JP5614750B2 - Laundry tub cleaner composition and method for producing the same - Google Patents

Description

  The present invention relates to an improvement in cleaning power of a washing tub cleaner.

  The back of the washing tub of the washing machine is littered with various types of dirt such as detergent residue, mold and other germs, laundry lint, sebum dirt, and dirt components such as protein from the laundry. Odors are generated, and dirt peeled off during washing adheres to the laundry and causes stains and dirt.

  As cleaning agents that remove such dirt while chemically decomposing, those using chlorine-based oxidants and hydrogen peroxide-based oxidants can be considered, but these oxides are dangerous substances and should be handled. Therefore, there is a problem for ordinary housewives and the like for daily use. For this reason, cleaning agents using sodium percarbonate have been developed as oxidizing agents that are less dangerous and mild in decomposition reactions than such oxidizing agents. (See Patent Documents 1 and 2.)

  Contains sodium percarbonate and alkali metal silicate coated with nonionic surfactant, polyethylene glycol or inorganic metal salt on the surface, and bleach activator, surfactant, buffer for adjusting pH It is disclosed that a detergent composition in which an agent, an enzyme and the like are appropriately blended has excellent detergency, suppresses substrate damage, and is excellent in storage stability. (See Patent Document 1)

  Also, a surfactant-free composition based on sodium percarbonate coated with a wax-like substance and an inorganic powder containing heavy calcium carbonate powder obtained by pulverizing limestone is used as a drain for a kitchen sink. It is disclosed that a sliming effect such as that can be maintained for a long period of time and that dirt inside the pipe can also be prevented. (See Patent Document 2.)

Japanese Patent Laid-Open No. 11-181484 Japanese Patent No. 3554603

  However, when the cleaning agent containing the surfactant described in Patent Document 1 is introduced into a river after use, the surfactant contaminates the water quality, killing organisms in the river (sea), generating malformations, water pollution, There is a problem in environmental protection in that wastewater from household (industrial) detergents causes pollution due to the generation of malodor.

  In addition, when lime is used as a detergent component as described in Patent Document 2, there has been a problem in environmental protection in that it adversely affects the surrounding environment (alkali influence).

  Therefore, the present invention has been made in view of the above problems, and is a composition that does not contain any surfactant and does not use lime as an alkali source, has excellent detergency, and affects the surrounding environment. Another object of the present invention is to provide a washing tub cleaner composition and a method for producing the same.

  In order to solve the above-mentioned problems, the present inventors have conducted research, and as a result, do not use a surfactant or an alkali builder, a sodium percarbonate powder coated with a specific component, an inorganic powder containing shell-fired calcium, and Mixing composition with inorganic powder containing water-soluble binder increases washing ability of washing tub by polishing, peeling action and proper maintenance of alkalinity against baked calcium calcium stains, and also affects the surrounding environment The present inventors have found that it can be improved and completed the present invention.

  That is, the present invention relates to a sodium percarbonate granule coated with a hydrophobic substance or a wax-like substance made of a water-insoluble or poorly water-soluble substance, an inorganic powder containing at least shell calcined calcium, and an inorganic substance containing a water-soluble binder. A laundry tub cleaner composition characterized by being a mixture obtained by mixing powder particles and a method for producing the same are provided.

  According to the present invention, a composition that does not contain any surfactant and does not use lime as an alkali source, has excellent detergency, and has little influence on the surrounding environment, and a method for producing the same Can be provided.

Hereinafter, modes for carrying out the present invention (hereinafter referred to as “embodiments”) will be described in detail.
The laundry tub cleaner composition of the present invention comprises a granular material of sodium percarbonate coated with a hydrophobic substance or a wax-like substance made of a water-insoluble or poorly water-soluble substance, an inorganic powder containing at least shell calcined calcium, and a water-soluble substance. It is a mixture obtained by mixing the inorganic granular material containing a conductive binder.

The sodium percarbonate in the present invention means a compound generally called sodium percarbonate, and 2Na ₂ CO ₃
A hydrogen peroxide adduct of sodium carbonate represented by a chemical formula such as 3H ₂ O ₂ , which is a general term for compounds that generate hydrogen by decomposition reaction using hydrogen peroxide and sodium carbonate as raw materials.

