JP4566620B2 - Granulated material - Google Patents

Description

  The present invention relates to a granulated product used by being dissolved in water or the like, and a cleaning composition containing the granulated product.

  Granules used by dissolving in water or the like are generally used in pharmaceuticals, foods, agricultural chemicals, fertilizers, bath agents, cleaning agents, and the like.

  The granulated product is obtained by mixing and solidifying a plurality of components, and is advantageous in terms of dustlessness, separation resistance in transportation and storage, and the like, compared with a mixture of only a plurality of components. Further, the granulated product is advantageous in that liquid and gas can be taken into the granulated product.

  However, it gives the granulated product rapid disintegration, solubility, and dispersibility in water, etc., and sufficient mechanical strength to withstand damage during manufacturing, storage, transportation and handling. It was difficult to achieve this simultaneously.

  For example, a tablet-type detergent using a neutralized product of a hydrophilic or hydrophobic monomer polymer as a binder is known (for example, see Patent Document 1). In addition, a method for producing a tablet-type detergent in which a water-soluble organic polymer binder is coated on the outside of the particles of the detergent composition is known (for example, see Patent Document 2). Moreover, the tablet-type cleaning agent which has the film | membrane containing a non-gelling binder is known (for example, refer patent document 3). In addition, a tablet-type detergent containing a granular dissolution accelerator such as citric acid is known (see, for example, Patent Document 4). However, these are techniques relating to relatively large granules, and are not suitable for granules having a small particle diameter generally used in pharmaceuticals, foods, detergents and the like.

  In addition, for example, granules or tablets containing saccharides and inorganic compounds are known (for example, see Patent Document 5). Moreover, the granule or tablet containing a crystalline cellulose is known (for example, refer patent document 6). However, these are not sufficiently soluble at low temperatures.

In addition, for example, a compression-molded detergent having a specific interparticle porosity is known (see, for example, Patent Document 7). However, much labor is required to determine the manufacturing conditions.
Japanese Patent Laid-Open No. 10-60485 US Pat. No. 5,916,866 Special table 2001-512784 gazette JP-A-7-286199 JP 2000-86537 A JP-A-8-104650 JP 2003-82399 A

  An object of the present invention is to provide a granulated product having sufficient mechanical strength that can rapidly disintegrate, dissolve, and disperse in water or the like and can withstand damage during manufacturing, storage, transportation, and handling.

  The present invention relates to a granulated product containing 0.1 to 30% by mass of a sulfate double salt of a monovalent cation and a divalent cation. Moreover, this invention relates to the cleaning composition containing the granulated material of the said invention. Moreover, this invention relates to the manufacturing method of the granulated material which manufactures the granulated material containing the sulfate double salt of a monovalent cation and a bivalent cation through a compression process.

  The granulate of the present invention has sufficient mechanical strength to disintegrate, dissolve, disperse rapidly in liquids such as water and to withstand breakage during manufacturing, storage, transportation and handling.

  The granulated product of the present invention contains a sulfate double salt of a monovalent cation and a divalent cation. The sulfate double salt of a monovalent cation and a divalent cation works as a mechanical strength enhancer in a dry state, and works as a dissolution accelerator when in contact with water. In terms of solubility and mechanical strength, the sulfated double salt of monovalent cation and divalent cation in the granulated product is 0.1 to 30% by mass, and 0.5 to 20% by mass. Is more preferable, and 1-10 mass% is still more preferable. Among them, the content is preferably 3% by mass or more.

Examples of the monovalent cation in the sulfate double salt of a monovalent cation and a divalent cation include lithium ion, sodium ion, potassium ion, rubidium ion, cesium ion, and ammonium ion. Examples of the divalent cation include beryllium ion, magnesium ion, calcium ion, strontium ion, and barium ion. Among these, from the viewpoint of solubility and mechanical strength, a sulfate double salt of sodium ion and / or potassium ion and magnesium ion is preferable, magnesium sulfate sodium and magnesium sulfate are more preferable, and magnesium sulfate is particularly preferable. As magnesium sulfate sodium, Na ₂ SO ₄ · MgSO ₄ · 4H ₂ O, Na ₂ SO ₄ · MgSO ₄ · 2.5H ₂ O, 3Na ₂ SO ₄ · MgSO _{4 and the} like are known, but among them Na ₂ SO Most preferred is ₄ · MgSO ₄ · 4H ₂ O.

