JP2002188059A - Composition for polishing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for polishing agents excellent in endurance, leveling property, gloss, water resistance, resistance to detergents and suitability for dry puff. SOLUTION: This composition for polishing agents comprises a copolymer obtained by carrying out emulsion polymerization of (A) 100 pts.wt. ethylenic unsaturated monomer mixture composed of (a) 3-30 wt.% ethylenically unsaturated carboxylic acid monomer, (b) 10-80 wt.% (meth)acrylic acid alkyl ester monomer and (c) 0-87 wt.% other monomer copolymerizable with these components (a) and (b) [wherein (a)+(b)+(c)=100 wt.%] with (B) 0.1-30 pts.wt. crosslinking unsaturated monomer. Swelling ratio of the copolymer-containing composition with a solvent is 10-500%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for a polishing agent which is suitable for polishing a floor material and the like, and has excellent durability, leveling property, water resistance, gloss, detergent resistance, dryness suitability and the like. .

[0002]

2. Description of the Related Art In general, a beautiful appearance is required for flooring materials of department stores and convenience stores, but these flooring materials are subjected to severe contact by customers' shoes (especially high heels for women). Coating agents (glazing agents) for flooring and the like are required to have high durability.

As a coating agent having excellent durability, for example,
Japanese Patent Publication No. Hei 8-50157 discloses an aqueous coating composition containing a monocarboxylic acid containing a metal sulfonate group containing a heavy metal such as copper or iron. Such coating compositions containing heavy metals have excellent durability and are widely used as polishes for floor materials and the like.

However, in recent years, with the growing interest in environmental issues, there is a need in the market for polishes for flooring and the like which are not directly related to the cause of water pollution and the like if handled under appropriate management. As a result, interest in the environment is increasing, and development of a polishing agent having high durability regardless of the use of such heavy metals is required.

[0005] As an aqueous polishing agent not using heavy metals, Japanese Patent Publication No. 1-59310 discloses an aqueous polishing agent using a crosslinkable unsaturated monomer. Such aqueous polishes containing no heavy metal and containing a crosslinkable unsaturated monomer are excellent in boiling resistance, but in recent years a higher level of durability has been demanded and satisfactory in durability. I couldn't do it.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide an environmentally friendly, glossy material having excellent durability, leveling properties, water resistance, gloss, detergent resistance, and dryness suitability regardless of the use of heavy metals. An object of the present invention is to provide a composition for a dispensing agent.

[0007]

According to the present invention, there is provided a composition for a polishing agent comprising (A) (a) 3 to 30% by weight of an ethylenically unsaturated carboxylic acid monomer, and (b) alkyl (meth) acrylate. 10 to 80% by weight of an ester monomer, and (c) 0 to 87% by weight of another monomer copolymerizable with the component (a) and the component (b) [where (a) + (b) + (C) = 1
00% by weight] and (B) a copolymer obtained by emulsion polymerization of 0.1 to 30 parts by weight of a crosslinkable unsaturated monomer. The composition containing the polymer has a solvent swelling ratio of 10 to 500%.

[0008] Here, the solvent swelling ratio is defined as the value obtained when diethylene glycol monoethyl ether (Carbitol (registered trademark)) is used as a solvent, and ₁ g of a polymer film is immersed in the solvent and expanded to become ₂ g. Swelling ratio ((w ₁ + w ₂ ) / w ₁ × 100 (%)). When the solvent swelling ratio is less than 10%, the film forming property may be poor. On the other hand, when the solvent swelling ratio exceeds 500%, black heel mark resistance, scuff resistance, and dryness suitability may be poor.

In this case, the copolymer is obtained by emulsion polymerization of (B) 0.1 to 10 parts by weight of a crosslinkable unsaturated monomer with respect to 100 parts by weight of the (A) ethylenically unsaturated monomer. More preferably, it is obtained by:

The above composition for a polishing agent can take the following modes (1) to (5).

(1) It is preferable that the difference ΔTa between the minimum temperature T1 and the maximum temperature T2 in the transition region of the copolymer is 30 ° C. or more in a differential calorimetry curve obtained by a differential scanning calorimeter. If the difference ΔTa is less than 30 ° C., the durability will be poor.

(2) The copolymer preferably has at least two glass transition points, and the difference ΔTb between the highest glass transition point and the lowest glass transition point is preferably 5 ° C. or more. If the difference ΔTb is less than 5 ° C., the effect of improving durability cannot be recognized.

(3) The molecular weight between crosslinking points of the copolymer is as follows:
Preferably from 1,000 to 100,000,
It is more preferably from 2,000 to 80,000,
More preferably, it is 4,000 to 50,000.

Here, the molecular weight between cross-linking points means a molecular weight determined from a swelling ratio when a polymer reaches a swelling equilibrium with a good solvent. In the present invention, a cross-linking point when toluene is used as a good solvent is used. Intermolecular weight.

The copolymer has a molecular weight between crosslinking points of 1,000.
If it is less than 0, the film formability may be poor. On the other hand, when the molecular weight between crosslinking points of the copolymer exceeds 100,000, black heel mark resistance, scuff resistance,
There is a case that the dry suitability is inferior.

(4) The copolymer preferably contains less than one chemical equivalent of an alkaline earth metal compound based on the carboxyl group contained in the copolymer. In this case, when the content of the alkaline earth metal compound exceeds 1 chemical equivalent, the water resistance is poor.

