol, bornyl acetate, milcenyl acetate, cedryl acetate, lavender acetate, citronellyl isobutyrate, terpinyl propionate, linalyl formate, citronellyl tigrate, nopyrulacetate, betiberyl acetate, rilal , Citronellyloxyacetaldehyde, 2,6,10-trimethyl-9-undecanal, yonon, damascon, nootkatone, cedol methyl ether, isomenthone, citronellal, linalool, citronellol, citral, p-menthane, α-pinene, β- Pinene, d-limonene, geraniol, α-terpineol, β-terpineol, γ-terpineol, 1,8-cineol, p-menthan-8-ene-1,2-diol, eugenol, benzylhomee Benzyl acetate, benzyl propionate, benzyl butyrate, benzyl valerate, benzyl caproate, linalool, α-hexylcinnamic aldehyde, lemongrass oil, lavender oil, orange oil, vetiver oil, patchouli oil, cananga oil , Clove oil, cajedput oil, citronella oil, nutmeg oil, pepper oil, sandalwood oil, bulk oil, gazin oil, ginger oil, campo oil, cubeve oil, corn oil, anise oil, Examples include Lang oil, cinnamon oil, mace oil, palomarosa oil, fennel oil, columnar oil, thyme oil, fresh oil, cinnamon leaf oil and the like.
These repellents may be used alone or in combination of two or more.

(UV absorber)
The ultraviolet absorber is not particularly limited as long as it is a substance that absorbs ultraviolet rays, converts them into infrared rays, visible rays, and the like and emits them. Specifically, aminobenzoic acid derivatives such as p-aminobenzoic acid, ethyl p-aminobenzoate, glyceryl p-aminobenzoate, amyl p-dimethylaminobenzoate, ethylene glycol salicylate, dipropylene glycol salicylate, octyl salicylate Salicylic acid derivatives such as myristyl salicylate, methyl diisopropylcinnamate, ethyl p-methoxycinnamate, isopropyl p-methoxycinnamate, p-methoxycinnamate-2-ethylhexyl, butyl p-methoxycinnamate, etc. Cinnamic acid derivatives, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, benzophenone derivatives such as 2,2′-dihydroxy-4-methoxybenzophenone, urocanic acid, ethyl urocanate Etc. Examples thereof include azole compounds and 4-t-butyl-4′-methoxybenzoylmethane.
These ultraviolet absorbers may be used alone or in combination of two or more.

(Antimicrobial agent)
The antibacterial agent is not particularly limited as long as it has an antibacterial action, such as a substance generally used as an antibacterial agent or a substance having an action other than the antibacterial action. Specific examples include an anionic or nonionic antibacterial agent, a cationic or zwitterionic antibacterial agent, and an inorganic antibacterial agent.
Anionic or nonionic antibacterial agents include phenolic (orthophenylphenol (OPP), etc.), carboxylic acid (benzoic acid, etc.), ester (glycerin fatty acid ester, etc.), ether (2,4,4 '-Trichloro-2'-hydroxydiphenyl ether (triclosan), etc.), nitrile (2,4,5,6-tetrachloroisophthalonitrile (TPN), etc.), halogen (N, N-dimethyl-N '-(dichloro) Fluoromethylthio) -N′-phenylsulfamide (dichrofluanide), etc.), pyridine-based (1-hydroxy-4-methyl-6- (2,4,4-trimethylpentyl) -2-pyridone monoethanolamine salt (Pyroctone olamine), bis (2-pyridylthio-1-oxide) zinc (zinc pyrithione, etc.), isothiazolone System (2-methyl-4-isothiazolin-3-one (caisson), etc.), imidazole system (2- (4′-thiazolyl) -benzimidazole (TBZ), etc.), anilide system (3,4,4′-trichloro) Carbanilide, etc.), carbohydrates (β-1,4-polyglucosamine (chitosan), etc.), tropolones (4-isopropyl-2-hydroxy-cyclohepta-2,4,6-trien-1-one (hinokitiol) ) Etc.).
Examples of cationic or zwitterionic antibacterial agents include surfactants (alkyldimethylbenzylammonium chloride (benzalkonium chloride), alkyldi (aminoethyl) glycine, etc.), biguanides (gluconic acid-1,1′-hexamethylene). And bis [5- (4-chlorophenyl) biguanide] (chlorhexidine gluconate) and the like.
Examples of inorganic antibacterial agents include metal ion systems (silver ions, copper ions, zinc ions, etc.) such as titanium oxide and zinc oxide.
These antibacterial agents may be used alone or in combination of two or more.

(Fungicide)
The disinfectant is not particularly limited as long as it kills bacteria. Specifically, isothiazolone organic sulfur compounds and benzisothiazoline organic sulfur compounds, 5-bromo-5-nitro-1,3-dioxane, 2-bromo-2-nitropropane-1,3-diol, 5- Examples include chloro-5-nitro-1,3-dioxane, 2-chloro-2-nitropropane-1,3-diol and the like.
In addition, commercially available products such as Bronidox L (manufactured by Henkel), Bronopol (manufactured by Inolex), Bronopol (manufactured by Yoshitomi Pharmaceutical), Myrside BT (manufactured by Boots), Myrside Pharma BP (manufactured by BASF) and the like are used. Also good.
Also, as benzoic acids, benzoic acid or a salt thereof, salicylic acid or a salt thereof, parahydroxybenzoic acid or a salt thereof, methyl paraoxybenzoate, ethyl paraoxybenzoate, propyl paraoxybenzoate, butyl paraoxybenzoate, benzyl paraoxybenzoate Etc. can also be used. Further, 3-methyl-3-isopropylphenol, o-phenylphenol, 2-isopropyl-5-methylphenol, resorcin, cresol, 2,6-di-tert-butyl-p-cresol, etc., should be used as the phenol compound. You can also.
These bactericides may be used alone or in combination of two or more.

