JP2003160763A - Floor-polishing composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a floor-polishing composition without danger of generating pollutant problems originated from phosphine and excellent in levelling and transparency. <P>SOLUTION: The floor-polishing composition is composed of a mixture of (A) an α,β-unsaturated carboxylic acid-based polymer and/or a urethane-based polymer and (B) one or two or more of ester alcohols such as 2,2,4- trimethylpentane diol-1,3-monoisobutyrate, and has essentially no plasticizer containing phosphine. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a floor polish composition used for forming a durable film on various floors, particularly a floor polish suitable as an aqueous composition containing substantially no phosphorus-containing plasticizer. It relates to a composition.

2. Description of the Prior Art Tributoxyethyl phosphate is conventionally used as a plasticizer and a leveling agent in floor polish compositions. This compound contains phosphorus, which is one of the three major nutrients of plants. Environment may cause environmental and pollution problems. In addition, phosphoric acid esters are generally pointed out to be toxic. On the other hand, JP-A-6-8
Japanese Patent No. 0933 proposes a floor polish composition containing a polishing component composed of a polymer or a polymer and waxes and an adipic acid ester. Here, adipates are used as alternatives to tributoxyethyl phosphate.
However, adipic acid esters have a problem that they are inferior in leveling property, water resistance and detergent resistance when applied to a floor material, as compared with the case where tributoxyethyl phosphate is used.

[0002]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a floor polish composition which is free from the problem of pollution due to phosphorus and is excellent in leveling property and transparency.

[0003]

According to the present invention, a specific ester alcohol, which is a fusing agent, not only functions as a fusing agent in a particular system, but also as a plasticizer, and is a commonly used triester. This specific ester alcohol, which is a fusing agent instead of a butoxyphosphate-based plasticizer, alone or together with other components, is combined with an α, β-unsaturated carboxylic acid-based polymer and / or a urethane-based polymer. It was made based on the finding that can be solved efficiently. That is, the present invention provides (A)
An α, β-unsaturated carboxylic acid polymer and / or a urethane polymer, and (B) an ester alcohol represented by the following general formula (1) or (2) or a mixture thereof, containing a phosphorus-containing plasticizer Provided is a floor polish composition characterized by being substantially free.

[Chemical 2] (In the formula, R ₁ and R ₃ each independently represent an alkyl group having 1 to 8 carbon atoms, and R ₂ represents an alkylene group having 1 to 8 carbon atoms.)

[0004]

BEST MODE FOR CARRYING OUT THE INVENTION α used as (A) of the present invention,
The β-unsaturated carboxylic acid polymer has a carboxyl group or a salt thereof in the molecule, for example, a polymer such as an unsaturated carboxylic acid such as (meth) acrylic acid or a partial ester or salt thereof, or the like. Monomer and vinyl acetate,
Copolymers with α, β-ethylenic monomers such as styrene, ethylene, propylene and vinyl chloride (see, for example, JP-A-62-205168), (meth) acrylic acid-based radically polymerizable monomers of aqueous urethane Examples thereof include polymers obtained by polymerization in the presence (see JP-A-63-23972 and JP-A-61-72071). Of these, the acid value is 20-200 mg
KOH / g is preferred, and further 30-130 mg KOH /
It is preferably g. As the urethane-based polymer, as a method of making polyurethane polyurethane aqueous, there are a case where an emulsifier is used and a case where an emulsifier is not used (self-emulsification). As a reference example of urethane-based polymer, Patent 20
The aqueous polyurethane resin of Reference Example 2 of 18649 is mentioned. Among these, those having a carboxyl group or a salt thereof introduced into the polymer are preferable.

As the component (A), one or more of (meth) acrylic emulsion, styrene- (meth) acrylic emulsion, (meth) acrylic-urethane emulsion, styrene- (meth) acrylic-urethane emulsion and polyurethane emulsion are used. Is preferred. These components (A) are calcium,
It is preferably crosslinked with a polyvalent metal such as zinc or aluminum. These polyvalent metal ions can be added as zinc ammonium carbonate, calcium hydroxide or the like. Further, the component (A) is preferably in the form of emulsion. The resin component (component (A) + alkali-soluble resin + synthetic and / or natural wax) in the floor polish composition provided by the present invention can be used in any amount. It is preferable to set it as the mass%, and it is more preferable to set it as 15 to 35% by mass in the floor polish composition. In the present invention, all of this resin component can be used as the component (A), but it is preferably 40 to 95% by mass, and more preferably 60 to 90% by mass in the resin component.

