JP3332752B2 - 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, and more particularly to a denture cleaning composition having high cleaning performance and little influence on denture materials.

[0002]

BACKGROUND OF THE INVENTION The purpose of a denture cleaner is, of course, to clean as quickly as possible the debris on the denture, especially on the surface generated when the denture is worn. The reason for this is that not only the denture becomes dirty and produces a bad smell, but also causes various kinds of diseases in the oral cavity, such as inflammation of the mucous membrane under the floor.

[0003] For this reason, various cleaning agents are commercially available as denture cleaning agents.
Many types are used, such as hypochlorite, acids, disinfectants, and enzymes. JP-A-59-205309 discloses a foaming detergent composition, and JP-A-63-86799 discloses a denture cleaning and / or cleaning composition containing a bleaching activator.

However, a denture cleaning agent having sufficient cleaning performance and having little influence on a base material (denture material) has not yet been found. Accordingly, an object of the present invention is to provide a denture cleaning composition having high cleaning performance and little influence on a base material (denture material).

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above problems can be solved by using a bleach activator having a specific structure, sodium percarbonate and an alkali metal silicate together. The present invention has been completed.

That is, the present invention provides: (a) a bleaching activator represented by the following general formula (I), which reacts with hydrogen peroxide in water to generate an organic peracid;

[0007]

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Wherein R represents a straight-chain alkyl group having 6 to 13 carbon atoms, and L represents the following formula (II) or (III):

[0009]

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And a leaving group represented by (B) 30 to 98% by weight of sodium percarbonate (c) 0.1 to 30% by weight of an alkali metal silicate is provided.

[0011]

Embodiments of the present invention will be described below in detail.

The component (a), which is an essential component of the present invention, is a bleach activator represented by the general formula (I), which reacts with hydrogen peroxide in water to generate an organic peracid. In the general formula (I), the alkyl group represented by R 1 is linear and has 6 to 13 carbon atoms. If the number of carbon atoms is 5 or less and the number of carbon atoms is 14 or more, preferable detergency cannot be obtained.

Particularly preferred among these bleach activators are compounds represented by the following formula (VI).

[0014]

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The amount of the bleaching activator (a) used in the present invention is 0.1 to 30% by weight, preferably 1 to 15% by weight, particularly preferably 2 to 10% by weight, based on the total weight of the composition. %. (a) If the amount of the component is less than 0.1% by weight, no cleaning effect is observed, and if it exceeds 30% by weight, no further effect is obtained, and it tends to be economically disadvantageous.

The composition of the present invention contains sodium percarbonate as the component (b), and the content in the composition is 30 to 98% by weight, preferably 50 to 90% by weight. When the content is less than 30% by weight, sufficient cleaning performance cannot be obtained, and when the content is more than 98% by weight, the cleaning performance is not so improved.

The alkali metal silicate which is the component (c) of the present invention includes amorphous alkali metal silicates such as sodium silicate and potassium silicate, and crystalline alkali metal silicates. Among them, crystalline alkali metal silicates are more preferable from the viewpoint of cleaning performance and storage stability of the composition.

Further, the crystalline alkali metal silicate used in the present invention has an ion exchange capacity of at least 100 mg CaCO ₃ / g, especially 200 m
Those having gCaCO ₃ / g or more, more preferably 270 mg CaCO ₃ / g or more are preferred.

Among the crystalline alkali metal silicates,
Preferred examples include those having the following compositions.

[0020] xM ₂ O · ySiO in _{2 · zMe m O n · wH} 2 O (IV) ( wherein, M is Group Ia elements of the periodic table, Me represents the periodic table II
a, IIb, IIIa, IVa or one or more elements selected from the group VIII elements, y / x = 0.5 to 2.6,
z / x = 0.01-1.0, n / m = 0.5-2.0, w = 0-20. ) M ′ ₂ O · y′SiO ₂ · wH ₂ O (V) (wherein M ′ represents an alkali metal, y ′ = 1.5 to 4.0, w
= 0 to 20. First, the crystalline alkali metal silicate having the above composition will be described.

In the general formula (IV), M is I in the periodic table.
The element is selected from group a elements, and examples of the group Ia element include Na and K. These can be used alone or, for example, with Na ₂ O
K ₂ O may be mixed to form the M ₂ O component. Me is selected from Group IIa, IIb, IIIa, IVa or VIII elements of the periodic table, and includes, for example, Mg, Ca, Zn, Y, Ti, Zr, Fe and the like. These are not particularly limited, but are preferably Mg and Ca from the viewpoint of resources and safety. Also,
These may be mixed alone or, for example MgO, or the like may be is mixed CaO constitute the Me _m O _n component.

