JP4437720B2 - Detergent goods - Google Patents

Description

  The present invention relates to a detergent article that does not cause a change in aroma during storage.

The technique using a fragrance | flavor for the objective of providing the deodorizing effect to the detergent for automatic dishwashers is already known, and patent documents 1-3 can be mentioned. Moreover, it is also known to use a laminated body in which an inorganic compound such as silica is deposited as a detergent packaging container, and examples thereof include Patent Documents 4 to 8. Among these, Patent Documents 4 to 6 describe that a container made of a laminate on which an inorganic oxide is deposited is excellent in oxygen gas and water vapor barrier properties, and also describes that it can be applied to detergents. In addition, it is also known to apply particulate fragrances to cleaning agents, and examples thereof include Patent Documents 9 to 10. Furthermore, nonpatent literature 1 can be mentioned as general knowledge of a fragrance composition.
JP 2003-213295 A Japanese Patent Laid-Open No. 10-245599 Japanese National Patent Publication No. 11-507096 JP 2001-225424 A JP 2001-301864 A JP-A-10-193502 Japanese Patent Laid-Open No. 62-179935 JP 60-49934 A JP 2000-233962 A Japanese Patent Laid-Open No. 2002-121583 Fragrance Chemistry The Chemical Society of Japan Industrial Chemistry Series Dai Nippon Books Ryoichi Akahoshi Published September 16, 1983

  In the process of washing dishes using an automatic dishwasher, since the temperature of the washing water is heated to 50 ° C. or higher for washing, an unpleasant odor derived from food is emitted during washing, and this improvement is required. As a means for solving this problem, Patent Document 1 discloses a technique for combining an oxygen bleach and a fragrance, but the effect of suppressing odor is not yet satisfactory. In addition, as a method of suppressing odor during washing, rinsing and drying, masking with a fragrance is conceivable. In this case, if a large amount of fragrance is not blended, the deodorizing effect is sustained during washing, rinsing and drying. Can't get. In addition, when a large amount of fragrance is used, the fragrance remains on the tableware after these steps are completed, and it often causes an unpleasant feeling. Therefore, there is a strong demand for a technique that continuously suppresses the odor of food derived from washing, rinsing, and drying in an automatic dishwasher and that does not leave a fragrance smell on the tableware after these steps are completed.

  On the other hand, due to environmental problems, a product in which a flexible thin-walled container for refilling is filled with a detergent is also used. At that time, it is preferable to use a transparent or translucent flexible thin container that can be seen from the aesthetic point of view for the powder or granular detergent such as a dishwasher detergent. However, depending on the composition of the fragrance composition, if such a transparent or translucent flexible thin container is used, the odor may deteriorate during storage and the value as a product may be significantly impaired. It is done.

  Therefore, the object of the present invention is to suppress the odor derived from food during washing, rinsing and drying by an automatic dishwasher, and after these steps are completed, there is no smell of fragrance on the tableware, and aesthetically. An object of the present invention is to provide a container-containing detergent article that exhibits a good transparent or translucent appearance and that suppresses deterioration of odor during storage.

  The present invention relates to a powder or granular detergent composition containing 0.05 to 1.0 mass% of a fragrance composition in which the ratio of a fragrance material having a vapor pressure at 20 ° C of 0.8 Pa or more is 60 mass% or more. Article for a transparent or translucent flexible thin container composed of a resin layer laminate having a thickness of 50 to 300 μm and containing one or more resin layers on which a deposited thin film of inorganic metal oxide is formed .

  According to the present invention, the smell derived from food during washing, rinsing and drying by an automatic dishwasher is suppressed, and after these steps are finished, the smell of the fragrance does not remain on the tableware and is aesthetically good. A container-containing detergent article having a transparent or translucent appearance and having suppressed odor deterioration during storage can be obtained.

<Detergent composition>
(1) Fragrance composition The detergent composition according to the present invention contains a fragrance composition composed of one or more fragrance materials. The fragrance material used here is a natural fragrance material or a synthetic fragrance material, and may be used after being distributed and scented according to the degree of volatilization. Moreover, in the fragrance | flavor composition which concerns on this invention, content of the fragrance | flavor raw material whose vapor pressure in 20 degreeC is 0.8 Pa or more is 60 mass% or more in order to reduce the residual fragrance property to the washing | cleaning target object after washing | cleaning. Yes, 70 mass% or more is preferable, 80 mass% or more is more preferable, and 90 mass% or more is particularly preferable. In order to reduce the residual fragrance, the content of the fragrance material having a vapor pressure at 20 ° C. of less than 0.13 Pa is preferably adjusted so as to be less than 10% by mass in the fragrance composition. It is particularly preferable to adjust to.

  In addition, the detergent composition according to the present invention is preferably 0.05 to 1.0% by mass, more preferably 0.1 to 0.7% by mass, and particularly preferably 0.1 to 0. 5% by mass is contained. Within such a range, the durability of the deodorizing effect during washing, rinsing and drying in an automatic dishwasher is satisfied, and it is possible to suppress the fragrance from remaining on the tableware after these steps are completed.

