JP2009120552A - Method for manufacturing toothpaste agent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To commercially advantageously manufacture a toothpaste agent composition that does not give a sticky feeling when used, exhibits excellent dispersiblity in the oral cavity, forms no lumps in its manufacturing process to give a smooth paste skin, has good stability with time of moldability and exhibits excellent preservation stability to cause no deposits during preservation. <P>SOLUTION: The toothpaste agent composition comprising a binding agent, a wetting agent, a polishing agent, a foaming agent and water is manufactured by a process comprising (1) a step of preparing a swollen aqueous solution comprising the binding agent and the wetting agent, (2) a step of mixing and kneading the polishing agent into the swollen aqueous solution and (3) a step of mixing the foaming agent with the kneadate of the polishing agent, wherein the swollen aqueous solution is prepared by mixing a mixed liquid of sodium alginate and the wetting agent with water and calcium citrate is subsequently added to the swollen aqueous solution to form alginic acid gel thereby causing the swollen aqueous solution to gel in the first step, then the second step is carried out, and sodium alkyl sulfate is used as the foaming agent in the third step. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention has no sticky feeling during use, is excellent in dispersibility in the oral cavity, does not form lumps during the production process, has a smooth kneaded skin, has good moldability over time, and is stable during storage. The present invention relates to a method for producing a toothpaste composition having no deposit and good storage stability.

  The basic compounding components of the toothpaste composition are a foaming agent, a binder, an abrasive, a wetting agent, water and the like. Here, the toothpaste composition is mixed with a binder such as sodium carboxymethylcellulose, carrageenan, guar gum, gelatin, xanthan gum, etc. in order to keep good moldability stably over time. Since the binder is a water-soluble polymer, it has a viscous property, so that there is a problem that the toothpaste composition is sticky at the time of use or inferior in oral dispersibility. Also, if the amount of the binder is increased for the purpose of improving the stability over time of the moldability, the stickiness during use becomes worse and the dispersibility in the oral cavity becomes worse. Conversely, if the amount of the binder is decreased Although the stickiness at the time of use and dispersibility in the oral cavity can be improved, the stability over time of the moldability is lowered, and it has been difficult to simultaneously solve the above conflicting problems in the toothpaste composition.

  Gels such as alginic acid gel can be included in the preparation as one means to ensure the stability over time of the moldability while improving the stickiness during use unique to viscous water-soluble polymers and the poor dispersibility in the oral cavity. For example, gelling water-soluble polymers can change the structure to avoid stickiness and poor dispersibility in the oral cavity due to the unique viscosity of water-soluble polymers. By containing a certain gel, it is considered that the stability over time of the moldability can be maintained without increasing the amount of the binder, and the above problems can be improved.

There are various proposals as a method for producing a preparation using an alginate gel. Specifically, as a 1-unit oral product coated with a film, an alginate gel-like mixture containing sodium alginate, flavoring agent, moisturizer, water and vegetable oil is shaped into a 1-unit dosage form. It is gelled by immersion in an aqueous coagulation bath containing calcium ions, solidified without drying to form a film, and when it is chewed in the mouth, it changes from a solid to a paste 1 Production method of unit-type toothpaste (Patent Document 1; Japanese Patent Laid-Open No. 62-223109), powder of alginic acid and calcium salt as gelling agent on the surface of drug-containing material coated with sustained-release coating film A method for producing a pharmaceutical composition that is coated with a water-soluble binder while being sprayed and granulated (Patent Document 2; JP-A-2003-34632) has been proposed.
However, the above method is a technique for forming a film with an alginate gel, and is difficult to apply to the production of a uniform paste-like toothpaste composition, and does not solve the above problems.

  Further, Patent Document 3 (Japanese Patent Laid-Open No. 2005-263948) contains an oil-soluble substance in which an oil-soluble substance and a calcium component are dispersed in an aqueous solution in the presence of a surfactant, and then a thickening stabilizer is added. Although a method for producing a powder has been proposed, this method is a method for producing a powder and cannot be applied as a production method for incorporating an alginic acid gel into a paste-like toothpaste composition.

On the other hand, as a method for producing a toothpaste, for example, a method including the following steps (Patent Document 4; JP-A-11-171743) has been proposed.
(1) Step of preparing a swelling aqueous solution containing a binder and a wetting agent (2) Step of mixing a fragrance with the swelling aqueous solution (3) Step of kneading an abrasive with the swelling aqueous solution mixed with the fragrance (4) A step of mixing a foaming agent into the abrasive kneaded product In addition to this, various methods for producing a toothpaste are disclosed (Patent Document 5; JP-A-11-171744, Patent Document 6; 11-171745, Patent Document 7; JP-A-11-171747, Patent Document 8; JP-A-2000-75756, Patent Document 9; JP-A-6-72833).
However, the above Patent Documents 5 to 9 do not contain a toothpaste containing an alginic acid gel nor a production method thereof.

  Patent Document 10 (Japanese Patent Laid-Open No. 2005-104966) discloses a solution obtained by dissolving a gelling agent selected from agar, duran gum, carrageenan, pectin and sodium alginate in a water-soluble solvent, such as an acidic substance or a metal salt. Viscosity at 25 ° C. of 1 to 5 containing microgel particles having an average particle size of 0.01 μm or more and less than 1,000 μm by carrying out a shearing process while gelling by addition of a crosslinking agent or by crosslinking and forced cooling A method for producing a composition for the oral cavity of 1,000 mPa · s has been proposed.

  In this Patent Document 10, a gelling agent is directly dissolved in a water-soluble solvent such as water to obtain an aqueous solution, and this dissolved solution is gelled by addition of a crosslinking agent or addition of a crosslinking agent and forced cooling to 2 m / s or more. It is described that an oral composition containing the microgel particles having fluidity and yield value can be produced by shearing and crushing with a shearing force of. However, this composition for oral cavity is filled in a spray-type container or the like and sprayed in the form of a mist, and has a viscosity of 1 to 5,000 mPa · s (0.001 to 5 Pa · s). In particular, the viscosity at 25 ° C. is 20,000 mPa · s (20 Pa · s) or more, and the shape is different from the pasty toothpaste with a viscosity of 20,000 mPa · s (20 Pa · s) or more. In such a low-viscosity composition for oral cavity, it is possible to contain a gel by the above-mentioned method, but if this method is adopted and an alginate gel is contained in a paste-like toothpaste composition, it is produced. There is a problem that remarkable lumps are formed in the process, and the stability of moldability with time is deteriorated, and it is difficult to solve the above problems.

