JP2010215806A - Detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a detergent composition resistant to loss of perfume ingredients in washing and emitting excellent long-lasting odor. <P>SOLUTION: The detergent composition contains (a) a composite mesoporous silica particle composed of a hollow silica particle having an outer skin with a mesoporous structure having an average pore diameter of 1-10 nm, and containing a perfume in the hollow silica particle, and (b) a surfactant. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a cleaning composition, and more particularly, to a cleaning composition that is excellent in residual fragrance properties without causing a fragrance component to be washed away during washing.

A fragrance | flavor is added to the composition for washing clothes for the purpose of masking of odor caused by raw material components and the like and giving comfort to the user. In that case, if the fragrance is added alone, it will be easily volatilized, or it will shift to the aqueous phase and be washed away during drainage, so an attempt has been made to increase the residual fragrance by holding the fragrance on various carriers. Yes.
For example, a sustained-release functional agent (Patent Document 1), silica, etc. embedded in a kneaded state of a functional material and a hydrophobic substance in pores of a hydrophilic porous body having a large number of pores opened on the surface A volatile component sustained release agent in which a fragrance is adsorbed on a holding material obtained by applying a coating agent to a granular inorganic material (Patent Document 2), and a fragrance composition for washing clothes comprising a fragrance and a hydrophobic polymer (Patent Document 3) ) Etc. have been proposed. However, in the above-described conventional techniques, satisfactory effects such as modulation of aroma, difficulty in increasing the concentration of the fragrance, and insufficient fragrance are not obtained.

On the other hand, hollow silica particles having a mesoporous structure are known. For example, Patent Document 4 discloses hollow silica particles in which the outer shell portion has a mesoporous structure and the outer shell portion is composed of a silicon compound having an organic group. A composite silica particle having a mesopore structure in a shell and a BET specific surface area of 100 m ² / g or more and including a hydrophobic organic compound inside the silica particle is disclosed. .
However, in patent documents 4 and 5, sufficient examination is not made about application to a detergent composition.

Japanese Patent Laid-Open No. 10-17846 JP 2000-41641 A JP 2001-335800 A JP 2008-110905 A JP 2008-150229 A

  This invention makes it a subject to provide the cleaning composition which was excellent in residual fragrance property, without the fragrance | flavor component being washed away during washing.

The present inventors have found that the above problem can be solved by combining composite mesoporous silica particles in which a fragrance is held inside hollow mesoporous silica particles having a uniform mesoporous structure and a surfactant. .
That is, the present invention comprises (a) hollow silica particles whose outer shell portion has a mesoporous structure, the mesopores have an average pore diameter of 1 to 10 nm, and a fragrance is retained inside the hollow silica particles. A cleaning composition containing the composite mesoporous silica particles obtained and (b) a surfactant is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the fragrance | flavor component does not run out during washing | cleaning and can provide the cleaning composition excellent in the remaining fragrance property.

  The cleaning composition of the present invention comprises (a) hollow silica particles whose outer shell part has a mesoporous structure, the average pore diameter of the mesopores is 1 to 10 nm, and the inside of the hollow silica particles It is characterized by containing composite mesoporous silica particles (hereinafter also simply referred to as “composite silica particles”) having a fragrance and (b) a surfactant.

<(A) Composite mesoporous silica particles>
[Hollow silica particles]
As for the hollow silica particle which comprises the composite mesoporous silica particle used by this invention, the outer shell part has a mesopore structure. The average pore diameter of the mesopore structure can be appropriately adjusted from the viewpoints of the desired residual fragrance period, the volatilization rate of the fragrance, etc., but is preferably 1 to 8 nm, more preferably 1 to 5 nm. The structure of the outer shell portion having a mesopore structure and the hollow portion inside the particle can be observed using a transmission electron microscope (TEM), and its pore diameter, pore regularity, from the outer shell portion to the inside It is possible to confirm how the pores are connected.
The mesopore structure of the hollow silica particles of the present invention is one of the features that the mesopore diameter is uniform. The mesopore diameter is preferably 70% or more, more preferably 75% or more, and particularly preferably 80% or more within ± 30% of the average pore diameter.
Since the mesopore diameter is affected by the size of micelles such as a surfactant used during production, when a cationic surfactant is used, the difference in the carbon number of the alkyl group of the surfactant, the alkyl chain Depending on the number, hollow silica particles having various pore sizes can be prepared.

The average particle diameter of the hollow silica particles can be adjusted from the viewpoints of application, remaining fragrance period, etc., but is preferably 0.05 to 10 μm, more preferably 0.05 to 5 μm, and further preferably 0.02 to 2 μm. The hollow silica particles preferably have a particle size of 80% or more, more preferably 85% or more, still more preferably 90% or more, and particularly preferably 95% or more of the whole particles within an average particle size of ± 30%. It is desirable that the particles are composed of a group of particles having a very uniform particle diameter.
If the average pore diameter and the average particle diameter of the mesopore structure of the hollow silica particles are uniform, the fragrance can be volatilized at a stable rate for a long period of time, so that desired volatilization control can be easily performed. .
The average particle diameter of the hollow silica particles can be adjusted by selecting a surfactant that can be used during production, the stirring power during mixing, the concentration and temperature of the prepared solution, and the like. In the production method using a polymer for the core of protocore-shell particles described later, the average particle diameter of hollow silica obtained and the degree of variation in particle diameter can be adjusted depending on the size and distribution of the polymer. In the production process of the hollow silica particles, when a surfactant such as a cationic surfactant is used, the surfactant may remain in the hollow silica particles, in the mesopores, or on the silica particle surfaces. If there is no problem even if the surfactant remains, it is not necessary to remove it, but if it is desired to remove the remaining surfactant, it can be removed by washing with water or an acidic aqueous solution for replacement.
Further, BET specific surface area of the hollow silica particles, from the viewpoint of sustained-release performance and the like, preferably 100~1500m ² / g, more preferably 200~1500m ² / g, more preferably 300~1500m ² / g.

The structure of the outer shell portion of the hollow silica particles varies depending on the silica source used. When an organic group having an organic group is used as the silica source, an outer shell of a silica structure having an organic group is obtained. In addition to the silica source, other elements such as Al, Ti, V, Cr, Co, Ni, By adding a metal raw material such as an alkoxy salt or a halogenated salt containing a metal such as Cu, Zn, Zr, B, Mn, Fe or the like, the metal is present in the outer shell of the silica particle. be able to. The structure of the outer shell part is preferably manufactured from tetramethoxysilane or tetraethoxysilane as a silica source from the viewpoint of stability, and the silica wall is substantially composed of silica oxide.
The hollow silica particles are a substance having periodicity in a meso region having one or more peaks at a diffraction angle corresponding to a range of d = 2 to 12 nm in a powder X-ray diffraction (XRD) pattern. In addition, when regularity becomes high, a peak is clarified and a high order peak may be seen.