  The wax-like substance for coating sodium percarbonate in the present invention is not particularly limited as long as it is a solid or semi-solid hydrophobic substance or water-insoluble or poorly water-soluble substance at room temperature. Specifically, commonly used waxes such as paraffin wax and polyolefin oligomer can be used, which may be natural wax or synthetic wax.

  In the present invention, the ratio of sodium percarbonate to the waxy substance is preferably 80 to 98% by mass of sodium percarbonate and 20 to 2% by mass of the waxy substance, more preferably 90 to 95% by mass of sodium percarbonate, and waxy. 10 to 5% by mass of the substance. When the amount of the wax-like substance is increased with respect to sodium percarbonate, the water repellency becomes strong, so the reaction of sodium percarbonate is slowed down, and the reaction does not end within 1 to 3 hours of the usual washing tub washing time, and the residue Will remain. If the amount of the wax-like substance is small relative to sodium percarbonate, the water repellency becomes weak and the sodium percarbonate reacts rapidly, so that the reaction ends before the washing tub washing time elapses. This is because, in a thin part of the coating, moisture in the air and sodium percarbonate react to cause caking.

  In the present invention, the ratio of the sodium percarbonate granules coated with the wax-like substance and the inorganic granules is 50 to 80% by mass, more preferably 60 to 80% by mass of the sodium percarbonate granules coated with the wax-like substance. Therefore, the range of 50 to 20% by mass of the inorganic granular material is preferable, and the range of 40 to 30% by mass is more preferable. When the amount of the inorganic powder is increased, the cleaning effect and the like are improved, but the effect of removing acidic dirt tends to be reduced. In addition, when the amount of the inorganic powder is small, the effect of removing acidic stains increases, but the cleaning effect and the like become small.

  As the inorganic powder used in the present invention, those which are sparingly soluble in water are preferred, carbonates such as calcium carbonate, calcium / magnesium carbonate, and magnesium carbonate, citrates such as sodium citrate, and aluminum hydroxide. , Hydroxides such as magnesium hydroxide, sulfates and sulfites such as calcium sulfate, calcium sulfite, and barium sulfate, oxides such as iron oxide, titanium oxide, and zinc oxide, talc, mica, kaolin clay, calcined clay , Bentonite, pyrophyllite, attapulgite, nepheline / sianite, diatomaceous earth, zeolite, sericite, calcium silicate, aluminum silicate, glass powder, and other mineral and silicate powders, silica gel, silica, and alumina Such as silicon oxide and aluminum oxide Click powders, and the like boron compounds anhydrides such as boron oxide. These inorganic powders may be used in combination of two or more. Among these, calcium carbonate is most preferable in consideration of stability such as sodium percarbonate and influence on the environment.

  Considering the detergency due to the polishing of the calcium carbonate powder, calcium carbonate powder having a relatively large particle size is preferable. Examples of such calcium carbonate powder include shell-calcined calcium powder obtained by pulverizing and firing shells, and the size of shell-calcined calcium powder added as a polishing / peeling material is a random crushed piece of 10 μm to 2 mm. It is desirable. Among the calcined calcium shells, high-quality scallop calcined calcium is particularly preferable because of its high production.

  In view of the polishing / peeling effect, the reason for using shell calcined calcium is its specific gravity rather than hardness. The calcinated shell shell calcined calcium is lighter than the crushed shell shell before firing, so that it easily floats in the cleaning agent and easily contacts the object to be cleaned. For the same reason, it is difficult to settle on the bottom of the cleaning agent. In addition, the collapse of the laminated structure in the shell-calcined calcium greatly affects the improvement of the polishing action. The shell is a composite material of calcium-protein and has a strong and characteristic structure in which 95% by mass of calcium carbonate and 5% by mass of chitosan are layered. This is the basis of the flexible curvature and strength of the shell, but in the baked shell, the bond between the layers becomes pie-like brittle. As a result, the coarsely crushed pieces of calcined calcium shells are peeled off repeatedly during washing, and become finer particles (large → small) to enhance the polishing effect.