  As described above, in the conventional technology, it is difficult to uniformly and stably disperse the alginic acid gel in the paste-like toothpaste composition, and it is difficult to disperse the above-mentioned feeling of use and oral dispersibility and moldability in the toothpaste composition. It has been difficult to solve the conflicting problem of stability over time. Furthermore, when a calcium salt is contained in the toothpaste composition, when sodium alkyl sulfate, which is widely used as a foaming agent, is used in the toothpaste composition, there is a problem that precipitates are generated during storage, and the quality is high. Is difficult to formulate.

  Therefore, it is desired to develop a technology capable of solving the above-mentioned problems of use, the dispersibility in the oral cavity and the temporal stability of the moldability and obtaining a high-quality toothpaste composition.

JP-A-62-2223109 JP 2003-34632 A JP 2005-263948 A Japanese Patent Laid-Open No. 11-171743 JP-A-11-171744 Japanese Patent Laid-Open No. 11-171745 JP-A-11-171747 JP 2000-75756 A JP-A-06-72833 JP 2005-104966 A

  The present invention has been made in view of the above circumstances, has no stickiness at the time of use, excellent in dispersibility in the oral cavity, has no formation of lumps in the manufacturing process, has a smooth knead appearance, and is stable over time in formability. It is an object of the present invention to provide a method for producing a toothpaste composition that can efficiently produce a toothpaste composition that is excellent in storage stability and excellent in storage stability.

As a result of intensive studies to achieve the above object, the inventors of the present invention have developed a toothpaste composition comprising a binder, a wetting agent, an abrasive, a foaming agent and water.
(1) A step of preparing a swelling aqueous solution containing a binder and a wetting agent (2) A step of kneading an abrasive in the swelling aqueous solution (3) A step including a step of mixing a foaming agent in the abrasive kneaded product In manufacturing, a mixed aqueous solution of sodium alginate and a wetting agent and water are prepared in the first step to prepare a swollen aqueous solution, and then calcium citrate is added to the swollen aqueous solution to form an alginate gel, After the swelling aqueous solution is gelled, the second step is performed, and in the third step, sodium alginate is mixed as a foaming agent, so that the sodium alginate is cross-linked by the addition of calcium citrate. A toothpaste composition is obtained, and such a toothpaste composition has little stickiness during use, is excellent in dispersibility in the oral cavity, and forms a dama in the manufacturing process. It has been found that it has a smooth kneading appearance, good moldability over time, no precipitation of alkyl sulfates, etc. during long-term storage, and good storage stability. It came to make.

  In the production method of the present invention, when the toothpaste composition is produced by performing the above steps (1) to (3), a mixture of sodium alginate and a wetting agent and water are mixed in the first step. Then, a calcium citrate is added to the swelling aqueous solution to form an alginic acid gel, and after the swelling aqueous solution is gelled, the second step is performed, whereby sodium alginate is added to the swelling aqueous solution. By uniformly adding calcium citrate to this swollen aqueous solution, calcium citrate is also uniformly dispersed, so that sodium alginate is rapidly crosslinked, and alginate gel is formed without the formation of sodium alginate lumps. And uniformly and stably dispersed, and the entire swollen aqueous solution is uniformly gelled. Then, kneading the abrasive in this gel, adding sodium alkyl sulfate as a foaming agent, the abrasive and sodium alkyl sulfate are also uniformly dispersed in the gel, and after the gelation, the abrasive is added, Finally, by adding and mixing sodium alkyl sulfate, it is possible to prevent precipitation of alkyl sulfate during storage by avoiding the formation of insoluble calcium alkyl sulfate by contacting calcium ions and sodium alkyl sulfate. .

In Patent Document 10, a gelling agent is directly dissolved in a water-soluble solvent such as water to obtain an aqueous solution, and this dissolved solution is gelled by addition of a crosslinking agent or addition of a crosslinking agent and forced cooling to 2 m / s. The composition for oral cavity having a viscosity of 1 to 5,000 mPa · s (0.001 to 5 Pa · s) containing microgel particles is manufactured by shearing and crushing with the above shearing force. When the alginic acid gel was incorporated into the paste-like toothpaste composition by adopting the above, there was a problem that remarkable lumps were formed during the production process, and the stability over time of the moldability deteriorated. Thus, in the paste-like toothpaste composition, the formation of lumps and the decrease in stability are caused by the above method. Sodium alginate is essential to be heated to 85 ° C. or higher in order to dissolve it directly in a water-soluble solvent such as water. In this temperature condition, it is difficult to control gelation, so that the formation of lumps is likely to occur, and even when forcedly cooled, the viscosity of the alginic acid solution varies significantly depending on the temperature condition, so that stirring can be performed under certain conditions. Because it becomes difficult, the formation of lumps is likely to occur. Furthermore, when the gel is gelled and sheared with a shearing force of 2 m / s or more, the gel is crushed into microgel particles, so the uniform gel necessary for the toothpaste is formed. It was not possible, and it was found that the cause was that the formability over time deteriorated.
On the other hand, in the present invention, a mixed aqueous solution of sodium alginate and a wetting agent and water are prepared in the first step to prepare a swollen aqueous solution, and then calcium citrate is added to the swollen aqueous solution to form an alginate gel. The second step is carried out after the swelling aqueous solution is gelled, and sodium alkyl sulfate is used as a foaming agent in the third step, so that sodium alginate can be uniformly formed without heating to 85 ° C. or higher. Since the viscosity of the alginic acid solution is not affected and changed by heating or forced cooling, it can be stirred under certain conditions, and the calcium citrate is evenly dispersed in the swelling aqueous solution. Therefore, by controlling the gelation, the above-mentioned problems can be solved, and when producing a toothpaste composition, it is Acid gel can be formed, alga acid gel is formed uniformly and stably without the formation of lumps during the manufacturing process of toothpaste composition, smooth kneaded skin, precipitation of alkyl sulfates etc. during long-term storage A toothpaste composition that does not generate any product is obtained, and such a toothpaste composition has excellent usability and dispersibility in the oral cavity, and is formable without increasing the amount of binder. Can be stably maintained over time. Therefore, according to the present invention, it is possible to obtain a toothpaste composition excellent in any of the contradicting characteristics such as a feeling of stickiness at the time of use and intra-oral dispersibility and stability of moldability.