The average thickness of the outer shell portion (mesoporous silica portion) is preferably thin as long as the hollow silica particles can maintain the strength as a carrier, and the average diameter (average volume) of the hollow portion is large from the viewpoint of retaining a large amount of perfume. Is preferred. From these viewpoints, the average thickness of the outer shell is usually 0.5 to 500 nm, preferably 2 to 400 nm, more preferably 3 to 300 nm.
The average thickness of the outer shell is also the size and concentration of the core material (polymer particles (a-1) or hydrophobic organic compound (a-2), hereinafter the same) of the protocore-shell particles described later, and the concentration of the silica source. It can be suitably prepared according to the relationship. For example, when the compounding concentration of the silica source is changed while keeping the size and concentration of the core material constant, the difference in the amount of the silica source affects the average thickness of the outer shell.
The ratio of [average thickness of outer shell portion / average particle diameter of hollow silica particles] is usually 0.01 to 0.9, preferably 0.05 to 0.8, more preferably 0.1 to 0. 7. This ratio is also appropriately adjusted according to environmental conditions such as the size of the core material, the concentration of the core material, the concentration of the silica source, and the temperature.
The average particle diameter, average outer shell thickness, BET specific surface area, average pore diameter, and powder X-ray diffraction (XRD) pattern of the hollow silica particles can be measured by the method described in the examples.

[Fragrance]
Although there is no restriction | limiting in particular in the fragrance | flavor used for this invention, The liquid fragrance | flavor and the fragrance | flavor with a quick volatilization rate are preferable from a viewpoint of making the sustained release property of a fragrance | flavor of this invention, and a temporal perfume property express effectively.
In the composite silica particles of the present invention, the perfume volatilization starts with the perfume volatilization held near the outer surface of the particle, and then the perfume retained in the hollow part and the mesopores is stable for a long time. Volatilization control is easy because it volatilizes at a reduced speed.
Among these fragrances, even if they are unstable in inorganic powders having catalytic activity such as acids, alkalis, zeolites, and the like, esters and acetals are stable if they are held inside the composite silica particles of the present invention. It is possible to obtain perfume particles that are retained in the water and are excellent in sustained release properties and residual fragrance with time.

Specific examples of perfumes include hydrocarbons, alcohols, phenols, esters, carbonates, aldehydes, ketones, acetals, ethers, nitriles, carboxylic acids, lactones, and other natural essential oils, 1 or more types chosen from a natural extract are mentioned.
Examples of the hydrocarbons include limonene, α-pinene, β-pinene, terpinene, cedrene, longifolene, and valencene.
Alcohols include linalool, citronellol, geraniol, nerol, terpineol, dihydromyrcenol, ethyl linalool, farnesol, nerolidol, cis-3-hexenol, cedrol, menthol, borneol, phenylethyl alcohol, benzyl alcohol, dimethylbenzylcarbi Examples of phenols include guaiacol, eugenol, and isoeugenol.

Examples of the esters include formic acid ester, acetic acid ester, propionic acid ester, salicylic acid ester, brassylic acid ester, tiglic acid ester, jasmonic acid ester, glycidic acid ester, and anthranilic acid ester.
Examples of formate include linalyl formate, citronellyl formate, and geranyl formate. Examples of acetate include n-hexyl acetate, cis-3-hexenyl acetate, linalyl acetate, citronellyl acetate, geranyl acetate, and neryl. Acetate, terpinyl acetate, nopyrucetate, bornyl acetate, isobornyl acetate, ot-butylcyclohexyl acetate, pt-butylcyclohexyl acetate, tricyclodecenyl acetate, benzyl acetate, styrylyl acetate, Examples include cinnamyl acetate, dimethylbenzylcarbinyl acetate, phenylethylphenyl acetate, 3-pentyltetrahydropyran-4-yl acetate, and propionic acid ester. The ether, citronellyl propionate, tricyclodecenyl propionate, allyl cyclohexyl propionate, ethyl 2-cyclohexyl propionate, benzyl propionate or the like.

Examples of the salicylic acid ester include methyl salicylate, n-hexyl salicylate, cis-3-hexenyl salicylate, cyclohexyl salicylate, benzyl salicylate, and the like. Examples of the brassic acid ester include ethylene brushate. Geranyl tiglate, 1-hexyl tiglate, cis-3-hexenyl tiglate and the like, and jasmonic acid esters include methyl jasmonate, methyl dihydrojasmonate, etc., and glycidic acid ester , Methyl 2,4-dihydroxy-ethylmethylphenyl glycidate, 4-methylphenylethyl glycidate and the like, and as anthranilate ester, methyl anthranilate, ethyl anthranilate Dimethyl anthranilate and the like.
Other, commercially available from Kao Corporation, Furuteto (ethyl tricyclo [5,2,1,0 ^2,6] decane-2-carboxylate: trade name: FRUITATE), and the like.

As carbonates, commercially available products from Kao Corporation, Jasma Cyclat (trade name: JASMACYCLAT), Kao Corporation, Flora Mat (trade name: FLORAMAT), International Flavor and Fragrance (IFF), Bioriff (Product name: VIOLIFF).
Examples of aldehydes include n-octanal, n-decanal, n-dodecanal, 2-methylundecanal, 10-undecenal, citronellal, citral, hydroxycitronellal, benzaldehyde, phenylacetaldehyde, phenylpropylaldehyde, syn Namic aldehyde, dimethyltetrahydrobenzaldehyde, 4 (3)-(4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carbaldehyde (IFF, trade name: Lilal), 2-cyclohexylpropanal, pt -Butyl-α-methylhydrocinnamic aldehyde, p-isopropyl-α-methylhydrocinnamic aldehyde, p-ethyl-α, α-dimethylhydrocinnamic aldehyde, α-amylcinnamic aldehyde, Examples include α-hexylcinnamic aldehyde, heliotropin, α-methyl-3,4-methylenedioxyhydrocinnamic aldehyde, and the like.

