JPS62161876A - Aqueous polishing agent - Google Patents

Abstract

PURPOSE:To provide an aqueous polishing agent capable of affording floorings, furniture, etc. with gloss for a long period, containing a water-dispersible silicone-modified vinyl polymer prepared by reaction between a specific water- dispersible vinyl polymer and organopolysiloxane. CONSTITUTION:The objective polishing agent containing a water-dispersible silicone-modified vinyl polymer prepared by reaction between (A) 100pts. by wt. of a water-dispersible vinyl polymer prepared from (i) 0.1-40wt% of an organosilicon monomer having in the molecule at least one polymerizable unsaturated group and at lest one hydrolyzable group directly bonded to silicon atom, (ii) 0.1-20wt% of a polymerizable unsaturated carboxylic acid and (iii) 40-99.8wt% of another polymerizable unsaturated monomer and (B) 0.2-1,000pts. by wt. of an organosiloxane having in the molecule at least one silicon atom with the average composition formula represented by the formula (R is 1-10C hydrocarbon; 0.2<=a<=2.5, 0.0005<=b<=1.0, 0.1<=a+b<=3.0).

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to an aqueous polish suitable for floors, furniture, etc. The aqueous polishing agent of the present invention can provide a glossy finish for the purpose of protecting and beautifying various flooring materials such as wooden floors, rubber floors, vinyl chloride resin tile floors, and inorganic floors, as well as wooden furniture. It has excellent adhesion, water resistance, stain resistance, powder ring resistance, etc., so it can maintain its beautiful appearance for a long time.

<Problems to be solved by conventional technology and the invention> Conventionally, polishing compositions such as polishing agents have problems in terms of performance such as odor, recoatability, leveling property, water resistance, heel mark resistance, and blocking resistance. It is necessary to satisfy a wide variety of requirements such as hardness, powdering resistance, adhesion, and removability. In particular, in recent years, many long flexible tiles have been used as flooring materials, and problems such as staining and stickiness of the coating surface of the polishing composition due to the 7-lead plasticizer have come to the fore. Therefore, it is desired to improve the performance and durability of polishing compositions. As this type of polishing composition, for example, Japanese Patent Publication No. 47-15
No. 597, Special Publication No. 50-19570, Special Publication No. 56-4
No. 66, etc., proposes a method of crosslinking a carboxyl group-containing polymer with a polyvalent metal ion. However, the properties of the dried film obtained by this method vary greatly depending on the crosslink density caused by metal ions; as the crosslink density increases, the film becomes brittle and may cause powdering, especially in winter; If it is too high, sufficient water resistance and stain resistance cannot be obtained, and there is a drawback that maintaining this balance is extremely difficult. Furthermore, JP-A No. 57-31969 proposes a method in which an unsaturated acrylamide derivative, a glycidyl group-containing unsaturated mono-Z form, etc. is copolymerized with other unsaturated m forms to make the polymer body crosslinkable. However, it has the drawback of achieving both high stain resistance and removability of the coating with alkali, etc. Furthermore, JP-A No. 5'5-110170 proposes a composition whose main component is an aqueous polymer dispersion having a hydrolyzable group directly bonded to a silicon atom in its molecule, but this composition also has plasticity. It has been difficult to prevent staining of the coating surface over a long period of time due to bleeding of the agent.

The present invention solves the above-mentioned problems of the prior art. Therefore, an object of the present invention is to provide a beautiful glossy finish with appropriate slipperiness to various flooring materials, wooden furniture, etc., and which has excellent water resistance, stain resistance, and powdering resistance, so that it remains hot for a long time. Water fit allows you to maintain your beauty! ! The goal is to provide a starting point.

Means and Effects for Solving the Problems The inventors of the present invention have conducted intensive research to obtain an inexpensive and highly durable aqueous polishing agent that does not have the above-mentioned problems. A blend of a water-dispersible silicone-modified vinyl polymer obtained by reacting a water-dispersible vinyl copolymer having a degradable group with an organopolysiloxane having a specific reactive group will achieve the above object. They discovered this and completed the present invention.

That is, the present invention is directed to an organosilicon monoomega substance (A) 0.1 to 40 wt 11% having at least one polymerizable unsaturated group and at least one hydrolyzable group directly bonded to a silicon atom in the molecule.
, polymerizable unsaturated carboxylic acid (B) 0.1-20% heavy protein and other polymerizable unsaturated monomer (C) 40-99.8%
Water-dispersible vinyl copolymer (I) 1001 Obu (non-volatile fraction exchanged) obtained from Lffi% (however, the total of components (A), (B) and (C) is 100% by weight)
and has at least one hydrogen atom directly connected to a silicon atom in the molecule and has an average compositional formula of RaHbSiOiii [wherein R is a carbon number of 1 to 101
11a is a substituted or unsubstituted monovalent hydrocarbon group, and a and b are each 0.2≦a≦2.5.0.00
05≦b≦1.0, and a+b is 0.3≦a+
b≦3.0. The present invention relates to an aqueous polishing agent comprising a water-dispersible silicone-modified vinyl polymer obtained by reacting 1 part of organopolysiloxane (II) represented by 0.2 to 1000 fflff.

