JP3157464B2 - Film-forming composition and floor brightener composition using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film-forming composition suitable for forming a surface protective film on flooring materials such as vinyl tiles made of, for example, polyvinyl chloride, and a method for using the same.
And a floor brightener composition .

[0002]

2. Description of the Related Art Conventionally, a coating film as a protective film has been applied by applying a floor brightener composition (film-forming composition) to the surface of a floor material such as a vinyl tile made of polyvinyl chloride or the like. And protects the flooring, and imparts gloss and durability to the flooring by the coating film.

For example, Japanese Patent Publication No. 62-4051 discloses that a monomer composition having a specific composition is emulsion-polymerized in the presence of a crosslinked polymer obtained by emulsion-polymerizing a monomer composition having a specific composition. A floor gloss composition comprising a crosslinked polymer is disclosed. As shown in FIG. 3, the coating structure of the coating film formed by forming the floor gloss composition has a structure in which a particulate crosslinked polymer 12 is uniformly dispersed in a crosslinked polymer 11. I have.
The crosslinked polymer 11 is in close contact with the floor material 20.

[0004] For example, Japanese Patent Publication No. 60-48542 discloses a bed containing a crosslinked polymer obtained by crosslinking a polymer obtained by emulsion polymerization of a monomer composition having a specific composition with zinc oxide. A gloss composition is disclosed. As shown in FIG. 4, the coating structure of the coating film formed by forming the floor gloss composition was, as shown in FIG. 4, the zinc oxide used for crosslinking in the crosslinked polymer 21 (in FIG. 13) are uniformly dispersed. The above crosslinked polymer 2
1 is in close contact with the floor material 20.

[0005]

In recent years, there has been a demand for further improvements in various properties such as gloss and durability to be imparted to floor materials. That is, various performances required for the floor brightener composition are increasing year by year. However, the coating film formed by forming the above-mentioned conventional floor gloss composition has a certain level of performance and is practical, but it is difficult to meet the demand for further performance improvement. That is, the above-mentioned conventional floor brightener composition (film-forming composition) has a problem that it is difficult to meet further demands for improved performance.

The present invention has been made in view of the above-mentioned conventional problems, and an object of the present invention is to provide a film-forming composition having various properties further improved as compared with the above-mentioned conventional film-forming composition. ,
And a floor brightener composition using the same .

[0007]

Means for Solving the Problems In order to solve the above-mentioned conventional problems, the present inventors have developed a film-forming composition ,
The floor brightener composition used was studied diligently. As a result, in JP-B-62-4051, a film-forming composition containing a cross-linked polymer obtained by cross-linking a polymer obtained by emulsion-polymerizing a monomer composition having a specific composition with a polyvalent metal compound is used. Although the product was judged to be inferior in film-forming properties and adhesion to the base material, it was further examined in detail, and it was found that it was possible to respond to the further demand for the above-mentioned performance improvement.

That is, for example, after a monomer composition A containing a polymerizable monomer component having a specific composition and a crosslinking agent is emulsion-polymerized to form a crosslinked polymer A, the presence of the crosslinked polymer A under,
The film-forming composition obtained by emulsion-polymerizing the monomer composition B having a specific composition to form a polymer b and then adding an aqueous dispersion of a polyvalent metal compound is used as the conventional film-forming composition. The inventors have found that various properties can be further improved as compared with the composition, and have completed the present invention.

That is, in order to solve the above-mentioned problems, the composition for film formation according to the first aspect of the present invention has an ester moiety having an ester moiety such that the glass transition temperature of the polymer is 0 ° C. or lower.
(Meth) acrylic acid ester having 1 to 12 carbon atoms in the kill group
, An aromatic vinyl compound, and an α, β-unsaturated carboxylic acid.
A polymerizable monomer component comprising a combination of acid, polymerizable unsaturated
A crosslinking agent having a saturated bond two or more, polymerizable monomer forming
Weight / crosslinking agent in the range of 90/10 to 60/40
Presence of the inner comprising a monomer composition A was an emulsion polymerization, including crosslinked polymer A, so that the glass transition temperature of the polymer is 50 ° C. or less exceed 0 ° C., alkyl group of the ester moiety
A (meth) acrylate having 1 to 12 carbon atoms;
An aromatic vinyl compound and an α, β-unsaturated carboxylic acid
Combining monomer composition B with monomer composition A
The weight ratio with the monomer composition B is 10/90 to 50/50.
The polymer b obtained by emulsion polymerization within the range, the polymer b
So that the ratio with respect to 1% by weight to 4% by weight
Polymer B obtained by crosslinking a divalent metal compound with
It is characterized by including .

According to the above structure , the first-stage emulsion polymerization for obtaining the crosslinked polymer A and the second-stage emulsion polymerization for obtaining the polymer b are performed in a so-called "1 pot". Can be formed into a film in which the crosslinked polymer A is uniformly dispersed. Then, since the crosslinked polymer A is formed using a polymerizable monomer component having a glass transition temperature of 0 ° C. or lower, the crosslinked polymer A has appropriate elasticity. Further, the polymer b is formed using the monomer composition B having a glass transition temperature of more than 0 ° C. and equal to or less than 50 ° C., and then crosslinked using a divalent metal compound. A film formed by film formation is excellent in film formability and adhesion to a substrate, and can impart gloss, durability, and the like to the substrate. As a result, it is possible to provide a film-forming composition having various properties further improved as compared with a conventional film-forming composition.

[0011] Claim 2 film forming compositions of the described invention, in order to solve the above problem, as the polymerizable monomer component, a glass transition temperature of the polymer is lower than -20 ℃ ,
The alkyl group of the ester moiety has 1 to 12 carbon atoms
TA) acrylic acid ester, aromatic vinyl compound,
α, β-unsaturated carboxylic acid in combination with
The body composition B has a glass transition temperature of the polymer of 10 ° C. or lower.
Above, the alkyl of the ester portion so as to be 40 ° C or less
(Meth) acrylate having 1 to 12 carbon atoms
, Aromatic vinyl compound and α, β-unsaturated carboxylic acid
And a combination of the above.

[0012]

[0013] film-forming composition of the invention of claim 3, wherein, in order to solve the above problems, the divalent metal compound is nitrous oxide
It is a lead, zinc carbonate, zinc acetate or zinc ammine complex .

[0014]

According to a fourth aspect of the present invention, there is provided a film-forming composition , wherein the divalent metal compound is zinc oxide.
It is characterized by being.

[0016]

In addition, the floor brightener composition according to the fifth aspect of the present invention does not have the first aspect in order to solve the above problems.
A film forming composition according to any one of Claims 4 to 4 .

According to the above-mentioned structure, a floor brightener composition having various properties such as gloss and durability can be provided as compared with the conventional floor brightener composition.

Hereinafter, the present invention will be described in detail. The method for producing a film-forming composition according to the present invention comprises emulsion-polymerizing a monomer composition A containing a polymerizable monomer component having a glass transition temperature of 0 ° C. or lower and a crosslinking agent. Cross-linked polymer A
Is formed, and in the presence of the crosslinked polymer A, a monomer composition B having a glass transition temperature of the polymer of more than 0 ° C and 50 ° C or less is emulsion-polymerized to form a polymer b, A method of adding an aqueous dispersion of a polyvalent metal compound.

Further, the method for producing a film-forming composition according to the present invention is directed to a monomer composition comprising a polymerizable monomer component having a glass transition temperature of 0 ° C. or less and a crosslinking agent. A is emulsion-polymerized to form a crosslinked polymer A, and then, in the presence of the crosslinked polymer A, a monomer composition B having a glass transition temperature of more than 0 ° C. and not more than 50 ° C. is emulsion-polymerized. To form a polymer b, and then cross-linking the polymer b using a divalent metal compound.