As the component (B) of the present invention, one or a mixture of two or more of the ester alcohols represented by the above general formula (1) or (2) can be used. In formula (1) or (2), R ₁ and R ₃ are preferably each independently an alkyl group having 1 to 4 carbon atoms, and particularly preferably n-propyl and isopropyl groups. Further, R ₂ is preferably an alkylene group having 2 to 6 carbon atoms, and particularly preferably a linear or branched butylene group. Of these, 2, 2,
4-Trimethylpentanediol-1,3-monoisobutyrate is preferable, and it is easily available as Texanol (manufactured by Eastman Kodak Company) or CS-12 (manufactured by Chisso Corporation). In the present invention, the component (B) can be used in any proportion, but the component (A) 100
The amount is preferably 5 to 120 parts by mass, more preferably 8 to 60 parts by mass with respect to parts by mass.

The floor polish composition of the present invention comprises:
In addition to the above components (A) and (B), various components can be blended. Of these, at least one selected from the group consisting of a fusing agent other than the component (B), a plasticizer other than the phosphorus-containing plasticizer, and a surfactant is preferably used in combination. Of these, examples of the fusing agent other than the component (B) include alkyls such as ethyl carbitol and methyl carbitol (alkyl groups having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms) carbitol, and dipropylene glycol monomethyl ether. 1 such as dipropylene glycol monoalkyl (alkyl group having 1 to 6 carbon atoms, preferably 1 to 3) ether, benzyl alcohol, N-methyl-2-pyrrolidone
Examples thereof include one kind or a mixture of two or more kinds. When these fusing agents are used in combination, the fusing effect and the drying property of the acrylic emulsion or the aqueous urethane resin as the component (A) can be adjusted appropriately. These can be used in an arbitrary ratio, but 0 to 115 relative to 100 parts by mass of the component (B).
It is preferable to set it as a mass part, More preferably, it is 2-72 mass parts. Examples of the plasticizer other than the phosphorus-containing plasticizer include one or a mixture of two or more adipates, citrate alkyl esters, and phthalates such as dibutyl phthalate and dioctyl phthalate. As such a citric acid alkyl ester, those represented by the following general formula (3) or (4) having a film forming action are preferable.

[0008]

[Chemical 3]

(In the formula, R _{4 to} R ₆ independently represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and any one of R _{4 to} R ₆ is an alkyl group having 1 to 18 carbon atoms. Represents a group, R ₇
Represents an alkyl group having 1 to 12 carbon atoms. ) Of these, R _{4 to} R ₆ preferably have 1 to 1 carbon atoms.
12, more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably all of R _{4 to} R ₆ are the above alkyl groups. R ₇ is preferably an alkyl group having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. The combined use of the above-mentioned plasticizer has an advantage that the hardness of the component (A) can be easily adjusted by cold and warm.

The above plasticizer can be used in any proportion, but in the floor polish composition, the component (A) 1
It is preferably 0.2 to 60 parts by mass, more preferably 2 to 30 parts by mass, and particularly preferably 5 to 25 parts by mass with respect to 00 parts by mass. Although any surfactant can be used as the surfactant, an anionic surfactant or a nonionic surfactant is preferable. In particular, one type of nonionic surfactant such as polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether or polyether modified silicone, anionic surfactant such as dioctylsulfosuccinate, fluorine-based surfactant, or the like. It is preferable to use a mixture of two or more kinds. The surfactant can be used in an arbitrary ratio, but it is preferably 0.001 to 5% by mass, more preferably 0.005 to 2% by mass in the floor polish composition.
When the above-mentioned surfactant is used in combination, the surface tension of the floor polish composition can be lowered to improve the wettability to the floor surface, and further the leveling property at the time of application and reapplication can be improved.

