JP2005343920A - Water-based composition and polishing agent composition for floor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-based composition in which resistance to black heel marking can sufficiently withstand walking while having a gloss-keeping property which did not exist in conventional polishing agent compositions. <P>SOLUTION: The water-based composition comprises at least (A) a coated film-forming water-based organic polymer substance and (B) a polyolefin wax emulsion and the polyolefin wax has 400-5,000 number average molecular weight (Mn) measured by using a gel permeation chromatography (GPC) and 65-130°C melting point measured by using a differential scanning calorimeter (DSC) and 850-980 kg density measured by density gradient pipe method and the wax is produced by using a metallocene catalyst. The polishing agent composition is composed of the water-based composition. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an aqueous composition, and more particularly, to an aqueous composition excellent in durability such as gloss maintenance, scratch resistance and black heel mark resistance, and a floor polish composition comprising the same.

  The classification of the floor polish composition is defined in Japanese Floor Polish Industry Association Standard-00. Among the floor polishes in this standard, the film-forming aqueous organic polymer type occupies the mainstream as a floor polish composition. This film-forming aqueous organic polymer type is disclosed in Japanese Patent Publication No. 49-1458, and is composed of an acrylic copolymer emulsion, a polyethylene wax emulsion, an alkali-soluble resin, a plasticizer, and the like. . With the widespread use of this film-forming aqueous organic polymer type, various things have been researched and developed to improve performance. For example, a polishing agent containing a polyurethane resin emulsion to obtain slip resistance (Japanese Patent Publication No. 53-22548), an aliphatic or alicyclic isocyanate and an aliphatic polyester for the purpose of improving the characteristics which are the disadvantages. Or a polishing agent containing an emulsion of a urethane resin produced from an aliphatic polyether (Japanese Patent Publication No. 6-6694), a polishing agent containing a urethane-acrylic resin emulsion (Japanese Patent Publication No. 6-6695), etc. is there. The raw material wax of the wax emulsion blended with these floor polish components includes natural wax and synthetic wax. Specifically, carnauba wax, candelilla wax, montan wax, montan derived wax, ceresin wax, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, amide wax, polyethylene wax or its carboxyl-modified wax, oxidized polyethylene wax or its carboxyl Examples thereof include modified wax, polypropylene wax or its carboxyl-modified wax, oxidized polypropylene wax or its carboxyl-modified wax, glycol-modified polyethylene oxide wax, glycol-modified oxide polypropylene wax, and ethylene-acrylic acid copolymer wax.

Conventionally, waxes to be blended in a floor polish composition are required to have a relatively high melting point and to be as hard as possible at room temperature, and high melting point polyethylene wax and polypropylene wax have been suitable. The role of such a wax is to relieve the impact applied to the coating film and to repair the scratches. However, if these high melting point waxes are used in an emulsion of an acrylic resin having a high glass transition temperature (Tg), Due to its hardness, it has the disadvantage that gloss maintenance and scratch resistance are deteriorated.
Japanese Patent Publication No.49-1458 Japanese Patent Publication No.53-22548 Japanese Patent Publication No. 6-6694 Japanese Patent Publication No. 6-6695

  An object of the present invention is to solve the above-mentioned conventional problems, and maintain a black heel mark resistance sufficient to withstand walking while maintaining an aqueous composition having a gloss maintenance property that is not found in conventional floor polish compositions. Is to provide things.

That is, the present invention
A water-based composition containing at least a film-forming aqueous organic polymer substance (A) and a polyolefin wax emulsion (B), wherein the polyolefin wax is a number average molecular weight measured by gel permeation chromatography (GPC). (Mn) is in a range of 400 to 5,000, a melting point measured by a differential scanning calorimeter (DSC) is in a range of 65 to 130 ° C., and a density measured by a density gradient tube method is 850 to 980 kg / m ^3. And an aqueous composition characterized by being a polyolefin wax produced using a metallocene catalyst, and a floor polish composition comprising the composition.

  The aqueous composition of the present invention is excellent in gloss, heel mark resistance, abrasion resistance and removability, and forms a film whose gloss can be easily recovered by buffing. Therefore, it is suitable for dry maintenance of the floor surface, and by this, it can fully meet the demands that have been increasing in recent years, such as shortening of work time, labor saving and rationalization, and is particularly useful as a floor polish. .

(Polyolefin wax)
The polyolefin wax used in the present invention is an ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms.

  Here, the α-olefin is preferably an α-olefin having 3 to 10 carbon atoms, more preferably propylene having 3 carbon atoms, 1-butene having 4 carbon atoms, 1-pentene having 5 carbon atoms. , 1-hexene having 6 carbon atoms, 4-methyl-1-pentene, 1-octene having 8 carbon atoms, etc., preferably propylene, 1-butene, 1-hexene, 4-methyl-1-pentene. It is.

  The polyolefin wax used in the present invention has a number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of 400 to 5,000, preferably 1,000 to 4,000, more preferably 1,500 to 5,000. It is in the range of 4,000.

  The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / Mn) measured by gel permeation chromatography (GPC) is usually 1.1 to 7.0 in the polyolefin wax used in the present invention. And preferably in the range of 1.2 to 6.0, more preferably 1.2 to 5.0.

  In addition, a weight average molecular weight (Mw) and a number average molecular weight (Mn) are the values of polystyrene conversion by gel permeation chromatography (GPC), and the measurement by GPC is the conditions of temperature: 140 ° C., solvent: orthodichlorobenzene. Done under.

The polyolefin wax has an intrinsic viscosity [η] measured in decalin at 135 ° C. of usually 0.04 to 0.47 dl · g ⁻¹ , preferably 0.05 to 0.47 dl · g ⁻¹ , more preferably 0.8. 07~0.20dl · ^{g -1,} even more preferably it is preferably in the range of 0.08~0.18dl · ^{g -1.}

  The polyolefin wax has a melting point measured by a differential scanning calorimeter (DSC) in the range of 65 to 130 ° C, preferably 70 to 120 ° C, more preferably 80 to 110 ° C.

The polyolefin wax has a density measured by a density gradient tube method of 850 to 980 kg / m ³ , preferably 870 to 970 kg / m ³ , more preferably 880 to 960 kg / m ³ .

  The polyolefin wax desirably has a penetration hardness of 30 dmm or less, more preferably 25 dmm or less, still more preferably 20 dmm or less, and most preferably 15 dmm or less. The penetration hardness can be measured according to JISK2207.

The polyolefin wax has an acetone extraction amount of preferably 0 to 20% by weight, more preferably 0 to 15% by weight.
The amount of acetone extracted is measured as follows.