  Examples of the fragrance material having a vapor pressure of 0.8 Pa or higher at 20 ° C. used in the fragrance composition according to the present invention include 1,4-cineole, 1,8-cineole, anethole, benzyl acetate, borneol, camphor , Carvacrol, citral, citronellal, dipentene, d-limonene, geraniol, geranyl acetate, isocyclocitral, isomenton, lavandulyl acetate, l-carvone, linalool, linalyl acetate, l-menthol, l-menton, methyl cinnamate, methyl heptenone , Nerol, ferrandolene, piperidone, isopulegol, eugenol, terpineol, and terpinolene. Among them, it is preferable to contain linalool, isomenton, 1-menthol, 1-mentholone, - menthol, it is particularly preferred to contain l- menthone. Moreover, it is preferable that the ratio in the fragrance composition according to the present invention is less than 10% by mass. Examples of the fragrance material having a vapor pressure at 20 ° C. of less than 0.13 Pa include vanillin, cedrol, plegon and the like. Among them, the ratio of plegon is preferably less than 5% by mass, and more preferably less than 3% by mass. The fragrance composition according to the present invention contains a fragrance material having a vapor pressure at 20 ° C. of 0.8 Pa or more, and further a fragrance material having a vapor pressure at 20 ° C. of less than 0.13 Pa. If the ratio is less than 10% by mass, naturally derived oils, essential oils and the like can be used as they are. Examples of naturally derived fragrance compositions include thyme oil, basil oil, peppermint oil, mint oil, rosemary oil, eucalyptus oil, marjoram oil, lavender oil, lemon oil, lemongrass oil, and orange oil. Among them, thyme oil, basil oil, peppermint oil, mint oil, marjoram oil, lavender oil, lemongrass oil, sage oil and clove oil are preferable, and mint oil is particularly preferable. Naturally derived fragrance compositions or fragrance materials are obtained by pressing, steam distillation, or solvent extraction using the whole plant or flowers, leaves, fruits, pericarp, seeds, roots, bark or stems of each plant as raw materials. It is done.

  The fragrance composition used in the present invention is preferably blended in whole or in part as fragrance particles. In particular, it is preferable that at least a part of the fragrance material having a vapor pressure of 0.8 Pa or more at 20 ° C. in the fragrance composition is contained as fragrance particles obtained by impregnating the fragrance material with an oil-absorbing carrier.

  Moreover, when mix | blending all or one part of a fragrance | flavor composition as a fragrance | flavor particle | grain, depending on the manufacturing conditions of a fragrance | flavor particle | grain, it volatilizes by heating and the residual rate in a fragrance | flavor particle decreases. Therefore, the content of the fragrance material having a vapor pressure at 20 ° C. of 150 Pa or more is preferably 40% by mass or less, and particularly preferably 30% by mass or less in the fragrance composition. Examples of the fragrance material having a vapor pressure of 150 Pa or higher at 20 ° C. include 1,8-cineole and d-limonene.

  Examples of the oil-absorbing carrier used for the perfume particles include one or more selected from white carbon, dextrin, sodium sulfate and the like.

  As white carbon, JP-A-62-191417, page 2, lower right column, line 19 to page 5, upper-left column, line 17 (particularly, the initial temperature is preferably in the range of 15 to 60 ° C.), JP-A-62. No. 191419, page 2, lower right column, line 20 to page 5, upper left column, line 11, amorphous aluminosilicate, JP-A-9-132794, JP-A-7-10526, Examples thereof include amorphous aluminosilicates (oil absorption capacity: 285 mL / 100 g) described in JP-A-6-227811 and JP-A-8-119622. Specifically, Toxeal NR (Tokuyama Soda Co., Ltd., oil absorption capacity: 210-270 mL / 100 g), Florite (Tokuyama Soda Co., Ltd., oil absorption capacity: 400-600 mL / 100 g), TIXOLEX 25 (Korean / French) Oil absorbing carriers such as those manufactured by Kagaku Co., Ltd., oil absorption capacity: 220 to 270 mL / 100 g), and Silo Pure (manufactured by Fuji Divison Co., Ltd., oil absorption capacity: 240 to 280 mL / 100 g) can be used.

  Dextrin is obtained by partial hydrolysis of starch. Starch molecules gradually become small molecules by hydrolysis, and eventually become glucose. Depending on the degree of hydrolysis, a mixture of various sugars is produced. For example, 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 (malto). Dextrin and the like), roasted dextrin and the like. Preferred are enzyme-modified dextrin (maltodextrin etc.) and roasted dextrin. Furthermore, the dextrose equivalent value defined by the following formula (hereinafter referred to as DE value) is 0 to 8 non-reducing end starch, water-soluble starch, modified starch or derivatives thereof, It is preferable to use starch produced by mixing starch having a terminal end at the reducing end in a predetermined ratio. Non-reducing end starch is a starch whose both ends are non-reducing ends (having no reducing ends).

D. E. Value = [direct reducing sugar (expressed as glucose) / solid content] × 100
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 the hydrogenation process was given in the range of 0-3, and mixed the starch which made the glucose terminal the reducing terminal is preferable.