The above glass transition temperature (Tg) is defined as
l. Am. Phys. Soc., Vol. 1, No. 3, page 123, Formula for calculating the glass transition temperature of the copolymer, indicated by Fox, (1 / Tg) = (W _a / T g _a) ) + (W _b / Tg _b ) +
(W _c / Tg _c ) +... In the above formula, Tg
Represents the glass transition _{temperature, W a, W b, W} c, ......
Represents the weight fraction of each monomer of the polymerizable monomer component or monomer composition _{B, Tg a, Tg b,} Tg c, ......
Indicates the glass transition temperature of the homopolymer of the corresponding monomer. The glass transition temperature of the homopolymer is described in, for example, "Polymer Handbook 2nd Edition" (John Wiley & Sons In
c., published in 1975) may be used.

The polymerizable monomer components constituting the monomer composition A are combined so that the glass transition temperature of the polymer obtained by polymerizing the polymerizable monomer components is 0 ° C. or lower. What is necessary is just to contain at least one kind of monomer having a polymerizable unsaturated bond. Further, the monomer composition B has a polymerizable unsaturated bond having a glass transition temperature of more than 0 ° C. and not more than 50 ° C. What is necessary is just to contain at least one kind of the monomer which has.

As the monomer having a polymerizable unsaturated bond, specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate,
Pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, (Meth) acrylic acid esters such as phenyl (meth) acrylate and benzyl (meth) acrylate; aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyltoluene; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( Α, β-unsaturated compounds having a hydroxyl group such as meth) acrylate; α, β-unsaturated compounds having a glycidyl group such as glycidyl (meth) acrylate; acrylic acid, methacrylic acid,
Α, β-unsaturated carboxylic acids such as crotonic acid, maleic acid, maleic acid monoester, fumaric acid, fumaric acid monoester, itaconic acid, itaconic acid monoester, citraconic acid, citraconic acid monoester; sodium styrene sulfonate; Α, β such as sodium vinyl sulfonate
-Unsaturated sulfonic acid; and the like, but are not particularly limited thereto.

If necessary, the polymerizable monomer component or the monomer composition B may be a monomer other than the above-mentioned monomers having a polymerizable unsaturated bond, for example, vinyl acetate, propionate, etc. Vinyl esters such as vinyl acrylate and vinyl caproate; diesters of fumarate such as diethyl fumarate, dipropyl fumarate, dibutyl fumarate, dioctyl fumarate, and di (2-ethylhexyl) fumarate; diethyl maleate, dipropyl maleate and maleate Maleic acid diesters such as dibutyl acrylate, dioctyl maleate, di (2-ethylhexyl) maleate; (meth) acrylamide, diacetone (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N -Ethoxymethyl (meth) acrylamide, dimethyl Minoechiru (meth) acrylate, diethylaminoethyl (meth) acrylate, (meth) acrylonitrile, vinyl chloride, vinylidene chloride;
Etc. may be included.

The polymerizable monomer components constituting the monomer composition A are combined in such a manner that the glass transition temperature becomes 0 ° C. or lower, preferably -20 ° C. or lower. Contains one or more monomers. A combination of monomers having a glass transition temperature of more than 0 ° C. results in a lack of elasticity of the crosslinked polymer A, resulting in a film (hereinafter referred to as a “coating film”) obtained by forming a film-forming composition. It is not preferable because gloss and durability are reduced.

The monomer composition B has a glass transition temperature of 0 ° C.
And at least 50 ° C., preferably at least 10 ° C. and no more than 40 ° C., containing one or more of the above exemplified monomers. Combinations of monomers having a glass transition temperature of 0 ° C. or lower are not preferred because the resulting coating film has reduced durability. Further, a combination of monomers having a glass transition temperature exceeding 50 ° C. is not preferable because it causes a film formation failure and makes it impossible to obtain a good coating film.

The polymerizable monomer component and the monomer composition B contain acidic monomers such as α, β-unsaturated carboxylic acid and α, β-unsaturated sulfonic acid. Is more preferable, and further preferably contains an α, β-unsaturated carboxylic acid. The resulting emulsion,
That is, the stability of the film-forming composition is further improved, and the adhesion of the coating film to the substrate (described later) is further improved. Further, by neutralizing the carboxyl group of the α, β-unsaturated carboxylic acid with a basic compound such as ammonia or amines, the stability of the obtained emulsion, that is, the composition for film formation is further improved. . When the polymerizable monomer component or the monomer composition B contains an α, β-unsaturated carboxylic acid, the α, β-unsaturated carboxylic acid in the polymerizable monomer component or the monomer composition B is used. Is not particularly limited, but is preferably about 5 to 20% by weight.

As a preferred combination of the above exemplified monomers, the alkyl group in the ester moiety has 1 to 12 carbon atoms.
Combinations of (meth) acrylic acid esters, aromatic vinyl compounds and α, β-unsaturated carboxylic acids are mentioned. The combination of the polymerizable monomer component and the monomer in the monomer composition B, that is, the composition of the polymerizable monomer component and the monomer composition B is not particularly limited.

The crosslinking agent constituting the monomer composition A may be any compound having two or more polymerizable unsaturated bonds, and is not particularly limited. Specific examples of the crosslinking agent include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and propylene glycol di (meth) acrylate. A) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate , 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di ( Data) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerol di (meth) acrylate, glycerol ants Loki Siji (meth) acrylate, 1,1,1
Tris (hydroxymethyl) ethanedi (meth) acrylate, 1,1,1-tris (hydroxymethyl) ethanetri (meth) acrylate, 1,1,1-tris (hydroxymethyl) propanedi (meth) acrylate, 1,
Polyfunctional (meth) acrylates such as 1,1-tris (hydroxymethyl) propane tri (meth) acrylate; triallyl cyanurate, triallyl isocyanurate,
Triallyl trimellitate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, divinylbenzene; and the like.

As a crosslinking agent, an unsaturated compound having a certain functional group and an unsaturated compound having a functional group which reacts with the functional group can be used in combination. Specific examples of the combination of these two types of unsaturated compounds include an unsaturated compound having an epoxy group such as glycidyl (meth) acrylate and an unsaturated compound having a carboxyl group such as (meth) acrylic acid and crotonic acid. Combinations with saturated compounds are preferred. A combination of an amine and a carbonyl compound; a combination of an epoxy compound and a carboxylic acid anhydride; a combination of an amine and a carboxylic acid anhydride; a combination of an alkylene imine and a carbonyl compound; A combination with an unsaturated compound having a hydroxyl group; a combination with an unsaturated compound having a hydroxyl group and an isocyanate; and the like.

The weight ratio of the polymerizable monomer component to the crosslinking agent in the monomer composition A (polymerizable monomer component / crosslinking agent) is:
It is preferably in the range of 99.9 / 0.1 to 50/50, and 9
The range of 0/10 to 60/40 is more preferable. When the weight ratio of the crosslinking agent is less than 0.1, the crosslinking polymer A
Is too low, and the durability of the resulting coating film is undesirably reduced. When the weight ratio of the crosslinking agent is 5
If it is more than 0, the polymerization stability of the crosslinked polymer A is undesirably reduced. In addition, the monomer composition A may contain a film-forming auxiliary agent (described later), a known chain transfer agent, and the like, if necessary.

The weight ratio of the monomer composition A to the monomer composition B (monomer composition A / monomer composition B) is 10/90.
It is preferably in the range of 50/50. When the weight ratio of the monomer composition B is more than 90, the elasticity of the crosslinked polymer A cannot be sufficiently exhibited, and the durability and the like of the coating film decrease, which is not preferable. On the other hand, if the weight ratio of the monomer composition B is less than 50, the film formability of the coating film is undesirably reduced.

