JP4822299B2 - Soft capsule and method for producing the same - Google Patents

Description

  The present invention relates to a soft capsule having carrageenan in the composition of the capsule film and a method for producing the same.

Soft capsules are widely used in fields such as pharmaceuticals, cosmetics, and health foods. In recent years, the application has been expanded, and not only a technique for increasing the strength of the capsule film to make it difficult to break, but also a technique for making it easy to break, has been demanded.
Examples of the use of the technology to make it easy to break include embedding a capsule containing fragrances in a cigarette filter to break the capsule when smoking and enjoy the scent, and enjoy the sound and feel when the capsule breaks Etc. However, there is no prior art that suitably realizes this.

Generally, in order to make the capsule easy to break, the capsule film is made thin. For example, Patent Document 1 discloses that in a soft capsule having a seam, an adhesive surface of the seam is inclined, or a fringe is provided using a special mold so that only the adhesive part is thickened. Patent Document 2 discloses that in a soft capsule with a seam for bathing agent, it is possible to prevent the adhesion portion of the film from being locally thinned.
However, when the capsule film is made thinner, the hardness is lowered, but the capsule film itself has a corresponding plasticity, so that the capsule is deformed without cracking comfortably.

In order to avoid the problem, if the content of the gelling agent in the capsule film is increased, the viscosity becomes high and capsule production becomes difficult.
For example, it is known to use carrageenan as a gelling agent for a film. However, carrageenan has a high thickening effect and has a high gelation rate, so that it contains a large amount of carrageenan, which hinders encapsulation. That is, when the content of carrageenan is high, the capsules have poor moldability such as poor sphericity and ease of solidification at the tip of the injection nozzle due to high viscosity and rapid gelation, and thus preferred capsules could not be produced. .

As a countermeasure, for example, in Patent Document 3, starch, dextrin, non-gelling polysaccharide or the like is blended with carrageenan as a base or filler for increasing the solid content concentration of the film, thereby reducing viscosity and gelling. It is disclosed to reduce the speed.
However, not only when gelatin, which is known to have high hygroscopicity, is used for the film, but also when carrageenan, which is considered to be less hygroscopic than gelatin, is used, starch, dextrin, non-gelling When sugars and the like are added, it becomes susceptible to humidity, and it is not possible to stably obtain additional values such as ease of cracking with fingers after drying, sound and touch when cracking, over time.

In addition, Patent Documents 4 to 5 disclose those having a high carrageenan content in the capsule film, but there is no particular mention of the action and effect thereof. Patent Document 4 describes the use of sodium citrate and a carbonate neutralizing agent and the like. The acid promotes the decomposition of carrageenan, but the neutralizing agent is disclosed to suppress deterioration. It stays.
Patent Document 6 describes that potassium citrate and the like are added to carrageenan, but the disclosure is limited to adjusting viscosity and elasticity.
Patent Documents 7 to 14 disclose that a capsule is embedded in a cigarette filter, but the manufacturability of the capsule, storage stability, ease of cracking with fingers after drying, Added value such as touch is not considered.

JP 2001-288075 A JP-A-5-51315 US6214376B1 Special table 2002-517378 Special table 2007-526210 JP 2008-237572 A Special table 2009-504175 Special table 2008-528053 Special table 2008-546400 JP 2008-43347 A Special table 2007-507230 Special table 2007-520204 JP2003-304856 JP-A-64-60363

  Therefore, the present invention maintains the hardness by increasing the content of carrageenan in the composition of the capsule film, while reducing the thickening effect and gelation rate by carrageenan, stabilizing the capsule productivity, and preservability. Another object of the present invention is to provide a soft capsule capable of obtaining added values such as ease of cracking with fingers after drying, sound and touch when cracked, and a method for producing the same.

  In order to solve the above problems, the soft capsule of the present invention is characterized in that the composition of the capsule film has at least carrageenan, an acidic pH adjuster, and a neutralizer.

Here, the composition of the capsule film may contain any one of a plasticizer, an alginate, a saccharide, a dextrin, a starch, and a processed starch.
For example, the plasticizer contributes to improvement of moldability, and the alginates contribute to improvement of durability against humidity. The alginates may be simply added, but may be subjected to gelation in an aqueous solution containing calcium ions.

  A carrageenan having a viscosity adjusted by decomposition with an acidic pH adjuster may be used to contribute to improvement of moldability.

  The content of carrageenan in the composition of the capsule film may be 50% or more, preferably 70% or more. This content rate is a value excluding moisture.

  The coating rate may be 5 to 20%, preferably 7 to 15%. In addition, this film | membrane rate is a ratio of the mass of the capsule film | membrane which occupies for the whole capsule.

  The thickness of the capsule film may be 40 μm or less, preferably 30 μm or less.