(5) The film made of the composition containing the copolymer preferably has a film breaking strength of 4 MPa or more.

In the present invention, the film breaking strength is:
About 0.15 m formed from the composition containing the copolymer
m refers to the maximum strength when a film having a thickness of m is pulled at a pulling speed of about 200 mm / min.

If the film breaking strength is less than 4 MPa, the durability, especially the scuff resistance, may be poor.

(6) The polishing composition can be used as a polishing material for flooring.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The polishing composition of the present invention will be described in detail below. In the present embodiment, (A) the ethylenically unsaturated monomer and (B) the crosslinkable unsaturated monomer used for the production of the composition for a polishing agent of the present invention are referred to as component (A) and ( Sometimes referred to as B) component.

(Composition for Polishing Agent) (Composition of Monomer) In the production of the composition for polishing agent of the present invention, (A) the ethylenically unsaturated monomer used for (A) the ethylenically unsaturated monomer Specific examples of the saturated carboxylic acid monomer or the one that changes to a carboxyl group-containing ethylenically unsaturated monomer during emulsion polymerization using an aqueous medium include the following.

(A) Monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid (b) Dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid (c) Methyl maleate, methyl itaconate and β-methacryloxy Half esters such as ethyl acid hexahydrophthalate (d) Anhydrides of the unsaturated carboxylic acids of the above (a) and (b). For example, acrylic anhydride, maleic anhydride, and the like are converted into carboxylic acids during emulsion polymerization in an aqueous medium, and thus can be used as monomers during emulsion polymerization.

(E) Potassium, sodium, ammonium, magnesium and calcium salts of (a) to (d). These can be used alone or in combination of two or more.

Among them, (a) the ethylenically unsaturated carboxylic acid monomer is more preferably (a) a monocarboxylic acid, (b) a dicarboxylic acid, (c) a half ester, and (d) a dicarboxylic acid. At least one selected from the group consisting of acid anhydrides is used.

The amount of the (a) ethylenically unsaturated carboxylic acid monomer in the (A) ethylenically unsaturated monomer in the copolymer is preferably from 3 to 30% by weight, preferably 4 to 30% by weight. -20% by weight, more preferably 5-1% by weight.
More preferably, it is 5% by weight. If it is less than 3% by weight, the durability may be reduced, and if it exceeds 30% by weight, the leveling property may be poor.

The (b) alkyl (meth) acrylate monomer used for (A) the ethylenically unsaturated monomer is a (meth) acrylic acid ester. (Meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n
-Butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, i-amyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , N-octyl (meth) acrylate, cyclohexyl (meth) acrylate, etc., preferably those having 1 to 8 carbon atoms in the alkyl group, more preferably methyl methacrylate, ethyl (meth) acrylate, n-butyl (meth) A) acrylate, i-butyl (meth) acrylate.

In the present invention, the amount of the (b) alkyl (meth) acrylate monomer used in the (A) ethylenically unsaturated monomer is preferably from 10 to 80% by weight, preferably from 20 to 70% by weight. %, More preferably 25 to 65% by weight. 1
If it is less than 0% by weight, the durability may be reduced, and if it exceeds 80% by weight, the gloss may be poor.

(A) (c) Other monomers used for the ethylenically unsaturated monomer include benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, alkylphenoxyethyl (meth) acrylate, and phenoxydiethylene glycol. (Meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, alkylphenol ethylene oxide (meth) acrylate, alkylphenol propylene oxide (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, ethylene glycol (meth) acrylate monophthalate, Ethylene glycol (meth) acrylate hydroxyethyl phthalate, etc .; hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate Hydroxyalkyl (meth)
Acrylates, polyethylene glycol and / or polypropylene glycol (meth) acrylate; vinyl compounds such as vinyl chloride, vinylidene chloride, vinyl acetate, and fatty acid vinyl ester; trifluoroethyl (meth) acrylate, pentadecafluorooctyl (meth) acrylate and the like Fluorine atom-containing monomer; styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene, 4-ethylstyrene, 4-ethoxystyrene, 3,4-dimethylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chloro-3-methylstyrene, 4-t-butylstyrene,
Aromatic vinyl monomers such as 2,4-dichlorostyrene, 2,6-dichlorostyrene and 1-vinylnaphthalene; ethylenically unsaturated carboxylic acids such as monoamines, aminoethyl acrylate, dimethylaminoethyl acrylate and butylaminoethyl acrylate Aminoalkyl esters of acids; Aminoalkylamides of ethylenically unsaturated carboxylic acids such as aminoethylacrylamide, dimethylaminomethylmethacrylamide, and methylaminopropylmethacrylamide; vinyl cyanide monomers such as (meth) acrylonitrile and α-chloroacrylonitrile The other monomer (c) may be used alone or as a mixture of two or more.

The amount of the other monomer (c) used in (A) the ethylenically unsaturated monomer in the copolymer is from 0 to 87.
%, More preferably 10 to 80% by weight, even more preferably 15 to 70% by weight. If it exceeds 87% by weight, the durability will be poor.

In the present invention, (B) a crosslinkable unsaturated monomer refers to a monomer that gives a crosslinked structure to a part of the polymer to be produced, and specific examples thereof include the following. .

