JPH06212126A - Floor polish composition - Google Patents

Abstract

PURPOSE:To provide an emulsified high-solid floor polish composition excellent in properties such as application workability, heel mark resistance and scratch resistance. CONSTITUTION:The floor polish composition contains an emulsion prepared by emulsion-polymerizing at least one vinyl monomer and adding 3-20wt.%, based on the vinyl monomer, solvent having a solubility of 5% or below in water at 20 deg.C and a molecular weight of 100-300 during the emulsion polymerization. In a desirable embodiment, this composition comprises 67-85 pts.wt. (in terms of the solid matter) this emulsion, 5-50 pts.wt. wax, and 3-10 pts.wt. alkali- soluble resin and has a solid content of 30-35wt.%.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a high-solids gloss composition for floors, which can be applied to a floor to impart excellent durability such as heel mark resistance and scratch resistance and high gloss. Floor polish).

[0002]

2. Description of the Related Art The floor occupying area of various buildings such as houses and shops is enormous. Various materials such as concrete and asphalt mortar floors to vinyl chloride tiles are used for floor materials, and a floor gloss composition is applied to these floor materials for the purpose of imparting beautiful luster and durability. It is often done. The conventional floor gloss composition has a solid content of 18-
It is about 22% by weight (hereinafter simply referred to as "%"), and is coated 3 to 4 times to obtain gloss and durability, but it requires a considerable amount of manpower to apply it multiple times over a wide area. Therefore, as one of the measures to save labor, a high-solids gloss composition for floors is required.

Many floor gloss compositions are harmless emulsion type, and these emulsion type floor gloss compositions contain 45% of ethyl carbitol which is a film forming aid in consideration of forming a film at room temperature. (To emulsion polymer) is included. If the emulsion type glossy composition for floor is simply subjected to high solidification as it is, there is a problem that due to the adverse effect of ethyl carbitol, it aggregates at the time of compounding, or it thickens with time and becomes a high viscosity during work, resulting in poor workability. There is. However, when the Tg of the emulsion constituent polymer is lowered to increase the film-forming property in order to reduce the amount of ethyl carbitol, the heel mark resistance of the coating film (the fact that after the heel of the shoe remains black on the floor is called the heel mark), The scratch resistance deteriorates,
It has been very difficult to obtain an emulsion type floor gloss composition having high performance and high solid content.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and does not deteriorate the coating workability or agglomerate even with a high solid content, and has heel mark resistance. An object of the present invention is to provide an emulsion type gloss composition for floors, which is excellent in properties such as scratch resistance and scratch resistance.

[0005]

Means for Solving the Problems The present invention, which has been able to solve the above-mentioned object, provides a gloss composition for floors which is an emulsion obtained by emulsion-polymerizing one or more vinyl monomers and has a solubility in water at 20 ° C. Is 5% or less and a solvent having a molecular weight of 100 to 300 is added to the vinyl monomer in an amount of 3 to 20% by weight during emulsion polymerization. Further, the emulsion as a solid content is 67 to 8
A floor gloss composition containing 5 parts by weight, 5 to 30 parts by weight of wax, and 3 to 10 parts by weight of an alkali-soluble resin and having a total solid content of 30 to 35% is a preferred embodiment of the present invention. Is.

[0006]

The gloss composition for floors of the present invention contains a specific emulsion, a wax and an alkali-soluble resin as main components. The present inventors have surprisingly found that a stable emulsion can be obtained even by adding a specific solvent during the emulsion polymerization of the emulsion to reduce the amount of ethyl carbitol used as a film-forming aid to achieve high solidification. It was found that the characteristics of the coating film obtained were good, and the present invention was achieved. The present invention will be described in detail below.

