JP2009118766A - Thickener - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thickener mixed with cellooligosaccharides, in addition to CMC-alkali metal salt, and which is improved in thickening properties and dispersibility, and to provide a food composition and a medical composition each of which is mixed with the thickener. <P>SOLUTION: This thickener is improved in thickening properties and dispersibility, by mixing cellooligosaccharides, in addition to CMC-alkali metal salt. The food composition and the medical composition each mixed with the thickener are also provided. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention comprises a thickener containing cellooligosaccharide and carboxymethylcellulose alkali metal salt (hereinafter referred to as CMC-alkali metal salt) and having improved viscosity and dispersibility, and a food composition containing the same, and The present invention relates to a pharmaceutical composition.

  CMC-alkali metal salts including sodium carboxymethylcellulose (hereinafter referred to as CMC-Na) are excellent thickeners that exhibit stable performance in a wide pH range. However, by reacting with a cation present in the liquid, particularly a polyvalent cation, a phenomenon occurs in which the potential performance is not sufficiently developed. This phenomenon is caused by the fact that Na in CMC-Na is substituted with polyvalent cations such as Mg and Ca in the liquid, that is, CMC-Na which is water-soluble is carboxymethylcellulose calcium (hereinafter referred to as water-insoluble). , CMC-Ca) and the like.

  When actually manufacturing a food composition or a pharmaceutical composition, the above-mentioned cation is contained in the tap water used. Although tap water in Japan is said to have a lower hardness than Europe and the like, it is mostly between 10 and 300 mg / L in hardness, and must be influenced by polyvalent cations. Furthermore, it is said that the hardness of tap water in Europe and other foreign countries is generally much higher than in Japan, and there is a concern that it will be affected even more strongly.

  As a method for alleviating this phenomenon, there are known a method of adding a chelating agent such as EDTA, and a method of making the solution alkaline with NaOH, sodium bicarbonate, etc., but CMC-Na is mainly used for foods and pharmaceuticals. Therefore, most substances cannot be used. Moreover, even if it is a substance which can be used, for example, baking soda, the quantity required for it exceeds the allowable range. Furthermore, ordinary foods are acidic to neutral, and those exceeding pH 8 are very rare, and are not industrially practical methods.

  In addition, CMC-Na and the like are food additives approved by the Food Sanitation Law, but the amount of use should be reduced as much as possible because the amount of use is restricted by the above laws and regulations. That is, if the potential performance is not sufficiently developed, it leads to an increase in the blending amount, which is a serious problem.

In Patent Document 1, there is a description of a cosmetic using a reaction between a zinc ion and a viscosity modifier having an ionizing group (—COO 2 ^—, etc.), but there is no description about the cellooligosaccharide of the present invention, and the purpose and use are also It is a completely different invention.
Patent Documents 2 to 5 disclose a CMC-Na stabilizer, but do not describe the combined use effect with cellooligosaccharide, which is different from the present invention.

Patent Document 6 describes a taste improver that uses a cellooligosaccharide and a high-intensity sweetener in combination, but does not mention CMC-alkali metal salts, and is a completely different invention.
Patent Documents 7 and 8 describe food compositions and pharmaceutical compositions characterized by containing cellooligosaccharides. However, no mention is made of CMC-alkali metal salt, which is different from the present invention.

Japanese Patent Laid-Open No. 7-291821 JP-A-5-161450 JP-A-8-208701 JP-A-8-208366 Japanese Patent Laid-Open No. 9-266779 JP 2002-223721 A WO / 2006/011479 WO / 2007/037249

  It is an object of the present invention to provide a thickener containing cellooligosaccharide and CMC-alkali metal salt and having improved viscosity and dispersibility, and a food composition and a pharmaceutical composition containing the same. .

  The inventor of the present invention can provide a thickener having improved viscosity and dispersibility, and a food composition and a pharmaceutical composition containing the same by blending cellooligosaccharide in addition to CMC-alkali metal salt. I found it. That is, since it becomes possible to reduce the amount of CMC-alkali metal salt, it has been found that not only the manufacturing cost of the above-mentioned food and pharmaceutical composition can be reduced, but also the safety to humans can be improved. It came to.

That is, the present invention is as follows.
(1) A thickener containing cellooligosaccharide and carboxymethylcellulose alkali metal salt.
(2) The thickener according to (1), wherein the carboxymethylcellulose alkali metal salt is sodium carboxymethylcellulose.
(3) The thickener as described in (2) whose etherification degree of sodium carboxymethylcellulose is 0.5-2.
(4) The thickener according to any one of (1) to (3), further comprising 1 ppm to 10% by mass of a high-potency sweetener.
(5) The thickener according to any one of (1) to (4), which contains cellooligosaccharide and carboxymethylcellulose alkali metal salt in a mass ratio of 1:99 to 99.9: 0.1.
(6) A food composition comprising the thickener according to any one of (1) to (5).
(7) A pharmaceutical composition comprising the thickener according to any one of (1) to (5).