When emulsion-polymerizing the monomer composition A,
A known emulsifier may be added. Specific examples of the emulsifier include anionic emulsifiers such as sodium lauryl sulfate, sodium dodecylbenzenesulfonate, alkyl allyl polyether sulfates such as ammonium polyoxyethylene nonyl phenyl ether sulfonate; polyoxyethylene nonyl phenyl; Nonionic emulsifiers such as ether and oxyethylene-oxypropylene copolymer;
And the like, but are not particularly limited. One of these emulsifiers may be used alone, or two or more thereof may be used in combination. Further, the amount of the emulsifier used is not particularly limited.

When emulsion-polymerizing the monomer composition A,
A known radical polymerization initiator may be added. Specific examples of the radical polymerization initiator include, for example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, p-
Menthol hydroperoxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxy-isopropyl carbonate, 1,1-bis (t-
Organic peroxides such as butylperoxy) -3,3,5-trimethylcyclohexane; inorganic peroxides such as ammonium persulfate, potassium persulfate, sodium persulfate and hydrogen peroxide; 2,2′-azobisisobutyi Azo compounds such as lonitrile; and the like, but are not particularly limited. One of these radical polymerization initiators may be used alone, or two or more thereof may be used in combination. further,
With the above peroxide, sulfite, bisulfite, thiosulfate,
A redox initiator can also be used in combination with a reducing agent such as formamidinesulfinic acid and ascorbic acid. The amount of the radical polymerization initiator used may be appropriately set according to the composition of the monomer composition A, reaction conditions, and the like, and is not particularly limited.

The reaction conditions such as the reaction temperature and the reaction time when the monomer composition A is emulsion-polymerized to form the crosslinked polymer A are, for example, the composition of the monomer composition A and water as a reaction solvent. The ratio (concentration) of the monomer composition A to the composition, or various physical properties desired for the film-forming composition may be appropriately set, and is not particularly limited. By adding an emulsifier, a radical polymerization initiator, and the like to the monomer composition A and performing emulsion polymerization, a crosslinked polymer A, that is, an emulsion containing the crosslinked polymer A is obtained. The crosslinked polymer A is in the form of particles and has appropriate elasticity.

When emulsion-polymerizing the monomer composition B in the presence of the crosslinked polymer A, a known emulsifier may be added. Examples of the emulsifier include the anionic emulsifier and the nonionic emulsifier exemplified above, but are not particularly limited. One of these emulsifiers may be used alone, or two or more thereof may be used in combination. Further, the amount of the emulsifier used is not particularly limited.

When emulsion-polymerizing the monomer composition B,
A known radical polymerization initiator may be added. Examples of the radical polymerization initiator include the above-described organic peroxides, inorganic peroxides, and azo compounds, but are not particularly limited. One of these radical polymerization initiators may be used alone, or two or more thereof may be used in combination. Further, the amount of the radical polymerization initiator used is not particularly limited.

The monomer composition B is subjected to emulsion polymerization to obtain a polymer b
The reaction conditions such as the reaction temperature and the reaction time for forming the polymer are, for example, the composition of the monomer composition B, the ratio (concentration) of the monomer composition B to water as a reaction solvent, or What is necessary is just to set suitably according to the various physical properties etc. desired for a composition,
There is no particular limitation. In the presence of crosslinked polymer A,
A polymer b, that is, an emulsion containing the polymer b is obtained by adding an emulsifier, a radical polymerization initiator, and the like to the monomer composition B and performing emulsion polymerization.

By cross-linking the polymer b with a polyvalent metal compound, a film-forming composition is produced. The polyvalent metal compound is not particularly limited as long as it is, for example, a compound that generates a polyvalent metal oxide, a polyvalent metal ion, or a polyvalent metal complex salt. As the polyvalent metal compound, specifically, for example, zinc oxide, zinc carbonate,
Examples thereof include a zinc ammine complex such as zinc acetate and zinc ammonium carbonate, and a zirconium ammine complex such as zirconyl ammonium carbonate. A divalent metal compound is more preferable. The polyvalent metal compound may be added to the emulsion after being converted into an aqueous dispersion (a polyvalent metal compound aqueous dispersion) or a complex salt by using a known method.

The ratio of the polyvalent metal compound to the polymer b is preferably in the range of 0.5% by weight to 5% by weight, more preferably in the range of 1% by weight to 4% by weight in terms of the polyvalent metal. preferable. When the proportion of the polyvalent metal compound (that is, the polyvalent metal) is less than 0.5% by weight, the crosslink density of the crosslinked polymer B becomes too small, and the durability of the obtained coating film decreases, so that it is preferable. Absent. Further, when the proportion of the polyvalent metal compound is more than 5% by weight, a film formation defect is caused,
It is not preferable because a good coating film cannot be obtained.

The reaction conditions such as reaction temperature and reaction time for crosslinking the polymer b with a polyvalent metal compound include, for example, the composition of the polymer b, the type of the polyvalent metal compound, the polymer b
What is necessary is just to set suitably according to the combination etc. of and a polyvalent metal compound, and it does not specifically limit. By crosslinking the polymer b using a polyvalent metal compound, a crosslinked polymer B, that is, an emulsion containing the crosslinked polymer B and the crosslinked polymer A (hereinafter, referred to as a base emulsion) is obtained.

Since the first-stage emulsion polymerization for obtaining the crosslinked polymer A and the second-stage emulsion polymerization for obtaining the polymer b are performed in a so-called “1 pot”, the film-forming composition is formed. Thereby, a coating film in which the crosslinked polymer A is uniformly dispersed can be formed.

The ratio of the solid content of the base emulsion (that is, the crosslinked polymers A and B) depends on the composition of the base emulsion, the use of the film-forming composition, the workability in forming a coating film, and the like. What is necessary is just to set suitably and it is not specifically limited. The base emulsion can be diluted with water, if necessary.

The composition for film formation according to the present invention comprises the base emulsion having the above constitution, a film formation auxiliary and a plasticizer, and if necessary, a wax, an alkali-soluble resin, a leveling agent, and a dehydrating agent. It further contains a foaming agent. The film-forming composition further containing a wax, an alkali-soluble resin, and a leveling agent is suitable as a so-called floor brightener composition.

As the film-forming auxiliary, specifically, for example,
Examples thereof include diethylene glycol monoethyl ether, diethylene glycol diethyl ether (hereinafter, referred to as ethyl carbitol), and butyl cellosolve. The addition amount of the film-forming auxiliary may be appropriately set according to the composition of the base emulsion, the use of the film-forming composition, and the like, and is not particularly limited.

Specific examples of the plasticizer include tributoxyethyl phosphate (TBXP) and dibutyl phthalate (DBP). These plasticizers may be used alone or in combination of two or more. The amount of the plasticizer to be added may be appropriately set according to the composition of the base emulsion, the use of the film-forming composition, and the like, and is not particularly limited.

As the wax, specifically, for example,
Hydrogenated oils such as beef tallow and lard, hydrogenated animal oils such as lanolin, beeswax, and spermaceti; hardened oils obtained by hydrogenating castor oil and the like, carnauba wax, candela wax, wood wax, bran wax, etc. Natural waxes such as vegetable waxes; mineral waxes such as montan wax, ceresin wax, paraffin wax, and microcrystalline wax; and synthetic waxes such as polyethylene wax and polypropylene wax having a molecular weight of about 500 to 5,000. These waxes may be used alone or in combination of two or more. The amount of the wax added may be appropriately set according to the composition of the base emulsion, the use of the film-forming composition, and the like, and is not particularly limited. The wax may be added to a base emulsion after appropriately adding a known emulsifier and emulsifying with an emulsifier or the like to form a water dispersion.