Starch hydrolysis can be carried out by standard methods such as acid catalyzed or enzyme catalyzed methods. Specific examples of dextrin include those produced by the production method described in JP-A-8-143603. Among these dextrins, those having a specific volume of 5 to 10 m ² / g are preferred because of their ability to absorb oil into the dextrin. The glass transition temperature of dextrin is preferably 200 ° C. or higher from the viewpoint of stability at high temperatures.

  A commercially available product can be used as mirabilite. For example, Shikoku Kasei Co., Ltd. A6 mirabilite etc. can be used. Among these commercially available products, from the viewpoint of solubility, specifically, those having a particle size of 20 μm or less in 90% by mass or more are preferable.

  The content of the oil absorbing carrier in the fragrance particles is preferably 50% by mass or more, and more preferably 60 to 75% by mass. In addition, it is preferable to contain dextrin as an oil-absorbing carrier in the fragrance particles, and the blending amount of dextrin in the fragrance particles does not cause the fragrance particles to be hard, and does not decrease solubility or productivity (granulation property). Further, from the viewpoint of not reducing the particle strength, 3 to 30% by mass, particularly 5 to 15% by mass is preferable.

  In the perfume particles used in the present invention, a thermoplastic water-soluble binder or the like can be used as a water-soluble binder, and particularly a group consisting of polyethylene glycol, polypropylene glycol, polyoxyethylene alkyl ether, polyoxyethylene phenyl ether, and the like. One or more selected from the above are preferred. The water-soluble binder preferably has a melting point or softening point of 35 to 80 ° C, more preferably 45 to 70 ° C, particularly preferably 50 to 65 ° C. In addition, melting | fusing point is measured by the method described in the melting | fusing point measuring method etc. of Japanese Industrial Standard JIS-K0064 (1192).

  When the water-soluble binder is a polymer compound, the weight average molecular weight is 4000 to 20000, more preferably 6000 to 13000, and particularly 7000 to 9000 in terms of viscosity when granulated by the GPC method using polyethylene glycol as a standard. Is preferable. In the present invention, from the viewpoint of handling at the time of production and uniformity of the particles, it is more preferable to use a molten binder obtained by melting the binder as described above and a solid binder in combination. The mass ratio is preferably 100/0 to 20/80, more preferably 80/20 to 30/70, and particularly preferably 70/30 to 40/60.

  The blending amount of the water-soluble binder in the fragrance particles is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, and particularly preferably 15 to 30% by mass from the viewpoint of maintaining the strength of the particles.

  In the fragrance particles used in the present invention, the mass ratio between the oil-absorbing carrier and the water-soluble binder is (oil-absorbing carrier) / (water-soluble binder) = 7/1 to 2/1 from the viewpoint of particle strength and production suitability. Particularly preferred is 5/1 to 2/1.

  The perfume particles used in the present invention can contain a disintegrant such as magnesium sulfate in order to further improve the solubility. Examples of magnesium sulfate include magnesium sulfate such as manufactured by Maui Kasei, Ako Kasei, Wako Pure Chemicals, and Tomita Pharmaceutical. Among these, from the viewpoint of solubility, particles having a particle size of 200 μm or less are preferably 90% by mass or more, particles having a particle size of 100 μm or less are more preferably 90% by mass or more, and particles having a particle size of 50 μm or less are 90% by mass. % Or more is particularly preferred.

  The perfume particles used in the present invention are desirably colored with a known colorant such as a pigment for the sake of aesthetics when dry-mixed in a detergent composition.

  Specific colorants are not particularly limited, but those having high solubility or dispersibility and strong resistance to alkali are preferable, and examples thereof include inorganic pigments, organic pigments, dyes, and the like. It is preferable to contain. The inorganic pigment is not particularly limited, but is preferably one that has high solubility or dispersibility, does not fade under the influence of light or temperature, and has low dyeability to the object to be cleaned. Specifically, inorganic pigments such as bengara and ultramarine and lionol green are preferred. Further, for coloring, other colorants may be mixed. For example, as specific colorants used in combination with Bengala, ultramarine blue, or lionol green, Red No. 40, Red No. 104, Red 106 No., Red No. 201, Red No. 226, Red No. 203, Red No. 404, Red No. 405, Blue No. 1, Blue No. 2, Yellow No. 203, Yellow No. 4, Yellow No. 5, Green No. 3 and their aluminum lakes Red 106, Red 226, Red 104, Blue 1 and the like are particularly preferable from the viewpoint of safety and resistance to alkali.

  Although there is no restriction | limiting in particular in content of the coloring agent in a fragrance | flavor particle | grain, 0.001-1.0 mass% is preferable, and 0.003-0.5 mass% is more from a viewpoint which suppresses the goodness | look of an aesthetics, and discoloration. preferable.

  The perfume particles used in the present invention are preferably produced by mixing and granulating each of the above components substantially without a drying step.

  In the present invention, “substantially without a drying step” means production in a state substantially free of water except for water present as “impurities” in the raw material used, This is because emission of volatile substances that normally occurs in the drying process can be suppressed.

  When using a water-soluble binder, the order of addition is not particularly limited. For example, a melted water-soluble binder and a solid water-soluble binder previously melted are added to a mixture of a heated fragrance and an oil absorbing carrier. Then, a method of granulating is preferable.