Accordingly, the present invention provides a toothpaste composition comprising a binder, a wetting agent, an abrasive, a foaming agent and water.
(1) A step of preparing a swelling aqueous solution containing a binder and a wetting agent (2) A step of kneading an abrasive in the swelling aqueous solution (3) A step including a step of mixing a foaming agent in the abrasive kneaded product In manufacturing, a mixed aqueous solution of sodium alginate and a wetting agent and water are prepared in the first step to prepare a swollen aqueous solution, and then calcium citrate is added to the swollen aqueous solution to form an alginate gel, Provided is a method for producing a toothpaste composition, wherein the second step is performed after the swelling aqueous solution is gelled, and sodium alkyl sulfate is mixed as a foaming agent in the third step.

  According to the present invention, there is no sticky feeling at the time of use, it is excellent in dispersibility in the oral cavity, there is no formation of lumps in the manufacturing process, the kneaded skin is smooth, and the stability over time of the moldability is good, A toothpaste composition excellent in storage stability in which no precipitate is produced during storage can be advantageously produced industrially.

Hereinafter, the present invention will be described in more detail. The toothpaste composition according to the present invention is a toothpaste composition comprising a binder, a wetting agent, an abrasive, a foaming agent and water.
(1) A step of preparing a swelling aqueous solution containing a binder and a wetting agent (2) A step of kneading an abrasive in the swelling aqueous solution (3) A step including a step of mixing a foaming agent in the abrasive kneaded product In manufacturing, a mixed aqueous solution of sodium alginate and a wetting agent and water are prepared in the first step to prepare a swollen aqueous solution, and then calcium citrate is added to the swollen aqueous solution to form an alginate gel, The second step is performed after gelling the swelling aqueous solution, and sodium alkyl sulfate is mixed as a foaming agent in the third step. Sodium alginate, calcium citrate, wetting agent, abrasive, foaming It contains sodium alkyl sulfate and water as an agent.

[Sodium alginate]
As the sodium alginate, a 1% by weight aqueous solution of sodium alginate having a viscosity of 20 to 1,100 mPa · s, particularly 80 to 400 mPa · s is preferable. If the viscosity is less than 20 mPa · s, the stability over time of moldability may not be ensured as a toothpaste, and if it exceeds 1,100 mPa · s, lumps may be formed in the production process.
The above-mentioned viscosity is BM type Brookfield viscometer, rotor No. 2, 20 rotations, 20 ° C., measurement time 1 minute (hereinafter the same).

  Examples of such sodium alginate include Kimika Argin I series manufactured by Kimika Co., Ltd., particularly Kimika Argin I-1 (viscosity of 1% aqueous solution: 80 to 200 mPa · s), Kimika Argin I-2 (viscosity of 1% aqueous solution). : 250-350 mPa · s), Kimika Algin I-3 (viscosity of 1% aqueous solution: 300-400 mPa · s), etc., especially the stability over time of moldability as a toothpaste and difficulty in forming lumps during the manufacturing process From this point, Kimika Argin I-2 is preferred.

  The blending amount of sodium alginate is preferably 0.2 to 5% (mass%, the same applies hereinafter) in the composition, particularly 0.5 to 2%. If it is less than 0.2%, the temporal stability of the moldability cannot be ensured, and if it exceeds 5%, the dispersion is not satisfactorily dispersed, and lumps may be formed in the manufacturing process.

[Calcium citrate]
Calcium citrate acts as a crosslinking agent that crosslinks sodium alginate to form a gel. In the present invention, it is essential to use calcium citrate as the crosslinking agent. Calcium citrate may be either a hydrate or an anhydride. For example, commercially available products such as calcium citrate tetrahydrate manufactured by Kanto Chemical Co., Ltd. and super colloid manufactured by Iwata Chemical Industry Co., Ltd. are used. be able to.

  The blending amount of calcium citrate is preferably adjusted according to the content of sodium alginate, but is 0.1 to 3%, especially 0.2 to 0.3% as calcium citrate tetrahydrate with respect to the whole composition. 1% is preferred. If it is less than 0.1%, the stability over time of moldability cannot be ensured, and if it exceeds 3%, it may not be satisfactorily dispersed, and lumps may be formed in the manufacturing process.

[Wetting agent]
Examples of the wetting agent include one or two kinds of polyhydric alcohols such as sorbitol, glycerin, ethylene glycol, propylene glycol, 1,3-butylene glycol, polyethylene glycol, polypropylene glycol, xylitol, maltitol, and lactitol, and sugar alcohol. The above can be blended.

  The blending amount of the wetting agent is preferably 20 to 60%, particularly preferably 30 to 50% of the entire composition. If it is less than 20%, it is difficult to mix and disperse sodium alginate and the like, which may cause lumps during the production process. If it exceeds 60%, stickiness may occur during use.

[Abrasive]
Examples of the abrasive include precipitated silica, silica gel, aluminosilicate, zirconosilicate, dibasic calcium phosphate dihydrate, dibasic calcium phosphate anhydrate, calcium pyrophosphate, aluminum hydroxide, alumina, titanium dioxide, crystalline zirconium. Silicate, polymethyl methacrylate, insoluble calcium metaphosphate, light calcium carbonate, heavy calcium carbonate, magnesium carbonate, tertiary magnesium phosphate, zeolite, zirconium silicate, tertiary calcium phosphate, hydroxyapatite, fluoroapatite, calcium deficient apatite 3 calcium phosphate, 4th calcium phosphate, 8th calcium phosphate, synthetic resin type abrasive | polishing agent, etc. are mentioned, These 1 type (s) or 2 or more types can be mix | blended.

