JPH10251699A - Detergent composition for outer wall of building - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the titled composition which has excellent detergency, shows little self-separation after drying, and is suitable for a recovery process, by employing, as an essential component, an emulsion which is prepared by subjecting to emulsion polymerization an unsaturated monomer mixture comprising an unsaturated monomer (a salt) having a carboxyl group and which has a specific film-forming temperature. SOLUTION: 0.1 to 20wt.% unsaturated monomer (a salt) having a carboxyl group such as (meth)acrylic acid, crotonic acid, maleic acid or a salt thereof, and 80 to 99.9% unsaturated monomer such as ethylene or methyl methacrylate, and 0.1 to 5wt.% cross-linking agent having a plurality of functional groups are subjected to emulsion polymerization in an aqueous medium containing an anionic and a nonionic emulsifiers in an amount of 0.5 to 15wt.% in the presence of a polymerization initiator, to thereby produce a detergent composition for an outer wall of a building comprising a micropolymer emulsion which has a viscosity (Brookfield viscometer) at a solids content of 40wt.% of 50 to 200 c.p., a mean particle diameter of 30 to 200nm, and a lowest film-forming temperature of 20 to 130 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a cleaning composition for building exterior walls.

[0002]

2. Description of the Related Art Conventionally, a dry cleaning method cannot provide a strong mechanical force to an object to be cleaned (JP-A-54-13).
No. 5502, JP-A-55-1557698, JP-A-55-157798
This is an excellent cleaning method that can be used in situations where drainage and scattering during cleaning are problematic. Therefore, it is a preferable cleaning method as a method for cleaning the outer wall of a building. However, in the case of dry cleaning, the resin film containing dirt does not self-peel, but it must be easily peeled at the time of recovery.There is no cleaning agent satisfying the conflicting performance, so it has not been widely used. Was. For example, JP-B-57-58999 and JP-A-59-58999.
189200 and JP-A-64-40600 disclose that the resin layer containing dirt is melted by the frictional heat generated during the peeling step, and contaminates the object to be cleaned. Will be. Further, in the composition specified in JP-A-6-225848, it is predicted that when it comes into contact with water after drying, it will be redissolved, and it will be difficult to peel it off, which limits the use conditions. Furthermore,
JP-A-61-179268, JP-T-61-50213
The composition described in Japanese Patent Publication No. 0 has a problem that self-peeling property after drying is high, the film peels off before the recovery step, and the recovery efficiency is reduced.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a cleaning composition for building exterior walls which is excellent in cleanability, has very little self-peeling after drying, and is suitable for a recovery step.

[0004]

In order to solve the above-mentioned problems, a cleaning composition for building exterior walls according to the present invention comprises a carboxyl group-containing unsaturated monomer and a salt thereof. The unsaturated monomer mixture containing the above is obtained by emulsion polymerization, and the lowest film formation temperature (MFT) is 20 to 13
It is characterized by containing a micropolymer emulsion at 0 ° C. as an essential component.

[0005] The cleaning composition for building exterior walls of the present invention has a micropolymer emulsion having an average particle diameter of 30 to 30.
The thickness is preferably 200 nm, and the micropolymer emulsion is preferably a crosslinked micropolymer emulsion.

In the present invention, by preparing the above-mentioned cleaning composition for building exterior walls and performing dry cleaning, it is possible to achieve a high cleaning power and a remarkable improvement in working performance in the peeling / recovering step. The reason why the dry cleaning composition exerts such an effect is that the micropolymer emulsion, which is an essential component, forms a finely packed structure when forming a film. In the densely packed structure formed by the micropolymer emulsion, there are many capillary voids containing dirt, and the capillary pressure is increased, so that the dirt from the object to be cleaned is improved, and the cleanability is remarkably improved. Further, in order to enhance the releasability as in the case of the micropolymer emulsion, a polymer emulsion having a minimum film formation temperature (MFT) set to room temperature or higher generally self-peels after dry film formation. However, the micropolymer emulsion, which has a finely packed structure after dry film formation, does not break down due to a fastener effect unless a certain amount of mechanical force is applied, so that self-peeling does not occur.
For this reason, the efficiency of the peeling / collecting step following the drying step is significantly improved.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the cleaning composition for building exterior walls of the present invention will be described in detail.