  The method for adding the water-soluble binder in the molten state is not particularly limited, but a spray method or the like is desirable for uniform addition. However, since it is difficult to spray uniformly when the temperature of the water-soluble binder is low, the temperature of the water-soluble binder in the molten state is preferably 80 to 90 ° C. Among the required aqueous solution binders, if the entire amount is made into a molten water-soluble binder, the temperature rises excessively due to heat generation such as heat storage and shearing, and the fragrance may be easily volatilized or the fragrance may be altered, The combined use of the water-soluble binder in the state can suppress the temperature rise. Moreover, 60-80 degreeC is preferable from a viewpoint of suppressing the amount of perfume volatilization, and especially the temperature of the mixture after water-soluble binder addition has preferable 60-70 degreeC.

  The perfume particles used in the present invention are sufficiently prepared in advance using a known mixer such as Henschel mixer (Mitsui Mining Co., Ltd.), high speed mixer (Fukae Industrial Co., Ltd., Nauter mixer (Hosokawa Micron Co., Ltd.)). And then the resulting mixture can be obtained by compression molding with a known extruder such as Pelleter Double (Fuji Powdal Co., Ltd.), Twin Dome Gran (Fuji Powdal Co., Ltd.) or the like. Further, a kneading and extruding apparatus such as Extrude Omix (manufactured by Hosokawa Micron Corporation) can be used, and in this case, the above-mentioned premixing can be omitted.

  The short axis particle diameter of the obtained fragrance particles is preferably 0.3 to 2.5 mm, more preferably 0.5 to 2.0 mm, and still more preferably about 0.7 to 1.0 mm. It can be extruded in the form of a noodle-like granulated product.

  The perfume particles obtained as described above may be pulverized or sized by a known method and apparatus.

  The equipment used when pulverizing or sizing is not particularly limited, and a known pulverizer (or pulverizer) can be used. For example, high-speed mixer (Fukae Kogyo Co., Ltd.), Malmerizer (Fuji Powdal Co., Ltd.), Spiler Flow (Freund Sangyo Co., Ltd.), Fitzmill (Dalton Co., Ltd.), Power Mill (Powrec Co., Ltd.) From the viewpoint of the amount of fine powder generated and productivity, it is preferable to use a pulverizer such as a power mill using a knife cutter or a comil that presses particles against an impeller and a screen to pulverize the particles.

  Examples of the power mill include an apparatus disclosed in Japanese Patent Laid-Open No. 5-96195. This device is a device with a cutter blade and a cylindrical screen. Particles thrown into the power mill inlet fall freely inside the power mill, and are crushed and adjusted by a pulverizing blade disposed on the cutter blade during this natural fall. Grained.

  An example of the comil is an apparatus disclosed in US Pat. No. 4,759,507. This device is an instrument having an impeller and a screen, and particles thrown into the comil inlet are pressed against the screen by the centrifugal force generated by the rotating impeller. Small particles ride on the swirl created instantly and due to the conical shape, and the raised particles are crushed and sized with an impeller.

The fragrance particles used in the present invention are obtained by mixing and granulating a fragrance and an oil-absorbing carrier and, if necessary, a binder as described above, and have an average particle size of 100 to 1500 μm, preferably 200 to 1300 μm. More preferably, it is preferably granulated to be 500 to 1000 μm. With respect to bulk density, preferably from ^{300~1000kg / m 3, 650~850kg / m} 3 being more preferred.

  Here, the average particle diameter and bulk density of the fragrance particles are values measured by the following methods.

<Measuring method of average particle size>
The average particle diameter is a median diameter, and is determined using a sieve specified in JIS Z 8801. For example, using a 9-stage sieve and saucer with openings of 2000 μm, 1400 μm, 1000 μm, 710 μm, 500 μm, 350 μm, 250 μm, 180 μm, and 125 μm, a low-tapping machine (made by HEIKOSEISAKUSHO, tapping: 156 times / min, rolling: 290 And a 100 g sample is vibrated for 5 minutes, and then the proportion of particles of each particle size is measured from the mass fraction according to the size of the sieve opening to determine the average particle size.

<Method for measuring bulk density>
The bulk density is measured by a method defined by JIS K 3362.

  As described above, in the detergent composition according to the present invention, a part or all of the fragrance material having a vapor pressure at 20 ° C. in the fragrance composition of 0.8 Pa or more, preferably 2.0 or more, and further less than 150 Pa. It is preferable to blend as perfume particles impregnated in an oil-absorbing carrier from the viewpoint of deodorant sustainability during washing, rinsing and drying by an automatic dishwasher. In particular, (A) 1-30% by mass of a fragrance composition containing 60% by mass or more of a fragrance material having a vapor pressure of 0.8 Pa or higher at 20 ° C., (B) an oil-absorbing carrier and (C) a water-soluble binder. , (B) / (C) = 7/1 to 2/1 (mass ratio). In the present invention, in the above fragrance composition, it is preferable to use 0.1 to 100% by mass, preferably 5 to 100% by mass in the fragrance material having a vapor pressure at 20 ° C. of 0.8 Pa or more and less than 150 Pa as the fragrance particles. In such a range, it is possible to further improve the deodorant persistence during washing, rinsing and drying, and it is possible to design the fragrance strength of the detergent composition within a preferable range.