  The blending amount of the abrasive is preferably 2 to 50%, particularly 10 to 40% of the whole composition, and if it is less than 2%, the temporal stability of the moldability may not be ensured. Dama may be formed.

As the foaming agent, sodium alkyl sulfate is blended. Specifically, one or more of sodium capryl sulfate, sodium lauryl sulfate, sodium myristyl sulfate and the like can be used, and sodium lauryl sulfate is particularly preferable.
As sodium alkyl sulfate, for example, commercially available products such as sodium lauryl sulfate manufactured by Toho Chemical Industry Co., Ltd., and NIKKOL SLS manufactured by Nikko Chemicals Co., Ltd. can be used.

  The blending amount of sodium alkyl sulfate is 0.1 to 3% in the composition, particularly preferably 0.2 to 1.5%. If it is less than 0.1%, the dispersibility in the oral cavity may be deteriorated. If it exceeds, precipitation of alkyl sulfate may occur during storage.

[water]
As the water, deionized water, distilled water, ultrapure water or the like can be used, and the blending amount is preferably 20 to 45% in the composition. When the blending amount is less than 20%, it is difficult to mix and disperse the blending components. When the blending amount exceeds 45%, it takes a long time to uniformly knead the abrasive, and in either case, lumps are formed during the manufacturing process. There is.

  Furthermore, in this invention, in addition to the said component, another arbitrary component can be added as needed in the range which does not prevent the effect of this invention as needed. Specifically, foaming agents other than sodium alkyl sulfate, binders other than sodium alginate, sweeteners, preservatives, fragrances, colorants, medicinal ingredients, pH adjusters, and the like can be blended.

  As a foaming agent, in addition to sodium alkyl sulfate, other anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants can be blended as long as the effects of the present invention are not hindered. . Other anionic surfactants include sodium N-lauroyl sarcosinate, sodium N-acyl sarcosinate such as sodium N-myristoyl sarcosinate, sodium dodecylbenzene sulfonate, hydrogenated coconut fatty acid monoglyceride sodium monosulfate, lauryl sulfoacetic acid Examples thereof include sodium, N-acyl glutamate such as sodium N-palmitoyl glutamate, sodium N-methyl-N-acyl taurate, sodium N-methyl-N-acylalanine, sodium α-olefin sulfonate, and the like. Examples of the cationic surfactant include alkyl ammonium and alkyl benzyl ammonium salts. Nonionic surfactants include sugar alcohol fatty acid esters such as sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sucrose fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyethylene glycol Polyhydric alcohol fatty acid ester such as fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene copolymer, polyoxyethylene alkylphenyl ether, ether type surfactant such as polyoxyethylene hydrogenated castor oil, lauric acid And fatty acid alkanolamides such as diethanolamide. Examples of amphoteric surfactants include betaine acetate, imidazolinium betaine, and lecithin. The blending amount of these other surfactants is usually 0 to 2%, and the total blending amount with sodium alkyl sulfate is preferably 0.3 to 4.5% of the entire composition.

  As the binder, in addition to sodium alginate, other binders may be blended within a range not impeding the effects of the present invention. Specifically, cellulose derivatives such as sodium carboxymethylcellulose, methylcellulose, and hydroxyethylcellulose, gums such as carrageenan, xanthan gum, tragacanth gum, karaya gum, and arabic gum, polyvinyl alcohol, crosslinked sodium polyacrylate, uncrosslinked sodium polyacrylate, etc. Carboxyvinyl polymers, organic binders such as polyvinylpyrrolidone, inorganic binders such as montmorillonite, kaolin and bentonite, and the like, and one or more of these can be blended. In addition, in order to sufficiently ensure the absence of stickiness at the time of use, which is the effect of the present invention, and excellent dispersibility in the oral cavity, it is preferable not to add other binders or to add a small amount even if added. The blending amount of the above-mentioned other binder is usually 0 to 2%, particularly preferably 0 to 0.5%.

  Sweeteners include sodium saccharin, aspartame, stevioside, stevia extract, paramethoxycinnamic aldehyde, neohesperidyl dihydrochalcone, and perilartine. Preservatives include parabens such as butylparaben and ethylparaben, paraoxybenzoate, benzoate. Examples include sodium acid.

  Examples of perfume ingredients include peppermint oil, spearmint oil, anise oil, eucalyptus oil, winter green oil, cassia oil, clove oil, thyme oil, sage oil, lemon oil, orange oil, peppermint oil, cardamom oil, coriander oil, mandarin Oil, lime oil, lavender oil, rosemary oil, laurel oil, camomil oil, caraway oil, marjoram oil, bay oil, lemongrass oil, origanum oil, pine needle oil, neroli oil, rose oil, jasmine oil, iris concrete Natural fragrances such as absolute peppermint, absolute rose, orange flower, etc., and fragrances that have been processed (front reservoir cut, rear reservoir cut, fractionation, liquid-liquid extraction, essence, powdered fragrance, etc.), And menthol, carvone, anethole, cineole, Methyl lithylate, synamic aldehyde, eugenol, 3-l-menthoxypropane-1.2-diol, thymol, linalool, linalyl acetate, limonene, menthone, menthyl acetate, N-substituted-paramentane-3-carboxamide, pinene , Octyl aldehyde, citral, pulegone, carbyl acetate, anisaldehyde, ethyl acetate, ethyl butyrate, allyl cyclohexane propionate, methyl anthranilate, ethyl methyl phenyl glycidate, vanillin, undecalactone, hexanal, ethyl alcohol, Propyl alcohol, butanol, isoamyl alcohol, hexenol, dimethyl sulfide, cycloten, furfural, trimethylpyrazine, ethyl lactate, Single flavors such as lulactate and ethyl thioacetate, as well as blended flavors such as strawberry flavor, apple flavor, banana flavor, pineapple flavor, grape flavor, mango flavor, butter flavor, milk flavor, fruit mix flavor, tropical fruit flavor, etc. Known perfume materials used in dentifrice compositions can be used, and these are preferably used alone or in combination, and further dissolved and dispersed in ethyl alcohol as necessary.