  The sulfuric acid double salt may be blended as a raw material or may be generated as a result of granulation. The latter is preferable in terms of cost. The following method is mentioned as a manufacturing method of sulfuric acid double salt. Components that are liquid at 20 ° C. consisting of monovalent sulfates, divalent sulfates, polyhydric alcohols and / or alcohols and / or fragrance components, and if necessary oil-absorbing carriers, so that the powder temperature is 60 ° C. To mix. A melted binder is added and mixed sufficiently, and then compacted by extrusion granulation or the like. After the granulated product is cooled, the granulated product containing the desired sulfate double salt can be produced by regulating the size. Here, the presence of the sulfate double salt can be confirmed by analyzing the X-ray diffraction pattern. Examples of the oil-absorbing carrier include crystalline aluminosilicate, amorphous aluminosilicate, crystalline silicate, silicon dioxide, clay mineral, silicate, tripolyphosphate, pyrophosphate and the like. Examples of alcohols include polyhydric alcohols such as monohydric alcohols having an alkyl group such as ethanol and oleyl alcohol, alkenyl groups and phenyl groups, glycerin, ethylene glycol, propylene glycol and derivatives thereof, and monosaccharide or polysaccharide derivatives such as alkyl glucosides. (Polyol). Of these, glycerin is more preferable. A specific manufacturing method will be described in Examples described later.

  The granulated product of the present invention preferably contains 0.1 to 30% by mass of a component that is liquid at 20 ° C. in terms of functionality, solubility, and mechanical strength, and 0.5 to 25% by mass. More preferably, 1-20 mass% is still more preferable, and 5-15 mass% is especially preferable. Examples of the liquid at 20 ° C. include alcohols such as polyhydric alcohols, solvents such as water, and fragrance components. However, the water in the granulated product of the present invention (water by the superheat loss method described in JIS K 3362: 1998) is preferably 10% by mass or less in terms of productivity, storage stability, etc., and 5% by mass or less. More preferred is 1% by mass or less, and particularly preferred is 0.1% by mass or less.

  Examples of the alcohol include monovalent alcohols having an alkyl group such as ethanol and oleyl alcohol, alkenyl groups and phenyl groups, glycerin, ethylene glycol, propylene glycol and derivatives thereof (for example, ethers), and monosaccharide or polysaccharide derivatives such as alkyl glucosides. And a polyhydric alcohol (polyol). In particular, glycerin, ethylene glycol, propylene glycol, and polyhydric alcohols such as ethers thereof, among which glycerin is preferable. The granulated product of the present invention preferably contains 0.1 to 10% by mass of polyhydric alcohol, more preferably 0.1 to 5% by mass.

  Examples of the fragrance component include linalool oxide, rubofix, hexenyl salicylate, florarozone, helional, ethylmethylphenylglycidate, raspberry ketone, undecalactone, deltadecalactone, gammadecalactone, deltown decalactone, deltadodecalactone, gamma Dodecalactone, deltanonalactone, raspberry ketone, poilenate, allylphenoxyacetate, α or β-damascone (2,6,6-trimethyl-trans-1-crotonylcyclohexene-1 or 2), dimethylbenzylcarbinyl acetate, furtate, Decenol, diphenylmethane, cis jasmon, dihydro jasmon, edion, dimethyl anthranilate, methyl anthranilate, cyclamenaldehyde ( -Isopropyl-α-methylhydrocinnamic aldehyde), methyl-β-naphthyl ketone, benzophenone, tonalide (7-acetyl-1,1,3,4,4,6-hexamethyltetrahydronaphthalene), phenylacetaldehyde, allyl ionone , Dihydro-β-ionone, ionone α, ionone β, cedryl methyl ether, mossine, cashelan, celestride, ethylene brushate, muscone, pentaride, civeton, phenylethylphenylacetate, ethyl vanillin, vanillin, heliotropin, heliotro Pyracetate, methylnonylacetaldehyde, allylcyclohexanepropionate, eugenol, citronenol, magnole, citronellyl acetate, diphenyl oxide, rosinol, hex Sylcinnamic aldehyde, lyial (p-tert-butyl-α-methylhydrocinnamic aldehyde), laral [4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde], helional, hydroxy Citronellal, methyl ionone, cedarwood oil, cedrol, cedryl acetate, acetyl cedrene, cedryl methyl ether, isoea super, sandal synth, patchouli oil, pearl ride, indole, cinnamic alcohol, coumarin, amyl salicylate, benzyl salicylate And hexyl salicylate.