The water-dispersible vinyl copolymer (I) used in the present invention is an organosilicon I41ω having in its molecule at least one polymerizable unsaturated group and at least one hydrolyzable group directly bonded to a silicon atom. (A) 0.1 to 40% by weight, polymerizable unsaturated carboxylic acid (B) 0.1 to 20% by weight, and other polymerizable unsaturated carboxylic acids (C) 40 to 99.8ffif
f1% (t::t, the sum of (A), (B) and (C) components is 100Q%).

Examples of the organosilicon monomer (A) include vinyl trimethoxysilane, vinyl 1-lyethoxysilane, vinyltributoxysilane, allyl 1-rimethoxysilane, allyltriethoxysilane, trime 1-xysilylpropylallylamine, γ -(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxybutylmethyldimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, N-vinylbenzyl-γ-aminopropyltrimethoxysilane, 2- styrylethyltrimethyl-l-xysilane, vinyltriacetoxysilane,
Examples include vinyltrichlorosilane, and one type or a mixture of two or more types selected from these groups can be used. In the present invention, the organic silicon content matrix (A)
The cross-linking reactivity and water-dispersible vinyl copolymer (I) and organopolysiloxane (I) of the resulting aqueous polishing agent
An essential component for the reaction with I), with a content of 0.1 to 40 in all single components.
It is necessary to use it in a heavy-duty type enclosure. 0.1% by weight
If the amount is less, the reaction between the water-dispersible vinyl copolymer (I) and the organopolysiloxane (IF) will be insufficient, resulting in poor water resistance, stain resistance, blocking resistance, etc. of the resulting aqueous polish. Durability decreases. Further, even if the amount exceeds 40% by weight, no improvement in performance can be expected, but rather an increase in price and a decrease in the stability of the resulting aqueous polish, which is not preferable.

The polymerizable unsaturated carboxylic acid (B) used in the present invention has one or more carboxyl groups in its molecule, such as unsaturated basic acids such as acrylic acid, methacrylic acid, and crotonic acid; maleic acid, Fumaric acid, Itacone!
Unsaturated dibasic acids such as i; monoester compounds of alkyl alcohols having 1 to 17 carbon atoms and unsaturated dibasic acids; dihydric alcohols such as ethyl alcohol, diethylene glycol, propylene glycol, butyl alcohol, ethyl alcohol , monoethers with lower monohydric alcohols such as butyl alcohol, monoester compounds with unsaturated dibasic acids, etc., and one type or a mixture of two or more types selected from these groups is used. I can do things. The hand-forming unsaturated carvone M (B) should be used within a range that achieves both the water resistance of the film of the resulting aqueous polish and the removability of the film with an alkaline film remover. 0.1-20%, preferably 1
．． It is used in a range of 0 to 15.0% by weight.

If it is less than 0.1% by weight, it will be difficult to remove the film with a release agent, and if it exceeds 20% by weight, the water resistance will decrease and the recoatability of the water-based polish will be poor. .

Other polymerizable unsaturated monomers (C) used in the present invention
Examples include methyl, ethyl, propyl, butyl, isobutyl, octyl, 2-ethylhexyl, or cyclohexyl esters of (meth)acrylic acid (
Meth)acrylic acid alkyl esters; unsaturated alcohols such as (meth)allyl alcohol, chloro]-alcohol, etc.; olefinic hydrocarbons such as ethylene, propylene, butylene, etc.; styrene, chlorostyrene, vinyl]-luene, etc. Vinyl aromatic hydrocarbons such as: vinyl halides such as vinyl fluoride, vinyl chloride, vinyl bromide, etc.; nylidene halides such as vinylidene fluoride, vinyl chloride, etc.; (meth)acrylonitrile,
Unsaturated di-1-lyl, such as croton-di-1-lyl; vinyl esters of monovalent carboxylic acids, such as acetic acid and propionic acid; vinyl ethers of monovalent alcohols, such as methyl alcohol, ethyl alcohol, and propyl alcohol; (meth) Unsaturated aldehydes such as acrolein, crotonaldehyde, etc.; (meth)acrylates containing amino groups such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, etc.; unsaturated aldehydes such as (meth)acrylamide, diacetone (meth)acrylamide, etc. Saturated acid amides; diene hydrocarbons such as butadiene and isoprene; mono(meth)acrylic acid esters of alkylene glycols such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate; glycidyl (meth)acrylate-1-
Unsaturated glycidyl esters such as W can be mentioned, and one type or a mixture of two or more types selected from these BTs can be used in an amount of 40 to 99.8% by weight based on the total weight of the BT.