  The present invention provides a thickener having improved viscosity and dispersibility by blending a cellooligosaccharide in addition to CMC-alkali metal salt, and a food composition and a pharmaceutical composition containing the same. Make it possible.

The present inventor can provide a thickener having improved viscosity and dispersibility, and a food composition and a pharmaceutical composition containing the same by blending cellooligosaccharide in addition to CMC-alkali metal salt. I found. In other words, since it is possible to reduce the amount of CMC-alkali metal salt, it has been found that not only the manufacturing cost of the above-mentioned food and pharmaceutical composition can be reduced, but also the safety to humans can be improved. It came to an eggplant.
Hereinafter, the present invention will be specifically described.

  The cellooligosaccharide of the present invention is an oligosaccharide having a structure in which about 2 to 6 glucopyranose units are linked by β-1,4, and consists of cellobiose, cellotriose, cellotetraose, cellopentaose and cellohexaose. 50 mass% or more of the main components selected from the group are contained. As this main component and its content, it is preferable to contain 70 mass% or more of cellobiose, and more preferably 90 mass% or more. This is because, among the above-mentioned cellooligosaccharide main components, the solubility in water is highest in cellobiose and is suitable for use.

Moreover, although the above-mentioned cellooligosaccharide may contain glucose as a subcomponent, it is preferable that content is 10 mass% or less from the problem of hygroscopicity or a calorie.
The method for producing the cellooligosaccharide of the present invention is not particularly specified, but from the viewpoint of safety, a cellulosic material such as pulp can be obtained by enzymatic decomposition with cellulase. preferable.

The energy conversion coefficient of cellobiose, which is the main component of the cellooligosaccharide in the present invention, is 2 kcal / g, which is an indigestible carbohydrate. From the viewpoint of consumers' recent health consciousness, there is a problem in using high-calorie digestible carbohydrates for the purpose of quality improvement.
The digestible saccharide referred to herein is a saccharide having an energy conversion coefficient corresponding to the health indication standard based on the health promotion method and having 4 kcal / g, and includes trehalose and the like.

  Cellulase as used herein is a generic term for enzymes that degrade cellulase, and includes all enzymes having cellulose-degrading activity. The cellulase enzyme source is not particularly limited, and examples thereof include cellulase-producing bacterial cells, purified cellulase enzymes, and formulated purified enzymes with additives. The dosage form is not particularly limited, and examples thereof include liquids, powders and granules.

  The origin of the cellulase is not particularly limited, and known cellulase-producing microorganisms include Tricoderma, Acremonium, Aspergillus, Bacillus, Pseudomonas, Penicillium, Aeromonus, Irpex, Sporotrum, Although there are genera, Cellobibrio genus, etc., as long as it is an enzyme that degrades cellulose, not only the above-mentioned known bacterially-derived enzymes but also novel bacterial-derived enzymes are included in the cellulase referred to in the present invention.

  The CMC-alkali metal salt of the present invention is one in which the hydroxyl group of cellulose is substituted with monochloroacetate and forms a salt with an alkali metal. That is, it is an alkali metal salt of polyvalent carboxymethyl ether of cellulose. Specific examples of the alkali metal salt of carboxymethyl cellulose include a sodium salt, a potassium salt, and a lithium salt, which may be used alone or in combination. Among these, it is preferable to use CMC-Na which is a sodium salt from the balance of the performance and price.

The degree of etherification of CMC-Na mentioned here is not particularly limited, but is preferably 0.5 to 2, more preferably 0.6 to 1.2, still more preferably 0.65 to 0. .95. In theory, the upper limit of the degree of etherification is 3, but if it exceeds 2, stable production is difficult, and if it is less than 0.4, it is difficult to dissolve in water, resulting in poor practicality.
The degree of polymerization of the CMC-alkali metal salt of the present invention is not particularly limited, but the viscosity tends to increase as the degree of polymerization increases, so it may be selected according to the purpose.

The CMC-alkali metal salt of the present invention may be used as it is, or may be used by coating the surface of another substance. For example, a crystalline cellulose preparation, a bacterial cellulose preparation, a microfibrous cellulose preparation, etc., whose surface is coated with a CMC-alkali metal salt are also included.
The ratio of the cellooligosaccharide of the present invention and the CMC-alkali metal salt is not particularly limited, but preferred mass ratio is cellooligosaccharide: CMC-alkali metal salt = 1: 99 to (99.9) :( 0.1). A more preferable mass ratio is cellooligosaccharide: CMC-alkali metal salt = 30: 70 to 90:10, and further preferably 50:50 to 70:30. If the mass ratio of the cellooligosaccharide is less than 1, the effect of improving the viscosity described later cannot be expected, and if the ratio of CMC-alkali metal salt is less than 0.1, the effect itself as a thickener becomes difficult to express. Because.

