Note: Descriptions are shown in the official language in which they were submitted.
WO 01/07529 CA 02389861 2002-O1-16 PCT/JP99/03942
DESCRIPTION
Aqueous Floor Polishing Composition
Technical Field
The present invention relates to an aqueous floor
polishing composition excellent in gloss restorability.
In particular, the present invention relates to an
aqueous floor polishing composition which is desirable
for the application to floor surface of wooden floor
material, floor material comprised of synthetic resin,
or stone floor made of concrete or marble, especially,
for dry maintenance which is carried out as daily
maintenance by using a combination of cleaning with an
automatic floor cleaning machine and buffing with a
high-speed polisher.
Background Art
Floor polishing agents have been used for the
floor surface of wooden floor material, chemical floor
material made of synthetic resin, or stone floor
material comprised of concrete or marble for the
purpose of keeping the beauties of the floor material
and protecting the floor surface. The floor polishing
agents generally include oil-type agents using
solvents, aqueous agents, emulsion-type agents and the
like. For example, Japanese Patent Publication Nos. Sho
47-14019 and Sho 47-15597 disclose floor polishing
compositions which use a polyvalent metal compound in a
polymer of an ethylenically unsaturated compound. The
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coating film obtained by applying and drying this floor
polishing composition is excellent in durability or
travelling, and nowadays, this type of floor polishing
composition is dominantly used.
A floor polishing agent containing an aqueous
emulsion of polyurethane resin has been developed for
the purpose of improving anti-slip properties. See,
e.g., Japanese Patent Publication No. Sho 53-22548. In
addition, Japanese Patent Application laid-Open No. Sho
61-148273 discloses that in order to improve heel-mark
resistance or scuff resistance, the film durability can
be enhanced by using a mixture of an aqueous resin with
colloidal silica and butoxyethyl phosphate in
combination. Furthermore, Japanese Patent Application
Laid-Open No. Sho 8-41382 discloses a method for
improving film durability. However, in the
aforementioned prior art, there is no disclosure of
significantly improving gloss restorability by buffing,
and hence, the development of new technique has been
desired in this field.
The buffing operations in dry maintenance are
carried out for restoring the floor surface by
plastically deforming or cut-removing small damages on
the coating surface caused by walking, etc. and
restoring gloss lowered by walking, etc.
In general, the improvement in the gloss
restorability by buffing with floor polish may be
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achieved by adjusting a composition of resin in an
acryl-styrene type emulsion which is a main component
of a polishing agent, but heel-mark resistance, scuff
resistance, etc. are deteriorated. Accordingly, it has
been very hard to obtain a floor polishing composition
which is excellent in gloss restorability by buffing,
and besides, excellent in heel mark resistance and
scuff resistance.
Disclosure of Invention
The present invention is to provide a novel,
aqueous floor polishing composition capable of forming
a coat showing excellent gloss restoration by buffing
while retaining general properties such as durability
required for floor polishing agents.
The inventors found out, as a result of eager
investigation and study, that the use of a butadiene
type copolymer component in an aqueous floor polishing
resin composition will readily afford the evenness of a
coat after buffing by means of a high-speed polisher,
thereby improving the gloss restoration by buffing.
Thus, according to the present invention, there is
provided an aqueous floor polishing composition
characterized by containing 5 to 100 parts as solid of
a styrene-butadiene type copolymer emulsion based on
100 parts as solid of an acryl-styrene type resin
emulsion.
