JP3342640B2 - Bleach composition for hard surfaces - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a kitchen surrounding, a bathroom,
The present invention relates to a bleaching agent composition for hard surfaces suitable for removing various types of stains such as drain pipes, bathtubs, washing tubs, and the like.

[0002]

2. Description of the Related Art In many cases, fats and oils derived from foods are deteriorated by the action of heat, sunlight, oxygen in the air, etc., and are sticky resinous or semi-dry. It is in a state where it has been done. For such altered oil stains, alkaline strong cleaning agents as shown in JP-B-53-1168, that is, alkaline agents such as ammonia, monoethanolamine, sodium hydroxide, etc.
A detergent composition comprising a water-soluble solvent such as cellosolve and carbitol, and a surfactant is disclosed. In addition, Japanese Patent Publication Nos. 3-1360 and 5-1758 disclose a foaming detergent composition containing sodium percarbonate as a main component. However, the above-mentioned cleaning agent does not provide sufficient cleaning effect for a complicated portion such as a filter of a range hood or a ventilation fan.

[0003] In recent years, there has been studied a cleaning agent which has a high cleaning effect on a complicated portion such as a filter or a ventilation fan of a range hood and has reduced damage to a target surface. For example, the present applicant has found a bleaching agent composition for hard surfaces using a hydrogen peroxide releasing material, a bleaching activator represented by the following general formula (VII), and a crystalline alkali metal silicate, and applied for a patent. (See Japanese Patent Application No. 8-67820).

[0004]

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Wherein R is a straight-chain alkyl group having 6 to 13 carbon atoms, and L is a group represented by the following general formula (VIII) or (IX):

[0006]

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The leaving group represented by However, the bleaching agent composition has a problem that the dissolution rate is reduced under conditions where the water temperature is low, such as in winter, and thus it is not possible to exert sufficient detergency.

Accordingly, an object of the present invention is to provide a high detergency regardless of the type and degree of dirt such as dirt in a kitchen, a bathroom, a drain pipe, a bathtub, and a washing tub. An object of the present invention is to provide a bleaching agent composition for hard surfaces that reduces damage to a surface, has excellent solubility even under conditions where the water temperature in winter is low, and can maintain sufficient detergency.

[0009]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, completed the present invention. That is, the present invention provides (a) a crystalline alkali metal silicate having at least 100 mgC
A substance having an ion exchange capacity of aCO ₃ / g or more or a hydrate thereof 0.1 to 30% by weight (b) a compound represented by the following general formula (I) or (II) which reacts with hydrogen peroxide in water to generate an organic peracid Expressed bleach activator
0.1-30% by weight

[0010]

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(Wherein, R represents a straight-chain alkyl group having 6 to 13 carbon atoms.) (C) Bleach composition for hard surface containing 30 to 98% by weight of a hydrogen peroxide releasing substance It provides things.

[0012]

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

[0013] Crystalline alkali metal silicate component (a) of the present invention is at least 100mgCaCO ₃ / g or more, preferably 200mgCaCO ₃ / g or more, particularly preferably 270mgCaCO ₃ / g
It is necessary to have the above-mentioned ion exchange capacity, and when the ion exchange capacity is less than 100 mgCaCO ₃ / g, the cleaning property is poor. Of the crystalline alkali metal silicates of the component (a), preferred are those having the following compositions.

[0014] _{xM 2 O · ySiO 2 · zMe} m O n · wH 2 O (III) ( 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 (IV) (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 (III), 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 (III), 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 bleach composition for hard surfaces. When y / x exceeds 2.6,
The alkalinity becomes low and it is insufficient as an alkaline agent.
z / x is from 0.01 to 1.0, preferably from 0.02 to 0.9. When z / x is less than 0.01, the water resistance is insufficient and 1.0
If it exceeds, the cleaning effect is reduced. x, y, z are the above y / x
The relationship is not particularly limited as long as the relationship is as shown in FIGS. As described above, xM ₂ O is, for example, x'Na
_{When 2} O · x "K ₂ O, x is x '+ x". This relationship is the same in the z in the case of ZME _m O _n component composed of two or more. Also, n / m = 0.5 to 2.
0 indicates the number of oxygen ions coordinated to the element, and is substantially selected from values of 0.5, 1.0, 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 having the composition of
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 of this composition is represented by the general formula (IV), where M ′ in the general formula (IV) represents an alkali metal, Na, K
Is preferred. Also, y 'and w are y' = 1.5 to 4.0, w = 0 to
Is a 20, y '= 1.7~2.2, preferably has a w = 0, the ion exchange capacity 100~400mgCaCO ₃ / g of what can be preferably used.