  If necessary, the thickener of the present invention can contain 1 ppm to 10% by mass of a high-intensity sweetener. The high-intensity sweetener of the present invention has a sweetness of several times to several tens of thousands of times as compared with sugar. For example, saccharin, saccharin Na, aspartame, acesulfame K, sucralose, licorice extract, stevia, Examples include thaumatin, glycyrrhizin and neotame.

The food composition of the present invention includes all foods and drinks except foods and quasi drugs specified by the Pharmaceutical Affairs Law and food additives specified by the Food Sanitation Law.
The food composition of the present invention is a composition generally provided as a food, and is not particularly limited. For example, “a gel food such as jelly, pudding, and vegetable fermented food”, “ Ice cream, ice milk, lacto ice, sherbet, frozen yogurt and other frozen desserts '', `` candy, gummy candy, troche, tablet confectionery, chocolate, biscuits, cookies, rice crackers, Japanese confectionery, sheep candy etc., Western confectionery, snack confectionery, Confectionery such as sugar confectionery and pudding, seasonings such as mayonnaise, dressing, sauces and sauces, cooked products such as fries, croquettes, dumplings, Chinese buns, curry, hayashi, meat sauce, "Retort food such as stew and soup", "Chilled food and frozen food such as noodles, soup and processed vegetables""Processed livestock products such as hamburger, bacon, sausage, salami sausage, ham", "Boiled products such as salmon, chikuwa, fish ham / sausage, fried rice cake", "Bread, cake, raw noodles, dried noodles, macaroni, spaghetti , Wheat processed foods such as Chinese bun skin, cake mix, premix, white sauce, dumplings and spring rolls, etc. "," Canned and bottling such as curry, sauce, soup, boiled and jam "," Paste such as vegetable paste, meat mince, fruit paste, seafood paste "," fruit juice, pulp drink, vegetable drink, acidic milk drink, milk drink, lactic acid bacteria drink, sterilized lactic acid bacteria drink, coffee drink, tea drink, green tea , Matcha, Cocoa Beverages, Oolong Tea, Sencha, Fruit Milk, Carbonated Beverages, Alcoholic Beverages, etc. "," Soy Milk, Prepared Soy Milk, Soy Milk Beverages, Fermentation " Soy milk such as milk and soy beverages, “milk such as milk, processed milk, low-fat milk”, “dairy products such as whipped cream, condensed milk, butter, fermented milk, cheese”, “margarine, fat spread, shortening Processed oils, liquid foods, nursing foods, etc.

  The pharmaceutical composition of the present invention is a pharmaceutical or quasi-drug composition defined by the Pharmaceutical Affairs Law, and examples thereof include solid preparations such as tablets, powders, fine granules, granules, extracts, and pills. In addition to the above solid preparations, they are used for foods such as confectionery, health foods, texture improvers, dietary fiber reinforcing agents, solid foundations, bath preparations, animal drugs, diagnostic agents, agricultural chemicals, fertilizers, ceramics catalysts, etc. Are also included in the present invention. Although its use is not particularly limited, it is suitable for oral compositions such as syrups and toothpastes.

  Examples of the dosage form of the quasi-drug composition include, for example, “hair-setting agents such as set lotions, hair sticks, hair creams, hair sprays, hair liquids” and “hair-care agents such as hair tonics, hair treatments, and hair lotions”. , "Hair-washing agents such as scalp, hair-washing powder, shampoo", "Hair rinses, oil-rinsing, cream-rinsing, body-rinsing, facial-rinsing, etc.", "Cleansing cream, facial cleansing cream, cleansing milk, cleansing lotion, powder-washing etc. Face wash "," packs, oily creams, neutral creams, weakly acidic creams, milk lotions, skin milks "," dry skin lotions, skin lotions for normal skin, skin lotions for oily skin , Makeup for men, lotion, men lotion, after shave lotion "Lipsticks such as lipstick, lip gloss, lip balm", "Bath salts and bath oils such as bath oil", "Cosmetic oils containing olive oil, baby oil", "Sunscreen cosmetics", "Sunscreen" “Cosmetics”, “oral compositions such as toothpaste, toothpaste, and oral spray” may be used.

As long as the effects of the present invention are not hindered, the thickener of the present invention and the food and pharmaceutical composition, in addition to the above ingredients, the following food materials, food additives, pharmaceuticals, pharmaceutical additives and the like are appropriately blended. You may do it.
The food material referred to here is a material that is generally used as a raw material of food. Except for pharmaceuticals and quasi-drugs specified by the Pharmaceutical Affairs Law and food additives specified by the Food Sanitation Law, All that is provided to is included.

The food additive referred to here is a substance added for the purpose of processing or storing food.
Examples of food additives are those specified by the Ministry of Health, Labor and Welfare's “designated additive list”, “existing additive list item list”, “natural fragrance-based raw material list”, and “food that is generally used for food and drink. Food additives listed in the “List of Items Used as Additives”, those that have been confirmed to be safe by international organizations such as JECFA, and food additives that are approved for use in other countries such as the United States and Europe Products, preservatives, shelf-life improvers, antioxidants, sweeteners, colorants / pigments, emulsifiers, thickening gelling agents, quality improvers, seasonings, acidulants, fortifiers, fragrances, enzymes And so on.