Examples of ketones include methylheptenone, 4-methylene-3,5,6,6-tetramethyl-2-heptanone, amylcyclopentanone, and 3-methyl-2- (cis-2-penten-1-yl) -2. -Cyclopenten-1-one, methylcyclopentenolone, rose ketone, carvone, menthone, camphor, acetyl cedrene, isolongifolanone, nootkatone, benzylacetone, anisylacetone, methyl β-naphthylketone, 2,5-dimethyl -4-Hydroxy-3 (2H) -furanone, maltol, muscone, civetone and the like are mentioned. Examples of the acetals include formaldehyde cyclododecylethyl acetal, acetaldehyde ethylphenylpropyl acetal, citral diethyl acetal and the like.
Examples of ethers include cedolyl methyl ether, anethole, β-naphthyl methyl ether, β-naphthyl ethyl ether, limonene oxide, rose oxide, nerol oxide, 1,8-cineol, rose furan, decahydro-3a, 6, 6 , 9a-tetramethylnaphtho [2.1-b] furan, and the nitriles include geranyl nitrile, citronellyl nitrile, dodecane nitrile and the like.
Examples of carboxylic acids include benzoic acid, phenylacetic acid, cinnamic acid, hydrocinnamic acid, butyric acid, 2-hexenoic acid, and lactones include γ-decalactone, δ-decalactone, γ-valerolactone, and γ-nonalactone. , Γ-undecalactone, δ-hexalactone, γ-jasmolactone and the like.

Natural essential oils and natural extracts include orange, lemon, lime, bergamot, vanilla, mandarin, peppermint, spearmint, lavender, camomil, rosemary, eucalyptus, sage, basil, rose, rock rose, geranium, jasmine, ylang ylang, Anise, cloves, ginger, nutmeg, cardamom, cedar, cypress, vetiver, patchouli, lemongrass, lovedanum and the like.
Although the said fragrance | flavor can be used individually or in combination of 2 or more types in arbitrary ratios, Especially, hydrocarbons, alcohols, ester, carbonates, aldehydes, etc. are preferable. If a plurality of perfumes are used in combination, and each is held in different hollow silica particles, a wide and effective perfume can be performed.

[Production method of composite silica particles]
Although there is no restriction | limiting in particular in the manufacturing method of the composite silica particle of this invention, According to the method containing following process (I) and (II), it can manufacture efficiently.
Step (I): Step of preparing hollow mesoporous silica particles Step (II): Step of impregnating the hollow silica particles obtained in Step (I) with a fragrance to obtain composite silica particles Steps (I) and (II) ) And the components used in each step will be described.

Process (I)
Step (I) is a step of preparing hollow silica particles. Although there is no restriction | limiting in particular if it is a method which can manufacture a hollow silica particle, The method containing following process AC is more preferable.
Step A: 0.1 to 50 g / L of the polymer particles (a-1) or 0.1 to 100 mmol / L of the hydrophobic organic compound (a-2), and the following general formulas (1) and (2) And 0.1 to 100 mmol / L of one or more (b) selected from quaternary ammonium salts represented by the formula (1)) and 0.1 to 100 mmol of silica source (c) that produces a silanol compound by hydrolysis. Step of preparing an aqueous solution containing / L.
[R ¹ (CH ₃ ) ₃ N] ⁺ X ⁻ (1)
[R ¹ R ² (CH ₃ ) ₂ N] ⁺ X ⁻ (2)
(In the formula, R ¹ and R ² each independently represents a linear or branched alkyl group having 4 to 22 carbon atoms, and X represents a monovalent anion.)
Step B: The aqueous solution obtained in Step A is stirred at a temperature of 10 to 100 ° C., has an outer shell composed of silica, and has polymer particles (a-1) or a hydrophobic organic compound (a -2) a step of preparing an aqueous dispersion of protocore-shell particles having Step C: a step of separating the protocore-shell particles obtained in Step B from the dispersion medium and baking

Hereinafter, steps A, B, and C will be described.
[Step A]
[Polymer particles (a-1)]
As the polymer particles (a-1) used in the step A, particles of one or more polymers selected from a cationic polymer, a nonionic polymer and an amphoteric polymer are preferable, and a substantially water-insoluble polymer is preferable.
[Cationic polymer]
The cationic polymer is preferably a polymer that can be dispersed as a polymer emulsion in a medium containing a continuous phase in an aqueous system in the presence of a cationic surfactant, and is cationic in the presence of a cationic surfactant. Those obtained by emulsion polymerization of a monomer mixture, particularly a monomer mixture containing an ethylenically unsaturated monomer having a cationic group, by a known method are preferred.
Examples of the cationic monomer include an acid neutralized product of a monomer having an amino group, or a quaternary ammonium salt obtained by quaternizing the monomer with a quaternizing agent.
As a specific example of the cationic monomer, a (meth) acrylate having a dialkylamino group or a trialkylammonium group is more preferable, and a (meth) acrylate having a dialkylamino group or a trialkylammonium group is most preferable.
In the present specification, (meth) acrylate means acrylate, methacrylate, or both.

  The cationic polymer contains a structural unit derived from the cationic monomer, but in addition to the cationic monomer structural unit, the cationic polymer is derived from a hydrophobic monomer such as an alkyl (meth) acrylate or an aromatic ring-containing monomer. It is more preferable to contain a structural unit. Preferable examples thereof include styrenic monomers such as alkyl (meth) acrylate, styrene or 2-methylstyrene having an alkyl group having 1 to 30 carbon atoms, preferably 3 to 22 carbon atoms, more preferably 3 to 18 carbon atoms. , Aryl esters of (meth) acrylic acid such as benzyl (meth) acrylate, aromatic group-containing vinyl monomers having 6 to 22 carbon atoms, or vinyl acetate. Of these, alkyl (meth) acrylate and styrene are most preferred.

The hydrophobic monomer means a polymerizable organic compound that has low solubility in water and forms a phase separation with water. Examples of the hydrophobic monomer include compounds having a LogP value of 0 or more, preferably 0.5 or more, and 25 or less. Here, LogP means a logarithmic value of a 1-octanol / water partition coefficient of a chemical substance, and is a numerical value calculated by a fragment approach by SRC's LOGKOW / KOWWIN Program. Specifically, the chemical structure of a chemical substance is decomposed into its constituent components, and the hydrophobic fragment constants of each fragment are integrated (Meylan, WM and PH Howard. 1995. Atom / fragment contribution method for octanol-water partition coefficients. See J. Pharm. Sci. 84: 83-92).
The cationic monomer constituting unit constituting the cationic polymer may be a small amount, and most constituting the cationic polymer may be constituted by a constituent unit derived from the hydrophobic monomer. The total amount of the cationic monomer constituent unit and the constituent unit derived from the hydrophobic monomer in the cationic polymer is 70 to 100% by weight, more preferably 80 to 100% by weight, and particularly preferably 95 to 100% by weight. In particular, the weight ratio of [(constituent unit derived from cationic monomer) / (constituent unit derived from hydrophobic monomer)] is preferably 0.001 to 0.5, more preferably 0.002 from the viewpoint of particle formation. It is -0.3, Most preferably, it is 0.003-0.1.