(Softener)
The softening agent is not particularly limited as long as it keeps the suppleness of the clothes after washing. Specifically, a flexible component such as a cationic surfactant having a dilong chain hydrocarbon group, a fiber deformation preventing component such as a water-soluble or water-dispersible polyurethane, a 2-6 functional polyalkylene oxide polyol, or 2 Examples thereof include shrink-proof components such as aliphatic isocyanate and / or aromatic isocyanate terminated with a hexafunctional polyalkylene oxide polyol, and pilling formation-preventing components.
Silicone and cellulose selected from dimethylpolysiloxane and modified dimethylpolysiloxanes with various organic functional groups for the purpose of improving water absorption, iron sliding, wrinkle resistance, faded clothing color, and fiber feel. Derivatives, modified starches and the like may be used.
These softening agents may be used alone or in combination of two or more.

(Recontamination inhibitor)
The anti-recontamination agent is not particularly limited as long as it has an effect of preventing a part of dirt that is separated from the fiber and dispersed in the washing liquid from being deposited again during the washing. Specific examples include cellulose derivatives such as polyethylene glycol and carboxymethyl cellulose, and soil release polymers.
These recontamination inhibitors may be used alone or in combination of two or more.

<Component (b): Silica particles>
Although it does not specifically limit as a silica particle, A porous thing is preferable.
Moreover, it is preferable that the oil absorption ability measured by JISK5101 is 100 ml / 100g or more. The average particle size is preferably 0.1 to 200 μm. The average particle diameter is a mass-based median diameter, and is determined by a Coulter counter method.
Examples of such silica particles include precipitated silica, dry silica, silica sol, and silica gel. Specifically, "NIPSIL", "NIPEGEL" (manufactured by Tosoh Silica Co., Ltd.), "Tokusil", "Fine Seal", "Hydrophilic Leolosil" (manufactured by Tokuyama Corporation), "Sycilia" (Fuji Silysia Chemical Co., Ltd.) And silica particles such as “Hydrophilic AEROSIL” (manufactured by Nippon Aerosil Co., Ltd.) can be used and can be easily obtained as a commercial product.
Alternatively, hydrophobic silica or cationic silica whose surface has been subjected to a hydrophobic treatment may be used. Hydrophobic silica is preferable from the viewpoint of retention of the functional substance during washing and rinsing, and cationic silica is preferable from the viewpoint of adsorption to clothing. Specifically, “Silo Hovic” (manufactured by Fuji Silysia Chemical Co., Ltd.), “AEROSIL: R972, R974, RX200, R805, RY200” (manufactured by Nippon Aerosil Co., Ltd.), “NIPSIL SS” "(Manufactured by Tosoh Silica Co., Ltd.)," hydrophobic Leolosil "(manufactured by Tokuyama Co., Ltd.), and the like. Examples of the cationized silica include “AEROSIL: RA200HS” (manufactured by Nippon Aerosil Co., Ltd.).
These silica particles may be used alone or in combination of two or more.

  The content of the silica particles is preferably 5 to 80% by mass, more preferably 5 to 50% by mass, and further preferably 10 to 30% by mass in 100% by mass of the additive particles for washing. When the lower limit of the content of silica particles is less than the above value, the retention of the functional substance is lowered. On the other hand, if the upper limit of the content is higher than the above value, the handling property and workability due to the fine powder will be reduced, and the proportion of the functional substance in the laundry additive particles will be reduced. descend.

<(C) Component: Fiber Adsorbing Substance>
The fiber-adsorbing substance is composed of at least one selected from clay minerals, cellulose, cationized cellulose, and cationic surfactants, and has an adsorption rate on cotton cloth of 20% or more. In addition, when mixing 2 or more types of fiber adsorbent substances, an adsorption rate is measured by the adsorption amount measuring method shown below in the state of a mixture, and the value should just be in the said range.
The content of the fiber adsorbing substance is preferably 5 to 80% by mass, more preferably 5 to 60% by mass, and further preferably 5 to 30% by mass in 100% by mass of the additive particles for washing. When the lower limit of the content of the fiber adsorbing substance is less than the above value, the adsorption to the fiber is lowered. On the other hand, when the upper limit value of the content is higher than the above value, it becomes difficult to form particles when manufacturing the additive particles for laundry, or the ratio of the functional substance in the additive particles for laundry is reduced. The effect exerted by the active substance is reduced.

(Adsorbability to cotton cloth)
The value of the adsorption rate in the present invention is a value obtained by the adsorption amount measuring method shown below. The adsorption rate to the cotton fabric is 20% or more, preferably 30 to 100%, more preferably 50 to 100%. When the adsorption rate is less than 20%, the desired effect cannot be obtained because the adsorption to the cotton cloth is weakened.
Adsorption amount measurement method;
A 500 ml beaker equipped with a propeller-type stirring blade (stirring portion size: 50 × 12 mm, shaft diameter φ: 8 × 400 mm, manufactured by Heidolph), a washing solution containing 0.01% by mass of a fiber adsorbing substance (aqueous solution) Alternatively, 300 g of a dispersion using distilled water) and 5 g of cotton towel (MUKOTOWEL 100% cotton, manufactured by Nitta Towel Co., Ltd.) are added and stirred for 20 minutes at a stirring temperature of 20 ° C. and a rotation speed of 200 rpm. Next, 100 ml of the washing solution is collected, and in the case of an aqueous solution, the mass of the fiber adsorbing substance in the washing solution is measured with a total organic carbon meter (“TOC-V _CSH ” manufactured by Shimadzu Corporation) and dispersed. In the case of liquid, it is filtered with a membrane filter (pore diameter 0.45 μm, diameter φ47 mm), the mass of the filtration residue is measured, and the adsorption rate to cotton cloth is calculated from the following formula.
Adsorption rate to cotton cloth (%) = [concentration (mass) of fiber-adsorbing substance in washing liquid before stirring−concentration (mass) of fiber-adsorbing substance in washing liquid after stirring] / washing liquid before stirring Concentration (mass) of fiber-adsorbing substance in the x100
The cotton towel was washed, rinsed and dehydrated three times using a standard detergent (20 ° C tap water) using a commercially available detergent (Lion Co., Ltd. “Top, manufactured in 2006”). Use dry one.

