JP3332833B2 - Denture cleaning composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a denture cleaning composition which has excellent cleaning performance at low temperatures and does not damage denture materials during cleaning.

[0002]

2. Description of the Related Art Leaving food residues and the like attached to a denture not only causes unpleasant odor, but also causes oral diseases such as inflammation of the subfloor mucous membrane. It is also a factor. For this reason, it is necessary to wash and remove food residue and the like on a daily basis with a denture cleaning agent. However, for the convenience of the user, it is desirable that the washing operation is simple and the washing can be completed in a short time. Therefore, in order to satisfy such requirements, without using lukewarm water,
Even when tap water is used as it is, it is important that the detergency is excellent, and it is also necessary that the material constituting the denture is not damaged.

[0003] Conventionally, many denture cleansing agents containing peroxide, hypochlorite, acid, disinfectant, enzyme and the like as a base are commercially available. As a prior art of denture cleaners, JP-A-59-205309 discloses an effervescent detergent composition and JP-A-63-867.
No. 99 discloses a denture cleaning and / or bleaching activator.
Or a cleaning composition is disclosed. However, none of the conventional denture cleaners including these conventional techniques sufficiently satisfy the above requirements.

[0004] The present invention provides a denture cleaning composition that can quickly remove food residues and the like adhering to a denture at room temperature or lower temperature and does not damage the denture material. The purpose is to:

[0005]

As a result of repeated studies, the present inventors have found that the above object can be achieved by using a free acid-type specific bleach activator together with other active ingredients. The present invention has been completed.

That is, the present invention provides (a) the following general formula (I) which reacts with hydrogen peroxide in water to generate an organic peracid:
R—C (＝ O) -L (I) wherein R represents a straight-chain alkyl group having 6 to 13 carbon atoms;
L is the following formula (II) or (III):

[0007]

Embedded image

0.1 to 30% by weight of a bleaching activator represented by the formula (1), (b) 30 to 98% by weight of sodium percarbonate and (c) an alkali metal silicate. The present invention provides a denture cleaning composition containing 1 to 30% by weight.

[0009]

The component (a) used in the present invention reacts with hydrogen peroxide in water to generate an organic peracid, and is represented by the general formula (I). R in the general formula (I) has 6 to 13 carbon atoms, preferably 8 to 12 in order to obtain sufficient detergency. As such a component (a), the following general formula (VI) or (VII)
Is preferably represented by

[0010]

Embedded image

[0011]

Embedded image

The content of the component (a) is 0.1 to 30% by weight, preferably 1 to 30% by weight, in consideration of economical efficiency and sufficient detergency in the denture cleaning composition.
To 15% by weight, particularly preferably 2 to 10% by weight.

The component (b) sodium percarbonate used in the present invention is a component that releases hydrogen peroxide in water. The content of the component (b) in the denture cleaning composition is 30 to 98% by weight, preferably 50 to 90% by weight, in consideration of imparting sufficient detergency and economical efficiency. Preferably it is 50 to 80% by weight.

Examples of the alkali metal silicate of the component (c) used in the present invention include alkali metal silicates such as sodium silicate and potassium silicate, and crystalline alkali metal silicates. These can be used alone or in combination of two or more. Among these, a crystalline alkali metal silicate is preferable because of its excellent cleaning performance and storage stability of the composition.

Moreover, (c) component, to improve the detergency by ion trapping ability, the ion exchange capacity preferably not less than 100mgCaCO ₃ / g, particularly preferably not less than 200mgCaCO ₃ / g And more preferably 270 mg CaCO ₃ / g or more.

The crystalline alkali metal silicate of the component (c) is represented by the following general formula (IV) or
And those represented by (V).

[0017] _{x (M 2 O) · y} (SiO 2) · z (Me m O n) · w (H 2 O) (IV) wherein, M represents a Group Ia elements of the periodic table, Me Is IIa, IIb, IIIa, IVa of the periodic table is selected from Group VIII elements
Indicates a species or a combination of two or more species, and y / x = 0.5 to
2.6, z / x = 0.01-1.0, n / m = 0.5-
2.0, w = 0 to 20].