  As coloring agents, Red No. 2, Red No. 3, Red No. 225, Red No. 226, Yellow No. 4, Yellow No. 5, Yellow No. 205, Blue No. 1, Blue No. 2, Blue No. 201, Blue No. 204, Green No. 3, mica titanium, titanium oxide and the like.

  As the medicinal component, fluorides such as sodium fluoride, potassium fluoride, stannous fluoride, strontium fluoride, sodium monofluorophosphate, water-soluble phosphate compounds such as potassium salt and sodium salt of orthophosphoric acid, Tranexamic acid, epsilon-aminocaproic acid, allantoin chlorohydroxyaluminum, hinokitiol, ascorbic acid, sodium chloride, dl-tocopherol acetate, dihydrocholesterol, α-bisabolol, chlorhexidine salts, azulene, glycyrrhetin, glycyrrhetinic acid, copper chlorophyllin sodium, chlorophyll, glyceroline Chelating phosphate compounds such as acids, copper compounds such as copper gluconate, aluminum lactate, strontium chloride, potassium nitrate, berberine, hydroxamic acid and its derivatives, Sodium polyphosphate, zeolite, methoxyethylene, maleic anhydride copolymer, polyvinyl pyrrolidone, epidihydrocholesterin, benzethonium chloride, sodium chloride, dihydrocholesterol, trichlorocarbanilide, zinc citrate, sweet cherry extract, buckwheat extract, chamomile , Extracts of clove, rosemary, hornon, safflower and the like.

  Examples of the pH adjuster include disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium hydroxide, potassium hydroxide, malic acid, lactic acid, tartaric acid, acetic acid, phosphoric acid, pyrophosphoric acid, glycerophosphoric acid, and various salts thereof. And so on.

  In addition, the compounding quantity of these arbitrary components can be made into a normal quantity in the range which does not prevent the effect of this invention.

  The toothpaste composition according to the present invention contains an alginic acid gel, and its viscosity at 25 ° C. is preferably 20 to 200 Pa · s, more preferably 30 to 120 Pa · s. The above-mentioned viscosity is BM type Brookfield viscometer, rotor No. It is a measurement value at 7, 20 rotations, 25 ° C., and measurement time of 3 minutes.

[Production method]
The method for producing the toothpaste composition of the present invention comprises:
(1) A step of preparing a swelling aqueous solution containing a binder and a wetting agent (2) A step of kneading an abrasive in the swelling aqueous solution (3) A step including a step of mixing a foaming agent in the abrasive kneaded product In manufacturing, in the first step (1-1) a step of preparing a swelling aqueous solution by mixing a mixture of sodium alginate and a wetting agent and water,
(1-2) Next, calcium citrate is added to the swelling aqueous solution to form an alginic acid gel, the swelling aqueous solution is gelled, then the second step is performed, and then the foaming agent is formed in the third step. As sodium alkyl sulfate.

  In the above-mentioned step 1-1, a swollen aqueous solution is prepared by mixing a mixture of sodium alginate and a wetting agent and water. By performing such a process, a mixed solution in which sodium alginate and a wetting agent are mixed is prepared, and this mixed solution is mixed with a mixed solution containing water and a water-soluble component and / or a water-dispersible component to obtain a swelling aqueous solution. By preparing, sodium alginate can be uniformly dispersed in the swelling aqueous solution in a short time. Subsequently, calcium citrate is added as a cross-linking agent in the next step 1-2, so that calcium citrate is added to the swelling aqueous solution. Evenly dispersed, sodium alginate quickly crosslinks and gels without formation of sodium alginate lumps, and stable moldability over time is obtained. In this case, a mixed solution in which sodium alginate and a wetting agent are mixed and a mixed solution of a water-soluble component and / or a water-dispersible component and water are prepared separately, and then both are mixed to prepare a swelling aqueous solution. can do.

  In step 1-1, a binder other than sodium alginate, which is an optional component, may be added to the mixed solution of sodium alginate and a wetting agent. In addition, the range which does not prevent the effect of this invention for other binders is desirable, and the compounding quantity is 0 to 2% of the whole composition, and 0 to 0.5% is especially preferable.

  The said 1-1 process can be performed, for example using a mixing tank provided with a paddle blade, a universal mixer, etc. In this case, a mixture of sodium alginate and a wetting agent and a mixture of water-soluble and / or water-dispersible components and water are prepared separately, and the same composition is used when mixing both to produce a swollen aqueous solution. If a tank is used, it can be uniformly mixed and dispersed in a shorter time.

  Next, calcium citrate is added and dispersed in the obtained swelling aqueous solution (step 1-2). Thus, after preparing the swelling aqueous solution in the above-mentioned step 1-1, calcium citrate is uniformly dispersed in the swelling aqueous solution in which sodium alginate is dispersed by adding calcium citrate, and the calcium salt of calcium citrate. In this case, the sodium alginate is cross-linked and gelled. At this time, the alginic acid gel is uniformly and stably dispersed without forming lumps, and the swelling aqueous solution is uniformly gelled. In Step 1-1, calcium citrate was added to prepare a mixed solution, or calcium citrate was added to water to prepare a swollen aqueous solution. As a result, lumps are formed and a uniform gel cannot be obtained. In addition, when calcium citrate is added after adding the abrasive in the second step and the third step is performed, it becomes difficult to control the gelation of sodium alginate, and in the third step, lumps are formed and uneven. In addition, calcium ions and sodium alkyl sulfate added in the third step, which is the next step, are in direct contact with each other to form insoluble calcium alkyl sulfate, which causes precipitation. If calcium citrate is added after adding sodium alkyl sulfate in the third step, calcium ions and sodium alkyl sulfate are in direct contact to form insoluble calcium alkyl sulfate, which causes precipitation during storage. End up.