(Clay mineral)
Clay minerals are generally hydrous silicates mainly containing metals such as aluminum, iron, manganese, magnesium, calcium, potassium, and sodium, and are aggregates of fine crystal pieces. In addition, there are many kinds of names depending on the composition, crystal form, arrangement of crystal pieces, grain shape, and the like. For example, smectites (montmorillonite, beidellite, nontronite, saponite, hectorite, soconite, stevensite, etc.), mica (sericite, illite, muscovite, phlogopite, etc.), vermiculite, chlorite, pyrophyllite, talc , Kaolin minerals, serpentine, sepiolite, allophane, hydrotalcite and the like.
These clay minerals are generally excellent in the adsorptivity to fibers, and also have the property of maintaining the adsorptivity to fibers even when various surfactants coexist, so that the adsorption rate to cotton fabric is 20% or more. Any of them can be used in the present invention. Among these, water-swellable clay minerals such as smectites and mica are preferable.
In addition, the clay mineral illustrated below may be used individually by 1 type, and may use 2 or more types together.

Smectites include natural products and synthetic products, both of which can be suitably used in the present invention. As natural smectites, for example, those containing montmorillonite include Wengel, Wenger HV, Wenger A, Wenger FW, Wengel 31, Wenger W-100 (manufactured by Toyoshun Mining Co., Ltd.), Kunipia G, and Kunipia F. (Kunimine Kogyo Co., Ltd.), Western Bond (American Colloid), Yellowstone (Dresser Minerals) and the like.
Examples of those containing saponite include Veegum T, Veegum HV, Veegum F, Veegum K (manufactured by Vander Build).
Examples of those containing hectorite include hectablite AW, hectablite 200, Benton EW (manufactured by American Colloid Co.), and macaloid (manufactured by National Reed).
Synthetic smectites include, for example, smecton SA (manufactured by Kunimine Kogyo Co., Ltd.), ionite H (manufactured by Mizusawa Chemical Co., Ltd.), SWN, SAN (manufactured by Corp Chemical Co., Ltd.), laponite (manufactured by Raporte Industries Co., Ltd.), etc. Is mentioned.
Examples of mica include swellable synthetic mica ME (manufactured by Coop Chemical Co., Ltd.), sodium tetrasilicon mica DP-DM (manufactured by Topy Industries Co., Ltd.), and the like.

  The exchangeable cation-substituted clay mineral obtained by substituting the exchangeable cation present in the water-swellable clay mineral with a monovalent or polyvalent cation is also added to the laundry according to the present invention in the same manner as the water-swellable clay mineral. It can be used for agent particles. Monovalent or polyvalent cations include alkali metal ions such as lithium ion, sodium ion and potassium ion, alkaline earth metal ions such as magnesium ion, calcium ion, strontium ion and barium ion, titanium ion, iron ion and copper. Examples thereof include transition metal ions such as ions and silver ions, zinc ions, and aluminum ions.

Furthermore, an alkali-treated product of acidic clay can be used as the water-swellable clay mineral. The acid clay is usually 5 to 6 or less in 1% aqueous dispersion, the degree of swelling is 10 ml / 2 g or less, and the content of SiO ₂ and Al ₂ O ₃ is SiO ₂ / Al ₂ O ₃ = 6- 10 things. For example, Nakajo, Odo, Kamayadani, Itoigawa, Mizusawa, Kawasaki, Matsune, Mikawa, Ome, Ushiamimi acidic white clay, and British fuller's earth, which shows similar properties to these acidic white clay, rice Examples include domestically produced Florida earth and German-made Warkel erde. Examples of the exchangeable cation present in these acidic clays include sodium ion, potassium ion, magnesium ion, and iron ion.
These acid clays have an adsorption rate of 20% or more when treated with an alkali, and can be used for the additive particles for laundry of the present invention in the same manner as the water-swellable clay mineral.

(cellulose)
Cellulose is made from wood such as leaves and broad-leaved trees, leaf fibers such as hemp, mitsumata, kouzo, gambi, straw, bagasse and bamboo, stem fibers, gin leather fibers, seed hair fibers such as momen, kiwata and kabok. It is said.
Examples of cellulose having an adsorption rate of 20% or more on cotton cloth include KC Flock W-400G (manufactured by Nippon Paper Industries Co., Ltd.), Arbocel BE-600 / 10, Arbocel HB120, Arbocel BE-600 / 30, Arbocel FD-600 / 30, Arbocel- Examples thereof include TF30HG, Arbocel BWW-40, Arbocel BC-200, Arbocel BE-600 / 20 (manufactured by Rettenmeier).
These celluloses may be used alone or in combination of two or more.