Examples of food materials and food additives include the following.
Examples of food materials mentioned here include fruits and vegetables and extracts thereof, processed fruits and vegetables (fruit preparations, fruit sauces, jams, etc.), dried fruits (raisins, dried pineapples, etc.), nuts and seeds (Walnuts, peanuts, almonds, macadamia nuts, pecan nuts, soybeans, sesame seeds, eggplants, etc.), milk, processed milk, soy milk, fruit juice, vegetable juice, eggs (liquid egg, egg yolk powder, etc.), cocoa powder, sugar and sugar alcohol , Meat and fish extracts, proteins, peptides, amino acids, dietary fiber, naturally derived polymers (collagen, hyaluronic acid, natural fiber, etc.), vitamins, physiologically active substances (coenzyme Q10, α-lipoic acid, β- Glucan, ceramide, etc.), starches, dextrin, fats and oils (salad oil, sesame oil, lard, rapeseed oil, shortening, etc.), al Cole, salt (minerals such as salt and Ca), seasoning (soy sauce, miso, vinegar, mirin, sugar, mayonnaise, dressing, sauce, soy sauce, sauces, etc.), spice (cinnamon, pepper, chili, etc.) ) Etc.

  Examples of preservatives and shelf-life improvers include, for example, hydrogen peroxide, sorbic acid and sorbic acid K, dehydroacetic acid Na, p-hydroxybenzoates, benzoic acid and sodium benzoate, propionic acid and salts thereof, hypochlorous acid, and the like. Na chlorate, acetic acid, sodium acetate, glycine, ethyl alcohol, polylysine and its preparation, protamine and its preparation, lysozyme and its preparation, pectin degradation product, alanine, thiamine lauryl sulfate, yuccaform extract, chitosan and its preparation, And propylene glycol.

Examples of the antioxidant include butylhydroxyanisole, butylhydroxytoluene, L-ascorbic acid and sodium ascorbate, erythorbic acid and sodium erythorbate, mixed cophenol and the like.
Examples of the sweetener include the above-described high-intensity sweetener, monosaccharide (allose, talose, growth, glucose, altrose, mannose, galactose, idose, fructose, ribose, lyxose, xylose, arabinose, apiose, erythrose, threose Glyceraldehyde, cedoheptulose, coliose, psicose, sorbose, tagatose, ribulose, xylulose, erythrulose, dihydroxyacetone, etc., disaccharides and oligosaccharides (sucralose, trehalose, cordobiose, nigerose, maltose, isomaltose, isotrehalose, sophorose, Laminaribiose, gentiobiose, lactose, sucrose, palatinose, trehalose, fructooligosaccharide, palatinose oligosaccharide, g Cosyl sucrose, lactosucrose, theandelose, galactosyl lactose, lactulose, α-linked galactooligosaccharide, malto-oligosaccharide, isomalto-oligosaccharide, panose, nigerooligosaccharide, trehalose, dextrin, cyclodextrin, branched cyclodextrin, gentiooligosaccharide, xylooligosaccharide, chitin Oligosaccharide, chitosan oligosaccharide, soybean oligosaccharide, raffinose, beet oligo, etc.), sugar alcohols (glycerol, erythritol, xylitol, ribitol, arabitol, galactitol, sorbitol, mannitol, reduced palatinose, malotriitol, isomaltitol , Maltotetritol, isomaltotetriitol, etc.), syrup, reduced starch syrup, sugar-containing syrup, liquid sugar, molasses, honey, etc. The chemical structure and properties (solid, liquid, granule, etc.) are not particularly limited.

Coloring agents include β-carotene pigment, extracted carotene pigment, vitamin B2, copper chlorophyll and copper chlorophyll Na, anato, red cabbage, red radish, squid misty, plant charcoal powder, turmeric, elderberry, cacao, carob, chlorophyll, gardenia Yellow, gardenia blue, gardenia red, grapeskin, cochineal, gorilla, perilla, shea nut, spirulina, tamarind, onion, tomato, paprika, beet red, grape juice, red beetle, safflower yellow, safflower red, marigold, purple potato, purple Examples include corn, rack and caramel.
Examples of the dye include Red No. 2, Red No. 3, Red No. 40, Red No. 102, Red No. 105, Red No. 106, Yellow No. 4, Yellow No. 5, Blue No. 1, Blue No. 2, Red No. 3 Lake. Red No. 40 rake, Yellow No. 4 rake, Yellow No. 5 rake, Blue No. 1 rake, Blue No. 2 rake and the like.

  Examples of the emulsifier include glycerin fatty acid ester, sorbitan fatty acid ester, PG ester, sucrose fatty acid ester, organic acid monoglyceride, polyglycerin fatty acid ester, polyglycerin condensed ricinoleic acid ester, propylene glycol fatty acid ester, lecithin (lecithin, enzymatic degradation) Lecithin, enzyme-treated lecithin, etc.) and plant sterols.