The one or more vinyl monomers used for preparing the emulsion in the present invention are not particularly limited as long as the obtained (co) polymer has a Tg of 10 to 55 ° C. Specifically, unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, etc. (Meth) acrylic acid esters synthesized by an ester forming reaction of (meth) acrylic acid with a C _{1 to} C ₁₈ alcohol; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Containing (meth) acrylic acid and hydroxyl groups such as polypropylene glycol or polyethylene glycol (meth)
Acrylic esters; (meth) acrylamide, N-
(Meth) acrylamide derivatives such as monomethyl (meth) acrylamide, N-monoethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide Ethyl 2-sulfonate (meth) acrylate and salts thereof; styrene, vinyltoluene, α -Styrene derivatives such as methylstyrene, chloromethylstyrene, styrenesulfonic acid and its salts; vinylsulfonic acid and its salts; vinyl acetate; vinyl chloride; (meth) acrylonitrile;
Glycidyl (meth) acrylate; ethylene; butadiene and the like can be mentioned, and of these, one kind or a mixture of two or more kinds can be used. Above all, (meta)
Acrylic acid and (meth) acrylic acid esters are preferably used from the viewpoint of durability and the like.

If the Tg of the emulsion (co) polymer after emulsion polymerization is lower than 10 ° C., the durability of the resulting coating film becomes poor, and if it exceeds 55 ° C., it becomes difficult to form a film at a low temperature near 0 ° C. Therefore, a large amount of film forming aid is required, which is contrary to the object of the present invention.

In the present invention, during the emulsion polymerization of the vinyl monomer, a solvent having a solubility in water at 20 ° C. of 5% or less and a molecular weight of 100 to 300 is 3 to 20% with respect to the monomer.
Existence is a mandatory requirement. This solvent acts as a film forming aid when forming a floor gloss composition into a film, and reduces ethyl carbitol which is a film forming aid, which has been conventionally used in an amount of 45% or more (to polymer), to 25 to 35%. In addition, it has a function of preventing problems such as aggregation and thickening even when a high-solids gloss composition for floors is produced using the above emulsion. When the amount of the solvent is less than 3%, these effects are not exhibited, and when the amount is more than 20%, the stability of emulsion polymerization is lowered and aggregation is apt to occur, which is not preferable. Moreover, even if these solvents are added after emulsion polymerization,
These solvents must be added during the emulsion polymerization as the emulsion will not agglomerate to give a high solids floor gloss composition.

A solvent having a solubility in water at 20 ° C. of more than 5% is not preferable because aggregation easily occurs during emulsion polymerization of the emulsion. Further, a solvent having a molecular weight of less than 100 cannot volatilize at a high rate to exhibit the effect as a film-forming aid, and if the molecular weight exceeds 300, the vapor pressure is generally low and the solvent in the coating film is It is not preferable because it will remain and the initial durability will be poor. The above molecular weight conditions can be rephrased as the boiling point conditions of the solvent, and a solvent having a boiling point of 150 to 250 ° C. under atmospheric pressure is preferably used.

Specifically, n-hexanol, n-heptanol, 2-heptanol, 3-heptanol, n-
Alcohols such as octanol, 2-octanol, 2-ethylhexanol, 3,3,5-trimethylhexanol, nonanol, n-decanol, trimethylnonyl alcohol, cyclohexanol, α-methylcyclohexanol, benzyl alcohol; ethylene glycol dibutyl ether. And polyhydric alcohol derivatives such as ethylene glycol dibutyl ether acetate and ethylene glycol monohexyl ether moth; esters such as 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, methylcyclohexyl acetate and benzyl acetate.

The emulsion used in the present invention is produced by a conventionally known emulsion polymerization method using an aqueous medium, and the method is not particularly limited. In addition, as the timing of adding the above-mentioned solvent, there is a method of dropping during the emulsion polymerization or charging all at once from the beginning of the polymerization. After emulsion polymerization, for the purpose of imparting durability such as heel mark resistance and scratch resistance as floor polish, zinc oxide or zinc ammine complex is added in an amount of 0.5 to 4 with respect to the total amount of monomers charged in terms of zinc oxide.
% Is preferably added. However, if it is added in an amount of 4% or more, the coating film may become cloudy in the case of zinc oxide, and the smell of ammonia may occur in the case of the zinc ammine complex, which is not preferable. If it is added in an amount of 0.5% or less, no durability manifesting effect is observed.