[Nonionic polymer]
Nonionic polymer means a polymer that has no charge in aqueous solution. The nonionic polymer is a polymer derived from a monomer having no charge, that is, a nonionic monomer, and can be obtained by polymerizing a nonionic monomer by a known emulsion polymerization method, non-emulsifier polymerization method or the like.
Nonionic monomers include the hydrophobic monomers (paragraph [0017]) mentioned in the description of the cationic polymer. Preferable examples thereof include one or more selected from alkyl (meth) acrylates having an alkyl group having 1 to 30 carbon atoms, preferably 3 to 22 carbon atoms, more preferably 3 to 18 carbon atoms, vinyl acetate, and styrene. Can be mentioned.
Specific examples of nonionic polymers include polystyrene, ethyl acrylate / ethyl methacrylate copolymer, ethyl acrylate / methyl methacrylate copolymer, octyl acrylate / styrene copolymer, butyl acrylate / vinyl acetate copolymer, methyl methacrylate / butyl. Examples thereof include acrylate / octyl acrylate copolymers, vinyl acetate / styrene copolymers, vinyl pyrrolidone / styrene copolymers, butyl acrylate, and polystyrene acrylate resins.

Among the cationic polymer, nonionic polymer and amphoteric polymer, the cationic polymer and nonionic polymer are preferable, and the cationic polymer is more preferable from the viewpoint of easy formation of the hollow silica particles.
For the production of hollow silica particles, a polymer that does not substantially dissolve in water is used. For this purpose, a method for increasing the polymerization ratio of a hydrophobic monomer, a method for crosslinking, and the like can be employed.
Preferred examples of such a polymer include a copolymer of a hydrophobic monomer selected from alkyl (meth) acrylate and styrene and a (meth) acrylate having a cationic group, and one or more hydrophobic properties selected from alkyl (meth) acrylate and styrene. Mention may be made of nonionic polymers composed of monomers.
Said polymer can be used individually or in mixture of 2 or more types.
The shape and form of the polymer particles are not particularly limited, and the size of the particles can be changed or the particles can be formed into a true spherical shape, an egg shape, or the like according to the purpose of use of the composite silica particles. By changing the size and particle size distribution of the polymer particles, the particle size of the hollow silica particles and the size of the hollow part can be appropriately adjusted.

[Hydrophobic organic compound (a-2)]
In the present invention, the hydrophobic organic compound (a-2) means a compound that has low solubility in water and forms a phase separation with water. Preferably, the compound is dispersible in the presence of the quaternary ammonium salt. Examples of such hydrophobic organic compounds include compounds having a LogP value of 1 or more, preferably 2 to 25.
(C) Examples of the hydrophobic organic compound include oils such as hydrocarbon compounds, ester compounds, fatty acids having 6 to 22 carbon atoms, alcohols having 6 to 22 carbon atoms, and silicone oils, and various kinds such as fragrances, agricultural chemicals, and pharmaceuticals. A base material etc. can be mentioned.
When using a hydrophobic organic compound, the particle size of the hollow silica particles and the size of the hollow part are affected by the size of the droplets of the hydrophobic organic compound, so the melting point, reaction temperature, and stirring speed of the hydrophobic organic compound , And can be adjusted as appropriate depending on the surfactant used.

[Quaternary ammonium salt (b)]
The quaternary ammonium salt (b) is used for forming mesopores and dispersing the polymer particles (a-1) or the hydrophobic organic compound (a-2).
R ¹ and R ² in the general formulas (1) and (2) are linear or branched alkyl groups having 4 to 22 carbon atoms, preferably 6 to 18 carbon atoms, and more preferably 8 to 16 carbon atoms. It is. Examples of the alkyl group having 4 to 22 carbon atoms include various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various decyl groups, various dodecyl groups, various tetradecyl groups, and various hexadecyl groups. , Various octadecyl groups, various eicosyl groups, and the like.
X in the general formulas (1) and (2) is preferably one selected from monovalent anions such as halogen ions, hydroxide ions, nitrate ions, and sulfate ions from the viewpoint of obtaining high crystallinity. That's it. X is more preferably a halogen ion, still more preferably a chlorine ion or a bromine ion, and particularly preferably a bromine ion.

Examples of the alkyltrimethylammonium salt represented by the general formula (1) include butyltrimethylammonium chloride, hexyltrimethylammonium chloride, octyltrimethylammonium chloride, decyltrimethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, hexadecyltrimethyl Ammonium chloride, stearyltrimethylammonium chloride, butyltrimethylammonium bromide, hexyltrimethylammonium bromide, octyltrimethylammonium bromide, decyltrimethylammonium bromide, dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide Bromide, stearyl trimethyl ammonium bromide, and the like.
Examples of the dialkyldimethylammonium salt represented by the general formula (2) include dibutyldimethylammonium chloride, dihexyldimethylammonium chloride, dioctyldimethylammonium chloride, dihexyldimethylammonium bromide, dioctyldimethylammonium bromide, didodecyldimethylammonium bromide, ditetradecyl. Examples thereof include dimethylammonium bromide.
Among these quaternary ammonium salts (b), from the viewpoint of forming regular mesopores, alkyltrimethylammonium salts represented by the general formula (1) are particularly preferred, and alkyltrimethylammonium bromide or alkyltrimethyl Ammonium chloride is more preferred, and dodecyltrimethylammonium bromide or dodecyltrimethylammonium chloride is particularly preferred.

[Silica source (c)]
A silica source (c) produces | generates a silanol compound by hydrolysis of alkoxysilane etc., and can mention the compound shown by following General formula (3)-(7).
SiY ₄ (3)
R ³ SiY ₃ (4)
R ³ ₂ SiY ₂ (5)
R ³ ₃ SiY (6)
Y ₃ Si—R ⁴ —SiY ₃ (7)
(In the formula, each R ³ independently represents an organic group in which a carbon atom is directly bonded to a silicon atom, R ⁴ represents a hydrocarbon group or a phenylene group having 1 to 4 carbon atoms, and Y represents A monovalent hydrolyzable group that becomes a hydroxy group by hydrolysis.)
More preferably, in the general formulas (3) to (7), each R ³ is independently a hydrocarbon group having 1 to 22 carbon atoms in which a part of hydrogen atoms may be substituted with fluorine atoms, Specifically, it is an alkyl group, a phenyl group, or a benzyl group having 1 to 22 carbon atoms, preferably 4 to 18 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 8 to 16 carbon atoms, and R ⁴ Is an alkanediyl group having 1 to 4 carbon atoms (methylene group, ethylene group, trimethylene group, propane-1,2-diyl group, tetramethylene group, etc.) or phenylene group, and Y is more preferably 1 to 22 carbon atoms. Is a C1-C8, particularly preferably C1-C4 alkoxy group or a halogen group excluding fluorine.