The floor polish composition of the present invention preferably contains a synthetic and / or natural wax. Examples of such waxes include synthetic waxes such as polyolefin wax emulsions and acrylic wax emulsions, and various natural wax emulsions. Such a wax can be used in any ratio, but it is preferably 5 to 60% by mass of the resin component, and more preferably 10 to 30% by mass. Further, it preferably contains an alkali-soluble resin or an alkali agent. As the alkali-soluble resin, one kind or a mixture of two or more kinds of styrene-maleic acid copolymer, acrylic resin, rosin-maleic acid copolymer and the like can be used. These are preferably used in the form of an alkali metal salt, ammonium salt, amine salt or the like. The alkali-soluble resin can be used in any proportion, but it is preferably 0 to 20 mass% in the resin component, and more preferably 5 to 10 mass%.

Examples of the fusing agent include ethylcarbitol, texanol (2,2,4-trimethylpentanediol-1,3-monoisobutyrate), dipropylene glycol monomethyl ether, N-methyl-2-pyrrolidone and the like. One kind or a mixture of two or more kinds can be used. These can be used in any proportion, but it is preferably 5 to 120 parts by mass, and more preferably 10 to 80 parts by mass with respect to 100 parts by mass of the component (A).
As the alkaline agent, a water-soluble alkaline agent is preferably used, and ammonia water or a water-soluble volatile amine is preferably used. The pH of the floor polish composition is preferably adjusted to 7 to 10 by using these. The balance of the floor polish composition of the present invention is water, but further contains components such as a water-soluble solvent, an antifoaming agent, an antibacterial agent, an ultraviolet absorber, a pigment, a fragrance, an acaricide, and a cockroach. You can

[0013]

Industrial Applicability According to the present invention, it is possible to provide a floor polish composition which is free from the problem of pollution due to phosphorus and is excellent in leveling property and transparency.
Further, the floor polish composition of the present invention can form a colorless and transparent film, and is excellent in adhesion to the floor material. Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

[0014]

EXAMPLES Production Example 1: Production of acrylic emulsion To a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen introducing tube, 20 g of pure water and 0.2 g of an emulsifier (sodium lauryl sulfate) were added. After enclosing nitrogen, the water bath was heated to 60 ° C. 0.2g in the dropping funnel
The polymerization initiator of (1) (ammonium persulfate) was dissolved in 10 g of pure water and attached to a reactor. 40 in another container with stirring
g of acrylic monomer (2.4 g of methacrylic acid, 2 g
5.6 g of methyl methacrylate, 12 g of butyl acrylate) and 0.1 g of a molecular weight regulator (lauryl mercaptan), 0.2 g of an emulsifier (sodium lauryl sulfate), 20 g of water are mixed, and after emulsification with a stirrer, separate. The emulsion was transferred to the dropping funnel and was gradually added dropwise over 2 hours to complete the polymerization to obtain an acrylic emulsion of 40% by mass (hereinafter abbreviated as%) of the active ingredient. Production Example 2: Styrene-acrylic emulsion 40 g of styrene-acrylic monomer (4.8 g of methacrylic acid, 12 g of styrene, 11.2 g of methyl methacrylate, 12 g of butyl acrylate), except that the type and blending amount were changed. Production was carried out in the same manner as in Example 1. The active ingredient was 40%.

Production Example 3: Production of aqueous polyurethane resin Polypropylene glycol (molecular weight 1000) 205
g, 73 g of tolylene diisocyanate, 18 g of dimethylolpropionic acid and 207 g of N-methylpyrrolidone are placed in a reactor equipped with a reflux condenser, a thermometer and a stirrer, and a urethanization reaction is carried out while maintaining the temperature at 80 to 100 ° C. to give a prepolymer. Was prepared. Then, 10 g of triethylamine was added to the prepolymer to neutralize it, and then 5 g of hexamethylenediamine was added. While adding distilled water, the temperature in the reaction vessel was kept at 35 ° C. or lower to carry out the polymerization reaction, and the reaction was completed. Then, 482 g of distilled water was added to obtain an aqueous polyurethane. The acid value per resin solid content of the aqueous polyurethane was 25. The active ingredient was 30%. Production Example 4: Production of acrylic-urethane emulsion A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen inlet tube was charged with 299.2 g of deionized water and 400 g of an aqueous polyurethane resin produced with Note 3) and stirred. While 6
Warm up to 0 ° C and add methyl methacrylate 21 at 60 ° C.
5 g, 65 g of n-butyl acrylate and 10 g of a 10% aqueous dispersion of t-butyl hydride peroxide and a 10% aqueous solution of sodium aldehyde sulfoxylate 1
0 g was also dropped. After the completion of the dropping, the reaction solution was kept at 70 ° C for 1 hour to complete the polymerization reaction, and the active ingredient of 40% acrylic
-A urethane emulsion is obtained.