(Cationized cellulose)
Cationized cellulose has good adsorptivity to fibers. As cationized cellulose having an adsorption rate of 20% or more on cotton cloth, commercially available Leogard GPS (nitrogen content 1.8% by mass, average molecular weight 900,000), Leogard GP (nitrogen), which is hydroxytrimethylammoniopropylhydroxyethylcellulose chloride. 1.8% by weight, average molecular weight 900,000), Leogard GPO (1.8% by weight of nitrogen, average molecular weight 900,000), Leogard LP (1.0% by weight of nitrogen, average molecular weight 900,000), Leogard KGP (1.8% by mass of nitrogen, average molecular weight 900,000), Leogard MGP (1.8% by mass of nitrogen, average molecular weight 2,000,000), Leogard MLP (0.6% by mass of nitrogen, average) Molecular weight 2,000,000), Leoguard MTY (nitrogen content 0.6% by weight, average molecular weight 900,0 00) [The above, manufactured by Lion Chemical Co., Ltd., the difference in grade depends on the molecular weight of cellulose, the addition of ethylene oxide (EO), the degree of cationization, and the like. ] Cellcoat H-100 (nitrogen content 1.0% by mass, average molecular weight 140,000) and Cellcoat L-200 (nitrogen content 2.0% by mass, average molecular weight 30), which are hydroxyethylcellulose dimethyldiallylammonium chloride polymers. 000), cell coat SC-240C (nitrogen content 2.0 mass%, average molecular weight 115,000), cell coat SC-230M (nitrogen content 2.0 mass%, average molecular weight 170,000) [above, manufactured by NSC Japan The difference in grade depends on the molecular weight of cellulose, the EO addition and the degree of cationization, etc.].
These cationized celluloses may be used alone or in combination of two or more.
The molecular weight of the cationized cellulose is preferably 10,000 to 10,000,000, more preferably 500,000 to 5,000,000. If the molecular weight is too small, the adsorption to the cloth will be small, and if the molecular weight is too large, the viscosity in the aqueous solution will increase and the solubility of the granules will deteriorate.

(Cationic surfactant)
As the fiber adsorbing substance used in the present invention, a cationic surfactant can be used.
Examples of cationic surfactants having an adsorption rate of 20% or more on cotton cloth include monoalkyltrimethylammonium salts having 8 to 18 carbon atoms in alkyl groups, dialkyldimethylammonium salts having 4 to 10 carbon atoms in each alkyl group, Examples thereof include alkyl benzyl dimethyl ammonium salts having 8 to 18 carbon atoms, alkyl pyridinium salts having 8 to 18 carbon atoms in an alkyl group, and ester type cations.
These cationic surfactants may be used alone or in combination of two or more.

<Optional component>
In the additive particles for laundry of the present invention, as other components, an excipient (binder), a shaping aid, a grinding aid, a coating agent, a colorant, and a cleaning agent are added as long as the effects of the present invention are not impaired. In addition, optional components such as a surfactant and a polymer can be appropriately blended.

Here, an embodiment of a method for producing laundry additive particles will be described.
The method for producing laundry additive particles of the present invention comprises a step of mixing the functional substance and the silica particles to prepare a powder mixture in which the silica particles are impregnated with the functional substance, the powder mixture, A step of granulating the fiber-adsorbing substance.

First, a functional substance is added to silica particles to prepare a powder mixture in which silica particles are impregnated with a functional substance. The method for adding the functional substance is not particularly limited, but spray addition is preferable.
Next, the powder mixture is granulated with a fiber adsorbing substance. As a granulation method, a granulation method having a granulation step of compacting, which is different from spray drying granulation or fluidized bed granulation, is preferable. For example, a kneading / kneading / crushing granulation method in which a powder mixture and a fiber adsorbing material are kneaded by a kneading and kneading machine, crushing granulation method, an extrusion granulation method for extruding while kneading, and compacting with stirring. In addition, a granulation method such as an agitation granulation method for granulation is preferable. Also preferred is a granulation method in which the mixture of the powder mixture and the fiber-adsorbing substance is compressed and molded into a predetermined particle size by a tableting machine, briquetting machine, compacting machine or the like. Among them, the kneading / kneading / pulverizing granulation method and the extrusion granulation method are particularly preferable, and unlike the method of simply mixing, it is possible to prepare a homogeneous mixture in which the powder mixture and the fiber adsorbing substance are in close contact with each other. it can.
The granulated product obtained by the above granulation treatment may be further sieved to adjust the particle size, whereby laundry additive particles having a uniform particle size are obtained.
In the present invention, the granulation step for compaction treatment means that the increase in the bulk density of the particles by the above granulation is based on the bulk density of the mixture of the powder mixture and the fiber adsorbing substance. , Preferably 0.1 g / ml or more, more preferably 0.15 to 0.9 g / ml.

The additive particles for laundry thus obtained are particles in a state where the silica particles impregnated with the functional material and the fiber adsorbing material are in close contact with each other by being granulated while being compacted and uniformly mixed. It has become.
The average particle diameter of the laundry additive particles is preferably 100 to 1000 μm. The average particle diameter is a mass-based median diameter.

[Clothing detergent]
The laundry detergent of the present invention is obtained by adding the above-described laundry additive particles to a detergent composition containing a surfactant. The composition of the detergent composition can be arbitrarily designed.
The content of the laundry additive particles is preferably 0.01 to 5% by mass, more preferably 0.05 to 2% by mass, and further 0.1 to 0.5% by mass in 100% by mass of the laundry detergent for clothing. preferable. When the lower limit of the content of the additive particles for washing is less than the above value, the effect becomes weak after washing. On the other hand, when the upper limit value of the content is higher than the above value, there may be a problem in stability, and in the case of a fragrance, the scent in the product or after washing may become too strong. Moreover, it is not economically preferable.
200-1500 micrometers is preferable and, as for the average particle diameter of the detergent for clothes, 350-1000 micrometers is more preferable. The average particle diameter is a mass-based median diameter.
The bulk density is preferably from 0.3 to 1.2 g / mL, more preferably from 0.6 to 1.0 g / mL. The bulk density can be measured according to JIS K3362.