  Since most of the stains in the washing tub are acidic, a cleaner composed of a surfactant and an alkali builder causes a neutralization reaction. As a result, the alkalinity of the cleaning liquid decreases and the cleaning power decreases. However, if shell calcined calcium is used without the use of a surfactant or alkali builder, the calcined shell calcium has a solubility of about 2% in water, so that the alkalinity lost in the neutralization reaction is appropriately compensated, and the cleaning solution Since the alkalinity of itself is kept constant, the detergency is not reduced due to the decrease in alkalinity.

  The washing tub cleaner composition of the present invention preferably contains a water-soluble binder. When such a water-soluble binder is used, the water-soluble binder is eluted in water by contact with water, whereby the surface partially collapses and inorganic powder is released. Due to the release of the inorganic powder, the wall of the washing tub is physically rubbed and cleaned. As a quantity of a water-soluble binder, 2-10 weight part is preferable with respect to 100 weight part of inorganic powder, More preferably, it is 4-8 weight part. Specific examples of such a water-soluble binder include, for example, polyethylene glycol, polypropylene glycol, polypropylene glycol addition polymer (polyoxyethylene polyoxypropylene block polymer, etc.), polyoxyethylene alkyl ethers, polyvinyl alcohol, polyacrylic acid. Mention may be made of synthetic and natural water-soluble polymers such as soda, sodium alginate, gelatin and the like.

  If necessary, other components can be added to the washing tub cleaner composition of the present invention. For example, a deodorant, an antibacterial agent, a bactericidal agent, a proteolytic enzyme, and the like can be added. In addition, it is preferable to use things other than a chlorine type as an antibacterial agent and a disinfectant.

  The manufacturing method of the washing tub cleaner composition of the present invention is a method capable of manufacturing a cleaning agent comprising the above-described washing tub cleaner composition of the present invention. The production method of the present invention includes a step of adding a waxy substance comprising a hydrophobic substance having a melting temperature of 47 to 69 ° C. or a water-insoluble or poorly water-soluble substance to sodium percarbonate and coating it to form a granular material; And a step of mixing the sodium percarbonate powder, an inorganic powder containing at least shell calcined calcium and an inorganic powder containing a water-soluble binder.

  The coating of sodium percarbonate with a wax-like substance is performed, for example, by heating the sodium percarbonate powder and the wax-like substance to a temperature higher than the melting temperature of the wax-like substance, stirring for a predetermined time, and then stirring. It can implement by the method of granulating by cooling to. As for the diameter of a sodium percarbonate granular material, about 0.1-5 mm is preferable, More preferably, it is 0.5-3 mm. The heating of the wax-like substance with stirring is preferably at a temperature of about 70 to 90 ° C, preferably about 75 to 80 ° C. When the temperature exceeds 80 ° C, sodium percarbonate begins to decompose, but the upper limit of the preferable heating temperature range is set to 90 ° C. It does not occur. The lower limit of the heating temperature range is set to 70 ° C., because when paraffin having a melting point of 47 ° C. is used as a wax-like substance, coating may not be performed well if the heating temperature is lower than this.

  Stirring of the mixture of sodium percarbonate and wax-like substance can be performed, for example, with a planetary mixer or a container equipped with a stirrer such as a kneader, and it is preferable to stir at a low speed of 500 rpm or less.

  In the production method of the present invention, an inorganic powder containing at least shell calcined calcium is mixed with the sodium percarbonate powder produced as described above.

  In the production method of the present invention, the inorganic powder is preferably granulated by adding a water-soluble binder with stirring to an inorganic powder containing at least shell calcined calcium. Such a water-soluble binder acts as a binder for the inorganic powder, and as described above, when it comes into contact with water, it elutes into the water and partially disintegrates to release the inorganic powder. As described above, the amount of the water-soluble binder is preferably 2 to 15 parts by weight, more preferably 4 to 10 parts by weight with respect to 100 parts by weight of the inorganic powder.

  An inorganic granular material can be manufactured as follows, for example. For example, while stirring an inorganic powder heated to 60 ° C. to 70 ° C., an aqueous solution containing a water-soluble binder is poured onto this and granulated. The obtained granulated material is dried at a temperature of, for example, 50 to 100 ° C. to obtain an inorganic powder.