The styrene-butadiene type copolymer emulsion
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which can be used for the present invention is
preferably that obtained by copolymerization of styrene
and butadiene. Any type of thus obtained copolymer may
be used regardless of molecular weight, molecular
structure and preparation method. For the
copolymerization of styrene and butadiene aromatic
and/or aliphatic monomers such as methyl methacrylate
and the like may be incorporated at an arbitrary
copolymerization ratio. Copolymerization with
unsaturated fatty acid such as acrylic acid and
methacrylic acid or dispersion into water using
emulsifiers may be conducted for water dispersibility
or water solubility. Such butadiene type copolymer
latex, including copolymers obtained by emulsion
copolymerization of butadiene and a variety of
monomers, is widely used for compositions for paper
coating or the like. A typical example of such latex
is described in Japanese Patent Publication No. 54-
6575. The water base floor polishing agent of the
present invention can be prepared by adding such
butadiene type copolymer latex into acryl-styrene type
resin emulsions. It can be also prepared by
polymerizing monomers containing butadiene in the
presence of acryl-styrene type copolymerization
components or polymerizing monomers such as aliphatic
unsaturated compounds and styrene in the presence of
butadiene type copolymerization components. Concerning
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the ratio of acryl-styrene type resin to styrene-
butadiene type copolymer emulsion, the styrene-
butadiene type copolymer emulsion is in the range of 5
to 100 parts, preferably in the range of 5 to 50 parts,
with respect to 100 parts of acryl-styrene type resin.
The butadiene in the styrene-butadiene type copolymer
emulsion is preferably in the range of 25 to 70 o by
weight, and the styrene in the styrene-butadiene type
copolymer emulsion is preferably in the range of 0 to
75 % by weight, and more preferably in the range of 30
to 75 % by weight.
An example of the acryl-styrene type resin
emulsion which can be preferably used in the present
invention is the resin composition disclosed in
Japanese Patent Publication No. 44-24409 or the like.
The composition comprises a copolymer of alpha, beta-
ethylenic unsaturated carbonic acids and ester
derivatives thereof, especially acrylic acid or
methacrylic acid and ester derivatives thereof, and
aromatic monomers such as styrene. Specifically an
ethylenic unsaturated compound is selected from the
group consisting of styrene, methylstyrene, acrylic
acid, methyl acrylate, ethyl acrylate, propyl acrylate,
butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate,
lauryl acrylate, methacrylic acid, methyl methacrylate,
ethyl methacrylate, propyl methacrylate, butyl
methacrylate, hexyl methacrylate, 2-ethylhexyl
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methacrylate, vinyl acetate, acrylonitrile, itaconic
acid, malefic acid and the like, thereby obtaining the
polymer emulsion by a known emulsion polymerization
method.
In the present invention, for the purpose of
satisfying various characteristics required for the
floor polishing agent, various additives can be
contained in the aqueous floor polishing composition.
Among the characteristics, an appropriate sliding
property can be obtained and its black heel mark
resistance and durability are made excellent by adding
a wax to the composition. As the wax, it is possible
to use an aqueous solution of a natural wax or a
synthetic wax dispersed therein which is generally used
for floor polishing. Specifically, the natural wax
includes carnauba wax, paraffin wax and the like. The
synthetic wax includes polyethylene, polypropylene and
oxides thereof as well as waxs obtained by polymerizing
unsaturated monomers such as ethylene, propylene and
the like or monomers selected from the group consisting
of a- or ~i-ethylenically unsaturated carboxylic acid,
alkyl esters thereof and the like. Though the wax
content in the aqueous floor polishing composition of
the present invention is optionally determined, 0 to 20
% by weight is preferable.
A crosslinking agent is added to the aqueous floor
polishing composition of the present invention to
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improve the duralibility of an obtained coating film.
The crosslinking used in the present invention includes
polyvalent metal salts or polyvalent metal complexes by
which a metal crosslinking can be formed.
