JP2002326030A - Method for preventing crosslinking of coating film of noncrosslinked gelatin capsule - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a noncrosslinked gelatin capsule which contains a material having high reactivity with gelatin, such as isocyanates or aldehydes as a core material, maintains hardness obtained when prepared and is stable with aging. SOLUTION: Crosslinking of the coating film of a noncrosslinked gelatin capsule is prevented by coating the noncrosslinked gelatin capsule with saccharides or sugar alcohols.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for preventing film cross-linking in a non-cross-linked gelatin capsule containing a core substance containing isothiocyanates and / or aldehydes.
More specifically, the present invention relates to coating non-crosslinked gelatin microcapsules prepared by a coacervation method containing isothiocyanates and / or aldehydes in a core substance with sugars and / or sugar alcohols. The present invention relates to a method for preventing film crosslinking and a microcapsule produced by using the method.

[0002]

2. Description of the Related Art When handling highly volatile and highly reactive substances such as isothiocyanates and aldehydes, they are conveniently used by encapsulation. Encapsulation technologies currently in practical use include natural or synthetic polymer materials as film materials, soft capsules covered with sheet-like films, seamless capsules prepared by orifice method, and microcapsules prepared by coacervation method. Capsules and the like are known. Apart from soft capsules having a large thickness, microcapsules having a small thickness are often produced by crosslinking to ensure the strength of the coating. Since a conventionally known crosslinking agent is glutaraldehyde or the like and is not suitable for food use, a combination of a gelatin film and transglutaminase has been proposed for food use (Japanese Patent Application Laid-Open No. 9-248137). However, crosslinked microcapsules have strength, but have the disadvantage that they are less soluble in water,
There was a problem that the form of the applied food was limited. The present inventors have previously proposed that non-crosslinked gelatin microcapsules having moderate hardness against various core substances can be produced by preparing a specific emulsifier and a specific coacervation method (Japanese Patent Application Laid-Open (JP-A) no. 2001-460
No. 10). However, even in this method, when isothiocyanates or aldehydes are contained in the core substance, the gelatin gradually reacts with the isothiocyanates or aldehydes, the film is cross-linked with time, and the microcapsules are insoluble in water. There was a problem that. In the field of pharmaceuticals, succinylated gelatin is used to solve the above problems, but it is not suitable as a food material, and further technical development has been desired.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a non-crosslinked gelatin capsule containing a core substance containing isothiocyanates and / or aldehydes, which maintains the hardness at the time of preparation and is stable over time. To provide.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that saccharides and / or saccharides are contained even in non-crosslinked gelatin capsules containing a core substance containing isothiocyanates and / or aldehydes. The inventors have found that coating with sugar alcohols can suppress the crosslinking of the film, and have completed the present invention. That is, the present invention relates to a method for preventing film cross-linking, characterized in that a non-cross-linked gelatin capsule containing a core substance containing isothiocyanates and / or aldehydes is coated with sugars and / or sugar alcohols. Gelatin capsule particle size 50
A cross-linking prevention method, characterized in that the non-cross-linked gelatin capsule is a microcapsule prepared as a film containing 60 to 100% by weight of gelatin as a solid content. A method for preventing film cross-linking, wherein the saccharide is one or a combination of two or more selected from the group consisting of monosaccharides, oligosaccharides, and yeast cell walls; Is glucose, and the oligosaccharide is one or two selected from the group consisting of galactose, sucrose, maltose, lactose, trehalose, pullulan, starch syrup, and cyclodextrin. A method for preventing film cross-linking, which is a combination of the above, and wherein the sugar alcohol is maltitol. Xylitol, a coating crosslinking prevention method, which is a one or more combinations selected from the group consisting of sorbitol, and the non-crosslinked gelatin capsules, 60 gelatin as solid
A microcapsule prepared as a film containing 99% by weight and 1 to 40% by weight of sugar or sugar alcohol, which is a method for preventing film cross-linking, and further comprising a core substance containing a fragrance. And a capsule which is manufactured by using the above-mentioned method for preventing film cross-linking and which is hard to cross-link the film.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The substance contained in the core substance in the present invention is not particularly limited as long as it is a substance which reacts with gelatin and crosslinks, and includes isothiocyanates, aldehydes, acids and sulfur-containing compounds. And nitrogen-containing compounds, but are typically isothiocyanates and / or aldehydes. As isothiocyanates, NCS
There is no particular limitation as long as the substance has a group, and allyl isothiocyanate, propyl isothiocyanate, 3-methylthiopropyl isothiocyanate,
Methylsulfinylpropyl isothiocyanate, butyl isothiocyanate, isobutyl isothiocyanate, sec-butyl isothiocyanate, tert-butyl isothiocyanate, 3-butenyl isothiocyanate, 4-methylthiobutyl isothiocyanate,
Methylsulfinylbutyl isothiocyanate, pentyl isothiocyanate, isopentyl isothiocyanate, 2-methylbutyl isothiocyanate, tert-
Pentyl isothiocyanate, 4-pentenyl isothiocyanate, 5-methylthiopentyl isothiocyanate, 5-methylsulfinyl pentyl isothiocyanate, hexyl isothiocyanate, isohexyl isothiocyanate, 5-hexenyl isothiocyanate, 6
-Methylthiohexyl isothiocyanate, 6-methylsulfinylhexyl isothiocyanate, cyclohexyl isothiocyanate, phenyl isothiocyanate, benzyl isothiocyanate, 4-hydroxybenzyl isothiocyanate, phenylethyl isothiocyanate, and the like, preferably allyl isothiocyanate, 3- Methylthiopropyl isothiocyanate,
3-butenyl isothiocyanate, 4-methylthiobutyl isothiocyanate, 4-pentenyl isothiocyanate, 5-methylthiopentyl isothiocyanate, 5
-Hexenyl isothiocyanate, 6-methylthiohexyl isothiocyanate, and most preferably allyl isothiocyanate. The aldehyde is not particularly limited as long as it has an aldehyde group, and is acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, isovaleraldehyde, caproaldehyde, enanthaldehyde, octanal, 2-octenal. , Nonanal, 2-nonenal, decanal,
Examples thereof include 2-decenal, 2,4-decadienal, undecanal, dodecanal and the like. Other examples include acetic acid, propionic acid, butyric acid, valeric acid, isovaleric acid, caproic acid, caprylic acid, capric acid, undecylenic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, e Icosapentaenoic acid,
Docosahexaenoic acid and the like are exemplified, and as the sulfur-containing compound, methyl mercaptan, ethyl mercaptan, propyl mercaptan, allyl mercaptan, and the like are exemplified.As the nitrogen-containing compound, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, pyrrole, N-methylpyrrole, pyrrolidine, pyridine, picoline, lutidine, piperidine, pyrazine, 2-methylpyrazine, 2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine, 2,3,5-trimethyl Pyrazine, tetramethylpyrazine, ethylpyrazine, 2,3-diethylpyrazine, 2,5-diethylpyrazine, 2,6-diethylpyrazine, 2,3-dimethyl-5-ethylpyrazine, piperazine, Lumpur, skatole, quinoline,
Examples thereof include quinoxaline, tetrahydroquinoxaline, anthranilic acid and derivatives thereof. The content of these substances in the core substance is preferably 0.01 to 50%, more preferably 0.1 to 30%, and most preferably 0.5 to 50%.
15%. If it is less than 0.01%, it is not necessary to apply the present invention. If it exceeds 50%, the effect of the present invention is weak. As an optional component in the core substance, fats and oils are suitably used as a diluting solvent. Examples of oils and fats include corn oil, soybean oil, rapeseed oil, palm oil, palm kernel oil, cocoa butter, olive oil, sesame oil, rice bran oil, wheat germ oil, sunflower oil, evening primrose oil, camellia oil, cottonseed oil, peanut oil and the like. Vegetable oils, sardine oil, mackerel oil, soybean oil, beef tallow, refined beef tallow, butter, mallow oil, chicken oil, animal fats such as lard, and hardened oils are exemplified, and those having a melting point of 30 ° C to 60 ° C are preferred. Used.

