Briquette-type effervescent bath additives

Abstract

To provide a briquette-type foamable bathing agent with favorable storage stability, suppressing granules from cracking / chipping, and also suppressing floating bubbles and floating matters from occurring on a hot water surface when the briquette-type foamable bathing agent is dissolved in hot water.SOLUTION: Provided is a briquette-type foamable bathing agent, which is the briquette-type foamable bathing agent containing: an organic acid (A); a carbonate (B); at least one kind selected from a group consisting of a silicic anhydride and a calcium silicate (C); a 25°C liquid oily component (D); and a 25°C liquid nonionic surfactant (E). The total content of the component (D) and the component (E) in the briquette-type foamable bathing agent is 2 mass % or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a briquette-type effervescent bath additive. [Background technology]

[0002] Bath additives containing organic acids and carbonates that react in the bath to generate carbon dioxide gas are known to be effective in promoting blood circulation and prevent chills after a bath (see Patent Document 1). However, to achieve sufficient blood circulation-promoting effects, the foaming bath additives must be fully dissolved before bathing. However, since it takes about five minutes for the above-mentioned bath additives to completely dissolve, many people end up finishing their bath before they can fully achieve the desired effect.

[0003] Therefore, it is known that in order to shorten the dissolution time, it is effective to make the bath additives into a briquette form with a large specific surface area (see Patent Document 2). A known technology for briquette-type bath additives is a method for improving storage stability while containing more than 2% by mass and not more than 10% by mass of components that are liquid at 25°C by adjusting the average surface area (see Patent Document 3).

[0004] Furthermore, a briquette-type bath additive is also known that increases the size of the briquette particles to improve the foaming durability and that can be produced stably (see Patent Document 4). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-97238 [Patent Document 2] JP 2014-43410 A [Patent Document 3] Japanese Patent Application Laid-Open No. 2014-76978 [Patent Document 4] Japanese Patent Application Laid-Open No. 2013-253056 Summary of the Invention [Problem to be solved by the invention]

[0006] The bath additive compositions described in the above patent documents are based on a blend of an organic acid, a carbonate, an oil, and a nonionic surfactant. However, with the composition of Patent Document 2, it is difficult to increase the size of the briquette particles. While a high liquid content, as in Patent Document 3, allows for sufficient molding at low production speeds, the reduced fluidity of the liquid component leads to uneven molding pressure, resulting in the problem of increased cracking and chipping of particles due to the clamshell effect characteristic of briquettes as production speeds increase. The composition of Patent Document 4 also requires improved storage stability and further suppression of floating bubbles.

[0007] Therefore, the present invention aims to provide a briquette-type effervescent bath additive that is suppressed from cracking or chipping of particles, has good storage stability, and suppresses floating bubbles and floating matter on the surface of hot water when dissolved in hot water. [Means for solving the problem]

[0008] The present invention includes, for example, the following [1] to [5]. [1] Organic acid (A), Carbonate (B), (C) at least one selected from the group consisting of silicic anhydride and calcium silicate; An oily component (D) that is liquid at 25°C, and Nonionic surfactants (E) that are liquid at 25°C The briquette type effervescent bath additive contains the above component (D), wherein the total content of component (D) and component (E) in the briquette type effervescent bath additive is 2 mass % or less. [2] Briquette-type effervescent bath additives according to [1], having a major axis of 15 to 25 mm and a thickness of 8 to 13 mm. [3] The briquette-type foaming bath additive of [1] or [2], wherein component (E) is at least one selected from the group consisting of polyethylene glycol fatty acid esters, polyoxyethylene glycerin fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbit fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene glycol, ethylenediaminetetrapolyoxyethylene polyoxypropylene, and polyoxyethylene hydrogenated castor oil. [4] The briquette type effervescent bath additive of any one of [1] to [3], wherein the component (A) contains succinic acid, and the succinic acid content in the briquette type effervescent bath additive is 10 to 30 mass %. [5] A briquette-type effervescent bath additive according to any one of [1] to [4], which has an effervescent duration of 100 seconds or less in 40°C water. [Effects of the Invention]

[0009] The briquette type effervescent bath additive of the present invention is inhibited from cracking and chipping of particles, has good storage stability, and inhibits floating bubbles and floating matter on the surface of hot water when dissolved therein. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention relates to a briquette-type effervescent bath additive containing an organic acid (A), a carbonate (B), at least one component (C) selected from the group consisting of silicic anhydride and calcium silicate, an oil component (D) that is liquid at 25°C, and a nonionic surfactant (E) that is liquid at 25°C, wherein the total content of components (D) and (E) in the briquette-type effervescent bath additive is 2% by mass or less.

