JP4583779B2 - Bleach cleaning composition in a container - Google Patents

Description

  The present invention has a high bleaching detergency, prevents expansion and rupture of the container due to outgassing during storage, does not cause caking during storage, and is excellent in the stability of perfume ingredients The present invention relates to a bleaching detergent composition.

  Bleaching agents can be divided into chlorine and oxygen. Chlorine bleaching agents are limited in the fibers that can be used. Recently, oxygen-based bleaching agents that do not have the above-mentioned disadvantages have been remarkably widespread. As this oxygen bleaching agent, sodium percarbonate and sodium perborate are used as powder bleaching agents, and hydrogen peroxide is used as a liquid bleaching agent.

  Sodium percarbonate used as a bleaching active species for powder bleaching detergents decomposes during storage to generate oxygen gas. For this reason, as the powder bleach detergent container, a thick, strong structure is usually employed. However, powder bleaching detergents packed in thinner plastic sachets have been demanded from the demand for cost reduction of packaging materials and improvement of packaging material appearance.

As such refillable plastic bag-like packaging containers, there are those disclosed in Patent Document 1 and Patent Document 2. However, when these containers are used, there is a problem that the generated oxygen gas causes the containers to significantly swell or burst during storage. In order to solve this problem, there is provided a container in which oxygen gas generated by opening a vent hole in a container is released to the outside air. However, the container provided with such a vent has a new problem that the contents cause caking due to moisture entering from the vent, and the commercial value is lowered. Therefore, Patent Document 3 proposes that caking can be prevented without reducing bleaching power by controlling the amount of oxygen generated by the decomposition of sodium percarbonate using a container having a vent hole.
Japanese National Patent Publication No. 3-505322 Japanese Utility Model Publication No. 3-123847 JP-A-11-172286

  Usually, when a fragrance is blended with a powder bleaching detergent, a liquid fragrance component is sprayed onto the powder bleaching detergent. The powder bleaching detergent thus obtained is passed through as in Patent Document 3. When stored in a container provided with pores, the stripped fragrance component may leak out of the container, and the intended scent may not be maintained.

  An object of the present invention is to provide a bleaching detergent composition in a container that is excellent in bleaching detergency, resistance to caking, and excellent in perfume stability.

  The present invention provides (A) particles containing a compound that releases hydrogen peroxide in water, (B) a water-soluble inorganic salt other than (A), and (C) a perfume component in a plastic container having a vent. Provided is a bleaching detergent composition in a container which is filled with a bleaching detergent composition containing fragrance particles containing -12% by mass.

  The container-containing bleaching detergent composition of the present invention prevents expansion and rupture of the container due to gas release during long-term storage, does not cause caking, and is excellent in perfume stability.

<Bleaching detergent composition>
In the present invention, the bleaching detergent composition to be filled in a plastic container having a vent comprises (A) particles that release hydrogen peroxide in water, preferably particles containing sodium percarbonate, sodium perborate, etc. B) It contains a water-soluble inorganic salt other than (A), and (C) specific perfume particles, and further contains components such as a metal sequestering agent and a bleach activator as required.

[(A) Particles containing a compound that releases hydrogen peroxide in water]
The compound that releases hydrogen peroxide in water is preferably sodium percarbonate, sodium perborate or the like. Sodium perborate is preferable in terms of stability, and sodium percarbonate is preferable in terms of solubility. The content of these compounds in the bleaching detergent composition is preferably 1 to 99% by mass, particularly preferably 1 to 90% in order to prevent swelling of the container during storage and to obtain a sufficient bleaching effect. It is mass%, More preferably, it is 20-90 mass%.

[(B) Water-soluble inorganic salts other than (A)]
Examples of the water-soluble inorganic salt other than (A) include sodium carbonate, potassium carbonate, sodium silicate, sodium tripolyphosphate, sodium sulfate, sodium hydrogen carbonate and the like, and sodium carbonate is particularly preferable. The content of the water-soluble inorganic salt other than (A) in the bleaching detergent composition is preferably 1 to 80% by mass, particularly preferably 1 to 50% by mass, and further preferably 10 to 50% by mass. is there.

[(C) perfume particles]
The fragrance | flavor particle | grains used for this invention contain 1-12 mass%, Preferably 1-6 mass% of fragrance | flavor components in this particle | grain.

As the fragrance, a fragrance conventionally blended in a detergent, for example, a fragrance described in JP-A No. 63-10196, dimethylbenzylcarbinyl acetate, tricyclo [5.2.1.0 ^2,6 ] -dec-3-ene-8 -Il acetate, tricyclo [5.2.1.0 ^2,6 ] -dec-3-ene-8-isopropionate, 3-amyl-4-acetoxytetrahydropyran, 4-tert-butylcyclohexyl acetate, 2-tert-butyl Cyclohexyl acetate, p-tert-butyl-α-methylhydrocinnamic aldehyde, 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde, α-hexylcinnamic aldehyde, α-amylcine Examples thereof include namic aldehyde and α, α′-dimethyl-p-ethylhydrocinnamic aldehyde. Of course, it is desirable to consider the blending ratio and blending amount of each fragrance component to be blended and depending on the case so as not to cause deterioration due to other detergent components.