  Thus, according to the method for producing laundry additive particles of the present invention, the retention of the functional material is enhanced by impregnating the silica particles with the functional material, and the functional material-containing silica particles and the fiber adsorption By granulating the active substance, the functional substance is adsorbed to the fibers while being retained in the particles even during washing due to the effect of the fiber adsorbing substance, and thus the effect can be maintained after washing. In addition, it is possible to produce additive particles for laundry containing a high concentration of functional substance, and since it is not necessary to treat at high temperature during production, the outflow of the functional substance can be suppressed and high effects can be expressed. Become.

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

[Raw materials]
(Functional substances)
Perfume ingredients: ethyl 2-methylbutyrate 0.5%, manzanate 0.5%, paramethylanisole 1%, allylheptanoate 1%, dihydromyrcenol 3%, linalool 7%, pt-butylcyclohexyl acetate 4.5%, citronellol 8%, fluitate 1%, β-damascone 0.2%, phenylethyl alcohol 2%, cyclamenaldehyde 13%, liliar 6%, ambroxan 0.2%, rosephenone 2%, hexyl salicylate 5.5%, heliotropin 3%, belt fix 1%, γ-undecalactone 3.4%, galaxolide (solution containing 50% benzyl benzoate) 20%, hexylcinnamic aldehyde 6%, tonalid 3.5%, Helional 0.5%, Coumarin 5.5%, Ethylvanillin 0.2%, Raspberry Ketone 1.5% (% denotes content in perfume ingredients.).
Repellent: Citronella.
Deodorant: Rosemary extract.
Antibacterial agent: Geraniol.
Softener: Polyether-modified silicone (manufactured by Toray Dow Corning).
(Silica particles)
Hydrophobic treated porous silica: Silo Hovic 200 (Fuji Silysia Chemical Co., Ltd.).
Porous silica: Toxeal NP (manufactured by Tosoh Silica Co., Ltd.).
(Fiber adsorptive substance (adsorption rate%))
Montmorillonite: Round rosyl DGA (48%) (manufactured by SUD-CHEMIE).
Cellulose: Arbocel BE-600 / 30 (68%) (manufactured by Rettenmeier).
Cationized cellulose 1: Leoguard MTY (69%) (manufactured by Lion Corporation).
Cationized cellulose 2: Leoguard GP (71%) (manufactured by Lion Corporation).
Cationized cellulose 3: Leogard KGP (50%) (manufactured by Lion Corporation).
Cationic surfactant 1: Arcard T-800 (98%) (manufactured by Lion Akzo).
Cationic surfactant 2: Arcard TES-85E (21%) (manufactured by Lion Akzo).
(Optional component)
Excipient: LPB (amidopropyl betaine laurate) (manufactured by Lion Corporation).

[Preparation of detergent composition]
<Raw materials>
LAS-K: Potassium salt of Raipon LH-200 (manufactured by Lion Corporation).
α-SF-Na: α-sulfo fatty acid methyl ester sodium (AI = 70%, carbon number 14: carbon number 16 = 18: 82), the remainder being unreacted fatty acid methyl ester, sodium sulfate, methyl sulfate, hydrogen peroxide , Water, etc.).
Soap: C12-18 fatty acid sodium (67% pure, titer 40-45 ° C., molecular weight 289).
Nonionic surfactant: C1214 natural alcohol (manufactured by P & G Co., Ltd.) ethylene oxide average 15 mol adduct (pure content 90%).
Zeolite: Shilton B (manufactured by Mizusawa Chemical Co., Ltd.) (pure content 80%).
Acrylic acid / maleic acid copolymer salt: Aqualic TL-400 (manufactured by Nippon Shokubai Co., Ltd.) (pure 40% aqueous solution).
Type A zeolite: slurry having a pure content of 47.5% (manufactured by Nippon Chemical Co., Ltd.).
Sodium carbonate: grain ash (Asahi Glass Co., Ltd.).
Potassium carbonate: Potassium carbonate (powder) (Asahi Glass Co., Ltd.).
Sodium sulfite: anhydrous sodium sulfite (manufactured by Shinshu Chemical Co., Ltd.).
Sodium sulfate: neutral anhydrous sodium sulfate (manufactured by Nippon Chemical Industry Co., Ltd.).

<Preparation>
Among ingredients used in Table 1, components other than nonionic surfactant, α-SF-Na, and 6.6% equivalent amount (to detergent composition, the same applies hereinafter) of grinding aid (A-type zeolite) A slurry having a water content of 38% was prepared by dissolving or dispersing in water, and then spray-dried using a countercurrent spray drying tower at a hot air temperature of 300 ° C. to obtain spray-dried particles having a water content of 3%.
A continuous kneader (2.3% equivalent of nonionic surfactant and water, with a concentrate of α-SF-Na of 11.0%, nonionic surfactant of 2.7% and spray-dried particles as described above (( Kurimoto Seiko Co., Ltd., “KRC-S4 type”), and kneaded under conditions of a kneading capacity of 120 kg / h and a temperature of 60 ° C. to obtain an amorphous solid detergent. This irregular solid detergent was extruded with a pelleter double equipped with a die having a hole diameter of 10 mm (“EXDFJS-100 type” manufactured by Fuji Powder Co., Ltd.) and cut with a cutter (cutter peripheral speed was 5 m / s) A pellet-shaped solid detergent having a length of about 5 to 30 mm was obtained.
Next, a 6.6% equivalent amount of A-type zeolite (average particle size 180 μm) was added to the obtained pellet-shaped solid detergent, and Fitzmill arranged in series in three stages under cold air (10 ° C., 15 m / s) ( Hosokawa Micron Co., Ltd. “DKA-3”) (screen hole diameter: 1st stage / 2nd stage / 3rd stage = 12 mm / 6 mm / 3 mm, rotation speed: all stages 4700 rpm), detergent composition A product was prepared.