  The above-mentioned 1-2 process can be performed using common stirring devices, such as a mixing tank provided with a paddle blade, a universal mixer, etc., for example, and the addition method of calcium citrate is carried out manually or using a hopper. Can be charged and stirred. Moreover, if the same mixing tank is used when producing the swelling aqueous solution, it can be uniformly mixed and dispersed in a shorter time. The conditions for mixing and stirring depend on the stirring device used, but the shearing force is preferably less than 2 m / s. If it is 2 m / s or more, the alginic acid gel is crushed and a uniform gel necessary for the toothpaste cannot be formed, and the stability over time of the moldability is deteriorated.

  Furthermore, in the present invention, a fragrance can be added as an optional component, but it is preferable to add the fragrance after adding calcium citrate, that is, after the first step and before performing the second step. By adding the fragrance before kneading the abrasive in the second step, it becomes easy to defoam due to the defoaming effect of the fragrance, and the fragrance can be improved. If a fragrance is added after adding an abrasive, a part of the fragrance (many fragrance ingredients are hydrophobic) will be excessively adsorbed on the surface of the abrasive that is solid before foaming. There is a risk that it will be easier to do and the fragrance will be lost.

  In the second step, an abrasive is added to the swollen aqueous solution in which the calcium citrate is dispersed to form an alginate gel and kneaded. By carrying out the fourth step before the addition step of sodium alkyl sulfate in the fifth step, the air brought in by the abrasive may be introduced when the interfacial tension is lowered by the blending of sodium alkyl sulfate in the third step. It is possible to prevent the air from being easily foamed more than necessary.

  For the addition of the abrasive in the second step, for example, it is preferable to employ a method of adding the abrasive by transferring the swelling aqueous solution containing the gel to a kneader.

  Furthermore, in the present invention, when an active ingredient is added, it is desirable to add the active ingredient after adding and mixing the abrasive, that is, after the second step and before the third step, thereby easily decomposing. The active ingredient can also be prevented from being adversely affected by excessive shearing force, and can be mixed more uniformly by mixing with sodium alkyl sulfate in the next step.

  In the next third step, sodium alkyl sulfate is mixed into the kneaded material in which the abrasive is kneaded. This step can also be performed using a kneader as in the second step.

  In the present invention, it is recommended that either or both of the abrasive kneaded material in the second step and the sodium alkyl sulfate-added kneaded material in the third step, preferably both, be degassed under reduced pressure. In this case, defoaming may be performed after kneading the abrasive or after adding and mixing sodium alkyl sulfate, but defoaming may be performed while kneading the abrasive or mixing sodium alkyl sulfate. Good.

  Here, the vacuum degassing is preferably performed under a pressure of 2 to 20 kPa, particularly 2 to 10 kPa, and efficient defoaming can be performed by performing in this pressure range. Moreover, when the fragrance | flavor which is an arbitrary component is added, two contradictory problems of efficient defoaming and prevention of excessive scattering of the low boiling point of a fragrance | flavor can be overcome. If it is performed at a pressure exceeding 20 kPa, defoaming may not be performed efficiently. If the degree of vacuum is less than 2 kPa, a low boiling point component in the fragrance is added when a fragrance is added as an optional component. May scatter excessively.

In the said manufacturing method, although the temperature conditions of each process can be selected suitably, all are 50 degrees C or less, Especially 10-50 degreeC is preferable and you may carry out at room temperature (15-30 degreeC). In this case, the preparation of the swelling aqueous solution in the first step is desirably performed at 10 to 50 ° C., particularly 15 to 40 ° C., and may be performed at room temperature (15 to 30 ° C.). By preparing at 10 degreeC or more, the swelling aqueous solution in which sodium alginate was uniformly disperse | distributed for a short time can be obtained, and if it is less than 10 degreeC, it may not swell uniformly. The addition of calcium citrate in the first step can also be performed under the same temperature range as described above, and there is no need to perform forced cooling or the like when gelling. Moreover, in a 2nd process, it can prevent scattering which has a bad influence on the product performance of the fragrance | flavor which is an arbitrary component by performing at 50 degrees C or less, and when it exceeds 50 degreeC, it may be inferior to product performance.
In the present invention, by performing each step under such a temperature condition, it is possible to produce from the preparation of the swollen aqueous solution to the subsequent steps without requiring heating or cooling.

  In addition, although there is no restriction | limiting in particular in the mixing | blending order of arbitrary components, About an active ingredient, it is as above-mentioned, and another water-soluble component can be added and mixed at the time of a 2nd process.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, the blending amount is mass%.

  Moreover, as each component used for preparation of a toothpaste, sodium lauryl sulfate (Toho Chemical Industry Co., Ltd., sodium lauryl sulfate), sodium alginate (Kimika Corporation, Kimika Argin I-2), calcium citrate tetrahydrate (Kanto Chemical Co., Inc.), calcium gluconate monohydrate (Kanto Chemical Co., Ltd.), calcium chloride dihydrate (Kanto Chemical Co., Ltd.), calcium hydrogen phosphate dihydrate (Tosoh Finechem Co., Ltd.) Company, dicalcium phosphate D grade), calcium carbonate (Calfine Co., Ltd., heavy calcium carbonate KS-1000), sodium carboxymethyl cellulose I (Nippon Paper Chemicals Co., Ltd., Sunrose F10LC), sodium carboxymethyl cellulose II (Daicel Chemical Co., Ltd.) Company, part number 1260) Sodium boxymethylcellulose III (Daicel Chemical Co., Ltd., product number 1220) and xanthan gum (Dainippon Sumitomo Pharma Co., Ltd., Keldent) are used. The one suitable for was used. About sorbit, 70% sorbite aqueous solution was used, but the compounding quantity of pure conversion was shown in the table | surface.

[Examples 1 to 3, Comparative Examples 1 to 10]
A toothpaste having the composition shown in Table 1 was prepared by the kneader method using the following production methods -1 to 4. In addition, 1.3 kg of kneaders were prepared using a laboratory one (special order product: manufactured by Ishiyama Shoten) that can prepare a toothpaste of about 1 L.