  In addition, as a method of mix | blending the said fragrance | flavor particle | grains with the detergent composition based on this invention, if it is a well-known method, there will be no limitation in particular.

  The amount of the fragrance particles added to the detergent composition according to the present invention is not particularly limited as long as the ratio of the fragrance composition in the detergent composition is in the range of 0.05 to 1.0% by mass. Depending on the type and blending ratio of the fragrance, it can be used by adjusting as appropriate, but it is preferably 0.1 to 10% by mass, more preferably 0.3 to 7% by mass.

<Other ingredients>
(1) Bleach In general, a detergent composition for an automatic dishwasher contains a bleach. However, when a refill container, which is the subject of the present invention, is filled with a fragrance, Conspicuously occurs when contained. In the present invention, even in a detergent composition containing a bleaching agent, by adopting the above configuration, it becomes possible to suppress the deterioration suppressing effect of the fragrance during storage to a satisfactory level.

  As the bleaching agent, percarbonate, preferably sodium percarbonate (hereinafter sometimes referred to as PC), perborate, preferably sodium perborate is suitable. Moreover, when employ | adopting percarbonate, it is suitable to use the percarbonate coated for the purpose of further improving the stability during storage of a fragrance | flavor.

  The coated percarbonate is preferably one coated with a water-soluble polymer or inorganic salt. As specific examples, sodium percarbonate coated by a known method can be used. For example, Japanese Patent Publication No. 47-32200 (PC coated with paraffin), Japanese Patent Publication No. 53-15717 (PC US Pat. No. 4,131,562 (PC coated with sodium perborate and alcohol ethylene oxide adduct), US Pat. No. 4120812 (PC coated with sodium perborate with polyethylene glycol), German patent No. 2712139 (PC coated with silicate), German Patent No. 2800916 (PC coated with boric acid), European Patent No. 30759 (PC coated with wax), JP-A-58-217599 (PC coated with boric acid) Coated with salt), JP-A-59-196399 (PC coated with borate), JP-A-4-31498 (PC coated with boric acid and silicate separately), etc. What was obtained by the method can be used.

Among these, (i) sodium borate, preferably sodium metaborate, percarbonate coated with sodium orthoborate at a ratio of 0.1 to 30% by mass with respect to the percarbonate, (ii) orthoboric acid Percarbonate coated with 0.3 to 20% by mass, preferably 0.5 to 10% by mass, particularly preferably 1 to 8% by mass of boric acid selected from metaboric acid and tetraboric acid with respect to the percarbonate And (iii) and (ii) further sodium metasilicate, sodium orthosilicate, water glass No. 1, No. 2, sodium salt, potassium metasilicate, ortho orthosilicate, preferably water glass No. 1, No. 2, No. 3 sodium carbonate converted to SiO ₂ with respect to the percarbonate, 0.1 to 10% by mass, 0.2 to 7% by mass, particularly preferably 0.3 to 5% by mass. Salts are preferred. In particular, the percarbonate of (i) is preferable from the viewpoint of storage stability. As the percarbonate, sodium percarbonate is preferred.

  The coated percarbonate of the present invention can be prepared by conventional methods. For example, it is possible to use a method in which a solution or powder containing the above-mentioned coating agent is mixed and adsorbed on a wet or dry percarbonate and dried.

  The coated percarbonate has an average particle diameter of 100 to 2000 μm, preferably 250 to 1500 μm, from the viewpoint of bleaching washing effect and classifying suppression effect. Moreover, it is preferably 1 to 70% by mass, more preferably 1 to 50% by mass, and particularly preferably 5 to 25% by mass in the composition.

(2) Surfactant In general, surfactants are used for detergents for the purpose of imparting a cleaning effect, but the detergent compositions according to the present invention have an interface for the purpose of suppressing residual fragrance on tableware after washing. It is suitable to reduce the activator as much as possible, preferably 10% by mass or less, more preferably 5% by mass or less.

(3) Others The detergent composition according to the present invention contains a polyoxypropylene having a weight average molecular weight of 600 to 5,000, preferably 2,000 to 4,000, and imparts a cleaning effect. It is preferable because the residual scenting property to the tableware after washing can be suppressed.

  In the detergent composition according to the present invention, the polyoxypropylene is preferably contained in an amount of 0.001 to 10% by mass, more preferably 0.005 to 5% by mass, and particularly preferably 1 to 5% by mass.