  The hardness of the capsule film is preferably 5 to 40N. If it is less than 5N, inconvenience is likely to occur during the manufacturing process, and if it exceeds 40N, the difficulty increases when crushing with a finger. More preferably, it may be 10 to 20N. In this case, a general “Kiya hardness tester” can be used for the hardness measurement. The “Kiya hardness tester” records a pressure when a sample is placed on a sample stage, a cylindrical pressurizer is gradually lowered from above, and bursts. In the examination in the present invention, “Fujiwara Seisakusho, Kiya type digital hardness tester KHT-20N type” was used. This apparatus is a type in which a cylindrical pressurizer is electrically driven at a constant speed, and has a lifting speed of 1 mm / second, a pressure surface diameter of 5 mm, and a sample stage diameter of 25 mm.

  The diameter of the capsule is preferably 0.5 to 15 mm. When the diameter is smaller than 0.5 mm, it is difficult to hold the finger because it is crushed by a finger. If the diameter exceeds 15 mm, the internal capacity increases, and there is a risk of contaminating the surroundings when crushed with a finger. More preferably, it may be 1 to 8 mm.

As a capsule, it can be usefully applied to a seamless capsule.
The seamless capsule can be produced, for example, by a conventionally known dropping method. A typical example of the dropping method uses a concentric double nozzle, the coating liquid containing the gelling agent aqueous solution and the like from the outer nozzle, the contents from the inner nozzle, and the coating liquid as a double droplet at the same time. It is a method of producing a seamless capsule by dripping into a liquid to be converted into a capsule film by gelling and curing the outer film liquid. It may also be called a submerged curing method or an orifice method. It is also possible to use multiple nozzles of triple or more instead of double nozzles.

  The excessive viscosity may be suppressed by setting the content of alginate to 50% or less of carrageenan.

  A coating made of waxes or waxes may be applied to contribute to moisture resistance.

  The method for producing a soft capsule of the present invention comprises a step of decomposing carrageenan, which is a composition of the capsule film, with an acidic pH adjuster and a step of stopping the decomposition with a neutralizing agent in the method for preparing the film. Features. That is, the molecular weight and the viscosity are reduced by decomposition with an acid, and the decomposition is stopped by neutralization with an alkali, so that the desired viscosity can be set.

  Here, the degree of decomposition of carrageenan may be adjusted to a preferred viscosity according to the contents of the capsule. The preferable viscosity in this case is 30 to 150 mPa · s, more preferably 50 to 100 mPa · s. Viscosity was measured using a “C-type viscometer / CVR-20 manufactured by Tokimec Co., Ltd.” at a liquid temperature of 75 ° C. and a rotor no. 0 is used, and when it exceeds 100 mPa · s, the rotor No. 1 can be used to measure.

  Alginates may be added as a composition of the capsule film, and the alginates may be gelled in an aqueous gelling aid solution containing calcium ions to contribute to moisture resistance.

  The gelling aid aqueous solution may contain ethanol and contribute to the washing of the capsule.

  According to the present invention, carrageenan can be decomposed with an acidic pH adjusting agent, and the decomposition can be stopped with a neutralizing agent to adjust to a desired viscosity. In addition, the gelation rate by carrageenan is reduced, and the manufacturability of the capsule can be stabilized. Hardness can be maintained by increasing the content of carrageenan, it can be easily broken by fingers, and it can provide added value such as sound and feel when cracked.

Below, embodiment of this invention is described based on the Example shown in Tables 1-8. Note that the embodiment is not limited to the following examples, and can be appropriately changed in design using a conventionally known technique such as the above-mentioned document without departing from the gist of the present invention.
The present inventor arrived at the present invention based on the knowledge that a useful result was obtained by treating carrageenan with an acid in the production of soft capsules.

The soft capsule according to the present invention has at least carrageenan, an acidic pH adjuster, and a neutralizing agent in the capsule film composition.
The main component carrageenan can be subdivided according to the type and raw materials such as κ, ι, λ, etc. Basically, among these, the κ type is essential, and both ι and λ can be used as appropriate. .
For example, in the Japanese Food Sanitation Law, purified carrageenan, processed Yukema algae and Yukema algae are defined as carrageenans that can be used as food additives, but any of these can be used and used as food additives. This depends on the laws and regulations of each country where the service is provided.
In the prior art, gelatin is mainly used as a main component, but those having carrageenan as a main component have advantages such as low adhesion and less influence by humidity.

Carrageenan, on the other hand, has a thickening effect and quick gelation, so if the content is increased, it becomes difficult to form capsules, such as solidification near the injection nozzle and deterioration of sphericity. become. On the other hand, when the content is lowered, the solid content of the film is reduced, the capsule strength is lowered, and there are problems such as inability to withstand the drying process. In general, when the coating rate is low, it becomes difficult to form capsules.
On the other hand, in the present invention, the problem caused by carrageenan is improved by containing any one or both of inorganic acid and organic acid and various cations, and the obtained capsule is subjected to humidity conditions. In addition, the hardness was a constant hardness of 40 N or less, and it could be easily broken with fingers, and the click sound and feel produced when the capsule was broken became comfortable. In addition, since a substantially spherical seamless capsule can be obtained, a preferable molding is easy from the viewpoint of beauty.