<Measurement of average particle diameter>
The obtained detergent composition (sample) was classified 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 tray. In the classification operation, a sieve with a small opening and a sieve with a large opening are stacked in the order of the sieve, and a sample of 100 g / time is put on the top of the top 1680 μm sieve. ) Made by Iida Manufacturing Co., Ltd., tapping: 156 times / minute, rolling: 290 times / minute) After shaking for 10 minutes, the sample remaining on each sieve and tray was collected for each sieve. .
By repeating this operation, 1410 to 1680 μm (1410 μm.on), 1190 to 1410 μm (1190 μm.on), 1000 to 1190 μm (1000 μm.on), 1000 to 710 μm (710 μm.on) 500 to 710 μm (500 μm.on) , 350 to 500 μm (350 μm.on), 250 to 350 μm (250 μm.on), 149 to 250 μm (149 μm.on), pan to 149 μm (149 μm.pass), and classification samples with respective particle diameters were obtained. ) Was calculated.
Next, the opening of the first sieve with a calculated weight frequency of 50% or more is defined as a (μm), and the opening of the sieve that is one step larger than a (μm) is defined as bv. The average particle size (weight 50%) was determined by the following equation, where c% was the cumulative weight frequency up to the sieve and d% was the weight frequency of the a (μm) sieve. The results are shown in Table 1.
Average particle diameter (weight 50% diameter) = 10 ^{[50- (cd / (log b-log a) × log b)] / [d / (log b-log a)]}

<Measurement of bulk density>
The bulk density of the obtained detergent composition was measured according to JIS K3362. The results are shown in Table 1.

[Example 1]
<Manufacture of additive particles for washing>
As shown in Table 2, 600 g of silica particles (hydrophobic-treated porous silica) was put into a Ladige mixer ("M-20 type" manufactured by Matsubo Co., Ltd., internal volume: 20 L, stirring blade diameter: 0.3 m), Agitation was started at a main shaft of 200 rpm and a chopper of 6000 rpm. Ten seconds after the start of stirring, 1100 g of the fragrance component was sprayed and added at a feed rate of 100 g / min using a two-fluid holographic cone nozzle with a spray angle of 70 ° C. to impregnate the fragrance component into silica particles. Subsequently, 360 g of the obtained powder (perfume component-impregnated silica particles) was collected, 90 g of excipient (LPB) as an optional component, and 150 g of montmorillonite as a fiber adsorbing substance, and a continuous kneader (Kurimoto Co., Ltd.). ("KRC-S1 type" manufactured by Seikosho), kneaded and granulated (kneaded) at a temperature of 30 ° C. The obtained kneaded product was pulverized with a table mill (manufactured by Trio Science Co., Ltd., “Trioblender”), classified using a sieve having an opening of 1000 μm, and particles passing through a sieve having an opening of 1000 μm were obtained. It was set as the additive particle for washing | cleaning containing a fragrance | flavor component. In addition, the compounding quantity of each raw material shown in Table 2 is a value when the additive particle for washing is 100%. Table 2 shows the content of the fragrance component in the laundry additive particles.

<Adsorption rate to fiber>
The adsorption rate of the fiber-adsorbing material used for the laundry additive particles to the fiber was determined from the above-described method of measuring the amount of adsorption. The results are shown in Table 2.

<Rescent fragrance evaluation>
Washing additive particles were added to the previously prepared detergent composition so that the fragrance component would be equivalent to 0.2% to prepare a garment detergent, and the residual fragrance on clothes was evaluated.
Put 1.5 kg of commercial cotton towel (100% cotton) and 30 L of tap water into a commercial washing machine (Hitachi Co., Ltd., “NW-70RS1 type”), add 20 g of laundry detergent, and rinse-dehydrate operation ( After rinsing (rinse for 3 minutes, dehydration for 2 minutes) twice, the cotton towel was taken out and left in a constant temperature and humidity room at a temperature of 25 ° C. and a humidity of 50% for 24 hours to dry. The cotton towel was washed, rinsed and dehydrated three times in a standard course of the washing machine (20 ° C. tap water) using a commercial detergent (manufactured by Lion Corporation, “Top, manufactured in 2006”). What was dried under the conditions was used.
Residual scent on clothes was sensory-evaluated according to the following evaluation criteria by five specialized panelists. The results are shown in Table 1.
5: The scent of the fragrance is very strong.
4: The scent of the fragrance is strong.
3: There is a scent of fragrance.
2: The remaining fragrance of the fragrance is weak.
1: There is no scent of the fragrance.

[Example 2]
Laundry additive particles were produced in the same manner as in Example 1 except that the fiber-adsorbing substance was changed to cationized cellulose 1 shown in Table 2, and then a laundry detergent was prepared and evaluated. The results are shown in Table 2.

[Example 3]
As shown in Table 2, the addition for washing was performed in the same manner as in Example 1 except that 75 g of montmorillonite and 75 g of cellulose were used as the fiber adsorbing substance, and the cationic surfactant 1 was used instead of the excipient (optional component). After producing the agent particles, a laundry detergent was prepared and evaluated. The results are shown in Table 2.
In addition, the adsorption rate to the fiber of the fiber adsorptive substance shown in Table 2 is obtained by measuring the adsorption rate of the mixture when all the used fiber adsorbing substances are mixed by the adsorption amount measuring method. The same applies hereinafter.