The water-dispersible vinyl copolymer (C) consists of a silicon monomer (A), a polymerizable unsaturated carboxylic acid (B) J'3, and other polymerizable unsaturated groups (C). One unit is obtained by emulsion polymerization of the monomer mixture in an aqueous medium.Emulsion polymerization can be carried out according to known methods using known polymerization initiators, emulsifiers, and other various additives if necessary. .

The water-dispersible silicone-modified vinyl polymer, which is an essential component of the aqueous polish of the present invention, is obtained by reacting the water-dispersible vinyl copolymer (I) with the organopolysiloxane (II). be.

The organopolysiloquiline (n) used in the present invention is
It has at least one hydrogen atom directly bonded to a silicon atom in the molecule and has an average compositional formula of Ra Hb Si O-L-(wherein R is a substituted or unsubstituted 1 having 1 to 10 carbon atoms). is a valent hydrocarbon group, a and b are each 0
．． 2≦a≦2.5.0.0005≦b≦1.0,
Katsu a+b is 0.3≦a−←b←3.0. ) is an organopolysiloxane represented by The hydrogen atom directly bonded to the silicon atom is a water-dispersible vinyl copolymer (I
) It is essential for the reaction with the silicon-based hydrolyzable group contained in the organopolysiloxane (■), and it is necessary to contain at least one per molecule of organopolysiloxane (■), preferably one or more per 100 silicon atoms. be. On the other hand, if the number of hydrogen atoms directly bonded to silicon atoms is more than 100 per 100 silicon atoms, aggregation tends to occur during the reaction with the water-dispersible vinyl copolymer (I), which is undesirable. . There is no particular limit to the number of silicon atoms contained in one molecule, but it is preferably between 4 and 2000, and if it is less than 4, it may be difficult to exhibit the characteristics of silicon, and if it is 2001 or more, has the drawbacks of low reactivity and separation and aggregation. Organopolysiloxane ([) is available as a liquid,
Alternatively, it can be appropriately used in the form of emulsification and dispersion in an aqueous medium in the presence of an emulsifier.

The reaction between the water-dispersible vinyl copolymer (I) and the organopolysiloxane (I) can be carried out by, for example, reacting the water-dispersible vinyl copolymer (I) obtained by the above polymerization with the organopolysiloxane (ff). It may be carried out by mixing, or the above-mentioned organosilicon may be carried out in the presence of organopolysiloxane (U).
body (A), polymerizable unsaturated carvone l! A monomer mixture consisting of I(B) and other polymerizable unsaturated monomers (C) may be polymerized, and the reaction may be performed simultaneously with the polymerization. In the latter method, for example, organopolysiloxane (II) can be mixed with organopolysiloxane (II).
A method of polymerizing by dropping the monomer mixture into a medium containing If), a method of polymerizing by dropping a premix of organopolysiloxane (II) and the monomer mixture, or a method of polymerizing by dropping a premix of organopolysiloxane (II) and the monomer mixture, or Various methods can be employed, such as a method in which the monomer mixture is separately added dropwise and polymerized.

Organopolysiloxane (n) is an essential component for imparting appropriate slipperiness, stain resistance, and powdering resistance to the resulting water-based polish, and is an essential component for imparting appropriate slipperiness, stain resistance, and powdering resistance to the water-based polishing agent obtained. 0.0 for 100 hanging parts (non-volatile content conversion).
It is used in 1.11 parts of 2 to 1000 parts by weight. If the weight is less than 0.2, the peeling properties, stain resistance, and powder ring resistance will be insufficient. If the amount of water exceeds 19%, the stability of the polishing agent solution will decrease.

The water-dispersible silicone-modified vinyl small polymer is produced by reacting the water-dispersible vinyl copolymer (I) and organopolysiloxane (ff) under temperature conditions of room temperature to 100°C, preferably 50 to 85°C. It is obtained by the reaction while removing by-product hydrogen from the system, but in order to shorten the reaction time, it is preferable to use an appropriate reaction catalyst.As a reaction catalyst, dibutyltin diacetate, dibutyltin dilaurate, etc. , stannous acetate, lead naphthenate, zinc caprylate, zirconium acetate, iron 2-ethylhexane, cobalt naphthenate, etc.: metal salts of carboxylic acids such as: tetrabutyl titanate, teranonyl titanate, and Titanate esters such as polymorphs; lithium hydroxide, thorium hydroxide, potassium hydroxide, sodium methylate,
Conventional reaction catalysts are effective for the condensation reaction between a silicon-based hydrolyzable group such as a basic substance such as ammonia, triethylamine, triethanolamine, etc. and a hydrogen atom directly bonded to a silicon atom. It can be used as a species or a mixture of two or more. Preferred catalyst uses include dibutyltincyatate, zinc caprylate,
It is to use a metal salt of carboxylic acid such as iron 2-ethylhexane in combination with a basic substance such as monolithium hydroxide, ammonia, triethylamine, etc. There is no particular restriction on the amount of the reaction catalyst to be used, but as a rough guide, it may be 0.05 to 10 parts by weight per 100 parts by weight of the nonvolatile content of the water-dispersible silicone-modified vinyl polymer. The reaction catalyst can be used before or after mixing the water-dispersible vinyl copolymer (I) and the organopolysiloxane (II).