  By adding a deodorant, an antibacterial agent or a disinfectant to such an inorganic powder, these components may be contained in the washing tub cleaner composition of the present invention. In such a case, a deodorant, an antibacterial agent, or a bactericidal agent can be added to the water-soluble binder solution. As a compounding quantity of a deodorizer, 2-15 weight part is preferable with respect to 100 weight part of inorganic granular materials, More preferably, it is 3-10 weight part. Moreover, as a compounding quantity of an antibacterial agent and a disinfectant, 0.5-3 weight part is preferable with respect to 100 weight part of inorganic granular materials, More preferably, it is 1-2 weight part. By blending such an antibacterial agent and bactericidal agent, the cleaning effect can be further enhanced.

  In one preferred embodiment according to the present invention, polyethylene glycol (PEG) and polyoxyethylene alkyl ether dibasic acid ester are used as the water-soluble binder. The blending amount is preferably 90 to 96 mass% inorganic powder, 0 to 6 mass% PEG, 2 to 8 mass% polyoxyethylene alkyl ether dibasic acid ester, more preferably 95 to 96 mass% inorganic powder, PEG2 -4 mass%, polyoxyethylene alkyl ether dibasic acid ester 2-6 mass%. When using a deodorant, an antibacterial agent, a bactericidal agent, etc., it is added to these components in the above compounding amounts.

  The laundry tub cleaner mixture composition of the present invention may be in any shape such as powder or tablet.

  A paraffin wax having a melting point of about 60 ° C. is used as a wax-like substance, sodium percarbonate and paraffin wax are mixed at a ratio shown in Table 1, and coated with the paraffin wax. Carbonic powder granules ”). As sodium percarbonate, a commercial product (trade name: PC-P) manufactured by Nippon Peroxide Co., Ltd. was used.

  Put sodium percarbonate and paraffin wax in a container equipped with a stirrer so that the blending ratio shown in Table 1 is reached, warm to about 75 ° C. while stirring at low speed, raise the temperature, stir for about 1 hour, and melt the paraffin wax. Was uniformly coated on the surface of sodium percarbonate, and then gradually cooled with stirring so that the powder particles did not form dumplings, to obtain percarbonate powder particles.

次に、無機粉粒体として炭酸カルシウム粉粒体（以下、「炭カル粉粒体」という）を作製した。ホタテ焼成カルシウム８５質量％、（圭酸カルシウム＋炭酸マグネシウム＋クエン酸ナトリウム＋無水ホウ酸）７質量％、ＰＥＧ（重合度２０００）４質量％、ポリオキシエチレンアルキルエーテル２塩基酸エステル４質量％、これらの合計１００重量部に対し（消臭剤＋たんぱく分解酵素）５重量部を配合した炭カル粉粒体を作製した。まず（消臭剤＋たんぱく分解酵素）及び水溶性バインダーとしてのＰＥＧ及びポリオキシエチレンアルキルエーテル２塩基酸エステルを、６０〜７０℃に加熱溶融し混合した後、これに７０℃の温水を加えてスラリー状物とした。攪拌機付きの容器に、ホタテ焼成カルシウム粉末と、（圭酸カルシウム＋炭酸マグネシウム＋クエン酸ナトリウム＋無水ホウ酸）粉末を入れ、これに対し攪拌下に、得られたスラリー状物を添加し、粒子径０．１〜１０ｍｍの造粒物を得た。この造粒物を８５℃で６時間乾燥した後、粒径５ｍｍ以上の粒子をふるい分けし、炭カル粉粒体とした。

