JPH04293914A - Polymer powder - Google Patents

Abstract

PURPOSE:To obtain a polymer powder excellent in coating workability, adhesive strength, redispersibility and storage stability by combining an alkyl (meth) acrylate and/or a conjugated diene with a functional monomer and monomers copolymerizable therewith and specifying the particle diameter. CONSTITUTION:This powder comprises 1-99.9wt.% alkyl (meth)acrylate and/or conjugated diene (a), 0.1-40wt.% functional monomer (b) and 0-98.9wt.% other monomers (c) copolymerizable with components (a) and (b) (the total of components (a) to (c) being 100wt.%) and has a particle diameter of 1-150mum.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer powder having excellent coating workability, storage stability, adhesiveness and redispersibility.

0002

[Prior Art] Compared to water-based latex, polymer powders are easier to mix on-site, have better handling and workability, can be mixed more accurately, and are easier to mix with other polymer powders. For these reasons, it is used as an admixture for cement-based and gypsum-based compositions, and as a component of paints and various adhesives. Generally known polymer powders include polyvinyl chloride, ethylene-vinyl acetate copolymer, and polyvinyl acetate. However, these polymer powders are used in cement admixtures, asphalt modifiers, carpet backing agents, and various adhesives, but none of them have sufficient adhesive strength, ease of application, or redispersibility. There is a problem with this.

0004

SUMMARY OF THE INVENTION The present invention has been made in view of the problems of the prior art described above, and has improved coating workability, adhesive strength, and redispersibility compared to conventional polymer powders.
Furthermore, it is an object of the present invention to provide a polymer powder having excellent storage stability.

[0005]

[Means for Solving the Problems] The present invention provides that the polymer component is (a) (meth)acrylic acid alkyl ester and/or
or 1 to 99.9% by weight of a conjugated diene, (b) 0.1 to 40% by weight of a monomer having a functional group, and (c) another monomer copolymerizable with the components (a) to (b) above. Quantity 0-98
．． 9% by weight [However, (a) + (b) + (c) = 100
% by weight] and has a powder particle size of 1 to 150 μm.

Among the monomers forming the polymer powder of the present invention, (a) (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, and (meth)acrylic acid. n-propyl, i-propyl (meth)acrylate, n-butyl (meth)acrylate,
(meth)acrylic acid i-butyl, (meth)acrylic acid n
Examples include -amyl, i-amyl (meth)acrylate, hexyl (meth)acrylate, 2-methylhexyl (meth)acrylate, i-nonyl (meth)acrylate, and decyl (meth)acrylate. Among component (a), the conjugated dienes include butadiene, isoprene, 2-chloro-1,3-butadiene, 2-methyl-1,
Examples include 3-butadiene. these(
Component a) can be used alone or in combination of two or more.

[0007] In the (b) monomer having a functional group, examples of the functional group include a carboxyl group, an acid anhydride group, a hydroxyl group, an amide group, an amino group, a glycidyl group, and preferably a carboxyl group. It is. this house,
Monomers having a carboxyl group include itaconic acid,
Ethylenically unsaturated (di)carboxylic acids such as (meth)acrylic acid, fumaric acid, maleic acid, and crotonic acid; Monomers with acid anhydride groups include ethylenically unsaturated dicarboxylic acids such as fumaric acid and maleic acid. Acid anhydrides; monomers with hydroxyl groups include hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, β-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate; amide Monomers having groups include (meth)acrylamide, N-methylol (meth)
Ethylenically unsaturated carboxylic acid alkylamides such as acrylamide, diacetone acrylamide, ethacrylamide, crotonamide, itaconamide, methyl itaconamide, maleic acid monoamide; monomers having an amino group include aminoethyl (meth)acrylate, Dimethylaminoethyl (meth)acrylate, β-aminoethyl vinyl ether, dimethylaminoethyl vinyl ether; monomers having a glycidyl group include glycidyl esters of ethylenically unsaturated carboxylic acids such as glycidyl (meth)acrylate; Examples of monomers having both a group and an amide group include aminoalkylamides of ethylenically unsaturated carboxylic acids such as aminoethylacrylamide, dimethylaminomethylmethacrylamide, and methylaminopropylmethacrylamide; as monomers having a glycidyl group; Examples include glycidyl esters of ethylenically unsaturated carboxylic acids such as glycidyl (meth)acrylate. (b) The monomer having a functional group can be used alone or in combination of two or more.

(c) Other monomers copolymerizable with the above components (a) to (b) include aromatic vinyl compounds such as styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, and acetic acid. Examples include vinyl, carboxylic acid vinyl esters such as vinyl propionate, and vinyl cyanides such as (meth)acrylonitrile and α-chloroacrylonitrile, with styrene and acrylonitrile being preferred. Component (c) can be used alone or in combination of two or more. The amount of components (a) to (c) used is 1 to 99.9% by weight, preferably 5 to 95% by weight of component (a).
% by weight, more preferably 10 to 90% by weight, component (b) 0.1 to 40% by weight, preferably 1 to 30% by weight, more preferably 2 to 25% by weight, component (c) 0 to 98% by weight.
9% by weight, preferably 10-94% by weight, more preferably 10-88% by weight [However, (a) + (b) + (c
)=100% by weight]. If the amount of component (a) used is less than 1% by weight, the adhesiveness of the resulting polymer powder will be poor;
b) When the component is less than 0.1% by weight [i.e. (a)
When the amount of the component exceeds 99.9% by weight], the resulting polymer powder has poor adhesiveness and poor redispersibility.

[0009] The polymer powder of the present invention is useful for various uses, but especially when used as a car mat lining, the glass transition temperature of the polymer powder usually ranges from -20 to +
The temperature is 115°C, preferably -5 to +110°C, more preferably +10 to +100°C. When the polymer powder of the present invention is used for car mat lining, if the glass transition temperature of the polymer powder is less than -20°C, drying properties will be poor;
If the temperature exceeds 115°C, it becomes difficult to obtain the rigidity of the car mat. Further, when the polymer powder of the present invention is used as a floor polish, it is preferable from the viewpoint of dispersibility in water that the types and proportions of the components (a) to (c) are as follows. (a) (meth)acrylic acid alkyl ester 30-85
Weight% (b) Ethylenically unsaturated carboxylic acid 1-30% by weight (c
) Other monomers copolymerizable with the components (a) to (b) above: 0
~69% by weight [where (a) + (b) + (c) = 10
0% by weight]

The polymer powder of the present invention has the above-mentioned (a) to (c)
It is obtained by removing water from a copolymer latex obtained by emulsion polymerizing components () in an aqueous medium. Here, the copolymer latex is added to an aqueous medium (usually water) (
It is obtained by carrying out emulsion polymerization by adding monomer components consisting of components a) to (c), a polymerization initiator, an emulsifier, a chain transfer agent, and the like. There are no particular restrictions on the polymerization initiator;
For example, hydroperoxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, and paramenthane hydroperoxide, peroxides such as benzoyl peroxide and lauroyl peroxide, and azo compounds such as azobisisobutyronitrile. Organic polymerization initiators and inorganic polymerization initiators such as persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate can be used. Note that the polymerization initiator can also be used as a so-called redox polymerization initiator in combination with a reducing agent such as sodium bisulfite.

There are no particular restrictions on the emulsifier, and any of anionic, nonionic and amphoteric surfactants can be used. These can be used alone or in combination of two or more. Among these, anionic surfactants include, for example, sulfuric acid ester salts of higher alcohols such as sodium lauryl sulfate, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, and sulfonic acid esters of aliphatic carboxylic acid esters such as sodium dioctyl sulfosuccinate. salt, sodium salt of naphthalene sulfonic acid formalin condensate, etc.
Examples of nonionic surfactants include polyethylene glycol alkyl ester types, alkylphenyl ether types, and alkyl ether types. In addition, as an amphoteric surfactant, carboxylate, sulfate ester salt, sulfonate,
Examples of phosphoric acid esters and phosphoric acid ester salts include those having amine salts and quaternary ammonium salts as cation moieties. Specifically, alkyl betaine salts include lauryl betaine, stearyl betaine, cocoamidopropyl betaine, and 2-undecylhydroxyethylimidazolium betaine salts, and amino acid types include lauryl-β-alanine and stearyl-betaine.
β-alanine, lauryl di(aminoethyl)glycine,
Octyldi(aminoethyl)glycine, dioctyldi(
Examples include salts such as aminoethyl)glycine. In order to obtain a good polymer powder, as a surfactant, sodium salt of naphthalene sulfonic acid formalin condensate and other anionic surfactants such as alkylbenzene sulfonate such as sodium dodecylbenzene sulfonate should be used. It is to use together.

There are no particular restrictions on the chain transfer agent, and α
- Methylstyrene dimer, preferably α-methylstyrene dimer containing 60% by weight or more of 2-4-diphenyl-4-methyl-1-pentene component, terpinolene, α
- Terpinene, γ-terpinene, dipentene, carbon tetrachloride, octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan, n-hexadecylmercaptan, diethylxanthogen disulfide, dimethylxanthogen disulfide, dimethylxanthogen disulfide, diisopropylxanthogen disulfide,
Tetramethylthiuram monosulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, dipentamethylenethiuram disulfide, etc. can be used, and these can be used alone or in combination of two or more. Furthermore, there are no particular limitations on the emulsion polymerization method and its conditions, and the emulsion polymerization can be carried out under conventionally known methods and conditions.

[0013] For example, the method of adding the monomer may be a one-time addition method, a divided addition method, a continuous addition method, a method of adding the monomer after emulsifying it in advance, or a combination thereof. Among these methods, the divided addition method, continuous addition method, or continuous addition method of emulsified monomers is preferable from the viewpoint of reducing the formation of coagulates and removing reaction heat. The resulting copolymer latex (aqueous dispersion) usually has a particle size of 0.01 to 2 μm, preferably 0.01 to 2 μm.
Contains particulate polymer of 0.05 to 0.5 μm. The viscosity of this copolymer latex is preferably 1 to 30,000 cp.
s, the solid content of which is preferably 10 to 65% by weight,
More preferably, it is 20 to 50% by weight. Although products with a solid content of less than 10% by weight can be produced, in consideration of the next water removal step, it is preferable that the solid content is 10% by weight or more.

In the present invention, methods for removing water from the copolymer latex and drying it into powder include spray drying, medium fluidized drying, and freeze-vacuum drying, but these methods are difficult to achieve in terms of production efficiency and cost. In this respect, the spray drying method is most preferred. In the present invention, the term "polymer powder" refers to one whose moisture content is usually 8% by weight or less, preferably 2% by weight or less. The spray drying process is usually performed in a temperature atmosphere of 50 to 170°C, preferably 70 to 120°C, using a device such as a two-fluid nozzle type atomizer, a pressure nozzle type atomizer, or a rotating disc type atomizer. Furthermore, conditions such as the inlet temperature, outlet temperature, air volume, flow rate, etc. of the spray drying device are appropriately selected depending on the type, composition, glass transition temperature, total solid content, etc. of the copolymer latex. The conditions for spray drying include, for example, an inlet temperature of 80 -
250℃, outlet temperature 50~150℃, air volume 0.5~0.
6m3/min, pressure 0.8-1.2kg/cm, flow rate 1
It is about 5 to 25 g/min.

In order to efficiently produce the polymer powder of the present invention, the copolymer latex must have a glass transition temperature of (a) -40 to +40°C. 30-99.5% by weight (solid content) and (
b) Copolymer latex over +40℃ 70~0.5
It is preferable to spray dry the mixture in which the weight percent (solids content) is mixed. (a) If the glass transition temperature of the copolymer constituting the copolymer latex is less than -40°C, (
b) Due to significant fusion of the polymer powder constituting the component, (
b) Even if copolymer latex or other lubricants are added, it is not possible to effectively prevent the fusion of component (a), and on the other hand, if the temperature exceeds +40°C, the adhesion and flexibility of component (a) will deteriorate. Therefore, when the resulting polymer powder is used as a modifier for cement compositions, mechanical strength such as bending strength and abrasion resistance may be insufficient, and the polymer powder may not be used in adhesives, etc. If it is used, a sufficient adhesive function cannot be obtained. On the other hand, (b) the glass transition temperature of the copolymer constituting the copolymer latex is higher than +40°C, preferably +5°C.
The temperature is higher than 0°C, more preferably +70 to +120°C. (b) If the glass transition temperature of the component is below +40℃,
(a) It cannot perform the function of preventing fusion of components.

Note that the glass transition temperature (T
g) is a differential scanning calorimeter (DS) manufactured by Rigaku Denki Co., Ltd.
C) under the following conditions. ■Approximately 5 g of the product is spread thinly on a glass plate and dried at 25°C for 7 days to obtain a polymer film. (2) Measure the Tg of the obtained dry film under the following conditions. Conditions: Temperature increase rate: 20°C/min Atmosphere: Nitrogen gas sample amount: 20 mg The mixing ratio of copolymer latex (a) and (b) is solid content weight ratio (a): (b) = 99.5: 0.5-30
:70, preferably 99.0:1.0 to 50:50. (b) If the proportion of the copolymer latex is less than 0.5% by weight, the effect of preventing fusion will be insufficient, and fusion will occur in the polymer powder after drying and powdering, resulting in poor blocking resistance. On the other hand, when the proportion of (b) copolymer latex exceeds 70% by weight, a polymer powder with good blocking resistance and excellent redispersibility can be obtained, but it cannot be used as an admixture in cement-based compositions, for example. In this case, the bending strength and compressive strength of the cement may decrease, and its function as a modifier may not be ensured.

[0017] In addition, when producing the polymer powder of the present invention, if necessary, especially if the glass transition temperature of the copolymer constituting the copolymer latex is less than +40°C, anti-fusing properties may be added before drying. A variety of lubricants can be added to the copolymer latex. Such lubricants include
For example, water-soluble cellulose ethers such as methylcellulose, carboxymethylcellulose, and hydroxymethylcellulose, various starches such as raw starch, oxidized starch, and esterified starch, organic salts such as calcium stearate and ammonium stearate, trimethoxysilane, and vinyltrimethoxysilane. Alkoxysilane compounds such as dextrin, polyvinylpyrrolidone,
Polyvinyl alcohol, metal salt of β-naphthalenesulfonic acid-formalin condensate, sodium tripolyphosphate,
Examples include polyvalent phosphates such as sodium pyrophosphate, and preferred are starch, dextrin, and cellulose ether. The amount of these lubricants added is 0.05 parts by weight (in terms of solid content) of the copolymer latex.
~50 parts by weight, preferably 0.1 to 35 parts by weight. By containing 0.05 to 50 parts by weight of the lubricant, a polymer powder with better blocking resistance can be obtained. However, if the lubricant exceeds 50 parts by weight, the hygroscopicity of the polymer powder may increase, resulting in poor storage stability.

The polymer powder of the present invention thus obtained has a particle size of 1 to 150 μm, preferably 2 to 1 μm.
The particle diameter is 30 μm, more preferably 5 to 100 μm, and the polymer powder having this particle size is contained in an amount of 60% or more, preferably 70% by weight or more, and even more preferably 80% by weight or more of the total amount. When the particle size of the polymer powder is less than 1 μm,
It becomes difficult to handle and has poor application workability.
On the other hand, if it exceeds 150 μm, redispersibility and adhesiveness will be poor.

The polymer powder of the present invention contains fillers, pigments,
Additives such as antifoaming agents, anti-aging agents, crosslinking agents, flame retardants, thickeners, and wetting agents can be added. Among these additives, specific examples of fillers include calcium carbonate, aluminum hydroxide, magnesium hydroxide, inorganic fillers such as glass fibers and metal fibers, plastic hollow particles such as polystyrene particles, synthetic fibers, natural fibers, etc. Examples of organic fillers include: The polymer powder of the present invention can be used as a backing agent for carpets, especially car mats, floor polishes,
Cement admixtures, adhesives, paints, paper coating adhesives, organic pigments, asphalt modifiers, tile carpet modifiers,
It is useful in a wide range of applications, including soil conditioners, dry construction materials, and muscant.

0003

[Examples] The present invention will now be described in more detail with reference to Examples. Note that parts and % in the examples are parts by weight and % by weight unless otherwise specified. Examples 1 to 7, Comparative Examples 1 to 6 ■ Production of copolymer latex In a separable flask with an internal volume of 5 liters, monomers of the type and amount shown in Table 1 and a polymerization initiator were added under a nitrogen gas atmosphere. Ammonium persulfate as an emulsifier, sodium lauryl sulfate and sodium polyoxyethylene nonylphenyl ether sulfate as an emulsifier, t-dodecyl mercaptan as a chain transfer agent, sodium ethylenediaminetetraacetate as a chelating agent, other polymerization stabilizers, water 100%
and emulsion polymerization with stirring at a polymerization temperature of 60 to 80° C. to produce 11 types of copolymer latexes. Note that the monomer was charged using a continuous addition method. The polymerization conversion rate of the obtained copolymer latex was 99.
．． The polymerization stability was 5% or more, and the polymerization stability was good, with almost no coagulum.

■Production of polymer powder The obtained copolymer latex (Examples 1 to 7, Comparative Example 1)
Regarding items 6) to 6), spray drying was performed to obtain polymer powders. In addition, regarding Comparative Example 6, spray drying was not performed for comparison with polymer powder. Spray drying was performed using L8 type manufactured by Okawara Kakoki Co., Ltd., with a rotating atomizer type nozzle at an inlet temperature of 150-170°C and a tank temperature of 70-80°C.
The test was carried out at 0°C. More than 98% of the polymer powder is in Table 1
The particle size was within the range shown in . (2) Evaluation of polymer powder Regarding the polymer powder obtained in (1) above, glass transition temperature, blocking resistance and particle size as shown below were measured by the methods described above. Blocking resistance (degree of fusion of polymer powder); 100
A load of 5 kg was applied to 1 g of polymer powder for 7 days, and the degree of fusion of the polymer powder was visually determined. ◎: No fusion ○: Partial fusion ×: Measurement of particle size of solidified polymer powder; Particle size was measured using a scanning electron microscope. Incidentally, scanning electron micrographs of the polymer powder of Example 1 are shown in FIGS. 1 to 3 (magnifications are as follows: FIG. 1 = 600 times, FIG. 2 = 1,500 times, FIG. 3 = 15,000 times).

■Evaluation of physical properties of carpet The obtained polymer powders (Examples 1 to 5, Comparative Examples 1 to 5) were sprinkled on a polyester needle-punched carpet with a cotton density of 450 g/m2 at a density of 200 g/m2. Then, the carpet was heated and pressed at 140° C. and 30 kg/cm 2 ×10 minutes to obtain a thermoformed carpet. For Comparative Example 6, a similar carpet was impregnated with copolymer latex to a solid content of 200 g/m2, and after drying,
A thermoformed carpet was obtained under the conditions of 30 kg/cm2 x 10 minutes at 40°C. The rigidity, thermoformability, heat-resistant shape retention, and water-blocking properties of this thermoformed carpet were evaluated using the following test methods. Rigidity: The thermoformed carpet was cut into a size of 2 cm x 10 cm, and the stiffness was evaluated when the obtained test piece was bent at an angle of 30° using an Olsen stiffness tester. The larger the number, the higher the rigidity.

[0023] Thermoformability: A thermoformed carpet was heated for 5 minutes in a hot air dryer at 130°C, and then molded using an uneven press molding machine, and the moldability was evaluated on a three-grade scale based on the following criteria. ◎...Good ○...Slightly unsatisfactory ×...Poor Heat-resistant shape retention;
C. and 60.degree. C. for 2 hours in a hot air dryer, and changes in shape at each temperature were evaluated using the following criteria. ◎... No deformation ○... Slight deformation ×... Significant deformation Water-blocking properties; Cut the thermoformed carpet into 30cm x 30cm pieces, pour 100cc of water onto the fiber surface, and test the polymer. The amount of water passing through to the crimping side of the powder (30 minutes) was evaluated. If the amount of water that passes through is large, the water-blocking properties will be poor. ◎... Amount of water passing through is less than 10 cc. O... Amount of water passing through is 10 to 50 cc. x... Amount of water passing through is more than 50 cc. The above results are shown in Table 1.

[0024]

[Table 1]

Examples 1-7 utilize polymer powders within the scope of the present invention as carpet backing adhesives. Among these, Examples 1 and 2 are cases in which (b) the type of monomer having a functional group was changed, and in both cases, it was confirmed that all physical properties were well balanced and had excellent characteristics. . Examples 3 and 4 are cases in which the glass transition temperature is high and low. In the case of Example 3, where the glass transition temperature is as high as 70°C, the heat-resistant shape retention is very good, and the glass transition temperature is high. In the case of Example 4, which is as low as 30° C., the rigidity is very good, and it can be seen that other physical properties are also well balanced in both Examples. Example 5 is a case in which butadiene is used as the component (a), and in this case as well, all physical properties are well balanced and exhibit excellent characteristics. Examples 6 and 7 are examples in which a latex having a high glass transition temperature was added after completion of polymerization in order to obtain a good polymer powder even when the glass transition temperature was low. Shows excellent blocking resistance and well-balanced carpet physical properties.

On the other hand, Comparative Examples 1 to 6 are cases in which polymer powders outside the scope of the present invention were used. Comparative Examples 1 and 5 show that (b) the monomer having a functional group is outside the scope of the present invention, and the rigidity and heat-resistant shape retention are poor, making it impossible to obtain well-balanced properties. Sex is also bad. Comparative Example 2 is a case in which the ratio of component (a) exceeds the range of the present invention, and the heat-resistant shape retention is particularly poor. Comparative Example 3 is a case in which the particle size of the polymer powder exceeds the range of the present invention, and the rigidity and heat-resistant shape retention are poor. Comparative Example 4 is a case in which component (c) exceeds the range of the present invention, and the thermoformability and heat-resistant shape retention are poor, indicating that well-balanced properties cannot be obtained. Comparative Example 6 is an example in which a copolymer latex is used, but the rigidity and water-blocking properties are poor.

Examples 8 to 10, Comparative Examples 7 to 12 ■ Production of copolymer latex A condenser, thermometer, and dropping funnel were attached to a glass reaction vessel (capacity 3 liters) equipped with a stirrer, and 100 parts of deionized water, Charge 1 part of sodium lauryl sulfate and 0.5 part of ammonium persulfate, replace the air inside with nitrogen gas, raise the internal temperature to 65°C while stirring to dissolve, and add 50 parts of deionized water in a separate container in advance. An emulsion was prepared by mixing and stirring 1 part of sodium lauryl sulfate and the monomers shown in Table 2, and the emulsion was continuously added dropwise over a period of 3 hours. During the dropwise addition, the reaction was carried out at 80° C. while introducing nitrogen gas. After completion of the dropwise addition, the mixture was further stirred at 85° C. for 2 hours, and then cooled to 25° C. to terminate the reaction, to obtain copolymer latexes (9 types of Examples 8 to 10 and Comparative Examples 7 to 12). The polymerization conversion rates of the obtained copolymer latexes were all 98% or more. Further, no coagulum was observed. The pH of the system maintained at 25° C. was then adjusted to 7 with sodium hydroxide.

■Production of polymer powder The obtained copolymer latex was subjected to a spray drying treatment,
Three types of polymer powders were obtained for the Examples (Examples 8 to 10) and five types of polymer powders were obtained for the Comparative Examples (Comparative Examples 7 to 11). Spray drying was carried out using a two-fluid nozzle, SD-1 desktop spray dryer manufactured by EYELA, under conditions of an inlet temperature of 80 to 120°C and an exhaust air temperature of 45 to 80°C. In addition, Comparative Example 12 is
No drying treatment was performed. ■ Preparation Examples 8 to 10 of aqueous composition for floor polish
Using the polymer powders (copolymer latex) obtained in Comparative Examples 7 to 12, floor polish (
An aqueous composition (for floors) was prepared.

[0029] Formulation of aqueous composition for floor polish
(Part) Polymer powder *1

80 Polyvalent metal compound *2

3.5 Wax emulsion *3
15 Alkali-soluble resin *4
5
Fluorine surfactant *5

0.5*1) Add a film-forming agent mixed in a ratio of tributoxyethyl phosphate/carbitol = 1/4 (weight ratio) to the polymer powder and raise the minimum film-forming temperature to 5°C.
The solid content was adjusted to 15% by adding deionized water. In addition, in Comparative Example 12, a copolymer latex was used, and the formulation and solid content were adjusted to be the same as above. *2) 14% polyvalent metal compound ZnO, 12% ammonium carbonate, 20% aminoacetic acid, 30% ammonia water, 100% deionized water,
Mixed and dissolved. *3) Wax emulsion; manufactured by Toho Chemical Co., Ltd., HY
TEC E-4B, solid content adjusted to 15%. *4) Alkali-soluble resin; ARCO Chemical
SMA-2625A (styrene-maleic acid resin with acid value = 220, molecular weight = 1,900) manufactured by Al Company, and the solid content was adjusted to 15%. *5) Fluorine surfactant; manufactured by Sumitomo 3M, FC-12
9 was adjusted to have a solid content of 1%.

■Evaluation of aqueous composition for floor polish Redispersibility: After making a 10% aqueous solution of the polymer powder, the pH of the aqueous solution was adjusted to 8.5 with aqueous ammonia and stirred.
Judgment was made visually. ○...Completely returned to the original emulsion state. Δ: Slightly dispersed, resulting in a creaming state. ×... Not dispersed at all. Drying property: 10 g of the aqueous floor polishing composition was applied per 1 m 2 on the homogeneous style, and the drying property was evaluated. ○: Dried in less than 5 minutes. △: Dry for 5 minutes or more and less than 10 minutes. ×: Dry for 10 minutes or more. Black heel mark resistance; homogeneous style,
10% of the aqueous composition for floor polish per 1 m2.
g was applied and then dried. This operation was repeated three times to prepare a sample. This sample was installed in a high traffic area for 10 days and the black heel mark (BH
The degree of adhesion of M) was observed. ○: Almost no BHM adhesion. △...BHM was slightly attached. ×...Things with a lot of BHM attached.

Leveling property: on homogeneous style,
10% of the aqueous composition for floor polish per 1 m2.
g was applied, diagonal lines were immediately drawn in an X shape, and then dried. This operation was repeated three times to prepare a sample. After drying this sample, the degree of disappearance of this line was determined. ○...Things that have completely disappeared. △・・・Almost disappeared. ×...What was left. Table 2 shows the evaluation results of each aqueous floor polish composition obtained in the above Examples and Comparative Examples.

[0032]

[Table 2]

Examples 8 to 10 are examples of aqueous compositions for floor polish using polymer powders within the scope of the present invention, and exhibit the desired performance of the present invention. On the other hand, in Comparative Example 7, the (meth)acrylic acid alkyl ester as component (a) was outside the scope of the present invention, and the redispersibility of the polymer powder in water was poor, resulting in poor drying properties and black heel resistance. Poor marking and leveling properties. In Comparative Example 8, the component (c), styrene, was outside the scope of the present invention, and the redispersibility and leveling properties of the polymer powder in water were poor. Comparative examples 9-10
The functional group-containing monomer as component (b) is outside the scope of the present invention, and the drying properties, black heel mark resistance, and leveling properties after tile application are poor. In Comparative Example 11, the particle size of the polymer powder was outside the range of the present invention, the redispersibility was poor, and the drying properties after tile application, black heel mark resistance, and leveling properties were poor. Comparative Example 12 is an example in which a copolymer latex within the scope of the present invention was applied to a tile, and although the physical properties of the tile were satisfactory, the drying properties were poor.

[0034]

As compared with conventional polymer powders, the polymer powder of the present invention has improved coating workability, adhesive strength, and redispersibility, and also has excellent storage stability.

[0035]

[Brief explanation of the drawing]

FIG. 1 is an electron micrograph at 600x magnification of the particle structure of a polymer powder.

[Figure 2] Figure 2 shows the particle structure of polymer powder at a magnification of 1,50.
This is a 0x electron micrograph.

FIG. 3 shows the particle structure of the polymer powder at a magnification of 15,0.
This is an electron micrograph at 00x magnification.

Claims (3)

[Claims] Claim 1: The polymer component is (a) (meth)acrylic acid alkyl ester and/or conjugated diene 1-9
9.9% by weight, (b) 0.1 to 4 monomers having functional groups
0% by weight, and (c) 0 to 98.9% by weight of other monomers copolymerizable with components (a) to (b) above [however, (
a)+(b)+(c)=100% by weight] and has a powder particle size of 1 to 150 μm. 2. Comprising the polymer powder according to claim 1,
A polymer powder for car mat lining, and having a glass transition temperature of -20 to +115°C. 3. The polymer component comprises (a) 30 to 85% by weight of (meth)acrylic acid alkyl ester, (b) 1 to 30% by weight of ethylenically unsaturated carboxylic acid, and (c) the above (a) to (b) Other monomers copolymerizable with component 0 to 6
A polymer powder for floor polishing comprising 9% by weight and having a powder particle size of 1 to 150 μm.