As a preferred embodiment of the present invention, as the fragrance particles, those containing the following components (C1), (C2), (C3), (C4) and (C5) [hereinafter referred to as fragrance particles (C)]. Can be mentioned.
(C1) Fragrance ingredient 1-12% by mass
(C2) Anionic surfactant represented by the following formula (I): 40 to 94% by mass
R-OSO ₃ Na (I)
[Wherein R represents a linear or branched alkyl or alkenyl group derived from a primary or secondary alcohol having 6 to 20 carbon atoms. ]
(C3) Water-insoluble solid particles having crystal water and an average particle size of 20 μm or less 3 to 30% by mass
(C4) Water-soluble polymer 1 to 10% by mass [However, the mass ratio of the component (C2) to the component (C4) is (C2) :( C4) = 5: 1 to 50: 1. ]
(C5) Water 0.1 to 10% by mass

  The (C1) fragrance component used in such fragrance particles (C) preferably contains one or more compounds selected from the following (C1-1) to (C1-9). Of course, other perfume compounds may be used in combination.

(C1-1): Hydrocarbon containing one or more double bonds (—C═C—) in the molecule. Examples include limonene, dipentene, terpinolene, α-pinene, and β-pinene.
(C1-2): Aldehyde For example, decyl aldehyde, undecyl aldehyde, dodecyl aldehyde, methylnonyl acetaldehyde, undecylene aldehyde, etc. as aliphatic aldehydes, citral, hydroxycitronellal, citronellal etc. as aromatic aldehydes as terpene aldehydes Benzaldehyde, hexylcinnamic aldehyde, lyial, heliotropin, vanillin, ethyl vanillin and the like, and other examples include rilal, mylac aldehyde, and the like.
(C1-3): ester For example, benzyl formate, linalyl formate, citronellyl acetate, linalyl acetate, isononyl acetate, geranyl acetate, terpinyl acetate, isobornyl acetate, tricyclodecenyl acetate, benzyl acetate, phenylethyl acetate, cinnamyl acetate, Examples include hexyl acetate, acetyl eugenol, acetyl isoeugenol, cedolyl acetate, and ot-butylcyclohexyl.
(C1-4): Lactone Examples include γ-octalactone, γ-nonalactone, σ-decalactone, and coumarin.
(C1-5): Phenol derivative For example, eugenol, isoeugenol, thymol, etc. are mentioned.
(C1-6): Alcohol having at least one double bond (—C═C—) in the molecule. Examples thereof include santalol, linalool, geraniol, citronellol, and dihydromyrcenol.
(C1-7): Ether having at least one double bond (-C = C-) in the molecule. Examples thereof include nerol oxide, rose oxide, linalool oxide, and the like.
(C1-8): Ketone having at least one double bond (-C = C-) in the molecule. Examples include ionone, methylionone, damascone, damascenone, dynascon, maltol and the like.
(C1-9): Nitrogen-containing or sulfur-containing organic compound Examples thereof include indole, skatole, citronellylnitrile, geranylnitrile and the like.

Moreover, the (C2) anionic surfactant used for the perfume particles (C) is represented by the following general formula (I).
R-OSO ₃ Na (I)
[Wherein R represents a linear or branched alkyl or alkenyl group derived from a primary or secondary alcohol having 6 to 20 carbon atoms. ]

  The anionic surfactant represented by the above general formula (I) is a mixture of a primary or secondary alcohol having 6 to 20 carbon atoms with a known method, then neutralized with an aqueous NaOH solution, and mixed with water. As obtained. In the present invention, the water content of the mixture of the anionic surfactant and water obtained by this method is desirably 10% by mass or less. In the present invention, it is desirable to use as a raw material powders, pellets, and needles obtained by drying a mixture of water and an anionic surfactant by spray drying, thin film drying under reduced pressure, or the like.

  The most preferable anionic surfactant in the present invention is obtained by sulfating a primary alcohol having an alkyl group or alkenyl group having 6 to 18 carbon atoms and having an iodine value of 5 or less, followed by neutralization. Examples of such anionic surfactants include decyl sulfate sodium salt, lauryl sulfate sodium salt, myristyl sulfate sodium salt, cetyl sulfate sodium salt, stearyl sulfate sodium salt or mixtures thereof.

  In addition, since the reaction rate during sulfation usually does not become 100%, unreacted alcohol is mixed, but the proportion of unreacted alcohol obtained by ordinary industrial production method (10% by mass with respect to anionic surfactant) May be mixed).

The (C3) water-insoluble solid particles having crystal water used for the perfume particles (C) of the present invention have an average particle size of 20 μm or less, preferably 0.1 to 10 μm. If the average particle size exceeds 20 μm, it may be recognized as undissolved when actually washed. As water-insoluble solid particles,
Na ₂ O ・ Al ₂ O ₃・ nSiO ₂・ wH ₂ O
(Where n is 1.3 to 3.0 and w is any positive number)
In general, a crystalline aluminosilicate represented by the formula 4A-type zeolite is desirable.

  Examples of the water-soluble polymer (C4) used in the perfume particles (C) of the present invention include polyacrylic acid, polyethylene glycol, acrylic acid-maleic acid copolymer, starch, cellulose, polyvinyl pyrrolidone and mixtures thereof. Each polymer has an average molecular weight of 3,000 to 100,000. The most preferred water-soluble polymers in the present invention are polyacrylic acid, polyethylene glycol, acrylic acid-maleic acid copolymer and polyvinylpyrrolidone.

  The blending amount of the (C1) fragrance component in the fragrance particles (C) of the present invention is 1 to 12% by mass in the fragrance particles (C), and a sufficient fragrance can be given to the fragrance particles in this range. The fluidity of the particles is also improved, and the handling properties are improved.

  The blending amount of the (C2) anionic surfactant in the perfume particles (C) of the present invention is 40 to 94% by mass, preferably 60 to 94% by mass in the perfume particles (C). Can be obtained.