The alkali-soluble resin is a resin having a relatively low molecular weight having a carboxyl group. Specifically, for example, a styrene-maleic acid resin, a rosin-modified maleic resin, (meth) acrylic acid- (meth) ) Acrylic ester resins and the like. One of these alkali-soluble resins may be used alone, or two or more thereof may be used in combination. The amount of the alkali-soluble resin to be added may be appropriately set depending on the composition of the base emulsion, the use of the film-forming composition, and the like, and is not particularly limited.
Incidentally, the alkali-soluble resin may be added to the base emulsion in a state of being dissolved using ammonia.

As the leveling agent, a known leveling agent such as a fluorine-based surfactant can be used, and the amount of addition can be appropriately set according to the composition of the base emulsion and the use of the film-forming composition. Well, it is not particularly limited. As the defoaming agent, a known defoaming agent can be used,
The addition amount may be appropriately set according to the composition of the base emulsion, the use of the composition for film formation, and the like, and is not particularly limited.

The film-forming composition having the above structure can be easily formed into a film by applying it to a substrate and then drying (curing) it at room temperature. That is, the workability is excellent, and a coating film can be easily formed on the surface of the base material. The base material is not particularly limited, but the base material when the film-forming composition is used as a floor brightener composition, that is, as a floor material, specifically, for example, poly Examples include vinyl tile made of vinyl chloride or the like, linoleum tile, rubber tile, wood surface-treated with urethane resin, concrete, asphalt mortar, and the like. By applying the film forming composition to the floor material surface to form a coating film which is a protective film, the floor material can be protected and gloss and durability can be imparted to the floor material. The gloss and durability can be balanced by appropriately changing the composition of the film-forming composition according to the type of flooring material and the like.

As shown in FIG. 1, the structure (coating structure) of the coating film formed by forming the film-forming composition according to the present invention is in the coating film, that is, in the crosslinked polymer B (1). And a structure in which particulate crosslinked polymer A (2) is uniformly dispersed. The crosslinked polymer B (1) is in close contact with the base material 10. In addition, the polyvalent metal compound used for crosslinking (in the figure, for convenience,
3) are uniformly dispersed in the crosslinked polymer B (1). That is, the film-forming composition according to the present invention can be easily formed into a film by being applied to the substrate 10 and then dried at room temperature, and the obtained film has the above structure. I have. In the above coating film, the crosslinked polymer A (2) has a moderate elasticity and the crosslinked polymer B
Since (1) is cross-linked by a polyvalent metal compound,
Excellent in various properties such as gloss and durability.

As described above, the method for producing a film-forming composition according to the present invention comprises a monomer containing a polymerizable monomer component having a glass transition temperature of 0 ° C. or lower and a crosslinking agent. After the crosslinked polymer A is formed by emulsion polymerization of the body composition A, a monomer composition B having a glass transition temperature of more than 0 ° C and not more than 50 ° C in the presence of the crosslinked polymer A Is subjected to emulsion polymerization to form a polymer b, and then an aqueous dispersion of a polyvalent metal compound is added. Further, as described above, the method for producing a film-forming composition according to the present invention includes a method for producing a monomer having a glass transition temperature of more than 0 ° C and 50 ° C or less in the presence of the crosslinked polymer A. In this method, the composition B is emulsion-polymerized to form a polymer b, and then the polymer b is crosslinked using a divalent metal compound.

According to the above-described method, the first-stage emulsion polymerization for obtaining the crosslinked polymer A and the second-stage emulsion polymerization for obtaining the polymer b are performed in a so-called “1 pot”. Can form a coating film in which the crosslinked polymer A having appropriate elasticity is uniformly dispersed.

Further, as described above, the film-forming composition according to the present invention has the above-mentioned crosslinked polymer A and, in the presence of the crosslinked polymer A, having a glass transition temperature of more than 0 ° C. The composition contains a crosslinked polymer B obtained by crosslinking a polymer b obtained by emulsion polymerization of a monomer composition B at 50 ° C. or lower with a divalent metal compound.

According to the above configuration, the coating film formed by forming the film-forming composition has a structure in which the crosslinked polymer A having appropriate elasticity is uniformly dispersed in the coating film. For this reason,
A coating film formed by forming a film-forming composition has excellent film-forming properties and adhesion to a substrate, and can impart gloss, durability, and the like to the substrate. This makes it possible to provide a film-forming composition having various properties further improved as compared with the conventional film-forming composition.

The coating film obtained by forming the film-forming composition according to the present invention is hardly damaged or stained. So, for example,
When the composition for film formation is applied to the surface of a flooring material as a base material to form a coating film as a protective film, so-called heel marks are less likely to be formed on the heel marks of the shoes. Therefore, because it can maintain a beautiful state for a long time,
The floor material can be protected, and gloss, durability, and the like can be imparted to the floor material.

When the first-stage emulsion polymerization and the second-stage emulsion polymerization are separately performed to form a film-forming composition, that is, the crosslinked polymer obtained by the first-stage emulsion polymerization is obtained. When a composition for film formation is formed by mixing an emulsion containing A and an emulsion containing a crosslinked polymer B obtained by crosslinking the polymer b obtained by the second-stage emulsion polymerization, In addition, the crosslinked polymer A is not uniformly dispersed in the coating film formed by forming the film forming composition. Therefore, it is impossible to form a coating film in which various properties such as gloss and durability are further improved.

Further, as described above, the coating film (coating) structure according to the present invention is a coating film obtained by forming the above-mentioned film-forming composition, wherein the crosslinked polymer A is contained in the coating film. The configuration is distributed.

According to the above configuration, the crosslinked polymer A is dispersed in the coating film, and the divalent metal compound used for crosslinking is also dispersed in the coating film. As a result, it is possible to obtain a film structure in which various properties such as gloss and durability are further improved as compared with a film structure formed by forming a conventional film-forming composition.

The above-mentioned coating film can be easily peeled (removed) from the substrate by using a releasing agent when it is soiled or when a predetermined period has passed. As the release agent,
A known release agent can be used and is not particularly limited, but a mixture of an alkali compound and an organic solvent is preferable. When the mixture is used, the cross-linking (metal cross-linking) of the cross-linked polymer B is removed by the alkali compound, so that the coating film easily swells with the organic solvent. Therefore, the coating film can be easily peeled from the substrate by applying an external force. In addition, it is preferable to apply a new film-forming composition to the surface of the substrate after the coating film is peeled off, and to form the coating film again.

In addition, as described above, the floor brightener composition according to the present invention provides a crosslinked polymer obtained by emulsion polymerization of a monomer composition A containing a polymerizable monomer component and a crosslinking agent. Merging A,
And a film-forming composition containing a crosslinked polymer B obtained by crosslinking a polymer b obtained by emulsion-polymerizing the monomer composition B with a divalent metal compound in the presence of the crosslinked polymer A. It is a configuration comprising.

According to the above construction, a floor brightener composition having various properties such as gloss and durability can be provided as compared with the conventional floor brightener composition.

[0063]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited thereto. Various properties of a coating film formed by forming a film-forming composition, that is, recoatability, leveling property, gloss,
The heel mark resistance and the scratch resistance were evaluated by the following methods. The “parts” described in Examples and Comparative Examples
Indicates “parts by weight” and “%” indicates “% by weight”.

(A) Overcoatability The film-forming composition was applied to a substrate at predetermined intervals for 30 minutes under predetermined conditions.
It was applied repeatedly. After drying for a predetermined time, the state of the surface (applied surface), that is, the state of the coating film, was visually evaluated.
The evaluation was made in three stages, "O" when the coating was completely formed, "、" when the portion where the coating was not formed was less than half of the total area, "△", no coating was formed The case where the portion exceeded half of the total area was designated as "x".

(B) Leveling property The composition for film formation was applied to a substrate at a 30-minute interval under predetermined conditions.
It was applied repeatedly. After drying for a predetermined time, the state of the surface, that is, the leveling state, was visually evaluated. The evaluation was made in three stages, "○" when the leveling state was good, "△" when the leveling state was partially defective, and "x" when the leveling state was poor.

(C) Gloss The composition for film formation was applied to a substrate at predetermined intervals for 30 minutes under predetermined conditions.
It was applied repeatedly. Then, after drying for a predetermined time, 60
° Specular reflection gloss was measured using a gloss meter and evaluated. The evaluation was performed in three stages. The case where the glossiness was 87 or more was rated as “○”, the glossiness was 80 or more, less than 87 was rated “△”, and the glossiness was less than 80 was rated “x”. .

(D) Heel mark resistance First, the composition for film formation was placed under a predetermined condition at 30 cm × 30 cm.
A substrate having a size of cm was coated three times at 30 minute intervals.
Thereafter, by drying for one day, a test panel was prepared. Six test panels were prepared.

Next, the heel mark resistance of the test panel was measured using a measuring device (Snell Capsule Tester) certified by the Japan Floor Polishing Industry Association. The configuration of the measuring device will be briefly described below.

As shown in FIG. 2, the measuring apparatus includes a snell capsule 31 having a hollow interior and a substantially hexagonal column shape, a motor 32 for rotating the snell capsule 31, and a support base 33. And The side surface of the snell capsule 31 has a square opening, so that a total of six test panels 34 can be inserted. That is, the snell capsule 31 is formed to have a size that allows the test panels 34 having the above dimensions to be inserted. The test panels 34 are inserted and fixed to the side surfaces of the snell capsule 31 such that the surface (application surface) faces inward.

A support shaft 35 penetrating in the axial direction is attached to the snell capsule 31, and the support shaft 35 is supported rotatably in a horizontal direction by support columns 36, 36 erected on a support base 33. Have been. That is, the snell capsule 31 is rotatably supported by the support base 33 with its axial direction being horizontal.

A pulley 37 is attached to the support shaft 35. The motor 32 mounted on the support base 33 is driven by a pulley 38 attached to the motor 32, a belt 39 hung between the pulleys 37 and 38, and a pulley 3.
7 and transmitted to the support shaft 35. Therefore, the motor 32
Is driven to rotate the snell capsule 31 at a predetermined speed.

Then, the heel portion (not shown) of the black shoe is placed in the snell capsule 31 of the measuring device having the above-described configuration.
I put them (4 pairs). Next, after fixing the test panels 34 to the snell capsule 31, the snell capsule 31
Was spun at 50 rpm for 30 minutes.

Then, the test panels 34 are removed and
The state of the surface of the test panel 34, that is, whether or not heel marks were formed, was visually observed to evaluate heel mark resistance (that is, black heel mark resistance). The evaluation was made in three grades, "○" when no heel mark was formed, "△" when some heel mark was formed, and "x" when many heel marks were formed.

(E) Scratch Resistance The same measurement as the above-mentioned heel mark resistance was carried out, and the state of the surface of the test panel, that is, the state of the scratch was visually observed to evaluate the scratch resistance. The evaluation was made in three stages, "○" when the scratch was shallow and small, "「 "when the scratch was shallow and large, and" x "when the scratch was deep and large.

Example 1 A 1 L separable flask equipped with a reflux condenser, two dropping funnels, a nitrogen gas inlet tube, a thermometer, and a stirrer was used as a reaction vessel. In this reaction vessel, 500 parts of deionized water and Hytenol N-08 (trade name; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
After charging 2 parts of polyoxyethylene nonyl phenyl ether sulfonate) and 1 part of Nonipol 200 (trade name; polyoxyethylene nonyl phenyl ether manufactured by Sanyo Chemical Industries, Ltd.) as an emulsifier, the system was purged with nitrogen gas. did.

On the other hand, methyl methacrylate (hereinafter MM)
A), 17 parts of butyl acrylate (hereinafter, referred to as BA), 52 parts of acrylic acid (hereinafter, referred to as AA) and 1 part of a polymerizable monomer component, and divinylbenzene as a cross-linking agent (hereinafter, referred to as A). , DVB) of 30 parts. Also, 34 parts of MMA,
A monomer composition B comprising 29 parts of BA, 27 parts of styrene (hereinafter, referred to as St), and 10 parts of methacrylic acid (hereinafter, referred to as MA) was prepared.

Then, the first-stage emulsion polymerization for obtaining the crosslinked polymer A was carried out. That is, 10 parts of the above monomer composition A was placed in one dropping funnel, and 5% aqueous solution of ammonium persulfate 3 as a radical polymerization initiator was placed in the other dropping funnel.
Put the part. Next, the temperature of the aqueous solution in the reaction vessel was raised to 70 ° C. while stirring, and while maintaining the temperature, the contents of both dropping funnels were dropped uniformly over 1 hour. After the completion of the dropwise addition, the mixture was aged at 70 ° C. for 30 minutes to form a crosslinked polymer A.

Next, a second-stage emulsion polymerization for obtaining the polymer b was performed. That is, 90 parts of the above monomer composition B was placed in one dropping funnel, and 3 parts of a 5% aqueous solution of ammonium persulfate was placed in the other dropping funnel. Therefore, the weight ratio of the monomer composition A to the monomer composition B (monomer composition A / monomer composition B) is 10/90. Next, while maintaining the temperature of the reaction solution in the reaction vessel at 70 ° C., the contents of both dropping funnels were uniformly dropped over 2 hours. After completion of the dropwise addition, the mixture was further aged at 70 ° C. for 2 hours to form a polymer b.

After the completion of the reaction, the reaction solution was cooled to 50 ° C.
On the other hand, zinc oxide as a polyvalent metal compound was formed into a dispersion having a solid content of 50% (a polyvalent metal compound aqueous dispersion) by employing a predetermined method. After adding 6 parts of the above zinc oxide dispersion (that is, 3 parts of zinc oxide) to the reaction solution,
Aging was performed at 0 ° C. for 1 hour to form a crosslinked polymer B. Then, the reaction solution was cooled to room temperature.

Thereafter, the obtained reaction solution was taken out through a 100-mesh filter. As a result, a base emulsion was obtained. The nonvolatile content (solid content) of the obtained base emulsion was 40.0%, and the pH was 8.0.
And the viscosity measured by a predetermined method is 20 mPa ·
S. The composition of the monomer compositions A and B, and
Table 1 summarizes the physical properties and the like of the base emulsion.

Next, the above-mentioned base emulsion 400
Parts, 72 parts of ethyl carbitol as a film forming aid, 12.8 parts of tributoxyethyl phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., hereinafter referred to as TBXP) as a plasticizer, and Hitec E-4B as a wax ( Brand name: Toho Chemical Industry Co., Ltd.) 75 parts, S as alkali-soluble resin
66.7 parts of a 15% aqueous solution of MA-2625A (trade name; manufactured by elf attochem) and 5 parts of a 1% aqueous solution of Futagent 150 (trade name; manufactured by Neos Co., Ltd., fluorine-based surfactant) as a leveling agent While adding, 368.5 parts of water was added for dilution. This allows
1,000 parts of the film-forming composition according to the present invention were prepared.
Table 3 summarizes the composition of the film-forming composition.

The Hi-Tech E-4B is an emulsion. The amount of ethyl carbitol added was determined as follows. That is, in the base emulsion,
8% TBXP based on the solid content of the base emulsion
Is added, and the minimum amount of ethyl carbitol required to form a film of the composition at 0 ° C. is measured using a thermal gradient tester. The amount of carbitol added was used.

Then, various properties of the coating film obtained by forming a film of the obtained film-forming composition were evaluated by the methods described above. As a result, the recoating property, leveling property, gloss, heel mark resistance and scratch resistance were all “O”. The above evaluations are summarized in Table 5.