The detergent composition according to the present invention is in the form of powder or granules, and in particular, it is preferably used in the form of powder or granules obtained by impregnating the polyoxypropylene with a powder or granular inorganic compound. Examples of the inorganic compound include sodium carbonate, potassium carbonate, silicate, aluminosilicate, and sodium sulfate, and an inorganic compound selected from sodium carbonate, zeolite, or silicate is particularly preferable. As the sodium carbonate, dense ash having an average particle diameter of 100 to 1500 μm is preferable. As the silicate, the silicate is amorphous sodium silicate such as No. 1 to No. 3 sodium silicate, JP-A-7-89712, JP-A-60. No. 227895 and Phys. Chem. Glasses. 7, p127-p138 (1966), Z. Kristallogr., 129, p396-p404 (1969). Crystalline sodium silicate marketed as "Na-SKS-6" (δ-Na ₂ Si ₂ O ₅ ) is preferred. As the aluminosilicate, amorphous aluminosilicate is preferable, and Japanese Patent Application Laid-Open No. 62-191417, page 2, lower right column, line 19 to page 5, upper left column, line 17 (particularly, the initial temperature ranges from 15 to 60 ° C. Amorphous aluminosilicate described in JP-A No. 62-191419, page 2, lower right column, line 20 to page 5, upper left column, line 11, and JP-A-9-132794, Examples thereof include amorphous aluminosilicate (oil absorption capacity: 285 mL / 100 g) described in JP-A-7-10526, JP-A-6-227811, and JP-A-8-119622. Specifically, Toxeal NR (Tokuyama Soda Co., Ltd., oil absorption capacity: 210-270 mL / 100 g), Florite (Tokuyama Soda Co., Ltd., oil absorption capacity: 400-600 mL / 100 g), TIXOLEX 25 (Korean / French) Oil absorbing carriers such as those manufactured by Kagaku Co., Ltd., oil absorption capacity: 220 to 270 mL / 100 g), and Silo Pure (manufactured by Fuji Divison Co., Ltd., oil absorption capacity: 240 to 280 mL / 100 g) can be used.

  A general commercial item can be used as sodium sulfate. For example, Shikoku Kasei Co., Ltd. A0-B mirabilite etc. can be used.

  In the present invention, the mass ratio of the polyoxypropylene to the powdered or granular inorganic compound is such that polyoxypropylene / inorganic compound = 1/8000 to 1/8, further 1/800 to 1/8, particularly 1/100 to 1. / 10 is preferable.

  In the detergent composition according to the present invention, the average particle size of the detergent particles is 100 to 500 μm, more preferably 150 to 400 μm, particularly 200 to 300 μm, so that the storage stability of the detergent composition, and the above-described fragrance particles and bleaching agents From the viewpoint of suppressing the classification.

  The detergent composition according to the present invention can contain components that can be used in ordinary automatic dishwashing detergents other than those described above, and include sequestering agents such as citrate, polyacrylic acid or acrylic acid / It can contain a dispersing agent such as a maleic acid copolymer, an enzyme such as a protease and amylase, a dye, and the like.

<Flexible thin container>
In the present invention, the above-mentioned detergent composition is made of a transparent or 50-300 μm thick resin laminate including one or more resin layers on which inorganic metal oxide vapor-deposited thin films (hereinafter referred to as vapor-deposited thin films) are formed. Fill a translucent flexible thin container. Here, examples of the inorganic metal oxide include silicon oxide (SiO _x such as SiO and SiO ₂ ) and aluminum oxide (Al _y O _z such as AlO, Al ₂ O ₂ and Al ₂ O ₃ ). However, silica and alumina are preferred.

  In the resin layer on which the deposited thin film is formed, preferable resins are polyolefins such as polypropylene and polyethylene, polyethylene terephthalate, polybutylene terephthalate, polyester such as polyethylene-2,6-naphthalate, polyamide such as nylon 6 and nylon 12, polycarbonate, polystyrene. , Polyvinyl chloride, polyvinylidene chloride, and polyvinyl alcohol. In the present invention, polypropylene, polyethylene, and polyethylene terephthalate are preferable from the viewpoint of transparency, strength, and flexibility of the resin, and polyethylene terephthalate is most preferable. In view of mechanical strength and transparency, these resins are preferably used in the form of an unstretched, uniaxially stretched, or biaxially stretched film. The thickness is 1 to 100 μm, preferably 1 to 50 μm, particularly preferably 5 to 20 μm.

  In this invention, the resin film in which the inorganic metal oxide was vapor-deposited on the said resin film and the vapor deposition thin film was formed is used. As a vapor deposition method, a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a vacuum vapor deposition method, a sputtering method, or an ion plating method, or a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, a photochemical vapor deposition method, or the like. Examples thereof include a chemical vapor deposition method (Chemical Vapor Deposition method, CVD method) such as a growth method. Further, the method described in JP-A-60-49934, or the vapor deposition method described in JP-A-2001-225424 can be employed. The thickness of the vapor-deposited thin film is preferably 100 to 5000 mm, more preferably 300 to 2000 mm, and particularly preferably 300 to 1000 mm in terms of fragrance stability.

  The container according to the present invention is composed of a laminate of resin layers including at least one resin layer (hereinafter also referred to as a vapor deposition resin layer) on which the above-described vapor deposition thin film is formed. It is preferable from the viewpoint of stability that the outermost layer) and the innermost layer (the layer in contact with the composition inside the container) do not contain a deposited thin film. In the present invention, a laminate having a three-layer structure in which a vapor deposition resin layer is sandwiched between the outermost layer and the innermost layer is preferable.