Specifically, it is possible to use calcium, magnesium,
zinc, barium, aluminum, zirconium, nickel, iron,
cadmium, strontium, bismuth, beryllium, cobalt, lead,
copper, titanium and antimony. In particular, calcium,
magnesium, zinc and aluminum are preferable. The
ligand for forming the polyvalent metal complexes
includes carbonate ion, acetate ion, oxalate ion,
malate ion, hydroxyacetate ion, tartrate ion, acrylate
ion, lactate ion, octate ion, formate ion, salicylate
ion, benzoate ion, gluconate ion, glutamate ion, and
glycine, alanine, ammonia, morpholine, ethylenediamine,
dimethylaminoethanol, diethyamionethanol,
monoethanolamine, diethnolamine, triethanolamine, as
well as inorganic acids, organic acids, amino acids,
amines and the like which are similar thereto. In
particular, zinc ammonium carbonate, calcium
ethylenediamine-ammonium carbonate, zinc ammonium
acetate, zinc ammonium acrylate, zinc ammonium malate,
zirconium ammonium malate, zic ammonium aminoacetate,
calcium ammonium alanine and the like are preferable.
In the aqueous floor polishing composition of the
invention, by incorporating an alkali-soluble resin, it
is possible to improve the leveling property,
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peelability and glossiness. As the alkali-soluble
resin, there can be included styrene-malefic acid
copolymer resin, rosin-malefic acid copolymer resin,
water-soluble acrylic resin, water-soluble polyester
resin, water-soluble epoxy resin, or the like. The
content of the alkali-soluble resin in the aqueous
floor polish composition of the present invention can
arbitrarily be determined.
In the aqueous floor polishing composition of the
invention, by incorporating an aqueous polyurethane
type resin, it is possible to improve the durability.
As the aqueous polyurethane type resin, there can
preferably be used one containing a carboxylic acid
and/or carboxylate bonded to a chain of a polyurethane
type resin. Such a resin can be obtained by, for
example, when producing a polyurethane type resin,
adding diol or the like having a carboxylic acid group
to diol and di-isocyanate, neutralizing the carboxylic
acid group as needed, and effecting polymerization.
The introduction of a carboxylic acid group affords an
aqueous polyurethane type resin having water-
dispersibility or water-solubility. Further, adding an
emulsifying agent can make the resin aqueous as needed.
The aqueous floor polishing composition of the
invention may contain an plasticizer or film-forming
assistant. As the plasticizer, there are included
dibutyl phthalate, dioctyl phthalate, 2-pyrrolidone,
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octyl diphenyl phosphate, tributoxyethyl phosphate, and
the like. As the film-forming assistant, there are
preferably used alkylene glycol monoalkyl ether,
dialkylene glycol monoalkyl ether, trialkylene glycol
monoalkyl ether, and there are specifically included
diethylene glycol monobutyl ether, diethylene glycol
monoethyl ether, dipropylene glycol monomethyl ether,
and the like.
The aqueous floor polishing composition of the
invention may contain silica sol. Further, the
composition may contain a fluorine type surfactant or a
preservative.
The present invention will be described below in
great detail by giving Examples and Comparative Example
which will illustrate the technical effects of the
present composition.
EXAMPLE 1
Ten (10) parts of a styrene-butadiene type
copolymer latex composed chiefly of styrene/butadiene =
60/40, having Tg of -1°C was added to 100 parts of an
acryl-styrene type resin emulsion composed of butyl
acrylate/methyl methacrylate/ styrene/methacrylic acid
- 32/28/20/20, having Tg of 46°C and an acid value of
130 to prepare an aqueous floor polishing composition 1
of the present invention.
EXAMPLE 2
An aqueous floor polishing composition 2 of the
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present invention was prepared in the same manner as in
Example 1 except that the amount of the styrene-
butadiene type copolymer latex was changed to 20 parts.
EXAMPLE 3
An aqueous floor polishing composition 3 of the
present invention was prepared in the same manner as in
Example 1 except that the amount of the styrene-
butadiene type copolymer latex was changed to 30 parts.
COMPARATIVE EXAMPLE
Only the acryl-styrene type resin emulsion used in
Example 1 was used and made an aqueous floor polishing
composition 4.
The aqueous floor polishing composition obtained
in Example 2 was dried at 60°C for 12 hours to prepare
a sample for analysis, which was then analyzed as to
the butadiene contained in the composition by using an
infrared spectrophotometer (KBr tablet method;
integration for 100 times using 60SX Fourier transform
infrared spectrophotometer manufactured by Nicolet).
As a result, absorption peaks were observed in the
wavelength regions of 960 to 970 cm-1 (trans 1,4 CH
bending vibration), 900 to 920 cm-1 (R-CH=CH bending
vibration) and 1640 cm-1 (C=C stretching vibration)
which are the characteristic absorption bands of
butadiene copolymer. Further, as a result of another
analysis which was carried out by using a thermal
decomposition gas chromatograph (HP5890A gas
WO 01/07529 CA 02389861 2002-O1-16 PCT/JP99/03942
chromatograph manufactured by Hewlett Packard Co.,
Ltd.; FID detection; high frequency furnace type
thermally decomposing apparatus manufactured by Nippon
Bunseki Kogyo K.K.; thermal decomposition at 590°C for
5 sec.), the butadiene monomer decomposed was
confirmed, so that it was confirmed that butadiene was
contained as the monomer component in the aqueous floor
polishing composition of the present invention.
The aqueous floor polish compositions 1 - 4
prepared in Examples 1-3 and Comparative Example 1 were
used to prepare floor polishing agents. To 100 parts
by solid weight of the composition, 10 parts of
tributoxyehtyl phosphate (a plasticizer), 25 parts of
diethylene glycol monoethyl ether (a filming aid), 0.05
parts of fluorine-based detergent Zonyl FSJ (25%
solid)(a product of Du pont), 6.37 parts of ammonium
carbonate zinc aqueous solution (12% solid), 6.25 parts
of styrene malefic acid resin SMA-2625A (15$ solid)(a
product of ATOCHEM), 18.76 parts of polyethylene wax
emulsion Hytec E-4B (40% solid) (a product of Toho
Kagaku Inc.), and 0.68 parts of Deltop (a preservative,
a product of Takeda Chemical Industries) are added
successively.
With each aqueous floor polishing agent thus
obtained, gloss restoration by buffing was determined.
The results are shown in Table 1. The determination
method is as follows:
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1. Glossiness: determined according to JIS K-3920 (Test
method for floor polish);
2. Gloss restoration by buffing: Onto a homogeneous
vinyl floor tile (a product of TORI Inc., product name:
MATICO S PLAIN No.5626), the sample polishing agent was
applied five times, and then the glossiness was
measured (a). After that, the gloss was removed by
using an automatic floor washing machine J-CRUISE ( a
product of Johnson Professional Inc.)((b)), then the
tile was buffed twice by using Ultra high speed
polisher SPRINT-2000BP(a product of Johnson
Professional Inc.) with a green pad (c and d), to
determine the gloss restoration by buffing from the
glossiness difference before and after buffing.
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Table 1
Glossiness Restoration by Buffing
Examples Comp. Example
1 2 3 4
Glossiness
(a) 5x application 73 72 70 75
(b) before buffing 51 50 52 52
( c ) after first
buffing 65 65 67 58
(d) after second
buffing 67 69 70 60
Gloss restoration(%)
after 1st buffing 64 68 83 26
before 2nd buffing 73 86 100 35
Gloss restoration(%)=(gloss after buffing - gloss before
buffing)/(gloss after 5x application - gloss before
buffing)
Effect of Invention
As shown in Table 1, high rates of gloss restoration
are attained by using the composition of the invention. In
other words, the use of an aqueous floor polishing
composition containing 5 to 100 parts as solid of a
styrene-butadiene type copolymer emulsion based on 100
parts as solid of an acryl-styrene type resin emulsion,
according to the invention, will afford both high gloss
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restorability in buffing and high durability that have
been long desired as properties for floor polishing
agents. The aqueous floor polishing composition of the
invention is particularly suitable for 'dry
maintenance' that is a daily maintenance work comprised
of washing by means of an automatic washer and buffing
by means of a high-speed polisher.
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