The content of carrageenan in the composition of the capsule film is 50% or more, preferably 70% or more. The coating rate is 5 to 20%, preferably 7 to 15%.
Even with such a low coating rate, good capsules without rupture or deformation were obtained in the drying process and the transport process.
From the viewpoint of manufacturability and ease of cracking, the capsule film has a hardness of 5 to 40 N, preferably 10 to 20 N, and the capsule film has a thickness of 40 μm or less, preferably 30 μm or less. From this point, it is preferable that the diameter of the capsule is 0.5 to 15 mm, preferably 1 to 8 mm.

The production of soft capsules includes a step of decomposing carrageenan, which is a composition of the capsule film, with an acidic pH adjuster, and a step of stopping the decomposition with a neutralizing agent. That is, the molecular weight and viscosity are reduced by decomposition with an acid, and the decomposition is stopped by neutralization with an alkali, and the desired viscosity is set.
The degree to which carrageenan is decomposed is adjusted to a preferable viscosity by taking into account the contents of the capsule.

  Acidic pH adjusters include citric acid, malic acid, acetic acid, formic acid, oxalic acid, lactic acid, phytic acid, hydrochloric acid, etc., weak acids / strong acids, organic acids / inorganic acids, neutral potassium phosphate, etc. Any solution can be used as long as the liquid in the region can be changed to the acidic region.

  As the neutralizing agent, an alkali corresponding to the acidic pH adjusting agent to be used can be used. For example, it is possible to neutralize the acid range liquid such as dipotassium hydrogen phosphate, sodium citrate, sodium hydrogen carbonate, and the like. Anything can be used.

  Usually, a plasticizer is added to improve moldability. Suitable plasticizers include glycerin, polyhydric alcohols such as polyethylene glycol, propylene glycol and polypropylene glycol, glucose, monosaccharides such as fructose, glucose and galactose, sucrose, maltose, trehalose and coupling sugar. Examples include saccharides and oligosaccharides, polysaccharides such as pullulan, gum arabic, arabinogalactan, and cellulose, and sugar alcohols such as sorbitol, maltitol, lactitol, palatinit, xylitol, mannitol, and galactitol.

Moreover, in order to improve the durability with respect to humidity, you may contain alginates. Examples of alginates include alginic acid, sodium alginate, potassium alginate, ammonium alginate and the like.
The alginate contained in the capsule may be subjected to gelation in an aqueous solution containing calcium ions (eg, calcium chloride aqueous solution, calcium lactate aqueous solution, etc., hereinafter referred to as gelling aid aqueous solution). .
Although calcium alginate is not suitable for use as a raw material, it can be changed from various alginates to calcium alginate by subsequent reaction with calcium ions in an aqueous gelling aid solution. May be included. As a method of gelation treatment, (1) a method of adding sodium alginate aqueous solution after dissolving sodium alginate at the time of coating solution preparation, (2) after capsule formation and before drying (the capsule membrane contains water) Examples thereof include a method of immersing in an aqueous gelation aid solution (in a state), and (3) a method of immersing a dried capsule in an aqueous gelation aid solution after capsule formation.
In the present invention, alginates are not essential components, but are optional additives for the purpose of preventing moisture absorption.

In the present invention, any of the methods (1), (2), and (3) can be applied to the method for gelling the alginate contained in the capsule, but the method (3) is optimal.
The immersion treatment time in the case of treating by the method (3) is not particularly limited, but the effect is not enhanced even if the treatment is performed for a very long time. The degree is most preferred.

The aqueous gelling aid solution to be immersed is not particularly limited as long as it generates calcium ions when converted into an aqueous solution. Examples thereof include a calcium chloride aqueous solution, a calcium lactate aqueous solution, a calcium bicarbonate aqueous solution, a calcium acetate aqueous solution, and a calcium nitrate aqueous solution. Can do.
The optimum aqueous solution concentration when a calcium chloride aqueous solution is used is 1% by mass or less.

  The aqueous gelling aid solution may contain ethanol. When a large amount of ethanol is contained, since the capsule washing process can be performed together, the convenience of manufacturing is enhanced.

  Although the quantity which mix | blends alginate is not specifically limited, It is preferable that it is the mass of 50% or less of carrageenan. If the content of alginate is too high, the viscosity increases, which may affect the moldability of the capsule.

Furthermore, in order to enhance moisture absorption prevention, coating may be performed with various coating agents such as waxes and waxes described later.
As a coating method, a method in which a coating agent is dissolved or dispersed in a volatile solvent or the like is sprayed or applied to the capsule after drying to volatilize the volatile solvent (top method), the coating agent is volatile solvent, etc. Examples include a method of immersing the capsule after drying in a solution dissolved or dispersed in it to volatilize the volatile solvent (dip method), a method of pre-dispersing and suspending the capsule film solution (kneading method), etc. There is no particular limitation on the method.
In addition, when introduce | transducing a coating agent into a capsule membrane | film | coat, in order to improve a dispersibility and suspendability, you may mix | blend an emulsifier suitably.

  In addition, dextrins, starch, processed starch and the like may be added as a base for adjusting the ease of cracking. Conversely, dextrins, starches and processed starches need not be added at all.

Various kinds of capsules can be contained.
Below, what can be contained in a capsule is illustrated. Each of these components can be contained in any part of the capsule.