  As resin layers other than the vapor deposition resin layer, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene -Ethyl acrylate copolymer, ethylene-acrylic acid or methacrylic acid copolymer, methylpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-chloride Vinylidene copolymer, poly (meth) acrylic resin, polyacrylonitrile resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester Resin, polyamide tree , Polycarbonate resin, polyvinyl alcohol resin, saponified ethylene-vinyl acetate copolymer, fluorine resin, diene resin, polyacetal resin, polyurethane resin, nitrocellulose, nylon In addition, it is preferable to use an unstretched, uniaxially stretched, or biaxially stretched resin.

  In the present invention, at least one selected from linear low density polyethylene, low density polyethylene, linear low density polyethylene, unstretched polypropylene, stretched nylon, stretched polypropylene and polyethylene terephthalate is used as the vapor deposition resin layer and other resin layers. Nylon and polypropylene are preferable for the outermost layer from the viewpoint of strength, and low density polyethylene and linear low density polyethylene are preferable for the innermost layer from the viewpoint of heat fusion.

  The thickness of the outermost layer is preferably 1 to 100 μm, more preferably 5 to 50 μm, and the thickness of the innermost layer is preferably 10 to 200 μm, more preferably 20 to 200 μm, and the total thickness of the laminate is 50 to 300 μm, preferably 50 to It is prepared to be 250 μm.

  In the present invention, in addition to these resin layers, from the aesthetic point of view, it is possible to further provide a colored layer on these laminates. For example, gray gravure ink, white gravure ink, black ink, silver ink or the like is applied to the colored layer. It is possible to make it. Further, these laminates can be provided with a barrier layer, a pinhole-resistant layer, a tear induction layer and the like.

  The flexible thin-walled container of the present invention can be easily manufactured by a known method. Examples of the manufacturing method include a dry laminating method, a T-die method, a coextrusion laminating method, an inflation method, and a tandem laminating method. Although the form of the packaging container is not limited, for example, 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.

  The flexible thin-walled container of the present invention is transparent or translucent, but here, transparent or translucent means that there is at least one wavelength region having a light transmittance of 30% or more in the range of 200 to 800 nm. It is defined as The light transmittance can be measured with a spectrophotometer.

<Manufacture of flexible thin-walled containers>
Invention product A
Two sets of 20 mm thick stretched nylon, 10 μm thick silica vapor deposited polyethylene terephthalate with 600 mm thick polyethylene terephthalate, and 100 μm linear low density polyethylene in this order were prepared in two sets, each having a thickness of 20 μm. The three stretched nylons were placed on the outside, and the three sides were heat sealed to produce a transparent sachet with a volume of 500 ml.

Invention product B
Two sets of rectangular shapes are prepared by superimposing stretched nylon with a thickness of 10 μm, polyethylene terephthalate with a thickness of 800 μm of alumina deposited film thickness of 800 μm, and 150 μm of linear low-density polyethylene in this order, each having a thickness of 10 μm The three stretched nylons were placed on the outside, and the three sides were heat sealed to produce a transparent sachet with a volume of 500 ml.

Comparative product A transparent container was prepared in the same manner as the product A of the present invention except that polyethylene terephthalate having no silica vapor deposition layer was used.

(1) Preparation of perfume particles Each perfume composition shown in Table 1 was used to produce each perfume particle. In addition, the fragrance | flavor particle | grains were produced as follows.

  Each fragrance composition 650 g, dextrin (Matsutani Chemical Co., Ltd .: Pineflow KH) 1560 g, sodium sulfate (Shikoku Kasei Kogyo Co., Ltd .: crushed A6 sodium sulfate) 5720 g, silicon dioxide (Tokuyama Soda Co., Ltd .: Toxeal NR) 1820 g, 2.6 g of edible iron sesquioxide (manufactured by Kasei Kasei Co., Ltd.), 0.91 g of red No. 106 (manufactured by Eisen Hodogaya Co., Ltd.) was charged into a Nauta mixer (Hosokawa Micron Co., Ltd.), and the jacket temperature was set to 75 ° C. The mixture was heated up. Next, when the temperature of the powder reaches 60 ° C., 2210 g of polyethylene glycol (Kao Corporation: KPEG-6000LA) melted in advance and 1040 g of polyethylene glycol (Kao Corporation: KPEG-6000LA) in a solid state are melted in advance. Was added, and after further mixing, the mixture was withdrawn. 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 an extrusion granulator (Fuji Paudal Co., Ltd .: Pelletter Double EDX-60 type) and consolidated. Further, after the extruded granulated product was cooled, it was pulverized with a granulator (pulverized once with a power mill and further pulverized once with a comil) to obtain perfume particles colored pink. At this time, in any case of using any of the fragrance compositions, there was almost no adhesion to the production equipment, and the production suitability was good.

・ Mint oil (brand name: light-loading white oil;
・ Sandalwood oil (Brand name Oil Sandal Mysore, manufacturer CHARABOT)

(2) Preparation of detergent composition A detergent composition was prepared at the blending ratio shown in Table 2, and a detergent article was obtained using the combination of the container and Table 2. The following evaluation was performed about them. The results are shown in Table 2.