First, in the present invention, a polymer forming a micropolymer emulsion will be described. The unsaturated monomer used for preparing the micropolymer emulsion particles includes at least one selected from the group consisting of a carboxyl group-containing unsaturated monomer and a salt thereof. As an unsaturated monomer having a carboxyl group and a salt thereof,
Acrylic acid, methacrylic acid, crotonic acid, maleic acid,
Fumaric acid, itaconic acid and their alkali metal salts, alkaline earth metal salts, ammonium salts, amine salts, substituted amine salts, etc., and the carboxyl groups in these unsaturated monomers may be salts. Good. In the case of maleic acid, fumaric acid or itaconic acid, monoester or monoamide may be used. Among these, it is particularly preferable to use acrylic acid and methacrylic acid, which have good copolymerizability.

[0009] The content of one or more monomers selected from the group consisting of unsaturated monomers having a carboxyl group and salts thereof is 0.1% in the unsaturated monomer mixture constituting the micropolymer emulsion. It is preferred that the copolymerization be carried out in an amount of 1 to 20% by weight, more preferably 0.5 to 10% by weight.
It is desirable to copolymerize in the range of weight%. If the content is less than 0.1% by weight, it is difficult to form a densely packed structure, and the cleaning property is reduced, the peeling resistance of the film is reduced, and the film is self-peeled. If the content exceeds 20% by weight, the drying efficiency is deteriorated and the water resistance of the obtained film is deteriorated.

The other unsaturated monomer used in the present invention is not particularly limited as long as it is an unsaturated monomer capable of obtaining a micropolymer emulsion. For example, dienes such as ethylene, propylene, butadiene and butylene can be used. ,
Acrylic esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, vinyl esters such as vinyl acetate and vinyl propionate, nitriles such as acrylonitrile and α-methylacrylonitrile, and styrene It is preferable to copolymerize styrenes such as styrene and α-methylstyrene, and vinyl ethers such as vinyl methyl ether and vinyl ethyl ether singly or in combination of two or more.

The other unsaturated monomer is suitably copolymerized in an amount of 80 to 99.9% by weight, preferably 90 to 99.5% by weight in the unsaturated monomer mixture constituting the micropolymer emulsion. is there.

In order to carry out the present invention more effectively,
The minimum film formation temperature (MFT) of the polymer emulsion obtained by copolymerizing the unsaturated monomer is preferably from 20 to 130 ° C, particularly preferably from 50 to 100 ° C. The reason why the value of the minimum film forming temperature (MFT) is limited as described above is that if the temperature is lower than 20 ° C., heat fusion is promoted by heating during drying, and a uniform film is formed. Or the frictional heat generated may cause the resin film to be melted, thereby contaminating the object to be cleaned. On the other hand, when the temperature is higher than 130 ° C., the film forming property is significantly reduced,
This is because the rate of self-peeling from the surface of the object to be cleaned increases, and the recovery efficiency deteriorates.

Further, in order to improve the performance derived from the resin film such as water resistance and chemical resistance, it is preferable to copolymerize a crosslinking agent having a plurality of functional groups in one molecule. Examples of these crosslinking agents include trimethylolpropane trimethacrylate, glycidyl acrylate, glycidyl methacrylate, bisphenol A polyoxyethylene adduct di (meth) acrylate, triallyl isocyanurate, N-methylol (meth) acrylamide, divinylbenzene and the like. Of these, divinylbenzene is preferred. The compounding ratio of the crosslinking agent is preferably in the range of 0.1 to 5% by weight, particularly preferably in the range of 0.5 to 1% by weight, in the unsaturated monomer mixture constituting the micropolymer emulsion. Good to use.