  The blending amount of the water-insoluble solid particles having crystal water (C3) in the fragrance particles (C) of the present invention is 3 to 30% by mass in the fragrance particles (C), and the fragrance components can be effectively retained in this range. In addition, the flowability of the perfume particles is improved, and the handling properties are improved. Moreover, if it is the compounding quantity of this range, the solubility of the fragrance | flavor particle | grains at the time of washing | cleaning will also become favorable, and the intensity | strength of desirable fragrance will be obtained.

  The blending amount of the (C4) water-soluble polymer in the perfume particles (C) of the present invention is 1 to 10% by mass in the perfume particles (C). In this range, the strength of the perfume particles can be maintained, which is not desirable for the composition. Fine particles can be prevented, and the odor stability after storage is improved.

  The mass ratio of (C2) anionic surfactant and (C4) water-soluble polymer in the perfume particles (C) of the present invention is (C2) :( C4) = 5: 1 to 50: 1. The intensity | strength of a fragrance | flavor particle | grain (C) can be maintained and fluidity | liquidity can be made favorable.

  The blending amount of (C5) water in the fragrance particles (C) of the present invention is 0.1 to 10% by mass in the fragrance particles (C). If the amount of water is within this range, odor dispersal due to storage is reduced, and odor quality can be prevented from changing.

  The perfume particles (C) of the present invention may be added with known dyes, pigments, fluorescent dyes, and inorganic salts such as sodium sulfate, sodium sulfite, soda ash, sodium tripolyphosphate, sodium silicate, and the like. The blending of the metal carbonate and the alkali metal silicate is preferably 5% by mass or less in the perfume particles (C). In some cases, the blending of alkali metal carbonate and alkali metal silicate may cause odor deterioration.

In addition, the following known dyes and pigments are added to the perfume particles (C) of the present invention, particularly for the beauty when the perfume particles (C) of the present invention are dry-mixed into the bleaching detergent composition. Is desirable.
<Dye>
CIAcid Red 52 (CI 45110); red 106 as an example
CIAcid Blue 9 (CI 42090); Blue No. 1 as an example
CIAcid Yellow 3 (CI 47005); Yellow 203 as an example <Pigment>
CIPigment Green 7 (CI 74260); Lionol Green FB as an example
CIPigment Blue 15 (CI 74160); Cyanine Blue BR as an example

  The average particle size of the perfume particles (C) of the present invention is preferably 100 to 3000 μm, more preferably 300 to 1500 μm. When the particle diameter is smaller than this range, the fragrance is dissipated due to the large surface area with respect to the volume. When the particle diameter is larger than this range, the solubility of the particles is poor and the fragrance is not released quickly.

  Other preferred forms of the present invention include particles containing a perfume component and dextrin, particularly alkali-resistant dextrin.

  Specifically, the dextrin used in the present invention is a water-soluble starch, a modified starch or a derivative thereof, which is an esterified starch (such as phosphate starch), an etherified starch (such as carboxymethylated starch), or an enzyme-modified dextrin. (Maltodextrin etc.), roasted dextrin, etc. are mentioned. Preferred are enzyme-modified dextrin (maltodextrin etc.) and roasted dextrin. Furthermore, (i) water-soluble starch, modified starch or derivatives thereof, dextrose equivalent value (hereinafter referred to as DE value) defined by the following formula (III) is 0-8 non-reducing end starch And (ii) a water-soluble starch, a modified starch, or a derivative thereof, preferably containing a starch carrier in which a starch having a glucose terminal as a reducing terminal is mixed by hydrogenation at a predetermined ratio, Particularly, a starch carrier in which the ratio of the reduced-end starch and the starch having the glucose end as the reducing end by hydrogenation of (ii) is (ii) / (i) = 5/95 to 50/50 (mass ratio) preferable.

D. E. Value = [direct reducing sugar (expressed as glucose) / solid content] x 100 (III)
In particular, as dextrin, D.I. E. Those having a value in the range of 0 to 8 and subjected to hydrogenation treatment are preferred. E. What contains the starch support | carrier which gave the hydrogenation process in the range of the value 0-3, and mixed the starch which made the glucose terminal the reducing terminal is preferable.

Starch hydrolysis can be performed by standard methods such as acid catalyzed or enzyme catalyzed methods. Specific examples of the dextrin of the present invention include those produced by the production method described in JP-A-8-143603. In addition, dextrin having a specific volume of 5 to 10 cm ³ / g is preferred from the viewpoint of oil absorption ability to dextrin. Furthermore, the glass transition temperature of dextrin is preferably 200 ° C. or higher from the viewpoint of stability at high temperatures.

  Moreover, an oil-absorbing carrier, a water-soluble binder, and a disintegrant are mentioned as other components mix | blended with the fragrance | flavor particle | grains of this invention. As the oil absorbing carrier, white carbon, sodium sulfate or the like can be used.

  The content of the fragrance component in the fragrance particles of the present invention is 1 to 12% by mass, preferably 1 to 6% by mass, and more preferably 2 to 4% by mass in order to maintain the desired fragrance balance. .

  The fragrance | flavor particle | grains of this invention have moderate hardness by mix | blending dextrin, and solubility and productivity (granulation property) become favorable. On the other hand, the content of dextrin in the fragrance particles is preferably from 3 to 30% by mass, and more preferably from 5 to 15% by mass from the viewpoint that there is a concern that the particle strength may be lowered when the dextrin is added too much.

Among the fragrance particles of the present invention, those containing dextrin are particularly preferably those satisfying the following conditions (a) and (b).
(A): Content of fragrance component is 1 to 12% by mass
(B): dextrin content of 3 to 30% by mass
The content of other components in the fragrance particles of the present invention is not particularly limited, but the oil-absorbing carrier is preferably blended in an amount of 50% by mass or more, and the water-soluble binder is preferably blended in an amount of 20% by mass or more. The agent is preferably blended in an amount of 3 to 10% by mass.