(3) Evaluation method of odor intensity during container filling and odor change before and after storage <Odor intensity during container filling>
When 400 ml of the detergent composition of Table 2 is put in the container and the smell intensity around the opening is sniffed by a panel of men and four women in their 30s (two each), it is not strong, weak or just right 3 points, 2 points for a slightly strong case, 1 point for a clearly strong case, the average score of the panel 4 people is 2.5 points or more ○, 1.75 points or more, less than 2.5 points △, 1 The odor intensity when filling the container was evaluated with x below 75 points.

<Odor change before and after storage>
400 mL of the detergent composition shown in Table 2 is placed in the container, heat sealed, sealed, stored in a room maintained at 40 ° C. and 50% humidity for 30 days, cooled to room temperature, and one side of the heat seal opened. However, the smell of the opening mouth is sniffed by the panel of men and four women in their 30s (two each), and the case where the smell has not deteriorated at all compared to before storage is slightly deteriorated. 2 is the acceptable range, 1 is clearly deteriorated, the average score of the four panelists is 3.0 points or more ○, 2 points or more, less than 3 points △, less than 2 points × As deodorant performance was evaluated.

(4) Evaluation method of deodorant performance and residual fragrance <cleaning conditions>
Washing machine used: An automatic dishwasher (model NP-C10) manufactured by Matsushita Electric Co., Ltd. was used on the standard course. This washer is gradually heated from 15 ° C. to 55 ° C. for cleaning, and then rinsed twice (not heated), and after the final rinse (slowly raised from 15 ° C. to 70 ° C. for rinsing) It is of a dry type.
Water used: 3.5 ° DH water Circulating water amount during washing: about 2.5 liters Detergent composition concentration: 0.2% by mass

<Preparation of contaminated dishes>
Three pieces of cocoon oil (manufactured by Sigma Aldrich Japan Co., Ltd.) applied to a magnetic dish having a diameter of 25 cm were subjected to washing.

<Deodorization performance evaluation method>
Set the above contaminated dish in the washing machine and let the smell of steam generated during the final rinse be sniffed by the panel of 4 males and 4 females (2 people each), and no odor is detected. 3 points when almost undetected, 2 points when slightly detected, 1 point when clearly detected, ◎ if the average score of 4 panelists is 3.5 points or more, 3.0 points or more The deodorizing performance was evaluated by giving less than 3.5 points as ◯, 2 points or more, and less than 3 points as Δ, and less than 2 points as x.

<Evaluation method of residual fragrance>
After drying, leave it for about 1 hour, open the lid of the washer, and smell the smell of the inside of the washer in the panel of 4 males and 4 females (2 each). 4 points when it is not detected, 3 points when it is hardly detected, 2 points when it is detected slightly, 1 point when it is clearly detected, and the average score of 4 panelists is 3.5 points or more. Residual fragrance was evaluated by giving 3.0 or more and less than 3.5 points as ◯, 2 or more and less than 3 points as Δ, and less than 2 points as x.

1) Polypropylene glycol, weight average molecular weight of about 3000, average condensation degree of about 50 (diol type, Wako Pure Chemical Industries, Ltd.)
2) Sokaran CP45 (B.A.S.F.)
3) Termamyl 60T (Novo Nordisk Bio Industry Co., Ltd.)
4) Sabinase 12.0T (Novo Nordisk Bio Industry Co., Ltd.)
5) Limonene / mint oil / peppermint oil / orange oil / eucalyptus oil / l-menthol / camphor / clove leaf oil / sage oil / basil oil = 47/30/11/5/2/2/2 / 0.6 / Mixed at 0.2 / 0.2 (mass ratio) 6) Pepper oil (Brand name Hakaku White Oil, manufacturer Nagaoka Jitsugyo Co., Ltd.)

  From the results of Table 2, it can be seen that according to the present invention, a good deodorizing effect is exhibited when the automatic dishwasher is used, and no residual fragrance is generated on the object to be cleaned. In addition, a detergent product in a container that exhibits an aesthetically pleasing transparent or translucent appearance and that suppresses odor deterioration during storage can be obtained.

Claims (4)

A polyoxypropylene having a fragrance composition having a vapor pressure at 20 ° C. of 0.8 Pa or more and a ratio of fragrance material of 60 mass% or more and 0.05 to 1.0 mass% and a weight average molecular weight of 600 to 5,000. 1 to 5% by mass, and the surfactant content is 5% by mass or less, including at least one resin layer on which a deposited thin film of inorganic metal oxide is formed. A detergent article for an automatic dishwasher , filled in a transparent or translucent flexible thin-walled container composed of a resin laminate having a thickness of 50 to 300 μm. The detergent article for an automatic dishwasher according to claim 1, wherein at least a part of the perfume composition is contained as perfume particles obtained by impregnating the perfume composition into an oil absorbing carrier. Materials constituting the laminate are polypropylene, polyethylene and other polyolefins, polyethylene terephthalate, polybutylene terephthalate, polyesters such as polyethylene-2,6-naphthalate, polyamides such as nylon 6 and nylon 12, polycarbonate, polystyrene, polyvinyl chloride, poly The detergent article for an automatic dishwasher according to claim 1 or 2 , wherein the detergent article is at least one selected from vinylidene chloride and polyvinyl alcohol. The detergent article for an automatic dishwasher according to any one of claims 1 to 3, wherein the detergent composition contains percarbonate or perborate.