As the emulsifier for emulsion polymerization used for preparing the micropolymer emulsion used in the present invention, the following anionic emulsifier and nonionic emulsifier are used.

[Representative Examples of Anionic Emulsifier] (1) Polyoxyalkylene alkylaryl ether sulfonate sulfate salt represented by the following formula (Formula 1)

[0016]

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(2) Polyoxyalkylene alkyl ether sulfate salt represented by the following formula (Formula 2)

[0018]

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(3) Polyoxyalkylene alkyl aryl ether sulfate represented by the following formula (Formula 3)

[0020]

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(4) Compound represented by the following formula (Formula 4)

[0022]

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(5) Compound represented by the following formula (Formula 5)

[0024]

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(6) Compound represented by the following formula (Formula 6)

[0026]

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(7) Compound represented by the following formula (Formula 7)

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(8) Compound represented by the following formula (Formula 8)

[0029]

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(9) Compound represented by the following formula (Formula 9)

[0031]

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[Representative Examples of Nonionic Emulsifier] (10) Polyoxyalkylene alkyl aryl ether represented by the following formula (Formula 10)

[0033]

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(11) Polyoxyalkylene alkyl ether represented by the following formula (Formula 11)

[0035]

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These anionic emulsifiers and nonionic emulsifiers can be used alone or in combination of two or more. Preferably, one or more anionic emulsifiers having an oxyethylene group and / or an oxypropylene group in the molecule are used. These emulsifiers are used in an amount of 0.5 to 15% by weight, preferably 0.5 to 10% by weight, more preferably 0.5 to 5% by weight, based on the unsaturated monomer mixture constituting the micropolymer emulsion. % Is preferably used. If it is less than 0.5% by weight, a micropolymer emulsion having a desired particle size cannot be obtained, which is not preferable. On the other hand, when the content exceeds 15% by weight, the water resistance of the film from which the micropolymer emulsion is obtained is reduced and the emulsion is re-emulsified, or the minimum film forming temperature of the micropolymer emulsion is reduced due to the plasticizing effect of the emulsifier,
Not preferred.

Examples of the polymerization initiator include hydrogen peroxide alone, a combination of hydrogen peroxide and a carboxylic acid such as tartaric acid, citric acid, and ascorbic acid, or a mixture of hydrogen peroxide and oxalic acid, sulfinic acid, and salts thereof. Combinations with oxyaldehydes, water-soluble iron salts, etc., and further peroxides such as persulfates, percarbonates, perborates, or 2,2′-azobis (2-aminodipropane) and salts thereof; 2,2'-azobis (N, N'-dimethylene-isobutylamidine) and its salt, 4,4'-azobis (4-
Water-soluble azo initiators such as (cyanovaleric acid) and salts thereof can be used. For preparing the micropolymer emulsion used in the present invention, among these, a persulfate initiator is preferred. As the mixing ratio of the polymerization initiator, it is preferable to use 0.1 to 3% by weight based on the unsaturated monomer mixture constituting the micropolymer emulsion.

The micropolymer emulsion used in the present invention uses the above unsaturated monomer, emulsifier and polymerization initiator,
It can be prepared by the following general emulsion polymerization.
That is, a monomer dropping method in which an emulsifier is dissolved in an aqueous phase, a part of the unsaturated monomer mixture is emulsified and solubilized, a polymerization initiator is added, and then the remaining unsaturated monomer is dropped as it is. Alternatively, an emulsifier, a part of water and an unsaturated monomer mixture may be previously mixed and emulsified, and the emulsion polymerization may be performed by a pre-emulsion method in which the emulsion is added dropwise. Alternatively, in order to reduce the amount of the polymer adhering to the stirring blade or the like, it is more preferable to use the pre-emulsification method.

The micropolymer emulsion used in the present invention has a viscosity of 50 to 200 cP at a solid content of 40% by weight.
(Brookfield viscometer) with good workability. In addition, those having a low viscosity can contain 50% by weight or more of a solid content. Emulsion concentration is 2
It is 0 to 50% by weight, preferably 35 to 40% by weight.

The average particle size of the micropolymer emulsion used in the present invention is desirably 30 to 200 nm, preferably 30 to 150 nm, and more preferably 30 to 100 nm. 200n average particle size
If it is larger than m, the fine packing property of the polymer particles decreases,
It is not preferable because it has an adverse effect on washability and preservation after film formation. On the other hand, if the average particle diameter is smaller than 30 nm, the viscosity of the obtained micropolymer emulsion is significantly increased, which causes disadvantages in handling during production and use.

When the micropolymer emulsion of the present invention is used as a cleaning agent for building exterior walls, if a contaminant can be identified, a surfactant, an acid, or an alkali may be mixed and used as needed to further improve the effect. Cleaning becomes possible. These additives are preferably used in the range of 0.1 to 10% by weight based on the micropolymer emulsion. If the amount is less than 0.1% by weight, the effect of the additive may not be sufficiently exhibited. If the amount is more than 10% by weight, problems such as lowering of the minimum film-forming temperature due to the plasticizing effect of the surfactant and inhibition of the stability of the micropolymer emulsion by acids and alkalis occur. It will be easier.

If the environment in which the micropolymer emulsion of the present invention is used as a cleaning agent for dry cleaning is in a cold region, or when a strong wind is constantly blowing, the predetermined performance cannot be obtained. In such a case, the performance can be prevented from deteriorating by adding a necessary amount of a plasticizer or a film-forming auxiliary, if necessary, but the minimum film-forming temperature is 0 ° C. or less, and the average particle diameter is reduced. Most preferably, a 30-200 nm micropolymer emulsion is added within 30% by weight.

The cleaning composition of the present invention is used for cleaning the exterior walls of buildings. When used as a cleaning agent for dry cleaning, the surface to be cleaned is tile, extruded panel, inorganic / organic board. It is preferable that the surface is smooth as in the above. This is because, when there are fine irregularities, or when the ALC wall or the like has a large water absorption, the cleaning agent component penetrates deep into the surface to be cleaned, making it difficult to peel and recover.

[0044]

The present invention will be described more specifically below with reference to examples and comparative examples. The “parts” and “%” shown below are all based on weight.

Examples 1 to 8 and Comparative Examples 1 to 3 Polymer emulsions Nos. Nos. 1 to 7 were prepared and their properties were confirmed. Further, a detergent composition was prepared by the following method, and its performance was evaluated. Table 4 shows the results.

[Preparation of polymer emulsion] (1) Polymer emulsion no. Emulsifier composition No. 1 shown in Table 1 was placed in a glass reactor equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a dropping funnel. 0.3 part of 1 emulsifier and 45.7 parts of water are charged and dissolved, and the system is replaced with nitrogen gas. The polymer emulsion Nos. No. 1 and 40.0 parts of the emulsifier composition No. 1 shown in Table 1. One emulsifier (0.07 part) and water (11.6 parts) are emulsified and mixed, and 2.53 part of the mixture is added to a reaction vessel and the temperature is raised to 75 ° C. After the temperature was raised, 0.16 part of sodium persulfate was dissolved in 0.5 part of water, added to the reaction vessel, and immediately the remaining unsaturated monomer emulsion was continuously dropped in the reaction vessel over 120 minutes. The polymerization is carried out at 75 ° C. After completion of the dropwise addition, the mixture is further aged at 90 ° C. for 60 minutes to complete the polymerization. After cooling to room temperature, the solid content was adjusted to 40% and the polymer emulsion N
o. It was set to 1.

(2) Polymer emulsion No. 2 to 7 Using the emulsifiers shown in Table 1 and the unsaturated monomers shown in Table 2, the above polymer emulsion Nos. 1 according to the preparation of polymer emulsion No. 1 2 to 7 were prepared.
Here, the amount of the emulsifier required for emulsifying the unsaturated monomer is shown in Table 2, and the values in parentheses are the amounts charged in advance with water.

[0048]

[Table 1]

[0049]

[Table 2]

[Confirmation of Properties of Polymer Emulsion] The average particle size of the obtained polymer emulsion was measured by a light scattering photometer (ELS-800, manufactured by Otsuka Electronics Co., Ltd.). The minimum film formation temperature was measured using a minimum film formation temperature tester (Yoshimitsu Scientific Instruments Co., Ltd. manufactured film temperature test apparatus II) by a temperature gradient plate method.

[Preparation of Cleaning Agent for Dry Cleaning] Example 1,
As for the cleaning agent for dry cleaning used in 2, 5, 6, 7, 8 and Comparative Example 1, the prepared polymer emulsion was used as it was. For Examples 3 and 4, polymer emulsion No. A surfactant obtained by adding a surfactant and an alkali agent to Table 2 in the amounts shown in Table 3 was used as a dry cleaning detergent. Furthermore, in Comparative Example 2, a commercially available aqueous styrene maleate resin solution was used, and in Comparative Example 3, a commercially available wet cleaning agent (Sunwash FM-10, manufactured by Lion Corporation) was used for comparison.

[Evaluation of performance of cleaning agent for dry cleaning] (1) Specimen to be cleaned A tile wall (1 × 3 m) left outdoors for one year or more was used as it was.

(2) Cleaning method Each dry cleaning agent was uniformly sprayed on the content plate at room temperature by a sprayer. -After applying the cleaning agent, it was dried at room temperature.・ After the detergent was dried, the tile surface was cleaned using a vacuum cleaner.

(3) Evaluation method of cleaning effect Detergency A color difference was measured using a Hunter color system before and after cleaning using a color computer, and the color difference amount was used as an index of detergency as shown in Table 3 below.

[0055]

[Table 3]

Recovery rate The resin solid content determined from the applied amount of the dry cleaning agent was (a) g,
From the amount of resin (b) g recovered by the vacuum cleaner, a provisional recovery rate was determined by the following equation.

[0057]

(Equation 1)

[0058]

[Table 4]

[Evaluation Results] As is clear from Table 4, the products of the present invention (Examples 1 to 8) show cleaning performance equal to or higher than that of the conventional wet cleaning agent (Comparative Example 3). In addition, it was clear that the cleaning performance was inferior when the conventional product (Comparative Example 2) and a polymer emulsion different from the present invention were used (Comparative Example 1). Therefore, it was confirmed that the cleaning agent for dry cleaning of the present invention exerts excellent cleaning performance when applied to a cleaning agent for building exterior walls. Further, using the cleaning agent for dry cleaning prepared in Example 4,
The building whose outer wall was contaminated by the fire was cleaned. As a result, the detergency exhibited a performance equal to or higher than that of the wet cleaning agent. It was confirmed that there was no generation of cleaning wastewater and the environmental load was extremely small, and it was clarified that the cleaning agent was optimal as a dry cleaning agent.

[0060]

The cleaning composition for building exterior walls of the present invention is used as a cleaning agent for dry cleaning in a cleaning machine provided with spraying, drying, peeling and collecting operations. Until now, a cleaning power comparable to the wet cleaning method using an activator or the like is obtained. Furthermore, since the cleaning composition for building exterior walls of the present invention does not discharge any cleaning wastewater, the environmental load is extremely small.

Claims (3)

[Claims] 1. A film formation temperature (MFT) obtained by emulsion polymerization of an unsaturated monomer mixture containing at least one selected from the group consisting of a carboxyl group-containing unsaturated monomer and a salt thereof. A cleaning composition for building exterior walls, comprising as an essential component a micropolymer emulsion having a temperature of 20 to 130 ° C. 2. The cleaning composition for building exterior walls according to claim 1, wherein the average particle size of the micropolymer emulsion is 30 to 200 nm. 3. The cleaning composition for building exterior walls according to claim 1, wherein the micropolymer emulsion is a crosslinked micropolymer emulsion.