  The production method of the fragrance particles of the present invention is not particularly limited, and examples thereof include an extrusion granulation method, a method of granulating an emulsion in which a fragrance, an emulsifier, water and the like are mixed in advance by spray drying, a rolling granulation method, and the like. It is done.

  The perfume particles of the present invention, preferably the perfume particles (C), are those that are dry-mixed into a powder or granular bleach detergent composition. In this case, the bleach detergent composition is (A) in water. A bleaching detergent composition having a conventionally known composition can be used as long as it contains particles containing a compound that releases hydrogen peroxide and a water-soluble inorganic salt other than (B) and (A). Moreover, it is preferable that the fragrance | flavor particle | grains of this invention, Preferably fragrance | flavor particle | grains (C) are mix | blended in the last bleach detergent composition in the quantity of about 0.1-50 mass%. The granular bleaching detergent composition preferably has a bulk density of 0.6 to 0.9 g / mL, and is prepared so that the final bulk density after blending the fragrance particles of the present invention is 0.6 to 1.2 g / mL. Is preferred.

[Other ingredients]
The bleaching detergent composition may further contain a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant that are generally used for bleaching agents.

As the nonionic surfactant, the following general formula (III) having an HLB of 4.5 to 10 determined by the method of Davis:
_{R- (OC 2 H 4) n} -OH (III)
[Wherein, R represents an alkyl group or alkenyl group having 6 to 18 carbon atoms or an aryl group optionally substituted with an alkyl group having 1 to 12 carbon atoms, and n represents an HLB determined by the method of Davis 4 The number selected to be 5-12. ]
Can be mentioned. Examples of such nonionic surfactants represented by the general formula (III) are:
C ₁₀ H ₂₁ (OC ₂ H ₄ ) _n -OH n = 6-18, HLB = 6.13-10.09
C ₁₂ H ₂₅ (OC ₂ H ₄ ) _n -OH n = 4-25, HLB = 4.52-11.45
C ₁₄ H ₂₉ (OC ₂ H ₄ ) _n -OH n = 10-25, HLB = 5.55-10.50
C ₁₆ H ₃₃ (OC ₂ H ₄ ) _n -OH n = 12-30, HLB = 5.26-11.20
C ₁₈ H ₃₇ (OC ₂ H ₄ ) _n -OH n = 15 to 35, HLB = 5.30 to 11.9
Etc.

  Anionic surfactants include alkyl benzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfate sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates. , Α-sulfo fatty acid salts, α-sulfo fatty acid esters, etc. Among them, alkylbenzene sulfonates having a C 10-18 alkyl group, polyoxyethylene alkyl ether sulfates or aliphatic alcohol sulfates Ester salts are preferred.

  Examples of the cationic surfactant include quaternary ammonium salts, and examples of the amphoteric surfactant include amine oxide, sulfobetaine, and carbobetaine.

  The amount of these surfactants is preferably 0.1 to 50% by mass, particularly preferably 0.5 to 30% by mass, and more preferably 0.5 to 30% by mass in the bleaching detergent composition in order to impart sufficient detergency. Preferably it is 0.5-20 mass%.

  A bleaching activator represented by the following general formula (I) or (II) can be further blended in the bleaching detergent composition.

[Wherein, M represents a hydrogen atom, an alkali metal atom or an alkaline earth metal atom, and R ¹ and R ² represent an alkyl group or alkenyl group having 7 to 18 carbon atoms or an alkyl group having 1 to 12 carbon atoms, respectively. The aryl group which may be substituted by is shown. ]

  Among the bleach activators represented by the above general formula (I) or (II), dodecanoyloxybenzenesulfonate such as dodecanoyloxybenzenesulfonic acid, sodium dodecanoyloxybenzenesulfonate, and decanoyloxybenzoate Acid, Decanoyloxybenzoate, Octanoyloxybenzoic acid, Octanoyloxybenzoate, Nonanoyloxybenzoic acid, Nonanoyloxybenzoate, 3,5,5-trimethylhexanoyloxybenzoic acid, 3,5,5- Trimethylhexanoyloxybenzoate is preferred.

  The blending amount of the bleach activator in the bleach detergent composition is preferably 0.01 to 20% by mass in order to prevent precipitation and increase in viscosity and to provide sufficient bleach detergency. Especially preferably, it is 0.1-10 mass%, More preferably, it is 0.5-10 mass%.

The bleaching detergent composition used in the present invention may further contain the following components as required.

(1) Alkaline agent As an alkali agent, amorphous alkali metal silicates such as JIS No. 1, No. 2, No. 3, etc. can be mentioned in addition to sodium carbonate collectively called dense ash and light ash. These inorganic alkaline agents are effective as a skeleton forming component of the particles when the detergent is dried, and can obtain a detergent that is relatively hard and excellent in fluidity.

(2) Acid agent An acid agent can be blended in order to prevent the pH of the washing liquid from becoming too high. As the acid agent, the compounds exemplified as the metal sequestering agent can be used, and polycarboxylic acids such as lactic acid, succinic acid, malic acid, and gluconic acid can be used.

(3) Bulking agent [neutral salt]
As a bulking agent [neutral salt], sodium sulfate generally called mirabilite can be blended. Sodium sulfate is effective in forming the skeleton of the detergent particles after drying, like the inorganic alkaline agent. Other preferable neutral salts include sodium chloride and potassium chloride.