The reaction between the water-dispersible vinyl copolymer (I) and the organopolysiloxane (T) is carried out after emulsion polymerization as described above and the organopolysiloxane (I). ) may also be carried out, or a method of emulsion polymerization of the water-dispersible vinyl copolymer (I) in the presence of the organopolysiloxane (U) may be used. The polysiloxane (■) component is easy to localize, and for example, when it is made into a film, more organopolysiloxane components can be concentrated on the surface, so the organopolysiloxane (II) component of the nail can be effectively utilized. As the emulsion polymerization method in the latter method, any conventionally known emulsion polymerization method can be applied, as in the case where organopolysiloxane (II) is not coexisting.

The aqueous polishing agent of the present invention contains the water-dispersible silicone-modified vinyl polymer as an essential component,
In addition, there are known and commonly used components that are incorporated into polishing agents, such as water-dispersible vinyl polymers having carboxyl groups in the molecule (hereinafter referred to as vinyl polymers (a)), polyvalent metal compounds (b), Water-based colloidal silica (c), a silane compound having a hydrolyzable group directly connected to a silicon atom in its molecule (
Hereinafter, it will be referred to as silane compound (d). ), an alkali-soluble resin (e), a wax (f), a film-forming property improver (g) typified by a plasticizer and a film-forming aid (g), etc., may be included as necessary.

The vinyl polymer (a) can be easily obtained by emulsion polymerizing a monomer mixture containing the polymerizable unsaturated carboxyl group M (8) in an aqueous medium, and is a commercially available carboxyl group-containing vinyl polymer. A polymer emulsion (for example, Acryset EMN6035, manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.) can be applied.

The blending of the vinyl polymer (a) is effective in reducing the amount of the water-dispersible silicone-modified vinyl polymer contained as an essential component in the aqueous polishing agent of the present invention. That is, even if a relatively inexpensive vinyl polymer (a) is used in combination with a water-dispersible silicone-modified vinyl polymer, the water-dispersible silicone-modified vinyl polymer component tends to localize on the surface of the coating, resulting in poor yield. It has the advantage that it has very little adverse effect on the performance aspects of the aqueous polishing agent, such as appropriate slipperiness, stain resistance, and anti-blocking properties. Therefore, the amount of the vinyl polymer (a) to be used is not particularly limited, but preferably not more than 1000 parts by weight (non-volatile parts) per 100 parts by weight (non-volatile parts) of the water-dispersible silicone-modified vinyl polymer. It is.

The polyvalent metal compound (b) is obtained by crosslinking the carboxyl groups contained in the water-dispersible silicone-modified vinyl polymer and the vinyl polymer (a) used as necessary with a polyvalent metal ion to increase the molecular weight of the polymer. This improves strength and water resistance.

Typical of such polyvalent metal compounds (b) are zinc ammonia complexes such as zinc ammonia carbonate, but other examples include zinc salts of organic acids, zinc chelates of bidentate amino ligands, etc. .

Zinc oxide dispersed in water using a suitable dispersant can also be used. Further, in place of zinc in the zinc compound, copper, calcium, magnesium, zirconium, barium, strontium, aluminum, antimony, lead, cobalt,
Gold exclusively for iron and nickel 1.・Things using z can also be used.

The aqueous polishing agent of the present invention does not require the use of a polyvalent metal compound (b) because it contains the aqueous dispersion ('l silicone-modified vinyl polymer); There is no problem in using it within a range that does not impede the stability, powdering resistance, etc., for example, a mixture of water-dispersible silicone-modified vinyl polymer and vinyl polymer (a) used as necessary. It is preferable to use it in a proportion of 50 parts by weight or less based on non-volatile content.

The aqueous polishing agent of the present invention may further contain an aqueous colloidal silica (c) and/or a silane compound (d), if necessary.