The crystalline alkali metal silicate having the following composition may be a hydrate. In this case, the amount of hydration is in the range of w = 0 to 20. In the general formula (IV), y / x is 0.5 to 2.6, preferably 1.5 to 2.2.
It is. If y / x is less than 0.5, the water resistance is insufficient,
It has a significant adverse effect on caking properties, solubility and powder properties of the detergent composition. If y / x exceeds 2.6, the alkalinity becomes low and the alkalinity is insufficient. z / x is 0.01
1.01.0, preferably 0.020.90.9. z / x is 0.
If it is less than 01, the water resistance is insufficient, and if it exceeds 1.0, the cleaning effect is low. x, y, and z are not particularly limited as long as they have the relationship shown in the above y / x and z / x. As described above, when xM ₂ O is, for example, x′Na ₂ O · x ”K ₂ O, x is x ′ + x”. Such a relationship, zM
The same applies to z in the case where e _m O _n component consist of two or more kinds. Further, n / m = 0.5 to 2.0 indicates the number of oxygen ions coordinated to the element, and is substantially 0.5 or 1.
It is selected from the values 0, 1.5, and 2.0.

The crystalline alkali metal silicate having the composition of M ₂ O, SiO ₂ ,
It has become than the three components of Me _m O _n. Therefore, in order to produce this crystalline alkali metal silicate, each component is required as a raw material, but in the present invention, a known compound is appropriately used without any particular limitation. For example, M ₂
O component, the Me _m O _n component, alone or oxides of the composite of each of the elements, hydroxides, salts, the element-containing minerals is used. Specifically, for example, as a raw material of M ₂ O _{component, NaOH, KOH, Na 2 CO} 3, K 2 CO 3, Na 2 SO 4 and the like, Me _m O
Raw materials for the _n component include CaCO ₃ , MgCO ₃ , Ca (OH) ₂ , Mg
(OH) ₂ , MgO ₂ , ZrO ₂ , dolomite and the like. SiO ₂
As the components, silica stone, kaolin, talc, fused silica, sodium silicate and the like are used.

The method for preparing the crystalline alkali metal silicate of the composition
The above-mentioned raw material components are mixed in a predetermined quantitative ratio so as to obtain the values of x, y, z, and are usually 300 to 1500 ° C, preferably 500 to 1000 ° C.
C., more preferably in the range of 600 to 900.degree. C. for crystallization. In this case, the heating temperature is 300
If the temperature is lower than ℃, the crystallization is insufficient and the water resistance is poor. The heating time is usually 0.1 to 24 hours. Such firing is usually
The heating can be performed in a heating furnace such as an electric furnace or a gas furnace. The particle size of the crystalline alkali metal silicate having the composition of is not particularly limited, but is preferably 0.01 to 100 μm
Is in the range.

Next, the crystalline alkali metal silicate having the above composition will be described. The crystalline alkali metal silicate having this composition is represented by the above general formula (V), wherein M ′ in the general formula (V) represents an alkali metal and N
a and K are preferred. Also, y 'and w are y' = 1.5 to 4.0, w
= 0 to 20, y '= 1.7 to 2.2, w = 0 are preferred, and those having an ion exchange capacity of 100 to 400 mg CaCO ₃ / g can be preferably used.

A method for preparing a crystalline alkali metal silicate having the above composition is described in JP-A-60-227895. Generally, amorphous glassy sodium silicate is prepared at 200 to 1000 ° C. It is obtained by firing to make it crystalline. For details of the synthesis method, see, for example, Phys. Chem. Glas.
ses, 7 , 127-138 (1966), Z. Kristallogr., 129 , 396
-404 (1969). The crystalline alkali metal silicate is available in powder or granule form, for example, under the trade name “Na-SKS-6” (δ-Na ₂ Si ₂ O ₅ ) from Hoechst. In the present invention, the crystalline alkali metal silicate having the composition is not particularly limited with respect to the particle size, similarly to the composition having
It is in the range of 0.01 to 100 μm.

In the present invention, the crystalline alkali metal silicates of the above and the above compositions may be used alone or in combination.
Used in combination of more than one species. (C) used in the present invention
The compounding amount of the alkali metal silicate component is 0.1 to 30% by weight, preferably 1 to 15% by weight, particularly preferably 2 to 10% by weight. (c) If the amount of the component is less than 0.1% by weight,
The damage to the target surface is not reduced, and even if it is added in an amount of more than 30% by weight, the effect does not change and it is economically disadvantageous.