[Example 4]
Laundry additive particles were produced in the same manner as in Example 1 except that 75 g of montmorillonite and 75 g of cellulose were used as the fiber-adsorbing substance, and then a laundry detergent was prepared and evaluated. The results are shown in Table 2.

[Example 5]
Laundry additive particles were produced in the same manner as in Example 1 except that 75 g of montmorillonite and 75 g of cationized cellulose 1 were used as the fiber adsorbing substance, and then a laundry detergent was prepared and evaluated. The results are shown in Table 2.

[Example 6]
Laundry additive particles were produced in the same manner as in Example 1 except that 75 g of montmorillonite and 75 g of cationized cellulose 2 were used as the fiber adsorbing substance, and then a laundry detergent was prepared and evaluated. The results are shown in Table 2.

[Example 7]
Washing additive particles were produced in the same manner as in Example 1 except that 75 g of montmorillonite and 75 g of cationized cellulose 3 were used as the fiber adsorbing substance, and then a laundry detergent was prepared and evaluated. The results are shown in Table 2.

[Example 8]
300 g of silica particles (porous silica) shown in Table 2 were put into a Ladige mixer, and stirring was started at a main shaft of 200 rpm and a chopper of 6000 rpm. Ten seconds after the start of stirring, 550 g of the fragrance component was sprayed and added at a feed rate of 100 g / min using a two-fluid holocorn nozzle with a spray angle of 70 ° C., and the fragrance component was impregnated into the silica particles. Subsequently, 212.5 g of excipient (LPB) as an optional component and 177 g of montmorillonite and cationized cellulose 1 as a fiber adsorbing substance were put into a 177 g Laedige mixer and stirred for 30 seconds to obtain a granulated product. . Subsequent operations were carried out in the same manner as in Example 1 to produce laundry additive particles, and then a laundry detergent was prepared and evaluated. The results are shown in Table 2.

[Example 9]
600 g of silica particles (porous silica) shown in Table 2 were put into a Ladige mixer, and stirring was started at a main shaft of 200 rpm and a chopper of 6000 rpm. Ten seconds after the start of stirring, 1201.8 g of the fragrance component was sprayed and added at a feed rate of 100 g / min using a two-fluid holographic cone nozzle with a spray angle of 70 ° C. to impregnate the fragrance component into silica particles. Subsequently, 360 g of the obtained powder (perfume component-impregnated silica particles) was collected, and 90 g of excipient (LPB) as an optional component and 75 g of montmorillonite and 75 g of cellulose as a fiber adsorbing substance were put into a continuous kneader. And kneaded and granulated at a temperature of 30 ° C. Subsequent operations were carried out in the same manner as in Example 1 to produce laundry additive particles, and then a laundry detergent was prepared and evaluated. The results are shown in Table 2.

[Example 10]
Washing additive particles were produced in the same manner as in Example 9 except that 75 g of montmorillonite and 75 g of cationized cellulose 1 were used as the fiber adsorbing substance, and then a laundry detergent was prepared and evaluated. The results are shown in Table 2.

[Example 11]
480 g of a powder in which a fragrance component is impregnated in silica particles (fragrance component-impregnated silica particles) is collected, and 60 g of an excipient (LPB) as an optional component and 60 g of a cationic surfactant 2 as a fiber adsorbing substance. A continuous kneader (manufactured by Kurimoto Steel Co., Ltd., “KRC-S1 type”) was added, and the subsequent operations were carried out in the same manner as in Example 1 to prepare laundry additive particles and evaluate them. The results are shown in Table 2.

[Example 12]
Granulated (kneaded) 360 g of perfume component-impregnated silica particles prepared in the same manner as in Example 1, 90 g of excipient (LPB) as an optional component, and 75 g of montmorillonite and cationized cellulose 1 as a fiber adsorbing substance. The laundry detergent particles were prepared in the same manner as in Example 1 except that they were blended, and then a laundry detergent was prepared and evaluated. The results are shown in Table 2.

[Comparative Example 1]
Mixing (granulating (kneading) operation) 80 g of fragrance component-impregnated silica particles prepared in the same manner as in Example 1 and 20 g of an excipient (LPB) as an optional component in a plastic bag having a thickness of 0.08 mm and 300 mm × 400 mm None) to produce laundry additive particles. Next, in the same manner as in Example 1, laundry detergent particles were added to the detergent composition so that the fragrance component would be equivalent to 0.2% to prepare a detergent for clothing, and the evaluation of the remaining fragrance on clothes was performed. went. The results are shown in Table 2.

[Comparative Example 2]
Horizontal cylindrical rolling mixer (Cylinder diameter: 585 mm, cylinder length: 490 mm, container: 131.7 L drum inner wall surface, with two baffle plates with clearance of 20 mm and height 45 mm from inner wall surface) In addition, while mixing the detergent composition prepared previously under the conditions of a filling rate of 30% by volume, a rotational speed of 22 rpm, and 25 ° C., the fragrance components shown in Table 2 were sprayed to an amount equivalent to 0.20%. A detergent was prepared. The obtained clothing detergent was evaluated in the same manner as in Example 1. The results are shown in Table 2.

As is clear from Table 2, the laundry detergent containing the laundry additive particles obtained in the examples was excellent in the scent of clothes. Note that the laundry additive particles of Example 5 obtained by granulating the perfume component-impregnated silica particles together with the fiber adsorbing substance were superior in residual fragrance compared to Example 12 produced without granulation. In the case of Example 12, it can be estimated that the fiber-adsorbing substance was not uniformly combined with the surface of the fragrance component-impregnated silica particles.
On the other hand, Comparative Example 1 did not contain a fiber-adsorbing substance and produced laundry additive particles without granulation. Therefore, the laundry detergent containing the laundry additive particles was compared with the Examples. The residual fragrance was inferior.
In Comparative Example 2, since the fragrance component was simply sprayed on the detergent composition to obtain a garment detergent, the garment after washing did not leave a scent.