The aqueous colloidal silica (c) is a water-based polishing agent that is combined with and integrated with the water-dispersible silicone-modified vinyl polymer in the manufacturing process of the water-dispersible silicone-modified vinyl m combination and/or in the subsequent process. It has the effect of further improving water resistance and stain resistance. The aqueous colloidal silica (c) is generally a condensation product of silicic acid with a particle size of 5 to 100 mμ, particularly 7 to 5 mμ.
It is preferably in the range of 0 mμ, and those normally supplied in the form of an aqueous dispersion can be used as they are.

Examples of such aqueous colloidal silica (c) include commercially available products such as "Snowtex OJ rSnowtex NJ rSnowtex NC3J rSnowtex 20", "Snowtex C" (manufactured by Nissan Chemical Co., Ltd.), and Cataloid S N. Jrcatal
oid Si-500J (manufactured by Catalysts Kasei Kogyo Co., Ltd.), etc., and surface-treated colloidal silica, such as "Cataroid S A J" treated with aluminic acid.
(manufactured by Catalysts Kasei Kogyo Co., Ltd.), and one or more selected from these groups can be used.

In order to blend aqueous colloidal silica (c), a water-dispersible silicone-modified vinyl polymer and aqueous colloidal silica (c) may be mixed, or a water-dispersible silicone-modified vinyl polymer may be mixed in the presence of aqueous colloidal silica (c). It may also be obtained by emulsion polymerization of the vinyl copolymer (I).

Water-based colloidal silica (c) is a water-dispersible silicone-modified vinyl polymer and a vinyl polymer (
It is preferably used in a proportion of 200 parts by weight or less, more preferably 100 parts by weight or less, per a total of 100 mm parts (in terms of non-volatile content) of (a).

If it is used in a multi-R condition exceeding 200 degrees, the fusion of the car particles will be impaired, and the water resistance of the resulting aqueous polish will be reduced, and the appropriate slipperiness of the coating surface will be impaired. There is.

The silane compound (d) has the effect of further strengthening the integration of the water-dispersible silicone-modified vinyl polymer and the aqueous colloidal silica (c), thereby further improving the water resistance of the resulting aqueous polish. .

Examples of such a silane compound (d) include, for example, the compound used as the above-mentioned right chorionic cord (△),
Aminomethyltriethoxysilane, N-β-aminoethylaminomethyltrimethoxysilane, γ-aminopropyl 1-rimethoxysilane, N-β-aminoethyl-γ
-aminoalkylalkoxysilanes such as aminopropyl-1-rime-1-xysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane; γ-glycidoxyprobyltrimethoxysilane, γ-glycidoxypropyl Methyldimethoxysilane, β-(3,4-
epoxycyclohexyl)ethyltrimethoxysilane,
Epoxyalkylalkoxysilane such as β-(3,4-epoxycyclohexyl)ethylmethyl 1-4 disilane; mercaptoalkylalkoxysilane such as γ-mercaptopropylmethyldimethoxysilane; tetramethoxysilane; Detraalkoxysilanes such as tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane; alkyltrialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, ethyltrimethoxysilane; dimethyl silane; Dialkyldialkoxysilanes such as toxysilane, dimethyljethoxysilane; halogenated alkylalkoxysilanes such as γ-chloropropyltrimethoxysilane, 3,3.3-1-lichloropropyltrimethoxysilane; methyltrimethoxysilane; Examples include alkyl acyloxysilanes such as acetoxysilane and dimethyljethoxysilane; hydrosilane compounds such as trime-1-xysilane and trie-1-hexysilane, and one type or a mixture of two or more types selected from these groups. can be used.

The amount of these silane compounds (d) to be used is determined in order to fully exhibit the desired effect and to keep the price of the resulting aqueous polish within an appropriate range. The amount is preferably 20 parts by weight or less per 11,100 parts by weight (in terms of non-volatile content) of the vinyl polymer (a) used.

The silane compound (d) can be added directly to 6rf during the production or use of the aqueous polish.

The alkali-soluble resin (e) imparts gloss, leveling properties, and alkali removability to the aqueous polishing agent. The alkali-soluble resin (e) that can be used usually has an acid value of 80 to
320, and the average molecular weight is in the range of 200 to 10.000, such as styrene-maleic acid copolymers, alkali-soluble alkyds, alkali-soluble acrylic copolymers, and the like. In terms of water resistance, the alkali-soluble resin (e) consists of a water-dispersible silicone-modified vinyl polymer and a vinyl polymer (a) used as necessary.
It is preferable to use it within a range of 100 parts by weight or less, based on 00 parts by weight LΔ (in terms of non-volatile content).

Since the aqueous polishing agent of the present invention contains a water-dispersible silicone-modified vinyl polymer, it has appropriate slipperiness and is excellent in stain resistance, etc., and does not particularly require the addition of wax. However, the total iooi of the water-dispersible silicone-modified vinyl polymer and the vinyl polymer (a) used as necessary
There is no use in using wax at a ratio of 100 parts per m part (nonvolatile equivalent).