<Production method-1>
Preparation of swelling aqueous solution:
Using the ingredients shown in Table 1, under a temperature condition of 25 ° C., saccharin and 70% sorbite aqueous solution were dissolved in purified water, calcium citrate and tetrahydrate added, and propylene glycol containing sodium alginate. After preparing the mixed B liquid separately, the A liquid and B liquid were stirred and mixed in a mixing tank equipped with paddle blades to obtain a swollen aqueous solution containing alginate gel.
Toothpaste preparation:
The obtained swollen aqueous solution containing an alginate gel was transferred to a kneader, added with a fragrance, and mixed with silicic anhydride. While this mixture was kneaded at a temperature of 25 ° C. and a pressure of 4 kPa, first-stage vacuum degassing was performed. Further, sodium lauryl sulfate was added, and second-stage vacuum degassing was performed while mixing at a temperature of 25 ° C. and a pressure of 4 kPa to prepare a toothpaste.

<Production method-2>
Preparation of swelling aqueous solution:
After preparing separately the liquid A which melt | dissolved saccharin and 70% sorbite aqueous solution in purified water, and the liquid B which mixed sodium alginate in propylene under the temperature condition of 25 degreeC using the compounding component shown in Table 1, Liquid A and liquid B were stirred and mixed in a mixing tank equipped with paddle blades to obtain a swollen aqueous solution. Then, subsequently, calcium citrate / tetrahydrate was added under the same temperature condition and mixed by stirring to disperse the calcium citrate, thereby obtaining a gel-like swelling aqueous solution containing an alginate gel.

Toothpaste preparation:
Under the above temperature conditions, the swollen aqueous solution containing alginic acid gel was transferred to a kneader, and after adding and mixing a fragrance, silicic anhydride was mixed. While this mixture was kneaded at a temperature of 25 ° C. and a pressure of 4 kPa, first-stage vacuum degassing was performed. Further, sodium lauryl sulfate was added, and second-stage vacuum degassing was performed while mixing at a temperature of 25 ° C. and a pressure of 4 kPa to prepare a toothpaste.

<Production method-3>
Preparation of swelling aqueous solution:
After preparing separately the liquid A which melt | dissolved saccharin and 70% sorbite aqueous solution in purified water, and the liquid B which mixed sodium alginate in propylene under the temperature condition of 25 degreeC using the compounding component shown in Table 1, Liquid A and liquid B were stirred and mixed in a mixing tank equipped with paddle blades to obtain a swollen aqueous solution.

Toothpaste preparation:
Under the above temperature conditions, the obtained swelling aqueous solution was transferred to a kneader, added with fragrance, mixed with anhydrous silicic acid, and then added with calcium citrate / tetrahydrate to form an alginate gel. While this mixture was kneaded at a temperature of 25 ° C. and a pressure of 4 kPa, first-stage vacuum degassing was performed. Further, sodium lauryl sulfate was added, and second-stage vacuum degassing was performed while mixing at a temperature of 25 ° C. and a pressure of 4 kPa to prepare a toothpaste.

<Production method-4>
Preparation of swelling aqueous solution:
After preparing separately the liquid A which melt | dissolved saccharin and 70% sorbite aqueous solution in purified water, and the liquid B which mixed sodium alginate in propylene under the temperature condition of 25 degreeC using the compounding component shown in Table 1, Liquid A and liquid B were stirred and mixed in a mixing tank equipped with paddle blades to obtain a swollen aqueous solution.

Toothpaste preparation:
Under the temperature conditions, the swollen aqueous solution was transferred to a kneader, a fragrance was added and mixed, and silicic anhydride was mixed. While this mixture was kneaded at a temperature of 25 ° C. and a pressure of 4 kPa, first-stage vacuum degassing was performed. Furthermore, after adding and mixing sodium lauryl sulfate, calcium citrate and tetrahydrate are added and mixed to form an alginate gel, and second stage vacuum degassing is performed while mixing at a temperature of 25 ° C. and a pressure of 4 kPa. A dentifrice was prepared.

  The obtained toothpaste was evaluated by the following methods for the presence or absence of lumps, stability over time of moldability, presence or absence of precipitates during storage, stickiness during use, and dispersibility in the oral cavity. The viscosity is a value measured by the following method. The results are shown in Table 1.

Assessment of the presence or absence of lumps:
A toothpaste 10 g was taken on a paper surface and visually observed, and formation of lumps was evaluated according to the following criteria.
○: Alginic acid gel is uniformly and stably formed and dispersed, and no formation of lumps is observed. ×: Alginic acid gel is formed but dispersed non-uniformly and formation of lumps is recognized.

Evaluation of moldability over time:
A toothpaste is filled in a container with an inner diameter of 6 mm and stored at 50 ° C. for 1 month. Ten test subjects take a suitable amount (about 1 g, about 2 cm) on a toothbrush and visually observe it. A sensory test was performed, and an average value was obtained and evaluated.
(Score)
3 points: The paste shape is maintained on the toothbrush and the dentifrice does not fall off from the toothbrush 2 points: The paste shape on the toothbrush is slightly broken, but the toothpaste does not fall off from the toothbrush 1 point: on the toothbrush The shape of the paste collapses, and the dentifrice falls from the toothbrush (formability evaluation criteria)
A: Formability average point 2.5 points or more ○: Formability average point 2.0 points or more to less than 2.5 points ×: Formability average point less than 2.0 points

Evaluation of the presence or absence of precipitates during storage:
About the toothpaste after 1 month preservation | save in a 10 degreeC thermostat, 10g was put on the paper surface and observed visually and the presence or absence of the precipitate was evaluated by the following reference | standard.
○: There is no precipitate on the surface or inside. Δ: There is no precipitate on the surface, but there is a precipitate inside. ×: There is a precipitate both on the surface and inside.