[0011] (A)Organic acid The briquette-type effervescent bath additive contains an organic acid (A). Such organic acids are preferably solid at room temperature (25°C), and examples thereof include malic acid, fumaric acid, succinic acid, citric acid, tartaric acid, malonic acid, pyrrolidonecarboxylic acid, monosodium citrate, monosodium succinate, monosodium fumarate, adipic acid, tartaric acid, benzoic acid, salicylic acid, glutaric acid, glycolic acid, lactic acid, glyceric acid, and pyruvic acid. There are no particular limitations on the stereoisomer of malic acid, and any isomer may be used. These may be used alone or in combination of two or more. Among these, from the viewpoints of ensuring the amount of carbon dioxide gas generated and maintaining good storage stability, it is preferable to contain at least one selected from the group consisting of fumaric acid, malic acid, and succinic acid, and it is more preferable to contain succinic acid. It is even more preferable to use a combination of three types of acid: malic acid, fumaric acid, and succinic acid.

[0012] The content of organic acid (A) in 100% by mass of the briquette-type effervescent bath additive is preferably 30 to 60% by mass, more preferably 40 to 50% by mass. When the amount of organic acid is within the above range, the amount of carbon dioxide gas is sufficient, foaming power is good, storage stability is good, and in the production process, roll adhesion and leaks are unlikely to occur during compression molding when making into a briquetting agent, burrs and the like are suppressed during crushing, and further, the problem of generation of insoluble matter during use does not occur, which is preferable. When the organic acid contains succinic acid, the content of succinic acid in 100% by mass of the briquette-type effervescent bath additive is preferably 10 to 30% by mass, more preferably 15 to 25% by mass. When the amount of succinic acid is within the above range, it is possible to obtain good foaming while suppressing the stuffiness that occurs when foaming, which is characteristic of succinic acid.

[0013] (B) Carbonate The briquette-type effervescent bath additive contains a carbonate (B). The carbonate can generate carbon dioxide gas together with the organic acid (A). Examples of carbonates include dialkali metal carbonates such as sodium carbonate and potassium carbonate; monoalkali metal carbonates such as sodium bicarbonate and potassium bicarbonate; carbonates of divalent or higher metals such as magnesium carbonate and calcium carbonate; ammonium carbonate, sodium sesquicarbonate, etc. These may be used alone or in combination of two or more. Among these, from the viewpoint of ease of availability, at least one selected from the group consisting of sodium carbonate and sodium bicarbonate is preferred, and it is more preferred to use two types of sodium carbonate and sodium bicarbonate in combination.

[0014] The content of carbonate (B) in 100% by mass of the briquette-type effervescent bath additive is preferably 30 to 65% by mass, more preferably 35 to 50% by mass. When the amount of carbonate is within the above range, the amount of carbon dioxide gas is sufficient, resulting in good effervescent power and good storage stability.

[0015] The average particle size of the carbonate (B) is preferably 100 to 450 μm, and more preferably 250 to 400 μm. When the average particle size is within the above range, the occurrence of clamshells is suppressed and sufficient crushing strength can be ensured. The average particle size is a value measured by a laser diffraction / scattering method, and if it is listed in a catalog, this value is used.

[0016] (C) at least one selected from the group consisting of silicic anhydride and calcium silicate The briquette-type effervescent bath additive contains at least one kind (C) selected from the group consisting of silicic anhydride and calcium silicate, of which silicic anhydride is preferred. The content of at least one selected from the group consisting of silicic anhydride and calcium silicate (C) in 100% by mass of the briquette-type effervescent bath additive is preferably 0.05 to 1.5% by mass, more preferably 0.1 to 1% by mass, and even more preferably 0.15 to 0.5% by mass. When the content of at least one selected from the group consisting of silicic anhydride and calcium silicate is within the above range, a decrease in the fluidity and binding strength of the raw material powder before molding can be suppressed, resulting in good moldability.