Next, calcium carbonate particles (hereinafter referred to as “charcoal cal particles”) were produced as inorganic particles. Scallop calcined calcium 85% by mass, (calcium oxalate + magnesium carbonate + sodium citrate + boric anhydride) 7% by mass, PEG (degree of polymerization 2000) 4% by mass, polyoxyethylene alkyl ether dibasic acid ester 4% by mass, Charcoal cal powder particles were prepared by blending 5 parts by weight of (deodorant + proteolytic enzyme) with respect to 100 parts by weight of these total. First, (deodorant + proteolytic enzyme), PEG as a water-soluble binder and polyoxyethylene alkyl ether dibasic acid ester are heated and melted at 60 to 70 ° C., and then mixed with warm water at 70 ° C. A slurry was obtained. Put scallop calcined calcium powder and (calcium oxalate + magnesium carbonate + sodium citrate + anhydrous boric acid) powder into a container equipped with a stirrer. A granulated product having a diameter of 0.1 to 10 mm was obtained. After this granulated product was dried at 85 ° C. for 6 hours, particles having a particle size of 5 mm or more were screened to obtain a charcoal powder.

  The charcoal cal particle and the percarbonate powder obtained as described above were mixed in the ratio shown in Table 2.

Supply 40 liters of water at a water temperature of 17 ° C. to the washing tub of a fully automatic washing machine with the residue of detergent residue, mold, sebum dirt, dark brown stains such as protein from the laundry on the outer wall of the washing tub,
The washing tank cleaner of the above example was added, and a washing course for about 40 minutes was carried out. After completion of the washing course, the bottom of the washing tub was observed for dehydration, followed by dehydration, water supply washing, dehydration, and rinsing. The outer wall of the washing tub was visually observed and the presence or absence of odor was confirmed.

  In an example in which the amount of paraffin wax coating on sodium percarbonate was as small as 5% by mass, it was observed that there was no residue at the bottom of the washing tub after completion of the cleaning course, and that the dirt on the outer wall of the washing tub was completely removed. . Further, there was no odor after rinsing, and the effect of adding a deodorant was confirmed.

  As is clear from the above, the washing tank cleaner of the present invention has a coating amount of paraffin wax on sodium percarbonate even in the shortest tank washing time of about 40 times in the tank washing course of a commercially available fully automatic washing machine. It was found that if the amount of was reduced, there was no residue due to residual unreacted sodium percarbonate or unreacted inorganic powder, and a sufficient tank cleaning effect was exhibited.

  As mentioned above, although this invention was demonstrated using embodiment, it cannot be overemphasized that the technical scope of this invention is not limited to the range as described in the said embodiment. It will be apparent to those skilled in the art that various modifications or improvements can be added to the above-described embodiments. Further, it is apparent from the scope of the claims that the embodiments added with such changes or improvements can be included in the technical scope of the present invention.

Claims (7)

Sodium percarbonate granules coated with a hydrophobic substance or a waxy substance consisting of a water-insoluble or poorly water-soluble substance,
An inorganic powder containing a shell-calcined calcium powder that is a random crushed piece having a particle size of 10 μm or more and 2 mm or less, and a water-soluble binder ,
Tub cleaner composition which is a mixture containing.   The laundry tank cleaner composition according to claim 1, wherein the inorganic powder is obtained by adding a water-soluble binder while stirring the inorganic powder. The granular material of sodium percarbonate, sodium percarbonate 85 to 98% by weight, according to claim 1 or 2, characterized in that it is formulated to be the ratio of the wax-like substance 15 to 2 wt% Laundry tub cleaner composition. The relative 50 to 80 wt% of the granular material of sodium percarbonate, are blended so that the ratio of the inorganic powder or granular material 50 to 20 wt%, the inorganic powder 100 weight water-soluble binder is an inorganic powder or granular material It contains so that it may become 2-15 weight part with respect to a part, The washing tub cleaner composition of any one of Claims 1-3 characterized by the above-mentioned.   The washing tub cleaner composition according to any one of claims 1 to 4, wherein the shell calcined calcium is scallop calcined calcium. Adding a waxy substance consisting of a hydrophobic substance or a water-insoluble or poorly water-soluble substance to sodium percarbonate and coating it into a powder;
Mixing the granules of the sodium percarbonate, the inorganic powder particles, each containing the inorganic powder containing calcined shell calcium is a random rough debris diameter water-soluble binder and particles 10μm or more and 2mm or less, the When,
A method for producing a washing tub cleaner composition comprising:   The method for producing a washing tub cleaner composition according to claim 6, wherein the inorganic powder is granulated by adding a water-soluble binder to the inorganic powder with stirring.