The preparation method of the crystalline alkali metal silicate having the above composition is described in Japanese Patent Application Laid-Open No. 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 , 396-4
04 (1969). The crystalline alkali metal silicate is available from Hoechst under the trade name “Na
Powders and granules can be obtained as “-SKS-6” (δ-Na ₂ Si ₂ O ₅ ). 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 of
It is in the range of 100100 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. (A) used in the present invention
The compounding amount of the crystalline alkali metal silicate is 0.1 to 30.
% By weight, preferably 1 to 15% by weight, particularly preferably 2 to
10% by weight. If the amount of the component (a) is less than 0.1% by weight, the damage to the target surface is not reduced, and if the amount is more than 30% by weight, the effect does not change and it is economically disadvantageous.

The component (b), which is an essential component of the present invention, is a bleach activator represented by the general formula (I) or (II), which reacts with hydrogen peroxide in water to generate an organic peracid. .
In the general formulas (I) and (II), the alkyl group represented by R is straight-chain and has 6 to 13 carbon atoms. 5 carbon atoms
Below, those having 14 or more carbon atoms cannot obtain a favorable detergency. Particularly preferred among these bleach activators are compounds represented by the following formula (V) or (VI).

[0023]

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The amount of the bleaching activator (b) 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. (b) If the amount of the component is less than 0.1% by weight, the cleaning effect is not recognized,
If the content exceeds 30% by weight, no further effect is obtained, and it tends to be economically disadvantageous.

The bleach activator of the component (b) reacts with hydrogen peroxide in water to generate an organic peracid, and the hydrogen peroxide releasing component of the component (c) is a particulate or powdery percarbonate. Salts, perborates, perphosphates, persilicates and the like are mentioned, and percarbonates, especially sodium percarbonate, are effective. The compounding amount of the hydrogen peroxide-releasing substance in the composition of the present invention is 30 to 98% by weight, preferably 50 to 90% by weight. If the amount is less than 30% by weight, sufficient bleaching performance cannot be obtained, and if the amount is more than 98% by weight, the bleaching performance is not significantly improved.

A surfactant may be used in combination with the bleaching composition of the present invention. Examples of the surfactant 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 bleaching 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,
Hydroxides of alkali metals such as potassium hydroxide, ammonium hydroxide, or amine derivatives such as mono, di, and triethanolamine; carbonates of alkali metals such as sodium carbonate and potassium carbonate; carbonates such as ammonium carbonate;
Non-crystalline alkali metal silicates such as sodium silicate and potassium silicate, and silicates such as ammonium silicate may be incorporated in the composition of the present invention in an amount of 0.01 to 30% by weight.

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 agent is self-decomposed by a trace amount of metal. When the above chelating agent is blended, the bleaching performance due to a trace amount of metal can be prevented and the 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, and triethylenetriaminepentaacetic acid. Ethylenetetramine hexaacetic acid and the alkali metal salts thereof, aminotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepenta-methylenephosphonic acid, N of aminotrimethylenephosphonic acid -Oxides and alkali metal salts thereof. The compounding amount of the above chelating agent is preferably 0.0001 to 10% by weight in the composition of the present invention, more preferably
0.001 to 3% by weight.

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.

[0031]

EXAMPLES The bleaching composition of the present invention is constituted as follows (a)
The present invention will be described in more detail with reference to a method for preparing the components, a synthesis example of the component (b), and Examples and Comparative Examples of the bleach 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.

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 at 700 ° C. in air for 1 hour, quenched, and then the fired body was pulverized to obtain a crystalline alkali metal silicate A of the present invention. Similarly, a crystalline alkali metal silicate B having the composition shown in Table 1 was prepared.
C and D were obtained.

The ion exchange capacity of the obtained crystalline alkali metal silicate was measured by the following method. Table 1 also shows the results. <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.

[0034]

[Table 1]

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

Example of synthesis of bleach activator (1) Method of synthesizing bleach activator (i) 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. Heated. 1.2 mol of lauric chloride was added dropwise from the dropping funnel over about 2 hours, and the mixture was aged for about 2 hours while removing HCl generated by blowing in N ₂ . The reaction product was distilled to obtain phenyl laurate.
96% yield, 97% purity.

0.8 mol of lauric acid phenyl ester synthesized by the above method was placed in dichloromethane in a four-necked flask.
After dissolving in 600 g, the mixture was cooled to -10 ° C. afterwards,
0.84 mol of liquid SO _{3 was} added dropwise 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 by an evaporator to obtain a target product represented by the following formula (i). 75% yield.

(2) Method for synthesizing bleach activator (ii) 1 mol of p-hydroxybenzoic acid which has been dehydrated in advance
Was dispersed in 300 g of a toluene solution, and 1 mol of decanoic acid chloride was added at 50 ° C and 30 ° C while stirring with a mechanical stirrer.
After dropping over a period of minutes, the mixture was reacted for 3 hours. Thereafter, the solvent was distilled off at 100 ° C. under reduced pressure (0.5 to 1 mmHg), washed with hexane, and recrystallized in a toluene solvent to obtain a bleaching activator represented by the following formula (ii). . 85% yield.

(3) Method of synthesizing bleach activator (iii) In the synthesis of bleach activator (i), except that nonyl acid chloride was used as the alkyl source instead of lauric chloride, the following formula was used. A bleach activator represented by (iii) was obtained. 92% yield

[0040]

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Examples 1 to 5 and Comparative Examples 1 to 3 A bleach composition for hard surfaces having the composition shown in Table 2 was prepared, and 1 g of this composition was subjected to a solubility test at 20 ° C. and 5 ° C. It carried out by the following method. Table 2 shows the results.

<Solubility test> A bleach composition for hard surfaces having the composition shown in Table 2 was prepared.
Alternatively, the mixture was mixed with 100 ml of water adjusted to 5 ° C., and gently stirred with a mechanical stirrer. After a certain period of time, the aqueous solution was filtered, and the presence or absence of insolubles was evaluated according to the following criteria.

Evaluation criteria ◎: Completely dissolved ○: Slightly insoluble matter is observed △: Clearly insoluble matter is observed X: A large amount of insoluble matter is observed

[0044]

[Table 2]

Note) * 1 Bleaching activator (iv): a compound represented by the following formula (iv).

[0046]

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* 2 AS: alkyl (C ₁₂ -C ₁₄ ) sodium sulfate (manufactured by Kao Corporation) * 3 Diquest 2015DN; 1-hydroxyethylidene-1,
1-diphosphonic acid trisodium salt (manufactured by Monsanto) Examples 6 to 13 and Comparative Examples 4 to 10 Bleach compositions for hard surfaces having the compositions shown in Table 3 were prepared, and were prepared at 20 ° C or 5 ° C by the following method. Detergency tests and corrosion tests on aluminum were performed. Table 3 shows the results.

<Detergency test> 1 part by weight of the bleach composition was added to 20 parts by weight.
To 100 parts by weight of tap water adjusted to 5 ° C. or 5 ° C., a dirty range filter was immersed without stirring. After leaving it for a certain period of time (1 hour) and performing immersion cleaning, the stain on the target surface after cleaning was visually determined based on the following criteria.

Evaluation Criteria 4: No stain left 3: Slight stain left 2: Stain remains mottled 1: Stain remains all over <Corrosion test for aluminum> Bleach composition Dissolve 1 part by weight of the sample in 100 parts by weight of tap water adjusted to 20 ° C or 5 ° C, place in a 100 ml glass bottle with a lid, hang from the top of the aluminum test panel so that the panel is in half contact with the liquid, and close the lid. At 50 ° C. for 2 days, the state of corrosion was visually observed, and evaluated according to the following criteria. Evaluation Criteria ○ No corrosion observed △ Cloudy over entire surface × Corrosion over entire surface

[0050]

[Table 3]

Note) * 1 to * 3 are the same as in Table 2.

────────────────────────────────────────────────── (5) References JP-A-8-337796 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C11D 7/14 C11D 7/26 C11D 7 / 34 C11D 7/54 C11D 7/60

Claims (6)

(57) [Claims] (A) a crystalline alkali metal silicate having an ion exchange capacity of at least 100 mg CaCO ₃ / g or a hydrate thereof 0.1 to 30% by weight (b) reacting with hydrogen peroxide in water Bleach activator represented by the following general formula (I) or (II), which generates organic peracid
0.1-30% by weight (Wherein, R represents a straight-chain alkyl group having 6 to 13 carbon atoms.) (C) A bleaching agent composition for hard surfaces, containing 30 to 98% by weight of a hydrogen peroxide releasing substance. 2. The bleaching agent composition for hard surfaces according to claim 1, wherein the crystalline alkali metal silicate of the component (a) has a composition represented by the following general formula (III). _{xM 2 O · ySiO 2 · zMe} m O n · wH 2 O (III) ( 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. ) 3. The bleaching agent composition for hard surfaces according to claim 1, wherein the crystalline alkali metal silicate of the component (a) has a composition represented by the following general formula (IV). M ′ ₂ O ・ y′SiO ₂・ wH ₂ O (IV) (wherein M ′ represents an alkali metal, y ′ = 1.5 to 4.0, w
= 0 to 20. ) 4. The bleaching agent composition for hard surfaces according to claim 1, wherein the hydrogen peroxide-releasing substance of the component (c) is sodium percarbonate. 5. The bleaching composition for hard surfaces according to claim 1, further comprising 0.1 to 20% by weight of an anionic surfactant. 6. The method according to claim 1, wherein the bleach activator of the component (b) is a compound represented by the following formula (V) or (VI). Bleach composition for hard surfaces. Embedded image