Example 1 The resin emulsions produced in Production Examples 1 to 4 were used as the component (A), texanol was used as the component (B), and the floor polish compositions shown in Table 1 were prepared as the other components. The performance was evaluated. The results are also shown in Table-1. The properties and origins of the components used and the method for evaluating the performance of the floor polish composition are shown below. 10 g of zinc oxide was added to and dispersed in 54.49 g of pure zinc carbonate solution . To this, 17.97 g of 28% ammonia water, 1
7.54 g of ammonia carbonate was added and stirred to obtain a zinc ammonium carbonate complex having a zinc content of 8.0337%. Styrene-maleic acid (alkali-soluble resin) solution Product name SMA2625A manufactured by Allied Chemical Co., USA
(Acid value 220) is dissolved in aqueous ammonia to give a solid content of 15
% Aqueous solution was obtained. Acrylic resin emulsion (alkali soluble resin) Product name Rohm and Haas Company USA Primal B-
644 (42% active ingredient)

Polyethylene Wax Emulsion Toho Chemical Industry Co., Ltd. trade name Hitec E-4B
(Active ingredient 40%) Polypropylene wax emulsion Toho Chemical Industry Co., Ltd. trade name Hitec P-50
43 (active ingredient 30%) Acrylic wax emulsion Product name CX-ST20 manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.
0 (active ingredient 40%) Surfactant (anion type) Sodium dioctyl sulfosuccinate surfactant (nonion type) Polyoxyethylene lauryl ether (EO: 3 mol adduct) Surfactant (polyether modified silicone type) BYK3 manufactured by BYK Japan KK
47 Surfactant (fluorine type) Asahi Glass Co., Ltd. product name Surflon S-111

Test Method Film Transparency 5 ml of each floor polish composition was dropped on a flat petri dish having a diameter of 99 mm and left at room temperature for 3 days to form a film, and the transparency of the film thus formed was visually observed according to the following criteria. evaluated. ⊚: Excellent ○: Good Δ: Normal ×: Poor phosphorus pollution Judged by the presence or absence of phosphorus in the raw material components. Leveling Property Japan Floor Polish Industry Association JFPA Standard-16
The evaluation was performed according to the leveling test method.

[0019]

[Table 1]

Continued front page    (72) Inventor Tsuyoshi Suganuma             1-2-20 Nishi-Ayase, Adachi-ku, Tokyo Nishi-Ayase Dormitory             105 (72) Inventor Mitsuru Takahashi             1-2-20 Nishi-Ayase, Adachi-ku, Tokyo Nishi-Ayase Dormitory             201 (72) Inventor Masanori Shimamura             2034-16 Takahagi, Hidaka City, Saitama Prefecture (72) Inventor Shinji Ogasawara             1-2-20 Nishi-Ayase, Adachi-ku, Tokyo Nishi-Ayase Dormitory             101 (72) Inventor Hiroyuki Shibui             3884-1, Morishita-cho, Mizukaido-shi, Ibaraki Green             Court Asahi B-201

Claims (6)

[Claims] 1. An (A) α, β-unsaturated carboxylic acid-based polymer and / or a urethane-based polymer, and (B) an ester alcohol represented by the following general formula (1) or (2) or a mixture thereof. A floor polish composition containing a plasticizer containing substantially no phosphorus-containing plasticizer. [Chemical 1] (In the formula, R ₁ and R ₃ each independently represent an alkyl group having 1 to 8 carbon atoms, and R ₂ represents an alkylene group having 1 to 8 carbon atoms.) 2. The composition according to claim 1, further comprising at least one selected from the group consisting of a fusing agent other than the component (B), a plasticizer other than the phosphorus-containing plasticizer, and a surfactant. 3. The composition according to claim 1, wherein the α, β-unsaturated carboxylic acid-based polymer of the component (A) is a polymer containing (meth) acrylic acid as a constituent component. 4. The composition according to claim 1, wherein the component (A) is crosslinked with a polyvalent metal. 5. The composition according to claim 1, wherein the component (A) is in the form of an emulsion. 6. The composition according to claim 1, further comprising a synthetic and / or natural wax.