  Examples of the thickening gelling agent include gelatin, alginic acid and salts thereof (for example, sodium alginate), propylene glycol alginate, carboxymethylcellulose calcium, hydroxypropylmethylcellulose, sodium starch glycolate, sodium starch phosphate, methylcellulose, Sodium polyacrylate, almond gum, gum arabic, xanthan gum, arabinogalactan, elemi resin, karaya gum, gaddi gum, dammar resin, tragacanth gum, peach resin, ama seed gum, cassia gum, guar gum, guar gum degradation product, locust bean gum, tara gum, psyllium seed Gum, mackerel mugwort seed gum, sesbania gum, tamarind seed gum, gellan gum, triacan Sugam, Alginic acid, Carrageenan, Fukuronori extract, Farserlan, Aloe vera extract, Okra extract, Kidachi aloe extract, Trolo aoi, Pectin, Aeromonas gum, Aureobasidium broth, Azotobacter vinelandie gum, Welan gum, Erwinia mitsuensis gum Enterobacter simanas gum, enterobacter gum, curdlan, gellan gum, sclerogum, dextran, natto gum, pullulan, soy polysaccharide, carrageenan, macrohomopsis gum, lambzan gum, levan, yeast cell wall, microfibrous cellulose and its preparation, Bacterial cellulose and its preparation, crystalline cellulose and its preparation, powdered cellulose and its preparation, chitin, chitosan, glucosamine, oligoglucosamine, Rukoman'nan, konjac flour, agar, dextrin, branched dextrin, indigestible dextrin, PGA, porphyran, furcellaran, and fucoidan like.

As quality improvers, stearoyl lactate Ca, phytic acid, propylene glycol, phosphate phosphate, Na phosphate, Na pyrophosphate, polyphosphate Na, meta-hexaphosphate Na, phosphate K, ammonium phosphate, phosphoric acid, baked Examples include alum, raw alum, whey protein, casein, caseinate, plasma powder, powdered soy protein, powdered wheat protein, pasty wheat protein, EDTA salts and the like.
Examples of the seasoning include sodium glutamate, nucleic acid seasoning, amino acid seasoning, extract seasoning, yeast extract, glycine, and alanine.
Examples of the acidulant include citric acid and salts thereof, lactic acid, malic acid, tartaric acid, succinic acid, fumaric acid, adipic acid, gluconic acid solution, glucono delta lactone and the like.

Examples of the fortifier include vitamin A, vitamin B1, vitamin B2, vitamin B6, vitamin B12, vitamin C, vitamin D, vitamin E, nicotinic acid and nicotinamide, folic acid, patenoic acid Ca, gluconic acid Ca, and lactate Ca , Natural Ca, milk Ca and the like.
Examples of the fragrance include fruit flavors such as peach flavor, orange flavor and lemon flavor, aroma flavors, sugar flavors such as maltol and furaneol, flavor enhancers such as sotron, polyphenols such as flavonoids and cacao mass, and precursors. Examples include flavors, meat flavors, coffee flavors, milk flavors, menthols, and decalactones.
Examples of the enzyme include α-amylase, β-amylase, glucoamylase, pullulanase, glucose isomerase, protease, rennet, pancreatin, and papain.

The term “medicine” as used herein refers to a drug prescribed by the Pharmaceutical Affairs Law. That is, it corresponds to the following (1) to (3), and many of medicinal medicinal ingredients are included in this.
(1) Items stored in the Japanese Pharmacopoeia (2) Items intended to be used for diagnosis, treatment or prevention of human or animal diseases, machinery, dental materials, medical supplies Non-sanitary products (hereinafter referred to as “machinery equipment”) (excluding quasi-drugs)
(3) Products that are intended to affect the structure or function of the human or animal body, and are not machinery or equipment (excluding quasi-drugs and cosmetics).

  Pharmaceutical additives mentioned here are substances other than active ingredients contained in pharmaceutical preparations that do not fall under the Pharmaceutical Affairs Law or quasi-drugs. It is a general term for substances added to pharmaceuticals and quasi-drugs for the purpose of “improving usefulness” and “increasing usability”. Depending on the application, excipients, disintegrants, binders, fluidizers, flavoring agents, fragrances, colorants, sweeteners, solvents, fats and oils, thickeners, surfactants, gelling agents, stabilizers, preservatives, It is classified into buffer, suspending agent, thickener and the like. Representative pharmaceutical additives are listed in “Pharmaceutical Additives Encyclopedia” (Pharmaceutical Daily Inc.), “Pharmaceutical Additives Handbook” (Pharmaceutical Daily Inc.), and the like.