Examples of waxes that can be used include carnauba, candilla, microcrystalline wax, lanolin, cocoa butter, cottonseed, stearin, wood wax, milage, nutmeg, palm kernel,
Examples include beeswax, mutton tallow, oxidized polyethylene, polyethylene, polypropylene, paraffin, ceresin, and the like.

The aqueous polishing agent of the present invention may contain film-forming improvers (g), such as plasticizers and film-forming aids, if necessary.

Such plasticizers and/or film-forming aids have the effect of improving film-forming properties and improving the gloss and leveling properties of the resulting aqueous polish. Examples of plasticizers that can be used include tos-11-xyethyl phosphate, dibutyl phthale-1, and benzyl butyl phthalate. Examples of film-forming aids include ethyl calpitol, butyl calpitol, ethyl cellosolve, and butyl cellosolve. ,
Examples include nibble cellosolve acetate and butyl cellosolve acetate.

If you use too much of the film forming property improver (g), 1! ′
? Blocking resistance, stain resistance,
Since drying properties etc. decrease, 100 parts by weight (9% by weight) per 100 parts by weight (non-volatile fraction) of the water-dispersible silicone-modified vinyl polymer and the vinyl polymer (a) used as necessary.
It is preferable to use the film-forming property improver (I~) in a proportion of 1 part or less.

The water-dispersible silicone-modified vinyl polymer obtained in this way is an essential component, and if necessary, the vinyl polymer (a)
, polyvalent metal compound (b), aqueous colloidal silica (c)
A composition containing a silane compound (d), an alkali-soluble resin (e), a wax (f), and a film-forming improver (I-) can be used as it is as the aqueous polishing agent of the present invention; If necessary, a known wetting agent, leveling agent, emulsifier, antistatic agent, etc. can be added, and it can also be used after being diluted as appropriate.

<Effects of the Invention> The aqueous polishing agent of the present invention is derived from 1 q of the right-sized monolayer (A>), polymerizable unsaturated carbon l! (B), and other polymerizable unsaturated monolayers (C). A water-dispersible silicone-modified vinyl polymer obtained by reacting a water-dispersible vinyl copolymer (I) with an organopolysiloxane (It) containing a specific reactive group, and a silane compound as an essential component, an alkali Contains a soluble resin, wax, plasticizer and/or film-forming aid, and is used as a protective covering for various flooring materials such as wooden floors, rubber floors, vinyl chloride resin tile floors, inorganic floors, and wooden furniture. It can give a glossy finish and has excellent adhesion, water resistance, powder ring resistance, etc., so it can maintain its beautiful appearance for a long time.

<Examples> The present invention will be described in detail below with reference to Examples, but the present invention is not limited to the following Examples. still,
All parts in examples are parts by weight, and all percentages are ffffli%.
This shows that. Furthermore, the organopolysiloxanes used in the examples are as follows.

Organopolysiloxane (I) Hei 1H1] 1t, formula (C) 13) tlst-1o, 95
sioo, 9s average molecular weight 2500 Organopolysiloxane (2) Average composition formula (CI+3) o, 91ct; )45)
t.

Ho, 3 Si 00.9 Average molecular ffi 1500 Organopolysiloxane (3) Average composition formula (CH3) 1.9 Ho, 1Si O Average molecular weight 30000 Aqueous emulsion of organopolysiloxane Methylhydrodiene polysiloxane 11 xane emulsion (
Product name: Poron M R1 (manufactured by Shin-Etsu Chemical Co., Ltd., active ingredient: 60%) Reference Example 1 Ionized water was added to a flask equipped with a dropping row 1-1 stirrer, an inert gas introduction tube, a thermometer, and a reflux condenser tube. 142 parts, sodium lauryl sulfate IM, 3 parts of polyoxyethylene oleate (HLB=9) and 0 potassium persulfate
．． Add 4 parts and slowly blow in nitrogen gas until 7.
The mixture was heated to 5°C and stirred to form a homogeneous aqueous solution. Next, a monochrome mixture consisting of 1 part of vinyltrimethoxysilane, 5 parts of acrylic acid, 60 parts of methyl methacrylate, and 34 parts of 2-ethylhexyl acrylate was added dropwise over 2 parts from the dropping funnel. After that, stirring was continued for 1 hour while maintaining the temperature at 75°C, and then after cooling to room temperature,
% ammonia water was added to adjust the pH to about 8 to obtain a water-dispersible vinyl copolymer (I) with a nonvolatile content of about 35%.

Reference Examples 2 to 8 A water-dispersible vinyl copolymer ( 2)～(
8) was obtained.