Surfactants can be used in combination with the detergent composition of the present invention. Examples of such surfactants include alkyl glycosides, polyoxyethylene alkyl ethers, and the like.
Nonionic surfactants such as sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, oxyethyleneoxypropylene block polymer (pluronic), fatty acid monoglyceride, and amine oxide; soap, alkyl sulfate, alkylbenzene sulfonic acid Anionic surfactants such as salts, polyoxyethylene alkyl ether sulfates and sulfosuccinic acid diester salts; cationic interfaces such as mono- or dialkylamines and polyoxyethylene adducts thereof, and mono- or di-long-chain alkyl quaternary ammonium salts Activator; examples include amphoteric surfactants such as carbobetaine, sulfobetaine, and hydroxysulfobetaine. Among these, anionic surfactants such as alkyl sulfates, alkylbenzene sulfonates, polyoxyethylene alkyl ether sulfates, and soaps are particularly excellent in terms of detergency. The amount of the surfactant is preferably 0.01 to 30% by weight, more preferably 0.1 to 30% by weight in the composition of the present invention.
-20% by weight, particularly preferably 1-5% by weight.

The effect of the detergent composition of the present invention can be further enhanced by adding a buffer for adjusting the pH. The pH of the stock solution of the composition of the present invention is suitably 5 to 13, preferably 9 to 11. When the pH is less than 5, the reactivity between the component (a) and the component (b) is reduced, so that the production rate of the organic peracid, which is an active ingredient, is reduced.
If H exceeds 13, the stability of the produced organic peracid will decrease.

Examples of the buffer include sodium hydroxide,
Alkali metal hydroxides such as potassium hydroxide, ammonium hydroxide, amine derivatives such as mono-, di-, and triethanolamine; alkali metal carbonates such as sodium carbonate and potassium carbonate; and carbonates such as ammonium carbonate. And 0.01 to 30% by weight of the composition of the present invention.

Further, it is preferable to add a chelating agent to the composition of the present invention. In general, it is known that an oxygen-based bleaching detergent is self-decomposed by a trace amount of metal. When the above chelating agent is added, a decrease in bleaching performance due to a trace amount of metal can be prevented, and storage stability can be improved. Examples of the chelating agent include alkali metal salts such as tripolyphosphoric acid, pyrophosphoric acid, orthophosphoric acid, and hexametaphosphoric acid, ethylenediaminetetraacetic acid, hydroxyiminodiacetic acid, dihydroxyethylglycine, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid,
Triethylenetetramine hexaacetic acid, and alkali metal salts thereof, aminotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepenta-methylenephosphonic acid, aminotrimethylenephosphonic acid N-oxide and alkali metal salts thereof are exemplified. The compounding amount of the above chelating agent is preferably 0.0001 to 10% by weight, more preferably 0.001 to 3% by weight in the composition of the present invention.

If necessary, the composition of the present invention may contain p
-Solubilizing agents such as sodium toluenesulfonate, sodium xylenesulfonate, sodium alkenylsuccinate, urea, enzymes such as proteases, esterases, lipases, cellulases, anti-caking agents, stabilizers for peroxides, penetrants, clays And other optional components such as a suspending agent, an abrasive, a pigment, a dye, and a fragrance.

[0033]

EXAMPLES The cleaning composition of the present invention is constituted as follows (a):
The present invention will be described in more detail with reference to Synthesis Examples of the components, the method for preparing the component (c), and Examples and Comparative Examples of the cleaning composition of the present invention. However, the present invention is not limited by these examples. The percentages in the examples are on a weight basis unless otherwise specified.

Example of synthesis of bleach activator (1) Method of synthesizing bleach activator (i) 100 g (0.46 mol) of sodium p-phenolsulfonate, which had been dehydrated in advance, was treated with dimethylformamide (DMF).
The mixture was dispersed in 300 g, and lauric acid chloride was added dropwise at 50 ° C. over 30 minutes while stirring with a mechanical stirrer. Then, the DMF was removed under reduced pressure.
(0.5-1 mmHg), distilled off at 100 ° C., washed with acetone, recrystallized in water / acetone (= 1/1 mol) solvent,
A bleach activator represented by the following formula (i) was obtained. (2) Method for synthesizing bleach activator (ii) In the synthesis of bleach activator (i), a dehydrate of sodium p-phenolcarboxylate was used in place of sodium p-phenolsulfonate. Except for the above, a bleach activator represented by the following formula (ii) was obtained in the same manner. 65% yield

[0035]

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Method for Preparing a Crystalline Alkali Metal Silicate A method for preparing a crystalline alkali metal silicate is shown with a composition within the scope of the present invention, but the preparation method is not particularly limited thereto. No. 2 sodium silicate (SiO ₂
/ Na ₂ O = 2.5) To 1000 parts by weight, 55.9 parts by weight of sodium hydroxide and 8.5 parts by weight of potassium hydroxide were added, and the mixture was stirred with a homomixer to dissolve sodium hydroxide and potassium hydroxide. Here, finely dispersed anhydrous calcium carbonate 5.
23 parts by weight and 0.13 parts by weight of magnesium nitrate hexahydrate were added and mixed using a homomixer. An appropriate amount of the mixture was placed in a nickel crucible, fired in air at 700 ° C. for 1 hour, quenched, and then the fired body was pulverized to obtain a crystalline alkali metal silicate A of the present invention. In the same manner, crystalline alkali metal silicates B, C, and D having the compositions shown in Table 1 were obtained.