  Using a filter (made by ADVANCE, No. 84) with a Soxhlet extractor (made of glass), 10 g of wax was set on the filter, and 200 ml of acetone was charged into a lower round bottom flask (300 ml) at 70 ° C. Extract in a hot water bath for 5 hours.

  Polyolefin wax is solid at normal temperature and becomes a low-viscosity liquid at 65 to 130 ° C. or higher.

    The polyolefin wax as described above is produced using, for example, the following metallocene catalyst comprising a metallocene compound of a transition metal selected from Group 4 of the periodic table and an organoaluminum oxy compound and / or an ionized ionic compound. be able to.

(Metallocene compound)
The metallocene compound that forms the metallocene catalyst is a metallocene compound of a transition metal selected from Group 4 of the periodic table, and specific examples include compounds represented by the following general formula (1).

M ¹ Lx (1)
Here, M ¹ is a transition metal selected from Group 4 of the periodic table, x is a valence of the transition metal M ¹ , and L is a ligand. Examples of the transition metal represented by M ¹ include zirconium, titanium, hafnium and the like. L is a ligand coordinated to the transition metal M ^1, and at least one of the ligands L is a ligand having a cyclopentadienyl skeleton, and the ligand having this cyclopentadienyl skeleton. The ligand may have a substituent. Examples of the ligand L having a cyclopentadienyl skeleton include a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, an n- or i-propylcyclopentadienyl group, n-, alkyl such as i-, sec- or t-butylcyclopentadienyl group, dimethylcyclopentadienyl group, methylpropylcyclopentadienyl group, methylbutylcyclopentadienyl group, methylbenzylcyclopentadienyl group, An alkyl-substituted cyclopentadienyl group; and an indenyl group, 4,5,6,7-tetrahydroindenyl group, a fluorenyl group, and the like. The hydrogen of the ligand having a cyclopentadienyl skeleton may be substituted with a halogen atom or a trialkylsilyl group.

  When the metallocene compound has two or more ligands having a cyclopentadienyl skeleton as the ligand L, the ligands having two cyclopentadienyl skeletons are ethylene, propylene. Or a substituted alkylene group such as isopropylidene or diphenylmethylene; a substituted silylene group such as a silylene group or a dimethylsilylene group, a diphenylsilylene group, or a methylphenylsilylene group.

Examples of ligands other than ligands having a cyclopentadienyl skeleton (ligands having no cyclopentadienyl skeleton) L include hydrocarbon groups having 1 to 12 carbon atoms, alkoxy groups, aryloxy groups, sulfones. Acid-containing group (—SO ₃ R ¹ ), halogen atom or hydrogen atom (where R ¹ is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group, an aryl group substituted with a halogen atom, or an alkyl group) A substituted aryl group).

(Example 1 of metallocene compound)
When the metallocene compound represented by the general formula (1) has a transition metal valence of 4, for example, it is more specifically represented by the following general formula (2).
R ² _k R ³ _l R ⁴ _m R ⁵ _n M ¹ (2)
Here, M ¹ is a transition metal selected from Group 4 of the periodic table, R ² is a group (ligand) having a cyclopentadienyl skeleton, and R ³ , R ⁴ and R ⁵ are each independently cyclopentadienyl. A group (ligand) having or not having a skeleton. k is an integer of 1 or more, and k + l + m + n = 4.

Examples of metallocene compounds in which M ¹ is zirconium and contains at least two ligands having a cyclopentadienyl skeleton are given below. Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium dichloride, bis (1-methyl-3-butylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate), bis (1, 3-dimethylcyclopentadienyl) zirconium dichloride and the like.

  Among the above compounds, compounds in which the 1,3-position substituted cyclopentadienyl group is replaced with a 1,2-position substituted cyclopentadienyl group can also be used.

As another example of the metallocene compound, in the general formula (2), at least two of R ² , R ³ , R ⁴ and R ⁵ , for example, R ² and R ³ are groups having a cyclopentadienyl skeleton ( A bridge type metallocene compound in which at least two groups are bonded via an alkylene group, a substituted alkylene group, a silylene group, a substituted silylene group, or the like. At this time, R ⁴ and R ⁵ are each independently the same as the ligand L other than the ligand having the cyclopentadienyl skeleton described above.

  Examples of such bridge-type metallocene compounds include ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, methyl And phenylsilylene bis (indenyl) zirconium dichloride.

(Example 2 of metallocene compound)
Moreover, as an example of a metallocene compound, the metallocene compound of Unexamined-Japanese-Patent No. 4-268307 represented by following General formula (3) is mentioned.

Here, M ¹ is a Group 4 transition metal of the periodic table, and specifically includes titanium, zirconium, and hafnium.

R ¹¹ and R ¹² may be the same or different from each other, and are a hydrogen atom; an alkyl group having 1 to 10 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms; Aryloxy group having 6 to 10 carbon atoms; alkenyl group having 2 to 10 carbon atoms; arylalkyl group having 7 to 40 carbon atoms; alkylaryl group having 7 to 40 carbon atoms; arylalkenyl group having 8 to 40 carbon atoms Or a halogen atom, and R ¹¹ and R ¹² are preferably chlorine atoms.

R ¹³ and R ¹⁴ may be the same or different from each other, and are a hydrogen atom; a halogen atom; an optionally halogenated alkyl group having 1 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms; (R ²⁰ ) ₂ , —SR ²⁰ , —OSi (R ²⁰ ) ₃ , —Si (R ²⁰ ) ₃ or —P (R ²⁰ ) ₂ groups. R ²⁰ is a halogen atom, preferably a chlorine atom; an alkyl group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms; or an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms. R ¹³ and R ¹⁴ are particularly preferably hydrogen atoms.

R ¹⁵ and R ¹⁶ are the same as R ¹³ and R ¹⁴ except that they do not contain a hydrogen atom, and may be the same or different from each other, preferably the same. R ¹⁵ and R ¹⁶ are preferably an optionally halogenated alkyl group having 1 to 4 carbon atoms, specifically, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, trifluoromethyl and the like. Particularly preferred is methyl.
In the general formula (3), R ¹⁷ is selected from the following group.

^{= BR 21, = AlR 21,} -Ge -, - Sn -, - O -, - S -, = SO, = SO 2, = NR 21, = CO, = PR 21, = P (O) R 21 , etc. . M ² is silicon, germanium or tin, preferably silicon or germanium. Here, R ²¹ , R ²² and R ²³ may be the same or different from each other, and are hydrogen atom; halogen atom; alkyl group having 1 to 10 carbon atoms; fluoroalkyl group having 1 to 10 carbon atoms; carbon atom An aryl group having 6 to 10 carbon atoms; a fluoroaryl group having 6 to 10 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; an alkenyl group having 2 to 10 carbon atoms; an arylalkyl group having 7 to 40 carbon atoms; An arylalkenyl group having 8 to 40 carbon atoms; or an alkylaryl group having 7 to 40 carbon atoms. “R ²¹ and R ²² ” or “R ²¹ and R ²³ ” may form a ring together with the atoms to which they are bonded. R ¹⁷ may be = CR ²¹ R ²² , = SiR ²¹ R ²² , = GeR ²¹ R ²² , -O-, -S-, = SO, = PR ²¹ or = P (O) R ^21. preferable. R ¹⁸ and R ¹⁹ may be the same as or different from each other, and examples thereof include the same as R ²¹ . m and n may be the same or different and are each 0, 1 or 2, preferably 0 or 1, and m + n is 0, 1 or 2, preferably 0 or 1.

Examples of the metallocene compound represented by the general formula (3) include the following compounds. rac-ethylene (2-methyl-1-indenyl) ₂ -zirconium dichloride, rac-dimethylsilylene (2-methyl-1-indenyl) ₂ -zirconium dichloride, and the like. These metallocene compounds can be produced, for example, by the method described in JP-A-4-268307.

(Example 3 of metallocene compound)
Moreover, as a metallocene compound, the metallocene compound represented by following General formula (4) can also be used.

In Formula (4), M ³ represents a transition metal atom of Group 4 of the periodic table, and specifically, titanium, zirconium, hafnium, and the like. R ²⁴ and R ²⁵ may be the same or different and are each a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, oxygen A containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group; R ²⁴ is preferably a hydrocarbon group, and particularly preferably an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl or propyl. R ²⁵ is preferably a hydrogen atom or a hydrocarbon group, particularly preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl or propyl. R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon having 1 to 20 carbon atoms. Indicates a group. Among these, a hydrogen atom, a hydrocarbon group, or a halogenated hydrocarbon group is preferable. At least one of R ²⁶ and R ²⁷ , R ²⁷ and R ²⁸ , and R ²⁸ and R ²⁹ may form a monocyclic aromatic ring together with the carbon atoms to which they are bonded. Good. When there are two or more hydrocarbon groups or halogenated hydrocarbon groups other than the group forming the aromatic ring, they may be bonded to each other to form a ring. When R ²⁹ is a substituent other than an aromatic group, it is preferably a hydrogen atom. X ¹ and X ² may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen atom-containing group or A sulfur atom-containing group is shown. Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, a divalent tin-containing group, -O -, - CO -, - S -, - SO -, - SO 2 -, - NR 30 -, - P (R 30) -, - P (O) (R 30) -, - BR ³⁰ — or —AlR ³⁰ — (wherein R ³⁰ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms).

In the formula (4), at least one pair of R ²⁶ and R ²⁷ , R ²⁷ and R ²⁸ , R ²⁸ and R ²⁹ is bonded to each other, and is coordinated to M ³ Examples of the ligand include those represented by the following formula.

（式中、Ｙは前式に示したものと同じである。）

(In the formula, Y is the same as that shown in the previous formula.)

(Example 4 of metallocene compound)
As the metallocene compound, a metallocene compound represented by the following general formula (5) can also be used.

In the formula (5), M ³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ are the same as those in the general formula (4). Of R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ , two groups including R ²⁶ are preferably alkyl groups, and R ²⁶ and R ²⁸ , or R ²⁸ and R ²⁹ are alkyl groups. preferable. This alkyl group is preferably a secondary or tertiary alkyl group. The alkyl group may be substituted with a halogen atom or a silicon-containing group. Examples of the halogen atom and silicon-containing group include the substituents exemplified for R ²⁴ and R ²⁵ . Of R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ , the group other than the alkyl group is preferably a hydrogen atom. R ²⁶ , R ²⁷ , R ^28, and R ²⁹ may form a monocyclic ring or a polycyclic ring other than an aromatic ring by combining two groups selected from these groups. Examples of the halogen atom are the same as those described above for R ²⁴ and R ²⁵ . Examples of X ¹ , X ² and Y are the same as those described above.

  Specific examples of the metallocene compound represented by the general formula (5) are shown below. rac-dimethylsilylene-bis (4,7-dimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,4,7-trimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2 , 4,6-trimethyl-1-indenyl) zirconium dichloride and the like.

  In these compounds, transition metal compounds in which zirconium metal is replaced with titanium metal or hafnium metal can also be used. The transition metal compound is usually used as a racemate, but can also be used in the R-type or S-type.

(Example of metallocene compound-5)
As the metallocene compound, a metallocene compound represented by the following general formula (6) can also be used.

In the formula (6), M ³ , R ²⁴ , X ¹ , X ² and Y are the same as those in the general formula (4). R ²⁴ is preferably a hydrocarbon group, particularly preferably an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl or butyl. R ²⁵ represents an aryl group having 6 to 16 carbon atoms. R ²⁵ is preferably phenyl or naphthyl. The aryl group may be substituted with a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms. X ¹ and X ² are preferably a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

  Specific examples of the metallocene compound represented by the general formula (6) are shown below. rac-dimethylsilylene-bis (4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl) -4- (α-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (β-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2 -Methyl-4- (1-anthryl) -1-indenyl) zirconium dichloride and the like. In these compounds, transition metal compounds in which zirconium metal is replaced with titanium metal or hafnium metal can also be used.

(Example of metallocene compound-6)
As the metallocene compound, a metallocene compound represented by the following general formula (7) can also be used.

LaM ⁴ X ³ ₂ (7)
Here, M ⁴ is a periodic table group 4 or lanthanide series metal. La is a derivative of a delocalized π bond group, and is a group imparting a constraining geometry to the metal M ⁴ active site. X ³ may be the same or different from each other, and is a hydrogen atom, a halogen atom, a hydrocarbon group having 20 or less carbon atoms, a silyl group containing 20 or less silicon, or a germanyl group containing 20 or less germanium.
Among these compounds, a compound represented by the following formula (8) is preferable.

In the formula (8), M ⁴ is titanium, zirconium or hafnium. X ³ is the same as that described in the general formula (7). Cp is a substituted cyclopentadienyl group having a π bond to M ⁴ and having a substituent Z. Z is oxygen, sulfur, boron or an element belonging to Group 4 of the periodic table (for example, silicon, germanium or tin). Y is a ligand containing nitrogen, phosphorus, oxygen or sulfur, and Z and Y may form a condensed ring. Specific examples of the metallocene compound represented by the formula (8) are shown below. (Dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane) titanium dichloride, ((t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl) titanium Dichloride etc. In the metallocene compound, a compound in which titanium is replaced with zirconium or hafnium can be exemplified.

(Example 7 of metallocene compound)
Moreover, as a metallocene compound, the metallocene compound represented by following General formula (9) can also be used.

In formula (9), M ³ is a transition metal atom of Group 4 of the periodic table, specifically titanium, zirconium or hafnium, preferably zirconium. R ³¹ may be the same as or different from each other, and at least one of them is an aryl group having 11 to 20 carbon atoms, an arylalkyl group having 12 to 40 carbon atoms, an arylalkenyl group having 13 to 40 carbon atoms, carbon An alkylaryl group having 12 to 40 atoms or a silicon-containing group, or at least two adjacent groups among the groups represented by R ³¹ , together with the carbon atoms to which they are bonded, one or more aromatic rings Or an aliphatic ring is formed. In this case, the ring formed by R ^31, it is 4 to 20 carbon atoms in all including carbon atoms to which R ³¹ is bonded. Aryl group, arylalkyl group, arylalkenyl group, an alkylaryl group and an aromatic ring, R ³¹ other than R ³¹ that forms an aliphatic ring is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms Or a silicon-containing group. R ³² may be the same as or different from each other, and may be a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a carbon atom. An arylalkyl group having 7 to 40 carbon atoms, an arylalkenyl group having 8 to 40 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group It is. Further, at least two adjacent groups among the groups represented by R ³² may form one or more aromatic rings or aliphatic rings together with the carbon atoms to which they are bonded. In this case, the ring formed by R ³² has 4 to 20 carbon atoms in all including carbon atoms to which R ³² is bonded, an aromatic ring, other than R ³² that forms an aliphatic ring R ³² is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a silicon-containing group. The group in which the two groups represented by R ^{32 form} one or more aromatic rings or aliphatic rings includes an embodiment in which the fluorenyl group has a structure represented by the following formula.

R ³² is preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl or propyl. A suitable example of such a fluorenyl group having R ³² as a substituent is a 2,7-dialkyl-fluorenyl group. In this case, the 2,7-dialkyl alkyl group includes 1 to 1 carbon atoms. 5 alkyl groups. R ³¹ and R ³² may be the same as or different from each other. R ³³ and R ³⁴ may be the same as or different from each other, and are the same hydrogen atom, halogen atom, alkyl group having 1 to 10 carbon atoms, aryl group having 6 to 20 carbon atoms, and 2 to 2 carbon atoms. 10 alkenyl groups, arylalkyl groups having 7 to 40 carbon atoms, arylalkenyl groups having 8 to 40 carbon atoms, alkylaryl groups having 7 to 40 carbon atoms, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, A nitrogen-containing group or a phosphorus-containing group. Of these, at least one of R ³³ and R ³⁴ is preferably an alkyl group having 1 to 3 carbon atoms. X ¹ and X ² may be the same or different and are each a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, sulfur A conjugated diene residue formed from a containing group or a nitrogen-containing group, or X ¹ and X ² . As the conjugated diene residue formed from X ¹ and X ² , residues of 1,3-butadiene, 2,4-hexadiene, 1-phenyl-1,3-pentadiene and 1,4-diphenylbutadiene are preferable. These residues may be further substituted with a hydrocarbon group having 1 to 10 carbon atoms. X ¹ and X ² are preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a sulfur-containing group. Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, a divalent tin-containing group, -O -, - CO -, - S -, - SO -, - SO 2 -, - NR 35 -, - P (R 35) -, - P (O) (R 35) -, - BR ³⁵ — or —AlR ³⁵ — (wherein R ³⁵ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms). Among these divalent groups, those in which the shortest linking portion of -Y- is composed of one or two atoms are preferable. R ³⁵ is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms. Y is preferably a divalent hydrocarbon group having 1 to 5 carbon atoms, a divalent silicon-containing group or a divalent germanium-containing group, more preferably a divalent silicon-containing group. Particularly preferred is silylene, alkylarylsilylene or arylsilylene.

(Example of metallocene compound-8)
As the metallocene compound, a metallocene compound represented by the following general formula (10) can also be used.

In formula (10), M ³ is a transition metal atom of Group 4 of the periodic table, specifically titanium, zirconium or hafnium, preferably zirconium. R ³⁶ may be the same as or different from each other, and includes a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and silicon-containing Group, oxygen-containing group, sulfur-containing group, nitrogen-containing group or phosphorus-containing group. The alkyl group and alkenyl group may be substituted with a halogen atom. Of these, R ³⁶ is preferably an alkyl group, an aryl group or a hydrogen atom, particularly a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl, n-propyl and i-propyl, phenyl, α-naphthyl. And an aryl group such as β-naphthyl or a hydrogen atom. R ³⁷ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a carbon atom. An arylalkyl group having 7 to 40 carbon atoms, an arylalkenyl group having 8 to 40 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group It is. Note that the alkyl group, aryl group, alkenyl group, arylalkyl group, arylalkenyl group, and alkylaryl group may be substituted with halogen. Of these, R ³⁷ is preferably a hydrogen atom or an alkyl group, and particularly a hydrogen atom or a carbon atom having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, i-propyl, n-butyl, or tert-butyl. A hydrogen group is preferred. R ³⁶ and R ³⁷ may be the same as or different from each other. One of R ³⁸ and R ³⁹ is an alkyl group having 1 to 5 carbon atoms, and the other is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. A silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group. Among these, it is preferable that any one of R ³⁸ and R ³⁹ is an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl, propyl, and the other is a hydrogen atom. X ¹ and X ² may be the same or different and are each a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, sulfur A conjugated diene residue formed from a containing group or a nitrogen-containing group, or X ¹ and X ² . Among these, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms is preferable. Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, a divalent tin-containing group, -O -, - CO -, - S -, - SO -, - SO 2 -, - NR 40 -, - P (R 40) -, - P (O) (R 40) -, - BR ⁴⁰ — or —AlR ⁴⁰ — (wherein R ⁴⁰ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms). Among these, Y is preferably a divalent hydrocarbon group having 1 to 5 carbon atoms, a divalent silicon-containing group, or a divalent germanium-containing group, and more preferably a divalent silicon-containing group. An alkylsilylene, an alkylarylsilylene or an arylsilylene is particularly preferable.

  The metallocene compounds described above are used alone or in combination of two or more. The metallocene compound may be diluted with a hydrocarbon or a halogenated hydrocarbon.

(Organic aluminum oxy compound)
The organoaluminum oxy compound may be a known aluminoxane or a benzene-insoluble organoaluminum oxy compound. Such a known aluminoxane is specifically represented by the following formula.

  Here, R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group or a butyl group, preferably a methyl group or an ethyl group, particularly preferably a methyl group, and m is 2 or more, preferably 5 to 40. Is an integer.

  The aluminoxane is an alkyloxyaluminum unit represented by the formula (OAl (R ′)) and an alkyloxyaluminum unit represented by the formula (OAl (R ″)) (where R ′ and R ″ are R And R ′ and R ″ represent different groups.) And may be formed from mixed alkyloxyaluminum units. The organoaluminum oxy compound may contain a small amount of a metal organic compound component other than aluminum.

(Ionized ionic compounds)
Examples of ionized ionic compounds (sometimes referred to as ionic ionized compounds and ionic compounds) include Lewis acids, ionic compounds, borane compounds, and carborane compounds. As the Lewis acid, a compound represented by BR ₃ (R is a phenyl group which may have a substituent such as a fluorine, a methyl group or a trifluoromethyl group or fluorine) can be used. Specific examples of the Lewis acid include trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris ( Pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron and the like.

  Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts. Examples of the trialkyl-substituted ammonium salt as the ionic compound include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, and tri (n-butyl) ammonium tetra (phenyl) boron. Examples of the dialkylammonium salt as the ionic compound include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

  Examples of the ionic compound include triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, and the like. .

  Examples of the borane compound include decaborane (9); bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] bis (dodecahydridododeca Examples thereof include salts of metal borane anions such as borate) nickelate (III).

  Examples of the carborane compound include 4-carbanonaborane (9), 1,3-dicarbanonaborane (8), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) nickel acid. And salts of metal carborane anions such as salt (IV).

  Such ionized ionic compounds may be used alone or in combination of two or more.

  In forming the metallocene catalyst, the following organoaluminum compounds may be used together with the organoaluminum oxy compound and / or the ionized ionic compound.

(Organic aluminum compound)
As the organoaluminum compound used as necessary, a compound having at least one Al-carbon bond in the molecule can be used. As such a compound, for example, an organoaluminum represented by the following general formula (11) Compound,

_{^{(R 6) m Al (OR}} 7) n H p X 4 q ... (11)
(In the formula, R ⁶ and R ⁷ may be the same or different from each other, and are a hydrocarbon group usually containing 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. X ⁴ is a halogen atom. Is a number satisfying 0 ≦ m <3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is 0 ≦ q <3, and m + n + p + q = 3) and the following general formula ( And a complex alkylated product of Group 1 metal and aluminum represented by 12).

(M ⁵ ) Al (R ⁶ ) (12)
(In the formula, M ⁵ is Li, Na or K, and R ⁶ is the same as R ^{6 in the} general formula (11).)

(polymerization)
The polyolefin wax used in the present invention is obtained by homopolymerizing ethylene in a normal liquid phase or copolymerizing ethylene and an α-olefin in the presence of the metallocene catalyst. At this time, a hydrocarbon solvent is generally used, but an α-olefin may be used as a solvent. The monomers used here are as described above.

  The polymerization method includes suspension polymerization in which polyolefin wax is polymerized in the presence of particles in a solvent such as hexane, gas phase polymerization in which a solvent is not used, and polymerization temperature of 140 ° C. or higher. Solution polymerization that polymerizes in the coexistence or melted state is possible, and among these, solution polymerization is preferable in terms of both economy and quality.

  The polymerization reaction may be performed by either a batch method or a continuous method. When the polymerization is carried out by a batch method, the above catalyst components are used in the concentrations described below.

  The concentration of the metallocene compound in the polymerization system is usually 0.00005 to 0.1 mmol / liter (polymerization volume), preferably 0.0001 to 0.05 mmol / liter.

  The organoaluminum oxy compound is supplied in an amount of 1 to 10,000, preferably 10 to 5,000, in terms of the molar ratio of aluminum atom to transition metal in the metallocene compound in the polymerization system (Al / transition metal).

  The ionized ionic compound is represented by the molar ratio of the ionized ionic compound to the metallocene compound in the polymerization system (ionized ionic compound / metallocene compound), and is supplied in an amount of 0.5 to 20, preferably 1 to 10. .

  When an organoaluminum compound is used, it is generally used in an amount of about 0 to 5 mmol / liter (polymerization volume), preferably about 0 to 2 mmol / liter.

The polymerization reaction is usually at a temperature of −20 to + 200 ° C., preferably 50 to 180 ° C., more preferably 70 to 180 ° C., and the pressure is usually greater than 0 to 7.8 MPa (80 kgf / cm ² , gauge pressure). Hereinafter, it is preferably carried out under the condition of more than 0 and 4.9 MPa (50 kgf / cm ² , gauge pressure) or less.

  In the polymerization, ethylene and the α-olefin used as necessary are supplied to the polymerization system in such an amount ratio that a polyolefin wax having the specific composition described above can be obtained. In the polymerization, a molecular weight regulator such as hydrogen can be added.

  When polymerized in this manner, the produced polymer is usually obtained as a polymerization solution containing the polymer, so that a polyolefin wax can be obtained by treatment by a conventional method.

  In the present invention, it is particularly preferable to use a catalyst containing the metallocene compound shown in (Example 6 of metallocene compound).

(Modified polyolefin wax)
The polyolefin wax used in the present invention may be a modified polyolefin wax obtained by oxidizing or modifying an unmodified polyolefin wax (hereinafter also referred to as “raw material polyolefin wax”).

(Oxidation modification)
The modified polyolefin wax that has been oxidatively modified is obtained by bringing the raw material polyolefin wax into contact with oxygen or an oxygen-containing gas under stirring in a molten state.

  The raw material polyolefin wax is usually melted at a temperature of 130 to 200 ° C, preferably 140 to 170 ° C.

  In oxidative modification, the raw material polyolefin wax is brought into contact with oxygen or an oxygen-containing gas under stirring in a molten state to carry out an oxidation reaction. The term “oxygen or oxygen-containing gas” is pure oxygen (ordinary liquid air Oxygen obtained by fractional distillation or water electrolysis, which may contain other components to the extent of impurities), a mixed gas (for example, air) of pure oxygen and another gas, and ozone are used.

  As a method for contacting the raw material polyolefin wax with oxygen or the like, specifically, a method in which an oxygen-containing gas is continuously supplied from the lower part of the reactor and brought into contact with the raw material polyolefin wax is preferable. In this case, it is preferable to supply the oxygen-containing gas so that the amount of oxygen is equivalent to 1.0 to 8.0 NL per minute per 1 kg of the raw material mixture.

  The acid value (JISK5902) of the modified polyolefin wax thus obtained is preferably 5 to 300 mgKOH / g, more preferably 10 to 200 mgKOH / g.

  Here, the acid value refers to the number of mg of potassium hydroxide required for neutralization per 1 g of the sample.

(Acid graft modification)
The acid-grafted modified polyolefin wax can be prepared by a conventionally known method. For example, [1] raw material polyolefin wax and [2] unsaturated carboxylic acid or its derivative or sulfonate, [3] In a solution obtained by melt-kneading in the presence of a polymerization initiator such as an organic peroxide, or [1] a raw material polyolefin wax and [2] an unsaturated carboxylic acid or derivative or sulfonate in an organic solvent. [3] It is obtained by kneading in the presence of a polymerization initiator such as an organic peroxide.

  Examples of unsaturated carboxylic acids or derivatives thereof used for acid graft modification include methyl acrylate, ethyl acrylate, butyl acrylate, acrylate-sec-butyl, isobutyl acrylate, propyl acrylate, isopropyl acrylate, acrylic Acid-2-octyl, dodecyl acrylate, stearyl acrylate, hexyl acrylate, isohexyl acrylate, phenyl acrylate, 2-chlorophenyl acrylate, diethylaminoethyl acrylate, 3-methoxybutyl acrylate, diethylene glycol ethoxy acrylate Rate, acrylic acid esters such as acrylic acid-2,2,2-trifluoroethyl; methyl methacrylate, ethyl methacrylate, butyl methacrylate, methacrylate-sec-butyl, methacrylate Isobutyl acid, propyl methacrylate, isopropyl methacrylate, -2-octyl methacrylate, dodecyl methacrylate, stearyl methacrylate, hexyl methacrylate, decyl methacrylate, phenyl methacrylate, -2-chlorophenyl methacrylate, diethylaminoethyl methacrylate, Methacrylic acid esters such as methacrylic acid-2-hexylethyl and methacrylic acid-2,2,2-trifluoroethyl; ethyl maleate, propyl maleate, butyl maleate, diethyl maleate, dipropyl maleate, dibutyl maleate Maleic acid esters such as ethyl fumarate, butyl fumarate, dibutyl fumarate, etc .; maleic acid, fumaric acid, itaconic acid, crotonic acid, nadic acid, methyl hexahydride Dicarboxylic acids such as phthalic acid; maleic anhydride, itaconic anhydride, citraconic anhydride, allyl succinic anhydride, glutaconic acid, and the like anhydrides such as nadic.

  In the modified polyolefin wax modified with an acid graft, the amount of modification with an unsaturated carboxylic acid or a derivative thereof is preferably 10 to 300 mgKOH, more preferably 30 to 200 mgKOH, in terms of KOH titration. .

(Aqueous organic polymer)
The aqueous organic polymer substance used in the present invention is not particularly limited as long as it is a component that protects the flooring material and imparts gloss and abrasion resistance to the polish film, but is not limited to styrene resin emulsion, styrene / acrylic system. A resin emulsion, an acrylic resin emulsion, etc. are mentioned, Each may be used independently or may be used in combination of 2 or more types as appropriate. These resin emulsions can be produced by a known emulsion polymerization technique or the like, and a copolymer emulsion having an arbitrary glass transition temperature (Tg) can be obtained depending on the composition of the vinyl monomer used. In addition, Tg in this invention was calculated | required by the known calculation method from Tg of the homopolymer of each monomer which comprises a copolymer, and the structure ratio of each monomer in a copolymer. It is.

  For example, monomers used for producing these resins include, for example, ethylenic aromatic hydrocarbons such as styrene and methylstyrene, cyanovinyl compounds such as acrylonitrile and methacrylonitrile, such as methyl methacrylate and methacrylic acid. Ethyl, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, (Meth) acrylates such as stearyl acrylate, cyclohexyl acrylate, diethyl maleate, diethyl fumarate, ethyl crotonic acid, such as acrylamide, methacrylamide, N, N-di Ethylenically unsaturated carboxylic acid amides such as tilacrylamide, for example, unsaturated carboxylic acid monomers such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, citraconic acid, mesaconic acid, vinylacetic acid ( These may be in the form of salts such as alkali metal salts and ammonium salts such as sodium and potassium.), For example, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxy methacrylate And (meth) acrylic acid hydroxyalkyl esters such as propyl, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, etc. May be used in combination of two or more. In order to obtain the desired breaking strength and elongation, monomers having elongation at room temperature and / or monomers having a small glass transition point (Tg) are preferably used. For the purpose of making it possible to easily remove the film with a weak alkaline detergent or the like, for example, water-soluble substances such as the unsaturated carboxylic acid monomer and the (meth) acrylic acid hydroxyalkyl ester are used. The monomer may be copolymerized with other monomers as long as the properties of the aqueous organic polymer substance are not impaired.

  The aqueous organic polymer material thus obtained can be used as an aqueous composition that has been subjected to a post-treatment method that is usually performed such as purification, or can be used as it is without purification. That's fine.

  Further, a metal cross-linking type to which a polyvalent metal chelating agent is added may be used, which is disclosed in Japanese Patent Publication No. 49-1548, Manufacturing Chemist and Aerosol News. June. 31 (1969).

  The resin for exhibiting the gloss maintenance property needs to have a Tg of 40 ° C. or lower, but if the Tg is too low, the tack becomes intense and the stain resistance deteriorates. Therefore, Tg needs to be 5 to 40 ° C. In addition, the acrylic resin used for improving the wear resistance does not improve the wear resistance when the Tg is 40 ° C. or lower, and the film forming property decreases when the Tg is 80 ° C. or higher. It needs to be 40-80 degreeC.

  The blending ratio (weight basis) of the resin emulsion and the wax emulsion is preferably a solid content ratio of 60:40 to 98: 2, more preferably 80:20 to 97: 3. When the wax emulsion exceeds 40% by weight, the scuff resistance becomes insufficient, and when it becomes less than 2% by weight, the scratch resistance becomes insufficient.

  Moreover, the compounding ratio of the resin having a Tg of 5 to 40 ° C. and the resin having a Tg of 40 to 80 ° C. is usually the solid content of the resin having a Tg of 40 to 80 ° C. with respect to the total solid content of both. 80% by weight or less, preferably 70% by weight or less, and more preferably 60% by weight or less.

  A polyurethane resin may be used as the resin component of the aqueous organic polymer material of the present invention. The polyurethane resin is, for example, a resin produced by a urethanization reaction between a polyol such as polypropylene glycol or an alkylene oxide adduct to a polyhydric alcohol and a polyvalent isocyanate such as tolylene diisocyanate or diphenylmethane diisocyanate. Various aqueous resin dispersions in which these polyurethane resins are finely dispersed in an aqueous medium are also commercially available. For example, Neo Rez R-960 and R-940 which are water-soluble polymer emulsions manufactured by Enomoto Kasei Co., Ltd. It can be used as the aqueous organic polymer material of the present invention.

   In addition to the water-insoluble polymer emulsion described above, the aqueous composition of the present invention further comprises an unsaturated carboxylic acid monomer, a (meth) acrylic acid hydroxyalkyl ester, and, if necessary, an ethylenically unsaturated monomer. A hydrosol emulsion obtained by alkali treatment of a vinyl copolymer emulsion obtained by copolymerizing the above may be contained.

(Polyolefin wackle emulsion (B))
The polyolefin wax emulsion (B) of the present invention is obtained by emulsifying a polyolefin wax, and is a component that imparts moderate smoothness to the polish film and improves heel mark resistance. This wax emulsion is produced by a conventionally known method, and can be obtained, for example, by adding an emulsifier to polyolefin wax and emulsifying and dispersing it with various emulsifying devices.

  Moreover, you may use together the wax conventionally used for the polish agent composition. These waxes include, for example, hydrogenated hard waxes such as beef tallow and lard, animal waxes such as lanolin, beeswax, and whale wax; waxes obtained by hydrogenating soybean oil, and hydrogenated castor oil. Waxes and plant waxes such as carnauba wax, candelilla wax, wood wax and nuta wax; mineral waxes such as montanic acid wax, paraffin wax and microcrystalline wax; oxidized polystyrene wax, polyethylene wax, polypropylene wax, acrylic polymer wax, Examples thereof include synthetic waxes such as ethylene / acrylic copolymer wax and ethylene / vinyl acetate copolymer wax.

  In addition to the essential components described above, the aqueous composition of the present invention includes a fusing agent such as diethylene glycol monoethyl ether and dipropylene glycol monomethyl ether, a plasticizer such as tributoxyethyl phosphate and dibutyl phthalate, and a fluorosurfactant. In addition to a wetting agent, a hydrophilic solvent, an antifoaming agent, a preservative, and the like, other optional components can be appropriately contained as long as the properties thereof are not impaired.

  The aqueous composition of the present invention is effective as a floor polishing agent for plastic floors such as vinyl-based and synthetic resin-coated floors, stones, cement-based flooring, wood-based flooring and the like.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. Unless otherwise specified, “part” described below means “part by mass”.

(Preparation of acrylic resin emulsion)
Acrylic resin emulsions A1 and A2 having a solid concentration of 40% by weight were prepared by a known emulsion polymerization method shown below.

  In a reaction vessel equipped with a stirrer, a thermometer, a dripping device, a gas introduction pipe and a reflux condenser, 47.9 parts of deionized water, 0.8 part of sodium lauryl sulfate as an emulsifier and 30 mol nonylphenol ethylene oxide adduct 1.2 And 0.1 part of ammonium persulfate as a polymerization initiator were added and the temperature was raised to 75 ° C. 37 parts of a monomer mixture having the composition (weight ratio) shown in Table 1 below was dropped over 180 minutes. The polymerization was continued at 75 ° C. for another 60 minutes after the completion of the dropping. Thereafter, the system was cooled to 50 ° C., and 13 parts of a zinc crosslinking agent consisting of 7 parts of zinc oxide, 12 parts of ammonium carbonate, 14 parts of 25% aqueous ammonia and 67 parts of deionized water was added dropwise over 30 minutes.

The physical properties of the wax were measured as follows.
(Melt viscosity)
Measurements were made at 140 ° C. using a Brookfield viscometer.
(Intrinsic viscosity [η])
Measured according to ASTM D1601.
(density)
It measured according to JIS K6760.
(Melting point)
Measured according to ASTM D3417-75.
(Softening point)
It measured according to JIS K2207.
(Acid value)
It measured according to JIS K5902.
(Hazen color number)
The melt hue at 150 ° C. was measured according to JIS K0071-1.
(Penetration)
It measured according to JIS K2207.

[Synthesis Example 1]
(Synthesis of polyolefin wax (1))
Using a metallocene catalyst, an ethylene / propylene copolymer (polyolefin wax (1)) was synthesized as follows.

960 ml of hexane and 40 ml of propylene were charged into a 2 liter stainless steel autoclave sufficiently purged with nitrogen, and hydrogen was introduced until the pressure reached 0.08 MPa (gauge pressure). Next, after raising the temperature in the system to 150 ° C., 0.3 mmol of triisobutylaluminum, 0.004 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate, (t-butylamido) dimethyl (tetramethyl-η ⁵⁾ Polymerization was initiated by injecting 0.02 mmol of -cyclopentadienyl) silane titanium dichloride (Sigma-Aldrich) with ethylene. Thereafter, only ethylene was continuously supplied to keep the total pressure at 2.9 MPa (gauge pressure), and polymerization was carried out at 150 ° C. for 20 minutes.

After the polymerization was stopped by adding a small amount of ethanol into the system, unreacted ethylene and propylene were purged. The resulting polymer solution was dried overnight at 100 ° C. under reduced pressure. As a result, [η] is 0.23 dl / g, melt viscosity is 720 mPa · s, Mn is 1900, Mw is 5900, density is 932 kg / m ³ , and melting point is 109 ° C. There was obtained 32.5 g of a metallocene wax having a softening point of 112 ° C., a penetration of 1 dmm and a propylene content of 5.3 mol%.

  The above synthesis operation was repeated 20 times, and the synthesized 20 metallocene waxes were melt mixed and then cooled to obtain polyolefin wax (1).

[Synthesis Example 2]
(Synthesis of polyolefin wax (2))
Using a metallocene catalyst, an ethylene / propylene copolymer (polyolefin wax (2)) was synthesized as follows.

980 ml of hexane and 20 ml of propylene were charged into a 2 liter stainless steel autoclave sufficiently purged with nitrogen, and hydrogen was introduced until the pressure reached 0.30 MPa (gauge pressure). Next, after raising the temperature in the system to 150 ° C., 0.3 mmol of triisobutylaluminum, 0.004 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate, (t-butylamido) dimethyl (tetramethyl-η ⁵⁾ Polymerization was initiated by injecting 0.02 mmol of -cyclopentadienyl) silane titanium dichloride (Sigma-Aldrich) with ethylene. Thereafter, only ethylene was continuously supplied to keep the total pressure at 2.9 MPa (gauge pressure), and polymerization was carried out at 150 ° C. for 20 minutes.

After the polymerization was stopped by adding a small amount of ethanol into the system, unreacted ethylene and propylene were purged. The resulting polymer solution was dried overnight at 100 ° C. under reduced pressure. As a result, [η] is 0.09 dl / g, melt viscosity is 18 mPa · s, Mn is 500, Mw is 1100, density is 938 kg / m ³ , and melting point is 113 ° C. There was obtained 27.5 g of a metallocene wax having a softening point of 115 ° C., a penetration of 10 dmm and a propylene content of 2.5 mol%.

  The above synthesis operation was repeated 20 times, and the synthesized 20 metallocene waxes were melt mixed and then cooled to obtain a polyolefin wax (2).

[Polypropylene wax (HWNP055)]
Propylene / ethylene copolymer produced by heat degradation of high molecular weight polypropylene, containing no functional group with an ethylene content of 3.5 mol% and an intrinsic viscosity of 0.12 dl / g Polypropylene wax (Mitsui Chemicals, HWNP055).

[Oxidation-modified polyolefin wax production example 1]
The oxidation reaction was carried out in a 2 L autoclave (equipped with a thermometer, pressure gauge, stirrer, gas introduction pipe, and gas exhaust pipe). After a mixture of 500 g of polyethylene wax (1) and 2 g of polypropylene wax (HWNP055) was melted and the internal temperature reached 165 ° C., the stirrer was set at 300 min ⁻¹ and air was supplied at 1.2 L / min. Introduced into the melt, the internal pressure was 0.69 MPa. While introducing air, the reaction temperature was maintained at 165 ° C., the stirring speed was maintained at 300 min ⁻¹ , and the pressure was maintained at 0.69 MPa, and the reaction was terminated after 5 hours. The product obtained has an [η] of 0.15 dl / g, a melt viscosity of 250 mPa · s, an Mn of 1100, an Mw of 5200, a density of 950 kg / m ³ and a melting point of It had a softening point of 104 ° C., a penetration of 1 dmm, an acid value of 19.8 KOH mg / g, and a 150-200 Hazen color number.

[Production Example 1 of Acid Graft Modified Polyolefin Wax]
Maleic anhydride melted at 60 ° C. in a ratio of 10 g of maleic anhydride to 90 g of polyolefin wax (2) by melting the polyolefin wax (2) synthesized in Synthesis Example 2 in a stainless steel autoclave at 170 ° C. Then, 0.4 g of ditertiary butyl peroxide as an initiator was uniformly added dropwise over 2 hours to 2 g of maleic anhydride. Stirring was continued for 1 hour after completion of the dropping, and then degassed under a reduced pressure of 10 mmHg. The product obtained has an [η] of 0.12 dl / g, a melt viscosity of 550 mPa · s, an Mn of 900, an Mw of 4700, a density of 968 kg / m ³ and a melting point of The softening point was 104 ° C., the penetration was 1 dmm, and the acid value was 101.9 KOH mg / g.

(Preparation of emulsion of polyolefin wax (B))
A polyolefin wax emulsion (B) having a solid content concentration of 30% by weight was prepared by a known emulsification method described below. That is, in a pressure vessel equipped with a stirrer, a thermometer, and a gas introduction tube, 70 parts of deionized water, 27 parts of the oxidized modified polyolefin wax obtained in Oxidized Modified Polyolefin Wax Production Example 1, and 10 mol nonylphenol ethylene oxide adduct as an emulsifier 2.5 parts and 0.5 parts of potassium hydroxide were added and stirred at 170 ° C. for 60 minutes to obtain a wax emulsion (1).

  The same operation was performed on the oxidation-modified polyolefin wax obtained in Production Example 1 of oxidation-modified polyolefin wax to obtain a wax emulsion (2).

  A wax emulsion (3) was obtained by performing the same operation using Epolene Wax E-10 (manufactured by Eastman Chemical Co., Ltd., melting point: 103 ° C.) as the polyethylene wax.

  In the following, the embodiment will be specifically described using Example 1 as a representative example. For Examples 2 to 6 and Comparative Examples 1 and 2, the same operations as in Example 1 were performed except for the conditions shown in Table 2, and aqueous compositions were obtained and evaluated. About these, the compounding ratio of resin and various additives and aqueous composition characteristic evaluation are shown in Table 3 together with Example 1.

[Example 1]
An aqueous composition was prepared at the ratio shown in Table 2. The materials used are as follows.
Alkali-soluble resin: styrene-maleic acid copolymer resin (manufactured by Alco Chemical Co., Ltd., trade name “SMA Resin 2625A”, solid content concentration 15% by weight)
Plasticizer: Tributoxyethyl phosphate Fusion agent: Diethylene glycol monoethyl ether wetting agent: Fluorosurfactant (manufactured by Ciba Geigy, trade name “Rhodain S-100”)

Describe test items and methods. Gloss maintenance property measured the glossiness according to JISK3920-14 for the suitable period after installing what was applied to the test tile separately on the floor.
Evaluation criteria ○: Glossiness of 70% or more, Δ: Glossiness of 50% or more and less than 70%, X: Glossiness of less than 50% The black heel mark resistance was tested according to JIS K3920-15. The amount of heel mark attached was visually evaluated.
Evaluation criteria ○: Good (small), Δ: Normal, ×: Defect scratch resistance was tested by a visual method.
Evaluation Criteria ○: Good, Δ: Normal, ×: Poor Also, the abrasion resistance was evaluated by measuring the gloss after the abrasion test with a Taber abrasion tester.
Evaluation criteria ○: Glossiness of 50% or more, Δ: Glossiness of 30% or more and less than 50%, ×: Glossiness of less than 30%

  The aqueous composition of the present invention has particularly excellent performance in terms of gloss maintenance without degrading the performance of black heel mark resistance. Therefore, when the aqueous composition of the present invention is applied to a floor surface having a large amount of walking, it is possible to maintain a high aesthetic appearance. Therefore, plastic floor materials such as vinyl-based and synthetic resin-coated floors, stone materials, and cement-based floors. It is useful as a floor polishing agent for wood and wood floors.

Claims (4)

A water-based composition containing at least a film-forming aqueous organic polymer substance (A) and a polyolefin wax emulsion (B), wherein the polyolefin wax is a number average molecular weight measured by gel permeation chromatography (GPC). (Mn) is in a range of 400 to 5,000, a melting point measured by a differential scanning calorimeter (DSC) is in a range of 65 to 130 ° C., and a density measured by a density gradient tube method is 850 to 980 kg / m ^3. And an aqueous composition characterized by being a polyolefin wax produced using a metallocene catalyst. The aqueous composition according to claim 1, wherein the polyolefin wax is a modified polyolefin wax that has been oxidized or acid graft-modified. 3. The aqueous composition according to claim 1 or 2, wherein the aqueous composition comprises a film-forming aqueous organic polymer substance (A) as a main component, and an emulsion (B) of a polyolefin wax is blended. . A floor polish composition comprising the composition according to claim 1.