  Furthermore, the following aldehydes, ketones, esters, ethers, alcohols and the like are preferable as those that are stable at high temperatures, and aldehydes, ketones, and esters are more preferable. Examples of aldehydes having a boiling point of 200 ° C. or higher at normal pressure include lyial (p-tert-butyl-α-methylhydrocinnamic aldehyde), cyclamenaldehyde (p-isopropyl-α-methylhydrocinnamic aldehyde), laral [4- (4-Hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde], helional, hydroxycitronellal and the like. Examples of ketones having a boiling point of 200 ° C. or higher at normal pressure include damascone (α-, β-isomer) (2,6,6-trimethyl-trans-1-crotonylcyclohexene-1 or 2), damasenone (α -, Β-isomer), methyl-β-naphthyl ketone, benzophenone, tonalide (7-acetyl-1,1,3,4,4,6-hexamethyltetrahydronaphthalene), acetyl cedrin, methyl cedrin, isomethyl ionone (α -, Β-isomer), Iron (α-, β-, γ-isomer), maltol, ethyl maltol, cis jasmon, dihydro jasmon, l-carvone and the like. Examples of esters include nonyl acetate, boronyl acetate, linalyl benzoate, flutate, poilenate, diethyl phthalate, ethyl cinnamate, hexyl salicylate, benzyl salicylate, terpinyl acetate, anisyl acetate, phenylethyl isobutyrate, dihydro Examples include methyl jasmonate, γ-undecalactone, γ-nonyllactone, and coumarin. Examples of ethers include thymol, galaxolide, methyl eugenol, and examples of alcohols include nerol, citronellol, eugenol, and the like, but these fragrances may be added. Perfume particles are a preferred embodiment of the granulated product of the present invention.

  In the granulated product of the present invention, the mass ratio between the sulfate double salt and the component that is liquid at 20 ° C. is preferably sulfate double salt / component that is liquid at 20 ° C. = 1/100 to 100/1. 1/20 to 20/1 is more preferable, and 1/10 to 5/1 is still more preferable.

  The granulated product of the present invention is a mass ratio of an inorganic compound (excluding sulfate double salt) that is solid at 20 ° C. and an organic compound that is solid at 20 ° C. in terms of productivity, solubility, and mechanical strength. Is preferably inorganic compound / organic compound = 1/2 to 10/1, more preferably 2/3 to 5/1, and still more preferably 1/1 to 3/1.

  Inorganic compounds that are solid at 20 ° C. include alkali metal, ammonium, alkylammonium chlorides, bromides, sulfates (excluding the sulfate double salt of the present invention), carbonates, crystalline aluminosilicates, amorphous Examples include aluminosilicates, crystalline silicates, silicon dioxide, clay minerals, silicates, tripolyphosphates and pyrophosphates.

  Organic compounds that are solid at 20 ° C. include starch, starch degradation products, aminocarboxylates, hydroxyaminocarboxylates, hydroxycarboxylates, cyclocarboxylates, ether carboxylates, higher alcohols, fatty acids ( Salt), polyethylene glycol and the like.