[Examples 13 to 16]
<Manufacture of additive particles for washing>
Washing additive particles were produced in the same manner as in Example 1 except that the functional substances shown in Table 3 were used, and 75 g of montmorillonite and cationized cellulose 1 were used as the fiber adsorbing substances. In addition, the compounding quantity of each raw material shown in Table 3 is a value when the additive particle for washing is 100%. Table 3 shows the content of the functional substance in the laundry additive particles and the absorption rate of the cotton adsorbent of the fiber adsorbing substance.

<Evaluation>
Laundry additive particles were added to the previously prepared detergent composition so that the functional substance would be equivalent to 0.2% to prepare a laundry detergent, and evaluated as follows. The results are shown in Table 3.
(Repellent effect)
Wear a long-sleeved cotton shirt treated with detergent for clothes, put it in the 30 × 30 × 30cm ³ sealed space with 5 mosquitoes from the elbow, and the number of mosquitoes that stopped on the clothing in 5 minutes as follows evaluated.
○: 1 time or less.
X: 5 times or more.

(Deodorant / antibacterial effect)
Using a laundry detergent, the effect of suppressing the generation of malodor was evaluated according to the following evaluation conditions.
After using and washing three new 100% cotton towels and three T-shirts in normal life 50 times (equivalent to one year), a two-tank washing machine (Mitsubishi Electric Co., Ltd., “CW- C30A1-H "), temperature 25C, tap water 30L, laundry detergent 15g, washing 10 minutes, rinsing 3 minutes + dehydration 1 minute x 2 times, washing at room temperature 25C, humidity 90% RH The odor of clothes when dried in the room for 24 hours was sensory-evaluated by 10 panelists according to the following evaluation criteria, and the evaluations of 10 persons were averaged. The results are shown in Table 3.
○: Almost no odor is felt.
X: A bad smell is felt.

(Flexibility effect)
Washing a commercial cotton knit (100% cotton) and polyester jersey (100% polyester) with a commercial clothing detergent "Top" (manufactured by Lion Corporation, manufactured in 2006) using a household two-tub washing machine 15 Minutes (detergent used standard amount, bath ratio 30 times, 45 ° C tap water), dehydration 5 minutes process repeated 2 cycles, then rinsed with running water 15 minutes, dehydration 5 minutes process 5 times, air dried Was used as a test cloth.
Wash the test cloth (cotton knit 100g and polyester jersey 100g) treated as above using the laundry detergent prepared as described above for 15 minutes. (Clothing detergent is standard use amount, bath ratio 30 times, 25 ° C) Of tap water). Then, it air-dried on the conditions of 20 degreeC and 40% RH, and performed the following evaluation.
Using a cotton knit and a polyester jersey treated without using a softening agent as a control, a pair of sensory comparisons in softness by 10 professional panelists were performed, and evaluation was performed according to the following evaluation criteria.
○: Better than the control product.
×: Almost the same as the control product.

[Comparative Examples 3 to 6]
The functional substances shown in Table 3 were mixed into the horizontal cylindrical rolling mixer similar to Comparative Example 2 while mixing the detergent composition prepared previously under the conditions of a filling rate of 30% by volume, a rotational speed of 22 rpm, and 25 ° C. A detergent for clothing was prepared by spraying to an amount corresponding to 0.20%. The obtained laundry detergent was evaluated in the same manner as in Examples 13-16. The results are shown in Table 3.

As is apparent from Table 3, the laundry detergents of the examples were able to sufficiently exert the effects of the functional substances contained in each.
On the other hand, since the detergent for clothing of the comparative example was simply sprayed with a functional substance on the detergent composition to obtain a detergent for clothing, the effect was not exhibited.

Claims (6)

The additive particle for washing | cleaning characterized by containing the component shown to following (a)-(c).
(A) Component: At least one functional substance selected from a fragrance component, a deodorant, a repellent, an ultraviolet absorber, an antibacterial agent, a bactericidal agent, a softening agent, and a recontamination preventive agent.
(B) Component: Silica particles.
(C) Component: A fiber-adsorbing substance composed of at least one selected from clay minerals, cellulose, cationized cellulose, and cationic surfactants, and having an adsorption rate on cotton cloth of 20% or more.   In 100% by mass of the additive particles for washing, the content of the component (a) is 5 to 70% by mass, the content of the component (b) is 5 to 80% by mass, and the content of the component (c) is The additive particle for laundry according to claim 1, which is 5 to 80% by mass.   The additive particle for laundry according to claim 1 or 2, wherein the component (a) is a fragrance component.   The additive particle for laundry according to claim 1 or 3, wherein the component (b) exhibits hydrophobicity.   A laundry detergent comprising the additive particles for laundry according to any one of claims 1 to 4. The following (a) component and the following (b) component are mixed to prepare a powder mixture in which the (b) component is impregnated with the (a) component, and the powder mixture is consolidated together with the following (c) component The manufacturing method of the additive particle | grains for washing | cleaning characterized by having the granulation process which carries out a chemical conversion process.
(A) Component: At least one functional substance selected from a fragrance component, a deodorant, a repellent, an ultraviolet absorber, an antibacterial agent, a bactericidal agent, a softening agent, and a recontamination preventive agent.
(B) Component: Silica particles.
(C) Component: A fiber-adsorbing substance composed of at least one selected from clay minerals, cellulose, cationized cellulose, and cationic surfactants, and having an adsorption rate on cotton cloth of 20% or more.