The gloss composition for floors of the present invention comprises 67-85 parts by weight (hereinafter simply abbreviated as "part") of the emulsion having the above-mentioned composition and 5-30 parts of wax.
Part, an alkali-soluble resin are mixed in an amount of 3 to 10 parts and the solid content is adjusted to 30 to 35% by adjusting the amount of a film forming aid and water described later.

As the wax, animal waxes such as beef tallow, hydrogenated cured product of lard, lanolin, beeswax and whale wax;
Castor oil hydrogenates, vegetable waxes such as carnauba wax, candela wax, wooden wax, and juvenile wax; natural waxes such as mineral waxes such as montan wax, ceresin wax, paraffin wax, and microcrystalline wax, and a molecular weight of 50
Synthetic waxes such as polyethylene wax and polypropylene wax of about 0 to 5000 can be used.

It is recommended that these waxes be added to the above-mentioned emulsion after they have been made into an aqueous dispersion by a method of appropriately adding a conventionally known emulsifier and emulsifying the same with an emulsifying machine or the like. The compounding amount of the wax is 5 to 30 parts with respect to 67 to 85 parts of emulsion solid content (5.88 to 44.7 when converted to 100 parts by weight of solid content of emulsion).
8 parts) is preferred. When the amount of wax is less than 5 parts, the resulting coating film is inferior in slipperiness and deteriorates in heel mark resistance.
Further, if it is added in an amount of more than 30 parts, water resistance, gloss, and recoatability deteriorate, which is not preferable. The more preferable addition amount is 10 to 20 parts (solid content).

As the alkali-soluble resin, one having a relatively low molecular weight having a carboxyl group in the molecule is suitable, and it is added to the base emulsion in a state of being dissolved in ammonia. Specifically, styrene-maleic acid resin,
A rosin-modified maleic acid resin, a (meth) acrylic acid- (meth) acrylic acid ester-based resin, or the like is used.

The amount of the alkali-soluble resin blended is 3 to 10 parts with respect to 67 to 85 parts of emulsion solids (3.5 to 100 parts by weight of solids of emulsion).
14.9 parts) is preferred. More preferable blending amount is 4 to 7
It is a department. After the gloss composition for floors has been applied to the floor for a certain period of time, it is peeled off with a specific peeling solution before being recoated, but when the amount of the alkali-soluble resin is less than 3 parts, the peelability is poor. Is not desirable. Also, the leveling property of the floor gloss composition is deteriorated. On the other hand, if the amount exceeds 10 parts, the gloss of the coating film becomes poor.

The floor gloss composition of the present invention contains ethyl carbitol as a film forming aid in addition to the emulsion containing a specific solvent, the wax and the alkali-soluble resin. The object of the present invention is to increase the solid content of the gloss composition for floors, but in the present invention, the amount of ethylcarbitol used can be reduced from the conventional 45%. This is because the base emulsion contains a solvent that can act as a film forming aid, and the appropriate amount of ethylcarbitol used in the present invention is 25 to 35%.

Further, a plasticizer may be added to the gloss composition for floor in order to help the film formation at room temperature and to impart the leveling property. As a plasticizer, tributoxyethyl phosphate (TBXP) or dibutyl phthalate (DBP)
Etc. are preferably used, and the blending amount is preferably about 6 to 10% with respect to the solid content of the emulsion. If necessary, a leveling agent or an antifoaming agent may be added to the floor gloss composition of the present invention.

[0020]

The present invention will be described in more detail with reference to the following examples, but the following examples do not limit the present invention.
All modifications and implementations that do not depart from the spirit of the description below are included in the technical scope of the present invention.

Reference Example 1 (Preparation of emulsion EM-1) A container equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel was charged with 180 parts of deionized water and 4 parts of potassium persulfate, The internal temperature was set to 80 ° C. In this, 300 parts of methyl methacrylate, 1 butyl acrylate
40 parts, 50 parts of methacrylic acid and Hitenol N-08 (polyoxyethylene nonylammonium phenylsulfate: manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 95 adjusted to a 15% aqueous solution in advance.
Parts, benzyl alcohol (molecular weight 108.1: boiling point 20
A dropping monomer emulsion consisting of 49 parts (10% of the total amount of the monomer) of 5%: solubility in water at 20 ° C, 3.8%) and 120 parts of deionized water was flowed in over 3 hours. During this time, the internal temperature was kept at 80 ° C. Then cool to 50 ° C,
15 parts of a zinc oxide dispersion (solid content 50%) was added, and the mixture was stirred for 1 hour and cooled to room temperature. After cooling, the produced content was taken out through an 80-mesh filter. The obtained emulsion (EM-1) has a nonvolatile content of 45% and a viscosity of 50c.
ps, pH 8.0.

Reference Example 2 (Preparation of emulsion EM-2) An emulsion EM-2 was obtained in the same manner as in Reference Example 1 except that the amount of benzyl alcohol was 24.5 parts (5% of the total amount of the monomers). This EM-2 has a nonvolatile content of 45%,
The viscosity was 50 cps and the pH was 8.0.

Reference Example 3 (Preparation of Emulsion EM-3) Instead of benzyl alcohol, ethylene glycol monobutyl ether acetate (molecular weight 161: boiling point 191).
Emulsion EM-3 was obtained in the same manner as in Reference Example 1, except that the solubility in water at 20 ° C: 1.1%) was used. This EM-3 has a nonvolatile content of 45% and a viscosity of 50 cp.
s, pH 8.0.

Comparative Reference Example 1 (Preparation of Emulsion EM-4) An emulsion EM-4 was obtained in the same manner as in Reference Example 1 except that benzyl alcohol was not added. This EM-4
Had a nonvolatile content of 45%, a viscosity of 50 cps, and a pH of 8.0.

Comparative Reference Example 2 (Preparation of Emulsion EM-5) Reference example except that dioctyl phthalate (molecular weight 390.5: boiling point 340 ° C .: solubility in water having a boiling point of 340 ° C .: 20 ° C. is not more than 0.02%) was used instead of benzyl alcohol. Emulsion EM-5 was obtained in the same manner as in Example 1. This EM-
No. 5 had a nonvolatile content of 45%, a viscosity of 50 cps and a pH of 8.0.

Comparative Reference Example 3 Emulsion polymerization was carried out in the same manner as in Reference Example 1 except that the amount of benzyl alcohol was increased to 147 parts (30% of the total amount of monomer) in Reference Example 1, but agglomerated during the polymerization. , No emulsion was obtained.

Comparative Reference Example 4 In the same manner as in Reference Example 1, except that ethanol (molecular weight 46.1: boiling point 78.3 ° C .: solubility in water at 20 ° C. ∞) was used in place of benzyl alcohol. Emulsion polymerization was carried out, but agglomeration occurred during the polymerization, and no emulsion was obtained. The above results are summarized in Table 1.

[0028]

[Table 1]

Examples 1 to 3 and Comparative Examples 1 to 6 Using the emulsions obtained in Reference Examples 1 to 3 and Comparative Reference Examples 1 and 2, gloss compositions for floors were prepared. The composition is shown in Table 2. The amount of ethyl carbitol used was tributoxyethyl phosphate (TB
XP) at 8% (relative to emulsion solids),
The minimum amount of ethyl carbitol required for forming a film at 0 ° C. was taken as a value measured by a thermal gradient tester. Hitec E-4B (manufactured by Toho Chemical Co., Ltd.) was used as the wax emulsion, and Duretsu PR-19788 (manufactured by Sumitomo Duretsu) was used as the alkali-soluble resin. Further, as a leveling agent, a fluorine-based surfactant, Fgentent 150 (manufactured by Nopco: solid content 1
%) In the floor gloss composition.

[0030]

[Table 2]

The resulting gloss composition for floors was evaluated by the following evaluation methods, and the results are shown in Table 3. A vinyl chloride-based homogeneous floor tile was used as the floor material. <Coating Workability> The viscosity of the glossy composition for floor at 25 ° C. was measured with a BM type rotational viscometer rotor No. 1 at 60 rpm. If the viscosity is high, it becomes difficult to apply the mop or the like.
The evaluation criteria are as follows.