Reference Example 9 Into the same flask as used in Reference Example 1, 258 parts of the water-dispersible vinyl copolymer (I) prepared in Reference Example 1 and 0.3 parts of dibutyltin diacetate were charged, and 75 parts of dibutyltin diacetate were added while stirring.
heated to ℃. Next, 3 parts of organopolysiloxane (I) having an average compositional formula (%) of 2500 was added dropwise from the dropping funnel over a period of 30 minutes. Then increase the temperature to 75
Stirring was continued for 2 hours while maintaining the temperature at °C, and then the mixture was cooled to room temperature to obtain a water-dispersible silicone-modified vinyl polymer (I).

Reference Examples 10 to 12 Water-dispersible vinyl copolymer, organopolysiloxane, reaction catalyst d3, and reaction conditions used in Reference Example 9 were changed according to the same operating procedure as shown in Table 2. Silicon-modified vinyl polymers (2) to (4) were obtained.

Comparative Reference Examples 1 to 4 Water-dispersible vinyl copolymer (I) used in Reference Example 9
) and the water-dispersible vinyl copolymers (5) obtained in Reference Examples 5 to 8.
) to (8), but following the same procedure, a comparative water-dispersible vinyl copolymer consisting of 1q of water-dispersible vinyl copolymer obtained from a composition outside the range of the present invention and organopolysiloxane (I) was prepared. Combined compounds (I) to (4) were obtained.

Comparative Reference Example 5 Following the same procedure as in Reference Example 9 except that the amount of organopolysiloxane (I) was changed to 1,500 parts, a comparative water-dispersible vinyl polymer (5) outside the scope of the present invention was used for the organopolysiloxane. Obtained.

Reference Example 13 Deionized water 14 was added to the same flask as used in Reference Example 1.
2 parts, sodium lauryl sulfate 1 part, polyoxyethylene oleate (HLB=9) 3 parts, organopolysiloxane (I) 3 parts, dibutyltin dilaurate 0.
3 parts of potassium persulfate and 0.4 parts of potassium persulfate were heated to 75° C. and stirred while gently blowing nitrogen gas to obtain a uniform aqueous solution. Next, 2 parts of a monomer mixture consisting of 5 parts of vinyl trime-1-xysilane, 5 parts of acrylic acid, 60 parts of methyl methacrylate, and 1-30 parts of butyl acrylate was added.
It was dripped from the dropping funnel over time. Then increase the temperature to 75
Stirring was continued for 2 hours while maintaining the temperature at °C, and then, after cooling to room temperature, 28% aqueous ammonia was added to adjust the pH to about 8 to obtain a water-dispersible silicone-modified vinyl polymer (5).

Example 1 Using the water-dispersible silicone-modified vinyl polymer (I) obtained in Reference Example 9, an aqueous polishing agent (I) having the following formulation was obtained.

Water-dispersible silicone-modified vinyl polymer (I) 60 parts Zinc ammonium complex solution (I) (Note 1> 1.5 parts''Duretz 19788'' (adjusted to 25% solids content) 10 parts (manufactured by Sumitomo Durez Co., Ltd.) alkali-soluble resin) Pahytec E-
4B ” (solid content 40%) 3 parts (polyethylene wax manufactured by Toho Chemical Industry Co., Ltd.) ■Tylcarpitol tributoxyethyl phosphate 2 parts” F C
- 1 2 8 ” (adjusted to 1% solid content) 1.0 part (fluorinated surfactant manufactured by Sumitomo 3M Co., Ltd.) Deionized water for aqueous polishing agent: Solid content concentration of 16 % (Note 1) Zinc ammonium complex solution (I) blended Zinc oxide 100 parts Deionized water 1000 parts 28x Ammonia aqueous solution 162 parts Ammonium carbonate 178 parts Evaluation was carried out according to the following method.The results are shown in Table 4.

Preparation of test piece A water-based polishing agent was applied to a white vinyl chloride resin tile of size 76 x 7611 III. After applying 3 m uniformly and drying at room temperature for 30 minutes, an additional 0. Apply 3 d and apply 2 at room temperature.
It was dried for 4 hours.

k3" leveling property when applying Otokusara water-based polish ◎～○～Δ～×
rated on a four-point scale.

Observe the surface gloss of the paint film after drying, and rate it as ◎～○～Δ～×.
Graded evaluation.

When preparing test pieces for recoatability, the surface condition at the time of second application of the aqueous polishing agent was observed and evaluated on a four-point scale from ◎ to ○ to Δ to ×.

Water resistance was determined using the method specified by Japan Floor Porridge Uniform. Water resistance was evaluated on a scale of 1 to 5, with grades 1 to 5 indicating no improvement in performance.