Epoxy compounds such as allyl glycidyl ether, glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate; divinylbenzene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate , Tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, butanediol di (meth) ) Acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra ( Data) acrylate, polyfunctional monomers such as allyl (meth) acrylate; (meth) acrylamide, N- methylol (meth) acrylamide, N- methoxymethyl (meth) acrylamide, N-
Acid amide compounds such as butoxymethyl (meth) acrylamide, N, N'-methylenebisacrylamide, diacetone acrylamide, maleic amide, and maleimide; γ-methacryloylpropanetrimethoxysilane;
silicone compounds such as reactive silicones such as α- (3-methacryloxypropyl) polydimethylsiloxane; aldehyde group-containing monomers such as acrolein, formylstyrene, formyl-α-styrene, (meth) acrylamidobivalinaldehyde; diacetone Keto group-containing monomers such as (meth) acrylamide, vinyl methyl ketone, vinyl ethyl ketone, vinyl n-propyl ketone, vinyl i-propyl ketone, vinyl n-butyl ketone, vinyl i-butyl ketone, vinyl sec-butyl ketone, and vinyl t-butyl ketone And acetoacetoxy (meth) acrylate and allyl acetoacetate.

In the present invention, when the amount of (A) the ethylenically unsaturated monomer used is 100 parts by weight, the amount of (B) the crosslinkable unsaturated monomer used is 0.1 to 30 parts by weight. Preferably, it is more preferably 0.1 to 10 parts by weight,
More preferably, it is 0.1 to 6 parts by weight. If the amount of the component (B) is less than 0.1 part by weight relative to the amount of the component (A), the durability may be reduced. If the amount is more than 30 parts by weight, the film formability may be poor.

(Solvent Swelling Ratio) The solvent swelling ratio is determined by polymerizing the component (A) and the component (B) and forming a film containing the copolymer into a solvent (diethylene glycol monoethyl ether). ) And swell.

In the present invention, the solvent swelling ratio is 10 to 5
It is preferably 00%, more preferably 50 to 450%, even more preferably 100 to 400%. If the solvent swelling ratio is less than 10%, the film forming property may be poor, while the solvent swelling ratio may be 500
%, Black heel mark resistance, scuff resistance, and dryness suitability may be poor.

(Differential calorific value curve) In the present invention, (A)
The copolymer obtained by polymerizing the component and the component (B) is:
In the differential calorimetry curve obtained by the differential scanning calorimeter, the difference ΔT between the minimum temperature T1 and the maximum temperature T2 in the transition region is shown.
a is preferably 30 ° C. or higher.

When there are a plurality of transition regions,
The temperature T1 indicates the lowest temperature in the transition region on the lowest temperature side, and the temperature T2 indicates the highest temperature in the transition region on the highest temperature side.

When the difference ΔTa between the minimum temperature T1 and the maximum temperature T2 in the transition region is 30 ° C. or more, when this copolymer is used as a polishing agent, a polishing agent having excellent durability can be obtained. Obtainable.

Further, the copolymer of the present invention may have only one glass transition point or a plurality of glass transition points in the transition region of the differential calorific value curve.

When there are at least two glass transition points in the transition region of the differential calorific value curve, the difference ΔTb between the highest glass transition point and the lowest glass transition point is preferably 5 ° C. or more. In the present invention, in the same particle, by having a hetero-phase structure in which a copolymer having a low glass transition point and a copolymer having a high glass transition point are present,
The desired performance is obtained. That is, the durability can be improved by having a copolymer having a low glass transition point in the particles. Further, by having a copolymer having a high glass transition point in the particles, other physical properties such as water resistance and rigidity can be maintained at a high level.

(Molecular Weight Between Crosslinking Points) The molecular weight between crosslinking points can be determined by a method based on swelling equilibrium. A good solvent for the polymer chains generally tries to dissolve and spread the polymer chains, but in crosslinked polymers this is suppressed by the elasticity of the network and reaches swelling equilibrium. Under the equilibrium condition, the following equation (Equation (1)) holds. Equation (1):

[0042]

(Equation 1)

V: crosslink density (mol / cm ² ) g: volume fraction of gel in polymer V: molar volume of solvent (molecular volume) = molecular weight / density V _r : polymer volume in expanded polymer gel Rate f: Functional number of crosslinking μ: Interaction parameter of polymer / solvent Here, 1 / v corresponds to the molecular weight between crosslinking points.

(Average Particle Size) The average particle size of the copolymer used in the present invention is preferably from 0.02 to 0.5 μm.
m, more preferably 0.05 to 0.2 μm, particularly preferably 0.06 to 0.1 μm. If it exceeds 0.5 μm, the gloss may be inferior, and if it is less than 0.02 μm, the leveling property may be inferior.

(Production Method of Floor Polishing Composition) The production method of the aqueous dispersion in the present invention is not particularly limited. For example, it can be obtained as an emulsion of a copolymer by a usual emulsion polymerization method. it can. More specifically,
For example, the above monomer, emulsifier, polymerization initiator, reducing agent, chain transfer agent, chelating agent, pH adjuster, etc. are added to an aqueous medium, and the polymerization reaction is carried out at a temperature of 30 to 100 ° C. for about 1 to 30 hours. An aqueous dispersion can be obtained by performing the method.

As a method of polymerizing the monomers in the above-mentioned monomers, a known method, for example, a method of charging all the monomer systems in a reaction system at once, a method of partially using each monomer, After charging and reacting, the remaining components can be continuously or dividedly charged, or each monomer can be charged continuously.

(Polymerization Initiator) In the emulsion polymerization, first, the polymerization initiator is radically decomposed in the presence of heat or a reducing substance to cause a polymerization initiation reaction, thereby effecting addition polymerization of monomers.