The thickening improving effect of the thickener of the present invention is expressed by the following formula based on the viscosity in a 0.01% by mass calcium chloride aqueous solution and based on the viscosity of the thickener solution not containing cellooligosaccharide. When the viscosity increase rate is 3% or more, it is determined that there is a thickening improvement effect.
Thickening rate (%) = (α−β) / β × 100
Here, α: viscosity of a thickener solution blended with cellooligosaccharide (mPa · s), β: viscosity of a thickener solution blended with no cellooligosaccharide (mPa · s)
The “0.01 mass% calcium chloride aqueous solution” referred to here is model tap water in Japan, and is prepared so that the hardness is about 90 mg / L. That is, how much performance is expressed in this model tap water is regarded as practical performance.

Next, the present invention will be described in more detail with reference to examples. The evaluation of various physical properties of the substance according to the present invention was based on the following method.
<Sugar composition>
The sugar composition analysis was performed under the following conditions.
Apparatus: High-performance liquid chromatograph “LC-20A type” (manufactured by Shimadzu Corporation)
Detector: Differential refractive index detector (RI detector)
Column: “Asahipak NH2P-50” (manufactured by Showa Denko KK)
Column temperature: 40 ° C
Mobile phase: acetonitrile / water = 75/25 (volume ratio)
Flow rate: 1 mL / min

<Degree of etherification of CMC-Na>
About 1 g of the sample was precisely weighed, wrapped in filter paper and placed in a magnetic crucible, and ashed in an electric furnace at 630 ° C. The produced sodium hydroxide was titrated with 0.1N sulfuric acid using phenolphthalein as an indicator. From the sulfuric acid amount A (ml) required for neutralization titration and the titer f of 0.1 N sulfuric acid, the degree of etherification was calculated according to the following formula.
Degree of etherification = 162 × A × f ÷ (10000−80 × A × f)

<PH>
The pH was measured with a pH meter (“HM-50G type” manufactured by Toa DKK Corporation).

<Viscosity (Ostwald viscometer)>
The sample solution was subjected to a measurement operation at 25 ° C. using an Ostwald viscometer according to “JIS Z 8803-1991: Viscosity of liquid—Measurement method”, “5. Viscosity measurement method using capillary viscometer”. The viscosity was calculated from a calibration curve prepared using “JIS Z 8809-2000: Viscometer Calibration Standard Solution”.

<Viscosity (rotary viscometer)>
The sample solution was filled into a beaker or an adapter and allowed to stand at a predetermined temperature for 3 hours. Furthermore, it set to the rotational viscometer (B type viscometer, the Toki Sangyo Co., Ltd. make, "TV-10 type"), the viscosity after 60 second was read, and the viscosity was measured. The rotor rotation speed was 60 rpm, and the rotor and adapter were appropriately changed depending on the viscosity.

<Determination of thickening improvement effect>
The thickening improving effect in the thickener of the present invention is based on the above-mentioned viscosity, and the thickening ratio represented by the following formula is 3% or more based on the viscosity of the thickener solution not containing cellooligosaccharide. If it is, it is determined that there is an effect of improving thickening.
Thickening rate (%) = (α−β) / β × 100
Here, α: viscosity of a thickener solution blended with cellooligosaccharide (mPa · s), β: viscosity of a thickener solution blended with no cellooligosaccharide (mPa · s)

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to these at all.
The raw materials used in the examples are shown in the following (1) to (10).
(1) Production of cellooligosaccharide: Trichoderma reesei, GL-1 strain (Incorporated Administrative Agency, National Institute of Advanced Industrial Science and Technology, Patent Biodeposition Center, receipt number FERM BP-10323) is inoculated on a normal agar medium and cultured at 37 ° C. for 7 days Thereafter, 1 platinum spore was removed from the surface of the medium, 1 g of polypeptone, 0.5 g of yeast extract, 2 g of potassium phosphate, 1.5 g of ammonium sulfate, 0.3 g of magnesium sulfate, 0.3 g of calcium chloride, 1 mL of trace element (boric acid) Purification of 6 mg, ammonium molybdate tetrahydrate 26 mg, iron (3) hexahydrate 100 mg, copper sulfate pentahydrate 40 mg, manganese sulfate tetrahydrate 8 mg, zinc sulfate heptahydrate 200 mg in a total volume of 100 mL Water dissolved), adecanol 1mL, crystalline cellulose (Asahi Kasei Chemicals Co., Ltd.) Was inoculated into Company Ltd. "Ceolus PH-101") medium were suspended and dissolved in 10g of purified water total amount 1L, for 5 days under aeration-agitation culture at 28 ° C..