(4) Other polymers Polyethylene glycol and polyvinyl alcohol having a weight average molecular weight of 200 to 200,000 as a binder and powder physical agent in the case of increasing the density, and further to impart an anti-recontamination effect on hydrophobic fine particles Etc. can be blended. Further, polyvinyl pyrrolidone can be blended in order to impart an effect of preventing color transfer.

(5) Enzymes Enzymes (enzymes that inherently perform enzyme action during the washing step) include hydrolases, oxidoreductases, lyases, transferases, and isomerases when classified according to enzyme reactivity. However, any can be applied to the present invention. Particularly preferred are proteases, esterases, lipases, nucleases, cellulases, amylases and pectinases. Specific examples of protease are pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, subtilisin, BPN, papain, promeline, carboxypeptidase A and B, aminopeptidase, aspergillopeptidase A and B, commercially available Examples of the product include sabinase, alcalase (Novo Industry), API 21 (Showa Denko KK), Maxacal (Gist Procaides), protease K-14 or K-16 described in JP-A-5-25492, and the like. be able to. Specific examples of the esterase include gastric lipase, buncreatic lipase, plant lipase, phospholipase, cholinesterase and phosphotase. Specific examples of the lipase include commercially available lipases such as lipolase (Novo Industries) and liposome (Showa Denko KK). Examples of the cellulase include a commercially available cellzyme (Novo Industry), the cellulase described in claim 4 of JP-A-63-264699, and the amylase includes a commercially available Termamyl (Novo Industry). Can be mentioned. The enzyme is granulated as separate stable particles and used in a dry blended state with detergent dough (particles).

(6) Enzyme stabilizer As an enzyme stabilizer, in order to remove chlorine in tap water, a reducing agent such as sodium sulfite and sodium bisulfite, calcium salt, magnesium salt, polyol, boron compound and the like can be blended. Sodium sulfite can also serve as an antioxidant.

(7) Blue tinting agent The blue tinting agent described in JP-B-49-8005, JP-B-49-26286 and JP-B-53-45808 can be blended.

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

(9) Antioxidants As antioxidants, tert-butylhydroxytoluene, 4,4'-butylidenebis- (6-tert-butyl-3-methylphenol), 2,2'-butylidenebis- (6-tert-butyl) -4-methylphenol), monostyrenated cresol, distyrenated cresol, monostyrenated phenol, distyrenated phenol, 1,1′-bis- (4-hydroxyphenyl) cyclohexane and the like can be blended.

(10) Fluorescent dyes As fluorescent dyes, 4,4′-bis- (2-sulfostyryl) -biphenyl salt, 4,4′-bis- (4-chloro-3-sulfostyryl) -biphenyl salt, 2- ( Styrylphenyl) naphthothiazole derivative, 4,4′-bis (triazol-2-yl) stilbene derivative, bis (triazinylamino) stilbenzylsulfonic acid derivative, Whiteex SA (manufactured by Sumitomo Chemical Co., Ltd.), Tinopearl CBS (Ciba Geigy) Etc.) can be blended. These fluorescent dyes can be blended in the composition in an amount of 0 to 2% by mass.

(11) Antifoaming agent Examples of the antifoaming agent include conventionally known ones such as silicone / silica, and this antifoaming agent is described in JP-A-3-186307, page 4, which will be described next. It is good also as an antifoamer granulated material manufactured using the method as described in a lower left column. First, 20 g of Dow Corning silicone (compound type, PS antifoam) as an antifoaming component is added to 100 g of maltodextrin (enzyme-modified dextrin) manufactured by Nissho Chemical Co., Ltd. and mixed to obtain a homogeneous mixture. Next, 50% of the obtained homogeneous mixture, 25% of polyethylene glycol (PEG-6000, melting point 58 ° C.) and 25% of neutral anhydrous sodium sulfate were mixed at 70 to 80 ° C., and then an extrusion granulator manufactured by Fuji Powder Co., Ltd. Granulate by (model EXKS-1) to obtain a granulated product.

<Plastic container>
The plastic container used in the present invention has one layer or two or more layers and has a vent hole.

  As a material for forming this plastic container, linear low density polyethylene, low density polyethylene, unstretched polypropylene, stretched nylon, stretched polypropylene and polyethylene terephthalate are used in order to maintain the residual ratio of effective oxygen.

  When the plastic container is composed of two or more layers, all of them can be formed of the same plastic, or can be formed of different plastics for each layer. One layer can be formed of two or more kinds of plastics. When the structure has two or more layers, for example, linear low density polyethylene is used on the inside of the container, and plastic having mechanical strength, such as stretched nylon or stretched polypropylene, is used for the outermost layer. be able to.

  Although it is possible to include paper in the constituent material of the container, it is preferable that the mass ratio of the plastic is 60% or more, further 80% or more, particularly 95% or more of the total container mass.

  The thickness of the plastic container is 5 to 300 μm, preferably 10 to 250 μm, more preferably 30 to 200 μm, and particularly preferably 50 to 150 μm in order to maintain the residual ratio of effective oxygen. The thickness of the plastic container is appropriately set within the above range depending on the type of plastic used.

  The shape and size of the vent hole provided in the plastic container is not particularly limited as long as the contents are not spilled even if it is turned upside down. Examples of the vent include a circular shape or a slit shape, and in the case of a circular shape, the diameter is preferably 0.1 to 5 mm, particularly preferably 0.1 to 0.2 mm. In the case of a slit shape, a linear ventilation hole having a width of 0.01 to 0.3 mm, further 0.1 to 0.5 mm, a length of 0.1 to 5 mm, and further 1 to 3 mm is preferable. Moreover, the container which put the slit in the thread part of the bottle is also suitable.

  The plastic container may be provided with a barrier layer, a pinhole-resistant layer, a tear induction layer, and the like. In addition, in order to reduce the light transmittance, when a plastic container is formed from a multilayer film, an aluminum foil layer and a colored layer can be sandwiched between the layers, and metal (aluminum, etc.) is deposited on the front surface and / or back surface. It is also possible to apply.

  The plastic film which comprises a plastic container can be easily manufactured by a well-known method. For example, as a method for producing a laminated film, a dry laminating method, a T-die method, a coextrusion laminating method, an inflation method, a tandem laminating method, and the like can be given. Although the form of the plastic packaging container is not limited, it is preferable to use a container that is heat-sealed around a plastic film having a desired size to form a bag (small bag) having a desired capacity.

Further, when the surface area in the plastic container is A (cm ² ) and the mass of the bleaching detergent composition in the container is B (g), A / B is in terms of resistance to caking and the residual ratio of effective oxygen. It is preferably 0.8 to 7.0, more preferably 0.85 to 3.5, and particularly preferably 0.95 to 3.0.

  Below, the manufacture example of the plastic container, the fragrance | flavor particle | grains, and high-density detergent which were used in Example 1 is shown.

<Production Example 1> (Production of plastic container 1)
Prepare two sets of rectangular shape by superposing stretched nylon with a thickness of 20 μm and linear low density polyethylene with a thickness of 130 μm, and superimpose each so that the linear low density polyethylene with a thickness of 130 μm is inside, The three sides were heat sealed. Thereafter, a linear ventilation hole having a length of 2 mm was formed in a corner near the opening, thereby obtaining a small-bag plastic container 1 having a volume of 1000 mL.

<Production Example 2> (Production of plastic container 2)
Production Example 1 using two sets of stretched polypropylene having a thickness of 20 μm and a linear low density polypropylene having a thickness of 100 μm which are overlapped with each other so that the linear low density polypropylene having a thickness of 100 μm is inside. In the same manner as described above, a small plastic container 2 having a volume of 1000 mL was obtained.

<Production Example 3> (Production of plastic container 3)
Two sets of 50 μm-thick stretched nylon and 270 μm-thick stretched polypropylene were stacked in a rectangular shape so that the 250 μm-thick stretched polypropylene was inside, and the volume was 1000 mL in the same manner as in Production Example 1. The sachet-shaped plastic container 3 was obtained.

<Production Example 4> (Production of plastic container 4)
Production Example 1 using two sets of stretched nylon having a thickness of 30 μm and a linear low density polyethylene having a thickness of 300 μm overlapped with each other so that the linear low density polyethylene having a thickness of 300 μm is inside. In the same manner as above, a small plastic container 4 having a volume of 1000 mL was obtained.

<Production Example 5> (Production of plastic container 5)
Using a multilayer sheet including an aluminum foil layer, it has a pair of front and rear front parts and a pair of left and right side folds that can be folded inside the front parts, and accommodates while opening the upper end outlet in a self-supporting state. A plastic container 5 in the form of a gusset bag in which an object can be taken out was obtained. This plastic container 5 has a linear air vent having a length of 2 mm in the corner near the opening and has a volume of 1000 mL. The plastic container 5 has an A / B of 1.0 when the surface area in the container is A (cm ² ) and the mass of the bleaching detergent composition filled in the container is B (g). Used for.

<Production Example A1> (Production of perfume particles 1)
Tokuju R type ribbon mixer R-1300 type (total volume 2000 liters, charge capacity 1300 liters, hereinafter referred to as mixer), 375 kg of lauryl sulfate sodium salt (Emal 10P manufactured by Kao Corporation) and 75 kg of 4A type zeolite were introduced. After rotating the mixer for 30 minutes at a rotation speed of 20 rpm, 25 kg of the fragrance component (i) was dropped into the mixer and rotated for 15 minutes, and 10 kg of polyethylene glycol (average molecular weight 6000) and 15 kg of water were mixed, and 60 ° C. What was melted in was dripped into the mixer and rotated for another 15 minutes. The powder thus obtained was passed through an extruder (former extruder, screen diameter: φ1.0 μm), extruded and granulated, and a granulator (FL-200 type, manufactured by Fuji Powder Co., Ltd., screen diameter: side φ3.0 mm) , Bottom 4.0 mm), and sieved 500 μm to obtain a sample (fragrance particle 1) on the sieve.

  The fragrance component (i) is 18.0% by mass of limonene, 0.5% by mass of citronellylnitrile, 0.2% by mass of nonylaldehyde, 0.1% by mass of methylnonylacetaldehyde, 0.1% by mass of Dynascon, 0.1% by mass of ligustral, 2.0% by mass of hexyl acetate, o-t-butylcyclohexyl 2.0% by mass, phenylethyl alcohol 4.0% by mass, hexylcinnamic aldehyde 10.0% by mass, laryl 10.0% by mass, lilyal 10.0% by mass, benzyl acetate 10.0% by mass, benzyl salicylate 15.0% by mass, indole 5.0% by mass %, Coumarin 1.0% by mass, ethyl vanillin 5.0% by mass, methylionone 2.0% by mass, heliotropin 5.0% by mass, and a total of 100.0% by mass.