Examples of the polymerization initiator include water-soluble and oil-soluble polymerization initiators.

Examples of the water-soluble polymerization initiator include persulfate, hydrogen peroxide, t-butyl hydroperoxide and the like, and these can be used in combination with a reducing agent if necessary.

The reducing agent includes, for example, sodium pyrobisulfite, sodium hydrogen sulfite, sodium thiosulfate, L-ascorbic acid and its salts, sodium formaldehyde sulfoxylate, ferrous sulfate and the like.

As the oil-soluble polymerization initiator, for example,
2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis-2,4-dimethylvaleronitrile, 1,1 '-Azobis-cyclohexane-1-carbonitrile, benzoyl peroxide, dibutyl peroxide, cumene hydroperoxide and the like. Among them, cumene hydroperoxide, isopropylbenzene hydroperoxide, paramenthane hydroperoxide, azobisisobutyronitrile, benzoyl peroxide, t-butyl hydroperoxide, 3,5,5-trimethylhexanol peroxide And t-butylperoxy (2-ethylhexanoate) are preferred.

These polymerization initiators can be used after being dissolved in a monomer or a solvent.

The content of these polymerization initiators is preferably 0.03 to 3 parts by weight, and more preferably 0.1 to 0.4 parts by weight, based on 100 parts by weight of all monomers. Is more preferred. When emulsion polymerization is performed using these polymerization initiators, the polymerization initiator is added to the reaction system all at once, or a part of the polymerization initiator is added batchwise, continuously added, or a combination of both. A method of adding can be used.

(Chain transfer agent) In order to adjust the molecular weight, a chain transfer agent may be added. Examples of the chain transfer agent include halogenated hydrocarbons (eg, carbon tetrachloride, chloroform, bromoform), mercaptans (eg, n-dodecyl mercaptan, t-dodecyl mercaptan, n-octyl mercaptan, alkyl thioglycolates), xanthogens (Eg, dimethyl xanthogen disulfide, diisopropylxanthogen disulfide), terpenes (eg, dipentene, terpinolene), 1,1-diphenylethylene,
α-methylstyrene dimer [2,4-diphenyl-4
-Methyl-1-pentene (I), 2,4-diphenyl-
It comprises at least one of 4-methyl-pentene (II) and 1,1,3-trimethyl-3-phenylindane (III), and is preferably (I) / ((II) + (I
II)) (weight ratio) = 40-100 / 0-60], unsaturated cyclic hydrocarbon compound (for example, 9,10-
Dihydroanthracene, 1,4-dihydronaphthalene,
Indene, 1,4-cyclohexadiene), unsaturated heterocyclic compounds (eg, xanthene, 2,5-dihydrofuran) and the like.

The amount of the chain transfer agent to be used is preferably 0 to 5 parts by weight based on 100 parts by weight of all monomers. In addition, the method of adding the chain transfer agent into the polymerization system includes batch addition,
Batch addition, continuous addition, or a combination thereof may be used.

(Emulsifier) Examples of the emulsifier include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and so-called reactive emulsifiers which can be copolymerized with the aforementioned monomers. And water-soluble polymers can be used alone or in combination of two or more.

Examples of the anionic surfactant include sulfates of higher alcohols, alkylbenzene sulfonates, aliphatic sulfonates, sulfates of polyethylene glycol alkyl ether and polyethylene glycol polypropylene glycol alkyl ether, and the like. For example, higher alcohol sulfate sodium salt, alkylbenzenesulfonic acid sodium salt,
Dialkyl succinate sodium sulfonate,
And sodium alkyldiphenyl ether disulfonate. Of these, lauryl sulfate sodium salt, polyoxyethylene polyoxypropylene alkyl ether sulfate, and polyoxyethylene alkyl ether sulfate are preferably used.

Examples of the nonionic surfactant include, for example,
Examples thereof include polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene nonylphenyl ether, and polyoxyethylene octylphenyl ether. Of these, polyoxyethylene alkyl ether and polyoxyethylene polyoxypropylene alkyl ether are preferred.

As the amphoteric surfactant, lauryl betaine is preferably used.

As the cationic surfactant, alkylpyridinyl chloride, alkylammonium chloride and the like can be used.

Examples of so-called reactive emulsifiers which can be copolymerized with the above-mentioned monomers include, for example, sodium styrenesulfonate, sodium allylalkylsulfonate, sulfates of polyoxyethylene alkyl allyl ether, polyoxyethylene polyoxypropylene alkyl allyl ether And the like can also be used as an emulsifier.

When a water-soluble polymer is used as an emulsifier,
Preferred water-soluble polymers include, for example, polyvinyl alcohol, polyacrylate, water-soluble (meth) acrylate copolymer, styrene-maleic acid copolymer,
Styrene- (meth) acrylic acid copolymer salt, poly (meth) acrylamide, poly (meth) acrylamide copolymer and the like can be mentioned. Among them, partially saponified polyvinyl alcohol, water-soluble (meth) acrylate copolymer, styrene-maleic acid copolymer salt,
Salts of carboxylated aromatic vinyl copolymers such as styrene- (meth) acrylic acid copolymer salts are preferred.

The amount of the emulsifier used is preferably 0.05 to 5 parts by weight based on 100 parts by weight of the total monomers.

These emulsifiers are preferably added to the polymerization system all at once, batchwise, continuously added, or a combination of both.