Preferable examples of the silica source (c) include the following compounds.
-The silane compound in which Y is a C1-C3 alkoxy group or a halogen group except a fluorine in General formula (3).
In general formula (4) or (5), Y is an alkoxy group having 1 to 3 carbon atoms or a halogen group excluding fluorine, and R ³ is a phenyl group, a benzyl group, or a part of a hydrogen atom Is a trialkoxysilane or dialkoxysilane, which is a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, substituted with a fluorine atom.
In General Formula (6), Y is an alkoxy group having 1 to 3 carbon atoms or a halogen group excluding fluorine, and R ³ is a phenyl group, a benzyl group, or a hydrogen atom partially substituted with a fluorine atom. Monoalkoxysilane which is a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.
A compound in which Y is a methoxy group and R ⁴ is a methylene group, an ethylene group or a phenylene group in the general formula (7).
Among these, tetramethoxysilane, tetraethoxysilane, phenyltriethoxysilane, and 1,1,1-trifluoropropyltriethoxysilane are particularly preferable.

Polymer particles (a-1) or hydrophobic organic compound (a-2) in the aqueous solution in step A (hereinafter, both are also collectively referred to as “component (a)”), quaternary ammonium salt (b), And the content of the silica source (c) is as follows.
The content of the component (a-1) is preferably 0.1 to 50 g / L, more preferably 0.3 to 40 g / L, and particularly preferably 0.5 to 30 g / L.
The content of the component (a-2) is 0.1 to 100 mmol / L, more preferably 1 to 100 mmol / L, and particularly preferably 5 to 80 mmol / L.
The content of component (b) is preferably 0.1 to 100 mmol / L, more preferably 1 to 100 mmol / L, particularly preferably 5 to 80 mmol / L, and the content of component (c) is And preferably 0.1 to 100 mmol / L, more preferably 1 to 100 mmol / L, and particularly preferably 5 to 80 mmol / L.
There is no restriction | limiting in particular in the order which contains (a)-(c) component. For example, (i) the suspension of the component (a), the component (b) and the component (c) are added in this order while stirring the aqueous solution, (ii) the suspension of the component (a) while stirring the aqueous solution, (B) Component and (c) component can be added simultaneously, (iii) Suspension of (a) component, (b) Component, (c) Stirring after addition of component, etc. can be employed. However, among these, the method (i) is preferable.
The aqueous solution containing the components (a) to (c) may contain other components such as an organic compound such as methanol and an inorganic compound as long as the formation of protocore-shell particles is not inhibited. As described above, when it is desired to carry other elements other than silica and organic groups, metal raw materials such as alkoxy salts and halide salts containing these metals can be added during or after production.

[Step B]
Step B is a step of preparing an aqueous dispersion of protocore-shell particles. The aqueous solution obtained in Step A is stirred for a predetermined time at a temperature of 10 to 100 ° C., preferably 10 to 80 ° C., and then allowed to stand to leave the polymer particles (a-1) or the hydrophobic organic compound (a-2). A protocore having mesopores formed by a quaternary ammonium salt (b) and a silica source (c) on the surface thereof, and containing polymer particles (a-1) or a hydrophobic organic compound (a-2) inside Shell particles can be precipitated. Although the stirring treatment time varies depending on the temperature, protocore-shell particles are usually formed at 10 to 80 ° C. for 0.1 to 24 hours. It should be noted that the mesopores of the protocore-shell particles obtained at this time are clogged with the surfactant used in the production.
The obtained protocore-shell particles are obtained in a state suspended in water. Depending on the application, it can be used as it is, but preferably the protocore-shell particles are used separately. As a separation method, a filtration method, a centrifugal separation method, or the like can be employed.
When the protocore-shell particles obtained in step B contain a cationic surfactant or the like, the cationic surfactant or the like can be removed by contacting the acidic solution once or a plurality of times. Examples of the acidic solution to be used include inorganic acids such as hydrochloric acid, nitric acid and sulfuric acid; organic acids such as acetic acid and citric acid; liquids obtained by adding a cation exchange resin or the like to water or ethanol. Hydrochloric acid is particularly preferable. The pH is usually adjusted to 1.5 to 5.0.
The particles from which the surfactant has been removed from the pores by the above method have a mesopore structure on the surface, and have a high BET specific surface area. Polymer particles (a-1) or hydrophobic organic compounds (a-2) Are protocore-shell particles.

[Step C]
In step C, the protocore-shell particles obtained in step B are separated from the dispersion medium and, if necessary, contacted with an acidic aqueous solution, washed with water, dried, or treated at a high temperature, and then preferably treated in an electric furnace or the like. Baking is performed at ˜800 ° C., more preferably at 450 ° C. to 700 ° C., for 1 to 10 hours to remove the internal polymer (a-1) or the hydrophobic organic compound (a-2). In the obtained hollow mesoporous silica particles, the basic structure of the outer shell portion is not changed, but the inner polymer (a-1) or hydrophobic organic compound (a-2) is removed by calcination.
In the present invention, since the protocore-shell particles containing the polymer (a-1) or the hydrophobic organic compound (a-2) are fired, the shape and form of the polymer particles (a-1) to be included are particularly desired. By controlling in advance to this state, hollow silica particles having a desired shape and form can be easily produced. For example, by firing protocore-shell particles having a true spherical polymer inside, hollow silica particles having an internal hollow shape and a true spherical shape can be produced.

Process (II)
In step (II), the hollow silica particles obtained in step (I) are impregnated with a fragrance (liquid fragrance) to obtain composite silica particles.
The impregnation treatment of the fragrance is not particularly limited as long as the fragrance can impregnate the hollow silica particles, and a known vacuum impregnation method or the like can be adopted. For example, a solution in which a fragrance is dissolved in a container and hollow silica particles are mixed, and the interior of the container is higher than the vapor pressure of the fragrance solution and smaller than the vapor pressure of nitrogen in the mesopores of the hollow silica particles to be used. It is preferable to impregnate. In this case, the vapor pressure of nitrogen in the mesopores is obtained from the nitrogen adsorption isotherm.
Under these conditions, the pores of the hollow silica particles are degassed to forcibly impregnate the fragrance solution, and after stirring for 1 minute to 10 hours, preferably 1 minute to 1 hour, the pressure in the container is once returned to atmospheric pressure, A method of introducing the fragrance solution into the hollow interior through the mesopores of the hollow silica particles by standing for 1 minute to 10 hours, preferably 1 hour to 10 hours, can be mentioned. The degree of impregnation is preferably performed until the fragrance solution is included in all the hollow portions of the hollow silica particles.
Further, from the viewpoint of solubilization, solubility, and storage stability of the fragrance, a known surfactant can be contained at about 5% by mass or less.

<(B) Surfactant>
The cleaning composition of the present invention contains (b) a surfactant as a cleaning component in addition to the (a) composite mesoporous silica particles.
The surfactant used is not particularly limited, and examples thereof include one or more selected from nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants. For example, a combination of a plurality of nonionic surfactants may be used, a combination of a plurality of anionic surfactants may be used, and various types of nonionic surfactants and anionic surfactants may be used. A plurality may be selected and used in combination. Preferably, the surfactant contains 50 to 100% by mass of nonionic surfactant, more preferably 65 to 100% by mass.

Examples of the nonionic surfactant include polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyethylene polyoxypropylene block polymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene Ethylene castor oil, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyethylene glycol fatty acid ester, fatty acid monoglyceride, polyglycerin fatty acid ester, sorbitan fatty acid ester, fatty acid alkanolamide, polyoxyethylene fatty acid amide, polyoxyethylene alkylamine , Alkylamine oxide and the like.
Among these, from the viewpoint of detergency, it is a polyoxyalkylene alkyl ether having an average addition mole number of alkylene oxide such as ethylene oxide of 4 to 8, preferably 10 to 16 carbon atoms, more preferably 10 carbon atoms. Polyoxyethylene alkyl ethers having an alkyl group of -14, more preferably 12-14 carbon atoms are preferred.
Among these, in the total content of the polyoxyalkylene alkyl ether having 1 to 12 addition moles, the content of the polyoxyalkylene alkyl ether having 4 to 8 addition moles is preferably 30% by mass or more, More preferably, it is 50 mass% or more.
The average added mole number can be determined, for example, by measuring the hydroxyl value. The addition mole number can be analyzed by a method using gas chromatography or LC-mass spectrum.

Examples of the anionic surfactant include linear alkyl benzene sulfonate, alkyl sulfate ester salt, polyoxyalkylene alkyl ether sulfate, preferably having an alkyl chain having 10 to 18 carbon atoms, more preferably 12 to 14 carbon atoms. Alkali metal salts such as salts, α-sulfo fatty acid methyl ester salts, alkyl or alkenyl ether carboxylates, alkyl or alkenyl phosphate esters or salts thereof, N-acyl amino acid surfactants, amino acid surfactants, and the like .
In these, the linear alkylbenzenesulfonic acid sodium salt and alkyl sulfate ester salt which have a C12-C14 alkyl chain are more preferable.
In addition, examples of the cationic surfactant include quaternary ammonium salts such as alkyltrimethylamine salts, and examples of the amphoteric surfactant include amphoteric surfactants such as carboxy type or sulfobetaine type.
Since the cleaning composition of the present invention has the ability to promote the re-adhesion of fine particles to the object to be cleaned, it is not preferable to use a cationic surfactant, but within the range not impairing the object of the present invention. Can be used. The cationic surfactant used is not particularly limited. The content of the cationic surfactant in the cleaning composition is preferably 2% by mass or less, more preferably 1% by mass or less, and most preferably not contained.

<(C) Alkaline agent>
Examples of the alkaline agent include alkali metal carbonates such as sodium carbonate and potassium carbonate, sodium silicate, sodium hydroxide, potassium hydroxide and the like. Among these, alkali metal carbonates form sesquicarbonates by the reaction of carbon dioxide in the air with water during storage, and cause caking, so from the viewpoint of sufficiently exerting the effects of the present invention, Particles containing alkali metal salts, especially sodium carbonate, are preferred.

<(D) Other ingredients>
As other components, the cleaning composition of the present invention includes builders, alkali agents, water-soluble polymers, anti-staining agents, softening agents, fluorescent whitening agents, foam control agents, enzymes, known in the field of detergents. Enzyme stabilizers, fragrances and the like can be included.
Examples of inorganic builders include crystalline aluminosilicate, amorphous aluminosilicate, crystalline sodium silicate, sodium tripolyphosphate, sodium pyrophosphate, etc., and crystalline aluminosilicate in terms of environmental impact and cleaning performance Is more preferable. The ratio of the builder is preferably 10 to 50% by mass in the composition and more preferably 15 to 40% by mass in terms of cleaning performance.
Examples of the alkali agent include carbonates, silicates, amines (alkylamines, alkanolamines, etc.), and carbonates and silicates are more preferable.
Examples of the water-soluble polymer include carboxylic acid polymers, carboxymethyl cellulose, soluble starch, saccharides and the like. Among them, a carboxylic acid polymer having a weight average molecular weight of 1,000 to 100,000 is preferable in terms of sequestering ability, dispersibility of solid dirt / particle dirt, and ability to prevent recontamination. Particularly preferred are salts of acrylic acid-maleic acid copolymers and polyacrylates. Here, examples of the salt include sodium salt, potassium salt, and ammonium salt.

<Combination ratio of each component>
In the cleaning composition of the present invention, the content of (a) composite mesoporous silica particles is usually preferably from 0.1 to 10% by mass in the cleaning composition from the viewpoint of cleaning performance, residual fragrance, etc. 2-8 mass% is more preferable, 0.3-6 mass% is still more preferable, and 0.4-5 mass% is especially preferable.
More specifically, in the case of a powder detergent, the content of (a) composite mesoporous silica particles is preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 6% in the cleaning composition. It is below mass%.
In the case of a liquid detergent, the content of the (a) composite mesoporous silica particles is preferably 8% by mass or less, more preferably 6% by mass or less, and further preferably 4% by mass or less in the cleaning composition.
Further, the content of the fragrance in the composite mesoporous silica particles (a) is not particularly limited, but is preferably 10% by mass or more, more preferably 30% by mass or more, and particularly preferably 50% from the viewpoint of imparting high residual fragrance properties. It is -300 mass%.