In the general formula (IV), M is Ia in the periodic table.
Na, K, etc., which are selected from group elements. These may be used alone or, for example, a mixture of Na ₂ O and K ₂ O to constitute the M ₂ O component.

In the general formula (IV), Me represents II in the periodic table.
Group a element, IIb element, IIIa element, IVa element or VI
Selected from Group II elements, for example, Mg, Ca, Zn, Y, T
i, Zr, Fe and the like. These are not particularly limited, but from a resource and security point of view,
Preferably, they are Mg and Ca. These may be used alone or in combination of two or more. For example, MgO, C
It may constitute the Me _m O _n component or the like is mixed aO-.

In the general formula (IV), y / x is 0.5 to
2.6, and preferably 1.5 to 2.2. y / x
If it is less than 0.5, the water resistance is insufficient and the caking property, the solubility, and the powder properties of the composition are significantly adversely affected. If y / x exceeds 2.6, the alkalinity becomes low and the alkalinity is insufficient. z / x is 0.01-1.
0, preferably 0.02 to 0.9. If z / x is less than 0.01, the water resistance is insufficient, and if it exceeds 1.0, the cleaning effect is reduced. Further, the alkali metal silicate of the general formula (IV) may be a hydrate, in which case w = 1 to 20.

X, y, and z are not particularly limited as long as they have the relationship shown in the y / x ratio and the z / x ratio described above. As described above, x (M ₂ O) is, for example, x ′ (Na ₂ O) · x ″ (K
If the ₂ O), x is the x '+ x ". This relationship is the same in the z in the case where z (Me _m O _n) component consists of two or more. Further, n / m indicates the number of oxygen ions coordinated to the element, and is substantially 0.5,
It is selected from the values of 1.0, 1.5, and 2.0.

The crystalline alkali metal silicates of the general formula (IV), M ₂ O, but is made of three components of SiO ₂ and Me _m O _n, is particularly limited, a raw material of each of these components Instead, known compounds can be used.
For example, raw materials for the M ₂ O component include NaOH, KO
H, Na ₂ CO ₃ , K ₂ CO ₃ , Na ₂ SO _{4 and the} like can be mentioned, and as a raw material of the SiO ₂ component, silica stone, kaolin, talc, fused silica, sodium silicate and the like can be mentioned. as a raw material of Me _m O _n component, CaCO _3, M
gCO ₃ , Ca (OH) ₂ , Mg (OH) ₂ , MgO, Z
rO ₂ , dolomite and the like can be mentioned.

The method for preparing the crystalline alkali metal silicate includes the steps of x, y,
The above-mentioned raw material components are mixed at a predetermined quantitative ratio so as to obtain a value of z, and usually 300 to 1500 ° C., preferably 500 to
A method of firing at a temperature of 00 ° C., particularly preferably in a range of 600 to 900 ° C. for crystallization can be mentioned. In this case, if the heating temperature is lower than 300 ° C., crystallization is insufficient and the water resistance is poor. If the heating temperature is higher than 1500 ° C., coarse particles are formed, and the ion exchange ability is reduced. The heating time is usually 0.1 to 24 hours. Such baking can be usually performed using an electric furnace, a gas furnace, or the like.

The particle size of the crystalline alkali metal silicate of the general formula (IV) is not particularly limited, but is preferably in the range of 0.01 to 100 μm.

M ₂ O · y ′ (SiO ₂ ) · w ′ (H ₂ O) (V) [wherein M represents an alkali metal and y ′ = 1.5 to 4.
0, w '= 0 to 20].

In the general formula (V), M has the same meaning as in the general formula (IV). y ′ and w ′ are such that y ′ is 1.7 to 2.2.
Wherein w ′ is 0. Further, those having an ion exchange capacity of 100 to 400 mg CaCO ₃ / g are preferred.