Example 2 In Example 1, the amount of the monomer composition A dropped was changed from 10 parts to 30 parts.
A base emulsion was obtained by performing the same reaction and operation as in Example 1 except that the amount of the monomer composition B dropped was changed from 90 parts to 70 parts.
Therefore, the weight ratio between the monomer composition A and the monomer composition B is 30/70. The non-volatile content of the obtained base emulsion is 40.0%, the pH is 8.0,
The viscosity was 20 mPa · S. The above monomer composition A
The composition of B, and the physical properties of the base emulsion,
The results are summarized in Table 1.

Next, the above-mentioned base emulsion 400
The same operation as that of Example 1 was performed using the parts to prepare 1,000 parts of the film-forming composition according to the present invention. Table 3 summarizes the composition of the film-forming composition.

Then, various properties of the coating film obtained by forming a film of the obtained film-forming composition were evaluated by the methods described above. As a result, the recoating property, leveling property, gloss, heel mark resistance and scratch resistance were all “O”. The above evaluations are summarized in Table 5.

Example 3 In Example 1, the amount of the monomer composition A dropped was changed from 10 parts to 50 parts.
A base emulsion was obtained by performing the same reaction and operation as in Example 1 except that the amount of the monomer composition B dropped was changed from 90 parts to 50 parts.
Therefore, the weight ratio between the monomer composition A and the monomer composition B is 50/50. The non-volatile content of the obtained base emulsion is 40.0%, the pH is 8.0,
The viscosity was 20 mPa · S. The above monomer composition A
The composition of B, and the physical properties of the base emulsion,
The results are summarized in Table 1.

Next, the above-mentioned base emulsion 400
The same operation as that of Example 1 was performed using the parts to prepare 1,000 parts of the film-forming composition according to the present invention. Table 3 summarizes the composition of the film-forming composition.

Then, various properties of the coating film formed by forming the obtained film-forming composition were evaluated by the methods described above. As a result, the recoating property, leveling property, gloss, heel mark resistance and scratch resistance were all “O”. The above evaluations are summarized in Table 5.

Example 4 In Example 1, trimethylolpropane trimethacrylate (hereinafter referred to as T) as a crosslinking agent was used in place of 30 parts of DVB constituting the monomer composition A.
MPTMA), and the amount of the monomer composition A was changed from 10 parts to 30 parts, and the amount of the monomer composition B was changed from 90 parts to 70 parts. By performing the same reaction and operation as in Example 1, a base emulsion was obtained. Therefore, the weight ratio between the monomer composition A and the monomer composition B is 3
0/70. The nonvolatile content of the obtained base emulsion was 40.0%, the pH was 8.0, and the viscosity was 20 mPa · S. Table 1 summarizes the compositions of the monomer compositions A and B, the physical properties of the base emulsion, and the like.

Next, the above-mentioned base emulsion 400
The same operation as that of Example 1 was performed using the parts to prepare 1,000 parts of the film-forming composition according to the present invention. Table 3 summarizes the composition of the film-forming composition.

Then, various properties of the coating film obtained by forming a film of the obtained film-forming composition were evaluated by the methods described above. As a result, the recoating property, leveling property, gloss, heel mark resistance and scratch resistance were all “O”. The above evaluations are summarized in Table 5.

Example 5 In Example 1, ethylene glycol dimethacrylate (hereinafter referred to as EGDM) as a crosslinking agent was used in place of 30 parts of DVB constituting the monomer composition A.
A) 30 parts, the amount of the monomer composition A dropped was changed from 10 parts to 30 parts, and the amount of the monomer composition B dropped was changed from 90 parts to 70 parts. By performing the same reaction and operation as in Example 1, a base emulsion was obtained. Therefore, the weight ratio of the monomer composition A to the monomer composition B is 30/70.
It is. The nonvolatile content of the obtained base emulsion was 4
0.0%, pH 8.0, viscosity 20 mP
a · S. Table 1 summarizes the compositions of the monomer compositions A and B, the physical properties of the base emulsion, and the like.

Next, the above-mentioned base emulsion 400
The same operation as that of Example 1 was performed using the parts to prepare 1,000 parts of the film-forming composition according to the present invention. Table 3 summarizes the composition of the film-forming composition.

Then, various properties of the coating film obtained by forming a film of the obtained film-forming composition were evaluated by the methods described above. As a result, the recoating property, leveling property, gloss, heel mark resistance and scratch resistance were all “O”. The above evaluations are summarized in Table 5.

[Comparative Example 1] In Example 1, the amount of the monomer composition A dropped was changed from 10 parts to 90 parts.
A base emulsion was obtained by performing the same reaction and operation as in Example 1 except that the amount of the monomer composition B dropped was changed from 90 parts to 10 parts.
The nonvolatile content of the obtained base emulsion is 40.0%
, PH was 8.0, and viscosity was 20 mPa · S. Table 2 summarizes the composition of the monomer compositions A and B, the physical properties of the base emulsion, and the like. In the base emulsion, the weight ratio between the monomer composition A and the monomer composition B is 90/10, which is out of the preferred range.

Next, the above-mentioned base emulsion 400
The same operation as in Example 1 was carried out using the parts to prepare 1,000 parts of a comparative film-forming composition.
Table 4 summarizes the composition of the film forming composition for comparison.

Then, various properties of the coating film obtained by forming the obtained film-forming composition for comparison were evaluated by the methods described above. As a result, the heel mark resistance was “△”, and the recoating property, leveling property, gloss and scratch resistance were “x”.
Met. Therefore, the performances of the coating film were remarkably inferior. The above evaluations are summarized in Table 5.

Comparative Example 2 Instead of using 30 parts of DVB constituting the monomer composition A in Example 1,
A from 52 parts to 82 parts, and the monomer composition A
The same reaction and operation as in Example 1 were carried out, except that the amount of monomer was changed from 10 parts to 30 parts and the amount of monomer composition B was changed from 90 parts to 70 parts. As a result, a base emulsion was obtained. Therefore, the weight ratio between the monomer composition A and the monomer composition B is 3
0/70. The nonvolatile content of the obtained base emulsion was 40.0%, the pH was 8.0, and the viscosity was 20 mPa · S. Table 2 summarizes the composition of the monomer compositions A and B, the physical properties of the base emulsion, and the like. In the base emulsion, since the monomer composition A does not contain a crosslinking agent, the polymer obtained by emulsion polymerization of the monomer composition A does not have a crosslinked structure.

Next, the base emulsion 400
The same operation as in Example 1 was carried out using the parts to prepare 1,000 parts of a comparative film-forming composition.
Table 4 summarizes the composition of the film forming composition for comparison.

Then, various properties of the coating film obtained by forming the obtained film-forming composition for comparison were evaluated by the methods described above. As a result, the recoating property, the leveling property and the gloss were “O”, but the heel mark resistance and the scratch resistance were “X”. Therefore, the coating film was remarkably inferior in durability. The above evaluations are summarized in Table 5.

Comparative Example 3 In Example 1, MM was used instead of using 52 parts of BA constituting the monomer composition A.
A from 17 parts to 69 parts, and the monomer composition A
The same reaction and operation as in Example 1 were carried out, except that the amount of monomer was changed from 10 parts to 30 parts and the amount of monomer composition B was changed from 90 parts to 70 parts. As a result, a base emulsion was obtained. Therefore, the weight ratio between the monomer composition A and the monomer composition B is 3
0/70. The nonvolatile content of the obtained base emulsion was 40.0%, the pH was 8.0, and the viscosity was 20 mPa · S. Table 2 summarizes the composition of the monomer compositions A and B, the physical properties of the base emulsion, and the like. In addition, in the base emulsion, the glass transition temperature of the polymer of the polymerizable monomer component constituting the monomer composition A exceeds 0 ° C.