The non-crosslinked gelatin capsule used in the present invention is not particularly limited as long as it is a capsule coated with a gelatin-containing material. Soft capsules, capsules formed by an orifice method, and microcapsules formed by a coacervation method are used. For example, capsules having a particle size of 50 to 2500 μm, preferably microcapsules having a particle size of 300 to 1500 μm are used.

Examples of the gelatin used in the present invention include, but are not limited to, unpurified gelatin, purified gelatin, acid-decomposed gelatin, and enzyme-decomposed gelatin. Preferably, purified gelatin is used. The weight ratio between the core substance and the gelatin is not particularly limited,
It is preferably used in the range of 100: 1 to 100: 100, more preferably 100: 10 to 100: 60. If this ratio is less than 100: 1, the capsule coating is too thin, and a problem may occur in the strength.
If it exceeds, the capsule film may be too thick and adversely affect the expression of the core substance. The gelatin content as a film-forming material is not particularly limited, but is preferably 60 to 100% by weight as a solid content. In addition, natural thickening polysaccharides such as gum arabic are used in combination as optional components,
In addition, sugars and sugar alcohols are used as a film-forming material composition for the purpose of adjusting the hardness of the film and imparting flexibility to the film. When using a sugar or a sugar alcohol, it is preferable to contain 1 to 40% by weight as a solid content.

When microcapsules produced by the coacervation method are used in the present invention, the coacervating agent used can be any of those commonly used for coacervation without any particular limitation. In particular, gum arabic, carrageenan, CMCs, maltitol, sorbitol, electrolyte substances consisting of organic or inorganic salts, for example, salts with cations such as sodium chloride, potassium chloride, magnesium chloride, ammonium chloride, sulfates, phosphorus Salts with anions such as acid salts, carbonates, acetates are used. A water-soluble liquid,
Liquid substances in which the film-forming material is less soluble than water can be used, for example, alcohols such as ethanol and propanol.

The coacervation step of the present invention is performed, for example, by the following method. The core substance is placed in an aqueous gelatin solution
The solution is added at ６０60 ° C., an aqueous edible salt solution is added under stirring, and the mixture is gradually cooled to form and harden coacervation around the emulsion particles. Microcapsules formed in the aqueous solution are removed by filtration or the like and dried.

The drying method used in the present invention is not particularly limited, and examples thereof include spray drying, reduced pressure drying, freeze drying, fluidized bed drying and the like. A fluidized bed drying method using a drying aid such as silicon oxide is used.

The saccharide or sugar alcohol used in the present invention is not particularly limited, and examples of the saccharide further include monosaccharides, oligosaccharides, and yeast cell walls. Examples of monosaccharides include glucose, mannose, galactose,
Examples include fructose, ribose, arabinose, and xylose, and glucose is preferably used. Examples of oligosaccharides include sucrose, maltose, lactose, trehalose, starch syrup, dextrins and the like, and preferably sucrose, lactose, maltose, lactose, trehalose. Examples of sugar alcohols include sorbitol, xylitol, maltitol and the like, and sorbitol is preferably used. One or a combination of two or more of these sugars or sugar alcohols can be used, and the amount used is not particularly limited, but is preferably 0.1% by weight to 10% by weight of the core substance. , More preferably 1 weight ~
Used at 8% by weight. If it exceeds 10%, the fluidity of the capsule will be impaired, and the encapsulation rate will decrease.
If it is less than 0.1%, the denseness of the film cannot be secured.

The method of coating the sugars and / or sugar alcohols can be added at any stage after the capsule forming step, but is preferably coated after the capsule drying step. As a method of addition, the saccharide is added as it is or as an aqueous solution having an arbitrary concentration. Preferably, the saccharide is added as it is in the case of a liquid state, and in the form of an aqueous solution of about 30% by weight in the case of a solid. You. In this case, if it is performed simultaneously with the drying step of the capsule, it is economically advantageous without increasing the number of manufacturing steps.