◯: 10 cps or less ×: more than 10 cp <Overcoating property> The surface condition of four times overcoating at intervals of 30 minutes was visually evaluated. If the stability of the floor gloss composition is poor, the recoatability will deteriorate. ◯: The coating film is completely formed. Δ: The non-coating portion is 50% or less. X: No coating film was formed.

<Leveling property> The surface condition of two overcoats at intervals of 30 minutes was visually evaluated. ○: Completely leveled. Δ: Not slightly leveled. ×: No leveling at all. <Gloss> Overcoat was applied twice at intervals of 30 minutes, and the 60 ° specular reflection gloss was measured with a gloss meter. ◯: The gloss value is 87 or more. Δ: The gloss value is 80 or more and less than 87. X: The gloss value is less than 80.

<Durability-1: Black Heel Mark Resistance> Eight black shoe heels are put in the Snell capsule 1 shown in FIG. The test panel 2 which was coated with the floor gloss composition twice at 30-minute intervals and dried for 1 day was attached to the window of the Snell capsule so that the coated surface was on the inside, and 50r
The state of adhesion of the black heel mark after rotating for 30 minutes at pm was visually observed. ○: Black heel mark is not attached at all. △: Black heel marks are slightly large. ×: There are many black heel marks. <Durability-2: Scratch resistance> The same test as the black heel mark resistance test was performed. ○: There are few scratches and there are few. Δ: Many scratches are shallow. X: Many scratches are deep.

<Peelability> 10 sample panels were applied to a 15 cm × 15 cm floor tile in a standard stripping solution specified by the Japan Floor Polish Industry Association at a rate of 15 g / m ^2.
The peeled state after immersing for a minute was observed. ◯: The coating film was completely peeled off. Δ: 50% or more peeled. X: Almost no peeling.

[0036]

[Table 3]

Comparative Examples 7 to 10 Using EM-1 obtained in Reference Example 1, gloss compositions for floors having different solid contents as shown in Table 4 were prepared. The performance of Example 1 is compared with the evaluation items described above, and shown in Table 5. However, Comparative Example 10 is EM-4 obtained in Comparative Reference Example 1.
Benzyl alcohol to the solid content of EM-4 at 10
%, But coagulation occurred at the time of addition and evaluation as a floor gloss composition could not be performed. The gloss and durability-1, 2 tests of Comparative Examples 7-9 are the results of three repeated coatings. In addition, the following dryness test was evaluated.

<Drying property test> Each sample was coated on a vinyl chloride type homogeneous floor tile so as to have a concentration of 30 g / m ^2, and immersed in water to measure the time until redispersion was stopped. ○: 0 minutes or more and less than 5 minutes. Δ: 5 minutes or more and less than 10 minutes. X: 10 minutes or more.

[0039]

[Table 4]

[0040]

[Table 5]

[0041]

EFFECTS OF THE INVENTION In the present invention, by adding a specific solvent during emulsion polymerization of an emulsion, it is stable even when highly solidified, and good film formation is possible even with a small amount of film-forming auxiliary. It was possible to provide a good emulsion. The gloss composition for floors based on this emulsion is excellent in various properties such as coating workability, drying property, durability and leveling property, and when applied to various floor materials, a coating film with beautiful gloss can be obtained. can get.

[Brief description of drawings]

FIG. 1 is an explanatory diagram of a test apparatus for checking black heel mark resistance.

Claims (2)

[Claims] 1. An emulsion obtained by emulsion-polymerizing one or more vinyl monomers, wherein a solvent having a solubility in water at 20 ° C. of 5% by weight or less and a molecular weight of 100 to 300 is 3 to the vinyl monomer. A gloss composition for floors, which comprises an emulsion added during 20% by weight emulsion polymerization. 2. 67 to 85 parts by weight of the emulsion according to claim 1 as a solid content, 5 to 30 parts by weight of wax,
And 3 to 10 parts by weight of an alkali-soluble resin, and the total solid content is 30 to 35% by weight.