Next, the above-mentioned base emulsion 400
The same operation as in Example 1 was carried out using the parts to prepare 1,000 parts of a comparative film-forming composition.
Table 4 summarizes the composition of the film forming composition for comparison.

Then, various properties of the coating film obtained by forming the obtained film-forming composition for comparison were evaluated by the above-mentioned methods. As a result, the recoating property, the leveling property, and the heel mark resistance were “」 ”, but the gloss and scratch resistance were“ △ ”. The above evaluations are summarized in Table 5.

Comparative Example 4 A comparative film-forming composition was prepared using two types of base emulsions (10).
That is, the emulsion containing the crosslinked polymer A obtained by the first-stage emulsion polymerization and the emulsion containing the crosslinked polymer B obtained by crosslinking the polymer b obtained by the second-stage emulsion polymerization are mixed. Thus, a film-forming composition for comparison was prepared.

First, a base emulsion was manufactured.
That is, 500 parts of deionized water and Hytenol N- were added to a reaction vessel having the same configuration as the reaction vessel used in Example 1.
08 (same as above) and Nonipol 200 (same as above)
After charging 1 part, the system was replaced with nitrogen gas. On the other hand, MM
A monomer composition A comprising 17 parts of A, 52 parts of BA, and 1 part of AA and a polymerizable monomer component and 30 parts of DVB was prepared.

Then, the first-stage emulsion polymerization for obtaining the crosslinked polymer A was carried out. That is, 100 parts of the monomer composition A was placed in one dropping funnel, and 3 parts of a 5% aqueous solution of ammonium persulfate was placed in the other dropping funnel. Next, the temperature of the aqueous solution in the reaction vessel was raised to 70 ° C. while stirring, and while maintaining the temperature, the contents of both dropping funnels were dropped uniformly over 1 hour. After completion of the dropwise addition, the mixture was aged at 70 ° C. for 1 hour to form a crosslinked polymer A. After the completion of the reaction, the reaction solution was cooled to room temperature.

Thereafter, the obtained reaction solution was taken out through a 100-mesh filter. As a result, a base emulsion was obtained. The nonvolatile content of the obtained base emulsion was 40.0%, the pH was 8.0, and the viscosity was 20 mPa · S. Table 2 summarizes the composition of the monomer composition A and the physical properties of the base emulsion. In addition, the base emulsion is a crosslinked polymer A
And does not contain the crosslinked polymer B.

Next, a base emulsion (10) was produced. That is, 500 parts of deionized water, 2 parts of Hytenol N-08 (same as above), and 1 part of Nonipol 200 (same as above) were charged into a reaction vessel having the same configuration as the reaction vessel used in Example 1. Thereafter, the system was replaced with nitrogen gas. on the other hand,
34 parts of MMA, 29 parts of BA, 27 parts of St, and MA
A monomer composition B consisting of 10 parts was prepared.

Then, the second-stage emulsion polymerization for obtaining the polymer b was carried out. That is, 100 parts of the monomer composition B was placed in one dropping funnel, and 3 parts of a 5% aqueous solution of ammonium persulfate was placed in the other dropping funnel. Next, the temperature of the aqueous solution in the reaction vessel was raised to 70 ° C. while stirring, and while maintaining the temperature, the contents of both dropping funnels were dropped uniformly over 2 hours. After completion of the dropwise addition, the mixture was further aged at 70 ° C. for 2 hours to form a polymer b.

After completion of the reaction, the reaction solution was cooled to 50 ° C.
On the other hand, zinc oxide is produced at a solid content of 50
% Dispersion. Then, after adding 6 parts of the zinc oxide dispersion (that is, 3 parts of zinc oxide) to the reaction solution,
After aging at 50 ° C. for 1 hour, a crosslinked polymer B was formed. Then, the reaction solution was cooled to room temperature.

Thereafter, the obtained reaction solution was taken out through a 100-mesh filter. Thus, a base emulsion (10) was obtained. The obtained base emulsion (1
The nonvolatile content of (0) was 40.0%, the pH was 8.0, and the viscosity was 20 mPa · S. Table 2 summarizes the composition of the monomer composition B and the physical properties of the base emulsion (10). In addition, the base emulsion (10)
An emulsion containing the crosslinked polymer B, wherein the crosslinked polymer A
Does not contain

Next, the above-mentioned base emulsion 120
The same operation as in Example 1 was performed using 280 parts of the base emulsion (10) and 1,000 parts of the base emulsion (10) to prepare 1,000 parts of a comparative film-forming composition. Therefore, the weight ratio between the monomer composition A and the monomer composition B is 30/70. Table 4 summarizes the composition of the film forming composition for comparison.

Then, various performances of the coating film obtained by forming the obtained film forming composition for comparison were evaluated by the above-mentioned methods. As a result, the recoating property, leveling property and scratch resistance are “△”, and the gloss and heel mark resistance are
It was "x". Therefore, the performances of the coating film were remarkably inferior. The above evaluations are summarized in Table 5.

Comparative Example 5 The same reaction and operation as in Comparative Example 4 were performed to obtain a base emulsion (10). Next, the above base emulsion (1
0) The same operation as in Example 1 was carried out using 400 parts to prepare 1,000 parts of a comparative film-forming composition. Table 4 summarizes the composition of the film forming composition for comparison.

Then, various properties of the coating film obtained by forming the obtained film-forming composition for comparison were evaluated by the above-mentioned methods. As a result, the recoating property, the leveling property and the gloss were “、”, but the heel mark resistance and the scratch resistance were “△”. Therefore, the coating film was inferior in durability. The above evaluations are summarized in Table 5.

Comparative Example 6 Deionized water 500 was added to a reaction vessel having the same structure as the reaction vessel used in Example 1.
, 2 parts of Hytenol N-08 (same as above) and 1 part of Nonipol 200 (same as above), and the system was purged with nitrogen gas. On the other hand, 17 parts of MMA, 52 parts of BA,
A monomer composition A consisting of a polymerizable monomer component consisting of 1 part of AA and 30 parts of DVB was prepared. Also, MMA34
Part B, 29 parts of BA, 27 parts of St, and 10 parts of MA were prepared as a monomer composition B.

Then, the first-stage emulsion polymerization for obtaining the crosslinked polymer A was performed. That is, 30 parts of the above monomer composition A was placed in one dropping funnel, and 3 parts of a 5% aqueous solution of ammonium persulfate was placed in the other dropping funnel. Next, the temperature of the aqueous solution in the reaction vessel was raised to 70 ° C. while stirring, and while maintaining the temperature, the contents of both dropping funnels were dropped uniformly over 1 hour. After completion of the dropwise addition, the mixture was aged at 70 ° C. for 1 hour to form a crosslinked polymer A.

Next, a second-stage emulsion polymerization for obtaining the polymer b was performed. That is, 70 parts of the above monomer composition B was placed in one dropping funnel, and 3 parts of a 5% aqueous solution of ammonium persulfate was placed in the other dropping funnel. Therefore, the weight ratio between the monomer composition A and the monomer composition B is 30/70.
Next, while maintaining the temperature of the reaction solution in the reaction vessel at 70 ° C., the contents of both dropping funnels were uniformly dropped over 2 hours. After completion of the dropwise addition, the mixture was further aged at 70 ° C. for 2 hours to form a polymer b.

After completion of the reaction, the reaction solution was cooled to room temperature.
Thereafter, the obtained reaction solution was taken out through a 100-mesh filter. Thereby, the base emulsion (1
1) was obtained. The nonvolatile content of the obtained base emulsion (11) was 40.0%, the pH was 8.0, and the viscosity was 20.
mPa · S. The composition of the monomer compositions A and B,
Table 2 summarizes the physical properties and the like of the base emulsion (11). The base emulsion (11) did not crosslink the polymer b.