  As fats and oils, avocado oil, almond oil, linseed oil, fennel oil, sesame oil, olive oil, olive squalene, orange oil, orange rafa oil, sesame oil, garlic oil, cocoa butter, pumpkin seed oil, chamomile oil, carrot oil, cucumber Oil, beef tallow fatty acid, cucumber nut oil, cranberry seed oil, brown rice germ oil, rice oil, wheat germ oil, safflower oil, shea fat, liquid shea fat, perilla oil, soybean oil, evening primrose oil, camellia oil, corn oil, rapeseed Oil, saw palmetto extract oil, pearl oil, persic oil, parsley seed oil, castor oil, sunflower oil, grape seed oil, borage oil, macadamia nut oil, meadowweed oil, cottonseed oil, peanut oil, turtle oil, mink oil, egg yolk oil, Fish oil, palm oil, palm kernel oil, owl, coconut oil, long chain, medium chain, Chain fatty acid triglycerides, diacyl glycerides, beef tallow, lard, squalene, squalane, pristane, and, and hydrogenated products of these fats and oils can be contained.

  As waxes and waxes, shellac wax, beeswax, carnauba wax, whale wax, lanolin, liquid lanolin, reduced lanolin, hard lanolin, cyclic lanolin, lanolin wax, candelilla wax, mole, montan wax, shellac wax, rice wax, etc. It is. As hardened oil, vegetable hardened oil obtained by hydrogenating vegetable fat and oil, beef tallow hardened oil, pork fat hardened oil, etc. can be contained.

  As mineral oil, liquid paraffin, petrolatum, paraffin, ozokelide, ceresin, microcrystalline wax and the like can be contained.

  As fatty acids, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, conjugated linoleic acid, linolenic acid, docosahexaenoic acid, eicosapentaenoic acid, 12-hydroxystearic acid, undecylenic acid, tall oil , Natural fatty acids such as lanolin fatty acid, isononanoic acid, caproic acid, 2-ethylbutanoic acid, isopentanoic acid, 2-methylpentanoic acid, 2-ethylhexanoic acid, isopentanoic acid and the like, and fats and oils containing these fatty acids as fatty acid composition Etc. can be contained.

  As vitamins, vitamin A group: retinol, retinal (vitamin A1), dehydroretinal (vitamin A2), carotene, lycopene (provitamin A), vitamin B group: fursultiamine, thiamine hydrochloride, thiamine sulfate (vitamin B1 ), Riboflavin (vitamin B2), pyridoxine (vitamin B6), cyanocobalamin, methylcobalamin (vitamin B12), folic acid, nicotinic acids, pantothenic acids, biotins, choline, inositols, vitamin C group: ascorbic acid or its derivatives, Vitamin D group: Ergocalciferol (vitamin D2), cholecalciferol (vitamin D3), dihydrotaxosterol, vitamin E group: vitamin E or its derivatives, ubiquinones, vitamin K group: phytonadione (vita) K1), menaquinone (vitamin K2), menatetrenone, menadione (vitamin K3), menadiol (vitamin K4), other essential fatty acids (vitamin F), carnitine, ferulic acid, γ-oryzanol, orotic acid, vitamin Ps (rutin) , Eriocitrin, hesperidin), vitamin U, and the like.

  Pepper tincture, capsicum oil, nonyl acid vanillamide, cantalis tincture, ginger tincture, ginger oil, peppermint oil, l-menthol, camphor, benzyl nicotinate and the like can be contained as stimulants.

  Benzophenone derivatives (2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, sodium 2-hydroxy-4-methoxybenzophenone-5-sulfonate, dihydroxydimethoxy) Benzophenone, dihydroxydimethoxybenzophenone-sodium sulfonate, 2,4-dihydroxybenzophenone, tetrahydroxybenzophenone, etc.), paraaminobenzoic acid derivatives (paraaminobenzoic acid, ethyl paraaminobenzoate, glyceryl paraaminobenzoate, amyl paradimethylaminobenzoate, para Octyl dimethylaminobenzoate), methoxycinnamic acid derivatives (ethyl paramethoxycinnamate, isopropyl paramethoxycinnamate, octyl paramethoxycinnamate, 2-methoxycinnamic acid 2-eth Ciethyl, sodium paramethoxycinnamate, potassium paramethoxycinnamate, diparamethoxycinnamate mono-2-ethylhexanoate glyceryl, etc.), salicylic acid derivatives (octyl salicylate, phenyl salicylate, homomenthyl salicylate, dipropylene glycol salicylate, ethylene glycol salicylate, myristyl salicylate, Methyl salicylate, etc.), anthranilic acid derivatives (methyl anthranilate, etc.), urocanic acid derivatives (urocanic acid, ethyl urocanate, etc.), coumarin derivatives, amino acid compounds, benzotriazole derivatives, tetrazole derivatives, imidazoline derivatives, pyrimidine derivatives, dioxane derivatives , Camphor derivatives, furan derivatives, pyrone derivatives, nucleic acid derivatives, allantoin derivatives, nicotinic acid derivatives, vitamin B Derivatives, umbelliferone, esculin, benzyl cinnamate, sinoxate, oxybenzone, dioxybenzone, octabenzone, thrisobenzone, benzoresorcinol, arbutin, guaiazulene, shikonin, baicalin, baicalein, berberine, neoheliopan, escalol, zinc oxide, talc, kaolin Etc. can be contained.