<Production Example A2> (Production of perfume particles 2)
Fragrance (components whose vapor pressure at 25 ° C. exceeds 133 Pa is 0%, (components of 0.13 to 133 Pa) / (components of less than 0.13 Pa) = 80/20): 1300 g, dextrin ( Matsutani Chemical Co., Ltd .: Pineflow KH, DE value: 1.61, hydrogenated product): 1300 g, Shirazo (Shikoku Kasei Kogyo Co., Ltd .: ground A6 Soda): 4940 g, white carbon (Tokuyama) Soda Co., Ltd .: Tokushir NR: 1950 g, Magnesium sulfate (Ako Kasei Co., Ltd .: Mg-OK): 650 g, Bengala (manufactured by Miyoshi Kasei Co., Ltd.): 1.5 g of Nauta mixer (Hosokawa Micron Co., Ltd.) )), The jacket temperature was set to 75 ° C., and the temperature was increased by mixing. Next, when the temperature of the powder reaches 60 ° C., polyethylene glycol (Kao Co., Ltd .: KPEG-6000LA) melted in advance: 2002 g and solid state polyethylene glycol (Kao Co., Ltd .: KPEG-) 6000 LA): 858 g was added, and after further mixing, the mixture was extracted. The temperature of the mixture at this time was 66 ° C. Next, the obtained mixture was extruded through a screen having a pore diameter of 0.7 mm by using an extrusion granulator (Fuji Paudal Co., Ltd .: Pelleter Double EDX-60 type), and consolidated. Further, the extruded granulated product was subjected to vibration cooling, and then pulverized by a granulator (pulverized once with a power mill and further pulverized once with a comil) to obtain perfume particles 2.

<Production Example A3> (Production of perfume particles 3)
Fragrance (same as Production Example A2): 1000 g, dextrin (Matsutani Chemical Co., Ltd .: Pine Flow KH, DE value: 1.67, hydrogenated product): 910 g, white carbon (Tokuyama Soda Co., Ltd.) ): Toxeal NR): 3250 g, Red No. 405: 0.5 g was charged into a mixer (Henschel mixer, Mitsui Mining Co., Ltd.), and the jacket temperature was mixed at 75 ° C. and heated. Next, polyethylene glycol (manufactured by Kao Corporation: KPEG-6000LA): 2548 g and solid state polyethylene glycol (manufactured by Kao Corporation: KPEG-6000LA): 1092 g were added and mixed, and then the mixture was mixed. Extracted. The temperature of the mixture at this time was 67 ° C. The obtained mixture was compacted through a screen having a pore diameter of 0.7 mm by an extrusion granulator (Fuji Paudal Co., Ltd .: Twin Dome Gran), and the resulting extrudate was cooled and then granulated (Paurec Co., Ltd.). The product was sized with a power mill) to obtain perfume particles 3.

<Production Example B1> (Production of high-density detergent)
4A zeolite 1.0kg, LAS 4.0kg, AE 0.3kg, AA-MA copolymer (acrylic acid-maleic acid copolymer) 0.5kg, carboxymethylcellulose 0.15kg, FA 0.1kg, JIS 2 sodium silicate 1.0kg, soda ash 0.5kg And a 60% solid water slurry from 0.05 kg of the fluorescent dye, and the particles obtained by spray-drying the slurry are put into a Redige mixer (manufactured by Matsusaka Giken Co., Ltd.), 1.0 kg of 4A zeolite, soda ash 0.5 kg, 0.1 kg of enzyme, and mirabilite used for balance were added, and 0.2 kg of AE heated to 70 ° C. was gradually added to the mixture and granulated. Further, 0.25 kg of 4A-type zeolite was added and granulated. Except those that did not pass through a 1410 μm sieve, a high-density detergent was obtained by spraying a perfume for spraying detergent dough (average particle size 450 μm, bulk density 0.75 g). / ML). The composition of this high density detergent is shown in Table 1.

  In Table 1, LAS is linear alkyl (12 carbon atoms) benzenesulfonic acid sodium salt, FA is tallow fatty acid sodium salt, AE is polyoxyethylene primary dodecyl ether (HLB = 13.1), and AA-MA copolymer is Socaran CP 5 (BASF), fluorescent dye is 4,4'-bis- (2-sulfostyryl) biphenyl salt, enzyme is API-21H (Showa Denko), lipolase 100T (Novo Nordisk), Cellzyme 0.1T (manufactured by Novo Nordisk), Termamyl 60T (manufactured by Novo Nordisk) at a ratio of 2: 1: 1: 1, carboxymethyl cellulose is Sunrose B2B (substitution degree: 0.45-0.55) manufactured by Nippon Paper Industries Co., Ltd. ), The detergent fabric spraying fragrance was S-LTA-6T (manufactured by Kao Corporation), and the salt was used so that the total amount was 100% by mass.

<Example 1>
Using the container obtained above, the fragrance particles, the high-density detergent, and the components shown in Table 2, a container-containing bleaching detergent composition was prepared and evaluated as follows. The results are shown in Table 2.

(1) Evaluation of change in fragrance For a sample after storing the bleaching detergent composition in a container for 60 days under the conditions of 30 ° C. and 40 to 80% relative humidity (96 hours as one cycle), before storage Using the sample as a control, the scent was compared and evaluated according to the following criteria.
<Evaluation criteria for fragrance>
(Scent intensity)
(0): Equivalent scent compared to control product (-1): Slight fragrance compared to control product (incense tone)
A: The fragrance is equivalent to the control product B: The fragrance is deteriorated compared to the control product

(2) Evaluation of caking resistance The content of the sample after storing the bleaching detergent composition in a container for 90 days under the conditions of 30 ° C. and 40 to 80% relative humidity (96 hours as one cycle) [ Mass W ₁ (g)] is transferred onto a 5 mm sieve mesh and the mass [W ₂ (g)] of the contents remaining on the sieve is measured, and [1- (W ₂ ÷ W ₁ )] × The sieve passage rate (%) was determined by 100. The higher the sieve passage rate, the better the caking resistance.