The total content of the surfactant (b) in the cleaning composition, particularly the total content of the nonionic surfactant and the anionic surfactant, is preferable from the viewpoint of cleaning performance and anti-redeposition property of dirt. Is 5% by mass or more, more preferably 15% by mass or more.
More specifically, in the case of a powder cleaning agent, since the nonionic surfactant is liquid at room temperature, the nonionic surfactant and the nonionic surfactant from the viewpoint of product quality due to exudation from the detergent particles. The total content of the anionic surfactant is preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 25% by mass or less.
On the other hand, in the case of a liquid detergent, since the blending of alkali builder components and the like is regulated, it is preferable that the total amount of the surfactant is large, but from the viewpoint of fluidity and the like, More preferably, it is 50 mass% or less.
The mass ratio of (nonionic surfactant / anionic surfactant) in the cleaning composition is 35/65 to 100/0, preferably 40/60 to 95/5, preferably 45/55. 90/10, more preferably 50/50 to 85/15, still more preferably 55/45 to 70/30.
(C) The ratio of the alkaline agent is preferably 5 to 50% by mass and more preferably 10 to 40% by mass in the cleaning composition in terms of cleaning performance.
The ratio of the water-soluble polymer is preferably 0.5 to 20% by mass and more preferably 1 to 10% by mass in the cleaning composition in terms of cleaning performance.

Various measurements of the silica particles obtained in Examples and Comparative Examples were performed by the following methods.
(1) Measurement of average particle diameter, average outer shell thickness, and hollow part diameter Measured at an acceleration voltage of 160 kV using a transmission electron microscope (TEM) JEM-2100 manufactured by JEOL Ltd. The diameter and outer shell thickness of all the particles in the five fields of view containing the particles are measured on a photograph. This operation is performed by changing the field of view five times. From the obtained data, the average particle diameter, the degree of distribution thereof, and the average thickness of the outer shell were determined. The standard of magnification of the transmission electron microscope is 10,000 to 100,000 times, but is appropriately adjusted depending on the size of the silica particles. The sample used for observation was prepared by adhering to a Cu mesh with a high resolution carbon support film (200-A mesh, manufactured by Oken Shoji Co., Ltd.) and removing the excess sample by blowing.

(2) Measurement of BET specific surface area and average pore diameter Using a specific surface area / pore distribution measuring device manufactured by Shimadzu Corporation, trade name “ASAP2020”, the BET specific surface area is measured by a multipoint method using liquid nitrogen. Then, values were derived within a range in which the parameter C becomes positive. The BJH method was adopted from the nitrogen adsorption isotherm, and the peak top was defined as the average pore diameter. The pretreatment was performed at 250 ° C. for 5 hours.

(3) Measurement of powder X-ray diffraction (XRD) pattern Using a powder X-ray diffractometer manufactured by Rigaku Denki Kogyo Co., Ltd., trade name “RINT 2500 VPC”, X-ray source: Cu-kα, tube voltage: 40 mA, tube current : 40 kV, sampling width: 0.02 °, divergence slit: 1/2 °, divergence slit length: 1.2 mm, scattering slit: 1/2 °, light receiving slit: 0.15 mm went. The scanning range was a diffraction angle (2θ) of 1 to 20 °, the scanning speed was 4.0 ° / min, and the continuous scanning method was used. The sample was crushed and then packed in an aluminum plate for measurement.

(4) Measurement of fragrance retention amount Decreases when the temperature is increased from room temperature to 700 ° C. at a rate of 10 ° C./minute using a differential differential thermobalance Thermo plus TG8120 manufactured by Rigaku Denki Kogyo Co., Ltd. The weight obtained was the weight of the fragrance, and the remaining weight was the weight of the silica. A value obtained by dividing the weight of the fragrance by the weight of silica was defined as the weight of the fragrance held on the particles (g (fragrance) / g (silica)).

Production Example 1
(1) Production of Cationic Polymer Particles 600 parts of ion-exchanged water, 99.5 parts of methyl methacrylate and 0.5 parts of methacryloyloxyethyltrimethylammonium chloride are placed in a 2 L-separable flask, and the temperature is raised to 70 ° C. I let you. Next, a solution in which 0.5 part of 2,2′-azobis (2-amidinopropane) dihydrochloride (manufactured by Wako Pure Chemical Industries, Ltd., trade name: V-50) was dissolved in 5 parts of ion-exchanged water as a water-soluble initiator. Was added and heated and stirred for 3 hours. Thereafter, the mixture was further stirred at 75 ° C. for 3 hours. After cooling, the resulting mixture is subjected to 200-mesh filtration (opening; approximately 75 μm), and the obtained filtrate is concentrated by heating with an evaporator. After cooling, the concentrated solution is filtered through a 1.2 μm membrane filter [Sartorius]. The product was filtered through a trade name, Minisart, and adjusted with ion-exchanged water to obtain a suspension of cationic polymer particles (solid content (effective content) content 40%, average particle size 312 nm).

(2) Production of polymer particle-encapsulated mesoporous silica particles 60 g of water, 20 g of methanol, 0.46 g of 1M sodium hydroxide aqueous solution, 0.35 g of dodecyltrimethylammonium bromide in a 100 ml flask, the cationic polymer particles obtained in the above (1) 0.11 g of the suspension was added and stirred. To the aqueous solution, 0.34 g of tetramethoxysilane was slowly added, stirred for 5 hours and then aged for 12 hours. The resulting white precipitate was filtered off, washed with water and dried. The dry powder was dispersed in 100 ml of water, adjusted to pH 2 with 1M hydrochloric acid, and stirred overnight. The obtained white precipitate was filtered off, washed with water and dried to obtain composite silica particles containing polymer particles and having an outer shell portion having a mesoporous structure.

(3) Production of hollow silica particles The polymer particle-containing mesoporous silica particles obtained in (2) above were heated to 600 ° C. at a rate of 1 ° C./min, and then calcined at 600 ° C. for 2 hours. Removal gave hollow silica particles whose outer shell part had a mesoporous structure. The average particle diameter of the obtained hollow silica particles was 0.56 μm, the average pore diameter of mesopores was 1.5 nm, and the thickness of the outer shell portion was 140 nm.
The hollow silica particles had one or more peaks at a diffraction angle corresponding to a range of d = 2 to 12 nm in a powder X-ray diffraction (XRD) pattern.

(4) Production of composite silica particles (fragrance-encapsulated silica particles) 0.1 g of the hollow silica particles obtained in (3) above is placed in a 20 ml sample bottle, and (R)-(+)-limonene is used as a fragrance on the bottle. 2.0 g (Wako Pure Chemical Industries, Ltd.) was poured. The container was transferred into a glass desiccator and decompressed for 3 minutes using a rotary pump. Then, nitrogen gas was filled and the internal pressure was returned to normal pressure. After repeating this operation three times, the sample was allowed to stand overnight. The next day, the mixture was filtered with a membrane filter (manufactured by ADVANTEC, PTFE, pore size 0.45 μm) to obtain composite silica particles enclosing a fragrance. The carrying amount of the fragrance was 2.7 g / g (silica). Table 1 shows the measurement results of the physical properties.

Production Example 2
In Production Example 1, the same operation as in Production Example 1 (4) was performed except that the hollow silica particles obtained by the following method were used instead of the hollow silica particles obtained in Production Example 1 (3). Perfume-carrying particles were prepared and evaluated. The carrying amount of the fragrance was 1.0 g / g (silica).
(3) Synthesis of Hollow Silica Particles A 100 ml flask was charged with 60 g of water, 20 g of methanol, 0.46 g of 1N aqueous sodium hydroxide solution and 0.35 g of dodecyltrimethylammonium bromide. To this aqueous solution, 0.17 g of tetramethoxysilane and 0.15 g of bistriethoxysilylethane were mixed and slowly added, followed by stirring for 5 hours and aging for 12 hours. The obtained white precipitate was filtered off, washed with water and dried, and then fired to 450 ° C. at a rate of 1 ° C./min. The hollow silica particles had one or more peaks at a diffraction angle corresponding to a range of d = 2 to 12 nm in a powder X-ray diffraction (XRD) pattern. Table 1 shows the measurement results of the physical properties.

Comparative production example 1
In Production Example 1, Production Example 1 (4) except that fumed silica (Aldrich fumed silica, average particle size 0.007 μm) was used instead of the hollow silica particles obtained in Production Example 1 (3). The perfume-carrying particles were prepared in the same manner as in (1). The carrying amount of the fragrance was 7.1 g / g (silica). Table 1 shows the measurement results of the physical properties.
Comparative production example 2
In Production Example 1, Production Example 1 (4) was used except that spherical silica particles (COSMO 55 produced by catalyst conversion, average particle size 0.50 μm) were used instead of the hollow silica particles obtained in Production Example 1 (3). A perfume-carrying particle was produced in the same manner as described above. The carrying amount of the fragrance was 0.54 g / g (silica). Table 1 shows the measurement results of the physical properties.
Comparative production example 3
In Production Example 1, the same operation as in Production Example 1 was carried out except that limonene was used as a fragrance without using the composite silica particles obtained in Production Example 1 (4). Table 1 shows the measurement results of the physical properties.

Examples 1-6 and Comparative Examples 1-5
Using the composite silica particles obtained in Production Example 1 and Comparative Production Example 2, each component was blended according to the formulation shown in Table 1 to obtain a detergent composition. About the obtained cleaning composition, the cleaning power and residual fragrance | flavor evaluation were performed with the following method. The results are shown in Table 2.
The details of each component in Table 2 are as follows.
-(A) Composite mesoporous silica particles: those obtained in Production Example-(b) Nonionic surfactant: polyoxyethylene alkyl ether An average of 6 moles of ethylene oxide was added to a primary alcohol having 10 to 14 carbon atoms. Things (product name: Emulgen 108, manufactured by Kao Corporation)
(B) Anionic surfactant: linear alkylbenzene sulfonate sodium alkyl group having 12 to 14 carbon atoms (manufactured by Kao Corporation, trade name: Neoperex G-15)
・ Sodium carbonate: Dense ash manufactured by Central Glass Co., Ltd. for sodium carbonate ・ Zeolite: Type A zeolite (Zeobuilder) manufactured by Zeobuilder
・ Sodium sulfate: Anhydrous neutral sodium sulfate manufactured by Shikoku Kasei Co., Ltd. ・ Monoethanolamine: Mitsui Chemicals

<Cleaning conditions and evaluation method>
According to the method for evaluating the cleaning power of a synthetic detergent for clothing described in JIS K 3362 (1998), a collar cloth was prepared, and the cleaning power of the detergent composition shown in Table 2 and the index detergent for determining cleaning power was compared. In addition, the use density | concentration of the detergent composition of Table 2 was 1.0 g / L.
(Evaluation criteria)
○: Superior to index detergent.
Δ: Equivalent to index detergent.
X: Inferior to index detergent.

<Evaluation method of residual fragrance>
(Preparation of evaluation towel)
Use a commercially available cotton towel (100% cotton) with a fully automatic washing machine ("NA-F70AP" manufactured by National), and use a commercially available laundry detergent (Kao Co., Ltd., liquid attack) as the pretreatment agent. Using the standard amount, the treatment was repeated 5 times on the standard course under the conditions of a water temperature of 20 ° C., a water amount of 40 L, and a bath ratio of 20, removing the treatment agent to obtain an evaluation towel.

(Residual odor evaluation)
Using the evaluation towel obtained above, 5.83 g of powder detergent composition containing fragrance particles in 7 L of water at 20 ° C. and 0.3 kg of cotton towel (four in half) were washed for 7 minutes. It was. After dehydration, it was rinsed with 5 L of water for 3 minutes, dehydrated, rinsed for 3 minutes (second time), dehydrated and air-dried. The amount of the composite silica particles containing the fragrance was adjusted so that 28 mg of the fragrance was added to 0.5 towels. Immediately after dehydration, 6 hours after drying, 1 day after drying, and after drying, after spraying water with spray, there are 3 levels (3: smell, 2: faint smell, 1: smell) Not).

  From the results of Table 2, the liquid detergent compositions of Examples 1 to 3 and the powder detergent compositions of Examples 4 to 6 have a perfume component that is washed compared to the liquid or powder detergent compositions of Comparative Examples. It turns out that it is excellent in residual fragrance property without being washed away.

Production Examples 3 and 4
In Production Example 1, as a result of using citronellol (Production Example 3) or δ-damascon (Production Example 4) instead of limonene as a fragrance, particles similar to those shown in Production Example 1 or 2 were obtained. Table 3 shows the measurement results of the physical properties.

Examples 7 and 8
Using the particles containing citronellol or δ-damascon obtained in Production Example 3 or 4, the same composition as in Example 4 was evaluated for detergency and aftertaste. As a result, the same results as in Example 4 were obtained. Results were obtained.

Claims (5)

  (A) A composite mesoporous silica in which the outer shell portion is composed of hollow silica particles having a mesopore structure, the mesopores have an average pore diameter of 1 to 10 nm, and a fragrance is held inside the hollow silica particles A detergent composition comprising particles and (b) a surfactant.   The cleaning composition of Claim 1 whose average particle diameter of a composite mesoporous silica particle is 0.05-10 micrometers.   The detergent composition according to claim 1 or 2, wherein the composite mesoporous silica particles have an average particle size of 0.05 µm to 10 µm, and 80% or more of the total particles have an average particle size within ± 30%. .   The cleaning composition in any one of Claims 1-3 whose fragrance | flavor hold | maintained inside a hollow silica particle is a liquid fragrance | flavor.   The cleaning composition according to any one of claims 1 to 4, wherein the cleaning agent is a laundry powder detergent.