Removal properties were determined by a precision method using a washability tester specified by the Japan Floor Porridge Union Association. Removability is 1
It is evaluated on a scale of 1 to 5, and grades 1 to 5 indicate that the performance improves sequentially.

Heel mark resistance Des 1-Shoe heel piece with the coated surface of the piece attached to the motor (cube, !1t5a, rotation radius 7 ctyt
) at rotational speeds of 300, 400, and 600 rpm for 1 minute, respectively, and observed the staining and 1-easy marks, and evaluated them in 4 stages from ◎ to ○ to Δ to X.

2) 10 x 10 m at 1 mm intervals on the coating surface of the L-dish test piece.
Cut a square of m, press the cellophane tape (manufactured by Chiban), peel it off, observe the peeling state of the paint film, ◎〜○〜
Evaluation was made on a 4-level scale from Δ to ×.

Examples 2 to 8 Aqueous polishing agents (2) to (8) were prepared according to the formulations in Table 3 below.
) was obtained. Performance evaluation of the obtained aqueous polishing agents (2) to (8) was conducted in the same manner as in Example 1. The results were as shown in Table 4.

Example 9 Into the same flask used in Reference Example 1, add 14 ml of deionized water.
2 parts, 1 part of lauryl sulfate, 1 part of polyoxyethylene oleate (+-I L B ~9>38
1i, water-based colloidal silica “Snowtex CJ
(manufactured by Nissan Chemical Co., Ltd., particle size 10-20 mμ, SiO2 content 20%), 5 parts of aqueous emulsion of 'luganoborisiloxane (60% active ingredient) and 0.5 part of potassium persulfate were added, and slowly 80℃ while blowing nitrogen gas
and stirred to form a homogeneous aqueous solution. Next, a 4+2 mixture consisting of 3 parts of vinyltriethoxysilane, 5 parts of acrylic acid, 60 parts of methyl methacrylate, 20 parts of ethyl acrylate, and 32 parts of butyl acrylate was added dropwise from the dropping funnel over a period of 3 hours. Next, 0.8 parts of dibutyltin dilaurate was added and the temperature was maintained at 80°C.
After continuing stirring for a period of time, the mixture was cooled, and a 28% ammonia aqueous solution was added to adjust the DH to about 7 to obtain a mixture of a water-dispersible silicone-modified vinyl citrate and an aqueous colloidal silica. Using this, an aqueous polishing agent (9) having the following formulation was obtained. Its performance was as shown in Table 4.

Mixture of water-dispersible silicone-modified vinyl polymer and aqueous colloidal silica 80 parts ``Duretz 19788'' (solid content adjusted to 25%) 10 parts Pahytec E-4B'' (solid content 40%) 2 parts ethyl carpi Thor 8 parts Tributoxyethyl phosphate 2 parts “FC-128” (adjusted to 1% solids) 1.0 parts γ-glycidoxypropyltrimethoxysilane 0.5 parts Deionized water (Note 1) ) Modification (Note 1) In Comparative Examples 1 to 4, water-dispersible silicone-modified vinyl polymer (I) to A comparative composition with the same formulation except that water-dispersible vinyl-based co-malloys (I) to (4) prepared in Reference Examples 1 to 4 without reacting organopolysiloxane were used instead of (4). Products (I) to (4) were obtained. Their performance was as shown in Table 4.

Comparative Examples 5-9 In Example 1, instead of the water-dispersible silicon-modified vinyl polymer (I), the comparative water-dispersible vinyl polymers (I) to (5) prepared in Comparative Reference Examples 1-5 were used. Comparative compositions (5) to (9) were obtained using the same formulations except that each of the following was used.The performance thereof was as shown in Table 4.

Claims (1)

[Scope of Claims] 1. Organosilicon monomer (A) having at least one polymerizable unsaturated group and at least one hydrolyzable group directly bonded to a silicon atom in the molecule (0.1 to 40) % by weight, 0.1 to 20% by weight of polymerizable unsaturated carboxylic acid (B) and 40 to 99.8% by weight of other polymerizable unsaturated monomers (C) (however, (A), (B) and (The total of component (C) is 100% by weight.) 100 parts by weight (in terms of non-volatile content) of water-dispersible vinyl copolymer (I) obtained from (100% by weight) and hydrogen directly bonded to at least one silicon atom in the molecule. atoms and has an average compositional formula of RaHbSiO(_4_-a_-_b)/_2 [in the formula R
is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and a and b are each 0.2≦a≦2.
5, 0.0005≦b≦1.0, and a+b is 0
．． 3≦a+b≦3.0. An aqueous polishing agent comprising a water-dispersible silicone-modified vinyl polymer obtained by reacting with 0.2 to 1000 parts by weight of organopolysiloxane (II) represented by: