JPH08291272A - Copolymer emulsion for floor glazing agent composition and floor glazing agent composition - Google Patents

Abstract

PURPOSE: To obtain a floor glazing agent composition excellent in water resistance without combinedly using a polyvalent metal and exhibiting a high gloss. CONSTITUTION: This copolymer emulsion for floor glazing agent composition is obtained by emulsion polymerization of 100 pts.wt. of a monomer mixture consisting of 4-23wt.% of an α,β-ethylenically unsaturated carboxylic acid, 5-55wt.% of an aromatic vinyl compound and 22-91wt.% of an acrylate or a methacrylate in the presence of 0.25-1.5wt.% of an anionic surfactant.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an emulsion copolymer for a floor polish composition which exhibits strong water resistance and high gloss and is excellent in durability, and a floor polish composition containing the same. Regarding

2. Description of the Related Art Generally, a polishing agent which is used for polishing a floor or the like is excellent in durability such as exhibiting and maintaining a beautiful luster and being hard to have a black heel mark or a scuff mark on shoes when walking. Things are required. BACKGROUND ART Conventionally, an aqueous polish composition has been known in which an acrylic resin emulsion is mixed with an alkali-soluble resin, a plasticizer, a wax agent, a surfactant and the like for the purpose of aesthetic appearance and protection of floors, furniture and the like. For these glossing emulsions, a method of crosslinking an acrylic resin containing a carboxyl group with a polyvalent metal ion (JP-A-47-15597) is used. The floor polish composition obtained by this method is effective in that the so-called metal crosslink increases the strength of the coating film and improves the water resistance and durability.

However, the polyvalent metals used in these polish compositions are zinc, cobalt, cadmium,
Nickel, chromium, zirconium, tin, tungsten,
It is a heavy metal such as aluminum and is not preferable from the viewpoint of environmental pollution. Furthermore, since such a polish composition requires skill in application, it requires professionally trained workers to use appropriate chemical products and tools, which poses a work problem for general household use. there were. On the other hand, a polish composition that does not use a polyvalent metal (JP-A-4-224810) is also used, but the film formed by this is not a problem even if it is splashed with water, but it is used for daily cleaning (wiping with a cloth). ) Caused a problem in water resistance such as easy peeling. Further, a method of improving water resistance by adding aqueous colloidal silica or copolymerizing with a silane compound has also been proposed (JP-A-62-1).
61876), however, the composition containing them has a problem in stability over time because the reaction proceeds even during storage, resulting in precipitation or gelation.

[0003]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide an emulsion copolymer for a floor polish composition which exhibits excellent water resistance and high gloss without using a polyvalent metal in combination, and the polish composition. It is an object of the present invention to provide a polish composition having excellent performance, which contains an emulsion copolymer for use.

The present inventors have found that when emulsion-copolymerizing a monomer mixture, the use of a very small amount of anionic activator as an emulsifier in a system using a specific monomer mixture leads to high gloss. That is, it was made based on the finding that a polish copolymer having excellent water resistance can be obtained.

That is, the present invention provides (1) α, β-ethylenically unsaturated carboxylic acid 4 to 23% by weight (2) aromatic vinyl monomer 5 to 55% by weight (3) acrylic acid ester / or methacrylic acid Monomer mixture 100 consisting of 22 to 91% by weight of acid ester monomer
An emulsion copolymer for a floor polish composition, characterized by being obtained by emulsion polymerization using an anionic emulsifier in a proportion of 0.25 to 1.5% by weight, based on parts by weight. To do. The present invention also provides a polish composition containing the above copolymer. (1) α, β-used in the present invention
The ethylenically unsaturated carboxylic acid imparts removability of the coating film with an alkaline solution. Any monomer containing one or more carboxyl groups may be used, and examples thereof include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid and aconitic acid having 3 to 6 carbon atoms,
Examples include β-ethylenically unsaturated carboxylic acids. Preferred are acrylic acid having 3 to 5 carbon atoms, methacrylic acid, itaconic acid and the like.

The above α, β-ethylenically unsaturated carboxylic acid is 4 to 23%, preferably 7 to 19% in the polymer.
If it is less than 4%, the removability with alkaline water tends to be poor, and if it is more than 15%, the water resistance decreases and the workability decreases due to thickening. The (2) aromatic vinyl monomer used in the present invention imparts excellent gloss to the film due to its high crystallinity, which is a physical property, and is a carbon such as styrene, methylstyrene, vinyltoluene, etc. Number 8 to 1
6, preferably an aromatic vinyl compound having 8 to 12 carbon atoms. Aromatic vinyl monomer is 5 to 55 in the polymer
%, Preferably 10 to 50%. If it is less than 5%, sufficient gloss is not exhibited, and if it exceeds 55%, black heel mark resistance and impact resistance are deteriorated.

The acrylic acid ester and / or methacrylic acid ester used in the present invention has, for example, a carbon number of an alkyl group such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate and the like. Examples thereof include methacrylic acid alkyl esters having 1 to 12 carbon atoms in the alkyl group such as 1 to 12 acrylic acid alkyl esters, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and hexyl methacrylate. When the number of carbon atoms of the alkyl group in these esters exceeds 5, the stain resistance is deteriorated, and when the number of carbon atoms approaches 1, the slightly residual monomer gives off a remarkable odor, which is not preferable in terms of work. Preferably, monomers having an alkyl group having 1 to 4 carbon atoms may be used alone or in combination. The amount of acrylic acid ester and / or methacrylic acid ester is 22 to 91%, preferably 31 to 75% by weight of the monomer in the polymer.

The polymer of the present invention comprises the above-mentioned monomers (1) to
It is a polymer having a specific monomer composition ratio of (3). Usually, this polymer has a glass transition temperature (hereinafter abbreviated as Tg) determined from the following Fox formula (I) of 313 to 37.
It preferably has a Tg of 3 ° K. In order to further exert the effect of the present invention, 323 to 363 ° K is particularly preferable. If it is lower than this, the black heel mark resistance is remarkably lowered, and if it is higher than this, the film forming property is lowered. Calculation formula of Tg (Fox formula) 1 / Tg = (W ₁ / Tg ₁ ) + (W ₂ / Tg ₂ ) ... + (W _n / Tg _n ) ... (I) In the formula, Tgn: Tg (absolute temperature) of homopolymer of composition monomer n Wn: weight fraction of composition monomer n

The copolymer for the polish composition of the present invention is preferably obtained by a usual emulsion polymerization method. The production by the emulsion polymerization method can be carried out according to the method described in JP-A-55-110170. As the surfactant used in the present invention, it is preferable to use an anionic emulsifier having a polyethylene oxide chain represented by the following general formula (II). This contributes to the improvement of water resistance because it has an emulsifying power even in a very small amount and has excellent compatibility with a resin. Particularly preferred is an alkyl ether sulfate ester salt in which R is a linear alkyl group. _{R-O- (CH 2 CH 2} O) n-SO 3 M (II) (R is an alkyl group having 12 to 18 carbon atoms, mono-alkylphenyl, dialkylphenyl, alkyl diphenyl group,
n represents 1 to 8, and M represents sodium, potassium or ammonium. )

The amount of the surfactant used is suitably 0.25 to 1.5% by weight, preferably 0.4 to 1%, based on the total amount of the radical-polymerizable monomer. If it is less than 0.25%, the reaction does not proceed because the emulsifying power is insufficient, and if it is more than 1.5%, the water resistance is significantly reduced. Further, when an anionic emulsifier other than this, such as sodium lauryl sulfate or alkylbenzene sulfonate, is used, it lacks compatibility with the resin and peels off with a force such as a rag.
Further, since the nonionic emulsifier has a weak emulsifying power, it must be used in an amount of 2% or more, and water resistance cannot be expected. As the polymerization initiator used in the production of the emulsion copolymer of the present invention, an initiator used in ordinary emulsion polymerization can be used, but as the peroxide initiator, hydrogen peroxide, benzoyl peroxide, acetyl peroxide, Persulfate, ammonium persulfate, percarbonate, perborate and the like are used as azo initiators such as azobis (2-methylpropionamidine) hydrochloride and azobis (2
Imidazoline 2-yl) propane hydrochloride, azobis (2-methylpropionic acid amide) dihydrate, azobis (2-methylpropane), azobis (isobutyronitrile) and the like can be mentioned.

The amount of the polymerization initiator to be used is appropriately 1.1 to 5% by weight based on the total amount of the radical-polymerizable monomer,
It is preferably 0.2 to 2%. The polymerization initiator may be added all at once at the beginning of the reaction, or a method of continuously adding may be employed. The reaction temperature is usually 40 to 90 ° C., but depending on the case, it may be lower or higher. In this way, the above monomers (1) to (4)
The average molecular weight of a polymer having a specific monomer composition ratio of
Generally, it has a high molecular weight of several hundreds of thousands or more, and a high degree of crosslinking may show a high molecular weight of tens of millions to 1 billion.
Preferably hundreds of thousands to tens of millions of polymers are used in the aqueous medium.
An aqueous dispersion having 0 to 60% by weight, preferably 30 to 50% by weight, is obtained. Here, an aqueous solvent such as ethanol may be added to the aqueous medium, and the water content may be adjusted by a known method after the aqueous dispersion is prepared by the above method.

The floor polish composition of the present invention comprises the above-mentioned emulsion copolymer as an active ingredient, and the common ingredients added to the aqueous polish composition such as wax, alkali-soluble resin and plasticizer. It can be prepared by adding one kind or a mixture of two or more kinds. Here, the content of the above-mentioned copolymer of the present invention in the polish composition may be arbitrary, but is usually 20 to 83% by weight, preferably 40 to
It is preferably 67% by weight. The wax that can be added to the floor polish composition of the present invention has a further gloss,
It imparts durability, abrasion resistance, etc. to the polish composition, and includes natural waxes (eg, candelia wax, carnauba wax, beeswax), synthetic waxes (eg polyethylene, polypropylene), partially synthetic esters (eg montan wax). Derivatives) are mentioned, and among them, synthetic wax such as polyethylene is preferable. The amount of wax added is 5 to 50%, preferably 5 to 35%, based on the resin solid content of the aqueous dispersion.

The alkali-soluble resin which can be added to the floor polish composition of the present invention imparts leveling property to the polish composition, and refers to a resin which is dissolved by an alkaline aqueous solution such as caustic soda and ammonia. , For example, α, β-ethylenically unsaturated acid or acid anhydride and styrene copolymer, alkali-soluble alkyd resin, rosin and condensation products of rosin and polyhydric alcohol, Manila gum, shellac, casein, terpene resin and the like. Can be mentioned. Preferred are copolymers of acid anhydride and styrene, modified products of rosin ester, and alkyl-soluble alkyd resins. The amount of alkali-soluble resin added is 0 to 40%, preferably 2 to 20%, based on the resin solid content of the aqueous dispersion.

The plasticizer which can be added to the floor polish composition of the present invention is a semi-permanent or temporary plasticizer capable of imparting film forming properties and leveling properties to the polish composition and adjusting the film hardness. Refers to solvents such as agents (film forming aids). For example, as the plasticizer, phthalic acid ester-based dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, and other phosphoric acid ester-based trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, etc. are useful, and a film-forming aid. Carbitols such as ethyl carbitol and butyl carbitol, cellosolves such as ethyl cellosolve, butyl cellosolve and iso-propyl cellosolve, and cellosolve acetates such as ethyl cellosolve acetate and butyl cellosolve acetate are useful as the solvent. The plasticizer is 5 to 75% of the emulsion resin solid content, preferably 10 to
A loading of 60% is practical. 5% plasticizer added
In the following, a continuous film is not formed, and if it exceeds 60%, the black heel mark resistance, blocking property and drying property are deteriorated. The type and amount of the plasticizer can be appropriately selected in consideration of the efficiency of lowering the film forming temperature and the compatibility.

In addition to the above-mentioned various components, various additives can be added to the floor polish composition of the present invention as required. For example, a fluoroalkyl group-containing fluorosurfactant that imparts extremely excellent leveling properties to the polish composition of the present invention, a defoaming agent, a bactericide, a fragrance, an antistatic agent, an antislip agent, etc. . The floor polish composition according to the present invention preferably has a dry solid content of 5 to 45%, more preferably 10 to 30%.

[0015]

EFFECT OF THE INVENTION By using the emulsion copolymer for floor polish composition of the present invention, a polish composition having excellent water resistance and high gloss and durability even without using a polyvalent metal together. Provide things. Next, the present invention will be described with reference to examples.

[0016]

【Example】

Example 1 An aqueous resin dispersion, which is a copolymer of the monomers shown below,
It was synthesized according to the emulsion polymerization method described in JP-A-55-110170. In the examples, parts and percentages are by weight unless otherwise specified. Methacrylic acid 15.0 parts Styrene 19.0 parts Ethyl acrylate 25.0 parts Methyl methacrylate 41.0 parts Sodium lauryl ether sulfate (EO = 3) 0.5 parts Ion-exchanged water 147.5 parts Ammonium persulfate 0.1. 5 parts 28% ammonia water 2.2 parts The obtained emulsion polymer A-1 has a pH of 7.5 and a solid content of 40.
%, A stable aqueous dispersion having a viscosity of 150 cP (25 ° C., 30 rpm, B type).

Example 2 Emulsion copolymers A-2 to A-8 were produced in the same manner as in Example 1 based on the raw materials shown in Table 1. However, A-5 and A-7 formed aggregates due to insufficient emulsifying power, and a good polymer could not be obtained. Note that A-2, A-3, A
-4 is the product of the present invention, and A-5, A-6, A-7 and A-8 are comparative products.

[0018]

[Table 1] Table 1 ────────────────────────────────── A-1 A-2 A-3 A -4 A-5 A-6 A-7 A-8 Methacrylic acid 15 10 10 10 10 10 10 10 10 Styrene 19 45 35 35 45 45 45 45 45 45 Methylmetha 41 29 10 29 29 29 29 29 29 Acrylate n-Butyl 16 10 16 16 16 16 16 16 Acrylate Ethyl acrylate 25 Emulsifier I (Note 1) 0.5 1.0 0.2 0.2 Emulsifier II (Note 2) 1.0 Emulsifier III (Note 3) 1.0 Emulsifier IV (Note 4) 1.0 3.0 Emulsion Copolymerizability Good Good Good Good Bad Poor Good Good Good

(Note 1) Lauryl ether (EO = 3) sodium sulfate (Note 2) Nonylphenyl ether (EO = 8 mol) sodium sulfate (Sanol NP-1930, manufactured by Lion Corporation) (Note 3) Dodecylbenzene Sodium sulfonate (Note 4) 30 mole adduct of nonyl phenyl ether EO (Liponox NC-300, manufactured by Lion Corporation)

Example 3 20.4 parts by weight of one of the aqueous dispersions A-1 to A-8 (solid content 45%), Hitec E-4B (solid content 40)
%) 3.8 parts by weight, SMA17352A (solid content 20
%) 2.6 parts by weight, tributoxyethyl phosphate
0.7 parts by weight, butyl cellosolve 2.9 parts by weight, Florard FC-129 (solid content 1%) 0.3 parts by weight and deionized water 24.8 parts by weight were mixed to prepare a polish composition. Here, Hitec E-4B is a polyethylene wax manufactured by Toho Chemical Industry Co., Ltd., SMA17352A.
Is a styrene-maleic anhydride-based alkali-soluble resin manufactured by ATOCHEM, solubilized with ammonia water,
Fluorard FC-129 is a fluorine-based surfactant manufactured by Sumitomo 3M Limited. In order to clarify the performance of the polish composition of the present invention, a performance test was conducted on each composition. The test items and test methods are described below.

(1) Glossiness A homogeneous floor tile (black) was used as the flooring material, and 0.6 g
Using a piece of gauze cut into pieces, spread it so that the application amount is 10 ± 2 ml / m ^2, and dry it for 60 minutes or more.
The glossiness (%) at 60 ° was measured according to Z8741 (specular gloss measurement method). (2) Water resistance (water resistance spot test) Japan Floor Polish Industry Association Standard (JFPA-13)
The following tests were performed according to That is, 0.1 ml of the test piece prepared by the above method was appropriately covered with a cover glass, allowed to stand for 1 hour, and then the remaining water droplets were sucked up.
The whitening state of the test piece after the lapse of time was visually evaluated. The display of this evaluation is as follows. ◯: No change in the film △: Some whitening in the film ×: Clear whitening of the film

(3) Water resistance (water wiping test) A flooring board was used as a flooring material, and spread with a gauze cut to 0.6 g so that the application amount was 10 ± 2 ml / m ² ,
It was dried for 60 minutes. Ten panelists wiped this with a rag and sensory-evaluated according to the following criteria to obtain an average value. ○: No abnormality in the film △: Part of the film peeled off ×: Film completely peeled off

(4) Durability Japan Floor Polish Industry Association Standard (JFPA-11)
The following test was performed using the heel mark tester described in 1. That is, the test piece (black) prepared by the above method
, When using a heel mark tester,
The degree of adhesion of scratches attached to the test piece was visually evaluated on a scale of 5 levels. The display of this evaluation is as follows. 5: No scratches are observed 4: Slight scratches are recognized 3: Scratches are recognized 2: Scratches are noticeable 1: Scratches are remarkable The results obtained are summarized in Table-2.

[0024]

[Table 2] Table 2 ────────────────────────────────── The present invention The present invention The present invention Comparison Examples Comparative Examples Emulsion Copolymer A-1 A-2 A-3 A-4 A-6 A-8 Types [Performance Evaluation] 60 ° Gloss 66 78 73 76 78 69 69 Water Resistance (Water Resistance ○ ○ ○ ○ △ △ △ Spot test) Water resistance ○ ○ ○ △ × × (Water wiping test) Durability 4 4 4 4 4 4

Claims (3)

[Claims] (1) α, β-ethylenically unsaturated carboxylic acid 4 to 23% by weight (2) aromatic vinyl monomer 5 to 55% by weight (3) acrylic acid ester / or methacrylic acid ester unit amount Monomer mixture 100 consisting of 22-91% by weight
An emulsion copolymer for a polish composition for floors, which is obtained by emulsion polymerization using an anionic emulsifier in a ratio of 0.25 to 1.5% by weight based on parts by weight. 2. The emulsion copolymer according to claim 1, wherein an alkyl ether sulfate ester salt is used as an emulsifier. 3. A floor polish composition comprising the emulsion copolymer according to claim 1 or 2.