The ion exchange capacity of the obtained crystalline alkali metal silicate was measured by the following method. Table 1 shows the results.
Shown in <Measurement method of ion exchange capacity> 0.1 g of a sample was precisely weighed, added to 50 ml of a calcium chloride solution (concentration: 1% as CaCO ₃ ), stirred at 25 ° C. for 60 minutes, and then filtered with 5 kinds of No. C filter paper. And filtration. Take 10 ml of the filtrate and determine the amount of Ca in the filtrate as E
It was measured by DTA titration, and the calcium ion exchange capacity of the sample was determined from the value.

[0038]

[Table 1]

Note) The crystalline alkali metal silicates A to C have a composition represented by the general formula (IV), and the crystalline alkali metal silicate D has a composition represented by the general formula (V). is there.

Examples 1 to 7, Comparative Examples 1 to 5 A powdery denture cleaning composition having the composition shown in Tables 2 and 3 was prepared, and the detergency was evaluated by the following detergency test. The corrosion test on the clasp was evaluated by a corrosion test. The results are shown in Tables 2 and 3.

<Detergency Test> (1) Soil Test Piece A denture resin with tea and coffee stains was used as a test piece. (2) Cleaning and evaluation method 1 liter of a cleaning solution obtained by dissolving 0.4 g of a powdery detergent having the composition shown in Tables 2 and 3 in 1 liter of tap water at 20 ° C. is placed in a beaker, and the test piece is immersed for 15 minutes. After immersion,
After rinsing well with water, the degree of removal of dirt was visually evaluated according to the following criteria.

Evaluation 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 a powdery detergent having the composition shown in Tables 2 and 3 was dissolved in 1 liter of tap water at 20 ° C. to prepare a sample solution, and 50 ml of this sample solution and 5 cm × 2 cm were used.
Was placed in a 100 ml glass bottle with a lid, and the lid was capped and left at 40 ° C. for 2 days, and the corrosion state of the clasp was visually observed according to the following criteria.

Evaluation criteria ○ No corrosion observed × Corrosion occurred

[0044]

[Table 2]

[0045]

[Table 3]

Note) * 1 AS: alkyl (C ₁₂ -C ₁₄ ) sodium sulfate (manufactured by Kao Corporation)

Continuation of the front page (51) Int.Cl. ⁷ identification code FI C11D 7/54 C11D 7/54 (56) References JP-A-6-316700 (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. .7, DB name) A61K ^7/ 00-7/50 C11D 1/00-19/00 CA (STN) REGISTRY (STN)

Claims (5)

(57) [Claims] (1) A bleach activator represented by the following general formula (I), which reacts with hydrogen peroxide in water to generate an organic peracid: 0.1 to 30% by weight Wherein R represents a straight-chain alkyl group having 6 to 13 carbon atoms, and L represents
The following formula (II) Represents a leaving group represented by ] (B) 30 to 98% by weight of sodium percarbonate; (c) 0.1 to 10 % by weight of an alkali metal silicate. 2. The composition according to claim 1, wherein the component (c) is a crystalline alkali metal silicate having an ion exchange capacity of at least 100 mg CaCO ₃ / g or a hydrate thereof. Denture cleaning composition. 3. The denture cleaning composition according to claim 1, wherein the component (c) is a crystalline alkali metal silicate having a composition represented by the following general formula (IV). xM ₂ O · ySiO in _{2 · zMe m O n · wH} 2 O (IV) ( wherein, M is Group Ia elements of the periodic table, Me represents the periodic table II
a, IIb, IIIa, IVa or one or more elements selected from the group VIII elements, y / x = 0.5 to 2.6,
z / x = 0.01-1.0, n / m = 0.5-2.0, w = 0-20. ) 4. The denture cleaning composition according to claim 1, wherein the component (c) is a crystalline alkali metal silicate having a composition represented by the following general formula (V). M ′ ₂ O · y′SiO ₂ · wH ₂ O (V) (wherein M ′ represents an alkali metal, y ′ = 1.5 to 4.0, w
= 0 to 20. ) 5. The bleaching activator of the component (a) is represented by the following formula (VI):
A compound represented by the formula:
The denture cleaning composition according to any one of the above. Embedded image