  As whitening agents, paraaminobenzoic acid derivatives, salicylic acid derivatives, anthranilic acid derivatives, coumarin derivatives, amino acid compounds, benzotriazole derivatives, tetrazole derivatives, imidazoline derivatives, pyrimidine derivatives, dioxane derivatives, camphor derivatives, furan derivatives, pyrone derivatives, nucleic acids Derivatives, allantoin derivatives, nicotinic acid derivatives, vitamin C or derivatives thereof (vitamin C phosphate magnesium salt, vitamin C glucoside, etc.), vitamin E or derivatives thereof, kojic acid or derivatives thereof, oxybenzone, benzophenone, arbutin, guaiazulene, shikonin , Baicalin, baicalein, berberine, placental extract, ellagic acid, lucinol, and the like.

  As tyrosinase activity inhibitors, vitamin C or a derivative thereof (vitamin C phosphate magnesium salt, vitamin C glucoside, etc.), hydroquinone or a derivative thereof (hydroquinone benzyl ether, etc.), kojic acid or a derivative thereof, vitamin E or a derivative thereof, N -Acetyltyrosine or its derivatives, glutathione, hydrogen peroxide, zinc peroxide, placenta extract, ellagic acid, arbutin, lucinol, silk extract, plant extract (camomile, mulberry, gardenia, touki, firewood, clara, mugwort, honeysuckle, Kihada, Dokudami, Matsuhodo, pearl barley, pearl millet, hops, hawthorn, eucalyptus, yarrow, altea, keihi, mankei, hamamelis, carraguwa or yamagwa, life-prolonging grass, bellflower, toshishi, goblin, NOTE, Ephedra Sinensis, Dokkatsu, Psycho, windproof, littoralis, Scutellaria, peony bark, peony, cranesbill, kudzu root, licorice, gallnut, aloe, Cimicifuga, safflower, green tea, black tea, Uncaria gambir Roxburgh) and can be contained.

  As a melanin pigment reducing or decomposing substance, phenylmercury hexachlorophene, mercuric oxide, mercuric chloride, hydrogen peroxide, zinc peroxide, hydroquinone or a derivative thereof can be contained.

  As a turnover promoting action and cell activator, hydroquinone, lactic acid bacteria extract, placenta extract, ganoderma extract, vitamin A, vitamin E, allantoin, spleen extract, thymus extract, yeast extract, fermented milk extract, plant extract (aloe, ougone) , Cedar, gentian, burdock, shikon, carrot, hammelis, hops, yokuinin, mandarin duck, sea bream, crested radish, ginseng, achacha, hypericum, cucumber, ginger, gecko, parsley) and the like.

  As astringents, succinic acid, allantoin, zinc chloride, zinc sulfate, zinc oxide, calamine, zinc paraphenolsulfonate, potassium aluminum sulfate, resorcin, ferric chloride, tannic acid (including catechin compounds) can be included is there.

  As the active oxygen scavenger, SOD, catalase, glutathione peroxidase and the like can be contained.

  As an antioxidant, vitamin C or a salt thereof, stearic acid ester, vitamin E or a derivative thereof, nordihydrogua ceretenoic acid, butylhydroxytoluene (BHT), butylhydroxyanisole (BHA), hydroxytyrosol, parahydroxyanisole, Propyl gallate, sesamol, sesamorin, gossypol, propolis and the like can be contained.

  Possible to contain β-carotene, plant extract (sesame cell culture, acha, hypericum, clam, clove, clove, melissa, birch, birch, salvia, mannenro, minamitenji, agetsu, ginkgo, green tea) as lipid peroxide production inhibitors It is.

  Anti-inflammatory agents include ictamol, indomethacin, kaolin, salicylic acid, sodium salicylate, methyl salicylate, acetylsalicylic acid, diphenhydramine hydrochloride, d-camphor, dl-camphor, hydrocortisone, guaiazulene, camazulene, chlorpheniramine maleate, glycyrrhizic acid or its salts In addition, glycyrrhetinic acid or a salt thereof, licorice extract, coconut extract, age extract, propolis and the like can be contained.