  As the granulated product of the present invention, stirring and mixing granulation, rolling granulation, extrusion granulation, crushing granulation, fluidized bed granulation, spray drying granulation, melt granulation, compression granulation, vacuum freeze granulation, Examples thereof include granules obtained by suspension aggregation granulation, coating granulation and the like. Among these, a granulated product obtained by any one of extrusion granulation, crushing granulation, and compression granulation is suitable. Moreover, in this invention, it is preferable to manufacture a granulated material (consolidated particle) through a compression process.

  The particle size of the granulated product of the present invention is not limited, but excellent solubility and disintegration can be obtained even with particles having an average particle size of 300 to 1000 μm, and even a small particle size of 500 to 800 μm.

  The granulated product of the present invention can be used as a product such as pharmaceuticals, foods, agricultural chemicals, fertilizers, bath agents, and cleaning agents by itself, and can be added to existing products as an additive. In particular, it is useful as an additive for a cleaning composition for clothing.

[Preparation of perfume particles]
In the proportions shown in Table 1, liquid fragrances (Lilyal, Frutate, α-Damascon, Poarenate, methyl-β-naphthyl ketone mixture), sodium sulfate (crushed mirabilite A6, manufactured by Shikoku Kasei Co., Ltd.), potassium sulfate, Magnesium sulfate (Mg-OK, manufactured by Ako Kasei Co., Ltd.), sodium carbonate (soda ash (granular), manufactured by Central), sodium chloride (baked salt S1000, manufactured by Japanese salt), silicon dioxide (Tokusil N, Tokuyama Soda Co., Ltd.) ), Dextrin (Pineflow KH, manufactured by Matsutani Chemical Co., Ltd.), carboxymethylcellulose (reagent, manufactured by Sigma), glycerin (reagent, manufactured by Katayama Chemical Co., Ltd.), water Nauter mixer (Hosokawa Micron Co., Ltd.) The jacket temperature was set to 75 ° C. and mixed to raise the temperature. Next, when the temperature of the powder reaches 60 ° C, polyethylene glycol (Kao Co., Ltd .: KPEG-6000LA) and solid polyethylene glycol (Kao Co., Ltd .: KPEG-6000LA) melted in advance are used. At a ratio of 70/30 (mass ratio) (that is, 70% by mass of the blended polyethylene glycol is added in a molten state and 30% by mass in a solid state), and after further mixing, the mixture is extracted. It was. 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. Furthermore, 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 remove particles having a particle size of 355 μm or less, thereby obtaining perfume particles. The presence of double sulfate was confirmed by analyzing the X-ray diffraction pattern.

[Evaluation]
About the obtained fragrance | flavor particle | grains, the mechanical strength and solubility were evaluated with the following method. The results are shown in Table 1.

[Mechanical strength evaluation]
The mechanical strength before and after storage when storing 20 g of a sample in a screw tube having a diameter of 35 mm and a height of 100 mm in a 30 ° C. and 70% RH environment without storing the lid for 1 week. A case where the difference was less than 150 kgf / cm ² was judged as good (◯), and a case where the difference was 150 kgf / cm ² or more was judged as bad (x). The mechanical strength at this time was obtained by measuring the strength of one particle averaged 10 times with a particle hardness measuring device (trade name Grano) manufactured by Okada Seiko Co., Ltd.

[Solubility evaluation]
Dissolution rate (measurement before and after storage) when 20 g of a sample was stored in a screw tube having a diameter of 35 mm and a height of 100 mm in an environment of 45 ° C. and 20% RH and the fragrance particles shown in Table 1 were stored for 1 week without closing the lid. The method was evaluated by the difference in the following). A case where the difference in dissolution rate was less than 5% was evaluated as good (◯), and a case where the difference was 5% or more was determined as bad (×). The measurement method is described below.