(Polymerization regulator) In the present invention, various polymerization regulators may be added as necessary. For example, pH
Regulators, various chelating agents and the like can be used.

As pH adjusters, aqueous ammonia, sodium hydroxide, potassium hydroxide, ammonium hydroxide,
Sodium hydrogen carbonate, sodium carbonate, potassium carbonate,
Disodium hydrogen phosphate and the like can be mentioned. Examples of various chelating agents include glycine, alanine, sodium ethylenediaminetetraacetate and the like. The amounts of the chelating agent and the pH adjuster used were 10
It is preferably about 0 to 1 part by weight and about 0 to 1 part by weight per 0 part by weight.

Solvents used as needed in the emulsion polymerization include small amounts of methyl ethyl ketone, acetone and trichlorotrichloride as long as workability, disaster prevention safety, environmental safety and production safety are not impaired. Fluoroethane, methyl isobutyl ketone, dimethyl sulfoxide, toluene, dibutyl phthalate, methyl pyrrolidone, ethyl acetate, alcohols, cellosolves, carbitols and the like are used. The amount of the solvent used is preferably about 0 to 5 parts by weight per 100 parts by weight of all monomers.

(Polymerization Conversion) The final polymerization conversion of the copolymer used in the present invention is 90 to 100% by weight, more preferably 95 to 100% by weight.

((C) Alkaline Earth Metal Compound) In the composition for a polishing agent of the present invention, (C) an alkaline earth metal compound is contained in addition to the components (A) and (B). Preferably contains less than 1 chemical equivalent of an alkaline earth metal compound, more preferably 0.01 to 0.9 chemical equivalent, based on the carboxyl group contained in the copolymer, More preferably, it contains 0.02 to 0.8 chemical equivalent. in this case,
When the content of the alkaline earth metal compound exceeds 1 chemical equivalent, water resistance is poor.

As the component (C) used in the present invention,
For example, calcium hydroxide, magnesium hydroxide, calcium acetate, alkaline earth metal salts such as magnesium acetate and the like can be mentioned, before and after addition of ammonia, ethanolamine, alkylaminoethanol, carbodiimide and its derivatives, and polycarbodiimide resin May be added and heated. Among them, calcium acetate,
Calcium hydroxide and the like are preferred.

(Other Additives) In addition to the component (A), the component (B) and the component (C) used as required, the composition for a polishing agent of the present invention further comprises (D) a wax. Contains additives such as emulsion, (E) alkali-soluble resin, (F) film-forming aid, (G) wetting agent, dispersant, leveling agent, colloidal silica, urethane emulsion, preservative, defoaming agent, etc. Can be.

Examples of the wax emulsion (D) include polyethylene emulsions. These are 0 to 40 parts by weight, preferably 5 to 30 parts by weight, in terms of solid content, based on 100 parts by weight of the copolymer.
More preferably, it can be contained in an amount of 10 to 30 parts by weight. If it exceeds 40 parts by weight, the gloss may be poor and the appearance may be impaired.

(E) Examples of the alkali-soluble resin include styrene-maleic acid copolymer resin, shellac,
Rosin-modified maleic resin and the like can be mentioned. These resins can improve the leveling property and the releasability of the composition for a polishing agent of the present invention. These resins are used in an amount of 0 in terms of solid content based on 100 parts by weight of the copolymer.
-50 parts by weight, preferably 5-40 parts by weight, more preferably 10-30 parts by weight. If it exceeds 50 parts by weight, the durability will be poor.

(F) Examples of the film-forming aid include alkylene glycols and esters thereof such as tributoxy phosphate, tributoxyethyl phosphate, polyhydric alcohols and diethylene glycol monoalkyl ether, isophorone, benzyl alcohol and Monoethyl such as methoxybutanol-1, monomethyl ether, benzyl butyl phthalate, dibutyl phthalate,
Additives such as dimethyl phthalate, triphenyl phosphate, and carbitol-based film-forming assistants, and pigments and other additives used in ordinary paints can be added. These are 0 to 50 parts by weight, preferably 5 to 40 parts by weight, more preferably 10 to 100 parts by weight, based on 100 parts by weight of the copolymer.
-30 parts by weight. If it exceeds 50 parts by weight, the durability will be poor.

(G) Additives such as wetting agents, dispersing agents, leveling agents, colloidal silica, urethane emulsions, preservatives, antifoaming agents, etc. Examples of the wetting agent include potassium salts of perfluoroalkyl carboxylic acids and silicon-based wetting agents. Agents, acetylene-based wetting agents and the like.

Examples of the dispersant include an anionic surfactant and a nonionic surfactant.

Examples of the leveling agent include rosin acid esters and the like.

As preservatives, for example, 2-methyl-4
-Isoazolin-3-one and 5-chloro-2-methyl-
A mixture of 4-isoazolin-3-one and the like can be mentioned.

A hydrazide compound such as adipic acid dihydrazide may be added to the carbonyl group-containing copolymer such as acrolein and diacetone acrylamide.

The composition for a polishing agent of the present invention can be used as a polishing agent for flooring, furniture, vehicles and the like. When the glazing composition of the present invention is used as a glazing agent for flooring, wiping with a usual method, brushing, applying by brush spray, drying quickly by air drying or heating,
A strong coating film can be formed.

[0081]

The present invention will be described below in detail with reference to examples. In this example, a composition for floor polishes used for polishes floor materials was prepared, and its properties were evaluated. In the examples, "%" and "part" mean "% by weight" and "part by weight", respectively, unless otherwise specified. In addition, the measurement of various physical properties in the examples was performed according to the following methods.

(Example 1) (Production method of floor polisher composition) (1) Preparation of dispersion liquid of copolymer A condenser, a thermometer, and a dropper were placed in a glass reactor (with a capacity of 3 liters) equipped with a stirrer. Attach a funnel, charge 100 parts by weight of ion-exchanged water, 0.5 parts by weight of sodium lauryl sulfate, and 0.1 parts by weight of ammonium persulfate. After replacing the air inside with nitrogen, adjust the internal temperature to 65 ° C. while stirring. Then, in a separate container, 50 parts by weight of ion-exchanged water, 1 part by weight of sodium lauryl sulfate, and 0.1 part of ammonium persulfate
A part by weight and the monomers shown in Table 1 were mixed and stirred to form an emulsion, which was dropped continuously for 3 hours. During the dropwise addition, the reaction was carried out at 80 ° C. while introducing nitrogen. After dropping,
After further stirring at 85 ° C. for 2 hours, the reaction was cooled to 25 ° C. to complete the reaction.

The polymerization conversion of the obtained copolymer was 98% by weight or more. Also, generation of coagulated material was hardly observed.

(2) Preparation of Copolymer Under stirring and maintaining at 25 ° C., the dispersion of the copolymer prepared above was adjusted to pH 7 with potassium carbonate, and calcium acetate was added as component (C) to (a). A) 0.04 chemical equivalent was gradually added to the carboxyl group of the component) to prepare a copolymer.

(Example 2) A similar apparatus was attached to the same reaction vessel as in Example 1, and 100 parts by weight of ion-exchanged water, 0.5 part by weight of sodium lauryl sulfate and 0.1 part by weight of ammonium persulfate were subjected to the reaction. After charging into a container and replacing the internal air with nitrogen, the internal temperature was adjusted to 80 ° C. while stirring. Then, in a separate container in advance, ion-exchanged water 1
0 parts by weight, 0.2 parts by weight of sodium lauryl sulfate, 0.02 parts by weight of ammonium persulfate, and an emulsion obtained by mixing and stirring the first-stage component monomers shown in Table 1 at 80 ° C.
After continuous dropping into the reaction vessel over 6 minutes, the reaction was carried out at the same temperature for 10 minutes. Subsequently, in a separate container, 40 parts by weight of ion-exchanged water, 0.8 parts by weight of sodium lauryl sulfate, 0.08 parts by weight of ammonium persulfate, and the second-stage component monomer described in Table 1 were mixed and stirred in advance. The resulting emulsion was continuously dropped at the same temperature over 144 minutes. The subsequent steps were carried out in the same manner as in Example 1 to obtain a copolymer having a polymerization conversion of 98% by weight or more.

Example 3 In Example 2, 40 parts by weight of ion-exchanged water and 0.8 part by weight of sodium lauryl sulfate were added when 40% equivalent of the emulsion of the first stage component shown in Table 1 was continuously dropped. Parts, and 0.08 parts by weight of ammonium persulfate, and the emulsion obtained by mixing and stirring the second-stage component monomers shown in Table 1 were placed in a container containing the first-stage component emulsion over 90 minutes. While continuously dropping, and continuously dropping continuously from the vessel containing the first-stage component emulsion to the reaction vessel, the subsequent steps are performed in the same manner as in Example 1 to obtain a copolymer having a polymerization conversion rate of 98% by weight or more. Obtained.

Example 4 In Example 4, except that the composition and amount of the monomer used were different.
A copolymer was prepared in the same manner as in the above method.

(Example 5) In Example 5, except that the composition and amount of the monomer used were different.
A copolymer was prepared in the same manner as in the above method.

(Comparative Examples 1 to 4) In Comparative Examples 1 to 4, copolymers were prepared in the same manner as in Example 1 except that the composition and amount of the monomers used were different. .

Comparative Example 5 In Comparative Example 5, except that the composition and amount of the monomer used and the amount of the polymerization initiator (ammonium persulfate) used were as large as 0.88 part by weight, A copolymer was prepared in the same manner as in Example 1.

Next, Examples 1 to 5 and Comparative Examples 1 to 5
For each of the copolymers obtained in the above, the differential calorimetric curve, the particle size, and the molecular weight between cross-linking points were determined by the following methods. Table 1 shows the results.

(A) Differential calorimetry curve A differential scanning calorimeter (DSC: manufactured by DuPont) was used to calculate A
The measurement was performed according to the STM method, and the differential calorific value curve was obtained. Thus, the difference ΔTa (° C.) between the minimum temperature T1 and the maximum temperature T2 in the transition region of each copolymer was determined.

The obtained copolymer was vacuum-dried at 100 ° C. for 20 hours to prepare a film. This dried film was measured using a differential scanning calorimeter (DSC: manufactured by DuPont) at a heating rate of 20 ° C./min according to the ASTM method.

Of the copolymers obtained in Examples 1 to 5,
For Examples 2 and 4, two glass transition points were observed from the DSC measurements. Therefore, in Examples 2 and 4, the minimum temperature T1 and the maximum temperature T2 in the transition region of the copolymer were determined.
From these glass transition points, together with the difference ΔTa (° C.), the difference ΔTb (° C.) between the highest glass transition point and the lowest glass transition point was determined. In addition, about Example 3,
Since the first-stage monomer component and the second-stage monomer component were continuously added, no clear glass transition point was observed and a broad peak in the transition region was obtained. Therefore, in Example 3, the minimum temperature T1 and the maximum temperature T1 in the transition region of the copolymer were determined.
2, and only the difference ΔTa (° C.) was determined.

(B) Molecular weight between cross-linking points The copolymer dispersion was placed in a Petri dish so that the film thickness was about 0.15 mm, and dried in a thermostat at 80 ° C. for 2 days. Weighed. Next, the obtained film piece was immersed in a solvent (toluene),
The swollen film that had been allowed to stand for a day was wiped off with filter paper, dried to remove the solvent (toluene), and weighed. The molecular weight between crosslinking points was determined using the above-mentioned calculation formula (formula (1)).

In the equation (1), g, V, V _r , f, μ
Were determined by the following methods. g: Determined by the following equation (Equation (2)), assuming that the volume fraction of gel in the polymer is divided by the weight fraction. That is, in the formula (2), the volume fraction was calculated by converting the weight fraction by the specific gravity. Formula (2): g ≒ weight of film after solvent removal / weight of film before immersion in toluene V: molar volume (molecular volume) of solvent = molecular weight / density was calculated using literature values. V _r : The polymer volume fraction in the swollen polymer gel is
It was determined by the following equation (Equation (3)). Equation (3):

[0097]

(Equation 2)

Here, the swelling solvent weight means the weight of the solvent (toluene) in the swelling film. In Examples 1 to 5 and Comparative Examples 1 to 5, the swelling solvent was obtained by subtracting the film weight after removing the solvent (toluene) from the weight of the film (swelling film) after immersion in toluene (in a state swollen with toluene). The weight was determined. The specific gravity of each polymer was calculated assuming that the specific gravity of each polymer obtained in Examples 1 to 5 and Comparative Examples 1 to 5 was 1.155. Further, the calculation was performed with the solvent specific gravity (toluene specific gravity) set to 0.866. f: The number of crosslinks is determined by the structure of the crosslinked polymer. In Examples 1 to 5 and Comparative Examples 1 to 5, f = 2. μ: The polymer / solvent interaction parameter is μ = 0.
Calculated as 52 (when the solvent is toluene).

(C) Average Particle Size The average particle size of the obtained copolymer was determined by a conventional method using LPA-3100 manufactured by Otsuka Electronics Co., Ltd.

(3) Preparation of composition for floor polishes A composition for floor polishes was prepared according to the following formulation. (Blending of composition for floor polisher) Copolymer * 1 80 parts by weight Wax emulsion * 2 15 parts by weight Alkali-soluble resin * 3 5 parts by weight Fluorinated surfactant * 4 0.5 parts by weight * 1 To the copolymer dispersions obtained in Comparative Examples 1 to 5 and Comparative Examples 1 to 5, a film-forming aid mixed at a ratio of tributoxyethyl phosphate / diethylene glycol monoethyl ether = 1/4 (weight ratio) was added. The minimum film forming temperature was adjusted to 5 ° C., and ion-exchanged water was further added to adjust the solid content to 20% by weight.

* 2 Wax emulsion; trade name: HYTEC E-4B, manufactured by Toho Chemical Co., Ltd .;
It was adjusted to 0% by weight.

* 3 Alkali-soluble resin; ARCO C
Product name: SMB manufactured by chemical Company
625A (styrene having an acid value of 220 and a molecular weight of 1,900,
Maleic acid resin), and the solid content was adjusted to 15% by weight.

* 4 Fluorinated surfactant; C ₆ F ₁₇ SO ₂
N (C ₂ H ₅ ) CH ₂ COOK, the solid content was adjusted to 1% by weight.

The composition as a floor polish was evaluated by the following method.

(A) Black heel mark resistance Black heel mark resistance and scuff resistance (described later)
Is an index for evaluating durability.

The above-mentioned composition for floor polish is applied on a homogeneous style in an amount of 10 g per 1 m ² , and then dried.

This is repeated three times to produce a sample.
The sample is placed in a busy place (50-100 round trips / day) for 10 days, and the black heel mark (BHM)
Was observed, and the following three-step evaluation was performed.

：: BHM adhesion is small Δ: BHM adhesion is slightly large ×: BHM adhesion is large (b) Scuff resistance A sample was prepared in the same manner as in the evaluation of the black heel mark.
Install, observe the degree of scuffing and shrinkage,
The following three-stage evaluation was performed.

：: Scuff generation and gloss shrinkage are small Δ: Scuff generation and gloss shrinkage are somewhat large ×: Scuff generation and gloss shrinkage are large (c) Gloss Sample similar to evaluation of black heel mark Was prepared, and the sample was measured for 60 ° reflection using a Murakami gloss meter.

(D) Leveling property The above-mentioned composition for floor polishes was placed on a homogeneous style for 1 m.
Apply 10 g per ² and immediately draw a diagonal line in an X shape,
Thereafter, the operation of drying was repeated three times to produce a sample. After the drying, the degree of disappearance of the line was determined, and the following three-stage evaluation was performed.

：: Almost disappeared Δ: Slightly residual X: Almost remaining (e) Water resistance A sample was prepared in the same manner as in the evaluation of the black heel mark, and 0.1 ml of the sample was formed at the center of the sample. Water was dropped, covered with a cover glass, and allowed to stand for 60 minutes. Then, the water was absorbed and allowed to stand for 1 hour. Then, the whitening state was determined, and the following three-stage evaluation was performed.

：: No whitening was observed Δ: Some whitening was left X: Almost whitening was left (f) Detergent Resistance The composition for floor polishes was sprinkled on a vinyl chloride tile. Was applied twice, dried, and one week later, the peeling state of the coating film after rubbing for 3 minutes while immersed in a 1% solution of household neutral detergent was observed, and evaluated by the following three steps.

A: No peeling occurred.

○: Almost no peeling occurred.

X: The film was remarkably peeled.

(G) Solvent swelling ratio The composition is applied on a glass plate or a PET sheet so as to have a film thickness of about 0.15 mm, and dried at room temperature for 3 days. 0.3 g of the obtained film was immersed in 100 g of a solvent (diethylene glycol monoethyl ether) and left for 3 days. The swollen film was taken out, and the solvent adhering to the surface was wiped off with a filter paper and weighed. The solvent swelling ratio was determined by the following formula (formula (4)). Equation (4):

[0117]

(Equation 3)

(H) Film breaking strength A film was prepared in the same manner as in (g) above, and the film was pulled at a pulling speed of 200 mm / min using an autograph manufactured by Shimadzu Corporation. The maximum strength (film breaking strength) was determined.

(I) Suitability for dry head The test piece (b) for which the scuff resistance was measured was subjected to 2,50 test using a high speed buff machine DE-500 manufactured by Amano Corporation.
The buffing was performed at 0 rpm, and the dryness suitability was determined by the following equation (Equation (5)). Equation (5):

[0120]

(Equation 4)

Table 1 shows the evaluation of the composition for floor polishes obtained in the above Examples.

[0122]

[Table 1]

The evaluation shown in Table 1 will be specifically described below.

Examples 1 to 5 are examples of the composition for floor polishes of the present invention, and include black heel mark resistance, scuff resistance, gloss, leveling, water resistance, detergent resistance, and dryness suitability. In all of the cases, excellent coating performance was observed.

Comparative Example 1 is an example in which the content of the component (A) is less than the range of the present invention and the solvent swelling ratio exceeds the range of the present invention. The results were poor.

Comparative Example 2 is an example in which the amount of the ethylenically unsaturated carboxylic acid monomer exceeds the range of the present invention.
The gloss was reduced, and the leveling property, water resistance, and detergent resistance were poor.

Comparative Example 3 is an example in which the content of the component (B) is less than the range of the present invention and the solvent swelling ratio exceeds the range of the present invention, and the black heel mark resistance and the scuff resistance , And poor suitability.

Comparative Example 4 is an example in which the content of the component (B) exceeds the range of the present invention, the solvent swelling ratio is less than 10%, and the molecular weight between crosslinking points is less than 1,000. This resulted in poor formability.

Comparative Example 5 was an example in which the solvent swelling ratio was beyond the range of the present invention, and resulted in inferior black heel mark resistance, scuff resistance, and dryness suitability.
In Comparative Example 5, the amount of the polymerization initiator used was larger than that in Examples 1 to 5 and Comparative Examples 1 to 4, and thus the solvent swelled due to the low molecular weight of the obtained copolymer. It is assumed that the rate is beyond the scope of the present invention. In Comparative Example 5, the molecular weight between crosslinking points of the copolymer in toluene was larger than 100,000, resulting in inferior durability and dryness.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Takeshi Mogi 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR Co., Ltd. F-term (reference) 4J100 AC03S AC04S AG04S AJ01Q AJ02Q AJ08Q AJ09Q AL03P AL04P AL08S AL09S AL10R AL41Q AL62R AL63R AM15R BC43S CA05 CA06 CA23 DA01 DA25 JA01

Claims (8)

[Claims] (A) (a) 3 to 30% by weight of an ethylenically unsaturated carboxylic acid monomer, (b) 10 to 80% by weight of an alkyl (meth) acrylate monomer, and (c) 0 to 87% by weight of another monomer copolymerizable with the component (a) and the component (b) [where (a) + (b) +
(C) = 100% by weight] and 100 parts by weight of an ethylenically unsaturated monomer consisting of
Including a copolymer obtained by emulsion polymerization of 1 to 30 parts by weight, the solvent swelling ratio of the composition containing the copolymer is 10 to 500
%, For polishes. 2. The copolymer according to claim 1, wherein the copolymer (A) is an ethylenically unsaturated monomer (1).
(B) 0.1 to 100 parts by weight of the crosslinking unsaturated monomer.
A composition for polishing agent obtained by emulsion polymerization of 10 parts by weight. 3. The difference ΔTa between the lowest temperature T1 and the highest temperature T2 in the transition region of the copolymer according to claim 1 or 2, in a differential calorimetric curve obtained by a differential scanning calorimeter. , Polish composition. 4. The copolymer according to claim 1, wherein the copolymer has at least two glass transition points, and a difference ΔTb between a highest glass transition point and a lowest glass transition point is 5 ° C. or more. , Polish composition. 5. The copolymer according to claim 1, wherein the molecular weight between crosslinking points of the copolymer is 1,000 to 10.
A composition for a polishing agent, wherein the composition is 0.000. 6. The polishing composition according to claim 1, wherein the composition contains less than 1 chemical equivalent of an alkaline earth metal compound to the carboxyl group contained in the copolymer. 7. The glazing composition according to claim 1, wherein a film comprising the composition containing the copolymer has a film breaking strength of 4 MPa or more. 8. The glazing composition according to claim 1, which is used as a glazing agent for flooring.