[0017] (D) Oily components that are liquid at 25°C The briquette-type effervescent bath additive contains an oily component (D) that is liquid at 25°C. The oily component (D) that is liquid at 25°C is not particularly limited, and examples thereof include hydrocarbons such as liquid paraffin, light liquid isoparaffin, squalane, squalene, and bristleton; fatty acid esters such as octyl palmitate, isopropyl palmitate, isostearyl palmitate, isopropyl myristate, myristyl myristate, isocetyl myristate, octyldodecyl myristate, cetyl octanoate, caprylic / capric triglyceride, decyl oleate, isocetyl stearate, and isotridecyl isononanoate; higher alcohols such as lauryl alcohol, oleyl alcohol, and hexyldodecanol; lemon oil, yuzu oil, rose oil, bergamot oil, calamus oil, lavender oil, orange oil, grapefruit oil, mandarin oil, geranium oil, sage oil, eucalyptus oil, neroli oil, patchouli oil, and cloves. Natural fragrances such as laurel oil, nutmeg oil, cedarwood oil, peppermint oil, spearmint oil, juniper berry oil, almond oil, chamomile oil, elemi oil, vetiver oil, camphor oil, lime oil, peppermint oil, jasmine oil, cypress oil, turpentine oil, Japanese cypress oil, lavandin oil, clove oil, thyme oil, rosemary oil, and pine oil; terpene-based fragrances such as α-pinene, β-pinene, d-limonene, camphene, and terpinene; alcohol-based fragrances such as leaf alcohol, sandalol, evanol, ambrinol, amber core, citronellol, geraniol, nerol, linalool, tetrahydrolinalool, dihydromyrcenol, ethyl linalool, isopulegol, menthol, terpineol, dihydroterpineol, farnesol, santalol, vetiverol, β-phenylethyl alcohol, and bacdanol;Alcohol-based fragrances such as aldehyde C-8, aldehyde C-9, aldehyde C-10, aldehyde C-11, aldehyde C-12, green leaf aldehyde, citronellal, citral, α-methylenecitronellal, isocyclocitral, dimethyltetrahydrobenzaldehyde, benzaldehyde, phenylacetaldehyde, α-amyl cinnamic aldehyde, α-hexyl cinnamic aldehyde, vanillin, ethyl vanillin, heliotropin, helional, cis-jasmone, dihydrojasmone, nectaryl, damascone, ionone, iso-e-super, calone, l-carvone, menthone, etc. Examples of suitable fragrances include synthetic fragrances such as aldehyde-ketone fragrances; blended fragrances that are any combination of the above natural fragrances and synthetic fragrances; natural oils and fats such as soybean oil, jojoba oil, rice bran oil, olive oil, and coconut oil, hardened oils obtained by hydrogenating these natural oils, and glycerides such as myristic acid glyceride; silicone oils such as methylpolysiloxane, methylcyclopolysiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, and various modified silicones; and higher fatty acids such as oleic acid, linoleic acid, linolenic acid, lanolinic acid, and isostearic acid, which may be used alone or in combination of two or more.

[0018] Among these, fatty acid esters and natural fats and oils are preferably used, and in particular, isopropyl palmitate, isopropyl myristate, octyldodecyl myristate, jojoba oil, etc. are more preferably used because of their excellent feel on the skin during bathing. In addition, it is preferable to incorporate a fragrance, such as the above-mentioned natural fragrances, synthetic fragrances, and blended fragrances, because the fragrance is imparted to the bath upon foaming.

[0019] The content of the oily component that is liquid at 25°C in 100% by mass of the briquette-type effervescent bath additive is preferably 0.1 to 5.0% by mass, more preferably 0.3 to 2.0% by mass, and even more preferably 0.5 to 1.3% by mass. When the amount of the oily component that is liquid at 25°C is within the above range, there are no problems with storage stability or the feel when used in the bath, and when made into briquettes, there is no decrease in productivity due to insufficient strength.

[0020] (E) A nonionic surfactant that is liquid at 25°C The briquette-type foaming bath additive contains a nonionic surfactant (E) that is liquid at 25°C. Examples of nonionic surfactants (E) that are liquid at 25°C include polyethylene glycol fatty acid esters such as polyoxyethylene glycol monolaurate and polyoxyethylene glycol monooleate; polyoxyethylene glycerin fatty acid esters such as polyoxyethylene (caprylic / capric) glyceryl and polyoxyethylene glyceryl oleate; sorbitan fatty acid esters such as sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, sorbitan monoisostearate, sorbitan sesquiisostearate, and sorbitan coconut oil fatty acid; polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan isostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan coconut oil fatty acid esters; Examples of suitable hydroxyl groups include polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbit monolaurate and polyoxyethylene sorbitan tetraoleate; polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene oleyl ether; polyoxyethylene polyoxypropylene glycol; ethylenediaminetetrapolyoxyethylene polyoxypropylene; and polyoxyethylene hydrogenated castor oil. These may be used alone or in combination of two or more. Among these, polyoxyethylene glycerin fatty acid esters, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and polyoxyethylene alkyl ethers are preferred, with polyoxyethylene sorbitan fatty acid esters and polyoxyethylene glycerin fatty acid esters being more preferred, polyoxyethylene sorbitan tetraoleate and polyoxyethylene caprylic / capric glyceryl being even more preferred, and polyoxyethylene caprylic / capric glyceryl being particularly preferred.

[0021] The content of the nonionic surfactant (E) that is liquid at 25°C in 100% by mass of the briquette-type effervescent bath additive is preferably 0.1 to 2.0% by mass, more preferably 0.1 to 1.5% by mass, and even more preferably 0.2 to 1.0% by mass. When the amount of the surfactant that is liquid at 25°C is within the above range, storage stability is good and floating bubbles and floating matter can be suppressed.

[0022] The total amount ((D) + (E)) of the oil component (D) that is liquid at 25°C and the nonionic surfactant (E) that is liquid at 25°C in 100% by mass of the briquette-type foaming bath additive is 2% by mass or less, preferably 0.5 to 2% by mass, more preferably 1 to 2% by mass, and even more preferably 1.6 to 2% by mass. If a liquid component is added in excess of the above range, the fluidity of the raw material powder before compaction will decrease, preventing uniform pressure from being applied during compression, resulting in a decrease in compactibility and making it more likely that floating matter will appear on the oil surface.

[0023] The mass ratio ((D) / (E)) of the oil component (D) that is liquid at 25°C to the surfactant (E) that is liquid at 25°C contained in the briquette-type foamable bath additive of the present invention is preferably 0.4 to 10, more preferably 0.5 to 5, and even more preferably 0.7 to 2. When (D) / (E) is within the above range, floating bubbles are unlikely to form on the oil surface, sufficient moldability can be obtained, and the warming effect of the oil component can be obtained.

[0024] <Other ingredients> (F) Other inorganic salts The briquette-type effervescent bath additive may further contain an inorganic salt other than silicic acid anhydride and calcium silicate. Examples of other inorganic salts include sodium sulfate, magnesium sulfate, sodium chloride, ammonium chloride, sodium nitrate, potassium nitrate, calcium nitrate, sodium polyphosphate, sodium phosphate, sodium iron sulfate phosphate, calcium oxide, magnesium oxide, aluminum sulfate, sodium thiosulfate, potassium chloride, potassium sulfide, alum, and metasilicic acid. These may be used alone or in combination of two or more. Among these, sodium sulfate, magnesium sulfate, and sodium chloride are preferred, and sodium sulfate is more preferred.

[0025] When other inorganic salts are blended, the content of the inorganic salts (excluding silicic anhydride and calcium silicate) in 100% by mass of the briquette-type effervescent bath additive is preferably 0.1 to 20% by mass, more preferably 1 to 18% by mass, and even more preferably 1 to 15% by mass. When the amount of inorganic salt is within the above range, moldability is good and the bath additive does not become too hard, which does not interfere with effervescence and does not cause the problem of undissolved salts when dissolved in hot water.

[0026] The briquette type effervescent bath additive may further contain any known ingredients that are added to bath additives, as long as the effects of the present invention are not impaired. For example, lubricants such as polyethylene glycol, talc, magnesium stearate, etc.; water-soluble polymers such as polyvinylpyrrolidone, methylcellulose, ethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, dextrin, sodium carboxymethylcellulose, starch, cationic cellulose, etc.; moisturizers such as sodium glutamate, sodium ascorbate, collagen, sodium hyaluronate, sodium chondroitin sulfate, etc.; herbal medicines such as Atractylodes Root, Atractylodes Root, Valerian, Magnolia, Cnidium, Cnidium, Orange Peel, Angelica Root, Powdered Ginger, Carrot, Cinnamon Bark, Peony, Mint Leaf, Scutellaria Root, Chinese Angelica, Poria Coccinea, Poria Root, Dokkatsu Root, Calamus, Root, Angelica Root, Saffron, Phellodendron Bark Extract, Citrus Fruit, Fennel, Citrus Fruit Powder, Chamomile, Melissa, Rosemary, Horse Chestnut, Yarrow, Arnica, etc.; Examples of ingredients include, but are not limited to, alcohols such as ethanol, stearyl alcohol, isopropyl alcohol, cetyl alcohol, and hexadecyl alcohol; polyhydric alcohols such as glycerin, propylene glycol, and sorbitol; titanium oxide, zinc oxide, talc, sulfur, mineral sand, hot spring deposits, casein, neutral clay, sodium salicylate, sodium carboxymethylcellulose, egg yolk powder, Iri bran, mica powder, skim milk powder, sterilizing preservatives, metal sequestering agents, pigments, and other ingredients necessary for formulation.

[0027] <Manufacturing method> In producing the briquette-type effervescent bath additive, first, the above-mentioned essential components (A) to (E) and optional components added as needed are mixed and pulverized using a Henschel mixer, high-speed mixer, universal mixer, SV mixer, vertical granulator, Ribocone mixer, or the like to prepare a compounded bulk.

[0028] The briquetting agent is then obtained by supplying this blended bulk to a briquetting machine and compression molding it to obtain a sheet-like primary compact in which multiple briquette particles are molded into a sheet via connecting parts, and by further crushing this, the briquetting agent is obtained.

[0029] The roll rotation speed in the briquetting machine is preferably 5 to 35 rpm, more preferably 15 to 30 rpm. The screw rotation speed in the briquetting machine is preferably 20 to 160 rpm, more preferably 50 to 130 rpm. When the roll rotation speed and screw rotation speed are within the above ranges, it is possible to produce briquettes that have excellent appearance and sufficient strength while ensuring a high production rate.

[0030] When the blended bulk is fed to the briquetting machine, the linear pressure between the rolls is preferably 10 to 25 kN / cm, more preferably 13 to 23 kN / cm, and even more preferably 15 to 20 kN / cm, by adjusting the size of the clearance between the rolls and the pressure of the feed screw. Within this range, the particles are free of burrs and chips during crushing, resulting in an excellent appearance, and roll adhesion and leakage during compression molding are suppressed, improving production efficiency.

[0031] <Dosage form> Briquette-type effervescent bath additives are molded into shapes such as pillow, lens, almond, prism, rod, and finger shapes. Preferably, the major axis is 15 to 25 mm and the thickness is 8 to 13 mm, and more preferably, the major axis is 18 to 23 mm and the thickness is 9 to 11 mm. Here, the major axis of the briquette agent refers to the maximum length of the briquette particle in the horizontal direction of the sheet-like primary compact, and the briquette thickness refers to the maximum length of the briquette particle in the vertical direction of the sheet-like primary compact. By achieving these sizes, the amount of dissolved carbon dioxide can be increased, resulting in an excellent hot bath effect when used as a bath additive. Of the above shapes, pillow and almond shapes are preferred from the viewpoint of moldability.