The core substance of the present invention may contain a fragrance as an optional ingredient. The fragrance used in the present invention is not particularly limited, and ethyl acetoacetate, acetophenone, anisaldehyde, α-amylcinnamaldehyde, methyl anthranilate, ionone,
Isoeugenol, isoamyl isovalerate, ethyl isovalerate, indole and its derivatives, γ-undecalactone, esters, ethyl vanillin, ethers, eugenol, octanol, ethyl octanoate, isoamyl formate, geranyl formate, citronellyl formate, Cinnamic acid,
Ethyl cinnamate, methyl cinnamate, ketones, geraniol, isoamyl acetate, ethyl acetate, geranyl acetate, cyclohexyl acetate, citronellyl acetate, cinnamyl acetate, terpinyl acetate, phenethyl acetate, butyl acetate, benzyl acetate, l-menthyl acetate, Linalyl acetate, methyl salicylate, allyl cyclohexylpropionate, citral, citronellal, citronellol, 1,8-cineole, fatty acids, aliphatic higher alcohols, aliphatic higher hydrocarbons, cinnamyl alcohol, cinnamaldehyde, thioethers, thiol , Decanol, ethyl decanoate, terpineol, limonene, pinene, myrcene, tapinolene, terpene hydrocarbons, γ-nonalactone, vanillin, paramethylacetophenone, hydroxycitronella Le, hydroxy citronellal dimethyl acetal, piperonal, phenyl isoamyl acetate, phenyl acetate, isobutyl phenylethyl acetate,
Phenol ethers, phenols, furfural and derivatives thereof, isoamyl propionate, ethyl propionate, benzyl propionate, allyl hexanoate, ethyl hexanoate, ethyl heptanoate, l-perilaldehyde, benzyl alcohol, benzaldehyde, aromatic alcohols , D-borneol, maltol, methyl N-methylanthranilate, methyl β-naphthyl ketone, dl-menthol, l-menthol, isoamyl butyrate, ethyl butyrate, cyclohexyl butyrate, butyl butyrate, lactones, linalool, etc. Citrus-based essential oils such as orange, lemon, lime, and grapefruit, and fruit-based essential oils such as apple, banana, grape, melon, peach, pineapple, and strawberry Flavor, milk, cream,
Milk-based extracted flavors such as butter, cheese and yogurt, recovered flavors of luxury items such as green tea, black tea, coffee, and cocoa, mint-based essential oils such as peppermint and spearmint, asanomi, asa fetida, ajowan, anise, angelica, fennel, turmeric, oregano , Allspice, orange nope, pepper, cassia, chamomile, mustard, cardamom, curry leaf, licorice, caraway, gardenia, cumin, watercress, cloves, poppy, caper, pepper, sesame, coriander, sassafras, saffron, savory, Salvia,
Salmon, perilla, cinnamon, shallot, juniper berry, ginger, star anise, spearmint, horseradish, celery, sorel, thyme, onion,
Tamarind, tarragon, chives, dill, capsicum, nutmeg, sagebrush, nigella, carrot, garlic, basil, parsley, peppermint, vanilla, paprika, hyssop, fenegreek, peppermint, horse mint, horseradish, marjoram, myoga, lavender, linden, linden Spice extract obtained from lemongrass, lemon balm, rose, rosemary, laurel, wasabi, iceland moss, red pheasant, akebi, asa, asafetida, asiantam, ajowan,
Adzuki bean, asparagus linen alice, apple mint, artichoke, anise, avocado, amacha, amachazur, amigasa lily, amyris, almond, alita sau, alkanna, artemisia, arnica, alfalfa, aloe, angstura, angoraweed, apricot, apricot apricot, apricot apricot Ambergris, ambrette, squid, epimedium, rush, yeast, knotweed, strawberry, fig, ginkgo, inokokochi, ylang-ylang, iwagugi, imperatoria, immortel, wintergreen, watercress,
Ukogi, turmeric, usubasaishin, woodruff, sea urchin,
Ume, Oolongcha, Egoma, Enokidake, Shrimp, Ebisugusa, Eligeron, Elder, Elleuterocock, Elecampen, Elemi, Engosaku, Ende, Endive, European Thistle, Ouren, Psyllium, Okazeri, Krill, Oak, Okemos, Okera, Osmanxus, Omansass Ominaeshi, Omodaka, Sennici of the Netherlands, Origanum, Oris, Olibanum, Olive, Allspice, Orange, Orange Flower, Kai, Seaweed, Kaininsou, Kakao, Oyster, Kasai, Cashew Nut, Cascala, Cascarilla, Castorium, Katakuri, Katsuobushi, Cassie, Cassia fistula, catechu, crab, carnation, valerian, chamomile, kayapte, mustard, mustard, mustard,
Guarana, Karamus, Galanga, Currant, Carissa,
Karin, Cardamom, Galvanum, Curry, Kawamidori, Licorice, Gambia, Kanran, Kiwifruit, Kikaiaratake, Kikyo, Chrysanthemum, Chrysanthemum, Catalpa, Cedar, Gibbon, Kichiachi aloe, Kina, Kihada, Kibana Ogi, Giboshi, Gimnemasilvelop, Captain , Cucumber, quilla, quince cypress, guava, guayak, wolfberry, cedar grass, kusa bokeh, kudzu, camphor tree, kusunohagashiwa, gooseberry, gardenia, kubeba, bearberry, gummy, cumin, ground ivy, clara, clary sage, cranberry, culinary, cranberry Grain of Paradise, Cretadi Thani, Grapefruit, Clover, Clove, Kromoji, Chlorella, Mulberry, Kwasher, Caper, Get , Cade, quebracho, Germanic loaders, Ken tulle, Kenponashi, cranesbill,