The crystalline alkali metal silicate of the general formula (V) is generally prepared by adding amorphous glassy sodium silicate to 200%.
It is obtained by firing at ~ 1000 ° C to make it crystalline. Details of the synthesis method, for example, Phys.Chem.Glasses.7,
p127-p138 (1966), Z.Kristallogr., 129, p 396-p404 (1
969). The crystalline alkali metal silicate of the general formula (V) may be in the form of powder or granules, for example, from Hoechst under the trade name “Na-SKS-6” (δ-Na ₂ Si ₂ O ₅ ). Is available.

The particle size of the crystalline alkali metal silicate of the general formula (V) is not particularly limited, but is preferably in the range of 0.01 to 100 μm.

The content of the component (c) is 0.1 to 30% by weight, preferably 1 to 30, in consideration of not damaging the object to be treated and economical efficiency in the denture cleaning composition.
To 15% by weight, particularly preferably 2 to 10% by weight.

[0030] The denture cleaning composition of the present invention may further contain a surfactant. Examples of surfactants include alkyl glycosides, polyoxyethylene alkyl ethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acid esters, oxyethylene oxypropylene block polymers (Pluronic, trade name, manufactured by BASF), fatty acid monoglycerides And non-ionic surfactants such as amine oxides; anionic surfactants such as soaps, alkyl sulfates, alkyl benzene sulfonates, polyoxyethylene alkyl ether sulfates, and sulfosuccinic acid diester salts; mono- or dialkylamines and their polyoxygens Cationic surfactants such as ethylene adducts and mono- or di-long-chain alkyl quaternary ammonium salts; amphoteric surfactants such as carbobetaine, sulfobetaine and hydroxysulfobetaine It can be mentioned. Of these, anionic surfactants such as alkyl sulfates, alkyl benzene sulfonates, polyoxyethylene alkyl ether sulfates, and soaps are preferred because of their excellent detergency. The amount of the surfactant is preferably 0.01 to 30% by weight, particularly preferably 0.1 to 30% by weight in the denture cleaning composition.
-20% by weight, more preferably 1-5% by weight.

[0031] The denture cleaning composition of the present invention further comprises a pH
May be added to adjust the buffer. As the buffer, sodium hydroxide, hydroxides of alkali metals such as potassium hydroxide, ammonium hydroxide, amine derivatives such as mono, di or triethanolamine, sodium carbonate, carbonates of alkali metals such as potassium carbonate, Examples thereof include carbonates such as ammonium carbonate. The amount of the buffer varies depending on the pH to be adjusted, but is preferably 0.01 to 30% by weight in the denture cleaning composition.

The denture cleaning composition of the present invention may further contain a chelating agent. It is generally known that an oxygen-based cleaning agent is self-decomposed by a trace amount of metal. By adding a chelating agent, it is possible to prevent a decrease in cleaning performance and improve storage stability. Examples of the chelating agent include alkali metal salts such as tripolyphosphoric acid, pyrophosphoric acid, orthophosphoric acid, and hexametaphosphoric acid, ethylenediaminetetraacetic acid (EDTA), hydroxyiminodiacetic acid, dihydroxyethylglycine, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, and diethylenetriaminepentaacetic acid. , Triethylenetetramine hexaacetic acid and their alkali metal salts, aminotrimethylene phosphonic acid, 1-
Examples include hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepenta-methylenephosphonic acid, N-oxides of aminotrimethylenephosphonic acid, and alkali metal salts thereof. The compounding amount of the chelating agent is preferably from 0.0001 to
It is 10% by weight, particularly preferably 0.001 to 3% by weight.

The denture cleansing composition of the present invention may further comprise, if necessary, a solubilizing agent such as sodium p-toluenesulfonate, sodium xylenesulfonate, sodium alkenylsuccinate, urea, protease, esterase, rivase, Enzymes such as cellulase, anti-caking agents, peroxide stabilizers, penetrants, clay and other suspending agents,
Abrasives, pigments, dyes, fragrances and the like can be blended.

The denture cleansing composition of the present invention enhances the reactivity of the components (a) and (b) to improve the production rate of the organic peracid, which is the active ingredient, and also improves the stability of the organic peracid. To increase the pH, the pH is preferably 5 to 13, and particularly preferably 9 to 11.

[0035]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Production Example 1-1 (Production of Bleaching Activator A) 1.2 mol of phenol was placed in a four-necked flask equipped with a cooling tube, a mechanical stirrer, a thermometer, and a dropping funnel, and heated to 100 ° C. 1.2 mol of lauric chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped by a dropping funnel over about 2 hours, and the mixture was aged for about 2 hours while blowing in nitrogen gas to remove generated hydrochloric acid. The reaction product was distilled to obtain phenyl laurate (96% yield, 97% purity).
%).

Then, lauric acid phenyl ester 0.8
mol was dissolved in 600 g of dichloromethane in a four-necked flask, and then cooled to -10 ° C. Thereafter, 0.84 mol of liquid SO _{3 was} dropped from the dropping funnel over 1 hour while suppressing heat generation, and the mixture was returned to room temperature and aged for 1 hour. Thereafter, dichloromethane was distilled off using an evaporator, and the formula (V
A bleach activator A represented by I) was obtained (75% yield).

Preparation Example 1-2 (Production of Bleaching Activator B) 1 mol of p-hydroxybenzoic acid which had been dehydrated in advance
Is dispersed in 300 g of a toluene solution, and lauric chloride (Wako Pure Chemical Industries, Ltd.) is stirred with a mechanical stirrer.
1 mol) was added dropwise at 50 ° C. over 30 minutes, and after the completion of the addition, the mixture was reacted for about 3 hours. Thereafter, the solvent was removed under reduced pressure (0.
(5-1 mmHg) at 100 ° C. Then, after washing with hexane, recrystallization is performed in toluene, and the formula (VI
A bleach activator B represented by I) was obtained (yield: 85%).

Production Example 2 (Crystalline alkali metal silicate A)
-D) No. ₂ sodium silicate (SiO ₂ / Na ₂ O = 2.5) 100
55.9 parts by weight of sodium hydroxide and 8.5 parts by weight of potassium hydroxide were dissolved in 0 parts by weight. 5.23 parts by weight of finely dispersed anhydrous calcium carbonate and 0.13 parts by weight of magnesium nitrate hexahydrate were added thereto, and mixed using a homomixer. Transfer appropriate amount of mixture to nickel crucible, 7
Calcination was performed in air at a temperature of 00 ° C. for 1 hour. After quenching, the obtained fired body was pulverized to obtain a crystalline alkali metal silicate A. In the same manner, crystalline alkali metal silicates B, C, and D were obtained. Table 1 shows their compositions. In Table 1, the crystalline alkali metal silicates A, B and C correspond to those represented by the general formula (IV), and the crystalline alkali metal silicate D is represented by the general formula (V). Equivalent to

The ion exchange capacities of these crystalline alkali metal silicates A, B, C and D were measured by the following method. <Method of measuring ion exchange capacity> 0.1 g of a sample was precisely weighed,
Calcium chloride solution (concentration is 1% as CaCO ₃ ) 5
0 ml, and stirred at 25 ° C. for 60 minutes.
It filtered using No. filter paper. 10 ml of the filtrate was taken to measure the amount of Ca in the filtrate by EDTA titration, and the calcium ion exchange capacity of the sample was determined from the value.

[0041]

[Table 1]

Examples 1 to 7 and Comparative Examples 1 to 5 Powdered denture cleaning compositions having the compositions shown in Table 2 were obtained. The detergency of these denture cleaning compositions was evaluated by the following detergency test, and the corrosion test for clasps was evaluated by a corrosion test. Table 2 shows the results. The numerical value of each component in Table 2 is represented by% by weight.

<Detergency Test> (1) Soil Test Piece A molded article of denture resin stained with tea or coffee was used as a stain test piece.