During the culture, the pH of the medium was adjusted to 2.8 to 4.7 using an aqueous sodium hydroxide solution. The cultured liquid is centrifuged, the supernatant is sterilized with a microfiltration membrane having an opening of 0.46 μm, and the filtrate is ultrafiltered with a molecular weight cut off of 13,000 (“Microza Pencil Type Module” manufactured by Asahi Kasei Chemicals Corporation). ACP-0013 ") was used to obtain a crude enzyme by concentration 10 times by volume.
Next, use a commercially available softwood-derived dissolving pulp, and hydrolyze it with a hydrochloric acid concentration of 0.4% aqueous hydrochloric acid at 120 ° C. for 1 hour to wash the acid-insoluble residue and filter to obtain a wet cake. It was. Using this wet cake as an aqueous dispersion with a concentration of 10% cellulose, using an ultra-high performance disperser / wet pulverizer (Ashizawa Co., Ltd., “Pearl Mill RL”, φ1 mm zirconia bead filling rate 80%) A grinding treatment was performed to obtain a cellulose fine particle dispersion.

The ground cellulose was suspended and dissolved in a 50 mM acetic acid-sodium acetate buffer solution (pH 4.5) so that the protein concentration was 2% by mass and the protein concentration was 0.25%, and the total volume was 1000 mL. .
The glass flask was placed in a 55 ° C. water bath and reacted for 4 hours while stirring the interior. After completion of the reaction, 300 μL of the reaction solution was dispensed in a suspended state, the enzyme and undegraded cellulose were removed using an ultrafiltration module (fractional molecular weight 10,000), and then the sugar concentration was analyzed by high performance liquid chromatography. . The sugar concentration of the reaction solution was 0.3% by mass of glucose and 1.5% by mass of cellobiose.

The reaction solution is filtered through an ultrafiltration membrane having a molecular weight cut off of 13,000 (“Asahi Kasei Chemicals Co., Ltd.,“ Micro-the Pencil type module ACP-0013 ”), and the resulting filtrate is deionized with a cation / anion exchange resin. Treatment and distillation under reduced pressure at 70 ° C. gave an aqueous solution with a 20-fold sugar concentration.
100 mL of the cellooligosaccharide aqueous solution obtained above was introduced into a 200 mL glass flask, cooled to 70 ° C. to 5 ° C. at a rate of 10 ° C. per hour while stirring, and then ethanol was added to water for crystallization. The cellooligosaccharide crystallized in the aqueous solution was filtered under reduced pressure, dried, pulverized, and sieved to obtain cellooligosaccharide powder. The sugar composition of the obtained cellooligosaccharide powder was 0.9 mass% glucose, 98.2 mass% cellobiose, 0.4 mass% cellotriose, and 0.2 mass% cellotetraose.

(2) Upper white sugar (Mitsui Sugar Co., Ltd.)
(3) Neotame (manufactured by NutraSweet)
(4) CMC-Na reagent (Wako Pure Chemical Industries, Ltd.)
(5) CMC-Na (Daiichi Kogyo Seiyaku Co., Ltd., food additive grade)
(6) Dextrin (Sanwa Starch Co., Ltd., DE = about 23)

(7) Microfibrous cellulose preparation Commercial wood pulp (average polymerization degree = 1720, α-cellulose content = 78% by mass) is cut into a 6 × 16 mm square so that the solid content concentration becomes 80% by mass. Water was added to the. This was passed once through a cutter mill (cutting head / horizontal blade gap: 2.03 mm, impeller rotation speed: 3600 rpm), taking care not to separate water and pulp chips as much as possible.
The cutter mill-treated product and water were weighed out so that the cellulose concentration was 1.5% by mass, and stirred until there was no fiber entanglement. This aqueous dispersion was treated with a grindstone rotary grinder (grinder rotation speed: 1800 rpm). The number of treatments was 2, and the grinder clearance was changed from 110 to 80 μm.

Next, the obtained aqueous dispersion was directly subjected to 18 passes with a high-pressure homogenizer (treatment pressure: 55 MPa) to obtain a microfibrous cellulose slurry.
Furthermore, CMC-Na and dextrin are added to the microfibrous cellulose slurry so that the microfibrous cellulose: CMC-Na: dextrin = 70: 18: 12 (mass ratio) in terms of dry weight, and 15 kg is stirred. A CMC-Na / microfibrous cellulose slurry mixed solution was obtained by stirring and mixing at 8000 rpm for 30 minutes with a type homogenizer (“Prim Auto Co., Ltd.,“ TK AUTO HOMO MIXER ”).
Next, this mixed solution was cast into an aluminum plate with a thickness of 2 mm using an applicator and dried at 120 ° C. for 45 minutes using a hot air dryer to obtain a film. This was pulverized with a cutter mill (manufactured by Fuji Paudal Co., Ltd.) to almost pass through a sieve having an opening of 1 mm to obtain a microfibrous cellulose preparation.

(8) Soy sauce (made by Kikkoman Corporation)
(9) Apple cider vinegar (Mizkan Co., Ltd., acidity 5.0%)
(10) Model tap water (0.01 mass% calcium chloride aqueous solution)
Calcium chloride was added to ion exchange water at 25 ° C. so as to be 0.01% by mass. Furthermore, it stirred and melt | dissolved for 5 minutes with the propeller stirring blade.