Koji, Kodake, Kocha, Kohone, Coca, Koganebana, Kokto, Kokului, Coconut, Goshyu, Pepper, Kostas, Kostmary, Copaipa, Coffee, Kobushi, Burdock, Sesame, Cola, Coriander, Coltshut, Golden Rod, Colombo, Konsai,
Consulango, kelp, comfrey, cypress, fish,
Sakura, cherry, pomegranate, salmon, sasasa, sasakusa, search, sassafras, saffron, sapodilla, cactus, sarashinasho, salsaparilla, salsify, sarnokoshake, hawthorn, sanshuyu, sansho, santa herb, sandalack, sandalwood, sandal red, Shiitake, Gene, Perilla, Cedar, Cedar, Citrus, Citronella, Synus, Civet, Shimaruba, Shimeji, Peony, Jasmine, Janohige, Jaborandi, Shallotte, Shuksha, Juniperberry, Ginger, Shoyu, Shouyuukas, Jouryush,
Ginger, white mushroom, ginseng, cinnamon,
Vinegar, watermelon, narcissus, cedar, star anise, star fruit, stylax, turtle, turtle mushroom, zudrabets, snake root, spikenard, spruce, spearmint, purslane, slow berry, savory, sekisho, sage, zedoary, senega, geranium, celery , Senkyu, Centauria, Sengen, St. John's Walt, Senna, Sauce, Rhubarb, Soybean, Thyme, Bamboo shoot, Octopus, Tade, Davana, Tamago, Tamagotake, Onion, Tamarind, Damiana, Tamagitake, Tarragon, Tarranoki, Tansy, Tangerine, Tanpopo , Cherimora, Cherry Laurel, Cherry Wild, Chigaya, Chicory, Cheese, Chichitake, Chives, Chervil, Champaka, Tuberose, Datura Chirata, horsetail, pickles,
Ivy, camellia, communis, carrot, turdkudami, diatang, thistle, ditany, dill,
Dates, Tendai-yaku, Tenma, Pepper, Touki, Dwarf Butbu Protein, Dwarf Butuyu,
Corn, corn, dokudami, eucommia, doggrass, tomato, dragon blood, durian, truffle, torubal sam, tonka, naginata koju, pear, nasta sham, nuts, natto, jujube, nutmeg, nadesico, nameko, naratake, niauli, nuuri Sankinbayoueki, carrot, garlic, rat mochi, nettle, almond, knotgrass, glue, violet, pineapple, hibiscus, malt, chickweed,
Basil, lotus, lotus cup, parsley cup, parsley, butter, butter oil, buttermilk, birch, honey, patchouli, mint, buck bean, hakkosh, hakkonu, hakkoumie, passion fruit, hatstake, buffalo berry, adlay, hanasuge, banana , Vanilla, Honeysuckle, Papaya, Barberry, Hamago, Hamasuge, Hamanas, Hamabofu, Hamamelis, Rose, Palmarosa, Pandana, Banreishi, Hikikoshi, Hishi, Pistachio, Hyssop, Hickory, Peanut, Hinoki, Hiba, Hippa, Himalayan , Loquat, betel nut, feijoa, feneglique, fennel, fujibakama,
Fujimodoki, Fusuma, Fuselyu, Petit Grain, Buchu, Grape, Grape Salmon Cas, Futomomo, Beech, Buna Haritake, Black Caraway, Blackberry, Plum, Bryonia, Prickly Ash, Primrose, Prunella, Blueberry, Breadfruit, Hay, Bay , Hazelnuts, vetiver, betel, safflower, penny royal, peppermint, snake, pepino, peptone, bergamot, bergamot mint, peruvian balsam, verbena, veronica, benzoin, boadrose, horhound, hoe, broom mushroom, housho, houho, hohoho Horse mint, horse radish, button, hop, poppy, poplar, popo, jojoba, squirt, bordeaux, bologna, maitake,
Magwalt, marshmallow, marjoram, mastic, masoi, matatabi, machiko, pine, matsuouji, mushroom, matsutake, matsubusa, matsuhod, matecha, mame, marigold, malvadaiou, quince, malaine, mallow, mango, mangosteen, mandarin orange, Mishima Psycho, Miso, Mitsumata, Beeswax, Meat, Mimosa, Myoga, Milk, Mirte, Milfoil, Myrrh, Myrobaran, Mugicha, Musk, Murasaki, Mesquite, Medosuite, Mehajiki, Maple, Melissa, Merilot, Melon, Melon, Mousenokeke, Monilia Baiyoe , Peach tree, peach, moroheiya, yakuchi, bayberry, eucalyptus, saxifrage, yuz, yucca, lily, hornbill, yogurusa, lions foot,
Lychee, life everlasting flower, lime,
Lilac, Lacanca, Lacanshaw, Raspberry, Latania, Radish, Rabdanum, Lavender, Langwald, Langmos, Rambutan, Liqueur,
Leak, Litzea, Linaloe, Longan, Ryofunsou, Ryokucha, Ryocha, Apple, Linden, Lindow, Lou, Lulissa, Reseda, Lemon, Lemongrass, Forsythia, Renge, Rembu, Rosemary, Robage, Laurel, Rongosa, Wasabi, Cottonweed, Worm Examples include natural flavors obtained from wood, worm seeds, bracken, warmoko, and the like, and flavors extracted from cooked foods such as curry, stew, and demiglace sauce, etc., which are appropriately selected and used. The amount of the fragrance added is not particularly limited, but is generally 0.1 to 50%, preferably 1 to 50%.
It is used in an addition amount of 40%, most preferably 5 to 30%. The capsule thus obtained has an effect that the core material is stably retained without the film being cured over time. Next, the present invention will be described more specifically with reference to examples.

[0014]

EXAMPLES Example 1 30 g of a hardened palm oil having a melting point of 35 ° C. in which 12% allyl isothiocyanate was dissolved was added to 50 g of an oil.
The solution was added to 60 mL of a 10% gelatin aqueous solution heated to ° C. to form oil droplets. 70 mL of water was added, and then a salt solution obtained by dissolving 0.6 g of metaphosphoric acid in 60 mL of water was added dropwise.
After completion of the dropwise addition, the gelatin solution was gradually cooled, and the precipitated coacervate droplets were adsorbed around the oil droplets to form a capsule film. The obtained capsules were separated by filtration and dehydrated.
5 g of an aqueous solution containing 5 g of sorbitol was sprayed. Air-drying was performed using starch as a drying aid to obtain 43 g of microcapsules having an average particle size of 1200 μm.

Example 2 30 g of hardened palm oil having a melting point of 35.degree.
Added to 60 mL of 10% gelatin aqueous solution heated to 0 ° C,
An oil droplet formed. 70 mL of water was added, and then a salt solution in which 0.6 g of metaphosphoric acid was dissolved in 60 mL of water was added dropwise. After the completion of the addition, the gelatin solution was gradually cooled, and the precipitated coacervate droplets were adsorbed around the oil droplets to form capsules. A film was formed. The obtained capsule is filtered off, dehydrated,
5 g of an aqueous solution containing 1.5 g of maltitol was sprayed.
Air-drying was performed using starch as a drying aid to obtain 43 g of microcapsules having an average particle size of 1200 μm.

Example 3 30 g of hardened palm oil having a melting point of 35 ° C. in which 12% allyl isothiocyanate was dissolved was added to 5 g of
Added to 60 mL of 10% gelatin aqueous solution heated to 0 ° C,
An oil droplet formed. 70 mL of water was added, and then a salt solution in which 0.6 g of metaphosphoric acid was dissolved in 60 mL of water was added dropwise. After the completion of the addition, the gelatin solution was gradually cooled, and the precipitated coacervate droplets were adsorbed around the oil droplets to form capsules. A film was formed. The obtained capsule is filtered off, dehydrated,
5 g of an aqueous solution containing 1.5 g of glucose was sprayed. Air-drying was performed using starch as a drying aid to obtain 43 g of microcapsules having an average particle size of 1200 μm.

Example 4 30 g of a hardened palm oil having a melting point of 44 ° C. in which 12% allyl isothiocyanate was dissolved was added to 5
Added to 60 mL of 10% gelatin aqueous solution heated to 0 ° C,
An oil droplet formed. 70 mL of water was added, and then a salt solution in which 0.6 g of metaphosphoric acid was dissolved in 60 mL of water was added dropwise. After the completion of the addition, the gelatin solution was gradually cooled, and the precipitated coacervate droplets were adsorbed around the oil droplets to form capsules. A film was formed. The obtained capsule is filtered off, dehydrated,
5 g of an aqueous solution containing 1.5 g of glucose was sprayed. Air-drying was performed using starch as a drying aid to obtain 43 g of microcapsules having an average particle size of 1200 μm.

[Reference product 1] Preparation of wasabi flavor 45 parts of allyl isothiocyanate, 2 parts of 3-butenyl isothiocyanate, 4-pentenyl isothiocyanate 2
, 5 parts of 5-hexenyl isothiocyanate, 1 part of 3-methylthiopentyl isothiocyanate, 5 parts of leaf wasabi extract and 43 parts of MCT, and the mixture was filtered through a filter paper to give 95 parts of wasabi flavor.

Example 5 30 g of hardened palm oil having a melting point of 44 ° C. in which 30% wasabi flavor was dissolved was added to 60 mL of a 10% aqueous gelatin solution heated to 50 ° C. to form oil droplets. 70 mL of water was added, and then a salt solution obtained by dissolving 0.6 g of metaphosphoric acid in 60 mL of water was added dropwise.
The gelatin solution was gradually cooled, and the precipitated coacervate droplets were adsorbed around the oil droplets to form a capsule film. The obtained capsule was separated by filtration, dehydrated, and sprayed with 1.5 g of maltitol. Using starch as a drying aid, air-drying was performed to obtain 40 g of microcapsules having an average particle size of 1200 μm.

Comparative Example 1 30 g of a hardened palm oil having a melting point of 35 ° C. in which 12% allyl isothiocyanate was dissolved was added to 5 g
Added to 60 mL of 10% gelatin aqueous solution heated to 0 ° C,
An oil droplet formed. 70 mL of water was added, and then a salt solution in which 0.6 g of metaphosphoric acid was dissolved in 60 mL of water was added dropwise. After the completion of the addition, the gelatin solution was gradually cooled, and the precipitated coacervate droplets were adsorbed around the oil droplets to form capsules. A film was formed. The obtained capsule is filtered off, dehydrated,
Using starch as a drying aid, air-drying was performed to obtain 47 g of microcapsules having an average particle diameter of 1200 μm.

Comparative Example 2 30 g of a hardened palm oil having a melting point of 35 ° C. in which 15% allyl isothiocyanate was dissolved was added to
Added to 60 mL of 10% gelatin aqueous solution heated to 0 ° C,
An oil droplet formed. 70 mL of water was added, and then a salt solution in which 0.6 g of metaphosphoric acid was dissolved in 60 mL of water was added dropwise. After the completion of the addition, the gelatin solution was gradually cooled, and the precipitated coacervate droplets were adsorbed around the oil droplets to form capsules. A film was formed. The obtained capsule is filtered off, dehydrated,
1.5 g of glycerin was sprayed. Using starch as a drying aid, air-dry to obtain an average particle size of 1200μ.
m of microcapsules was obtained.

Comparative Example 3 30 g of hardened palm oil having a melting point of 35 ° C. and 12% of allyl isothiocyanate was dissolved in 5
Added to 60 mL of 10% gelatin aqueous solution heated to 0 ° C,
An oil droplet formed. 70 mL of water was added, and then a salt solution in which 0.6 g of metaphosphoric acid was dissolved in 60 mL of water was added dropwise. After the completion of the addition, the gelatin solution was gradually cooled, and the precipitated coacervate droplets were adsorbed around the oil droplets to form capsules. A film was formed. The obtained capsule is filtered off, dehydrated,
1.5 g of glycerin was sprayed. Using starch as a drying aid, air-dry to obtain an average particle size of 1200μ.
m of microcapsules was obtained.

Test Example 1 Examples 1 to 5 and Comparative Examples 1 to
The microcapsules of 3 were subjected to a heating abuse test at 50 ° C. The evaluation method was as follows: 0.05 g (approximately 50) of microcapsules were weighed every day during the abuse test, added to 80 ° C. hot water, and the number of insoluble microcapsules after 5 minutes was counted to determine the residual rate Obtained. Table 1 shows the results.

[Table 1] Dissolution test of microcapsules in hot water In Comparative Examples 1 to 3, most of the samples had already been crosslinked and insolubilized at the time of one day after the abuse test, but in Example 2, almost all dissolved even after three days had passed, and obvious crosslink prevention was observed. The effect was seen.

Example 6 30 g of rapeseed oil having a melting point of 34 ° C. in which 1% hexanal was dissolved was added to 60 mL of a 10% aqueous gelatin solution heated to 50 ° C. to form oil droplets. 70 mL of water was added, and then a salt solution obtained by dissolving 0.6 g of metaphosphoric acid in 60 mL of water was added dropwise.
The gelatin solution was gradually cooled, and the precipitated coacervate droplets were adsorbed around the oil droplets to form a capsule film. The obtained capsule was separated by filtration, dehydrated, and sprayed with 1.5 g of maltitol. Using starch as a drying aid, air drying was performed to obtain 45 g of microcapsules having an average particle size of 600 μm.

Comparative Example 4 30 g of rapeseed hardened oil having a melting point of 34 ° C. in which 1% hexanal was dissolved was added to 60 mL of a 10% aqueous gelatin solution heated to 50 ° C. to form oil droplets. 70 mL of water was added, and then a salt solution obtained by dissolving 0.6 g of metaphosphoric acid in 60 mL of water was added dropwise.
The gelatin solution was gradually cooled, and the precipitated coacervate droplets were adsorbed around the oil droplets to form a capsule film. The obtained capsule was separated by filtration, dehydrated, and sprayed with 1.5 g of glycerin. Air drying was performed using starch as a drying aid to obtain 47 g of microcapsules having an average particle size of 600 μm.

Test Example 2 After abuse of the microcapsules of Example 6 and Comparative Example 4 at 40 ° C. for 9 days, 0.1 g of the microcapsules were weighed and added to 80 ° C. hot water.
The dissolution state of the insoluble microcapsules after a minute was visually observed.
In the microcapsules of Comparative Example 4, 50% or more insoluble microcapsules were confirmed, but the microcapsules of Example 6 were almost dissolved.