Evaluation of stickiness during use:
Ten subjects used an appropriate amount (about 1 g, about 2 cm) of a toothpaste on their toothbrushes to brush their teeth, and then use them to brush their teeth. A sensory test was conducted by absolute evaluation in seven stages of stickiness during use, and an average value was obtained for evaluation.
(Score)
7 points: No stickiness felt 6 points: Little stickiness felt 5 points: Slight stickiness felt 4 points: Weak stickiness felt 3 points: Feeled sticky 2 points: Strong stickiness felt 1 point: Remarkable stickiness

(Evaluation criteria for stickiness during use)
◎: Average score of stickiness 6 points or more ○: Average score of stickiness 5 points to less than 6 points △: Average score of stickiness 4 points to less than 5 points ×: Average score of stickiness Less than 4 points

Evaluation of intraoral dispersibility:
Ten subjects used an appropriate amount (about 1 g, about 2 cm) of a toothpaste on their toothbrushes to brush their teeth, and then use them to brush their teeth. The dispersibility of the toothpaste in use was subjected to a sensory test by absolute evaluation according to the following criteria, and evaluated according to the following criteria.

(Score)
4 points: Dispersibility is quite good 3 points: Dispersibility is good 2 points: Dispersibility is bad 1 point: Dispersibility is quite bad (Evaluation criteria for intraoral dispersion)
○: Dispersibility average point 3.0 points or more Δ: Dispersibility average point 2.0 points to less than 3.0 points ×: Dispersibility average point less than 2.0 points

Measuring the viscosity of a toothpaste:
The viscosity is BM Brookfield viscometer, rotor no. The measurement was performed at 7, 20 rotations, 25 ° C., and a measurement time of 3 minutes.

  From the results of Table 1, when the addition process of calcium citrate is different (Comparative Examples 1 to 3), when calcium citrate is not blended or when a calcium salt other than calcium citrate is blended (Comparative Examples 4 to 8) 10) When no other sodium alginate is added and another binder is blended (Comparative Example 9), the gelation of the alginate gel is insufficiently controlled or the dispersion becomes non-uniform, resulting in the formation of lumps. The method of production of the present invention is inferior to any of the evaluations such as inferior in stability of moldability over time, precipitate during storage, stickiness during use, and poor dispersibility in the oral cavity. The toothpastes (Examples 1 to 3) obtained by the above were formed and dispersed uniformly and stably in the alginic acid gel, no lumps were formed during the production process, no stickiness during use, Excellent dispersibility Sexual temporal stability was good, it was confirmed nor precipitate during storage.

  Next, a toothpaste with the following composition was prepared by the method of Production Method-2 described in the above Example and evaluated in the same manner as in the above Example. In all cases, the alginate gel was uniformly and stably formed and dispersed. A toothpaste that does not form lumps in the process, does not feel sticky during use, has good oral dispersibility, has excellent moldability over time, and has no deposits during long-term storage. It was confirmed.

[Example 4] Toothpaste sodium lauryl sulfate 0.7
Sodium alginate 1.0
Calcium citrate tetrahydrate 0.5
Silicic anhydride 10
Propylene glycol 3.0
Sorbit 42
Sodium benzoate 0.2
Saccharin sodium 0.2
Sodium fluoride 0.21
Fragrance 1.0
Purified water 41.19
Total 100.0%
Viscosity of composition (25 ° C.); 41.7 Pa · s

[Example 5] Toothpaste, sodium lauryl sulfate 0.8
Sodium alginate 0.8
Calcium citrate tetrahydrate 0.5
Silicic anhydride 20
Propylene glycol 3.0
Sorbit 35
Sodium carboxymethylcellulose III 0.1
Sodium benzoate 0.2
Saccharin sodium 0.2
Sodium fluoride 0.21
Fragrance 1.0
Purified water 38.19
Total 100.0%
Viscosity of composition (25 ° C.); 42.4 Pa · s

[Example 6] Toothpaste sodium lauryl sulfate 1.2
Sodium alginate 0.9
Calcium citrate tetrahydrate 0.5
Aluminum hydroxide 40
Propylene glycol 3.0
Sorbit 30
Xanthan gum 0.2
Saccharin sodium 0.2
Sodium monofluorophosphate 0.73
Fragrance 1.0
Purified water 22.27
Total 100.0%
Viscosity of composition (25 ° C.); 46.1 Pa · s

[Example 7] Toothpaste sodium lauryl sulfate 0.7
Sodium alginate 1.0
Calcium citrate tetrahydrate 0.5
Silicic anhydride 15
Propylene glycol 3.0
Glycerin 35
Sodium benzoate 0.2
Saccharin sodium 0.2
Sodium fluoride 0.21
Fragrance 1.0
Purified water 43.19
Total 100.0%
Viscosity of composition (25 ° C.); 47.1 Pa · s

[Example 8] Toothpaste sodium lauryl sulfate 1.0
Sodium alginate 1.0
Calcium citrate tetrahydrate 0.5
Aluminum hydroxide 40
Propylene glycol 3.0
Glycerin 25
Saccharin sodium 0.2
Sodium monofluorophosphate 0.73
Fragrance 1.0
Purified water 27.57
Total 100.0%
Viscosity of composition (25 ° C.); 65.9 Pa · s

[Example 9] Toothpaste sodium lauryl sulfate 1.2
Sodium alginate 0.9
Calcium citrate tetrahydrate 0.5
Aluminum hydroxide 40
Propylene glycol 3.0
Sorbit 30
Saccharin sodium 0.2
Sodium monofluorophosphate 0.73
Anhydrous sodium pyrophosphate 0.2
Fragrance 1.0
Purified water 22.27
Total 100.0%
Viscosity of composition (25 ° C.); 58.1 Pa · s

Claims (2)

A toothpaste composition comprising a binder, a wetting agent, an abrasive, a foaming agent and water,
(1) A step of preparing a swelling aqueous solution containing a binder and a wetting agent (2) A step of kneading an abrasive in the swelling aqueous solution (3) A step including a step of mixing a foaming agent in the abrasive kneaded product In manufacturing, a mixed aqueous solution of sodium alginate and a wetting agent and water are prepared in the first step to prepare a swollen aqueous solution, and then calcium citrate is added to the swollen aqueous solution to form an alginate gel, A method for producing a toothpaste composition comprising performing a second step after gelling a swelling aqueous solution and mixing sodium alkyl sulfate as a foaming agent in the third step.   The method for producing a toothpaste composition according to claim 1, wherein the toothpaste has a viscosity of 20 to 200 Pa · s at 25 ° C.