(3) Evaluation of residual ratio of available oxygen Bleaching detergent composition after storing bleached detergent composition in a container for 30 days under the conditions of 30 ° C. and 40 to 80% relative humidity (96 hours as one cycle) , And the bleaching detergent composition before storage, the effective oxygen concentration is measured by the following methods, respectively, and the effective oxygen concentration (X ₁ ) before storage and the effective oxygen concentration (X ₂ ) after storage are determined from (X ₂ ÷ X ₁ ) × 100, the effective oxygen residual rate (%) was determined. The higher the effective oxygen residual rate, the better the storage stability.
<Method for measuring effective oxygen concentration>
Add 20 mL of 20% aqueous sulfuric acid to 1 L of ion exchange water. The bleach detergent composition 10g is thrown there and it stirs at 600 rpm for 15 minutes. After the stirring is completed, 60 mL of the stirring mixed solution is collected and mixed with 10 mL of 20% aqueous sulfuric acid solution to prepare a test solution. This test solution was titrated with a 1 / 10N potassium permanganate aqueous solution, the titration amount of the liquid color was red, and the effective oxygen amount was calculated by the following formula.

In Table 2, sodium perborate is manufactured by Degussa AG, sodium percarbonate is SPC-HGD manufactured by Mitsubishi Gas Chemical Co., Ltd., sodium carbonate is manufactured by Shikoku Kasei Kogyo Co., Ltd., and bleach activator is lauroyloxybenzenesulfonic acid. The sodium and paper container is a box-shaped container having a volume of 2160 cm ³ made of coated cardboard having a basis weight of 630 g / m ² coated with an oil-resistant varnish for a general detergent.

  As is apparent from Table 2, despite the storage test under severe conditions, the bleaching detergent composition in the container of the present invention has no or almost no caking, and under normal storage conditions during distribution. It was confirmed that it was sufficiently practical. Moreover, it was confirmed that the stability of the scent after storage is excellent.

Claims (8)

1 to 12 masses of (A) particles containing a compound that releases hydrogen peroxide in water, (B) water-soluble inorganic salt other than (A), and (C) perfume ingredient in a plastic container having a vent. % , Dextrin 5 to 15% by mass , an oil absorbing carrier selected from white carbon and sodium sulfate 50% by mass or more, and a bleaching detergent composition containing perfume particles containing a water-soluble binder 20% by mass or more . Bleach cleaning composition in a container. 1 to 12% by mass of (A) particles containing a compound that releases hydrogen peroxide in water, (B) water-soluble inorganic salt other than (A), and (C) perfume ingredient in a plastic container having a vent. A bleaching detergent composition in a container filled with a bleaching detergent composition containing perfume particles,
(C) A bleaching detergent composition in a container, wherein the perfume particles contain the following components (C1), (C2), (C3), (C4) and (C5).
(C1) Fragrance ingredient 1-12% by mass
(C2) Anionic surfactant represented by the following formula (I): 40 to 94% by mass
R-OSO ₃ Na (I)
[Wherein R represents a linear or branched alkyl or alkenyl group derived from a primary or secondary alcohol having 6 to 20 carbon atoms. ]
(C3) 4A-type zeolite having crystal water and an average particle size of 20 μm or less 3 to 30% by mass
(C4) Water-soluble polymer 1 to 10% by mass [However, the mass ratio of the component (C2) to the component (C4) is (C2) :( C4) = 5: 1 to 50: 1. ]
(C5) Water 0.1 to 10% by mass The bleaching detergent composition in a container according to claim 2 , wherein the perfume component of the component (C1) contains one or more compounds selected from the following compounds (C1-1) to (C1-9).
(C1-1): Hydrocarbon (C1-2) containing at least one double bond (-C = C-) in the molecule: Aldehyde (C1-3): Ester (C1-4): Lactone (C1- 5): Phenol derivative (C1-6): Alcohol (C1-7) having at least one double bond (-C = C-) in the molecule: Double bond (-C = C-) in the molecule Having at least one ether (C1-8): ketone having at least one double bond (—C═C—) in the molecule (C1-9): nitrogen-containing or sulfur-containing organic compound (C) In the perfume particles, the alkyl group or alkenyl group derived from a primary alcohol containing 60% by mass or more of the component (C2) and R in the general formula (I) having 6 to 18 carbon atoms and an iodine value of 5 or less. The bleaching detergent composition in a container according to claim 2 or 3 . Component (C4) is a water-soluble polymer having a weight average molecular weight of 3,000 to 100,000 selected from polyacrylic acid, polyethylene glycol, acrylic acid-maleic acid copolymer, starch, cellulose and polyvinylpyrrolidone. Item 5. The bleach detergent composition in a container according to any one of Items 2 to 4 . The container is composed of a film having a thickness of 5 to 300 µm made of one or more materials selected from linear low density polyethylene, low density polyethylene, unstretched polypropylene, stretched nylon, stretched polypropylene and polyethylene terephthalate. The bleaching detergent composition in a container according to any one of 5 . The bleach detergent composition in a container according to any one of claims 1 to 6 , wherein the bleach detergent composition contains a bleach activator represented by the following general formula (I) or (II).

[Wherein, M represents a hydrogen atom, an alkali metal atom or an alkaline earth metal atom, and R ¹ and R ² represent an alkyl group or alkenyl group having 7 to 18 carbon atoms or an alkyl group having 1 to 12 carbon atoms, respectively. The aryl group which may be substituted by is shown. ] The bleaching detergent composition in a container according to any one of claims 1 to 7 , wherein the air vent of the container has a circular shape having a diameter of 0.1 to 5 mm or a slit shape having a length of 0.1 to 5 mm.