[Example 1]
0.3% by mass of CMC-Na reagent and 3% by mass of cellooligosaccharide are mixed to obtain a mixed powder. The mixed powder was added to 25 ° C. model tap water so that the total amount became 100 mass% while stirring at 400 rpm using a propeller stirring blade. At this time, the large thickener of thickener was not generated and the dispersibility was good.
Next, while maintaining the temperature, stirring is continued for another 10 minutes, and then the mixture is transferred to a closed container. Furthermore, what was left still for 1 hour in 25 degreeC atmosphere was made into the thickener solution A, and the evaluation result is shown in Table 1. As a result, it was found that there was a thickening improving effect as compared with the reference of Comparative Example 1. Moreover, instead of cellooligosaccharide, the viscosity was higher than the viscosity of Comparative Example 2 in which upper sucrose (sucrose) was added, suggesting that the effect was exhibited by adding cellooligosaccharide. The viscosity of the thickener solution A was determined with an Ostwald viscometer.
The degree of etherification of CMC-Na was measured and found to be 0.84.

[Example 2]
0.4% by mass of microfibrous cellulose preparation and 5% by mass of cellooligosaccharide are mixed to obtain a mixed powder. Using a rotary homogenizer (Primix Co., Ltd. “TK homomixer”), the mixed powder was added to 25 ° C. model tap water so that the total amount would be 100 mass% while stirring at 8000 rpm. . At this time, the large thickener of thickener was not generated and the dispersibility was good.
Next, while maintaining the temperature, stirring is continued for another 10 minutes, and then the mixture is transferred to a beaker. Furthermore, what was left still at 25 degreeC for 3 hours was made into the thickener solution B, and the evaluation result is shown in Table 2. As a result, it was found that there was a thickening improving effect as compared with the reference of Comparative Example 3. The viscosity of the thickener solution B was determined with a rotational viscometer.

[Example 3]
According to the composition of Table 3, grated weeping C was produced by the following procedure.
CMC-Na, cellooligosaccharide, and sucrose are mixed to obtain a mixed powder. The mixed powder was added to 25 ° C. model tap water so that the total amount became 100 mass% while stirring at 400 rpm using a propeller stirring blade. At this time, the large thickener of thickener was not generated and the dispersibility was good.

Further, soy sauce, salt, grated radish, grated garlic and neotame are added and stirring is continued until the temperature reaches 80 ° C. for sterilization. Then, apple vinegar was added and mixed, filled in a sealed container and stored at 10 ° C. for 3 days, and grated C. The pH was 4.2.
The solid matter of grater C was removed, transferred to a beaker, and allowed to stand at 10 ° C. for 3 hours, and the viscosity was measured using a rotational viscometer. The evaluation results are shown in Table 4. As a result, it was found that there was a thickening improving effect as compared with the reference of Comparative Example 4.

[Comparative Example 1]
Table 1 shows the results of preparing and evaluating the thickener solution W by the same method as in Example 1 without adding the cellooligosaccharide of Example 1. In addition, a large number of mamako was generated when the thickener was added, and there was a problem in dispersibility.
Compared with Example 1, the viscosity was remarkably low.

[Comparative Example 2]
Table 1 shows the results of preparing and evaluating the thickener solution X in the same manner as in Example 1 using super white sugar (sucrose) instead of the cellooligosaccharide of Example 1.
Compared with Example 1, the viscosity was remarkably low.

[Comparative Example 3]
Table 2 shows the results of preparing and evaluating the thickener solution Y by the same method as in Example 2 without adding the cellooligosaccharide of Example 2.
Compared to Example 2, the viscosity was significantly lower.

[Comparative Example 4]
Table 4 shows the results of preparing and evaluating grated weeping Z in the same manner as in Example 3 by adding upper white sugar instead of the cellooligosaccharide of Example 3 according to the formulation in Table 3.
Compared with Example 3, the viscosity was low.

  The present invention provides a thickener having improved viscosity and dispersibility by adding a cellooligosaccharide in addition to CMC-alkali metal salt, and a food composition and a pharmaceutical composition containing the same. Is possible. That is, since the amount of CMC-alkali metal salt can be reduced, not only the manufacturing cost of the food and pharmaceutical composition described above can be reduced, but also safety for humans can be improved.

Claims (7)

Thickener containing cellooligosaccharide and carboxymethylcellulose alkali metal salt. The thickener according to claim 1, wherein the carboxymethylcellulose alkali metal salt is sodium carboxymethylcellulose. The thickener of Claim 2 whose etherification degree of sodium carboxymethylcellulose is 0.5-2. The thickener according to any one of claims 1 to 3, further comprising 1 ppm to 10 mass% of a high-intensity sweetener. The thickener according to any one of claims 1 to 4, comprising cellooligosaccharide and carboxymethylcellulose alkali metal salt in a mass ratio of 1:99 to 99.9: 0.1. The food composition containing the thickener in any one of Claim 1 to 5. A pharmaceutical composition comprising the thickener according to any one of claims 1 to 5.