JPS6154069B2 - - Google Patents

Description

[Detailed description of the invention]

This invention has as its main component [C] an aqueous polymer dispersion obtained by polymerizing [B] a monoethylenic monomer using [A] a carboxyl group-containing alkali water-soluble copolymer as an emulsifying dispersant. , relating to a new [D] floor polishing agent. In particular, the present invention relates to an alkali-removing floor polish that protects flooring materials and imparts luster to them, and which is not removed by detergents and water used for floor washing but is easily removed by aqueous alkaline cleaners. . The main raw material for this type of floor polishing agent is an aqueous dispersion of a resin copolymerized with a monomer containing a carboxyl group, and this is combined with an alkali-soluble resin, wax (hereinafter sometimes referred to as wax), a plasticizer, and a dispersant. , emulsifiers, compatibilizers, and polyvalent metal compounds are mainly used. Although floor polishing agents are made by blending many raw materials, their performance largely depends on the properties of the carboxyl group-containing polymer, which is the main raw material, and there are many patents related to this. For example, those using copolymers of α/β-unsaturated carboxylic acid monomers and acrylic monomers (Tokuko Showa)
47-14019), emulsion polymerization of a mixture of ethylenically unsaturated carboxylic acid monomer, acrylic monomer and other monomers in two stages (JP-A-49-30474), methacrylic acid Those using partial hydrolysates of ester oligomers (Special Publications 1973-
151941). However, these are too sensitive to alkali and have poor water resistance, so they do not satisfy the characteristics required as a floor polishing agent in a well-balanced manner. In order to solve this problem, the present inventor synthesized various polymers, created a floor polishing agent blended with the polymers, and evaluated the required properties. Discovered that a floor polishing agent with well-balanced properties could be obtained by using a copolymer as an emulsifying dispersant and an aqueous dispersant obtained by polymerizing a monoethylene monomer, and completed this invention. did. This invention provides the following. In polymerizing [B] using [A] as an emulsifying dispersant, (i) [A] is (a) 10 to 25% by weight of methacrylic acid and/or acrylic acid, (b) 5 to 40% by weight of styrene, (c) Acrylic acid alkyl ester whose alkyl group is C ₂ to C ₈ and/or whose alkyl group is
Methacrylic acid alkyl esters from _C1 to _C12
A copolymer obtained by solution polymerizing 35 to 85% by weight of _C1 to _C4 saturated monohydric alcohol, and the glass transition temperature of the copolymer is 20 to 100°C and 0.3 dl/g in tetrahydrofuran. Use an alkaline aqueous solution of a carboxyl group-containing alkali water-soluble copolymer having the following intrinsic viscosity in an amount of 20 to 80 parts by weight as a solid content, (ii) [B] is styrene, and the alkyl group is _C2 to _C8 . Using 100 parts by weight of one or more monostyrene monomers selected from acrylic acid alkyl esters and methacrylic acid alkyl esters having an alkyl group of C ₁ to _{C 12} , [B′] produced (co)polymer The glass transition temperature of the polymer is 20 to 105°C, and (iii) it is in an aqueous medium with a pH of 7 or higher. Features [D] Floor polishing agent. The feature of this invention is to use an aqueous polymer dispersion containing almost no ordinary low-molecular-weight emulsifier or electrolyte, and to use a polymer whose alkaliphilicity and hydrophobicity are suitably balanced. . Generally, the particle size of the polymer in an aqueous polymer dispersion tends to be large in order to reduce the amount of emulsifier used due to problems such as water resistance. However, in the present invention, the particle size of the polymer is small, about 800 Å (angstroms) or less, and therefore has excellent gloss which is easily affected by the particle size. [A] The carboxyl group-containing alkali water-soluble copolymer used in this invention is (a) methacrylic acid and/or
or acrylic acid 10-25% by weight, preferably 15-25%
20% by weight, (b) styrene 5-40% by weight, preferably 16
~35% by weight, (c) acrylic acid alkyl ester and/or alkyl group with a _C2 to _C8 alkyl group;
_C1 - _C12 methacrylic acid alkyl esters 35-85
It consists of % by weight. (a) If the amount of methacrylic acid and/or acrylic acid used is less than 10% by weight, the solubility of the copolymer in alkaline aqueous solutions will decrease, and at the same time, when used as a floor polishing agent, the peelability of alkaline cleaners will decrease.
Glossiness deteriorates. If it is more than 25% by weight, the copolymer will have a high viscosity when dissolved in an alkali, resulting in poor workability. Furthermore, the stability of the monoethylenic monomer during polymerization is poor, and when used as a floor polishing agent, the alkali solubility is too high, resulting in poor water resistance and detergent resistance.
Furthermore, when multiple layers are applied, the lower layer is re-dissolved and the gloss is significantly reduced. Methtallic acid and/or acrylic acid are used as acidic monomers. Among these, methacrylic acid is preferable because it has an excellent balance of water resistance, detergent resistance, and removability. In addition, α and β other than methacrylic acid and acrylic acid
Ethylenically unsaturated carboxylic acids, such as monocarboxylic acids such as crotonic acid, itaconic acid, maleic acid,
Dicarboxylic acids such as fumaric acid and monoalkyl esters of these dicarboxylic acids improve the alkali solubility of the copolymer, the polymerization stability of the monoethylenic monomer, the gloss when used as a floor polishing agent, water resistance,
It is not used in the present invention because of its poor detergent resistance. In particular, when a copolymer containing a dicarboxylic acid is used, the resulting copolymer has a large particle size, and when used as a floor polishing agent, the gloss is extremely poor and the water resistance is also poor. [A] The carboxyl group-containing alkali water-soluble copolymer (b) contains 5 to 40% by weight of styrene, which is effective in improving workability, gloss, water resistance, and detergent resistance. If styrene is less than 5% by weight, C ₁ ~
When solution polymerizing a copolymer in a _C4 saturated monohydric alcohol, the solution viscosity is high and workability is poor. Also, when used as a floor polish, it has poor water resistance, detergent resistance, gloss and recoatability. If the styrene content is more than 40% by weight, the copolymer will be difficult to dissolve in alkaline water. Furthermore, when used as a floor polishing agent, it economically deteriorates the removability of alkaline cleaners. (c) Among acrylic acid alkyl esters having an alkali group of _C2 to _C8 and methacrylic acid alkyl esters having an alkyl group of C1 _{to C12} , particularly preferred are ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, It is methyl methacrylate. [A] The glass transition temperature (Tg) of the carboxyl group-containing alkali water-soluble copolymer is preferably 20 to 100°C, more preferably 40 to 90°C. Tg is 20
If it is lower than °C, the polymerization stability of the monoethylenic monomer will be poor. Furthermore, when used as a floor polishing agent, scratches and stains are likely to occur. When Tg is higher than 100°C, the solution viscosity is high and workability is poor when solution polymerizing a carboxyl group-containing alkali water-soluble copolymer. In addition, when used as a floor polisher, there is a tendency for powdering.
Poor removability with alkaline cleaners. In addition, [A] carboxyl group-containing alkali water-soluble copolymer was prepared at 0.3 dl/in tetrahydrofuran at 30°C.
It is necessary to have an intrinsic viscosity of less than g. 0.3
If it is larger than dl/g, the polymerization stability of the monoethylenic monomer will be extremely poor, and when used as a floor polishing agent, it will have an adverse effect on leveling properties. The lower limit of the intrinsic viscosity is preferably about 0.1 dl/g. If it is smaller than this, it is not preferable because it tends to cause a decrease in gloss during overcoating and a decrease in detergent resistance. Note that the glass transition temperature (Tg) of the copolymer referred to in this patent is calculated using the following formula (). 1/Tg(c)=W ₁ /Tg ₁ +W ₂ /Tg ₂ +W ₃ /T
g ₃ +...() Here, W ₁ ; weight fraction of monomer 1 in the copolymer, W ₂ ; weight fraction of monomer 2 in the copolymer,
W ₃ ; weight fraction of monomer 3 in the copolymer,
Tg ₁ ; Tg expressed as the absolute temperature of the homopolymer of monomer 1, Tg ₂ ; Tg expressed as the absolute temperature of the homopolymer of monomer 2, Tg ₃ ; Tg of the homopolymer of monomer 3; Tg, Tg(c) expressed in absolute temperature; Tg expressed in absolute temperature of the copolymer. The Tg of the homopolymer is, for example, polystyrene 100°C, polymethyl methacrylate 105°C, polybutyl methacrylate 20°C, polybutyl acrylate -55
℃, polyethyl acrylate -24℃, polymethacrylic acid 185℃, etc. are used. [A] The carboxyl group-containing alkaline water-soluble copolymer is produced by solution polymerization because it is easy to obtain a low molecular weight copolymer and polymerization can be carried out without using an emulsifier. In this case, solution polymerization is particularly preferably carried out in C ₁ -C ₄ saturated monohydric alcohols (methyl, ethyl, propyl, butyl alcohol and their isomers), which can be easily handled industrially, and methyl alcohol. If the alcohol has a _C5 or higher, its volatility will be poor and it will have a negative effect on the painted surface. When producing a copolymer, organic peroxides such as benzoyl peroxide, lauryl peroxide, and cumene peroxide, and azo compounds such as azobisisobutyronitrile are used as polymerization initiators. In particular, azobisisobutyronitrile and azobisdimethylvaleronitrile are preferred because they provide a high conversion rate and are easy to handle. Also, conventional chain transfer agents such as tertiary dodecyl mercaptan and 2-ethylhexyl thioglycolate can be used. When the copolymer is used as an emulsifying dispersant, it must be dissolved in an alkaline aqueous solution to have a pH of 7 or higher. As the alkali, aqueous ammonia, sodium hydroxide, potassium hydroxide and amines are used. Particularly preferred are water-resistant, detergent-resistant to volatile ammonia or amines, or mixtures thereof. If the pH of the alkaline aqueous solution of the copolymer is less than 7, the solubility will be poor, and when it is used as an emulsifying and dispersing agent, the polymerization stability of the monoethylenic monomer will be poor, and the particle size of the obtained polymer will be It grows larger and becomes less glossy when used as a floor polisher. The preferred upper limit for PH is about 11. If this value is exceeded, the viscosity tends to become too large. The amount of alkali used is preferably 0.4 to 1.6 equivalents per equivalent of carboxyl group in the copolymer. The viscosity when dissolved in an alkaline aqueous solution is preferably 5 to 5000 cps at a solid content of 20% by weight and 20°C. If the viscosity is outside this range, not only the workability during production but also the leveling of the floor polishing agent will deteriorate, which is not preferable. Next, the amount of [A] carboxyl group-containing alkali water-soluble copolymer used in the polymerization of [B] monoethylenic monomer is 20 to 80 parts by weight per 100 parts by weight of [B].
Must be parts by weight. The preferred range of [A] is 30 to 60 parts by weight. If the amount of [A] used is less than 20 parts by weight, the polymerization stability of [B] will be poor;
Furthermore, the particle size of the resulting polymer is too large to be used as a floor polishing agent, resulting in poor gloss and poor removability with an alkali cleaner. When the amount of [A] used is more than 80 parts by weight, the viscosity of the polymer dispersion increases, and the leveling properties tend to be poor when used in a floor polishing agent. Moreover, recoatability, water resistance, and detergent resistance are also reduced. [B] The monoethylenic monomer is one or more monomers selected from styrene, acrylic acid alkyl esters having an alkyl group of _C2 to _C8 , or methacrylic acid alkyl esters having an alkyl group of _C1 to _C12 . It is a quantity. Among these, ethyl acrylate is preferred;
They are n-butyl acrylate, 2-ethylhexyl acrylate and methyl methacrylate. In addition to the above-mentioned monomers, as component [B], a relatively small amount of other copolymerizable monomers such as acrylonitrile and (meth)acrylamide can be used. These [B] monomers have a glass transition temperature Tg of 20 to 105°C, preferably 40°C.
Use at a ratio that will result in a temperature range of ~90℃. this
If the Tg is less than 20°C, scratches are likely to occur when used as a floor polisher, and removability with alkaline cleaners is poor. If the temperature exceeds 105℃, powdering will occur easily. These [B] monoethylenic monomers, [A]
When polymerizing a carboxyl group-containing alkaline water-soluble copolymer as an emulsifying and dispersing agent, the polymerization must be carried out in an aqueous medium with a pH of 7 or higher. When the pH is lower than 7, polymerization stability deteriorates. As the polymerization initiator, persulfates, peroxides such as benzoyl peroxide, azo compounds such as azobisisobutyronitrile, azobisdimethylvaleronitrile, etc. are used. Particularly preferred are azobisisobutyronitrile and azobisdimethylvaleronitrile, in which case it is usually from 0.05 to 100 parts by weight of [B] monoethylenic monomer.
3.0 parts by weight are used. Further, conventional chain transfer agents such as tertiary dodecyl mercaptan and 2-ethylhexyl thioglycolate can also be used. In this invention, [A] a carboxyl group-containing alkali water-soluble copolymer is used as an emulsifying and dispersing agent.
Although the use of ordinary low molecular weight emulsifiers is not preferred for water resistance and detergent resistance, they may be used in small amounts for polymerization stability, chemical stability, and particle size control. For example, anionic emulsifiers such as sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, and alkylaryl polyether sulfates, and nonionic emulsifiers such as polyoxyethylene lauryl ether and polyoxyethylene nonylphenol ether are appropriately selected. Can be used. These conventional emulsifiers are used in amounts of 5 parts by weight or less, preferably 33 parts by weight or less, per 100 parts by weight of the monoethylene monomer (B). Examples of the alkali-soluble resins used in the present invention include colophonium-maleinate resins, silica resins, styrene-maleinate resins, and polyester resins. Further, the waxes used in the present invention include partially synthetic esters (for example, montan wax derivatives), natural waxes (for example, candelia wax, carnauba wax, honeysuckle), synthetic waxes (for example, polyethylene wax, microcrystalline wax, Synthetic paraffin-oxidate)
ionic or nonionic emulsions, etc. In addition, commonly used plasticizers, dispersants or emulsifiers, compatibilizers, polyvalent metal compounds, etc. may be added to the floor polishing agent of the present invention as required. Parts and percentages shown in the following examples mean parts by weight and percentages by weight, unless otherwise specified. Example 1 ([A] Preparation of carboxyl group-containing alkaline water-soluble copolymer) In a reactor equipped with a stirrer, a thermometer, and a reflux condenser, 50 parts of methanol was used as a medium, and acrylic acid n
- Charge 100 parts of butyl, methyl methacrylate, styrene, and methacrylic acid according to the prescribed amounts in Table 1, add 2.0 parts of azobisisobutyronitrile and 0.3 parts of tertiary dodecyl mercaptan, and convert at 65°C.
The reaction was allowed to reach 98% or more. After pouring the obtained [A] carboxyl group-containing alkaline water-soluble copolymer into water, methacrylic acid
Add 0.8 equivalent of ammonia water and dissolve to reduce solid content to 20
% alkaline aqueous solution (pH 7 or higher) was obtained. ([B] Polymerization of monomethylene monomer) Using the alkaline aqueous solution of the copolymer obtained above, n-butyl acrylate and methyl methacrylate were charged according to the prescribed amounts in Table 1, and azobisisomer Using 0.3 part of butyronitrile, distilled water was added so that the total solid content was about 40% after the polymerization reaction, and if necessary, a small amount of aqueous ammonia was added to adjust the pH to 7 or higher. This was polymerized in a reactor at 65° C. for 12 hours to synthesize an aqueous (co)polymer dispersion [C] at a conversion rate of 99% or more. The particle size of this (co)polymer is approximately
It was 500Å. ([D] Preparation of floor polish composition) [D] Floor polish composition was prepared according to the following formulation. [D] Floor polishing agent part [C] Aqueous copolymer dispersion (solid content 15%) ^*1 80 Wax emuldiene (solid content 15%) ^*2 15 Alkali-soluble resin (solid content 15%) ^*3 5 Fluorine surfactant (solid content 1%) ^*4 0.5 *1 A trace amount of butyl carbitol acetate was added to each [C] aqueous copolymer dispersion to set the minimum film forming temperature (MFT) to 0°C. Using. *2 Wax emulsion; Toho Chemical
HYTEX E-4B *3 Alkali-soluble resin; Arco Chenucal
Company SMA-2625A (styrene, maleic acid resin with acid value 220 and molecular weight 1900) *4 Fluorine surfactant; C ₃ F ₁₇ SO ₂ N
(C ₂ H ₅ )CH ₂ COOK [C] The properties of the aqueous copolymer dispersion and the properties of the [D] floor polish obtained using the same were measured by the following method. (1) Fluidity before ammonia dissolution: Solution viscosity of [A] carboxyl group-containing alkaline water-soluble copolymer polymerized in methanol before ammonia dissolution.
Measurement was performed at 20°C and 60 rpm using a BM type rotational viscometer. ◎ Less than 10,000 cps 〇 10,000 to 100,000 cps × More than 100,000 cps (2) Ammonia solubility; [A] After pouring the carboxyl group-containing copolymer into water, add ammonia water to make the solid content 20%. The mixture was heated and stirred at 60°C, and the time until complete dissolution was measured. ◎Less than 1 hour 〇1 to 3 hours x longer than 3 hours (3) Viscosity (cps): 20 using a BM type rotational viscometer
Measured at 60 rpm. (4) Coagulated product (%): Calculated from the number of grams obtained by filtering the aqueous polymer dispersion [C] containing 100 g of polymer through a 120-mesh wire mesh, drying and weighing the coagulated material remaining on the wire mesh after washing with water. %. (5) Leveling property: Immediately after applying [D] floor polish to half of a 9-inch square black vinyl chloride
Draw a diagonal line. Judgment was made based on the degree to which this line disappeared after drying. ◎Things that completely disappeared 〇 Things that almost disappeared × Things that remained (6) Water resistance: Apply [D] floor polish twice with a brush on the vinyl chloride tile, let it dry, and leave it for a week. Water was dropped onto the coating, and the coating film was evaluated based on the whitening state after one hour and the whitening state after the water droplets had dried. ◎ No whitening at all ○ Negligible whitening × Significant whitening (7) Detergent resistance: Spread [D] floor polish on the vinyl chloride tile and apply it twice, then dry. After one week, soak in a 1% solution of household neutral detergent,
The peeling state of the coating film after being worn for minutes was evaluated. ◎No peeling at all 〇 Almost no peeling × Significantly peeling (8) Gloss (%); Samples similar to (6) and (7)
It was left in a constant temperature and humidity room at 20°C and 60% RH, and evaluated by measuring 60° specular reflection with a gloss meter. (9) Alkaline cleaner removability: Samples similar to (6) and (7) were mixed with (18.22 parts of polyoxyethylene nonylphenol ether HLB, 5 parts of sodium dodecylbenzenesulfonate, 5 parts of 28% aqueous ammonia, water Evaluation was made based on the peeling state of the coating film when worn while soaking in an alkaline cleaner consisting of 88 parts). ◎The paint film is completely peeled off within 1 minute 〇The paint film is 80% peeled off within 1 minute x The paint film is hardly peeled off (10) Scratch and stain resistance; (6) and (7) A similar sample was placed in a high-traffic area for one month and the occurrence of scratches and stains was observed. ◎ Items with almost no scratches or stains 〇 Items with some scratches or stains × Items with extremely large numbers of scratches or stains From the results in Table 1, the glass transition temperature of [A] carboxyl group-containing alkali water-soluble copolymer is 20 ~
It can be seen that (a) the amount of methacrylic acid at 100°C is preferably 10 to 25% by weight. Further, the glass transition temperature of the polymer of [B] monoethylenic monomer is 20 to 105°C, and [A] carboxyl group-containing alkali water-soluble copolymer is added to 100 parts of [B] monoethylenic monomer. It can be seen that it is preferable to use a combined amount of 20 to 80 parts by weight as an emulsifying powder. Example 2 [2- to 2-] Azobisisobutyronitrile as a polymerization initiator
In addition to 2.0 parts, 2-ethylhexyl thioglycolate was used as a chain transfer agent, methanol and water (comparative example) were used as polymerization media, and other monomers shown in Table 2 were used in the proportions shown in Table 2. The reaction was carried out in the same manner as in 1. The polymerization conversion rate was 98% or more in all cases. The obtained copolymer has a pH of 7
Using the above ammonia aqueous solution and using it as an emulsifying powder, monoethylenic monomer [B] was polymerized in the same manner as in Example 1 under the conditions shown in Table 2. The polymerization rate was 98% or more in all cases. These were mixed into [D] floor polishing agent and tested in the same manner as in Example 1, and the results shown in Table 2 were obtained. For comparison, the following polymerizations were carried out and each was tested as a [D] floor polishing agent. [2-, 2-] [A] In the polymerization of the carboxyl group-containing copolymer, instead of polymerizing in methanol, 1 part of sodium salt of lauryl sulfate was used as an emulsifier and 0.3 part of ammonium persulfate was used as a polymerization initiator. Emulsion polymerization was carried out in an aqueous medium. Then PH with ammonia water
7 or higher, the monoethylenic monomer [B] was polymerized. [2-] [A] An ammoniacal alkali aqueous solution of a carboxyl group-containing alkali water-soluble copolymer as it is,
[D] Blended in floor polishing agent. [2-, 2-] [A] Emulsion polymerization was carried out using 1.0 part of sodium salt of lauryl sulfate as an emulsifier and 0.3 part of potassium persulfate as a polymerization initiator without using a carboxyl group-containing alkali water-soluble copolymer. . After polymerization, the pH was adjusted to 8 with aqueous ammonia and blended into [D] floor polishing agent. [2-] 40 parts by dry weight of the aqueous alkaline solution of the copolymer obtained in 2- is mixed with 100 parts by dry weight of the aqueous dispersion of the monoethylenic monomer [B] obtained in 2-, This was blended into a floor polish. From the results in Table 2, it can be seen that the intrinsic viscosity of the carboxyl group-containing alkali water-soluble copolymer (A) of the present invention in tetrahydrofuran is required to be 0.3 dl/g or less at 30°C. Furthermore, the polymer dispersion of the present invention is useful as a [D] floor polishing agent, and has a better balance of gloss, detergent resistance, and alkali cleaner removability than the polymer dispersion obtained by ordinary emulsion polymerization. I know that there is. [A] By simply mixing an aqueous ammonium solution of a carboxyl group-containing alkaline water-soluble copolymer with a polymer dispersion obtained by ordinary emulsion polymerization, sufficient physical properties, which are the characteristics of this invention, cannot be obtained. [C] It can be seen that the polymer dispersion is superior. Example 3 Each monomer was used in the prescribed amounts shown in Table 3, 2.0 parts of 2,2'-azobis-(2,4-dimethylvaleronitrile) was used as a polymerization initiator, and 1.0 parts of 2-ethylhexyl thioglycolate was used as a chain transfer agent. A carboxyl group-containing alkaline water-soluble copolymer was obtained in the same manner as in Example 1, except that 1. After pouring the obtained carboxyl group-containing alkaline water-soluble copolymer into water, 1.0 equivalent of carboxylic acid in ammonia water was added and dissolved to obtain an aqueous solution of the corresponding polymer (PH7 or higher) with a solid content of 20%. Next, this [A] copolymer aqueous solution was used as an emulsifying powder, and 2,2'-azobis-
[C] Aqueous polymer powder was synthesized in the same manner as in Example 1 except that 0.3 part of 2,4-dimethylvaleronitrile was used. The polymerization conversion rate was 99% or more. [C] Properties of the aqueous polymer dispersion and [D] floor polish obtained using the same were tested in the same manner as in Example 1. For comparison, a monoethylenic monomer [B] was polymerized in the presence of a carboxyl group-containing alkali water-soluble copolymer before dissolving ammonia without using any other emulsifier (3-). . From the results shown in Table 3, the [C] polymer dispersion in which the (b) styrene content in the carboxyl-containing alkali water-soluble copolymer (A) is within the range of 5 to 40% by weight is [D]. ] It can be seen that it has excellent characteristics as a floor polishing agent. On the other hand, in the presence of a carboxyl group-containing copolymer that has not yet been dissolved in ammonia, monoethylenic monomer [B] is polymerized without using an emulsifier, and the resultant product is a coagulated product that cannot be evaluated as a floor polishing agent. It was hot. Example 4 A carboxyl group-containing alkali water-soluble copolymer was obtained in the same manner as in Example 3 using the monomer composition ratios shown in Table 4. After pouring the obtained [A] carboxyl group-containing alkaline water-soluble copolymer into water, methacrylic acid was added.
0.3, 0.5, 0.8, 1.2 equivalents of aqueous ammonia and 0.8
Equivalent amounts of monoethylamine and monomethylamine were added and dissolved to obtain an aqueous copolymer solution with a solid content of 20%. These PHs are 6.2, 7.2, 7.7, respectively.
They were 9.0, 7.9 and 7.9. Next, in the same manner as in Example 3, an aqueous polymer dispersion [C] was produced. The polymerization conversion rate was 98% or more in all cases. The properties of these polymers and the [D] floor polish obtained using them were tested in the same manner as in Example 1. From the results in Table 4, the alkaline aqueous solution of [A] carboxyl group-containing alkali copolymer has a pH of 7 or higher;
It was found that approximately 0.4 equivalent or more is required as the equivalent amount of alkali to carboxyl group. Example 5 [D] Floor polishing agent was synthesized in the same manner as in Example 1 except that the monomer composition ratios shown in Table 5 were used and the type of carboxylic acid was changed. These test results are shown in Table-5. Note that examples using acids other than methacrylic acid and acrylic acid are comparative examples. From the results shown in Table 5, good results were obtained with (a) the carboxyl group-containing alkali water-soluble copolymer containing methacrylic acid and/or acrylic acid, but other carboxylic acids other than itaconic acid The aqueous alkaline solution could not be obtained because of poor alkali solubility. In a floor polishing test, the product using itaconic acid had poor detergent resistance and poor gloss.

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[Table] Example 6 [A] of Sample No. 1- in Table 1 of Example 1
Using 40 parts (solid content equivalent) of a carboxyl group-containing alkaline water-soluble copolymer as an emulsifying and dispersing agent, the emulsifier was selected from 2-ethylhexyl acrylate (2EHA), butyl methacrylate (BMA), acrylonitrile (AN), and styrene (ST). [B] 100 parts of the monoethylenic monomer was emulsion polymerized, and the obtained [C] aqueous polymer dispersion was prepared as a floor polishing agent according to the preparation of [D] floor polishing composition in Example 1. I got it. [B] The content of the monoethylenic monomer and the properties of the [D] floor polishing agent are shown in Table 6. As can be seen from Table 6, good results were also obtained when copolymers of 2-ethylhexyl acrylate, butyl acrylonitrile methacrylate, styrene, etc. were used as the monoethylenic polymer [B].

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Claims (1)

[Claims] 1 In polymerizing [B] using [A] as an emulsifying dispersant, [A] is (a) 10 to 25% by weight of methacrylic acid and/or acrylic acid, (b) styrene. 5 to 40% by weight, (c) 35 to 85% by weight of an acrylic acid alkyl _ester whose alkyl group is _C2 to _C8 and/or a methacrylic acid alkyl ester whose alkyl group is _C1 to _C12 ; A copolymer formed by solution polymerization in a _C4 saturated monohydric alcohol, with a carboxyl group having a glass transition temperature of 20 to 100°C and an intrinsic viscosity of 0.3 dl/g or less at 30°C in tetrahydrofuran. The solid content of alkaline aqueous solution of alkaline water-soluble copolymer is 20~
Use 80 parts by weight, [] [B] is styrene, the alkyl group is C ₂ - _{C 8}
Using 100 parts by weight of one or more monoethylenic monomers selected from acrylic acid alkyl esters, and methacrylic acid alkyl esters having an alkyl group of C ₁ to _{C 12} , [B′] is produced (co). The glass transition temperature of the polymer is 20 to 105°C, [] It is in an aqueous medium with a pH of 7 or higher, and the resulting [C] aqueous polymer dispersion, alkali-soluble resin, and wax are used. [D] Floor polishing agent characterized by: 2 [A] The intrinsic viscosity of the carboxyl group-containing alkali water-soluble copolymer at 30°C in tetrahydrofuran
2. The floor polishing agent according to claim 1, which has a concentration of 0.1 to 0.3 dl/g. 3 [A] The bed according to item 1, wherein (a) methacrylic acid and/or acrylic acid in the carboxyl group-containing alkaline water-soluble copolymer is 15 to 20% by weight and (b) styrene is 16 to 35% by weight. Polishing agent. 4. The floor polishing agent according to item 1, which uses [A] the carboxyl group-containing alkaline water-soluble copolymer having a glass transition temperature in the range of 40 to 90°C. 5 [A] Carboxyl group-containing alkaline water-soluble copolymer containing ammonia and/or amine in an amount of 0.4 equivalent or more of the carboxyl group, and the viscosity of an aqueous solution with a solid content of 20% by weight is 5 to 5000 cps at 20°C.
2. The floor polishing agent according to item 1, which uses an alkaline aqueous solution of a carboxyl group-containing alkaline water-soluble copolymer having a pH of 7 to 11. 6 [B′] The glass transition temperature of the produced (co)polymer is
2. The floor polishing agent according to item 1, which uses the monoethylenic monomer [B] in the range of 40 to 90°C. 7. [B] 30 to 60 parts by weight of the solid content of an alkaline aqueous solution of a carboxyl group-containing alkali water-soluble copolymer based on 100 parts by weight of the monoethylenic monomer [B] is used as an emulsifying dispersant. floor polisher. 8. [A] The floor polishing agent according to item 1, wherein the acid in (a) is methacrylic acid. 9. The floor polishing agent according to item 1, wherein the ester in [A](c) is at least one selected from ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and methyl methacrylate. 10 [B] The floor polishing agent according to item 1, wherein the monoethylenic monomer is at least one selected from ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and methyl methacrylate.