(2) Washing and Evaluation Method One liter of a cleaning solution prepared by dissolving 0.4 g of the denture cleaning composition in 1 liter of tap water at 20 ° C. or 10 ° C. was placed in a beaker, and the stained test piece was immersed for 15 minutes. Thereafter, the well was rinsed with water, and the degree of stain removal was visually observed, and evaluated according to the following criteria. 4: Dirt is completely removed 3: Dirt is almost completely removed 2: Dirt is partially removed 1: Dirt is hardly removed 0: Dirt is not completely removed.

<Corrosion Test for Clasp> 0.5 g of the denture cleaning composition was dissolved in 1 liter of tap water at 20 ° C. to prepare a sample solution. 50 ml of this sample solution and a clasp (5 ×
2 cm) was placed in a 100-ml glass bottle with a lid, covered, and allowed to stand at 40 ° C. for 2 days. The state of corrosion of the clasp was visually observed and evaluated according to the following criteria. ：: No corrosion observed ×: Corrosion observed

[0046]

[Table 2]

The compositions of Examples 1 to 7 exhibited sufficient detergency in a short time even at a low temperature of 10 to 20 ° C. Also,
No corrosion was observed. The composition of Example 7 was
(C) The detergency reduced by using sodium silicate having an ion exchange capacity of 0 mg / g as a component was compensated for by using a surfactant in combination, and the detergency equivalent to that of the other examples was obtained. It is. Therefore, the effect of improving detergency by using a crystalline alkali metal silicate having a high ion exchange capacity as the component (c) was confirmed.
In the composition of No. 6, it was also confirmed that the detergency could be further improved by using a surfactant in combination.

[0048]

The denture cleansing composition of the present invention exerts sufficient detergency in a very short time even at normal temperature or lower temperature, and does not damage the denture material at that time. . Therefore, if the denture cleaning composition of the present invention is used, the denture cleaning process in each home becomes easy, and the burden on the user can be reduced.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-9-286996 (JP, A) JP-A-61-36216 (JP, A) JP-A-3-215413 (JP, A) JP-A-1- 246215 (JP, A) U.S. Pat. No. 4,409,118 (US, A) WO 94/26246 (WO, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) A61K ^7/ 00-7/50 C11D 1 / 00-19/00 CA (STN) REGISTRY (STN)

Claims (5)

(57) [Claims] (1) The following general formula (I) which reacts with hydrogen peroxide in water to generate an organic peracid: RC (=
O) -L (I) wherein R represents a straight-chain alkyl group having 6 to 13 carbon atoms;
L is the following formula (III) : A bleaching activator represented by the formula: 0.1 to 30% by weight, (b) 30 to 98% by weight of sodium percarbonate and (c) an alkali metal silicate 0.1 to 10 What is claimed is: 1. A denture cleaning composition comprising: 2. The denture cleaning composition according to claim 1, wherein the component (c) is a crystalline alkali metal salt or a hydrate thereof and has an ion exchange capacity of 100 mg CaCO ₃ / g or more. 3. The crystalline alkali metal silicate or hydrate thereof is represented by the following general formula (IV): x (M ₂ O) .y (SiO ₂ ) .z (Me
_{m O n) · w (H} 2 O) (IV) [ wherein, M is Group Ia elements of the periodic table, Me represents IIa, II
at least one element selected from the group consisting of b, IIIa, IVa and VIII, y / x = 0.5 to 2.6, z / x = 0.01 to
1.0, n / m = 0.5 to 2.0, w = 0 to 20]. 4. The crystalline alkali metal silicate or hydrate thereof is represented by the following general formula (V): M ₂ O.y ′ (SiO ₂ ) .w ′ (H ₂ O)
(V) [wherein, M represents an alkali metal, and y '= 1.5 to 4.
0, w '= 0 to 20]. 5. The bleaching activator of the component (a) is represented by the following formula (V)
II) : The denture cleaning composition according to claim 1 or 2, which is represented by the following formula: