JP2011126868A - Liquid composition for denture washing - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid composition for denture washing capable of being directly applicable without dilution at the point of use, never damaging the denture material, exerting excellent removal activity to the stain of the denture even in a very short time, good in storage stability and especially excellent in temporal stability of sulfurous acid ion concentration and appearance stability in low temperature storage. <P>SOLUTION: This liquid composition for denture washing contains a surfactant (A), a sulfite acid salt (B), a linear or cyclic polyphosphate (C) and a polyhydric alcohol (D), and content of component (D) is 25-35 mass%, water content in the composition is 50-65 mass% and pH at 25°C is 6.5-8.0. Phenoxy ethanol (E) and an ethylenediamine tetraacetate (F) are further compounded to the composition. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention is superior in storage stability and appearance storage stability of sulfite in a liquid composition, exhibits excellent stain removal power against denture dirt without damaging the denture material, and has long stain removal power. The present invention relates to a denture cleaning liquid composition that persists even after storage.

  Denture plaque, food residues, stains (colored deposits), tartar, etc. are included in the stains attached to dentures. To clean these, either denture brushing and / or washing with denture cleaner Done. Dentures have not only teeth but also palatal mucosa and gingival parts made of resin or metal, so the area to be soiled is wide and dirt is easily noticeable. In particular, the adhesion of stains to dentures is not preferable from the viewpoint of hygiene and aesthetics, and the removal of stains is a major target for denture cleaning agents.

  Conventionally, denture cleaning agents used for denture cleaning are mainly effervescent tablet types in which a solid cleaning agent mainly composed of peroxide is dissolved in water and foamed when dissolved. There has been proposed a solid denture cleaning agent containing an organic acid and a carbonate foamed by a reaction and a surfactant (Patent Document 1).

  However, the conventional solid-type cleaning agents as described above are individually packaged, and the amount of use cannot be adjusted when the size of the denture differs greatly among individuals, such as partial dentures. Often become dissatisfied. In addition, the chemical cleaning of immersion cleaning within the set concentration range is insufficient in cleaning power, and the effect of removing stain stains in a short period of time is low. There is a possibility of discoloration.

  From this point, a denture cleaning agent that is easy to apply to a denture without containing a peroxide or a bleaching agent and that is provided in a foam-like form that does not require a long cleaning time has been proposed (Patent Document 2). ). However, this technique is an emulsion containing about 50-99% w / w aqueous phase and about 1-50% water-immiscible oil phase, which is separated if not shaken before use. The appearance stability inside is low, and it is difficult to maintain the effect uniformly. Moreover, since this denture cleaning agent has many oil phases, it may feel malfunctions, such as a null, while applying to a denture and brushing. Furthermore, since it does not contain a bleach component and the pH of the cleaning solution is low, the ability to remove stain stains is low even with brushing.

  In addition to peroxides, sulfite is considered as a component that is expected to have an effect on denture stain stains, but sulfite is easily oxidized by dissolved oxygen in aqueous solution to produce sulfate, and sulfite ion concentration Therefore, it is a problem that the reducing power is remarkably lowered with time. Moreover, since the sulfate produced by oxidation has low solubility in water, precipitation may occur in a liquid preparation containing sulfite. As sulfite stabilizers, various chelating agents (Patent Document 3), reducing agents (Patent Document 4), saccharides (Patent Document 5), aromatic compounds having three or more OH groups (Patent Document 6), etc. As is known, in all cases, the effect of stabilization is short, and is insufficient for practical use. In addition, the composition of these techniques may cause precipitation during low-temperature storage, and does not achieve both storage stability of sulfite over time and appearance storage stability.

  Therefore, it solves these problems, it is easy to apply, does not require long-term cleaning, and continuously exhibits excellent stain removal power to the denture without damaging the denture metal, and also has good storage stability. An excellent denture cleaning liquid composition is desired.

JP 11-181500 A JP 2007-254471 A JP-A-57-205314 JP 2000-109305 A JP 7-309610 A JP 57-21912 A

  The present invention has been made in view of the above circumstances, can be directly applied to dentures, can be easily cleaned in a short time without requiring long-time cleaning, and is stable over time of sulfite in a liquid composition. An object of the present invention is to provide a liquid composition for cleaning dentures that exhibits excellent stain removal power for dentures without damaging the denture material and has good appearance preservation stability.

As a result of intensive studies to achieve the above object, the present inventors have found that (A) a surfactant, (B) a sulfite, (C) the following general formula (1)
M _{n + 2} P _n O _{3n + 1} (1)
(However, M represents Na or K, and n ≧ 2.)
A linear polyphosphate represented by the following general formula (2)
(MPO ₃ ) _m (2)
(However, M represents Na or K, and m ≧ 3.)
1 type or 2 or more types of polyphosphate chosen from cyclic polyphosphate represented by (D) and a polyhydric alcohol are mix | blended, and the compounding quantity of (D) component is 25-35 mass%. And by adjusting the water content in the composition to 50 to 65% by mass and the pH at 25 ° C. to 6.5 to 8.0, it is directly applied to the denture without diluting at the time of use. With a simple cleaning, the stain stain of the denture can be effectively removed, and the denture cleaning liquid composition is excellent in sulphite storage stability over time and low-temperature storage stability (appearance stability) without damaging the denture material. It was discovered that a product was obtained, and the present invention was made.

Further, the component (D) is preferably glycerin and / or sorbite, and more preferably glycerin and sorbite are used in combination, and the mass ratio of glycerin / sorbite is more preferably 0.2 to 2, whereby polyphosphate The low-temperature stability of can be further improved, and the appearance stability can be improved more effectively.
In addition, (A) surfactants include sulfate anion surfactants such as polyoxyethylene alkyl ether sulfates and alkyl sulfates, polyoxyethylene alkyl ethers, polyoxyethylene hydrogenated castor oil, and the like. The combined use with a polyethylene glycol type nonionic surfactant is preferred. Thereby, the low temperature stability of a composition can be improved more.

  The liquid composition for cleaning dentures of the present invention preferably further contains (E) phenoxyethanol, which can further improve the temporal stability and stain removal power of sulfite in the composition, and after storage High stain removal power is demonstrated. In addition, by blending component (E), appearance stability due to low-temperature storage, especially polyphosphate (especially pyrophosphate) is crystallized when freeze-thawed (-10 ° C or -20 ° C → 10 ° C). The suppression effect is enhanced, and the appearance stability is excellent even under severe storage conditions in which the process of thawing after freezing at −20 ° C. is repeated a plurality of times. Furthermore, it is preferable to blend (F) ethylenediaminetetraacetate, thereby providing a removal force against stubborn stain stains containing calcium.

  In addition, as described above, in the prior art, a process for dissolving and diluting a solid type denture cleaning agent with water is necessary, and the cleaning operation is troublesome, the compounding components and the amount of each component are inappropriate, and the above-mentioned problem However, according to the present invention, the components (A) to (D) are combined, and the content of the component (D), the amount of water in the composition, and the pH are within an appropriate range. It can be applied directly to dentures without being diluted at the time of use, and since it does not require long-term cleaning, it can be cleaned quickly and easily, and it has excellent stains without damaging the metal or resin of the denture material. Combined with the ability to exert the removal power, suppress the decrease in sulfite ion concentration over time, and have excellent low-temperature stability (appearance stability) with almost no precipitation, liquid separation, and orientation. You can (E) By blending the components, the characteristics are enhanced.

  In addition, the applicant contains (A) a surfactant, (B) a sulfite, and (C) a water-soluble polyphosphate in an appropriate amount and ratio in Japanese Patent Application No. 2008-329748, and has a pH of 6.0. The liquid composition for denture cleaning, in which (D) ethanol and / or (E) polyol is further blended, has been proposed. It has been found that there is still room for improvement in stability, low-temperature storage stability under severe conditions, stain removal ability, and the like. According to the present invention, (D) 25-35 mass% of (D) polyhydric alcohol is mix | blended with the liquid composition for denture cleaning containing (A) surfactant, (B) sulfite, and (C) polyphosphate. In addition, when the water content in the composition is 50 to 65% by mass and the pH is 6.5 to 8.0, the above problem can be solved and cannot be achieved if any of these essential requirements is lacking. It was possible to combine excellent characteristics at the same time.

  Since the liquid composition for cleaning dentures of the present invention can be applied to dentures with the liquid formulation as a stock solution, the amount of the formulation used for cleaning can be easily and appropriately adjusted according to the size of the dentures and the like. Furthermore, the denture cleaning liquid composition of the present invention can combine a chemical method using a combination of sulfite and polyphosphate with a physical method such as brushing, which effectively removes stains on dentures even after long-term storage. The denture can be easily and quickly cleaned and the aesthetic appearance can be maintained.

Accordingly, the present invention provides the following denture cleaning liquid composition.
Claim 1:
(A) a surfactant,
(B) sulfite,
(C) The following general formula (1)
M _{n + 2} P _n O _{3n + 1} (1)
(However, M represents Na or K, and n ≧ 2.)
A linear polyphosphate represented by the following general formula (2)
(MPO ₃ ) _m (2)
(However, M represents Na or K, and m ≧ 3.)
1 type or 2 or more types of polyphosphates chosen from the cyclic polyphosphate represented by these, and (D) polyhydric alcohol, the compounding quantity of (D) component is 25-35 mass%, and A liquid composition for denture cleaning, characterized in that the water content in the composition is 50 to 65% by mass and the pH at 25 ° C. is 6.5 to 8.0.
Claim 2:
The liquid composition for denture cleaning according to claim 1, wherein the component (D) is glycerin and / or sorbit.
Claim 3:
The liquid composition for denture cleaning according to claim 1, wherein the component (D) is glycerin and sorbit, and the mass ratio of glycerin / sorbite is 0.2-2.
Claim 4:
The denture according to claim 1, 2 or 3, comprising 1 to 5% by mass of component (A), 0.5 to 2.5% by mass of component (B), and 0.3 to 2% by mass of component (C). Liquid composition for cleaning.
Claim 5:
The denture cleaning liquid according to any one of claims 1 to 4, wherein (A) the surfactant is a combined use of a sulfate ester type anionic surfactant and a polyethylene glycol type nonionic surfactant. Composition.
Claim 6:
The liquid composition for denture cleaning according to any one of claims 1 to 5, further comprising (E) phenoxyethanol.
Claim 7:
Furthermore, (F) ethylenediaminetetraacetate is contained, The liquid composition for denture cleaning of any one of Claim 1 thru | or 6 characterized by the above-mentioned.

  The liquid composition for cleaning dentures of the present invention can be directly applied to dentures without requiring dilution at the time of use, and is excellent for stain stains of dentures even with very short cleaning without damaging the denture materials. Excellent storage stability, especially excellent stability over time of sulfite ion concentration and appearance stability in low-temperature storage, and chemical methods and physical methods such as brushing after long-term storage In combination, it is possible to remove stain stains of the denture more effectively, clean the denture, and maintain an aesthetic appearance.

It is a schematic sectional drawing of the non-gas type foam container (former pump YF-9413 made from Yoshino Kogyo) used in the Example of this invention.

Hereinafter, the present invention will be described in more detail. The denture cleaning liquid composition of the present invention is a denture cleaning liquid composition that can be directly applied to a denture, and comprises (A) a surfactant, (B) a sulfite,
(C) The following general formula (1)
M _{n + 2} P _n O _{3n + 1} (1)
(However, M represents Na or K, and n ≧ 2.)
A linear polyphosphate represented by the following general formula (2)
(MPO ₃ ) _m (2)
(However, M represents Na or K, and m ≧ 3.)
One or two or more polyphosphates selected from cyclic polyphosphates represented by the formula: and (D) a polyhydric alcohol, and further comprising (E) phenoxyethanol and (F) ethylenediaminetetraacetate. Can be contained.

  (A) Surfactant will not be specifically limited if it is a surfactant normally used for an oral composition, A well-known anionic surfactant, cationic surfactant, nonionic surfactant, amphoteric A surfactant can be used. For example, the following surfactants may be mentioned.

  Examples of the anionic surfactant include sulfates such as alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenol ether sulfates, alkyl sulfonates, alkyl benzene sulfonates, α-olefin sulfones. Sulfonates such as acid salts, alkyl (or alkoxy) naphthalene sulfonates, alkyl diphenyl ether disulfonates, alkyl ether sulfonates, alkyl (or formalin condensates) -β-naphthalene sulfonic acid (salts), higher alcohol phosphorus Acid monoester salt, polyoxyalkylene alkyl ether phosphate (salt), polyoxyalkylene phenyl ether phosphate, polyoxyalkylene alkyl phenyl ether phosphate, polyoxyethylene Alkyl ether acetate, alkanoyl sarcosine, alkanoyl sarcosinate, alkanoyl methyl alanine salt, N-acyl sulfocarboxylate, alkyl sulfoacetate, acyl methyl taurate, alkyl fatty acid glycerine sulfate, hydrogenated coconut oil fatty acid Glyceryl sulfate, alkylsulfocarboxylic acid ester salt, alkylsulfosuccinate, dialkylsulfosuccinate, alkylpolyoxyethylenesulfosuccinate, amidopolyoxyethylenesulfosuccinate, sulfosuccinic acid monooleylamide, fatty acid soap surfactant Etc. The above salts include alkali metal salts, triethanolamine salts, ammonium salts and the like.

  Cationic surfactants include tetra-lower alkyl ammonium halide, alkyl trimethyl ammonium halide, hydroxyethyl alkyl imidazoline, polyoxyethylene alkyl methyl ammonium halide, alkyl benzalkonium halide, dialkyl dimethyl ammonium halide, alkyl dimethyl benzyl ammonium halide, alkyl Examples include amine hydrochloride, alkylamine acetate, alkylamine oleate, alkylaminoethylglycine, and alkylpyridinium halide. In addition, you may mix | blend a cationic surfactant as a bactericidal component.

  Nonionic surfactants include polyoxyalkylene alkyl ethers (or esters), polyoxyalkylene phenyl (or alkylphenyl) ethers, polyoxyalkylene naphthyl (or alkylnaphthyl) ethers, polyoxyalkylene styrenated phenyl ethers (or Polyoxyalkylene styrenated phenyl ether in which a polyoxyalkylene chain is further added to the phenyl group), polyoxyalkylene bisphenol ether, polyoxyethylene alkylene sorbite fatty acid ester, polyethylene glycol fatty acid ester, polyoxyalkylene glycerin fatty acid ester, polyoxyalkylene Alkylamine, polyoxyalkylene condensate of ethylenediamine, polyoxyalkylene fatty acid amide, polyol Sialkylene hydrogenated castor oil, polyoxyalkylene alkylphenyl formalin condensate, glycerin (or polyglycerin) fatty acid ester, pentaerythritol fatty acid ester, sorbitan mono (or sesqui or tri) fatty acid ester, higher fatty acid mono (or di) ethanolamide, Examples thereof include alkyl / alkylolamide, oxyethylene alkylamine and the like.

  Amphoteric surfactants include 2-alkyl-N-carboxymethyl (or ethyl) -N-hydroxyethyl (or methyl) imidazolinium betaine, 2-alkyl-N-carboxymethyl (or ethyl) -N-carboxymethyl. Oxyethylimidazolinium betaine, 2-alkyl-N-carboxymethyl (or ethyl) -N-hydroxyethyl (or methyl) imidazoline, dimethylalkylbetaine, N-alkyl-β-aminopropionic acid (or salt thereof), alkyl (Poly) aminoethylglycine, N-alkyl-N-methyl-β-alanine (or a salt thereof), fatty acid amidopropyldimethylaminoacetic acid betaine, coconut oil fatty acid amidopropyl betaine and the like can be mentioned. The above salts include alkali metal salts, triethanolamine salts, ammonium salts and the like.

The surfactant (A) is preferably an anionic surfactant and / or a nonionic surfactant from the viewpoint of low-temperature stability, and an anionic surfactant or a nonionic surfactant may be added. The combined use of an anionic surfactant and a nonionic surfactant is more preferred.
In this case, the anionic surfactant is particularly preferably a sulfate ester salt, particularly a polyoxyethylene alkyl ether sulfate ester salt and an alkyl sulfate ester salt (particularly lauryl sulfate salt). Among these, polyoxyethylene alkyl ether sulfates are preferred, more preferably polyoxyethylene alkyl ether sulfates (sodium and the like) having an alkyl group with 10 to 16 carbon atoms and an average added mole number of ethylene oxide of 1 to 3. Alkali metal salt).
As the nonionic surfactant, polyethylene glycol type, especially polyoxyethylene alkyl ether and polyoxyethylene hydrogenated castor oil are particularly preferable. Among these, polyoxyethylene alkyl ether is preferable, and more preferable is polyoxyethylene alkyl ether having 12 to 20 carbon atoms in the alkyl group and 10 to 20 added moles of ethylene oxide.
(A) The surfactant is most preferably combined with polyoxyethylene lauryl ether sodium sulfate having an average addition mole number of ethylene oxide of 1 to 3 and polyoxyethylene lauryl ether of 10 to 20 mole addition of ethylene oxide. preferable.

  (A) Surfactant can be used singly or in combination of two or more, but the blending amount is one of the factors of stain removal power and low temperature stability. 1-5 mass% with respect to the whole thing, 2-4 mass% is especially suitable. If the blending amount is less than 1% by mass, the stain removal power is not satisfactorily exhibited. Further, when an oily component such as a fragrance is blended, it may be separated after long-term storage. In some cases, precipitates and the like are generated under low temperature storage, resulting in poor appearance stability. In addition, when rinsing with water, the surfactant-derived nulling becomes large, and the usability may be reduced.

  (B) Sulphite is a component that exhibits a stain removal effect by its bleaching action, and also has a bactericidal action. The sulfite may be any compound that releases sulfite ions in an aqueous solution, and alkali metal salts such as sodium and potassium sulfites, ammonium salts, and the like can be used. Specific examples include sodium sulfite, potassium sulfite, ammonium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, ammonium hydrogen sulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite, and the like. From the viewpoint of low-temperature stability, sodium sulfite, sodium hydrogen sulfite, and particularly sodium sulfite are preferred.

  Note that the object of the present invention cannot be achieved even if other peroxides having a bleaching action, such as percarbonates and perborates, are used instead of sulfites.

  The blending amount of sulfite is one of the factors of stain removal power and low-temperature stability. From this point, 0.5 to 2.5% by mass, particularly 0.75 to 2% by mass is preferable based on the whole composition. If the amount is less than 0.5% by mass, the stain removing ability is poor. If the amount exceeds 2.5% by mass, precipitation or salt precipitation may occur under low temperature storage, resulting in poor low temperature stability.

(C) As polyphosphate, following general formula (1)
M _{n + 2} P _n O _{3n + 1} (1)
(However, M represents Na or K, and n ≧ 2.)
In other words, sodium pyrophosphate and potassium pyrophosphate having a polymerization degree n = 2, sodium tripolyphosphate and potassium tripolyphosphate having n = 3, sodium tetrapolyphosphate and potassium tetrapolyphosphate having n = 4, high polymerization degree Linear polyphosphates such as sodium metaphosphate and potassium metaphosphate, and the following general formula (2)
(MPO ₃ ) _m (2)
(However, M represents Na or K, and m ≧ 3.)
In other words, cyclic compounds such as sodium trimetaphosphate and potassium trimetaphosphate having a polymerization degree m = 3, sodium tetrametaphosphate and potassium tetrametaphosphate having m = 4, and sodium hexametaphosphate and potassium hexametaphosphate having m = 6 A polyphosphate etc. can be mix | blended.

  These polyphosphates can be used singly or in combination of two or more. Among them, from the viewpoint of stain removal ability and low temperature stability, the linear polyphosphorus represented by the above formula (1) Acid salts are preferred, with pyrophosphate being particularly preferred.

  The blending amount of (C) polyphosphate is one of the factors of stain removal power and low-temperature stability, and further is a metal harm factor. From this point, 0.3 to 2% by mass of the whole composition, particularly 0.5 to 1.8% by mass is preferable, and if it is less than 0.3% by mass, the stability of the sulfite is lowered, and the stain removal ability is not satisfactorily exhibited. If it exceeds 2% by mass, precipitation or salt precipitation occurs at low temperature storage. May occur and may be inferior in low-temperature stability, and may be inferior in denture metal damage.

  The mass ratio ((B) / (C)) between (B) sulfite and (C) polyphosphate is one of the factors that develops high stain removal power in a short time treatment. 3-4, especially 0.5-3 are preferred. When (B) / (C) is less than 0.3, the appearance stability under low-temperature storage is poor, and when it exceeds 4, it is difficult to develop a satisfactory stain stain removal ability even if the composition is repeatedly used and washed. There is.

(D) As the polyhydric alcohol, known ones that are usually used in oral compositions can be used. Here, the polyhydric alcohol is a chain sugar in which a carbonyl group of a sugar molecule is reduced in addition to a polyhydric alcohol in which two or more hydrogen atoms of an aliphatic hydrocarbon are substituted with a hydroxyl group (hydroxy group). Also includes alcohol.
Examples of the polyhydric alcohol in which two or more hydrogen atoms of the aliphatic hydrocarbon are substituted with a hydroxyl group include dihydric alcohols and trihydric alcohols such as glycerin, 1,3-butylene glycol, propylene glycol, and ethylene glycol, Examples include polyalkylene glycols obtained by polymerizing alkylene glycols such as polypropylene glycol and polyethylene glycol. Examples of the sugar alcohol in which the carbonyl group of the sugar molecule is reduced include sorbitol, erythritol, xylitol and the like.

  (D) Polyhydric alcohols can be used singly or in combination of two or more, but a combination of a polyhydric alcohol in which two or more of the hydrogen atoms of the aliphatic hydrocarbon are substituted with a hydroxyl group and a sugar alcohol is preferred. The component (D) is particularly preferably glycerin and / or sorbit, particularly a combination of glycerin and sorbit. In this case, it is preferable to use glycerin and sorbit together in a mass ratio of 0.2 to 2, particularly 0.3 to 1.2, whereby the appearance stability under low temperature storage, particularly when freeze-thawed It is possible to improve the restorability of the image.

  (D) The compounding quantity of component is 25-35 mass% from this point in one of the factors of the temporal stability of a sulfite, and the low temperature stability of a polyphosphate, and 28-32 mass% is especially preferable. If the blending amount is less than 25% by mass, the stability of sulfite is inferior over time, and the low-temperature stability of the polyphosphate is not satisfactorily improved. If it exceeds 35% by mass, the stain removal power is inferior, and further Usability may be reduced due to increased null-stick.

  In the present invention, the amount of water in the composition is 50 to 65% by mass, preferably 50 to 60% by mass, more preferably from the point of being one of the factors of low temperature stability of sulfite and polyphosphate. Is 55-60 mass%. If the water content is less than 50% by mass, the stain removal power is inferior, the denture during brushing becomes stronger and the usability is reduced, and the solubility of water-soluble components such as sulfites and polyphosphates is reduced. Low temperature stability due to precipitation of salt under low temperature storage. If it exceeds 65% by mass, the low-temperature stability is not satisfactorily improved due to precipitation of polyphosphate under low-temperature storage, and sulfite decomposes during long-term storage, making it difficult to maintain high stain removal power. .

  Further, the pH of the composition at 25 ° C. is 6.5 to 8.0 from one of the factors of stain removal power and denture metal harm, and 7.0 to 7.8 is particularly preferable. If the pH is less than 6.5, the stain removal ability and sulfite stability are inferior, and if it exceeds 8.0, polyphosphate precipitates under low temperature storage, resulting in poor low temperature stability, and dentures obtained by repeated denture washing. Material deterioration occurs. The pH value is a value measured by the same method as in Examples described later.

  In addition, the pH of the preparation may gradually become 6.5 to 8.0, but if necessary, sodium hydroxide, hydrochloric acid, phosphoric acid or its salt, citric acid or its salt, sodium carbonate, hydrogen carbonate You may adjust by mix | blending pH adjusters, such as sodium, boric acid, or its salt. Of these, sodium hydroxide, potassium hydroxide, and hydrochloric acid are preferably used.

Furthermore, the composition of the present invention contains (E) phenoxyethanol for the purpose of further enhancing the stability of sulfite over time, the appearance stability under low-temperature storage (particularly, the restoration property when frozen and thawed), and the stain removal ability. It is preferable to mix.
(E) When mix | blending phenoxyethanol, the compounding quantity is 0.1-0.8 mass% of the whole composition, and 0.2-0.5 mass% is especially preferable. If the blending amount is less than 0.1% by mass, the low-temperature storage stability and stain removal ability cannot be enhanced satisfactorily. If the blending amount exceeds 0.8% by mass, the denture material is more harmful to the resin, and the denture base is cracked. Cracks and the like may occur and the compatibility of the denture may be inferior.