Next, the above-mentioned base emulsion (11) 40
The same operation as in Example 1 was performed using 0 parts to prepare 1,000 parts of a comparative film-forming composition. Table 4 summarizes the composition of the film forming composition for comparison.

Then, various properties of the coating film obtained by forming the obtained film-forming composition for comparison were evaluated by the methods described above. As a result, the recoating property, the leveling property, and the gloss were “O”, but the heel mark resistance was “Δ”, and the scratch resistance was “X”. Therefore, the coating film was remarkably inferior in durability. The above evaluations are summarized in Table 5.

[0123]

[Table 1]

[0124]

[Table 2]

[0125]

[Table 3]

[0126]

[Table 4]

[0127]

[Table 5]

As is evident from the results of Examples 1 to 5 and Comparative Examples 1 to 6, the coating film formed by forming the film-forming composition according to this example has a recoating property, leveling property, and gloss. ,
The heel mark resistance and the scratch resistance are all “O”, indicating that these various properties are excellent. In particular, the film formed by forming the film-forming composition according to this example has a higher heel mark resistance and a higher scratch resistance than the film formed by forming the film-forming composition for comparison. It can be seen that the durability was further improved.

As is clear from the results of Comparative Example 4, the emulsion containing the crosslinked polymer A obtained by the first-stage emulsion polymerization was crosslinked with the polymer b obtained by the second-stage emulsion polymerization. When a film-forming composition is formed by mixing an emulsion containing the crosslinked polymer B formed as described above, the crosslinked polymer A is not uniformly dispersed in the coating film. It can be seen that a coating film with further improved performance cannot be formed.

[0130]

As described above, the film-forming composition according to claim 1 of the present invention has a polymer having a glass transition temperature of 0 ° C.
As shown below, the carbon number of the alkyl group in the ester moiety
(Meth) acrylic acid ester having 1 to 12
Combination of carbonyl compound and α, β-unsaturated carboxylic acid
It was a polymerizable monomer component comprising, a polymerizable unsaturated bond two
The crosslinking agent having the above , the polymerizable monomer component and the crosslinking agent
The presence of a crosslinking polymer A weight ratio is a monomer composition A containing in the range of 90 / 10-60 / 40 by emulsion polymerization,
The alkyl group of the ester moiety has 1 to 1 carbon atom such that the glass transition temperature of the polymer is more than 0 ° C and 50 ° C or less .
12 (meth) acrylates and aromatic vinylation
Compound and α, β-unsaturated carboxylic acid
That a monomer composition B, a monomer composition A and a monomer composition B
The polymer b obtained by emulsion polymerization in a weight ratio of 10/90 to 50/50 with respect to
The divalent metal compound is contained in the range of 1% by weight to 4% by weight.
And a crosslinked polymer B crosslinked using a product .

The film-forming composition according to claim 2 of the present invention comprises:
As described above, the polymerizable monomer component has an ester moiety such that the glass transition temperature of the polymer is −20 ° C. or lower.
(Meth) acrylic acid having 1 to 12 carbon atoms in the alkyl group
Ester, aromatic vinyl compound, α, β-unsaturated
Combined with rubonic acid, the monomer composition B has a polymer having a glass transition temperature of 10 ° C. or higher and 40 ° C. or lower such that the alkyl group in the ester moiety has 1 to 1 carbon atom.
12 (meth) acrylates and aromatic vinylation
Compound and α, β-unsaturated carboxylic acid
Configuration .

[0132]

The film-forming composition according to claim 3 of the present invention comprises:
As described above, the divalent metal compound is zinc oxide, zinc carbonate,
The configuration is a zinc acetate or zinc ammine complex .

[0134]

The film-forming composition according to claim 4 of the present invention comprises:
As described above , the configuration is such that the divalent metal compound is zinc oxide .

Therefore, a film formed by forming a film-forming composition is used.
The film has a crosslinked polymer A having an appropriate elasticity in the film.
It has a uniformly dispersed structure. And the composition for film formation
Is excellent in film formability and adhesion to substrate
And can impart gloss and durability to the substrate.
it can. Thereby, compared with the conventional film-forming composition,
An effect that it is the this <br/> to provide a film forming composition for various properties was more is further improved.

The floor brightener composition according to the fifth aspect of the present invention is, as described above, described in any one of the first to fourth aspects.
The composition comprises the film-forming composition described above.

As a result, there is an effect that a floor brightener composition having further improved various properties such as gloss and durability as compared with the conventional floor brightener composition can be provided.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view showing a structure of a coating film formed by forming a film-forming composition according to an embodiment of the present invention.

FIG. 2 is a schematic perspective view of a measuring device for measuring heel mark resistance of a coating film formed by forming a film forming composition according to an example of the present invention.

FIG. 3 is a schematic cross-sectional view showing the structure of a coating film formed by forming a conventional film-forming composition.

FIG. 4 is a schematic cross-sectional view showing the structure of a coating film formed by forming another conventional film-forming composition.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Crosslinked polymer B 2 Crosslinked polymer A 3 Polyvalent metal compound 10 Base material 31 Snell capsule 34 Test panel

Continuation of the front page (56) References JP-A-56-65013 (JP, A) JP-A-7-286137 (JP, A) JP-A-7-34027 (JP, A) JP-A-50-115298 (JP, A) JP-A-2-41351 (JP, A) JP-A-7-70215 (JP, A) JP-A-7-41683 (JP, A) JP-A-63-120771 (JP, A) 5-263046 (JP, A) JP-A-8-60102 (JP, A) JP-A-51-33129 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 1/00 -201/10 C08F 251/00-292/00 C08F 8/00-8/50 C08F 2/00-2/60 C09G 1/00-3/00

Claims (5)

(57) [Claims] An alkyl group in the ester portion has 1 to 1 carbon atom so that the glass transition temperature of the polymer is 0 ° C. or lower .
12 (meth) acrylates and aromatic vinylation
Compound and α, β-unsaturated carboxylic acid
That a polymerizable monomer component, a polymerizable unsaturated bond and two or more organic
The weight ratio of the crosslinking agent, a polymerizable monomer component and a crosslinking agent
There becomes 50 ° C. or less beyond the presence of a crosslinking polymer A comprising a monomer composition A is emulsion polymerization, the glass transition temperature of the polymer is 0 ℃ comprise in the range of 90 / 10-60 / 40 Thus, the carbon number of the alkyl group in the ester moiety is 1 to
12 (meth) acrylates and aromatic vinylation
Compound and α, β-unsaturated carboxylic acid
That a monomer composition B, a monomer composition A and a monomer composition B
The polymer b obtained by emulsion polymerization in a weight ratio of 10/90 to 50/50 with respect to
The divalent metal compound is contained in the range of 1% by weight to 4% by weight.
A composition for film formation , comprising a crosslinked polymer B obtained by crosslinking using a substance. 2. The polymerizable monomer component has an ester moiety such that the glass transition temperature of the polymer is -20 ° C. or lower .
(Meth) acrylic acid having 1 to 12 carbon atoms in the alkyl group
Stel, aromatic vinyl compound, α, β-unsaturated
When the monomer composition B has a glass transition temperature of 10
The temperature of the ester moiety should be between
(Meth) acrylic acid ester having 1 to 12 carbon atoms in the kill group
, An aromatic vinyl compound, and an α, β-unsaturated carboxylic acid.
2. The method according to claim 1, wherein said acid is combined with an acid.
A film-forming composition. 3. The divalent metal compound is zinc oxide, zinc carbonate, vinegar.
Characterized by zinc acid or zinc ammine complex
The composition for film formation according to claim 1 . 4. The film-forming composition according to claim 1 , wherein the divalent metal compound is zinc oxide . 5. A floor brightener composition comprising the film-forming composition according to any one of claims 1 to 4 .