  Antibacterial / bactericidal / disinfectant agents include acrinol, sulfur, calcium gluconate, chlorhexidine gluconate, sulfamine, mercurochrome, lactoferrin or its hydrolyzate, alkyldiaminoethylglycine chloride solution, triclosan, sodium hypochlorite, chloramine T, salashi Powder, iodine compound, iodoform, sorbic acid or its salt, propionic acid or its salt, salicylic acid, dehydroacetic acid, parahydroxybenzoic acid esters, undecylenic acid, thiamine lauryl sulfate, thiamine lauryl nitrate, phenol, cresol, p- Chlorophenol, p-chloro-m-xylenol, p-chloro-m-cresol, thymol, phenethyl alcohol, O-phenylphenol, Irgasan CH3565, halocarban, hexachlorophene, chlorohe Shidin, ethanol, methanol, isopropyl alcohol, benzyl alcohol, ethylene glycol, propylene glycol, 2-phenoxyethanol, 1,2-pentanediol, zinc pyridione, chlorobutanol, isopropylmethylphenol, nonionic surfactant (polyoxyethylene lauryl) Ether, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, etc.), amphoteric surfactant, anionic surfactant (sodium lauryl sulfate, lauroyl sarcosine potassium, etc.), cationic surfactant (cetyltrimethylammonium bromide, chloride) Benzalkonium, Benzethonium chloride, Methylrosaniline chloride), Formaldehyde, Hexamine, Brilliant green, Malachite green, Chris Tal violet, jarmal, photosensitizer 101, photosensitizer 201, photosensitizer 401, N-long chain acyl basic amino acid derivatives and acid addition salts thereof, zinc oxide, hinokitiol, kudin, propolis and the like can be contained.

  As humectants, glycerin, propylene glycol, 1,3-butylene glycol, polyethylene glycol, glycerin tricaprylcaprate, glycolic acid (α-hydroxy acid), hyaluronic acid or its salt, chondroitin sulfate or its salt, water-soluble chitin or its Derivatives or chitosan derivatives, pyrrolidone carboxylic acid or salts thereof, sodium lactate, urea, sorbitol, amino acids or derivatives thereof (valine, leucine, isoleucine, threonine, methionine, phenylalanine, tryptophan, lysine, glycine, alanine, asparagine, glutamine, serine, Cysteine, cystine, tyrosine, proline, hydroxyproline, aspartic acid, glutamic acid, hydroxylysine, arginine, ornithine, histidine, These sulfates, phosphates, nitrates, citrates, or pyrrolidone carboxylic acid), or the like may be contained.

  As various organic acids, glycolic acid, citric acid, malic acid, tartaric acid, lactic acid, ferulic acid, phytic acid, and the like can be contained.

  For hair, selenium disulfide, alkylisoquinolinium bromide, zinc pyrithione, biphenamine, thianthol, castari tincture, pepper tincture, pepper tincture, quinine hydrochloride, strong ammonia water, potassium bromate, sodium bromate, thioglycol An acid etc. can be contained.

  As perfumes, natural animal fragrances such as musk, civet, castorium, ambergris, anise essential oil, angelica essential oil, ylang ylang essential oil, iris essential oil, fennel essential oil, orange essential oil, cananga essential oil, caraway essential oil, cardamom essential oil, guayakwood essential oil, cumin Essential oil, black letter essential oil, cinnamon essential oil, cinnamon essential oil, geranium essential oil, copaiba balsam essential oil, coriandel essential oil, perilla essential oil, cedarwood essential oil, citronella essential oil, jasmine essential oil, gingergrass essential oil, cedar essential oil, spearmint essential oil, western peppermint essential oil, large Perfume essential oil, tuberose essential oil, clove essential oil, orange flower essential oil, winter green essential oil, trout balsam essential oil, buttery essential oil, rose essential oil, palmarosa essential oil, persimmon essential oil, hiba essential oil, sandalwood essential oil, petit gren essential oil, bay essential oil, vetiva essential oil, bergamoc Plant oils such as essential oil, Peruvian balsam essential oil, Boadrose essential oil, melamine essential oil, mandarin essential oil, eucalyptus essential oil, lime essential oil, lavender essential oil, linaloe essential oil, lemongrass essential oil, lemon essential oil, rosemary (mannenrou) essential oil, Japanese mint mint essential oil A fragrance | flavor and other synthetic fragrance | flavors, such as coffee flavor and a yoghurt flavor, etc. can contain.

Various uses are possible depending on such inclusions.
For example, if a capsule containing a fragrance or the like is embedded in a filter attached to a cigarette or a filter for attaching to a cigarette, the sound, touch and scent of the capsule being crushed by a finger when smoking can be obtained. In addition, if a capsule containing a component such as menthol, which volatilizes, evaporates, or sublimes to improve the condition of the nose, is embedded in the mask, the capsule can be crushed and the nasal congestion can be improved. In addition, if a capsule containing flavors is installed in the grating card, the recipient can crush the capsule to obtain sound, feel and aroma.
In addition, it is applicable to daily products such as pharmaceuticals, health foods, foods, cosmetics, and cleaning products.

Example 1
Table 1 is a table | surface which shows the composition of the capsule membrane | film | coat of the Example by this invention.

As capsule contents, l-menthol 30% MCT solution was filled into capsules having a film rate of 8.0%, a film thickness of 25.0 μm, and a diameter of 4 mm to produce seamless capsules. However, in this example, the treatment for replacing sodium alginate with calcium alginate by calcium treatment is not performed.
When the hardness after drying was measured, it was 15N (manufactured by Fujiwara Seisakusho, Kiya-type digital hardness tester KHT-20N type, number of samples 20).
When the resulting soft capsule was embedded in a tobacco filter after drying, it was easily cracked with a finger and enjoyed the sound and feel of the capsule breaking. I also enjoyed the refreshing scent of menthol.
Furthermore, as a stability test under high humidity conditions, a cigarette with a capsule embedded in a filter was allowed to stand in an environment of 25 ° C. and 85% RH for 10 minutes, and the same test was performed. was gotten.

(Comparative Example 1)
Table 2 is a table showing the composition of the capsule film of Comparative Example 1.

As capsule contents, l-menthol 30% MCT solution was filled into capsules having a coating rate of 9.0%, a coating thickness of 45.0 μm, and a diameter of 4 mm to produce seamless capsules. In the case of a gelatin film, it was difficult to obtain good capsules when the film rate was lower than 9.0%.
When the hardness after drying was measured, it was 40 N (manufactured by Fujiwara Seisakusho, Kiya-type digital hardness meter KHT-20N type, number of samples 20).
When the obtained soft capsule composition was embedded in a tobacco filter in the same manner as in Example 1 and sandwiched between fingers, it was cracked, but it was hard to break, causing pain in the finger, and it was not possible to enjoy the feel and sound of cracking.
Further, as in Example 1, when the tobacco with the capsule embedded in the filter was allowed to stand for 10 minutes in an environment of 25 ° C. and 85% RH, the capsule softened and deformed, but became more difficult to break.

(Comparative Example 2)
Table 3 is a table showing the composition of the capsule film of Comparative Example 2.

As capsule contents, 1-menthol 30% MCT solution was tried to form seamless capsules with a coating rate of 9.0% and a diameter of 4 mm.
However, the capsule was broken during drying, and the product could not be manufactured.

(Comparative Example 3)
When the coating rate was changed to 30% under the same conditions as in Comparative Example 2, a seamless capsule having a diameter of 4 mm could be produced. The hardness after drying was 40N.
However, it was difficult to split with fingers.

(Comparative Example 4)
When the coating rate was changed to 20% under the same conditions as in Comparative Example 2, a seamless capsule having a diameter of 4 mm could be formed.
However, about 20% of the capsules were broken at the time of drying, the yield was poor, and stable production could not be performed. Further, due to the hygroscopic property of dextrin, the capsule was irregular in shape and spherical capsules could not be produced.
When few good products were selected and subjected to the test, the hardness of the manufactured product after drying was 25N. When cracked with fingers, it cracked, but it was difficult to break, causing pain in the fingers. Further, when left in an environment of 25 ° C. and 85% RH for 10 minutes, the capsules became full of wrinkles and softened.

(Example 2)
In order to improve the durability against humidity using the capsule obtained in Example 1, the gelation treatment was performed in an aqueous solution containing calcium ions, and then the immersion treatment time was examined in the re-dried sample. did.
Table 4 is a table showing the evaluation of the influence due to the immersion treatment time.

After the capsule formation of Example 1 in the previous period, the dried capsule was subjected to a gelation treatment using a 5% aqueous solution of calcium chloride as an aqueous gelling aid solution, and then the re-dried sample was subjected to storage conditions at 40 ° C. and 75% for a certain time Storage (the storage container lid was opened. This is hereinafter referred to as “capsule opening”). Numerical values such as 1/10 in Table 5 indicate the ratio of the number of capsules after storage that did not collapse with fingers.
As a result of comparing the immersion treatment time of 1 minute, 10 minutes, and 60 minutes, those of 1 minute were optimum. As the immersion time became longer, the re-drying time became longer and the effect of the calcium treatment diminished.

(Example 3)
Similarly, the capsule obtained in Example 1 was subjected to a gelation treatment in an aqueous solution containing calcium ions in order to improve durability against humidity, and then re-dried, the calcium concentration It was investigated.
Table 5 is a table showing the evaluation of the influence due to the calcium concentration. Note that the fractions in the lower two rows of the table represent the ratio (NG number / n number) of the samples that were crushed poorly as a result of the test of crushing capsules with fingers.

After forming the capsules of Example 1, the dried capsules were gelled with an aqueous solution of calcium chloride and calcium lactate pentahydrate as an aqueous gelling aid solution, immersed in a treatment time of 1 minute, and then dried again. And stored at 25 ° C. and 90% for 12.5 hours and 21.5 hours (capsule release).
As a result of comparing 0 (control), 0.2, 0.5, 1, 3, 5 mass% (external ratio with respect to water) as the concentration of calcium chloride, the optimal concentration is more than 0% and 1% or less. there were. The concentration of calcium lactate pentahydrate equivalent to these optimum results was 5% by mass externally attached.

Example 4
Similarly, using the capsule obtained in Example 1 above, after immersion treatment in an ethanol solution containing calcium in order to improve durability against humidity, a solution to be immersed in a sample from which ethanol has been removed The difference in the effect due to the difference in the composition of the two was examined.
Table 6 is a table showing the processing conditions, Tables 7 and 8 are tables showing the evaluation of the influence of the storage conditions, and Table 7 is the result of the test for crushing with fingers (the fraction is the result of the test for crushing capsules with fingers) As a result, the ratio (NG number / n number) of the samples that were badly crushed was represented.) Table 8 represents the hardness. In addition, the hardness in Table 8 is a unit N, and represents the average value of the number of samples 10, MAX, MIN, and R, respectively.

Samples 4A to C are comparative examples. Sample 4A is not treated with calcium, Sample 4B is immersed in ethanol containing calcium chloride and lecithin, and Sample 4C is immersed in a mixed solution of calcium chloride aqueous solution and ethanol. It is.
Sample 4D was subjected to gelation treatment (primary treatment) in an aqueous calcium chloride solution (0.5% by mass (external ratio with respect to the solvent)) for 1 minute, followed by re-drying treatment by air blowing, and 1 in ethanol. It is a part of the capsule surface from which ethanol has been removed by submerging (secondary treatment). As a method for removing ethanol, methods such as natural volatilization, volatilization by blowing, and centrifugation can be used. Industrially, centrifugation is preferably used.
Samples 4E to 4K are immersed (1 minute) in a mixed solution (ethanol 30, 50, 60% by mass) of an aqueous calcium chloride solution (0.25, 0.5% by mass) and ethanol, and subsequently immersed in ethanol or ethanol. After immersing (2 minutes) in a solution in which calcium chloride (0.5% by mass) is dissolved, ethanol on the capsule surface is removed.
All were stored under high humidity conditions of 25 ° C. and 90% (capsule release).

As a result of the crushing test with fingers, Samples 4D to 4K were good. Samples 4D to K were also good in terms of hardness.
When immersion treatment is performed with an aqueous calcium solution, re-drying after treatment is necessary. On the other hand, when immersion treatment is performed with a solution in which calcium is dissolved in ethanol, the effect of hardening treatment with calcium is reduced. There was a tendency to end up. On the other hand, as in samples 4E to 4K of this example, primary immersion treatment is performed with a mixed solution of calcium aqueous solution and ethanol, and then secondary immersion treatment is performed with ethanol or ethanol containing calcium chloride. The method of removing ethanol is preferable in terms of work efficiency, capsule finish, and moisture resistance.

(Example 5)
Similarly, in order to improve durability against humidity, alginates were added, gelled in an aqueous solution containing calcium ions, and then re-dried, the amount of alginate and plasticizer was examined.
Table 9 is a table showing an evaluation of the influence due to the blending amount of the alginate and the plasticizer.

For the composition of the capsule film, 1.0 and 5.0% by mass of sodium alginate are used, and 3.0, 6.0, and 10.0% by mass of glycerin as a plasticizer are used. After the capsule formation, the dried capsule is subjected to an immersion treatment using an aqueous calcium chloride solution as a gelling aid aqueous solution (calcium chloride concentration of 0.5, 1% by mass (external ratio to water)), and then dried again. The obtained samples were stored (capsule opened) for 13, 38, 60, and 92 hours at 25 ° C. and 90% storage conditions.
As a result, neither a difference due to the blending amount of sodium alginate nor a difference due to the blending amount of glycerin as a plasticizer was recognized.

  The capsules according to the present invention have good storage stability and are easily broken by fingers, so that it is possible to obtain added value such as sound and touch when cracking, and can be applied to various uses, so it is practical and has industrial utility value. high.

Claims (11)

In the preparation of the seamless soft capsule film, carrageenan, which is the composition of the capsule film, is decomposed with an acidic pH adjuster, the decomposition is stopped with a neutralizing agent, and alginates are added as calcium capsules as the composition of the capsule film. treating gel in gel Kasukezai aqueous solution containing, a seamless soft capsule produced by,
The composition of the capsule shell, carrageenan and, soft capsule and having at least a alginates. The soft capsule of Claim 1 which has at least any one of a plasticizer, saccharides , dextrins, starch, and processed starch in the composition of a capsule membrane | film | coat.   The soft capsule according to claim 1 or 2, wherein the carrageenan has a viscosity adjusted by decomposition with an acidic pH adjuster.   The soft capsule according to any one of claims 1 to 3, wherein the content of carrageenan in the composition of the capsule film is 50% or more, preferably 70% or more.   The soft capsule according to any one of claims 1 to 4, having a coating rate of 5 to 20%, preferably 7 to 15%.   The soft capsule according to any one of claims 1 to 5, wherein the capsule film has a thickness of 40 µm or less, preferably 30 µm or less.   The soft capsule according to any one of claims 1 to 6, wherein the capsule film has a hardness of 5 to 40N, preferably 10 to 20N.   The soft capsule according to any one of claims 1 to 7, wherein the capsule has a diameter of 0.5 to 15 mm, preferably 1 to 8 mm. The soft capsule according to any one of claims 1 to 8 , wherein the content of alginate is 50% or less of carrageenan. A method for preparing a film of a seamless soft capsule, comprising the steps of decomposing carrageenan, which is a capsule film composition, with an acidic pH adjuster , and stopping the decomposition with a neutralizing agent , and a capsule film composition A method for producing a soft capsule, characterized by comprising alginates as a gel, and the alginate is gelled in an aqueous gelling aid solution containing calcium ions . The method for producing a soft capsule according to claim 10 , wherein ethanol is contained in the gelling aid aqueous solution.