The denture cleaning liquid composition of the present invention can further contain (F) ethylenediaminetetraacetate, thereby imparting a removal effect on stubborn stain containing calcium.
When the component (F) is blended, the blending amount is preferably 0.3 to 1.5%, particularly preferably 0.5 to 1.0% from the viewpoint of the effect of removing the calcium-containing stain stain and the appearance stability. If the blending amount is less than 0.3%, the effect of removing calcium-containing stain stains may be weak. If the blending amount exceeds 1.5%, the appearance stability may be lowered under low temperature storage.

  In the denture cleaning liquid composition of the present invention, in addition to the above-described components, known components according to the purpose can be blended as necessary within a range not inhibiting the effects of the present invention. As an arbitrary component, a fragrance | flavor, a coloring agent, a disinfectant, an enzyme etc. are mentioned, for example.

  Perfumes include spearmint oil, peppermint oil, anise oil, eucalyptus oil, wintergreen oil, cassia oil, clove oil, thyme oil, sage oil, lemon oil, orange oil, peppermint oil, cardamom oil, coriander oil, mandarin oil, Natural flavors such as lime oil, lavender oil, rosemary oil, laurel oil, camomil oil, caraway oil, marjoram oil, bay oil, lemongrass oil, origanum oil, pine needle oil, cinnamon bark oil, and menthol , Menthone, carvone, ethyl butyrate, vanillin, ethyl maltol, anethole, methyl salicylate, cinnamic aldehyde, cineole, eugenol, ethyl vanillin, maltol, limonene, citronellol, linalool, linalyl acetate, menthyl acetate, pici Single fragrances such as ethyl acetate, allyl cyclohexane propionate, methyl anthranilate, ethyl methyl phenyl It is possible to use known fragrances used in oral compositions such as singular fragrances such as glycidate, undecalactone, hexanal, ethyl alcohol, propyl alcohol, butanol, isoamyl alcohol and / or various blended fragrances including natural fragrances. it can.

  In the denture cleaning liquid composition, a fragrance can be blended to impart a refreshing sensation, whereby the user can more comfortably clean the denture or feel a refreshing feeling when the denture is mounted. In addition, the blending amount of the fragrance is preferably 0.1 to 1% by mass of the whole composition, and if it is less than 0.1% by mass, the feeling of refreshing and refreshing feeling when the denture is mounted becomes insufficient. If it exceeds 50%, satisfactory appearance stability may not be obtained even if a surfactant is added, or discoloration may occur significantly during long-term storage.

  As colorants, 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 etc. Legal dye, caramel dye, safflower dye, gardenia dye, cochineal dye, anato dye, mica titanium, titanium oxide and the like.

  As the disinfectant, isopropylmethylphenol, thymol, triclosan, benzoic acid or a salt thereof, salicylic acid or an ester thereof or a salt thereof, parabens, phenol or the like can be used.

  The denture cleaning liquid composition of the present invention can be used as a denture cleaning agent that can be applied to a denture as it is without being diluted at the time of use, the form is not particularly limited, and can be prepared in a liquid or foam form, It does not have to be an emulsion.

  In order to clean a denture such as a partial denture and a complete denture with the denture cleaning liquid composition of the present invention, the composition is applied to the denture in a liquid or foam form, or the liquid composition is applied to a container such as a cup. And soak the denture in it, bring the liquid composition into contact with the denture for about 30 seconds to 5 minutes, and then use it with a brush such as a toothbrush, electric toothbrush, denture brush, etc. that is held in the hand for 30 seconds to It is recommended to brush for 3 minutes, especially 1 minute. By applying the denture cleaning liquid composition to the denture and performing brushing, stain stains on the denture can be effectively removed by chemical action and physical action. After washing, the composition can be rinsed with running water for about 10 seconds to 1 minute before the denture can be attached.

  When applying the denture cleaning liquid composition of the present invention to a denture as a liquid, the container is not particularly limited, and can be used by filling a container applied to the oral composition. Specifically as such a container, a polyethylene layer, an ethylene methacrylic acid copolymer layer, a polyethylene terephthalate layer, an aluminum layer, a glass vapor deposition layer, a polyvinyl alcohol layer, an ethylene vinyl alcohol copolymer layer, an acrylonitrile copolymer layer, Paper, laminated containers made of recycled plastic layers, or polyethylene containers, polyethylene terephthalate containers, polypropylene containers, etc. can be used, and are usually used to contain liquid oral compositions such as tube containers and film packaging containers such as pillow packaging. Various containers can be used.

  When applying the denture cleaning liquid composition to a denture in the form of a foam, the liquid composition can be stored in a container that can be ejected in the form of a foam, and by applying a pressing force to the contents, The contents can be mixed with air and filled into a container, particularly a non-aerosol type non-gas normal pressure container, which is ejected in a foam form from the outlet, and can be applied in the form of a foam at the time of use. In addition, by applying the denture cleaning liquid composition in the form of foam to the denture, the composition easily adheres to the denture, and the stain removal effect is quickly exhibited after application, so that the denture can be cleaned more easily.

  When the denture cleaning liquid composition of the present invention is foamed and applied to a denture, the container is not particularly limited as long as it has a structure capable of ejecting the contents into a foam. A known squeeze type or dispenser type can be used. Specifically, a pressing portion of the spray unit that is provided in close contact with the upper opening of the container main body, including a container main body such as a plastic bottle for storing the contents, and a spray unit having an ejection mechanism such as a pump dispenser. By pressing the liquid piston and the air piston simultaneously, the contents and air are simultaneously supplied to the gas-liquid mixing chamber, mixed and then foamed by passing through the foaming mesh, and the contents discharge port ( Nozzle). In this case, it is preferable to have a diameter capable of discharging about 0.5 to 1.5 g of contents by one ejection.

  Commercially available products may be used as such containers, for example, those described in Japanese Utility Model Publication Nos. 7-6108, 7-8251, and 4-102666.

  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, “%” means “% by mass” unless otherwise specified, and the compounding amount in the table is a pure conversion value.

Moreover, the following were used as each component of a raw material.
Polyoxyethylene (15) monolauryl ether (ethylene oxide addition mole number 15 (EO.15)); manufactured by Shell Japan, LAO-90N (90% product)
Polyoxyethylene (2) alkyl (C12-14) ether sodium sulfate; Shin-Nihon Rika Co., Ltd., Sinoline SPE-1200K (24-27% product)
-Sodium lauryl sulfate; manufactured by Toho Chemical Industry Co., Ltd., sodium lauryl sulfate-polyoxyethylene hydrogenated castor oil (average number of moles of added ethylene oxide: 60); manufactured by Nikko Chemicals Co., Ltd., HCO-60
・ Decaglyceryl laurate; manufactured by Taiyo Kagaku Co., Ltd., Sunsoft M-12J
・ Sucrose stearate; manufactured by Mitsubishi Chemical Foods Co., Ltd., Ryoto Sugar Ester S-1570
・ Sodium sulfite; manufactured by Nisso Metal Chemical Co., Ltd., refined anhydrous sodium sulfite ・ disodium dihydrogen pyrophosphate; manufactured by Taihei Chemical Sangyo Co., Ltd., disodium dihydrogen pyrophosphate ・ tetrasodium pyrophosphate anhydrous; Taihei Chemical Industry ( Co., Ltd., tetrasodium pyrophosphate / sodium tripolyphosphate; manufactured by Taihei Chemical Sangyo Co., Ltd., sodium tripolyphosphate / glycerin; manufactured by Sakamoto Pharmaceutical Co., Ltd. ) Sorbit liquid (70% product), sorbitol D-70
・ Propylene glycol; Showa Denko Co., Ltd. ・ Phenoxyethanol; Sanyo Kasei Kogyo Co., Ltd., New Pole EFP
・ Edetic acid disodium; ethylenediaminetetraacetate, manufactured by Lion Co., Dissolvin NA2
・ Other optional ingredients; all use Japanese Pharmacopoeia or quasi-drugs

[Examples and Comparative Examples]
Preparations (liquid compositions for denture cleaning) having the compositions shown in Tables 1 to 5 below were prepared by the following manufacturing method, and the following methods were used to stabilize sulfite over time, stain removal power, removal power against calcium-containing stain soil, and dentures. Metal or resin damage and storage stability were evaluated. The results are shown in Tables 1-5. In addition, since the sodium hydroxide and hydrochloric acid which are mix | blended as a pH adjuster are trace amounts, the water content was computed considering that a compounding quantity was zero.

<Production method>
(1) Polyphosphate, sulfite and the like were mixed and dissolved in purified water, and when added, water-soluble components such as benzoic acid were added and mixed and dissolved. Further, disodium edetate was added and dissolved as necessary.
(2) The heated and melted surfactant was added to a polyhydric alcohol (such as glycerin and / or sorbit) and stirred sufficiently until uniform.
(3) (2) was added to (1) and stirred well until uniform.
(4) Oil-soluble components such as phenoxyethanol, fragrance, and oil-soluble disinfectant were dissolved in ethanol as needed, and this was added to the mixed solution of (3).
(5) If necessary, the pH was adjusted with 1N hydrochloric acid or 10% aqueous sodium hydroxide to obtain a denture cleaning liquid composition.

<PH measurement method>
About the sample solution transferred to the glass container, the value after 2 minutes at 25 ° C. was measured with a pH meter (manufactured by Toa Denpa Kogyo Co., Ltd., HM-30V) and a pH electrode (manufactured by Toa Denpa Kogyo Co., Ltd., GST-5421C). It was measured.

Test Example 1 Evaluation of stability of sulfite over time The liquid composition for cleaning dentures is a non-gas type foam container shown in FIG. 1 (former pump YF-9413 made by Yoshino Kogyo, dip tube length 35 mm, discharge amount of 1 push is about 1 g, 100 mL polyethylene bottle) was filled with 100 mL and stored at room temperature or 40 ° C. for 1 month. After returning to room temperature after storage, sulfite ions in the composition were quantified by the following method using ion chromatography and evaluated.

<Method of quantifying sulfite ion>
The denture cleaning liquid composition was diluted to 20 times volume with methanol / pure water = 1/9 (volume ratio), and further subjected to solid phase extraction treatment with Bond Elut C18 in order to remove organic components. 20 μL of the sample was analyzed under the following conditions.
・ Pump: LC-3A manufactured by Shimadzu Corporation
Column oven: SSC-2100 manufactured by Senshu Kagaku Co., Ltd.
-Detector: Electrical conductivity detector, Shodex CD-5
Column: Shodex IC I-524 (4.6 mm x 100 mm)
-Mobile phase: 0.25 mM p-hydroxybenzoic acid (adjusted to pH 9.7 with N, N-diethylethanolamine) + 10% methanol-Column temperature: 50 ° C
-Flow rate: 1.2 mL / min-Suppressor: None-Solid-phase extraction: Column was conditioned by passing approximately 4 mL of methanol / pure water = 1/9 (volume ratio) after passing approximately 4 mL of methanol . Furthermore, about 3 mL of the sample solution was passed through the column, and the column was replaced with the sample solution. Thereafter, about 3 mL of the sample solution was passed through to obtain an analysis target sample of ion chromatography.
Calibration curve: 200 mg of sodium sulfite was precisely weighed and dissolved in a solvent of methanol / pure water = 1/9 (volume ratio) to make 100 mL. This solution was diluted to obtain a standard solution (125 μg / mL, 500 μg / mL). A calibration curve for sulfite ions was prepared from the analytical value of the standard solution by the least square method.

<Evaluation method of aging stability of sulfite>
From the quantitative value of sulfite ion, the residual rate of sulfite ion in the composition was calculated according to the following formula (3), and the sulfite ion stability was evaluated according to the following criteria.
Formula (3)
Sulfite ion residual ratio (%) = [residual concentration (%) / mixing concentration (%)] × 100
<Evaluation criteria>
Sulfite ion residual rate 80% or more: ◎
70% to less than 80%: ○
60% or more and less than 70%: △
Less than 60%: ×

Test Example 2 Removability test against stain stain In order to verify the removal power against stain stain of a product immediately after preparation of a denture cleaning liquid composition, a tannin stain model was prepared and evaluated.

<Production method of tannin stain model>
The surface of a white methacrylic resin plate (20 mm × 20 mm, paraglass 5 mm, manufactured by Kuraray Co., Ltd.) is polished for 10 to 15 seconds with sand blast, ultrasonically washed with ion-exchanged water containing detergent, and then rinsed thoroughly with water. Immerse in ion exchange water in the evening. On the next day, the sample was sufficiently dried, the color difference was measured with a color difference meter, the average value was calculated, and used as the initial value of the acrylic white board. Three types of solutions ([1] albumin solution (albumin 6.0 g / 1,200 mL), [2] tannin solution (50 g of Japanese tea and 5 packs of black tea) with ion-exchanged water, filtered and dissolved 12 g of instant coffee ), [3] iron solution (iron (III) ammonium citrate 6.85 g / 1200 mL)) was prepared, and an acrylic white plate was [1] albumin solution → [2] tannin solution → [3 The operation of dipping and drying in the order of the iron solution was performed (this is one cycle). The first 5 cycles were repeated for 20 minutes at 45 ° C., and the sixth and subsequent cycles were repeated for immersion and drying at 50 ° C. for 10 minutes. After 30 cycles, the color difference was measured to confirm that the L value was around 22, and used as an evaluation model for the removal force test.

<Removal power test>
The non-gas type foam container shown in FIG. 1 (former pump YF-9413 manufactured by Yoshino Kogyo Co., Ltd., dip tube length 35 mm, 1 push discharge amount is about 1 g, capacity 100 mL polyethylene bottle) shown in FIG. After filling, about 1 g of the evaluation sample was applied in a foam form to the stain model, and brushing was performed for 1 minute using an electric brush. Then, after rinsing with running water for 1 minute and drying well, the color difference was measured using a color difference meter. Stain removal power was calculated according to the following formula (4) from the color difference values of ΔE1 after stain adhesion and ΔE2 after treatment with the cleaning agent before stain adhesion, and the stain removal power of the immediately following product was evaluated.
Formula (4)
Stain removal power (%)
= [(ΔE1 before washing ΔE2 after washing) / ΔE1 before washing] × 100
<Evaluation criteria>
Stain removal power 50% or more: ◎
30% to less than 50%: ○
10% or more and less than 30%: △
Less than 10%: ×

  FIG. 1 is a schematic cross-sectional view of the non-gas type foam container, which includes a bottle main body a for storing contents and a former pump part b having a spray mechanism, and an upper opening of the bottle main body a. The former pump part b is closely attached by a cap c having a packing, and the former pump part b has a pump head 1, a foam mesh 2, a gas-liquid mixing chamber 3, It has a ball 4 for adjusting the flow rate, an air piston 5, an air tank 6, an air cylinder 7, a liquid piston 8 and a liquid cylinder 9, and the lower protrusion of the liquid cylinder 9 serving as a content inflow path is inserted into the bottle body a. ing. In this container, when the pump head 1 is pressed, the air piston 5 in the air cylinder 7 moves up and down, and the liquid piston 8 moves up and down along the liquid cylinder 9 due to the pressure difference inside the air tank 6 in the air cylinder 7. As a result, the contents in the bottle body a are sucked up from the lower opening of the liquid cylinder 9 and sucked through the ball 4 for adjusting the flow rate in the air cylinder 7, passing through the gas-liquid mixing chamber 3 and the foaming mesh 2. Then, it is sprayed and discharged from the content discharge port 10.

<Stain removal power of stored products>
The non-gas type foam container shown in FIG. 1 was filled with 100 mL of the denture cleaning liquid composition and stored at 40 ° C. for 1 month in a state of standing still. Thereafter, the composition was lowered to room temperature for 1 day at room temperature, and the stain removal power of the stored product was evaluated according to the procedure shown in the above-mentioned removal power test.

Test Example 3 Removability test for calcium-containing stain stain A calcium-containing tannin stain model was created and evaluated in order to verify the removability of the denture cleaning liquid composition immediately after preparation of the calcium-containing stain stain.

<Method for producing calcium-containing tannin stain model>
The calcium-containing tannin stain model follows the method for preparing the tannin stain model shown in Test Example 2 above: [1] Artificial saliva (KCl; 50 mM, KH ₂ PO ₄ ; 1 mM, CaCl ₂ ; 1 mM, MgCl ₂ ; 0.1 mM, adjusted to pH 7.0). The acrylic white board was immersed and dried in the order of [1] albumin solution → [2] tannin solution → [3] iron solution (this is one cycle). The first two cycles were repeated at 45 ° C. for 15 minutes, and the third and subsequent cycles were repeated by dipping and drying at 50 ° C. for 10 minutes. The color difference was measured, and it was confirmed that the L value was around 24, which was used as an evaluation model for the removal force test.

<Removal power test>
The non-gas type foam container shown in FIG. 1 (former pump YF-9413 manufactured by Yoshino Kogyo Co., Ltd., dip tube length 35 mm, 1 push discharge amount is about 1 g, capacity 100 mL polyethylene bottle) shown in FIG. After filling, about 1 g of the evaluation sample was applied in a foam form to the stain model, and brushing was performed for 1 minute using an electric brush. Thereafter, it was rinsed with running water for 1 minute and dried well. After repeating this process three times, the color difference was measured using a color difference meter. From the color difference values of ΔE1 after stain adhesion and ΔE2 after treatment with the cleaning agent three times before stain adhesion, the removal power against calcium-containing stain soil was calculated according to the following formula (5).
Formula (5)
Removal power against calcium-containing stain stains (%)
= ((Before washing ΔE1−after washing 3 times ΔE2) / before washing ΔE1) × 100 (5)

<Evaluation criteria>
Removability 50% or more: ◎
30 to less than 50%: ○
Less than 10-30%: △
Less than 10%: ×

Test Example 4 Denture metal or resin hazard test For the denture cleaning liquid composition, the denture metal hazard was evaluated by the following method.
<Denture metal hazard test>
The surface of the denture metal material processed into a plate shape was polished by sandblasting, immersed in an evaluation reagent (denture cleaning liquid composition), and stored overnight in a thermostatic bath at 50 ° C. After storage, the denture material was taken out of the evaluation solution, washed with water, and dried. The color difference of the denture metal plate after drying was measured, and the initial metal material and the color difference after the immersion treatment were set to ΔE1 and ΔE2, respectively, and the denture metal hazard was calculated according to the following formula (6).
Formula (6)
Denture metal hazard (%) = [(ΔE1 before immersion−ΔE2 after immersion) / ΔE1 before immersion] × 100
<Evaluation criteria>
Denture metal damage less than 3%: ◎
3% to less than 4%: ○
4% to less than 6%: △
6% or more: ×

About the liquid composition for denture cleaning, resin harmfulness was evaluated by the following method.
<Resin hazard test>
Acrylic and polycarbonate, which are resins for dentures, were processed into a plate shape (20 mm × 10 to 15 mm), polished with water-resistant paper, immersed in ion-exchanged water, and ultrasonically cleaned for 5 minutes. 10 mL of the evaluation test solution (denture cleaning liquid composition) was taken in a 50 mL glass vial, and the resin was immersed therein and stored at 50 ° C. for 2 weeks while replacing the immersion liquid once or twice a week. The color difference of the resin plate after storage was measured, and the initial resin plate and the color difference after storage were ΔE1 and ΔE2, respectively, and the resin damage was calculated according to the above formula (6).
<Evaluation criteria>
Resin hazard: Less than 1.5%: ◎
1.5% to less than 3%: ○
3% to less than 6%: △
6% or more: ×

Test Example 5 Storage stability (low-temperature stability and restorability after freezing and thawing) test The low-temperature stability of the blended products (liquid compositions for denture cleaning) shown in Tables 1 to 5 was evaluated by the following method. Moreover, the freeze-thaw test was done by the following method about the compounded goods shown to Tables 2-5, and the restoring property after freeze-thaw was evaluated.
<-10 ° C, 1 month low temperature stability>
About 80 g of the liquid composition was filled into a 100 mL transparent PET container with a lid and stored at -10 ° C for 1 month. After storage, it was transferred to 10 ° C., and appearance stability (precipitate, sediment, liquid separation) after 1 day was evaluated.
<Evaluation criteria>
No change is observed in any of the precipitate, sediment, and liquid separation: ◎
Slight changes are observed in any of the items of sediment, sediment, and liquid separation, but there is no problem: ○
Changes are observed in any of the items of sediment, sediment, and liquid separation: △
Changes are observed in any of sediment, sediment, and liquid separation: ×

<−20 ° C. freeze-thaw test>
Appearance stability (precipitation) when filling a 100 mL transparent PET container with a lid with about 80 g of the liquid composition, freezing at −20 ° C. for 2 days, and then leaving it at 10 ° C. for 1 day to melt for 5 times. (Product / ori / liquid separation) was evaluated.
<Evaluation criteria>
No change is observed in any of the precipitate, sediment, and liquid separation: ◎
Slight changes are observed in any of the items of sediment, sediment, and liquid separation, but there is no problem: ○
Changes are observed in any of the items of sediment, sediment, and liquid separation: △
Changes are observed in any of sediment, sediment, and liquid separation: ×

From the results of Tables 1 to 5, the denture cleaning liquid composition of the present invention can be applied directly to the denture without being diluted at the time of use, and stain stains of the denture can be effectively removed with a short time and simple cleaning. It is possible to obtain a denture cleaning liquid composition that is superior in sulphite stability over time and appearance stability during low-temperature storage without damaging the denture metal or resin, and that maintains good stain removal even after long-term storage. all right. From the results of Table 2, when glycerin and sorbit are used in an appropriate ratio as the component (D), the low-temperature stability (particularly, the recoverability when frozen and thawed) is further improved. From the results of Tables 4 and 5, Furthermore, when (E) phenoxyethanol is added, the sulphite stability over time, low-temperature stability (especially reconstitution when frozen and thawed) and stain removal ability are further improved, and high stain removal ability is exhibited even after storage. I understood it. Moreover, from the result of Table 5, when (F) ethylenediaminetetraacetate was further blended, it was found that the removal power against calcium-containing stain soil was developed.
From the above results, the liquid composition for cleaning dentures of the present invention is stable with time for sulfite in the liquid composition, appearance stability when stored at low temperatures, stain stain removal power of dentures, denture metal or resin damage. It was confirmed that it was excellent in all of the properties.

a Bottle body b Former pump c Cap 1 Pump head 2 Foaming mesh 3 Gas-liquid mixing chamber 4 Ball 5 Air piston 6 Air tank 7 Air cylinder 8 Liquid piston 9 Liquid cylinder 10 Contents outlet

Claims (7)

(A) a surfactant,
(B) sulfite,
(C) The following general formula (1)
M _{n + 2} P _n O _{3n + 1} (1)
(However, M represents Na or K, and n ≧ 2.)
A linear polyphosphate represented by the following general formula (2)
(MPO ₃ ) _m (2)
(However, M represents Na or K, and m ≧ 3.)
1 type or 2 or more types of polyphosphates chosen from the cyclic polyphosphate represented by these, and (D) polyhydric alcohol, the compounding quantity of (D) component is 25-35 mass%, and A liquid composition for denture cleaning, characterized in that the water content in the composition is 50 to 65% by mass and the pH at 25 ° C. is 6.5 to 8.0.   The liquid composition for denture cleaning according to claim 1, wherein the component (D) is glycerin and / or sorbit.   The liquid composition for denture cleaning according to claim 1, wherein the component (D) is glycerin and sorbit, and the mass ratio of glycerin / sorbite is 0.2-2.   The denture according to claim 1, 2 or 3, comprising 1 to 5% by mass of component (A), 0.5 to 2.5% by mass of component (B), and 0.3 to 2% by mass of component (C). Liquid composition for cleaning.   The denture cleaning liquid according to any one of claims 1 to 4, wherein (A) the surfactant is a combined use of a sulfate ester type anionic surfactant and a polyethylene glycol type nonionic surfactant. Composition.   The liquid composition for denture cleaning according to any one of claims 1 to 5, further comprising (E) phenoxyethanol.   Furthermore, (F) ethylenediaminetetraacetate is contained, The liquid composition for denture cleaning of any one of Claim 1 thru | or 6 characterized by the above-mentioned.