<Dissolution rate measurement method>
1 L hard water (Ca / Mg molar ratio 7/3) equivalent to 71 mg CaCO ₃ / L cooled to 10 ° C. is a 1 L beaker (inner diameter 105 mm, height 150 mm cylindrical type, for example, 1 L glass manufactured by Iwaki Glass Co., Ltd.) With a stirrer (length: 35 mm, diameter: 8 mm, for example, model: ADVANTEC, Teflon (registered trademark) round thin type) in a state where the water temperature is kept at 10 ° C. Stirring is performed at a rotation speed (800 r / min) at a depth of 1/3. The perfume particles weighed so as to be 2.000 ± 0.001 g are charged and dispersed in water with stirring, and stirring is continued. 300 seconds after charging, the fragrance particle dispersion in the beaker is filtered through a standard sieve (diameter: 100 mm) with an aperture of 74 μm defined by JIS Z 8801 (corresponding to ASTM No. 200) with a known mass, and the water content remaining on the sieve The perfume particles are collected together with a sieve in an open container of known mass. The operation time from the start of filtration until the sieve is collected is 10 ± 2 seconds. The recovered residue of the recovered fragrance particles is dried for 1 hour in an electric dryer heated to 105 ° C., and then cooled in a desiccator (25 ° C.) containing silica gel for 30 minutes. After cooling, the total mass of the dried scented particles, sieve and collection container is measured, and the dissolution rate (%) is calculated by the following equation. The mass is measured using a precision balance.
Dissolution rate (%) = [1- (T / S)] × 100
S: input mass of perfume particles (g)
T: Dry mass (g) of dissolved residue of fragrance particles

  From the results in Table 1, it is possible to obtain a granulated product having solubility in water and sufficient mechanical strength by blending a sulfate double salt of a monovalent cation and a divalent cation. Recognize.

Claims (9)

0.1 to 30% by mass of a sulfate double salt of a monovalent cation and a divalent cation selected from sodium magnesium sulfate and potassium potassium sulfate, and 0.1 to 10 polyhydric alcohol which is liquid at 20 ° C. A granulated product which is contained by mass and has a water content of 10% by mass or less according to the superheat loss method described in JIS K 3362: 1998 . A monovalent cation selected from magnesium sulfate and potassium magnesium sulfate obtained by mixing and granulating a monovalent sulfate, a divalent sulfate, and a component containing a polyhydric alcohol that is liquid at 20 ° C. A granulated product containing 0.1 to 30% by mass of a sulfate double salt of divalent cation and 0.1 to 10% by mass of a polyhydric alcohol which is liquid at 20 ° C. The granulated product according to claim 1 or 2 , wherein the sulfate double salt of a monovalent cation and a divalent cation is sodium magnesium sulfate. 2. The mass ratio of an inorganic compound that is solid at 20 ° C. (excluding the sulfate double salt) and an organic compound that is solid at 20 ° C. is inorganic compound / organic compound = 1/2 to 10/1. -Granulated material in any one of 3. The granulated product according to any one of claims 1 to 4, wherein the granulated product is obtained through any one of an extrusion granulation method, a crushing granulation method and a compression granulation method. A cleaning composition containing the granulated product according to claim 1. 0.1 to 30% by mass of a sulfate double salt of a monovalent cation and a divalent cation selected from magnesium magnesium sulfate and potassium potassium sulfate, and 0.1 to 10 polyhydric alcohol which is liquid at 20 ° C. The manufacturing method of the granulated material which manufactures the granulated material which contains a mass% and whose water | moisture content is 10 mass% or less by the overheat loss method of description of JISK3362: 1998 through a compression process. By mixing and granulating a monovalent sulfate, a divalent sulfate, and a component containing a polyhydric alcohol that is liquid at 20 ° C., a monovalent cation selected from magnesium sulfate and potassium sulfate A granulated product produced by producing a sulfate double salt with a divalent cation and containing 0.1 to 30% by weight of the sulfate double salt and 0.1 to 10% by weight of a polyhydric alcohol which is liquid at 20 ° C. A method for producing a granulated product. The production method according to claim 7 or 8 , wherein the sulfate double salt of a monovalent cation and a divalent cation is magnesium sulfate.