[0032] (Surface area of briquette-type effervescent bath additives) Briquette-type effervescent bath additives have a surface area of 350 to 850 mm 2 / piece is preferable, 450~750mm 2 When the amount is within the above range, foaming does not occur suddenly, and gentle, long-lasting foaming can be obtained.

[0033] (Crushing strength of briquette-type bath additives) Furthermore, the crushing strength of the resulting briquette-type effervescent bath additive immediately after production is preferably 80N or more, and more preferably 90N or more. Within this range, gentle, long-lasting effervescence can be obtained. This is also preferable because it reduces the occurrence of chipping during deburring during crushing, improves appearance, and improves production efficiency. In the present invention, the crushing strength is a value determined by the following measurement method. Using a Kiya hardness tester, place the briquette-type effervescent bath additive on a stand, and lower a rod with a φ5mm tip vertically from the pocket mating surface while pressing it against the briquette-type effervescent bath additive, and measure the load value when the briquette-type effervescent bath additive breaks.

[0034] (Bubble duration of briquette-type bath additives) Briquette-type effervescent bath additives preferably have a foaming duration of 100 seconds or less in water at 40°C, more preferably 90 seconds or less, and even more preferably 80 seconds or less. In the present invention, "foaming duration" refers to the time required from the time 50 g of briquette-type effervescent bath additive is added to 200 L of hot water at 40°C until the foaming preparation is completely dissolved. This does not include the time required for the preparation to dissolve after foaming has finished. If the foaming duration is within the above range, foaming will be completed while you are bathing, and you can fully enjoy the effects of the briquette-type effervescent bath additive while bathing. [Example]

[0035] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The following commercially available components were used in the examples. Polyethylene glycol 6000: PEG6000 (manufactured by Toho Chemical Industry Co., Ltd.) Fragrance: A citrus-based blend of fragrance ingredients (manufactured by Takasago International Corporation) consisting solely of oil-based fragrance ingredients that are liquid at 25°C, including d-limonene. Polyoxyethylene (caprylic / capric acid) glyceryl: Softigen 767 (manufactured by IOI Oleo) Polyoxyethylene sorbitol tetraoleate: NIKKOL (registered trademark) GO-430NV (manufactured by Nikko Chemicals Co., Ltd.)

[0036] [Examples 1 to 6 and Comparative Examples 1 to 4] A total of 50 kg of the formulation shown in Table 1 was mixed in an SV mixer until uniform, preparing a bulk, which was then fed into a briquetting machine to form a briquette. A roll with round-corner pillow-shaped pockets measuring 20 mm in diameter and 3.5 mm in depth was used, with the roll rotation speed set to 15 rpm and the screw rotation speed set to 60 rpm (assuming a speed of 300 kg / h). The clearance between the rolls and the pressure of the feed screw were adjusted to a linear pressure of 20 kN / cm between the rolls. After forming the briquette, it was crushed using a vibrating sieve to obtain a foaming briquette-type bath additive with a diameter of 20 mm and a thickness of 9.4 mm. The surface area of this foaming briquette-type bath additive was 685 mm. 2 / piece.

[0037] The results of the above evaluations are shown in Table 1. The blend amounts in the table are in mass %. The average particle size of sodium carbonate is 120 μm, and that of sodium bicarbonate is 300 μm. The average particle size was measured by laser diffraction / scattering method using a HORIBA LA-960 laser diffraction / scattering particle size distribution analyzer.

[0038] [evaluation] The briquette-type effervescent bath additives obtained in the examples and comparative examples were evaluated as follows. Evaluations of "particle state," "storage stability," and "water surface state" were carried out by 20 male and female monitors according to the following evaluation criteria. The evaluation results were decided by discussion among all monitors. The "grain state" and "crushing strength" are indicators of moldability.

[0039] (Grain state) Briquette-type effervescent bath additives were continuously produced under the conditions described in the examples, and 1 kg of the molded pellets were visually evaluated for cracks, chips, and clamshells according to the following criteria. Note that clamshells refer to a state in which the center of the briquette is cracked due to air entrapment or other reasons, leaving a shape resembling an open shell.

[0040] [Evaluation criteria] ◎: No cracks or chips are found in the grains, and only a small amount of clamshells are formed. 〇: There are a few cracked or chipped grains, but some clamshells have occurred. △: There are a relatively large number of grains with cracks and chips, and many clamshells have occurred. ×: Many grains were cracked and chipped, and many clamshells were also formed.

[0041] (crushing strength) The crushing strength (unit: N) of the formulation immediately after production was determined using a Kiya hardness tester (product name: KHT-40N, manufacturer: Fujiwara Seisakusho Co., Ltd.) by placing the briquette-type effervescent bath additive on a stand, pressing a rod with a φ5mm tip vertically against the pocket mating surface while lowering it, and measuring the load value when the briquette-type effervescent bath additive broke. If the crushing strength is 80N or more, the moldability is good.

[0042] (Storage stability) 50 g of the preparation was packaged in an aluminum pillow and placed in a thermostatic bath at 50°C. After 30 days, the condition of the aluminum pillow was visually evaluated according to the following evaluation criteria. [Evaluation criteria] 〇: No bulging of the aluminum pillow △: Slight swelling observed in the aluminum pillow ×: Blisters observed in aluminum pillow

[0043] (Foam duration) 50 g of the preparation was poured into 200 L of bath water at 40°C, and the time (seconds) required from the time of pouring until the preparation was completely dissolved accompanied by foaming was measured. The effervescent duration was determined to be good if it was 100 seconds or less, better if it was 90 seconds or less, and even better if it was 80 seconds or less, because ensuring that the bathing time is long enough for the preparation to be completely dissolved and for the carbon dioxide gas to be sufficiently dissolved enhances the effect of the bath.

[0044] (Water surface condition) 50 g of the preparation was poured into 200 L of bath water at 40°C, and the state of the water surface immediately after foaming of the preparation was completed was visually observed and evaluated according to the following criteria. ◎: No noticeable bubbles or white floating matter 〇: Floating bubbles and white floating matter are hardly noticeable. △: Floating foam and white floating matter are a bit noticeable ×: Floating bubbles or white floating matter are noticeable

[0045] [Table 1]

[0046] Examples 1 to 4 have good granular condition and a crushing strength of 80N or more, and therefore have good moldability, good storage stability and foaming rate time, and are less likely to produce floating bubbles or particles on the surface of the hot water. Comparisons between Example 1 and Comparative Example 1, and Example 2 and Comparative Example 2 show that if the briquette-type effervescent bath additive does not contain silicic anhydride, the particle condition is poor, the crushing strength is reduced, and moldability is poor. Comparing Examples 1 to 4 with Comparative Example 3, it can be seen that when the total amount of liquid components, which is the sum of the liquid oily component and the surfactant, exceeds 2 mass%, the particle condition is poor, the crushing strength is reduced, moldability is poor, and the surface condition of the molten metal is also poor. Comparing Examples 1 to 4 with Comparative Example 4, it can be seen that if the briquette-type foaming bath additive does not contain a liquid surfactant, the granular condition is poor, the crushing strength is reduced, moldability is poor, and the storage stability and water surface condition are also poor.

Claims

1. organic acid (A), Carbonate (B), Silica anhydride (C), An oil component (D) that is liquid at 25°C, and Nonionic surfactant (E) that is liquid at 25°C A briquette-type effervescent bath additive containing the component (D) and the component (E), wherein the total content of the component (D) and the component (E) in the briquette-type effervescent bath additive is 2% by mass or less, The component (A) contains succinic acid, and the succinic acid content in the briquette type effervescent bath additive is 10 to 30 mass %.

2. 2. The briquette-type effervescent bath additive according to claim 1, wherein the major axis is 15 to 25 mm and the thickness is 8 to 13 mm.

3. 3. The briquette-type effervescent bath additive according to claim 1, wherein component (E) is at least one selected from the group consisting of polyethylene glycol fatty acid esters, polyoxyethylene glycerin fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbit fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene glycol, ethylenediaminetetrapolyoxyethylene polyoxypropylene, and polyoxyethylene hydrogenated castor oil.

4. The briquette type effervescent bath additive according to any one of claims 1 to 3, wherein the effervescent duration in water at 40°C is 100 seconds or less.

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