[Reference product 2] Preparation of katsuobushi fragrance 1-penten-3-ol 0.5 part, cis-3-penten-1-ol 0.8 part, n-hexanol 0.2 part, 1-octen-3-ol 0.5 part, Ciscis-2,5-octadien-1-ol 3.4 parts, cis-1,5,8-undecatrien-3-ol 1.0 parts, 2-octenal 0.2
Parts, 2-nonenal 0.2 parts, 2-decenal 0.5 parts, 2,
0.1 parts of 4-decadienal, 7.4 parts of o-cresol, p-
Cresol 5.7 parts, 2,4-dimethylphenol 9.4 parts,
8.4 parts of 2,6-dimethoxyphenol, 4.1 parts of 2,6-dimethoxy-4-methylphenol, 2.1 parts of 2,6-dimethoxy-4-ethylphenol, 2.2 parts of guaiacol,
1.6 parts of 4-methyl guaiacol, 0.7 parts of 4-ethyl guaiacol, 1.4 parts of 1,2-dimethoxybenzene, 1,2-
1.2 parts of dimethoxy-4-methylbenzene, 4.4 parts of 1,2-dimethoxy-4-ethylbenzene, 170 parts of a supercritical extract of katsuobushi, and 774 parts of MCT were blended and filtered through a filter paper to obtain 945 parts of a katsuobushi fragrance.

Example 7 30 g of rapeseed hardened oil having a melting point of 34 ° C. in which 5% beetroot flavor was dissolved was added to 60 mL of a 10% aqueous gelatin solution heated to 50 ° C. to form oil droplets. Add 70 mL of water, then add 0.6 g of metaphosphoric acid
Was dissolved in 60 mL of water, and after completion of the dropwise addition, the gelatin solution was gradually cooled, and the precipitated coacervate droplets were adsorbed around the oil droplets to form a capsule film. The obtained capsule was separated by filtration, dehydrated, and sprayed with 1.5 g of maltitol. Using starch as a drying aid, air drying was performed to obtain 45 g of microcapsules having an average particle size of 600 μm.

Comparative Example 5 30 g of rapeseed hardened oil having a melting point of 34 ° C. in which 5% beetroot flavor was dissolved was added to 60 mL of a 10% aqueous gelatin solution heated to 50 ° C. to form oil droplets. Add 70 mL of water, then add 0.6 g of metaphosphoric acid
Was dissolved in 60 mL of water, and after completion of the dropwise addition, the gelatin solution was gradually cooled, and the precipitated coacervate droplets were adsorbed around the oil droplets to form a capsule film. The obtained capsule was separated by filtration, dehydrated, and sprayed with 1.5 g of glycerin. Air drying was performed using starch as a drying aid to obtain 47 g of microcapsules having an average particle size of 600 μm.

Test Example 3 After abuse of the microcapsules of Example 7 and Comparative Example 5 at 40 ° C. for 9 days, 0.1 g of the microcapsules were weighed and added to 80 ° C. hot water.
The dissolution state of the insoluble microcapsules after a minute was visually observed.
In the microcapsules of Comparative Example 4, 50% or more insoluble microcapsules were confirmed, but the microcapsules of Example 8 were almost dissolved and the change in flavor was small.

Continued on the front page F term (reference) 4B047 LB10 LE08 LG18 LG22 LG23 LG25 LG26 LG28 LP09 4G005 AA01 AB21 BA06 BB01 BB24 BB30 DB06Z DC12X DC18Z DC46X DC51X DE01Z EA05

Claims (10)

[Claims] 1. A method for preventing film cross-linking, comprising coating a non-crosslinked gelatin capsule containing an isothiocyanate and / or aldehyde in a core substance with a saccharide and / or a sugar alcohol. 2. A non-crosslinked gelatin capsule having a particle size of 50 to 50.
2. The method according to claim 1, wherein the thickness is 2500 μm. 3. The method according to claim 1, wherein the non-crosslinked gelatin capsule is a microcapsule prepared as a film containing 60 to 100% by weight of gelatin as a solid content. 4. The method according to claim 1, wherein the saccharide is at least one selected from the group consisting of monosaccharides, oligosaccharides and yeast cell walls. 5. The method according to claim 4, wherein the monosaccharide is glucose. 6. The method according to claim 4, wherein the oligosaccharide is one or a combination of two or more selected from the group consisting of galactose, sucrose, maltose, lactose, trehalose, pullulan, starch syrup and cyclodextrin. The method for preventing film cross-linking described in the above. 7. The method according to claim 1, wherein the sugar alcohol is one or a combination of two or more selected from the group consisting of maltitol, xylitol and sorbitol. 8. The non-crosslinked gelatin capsule is a microcapsule prepared as a film containing 60 to 99% by weight of gelatin and 1 to 40% by weight of sugar or sugar alcohol as solids. 8. The method for preventing film cross-linking according to any one of 1 to 7. 9. The method according to claim 1, wherein the core substance further contains a fragrance. 10. A capsule which is hardly crosslinked by a film produced by using the method for preventing film crosslinkage according to claim 1.