WO2009122921A1

WO2009122921A1 - Emulsion composition for floor polishing and floor polishing composition using the emulsion composition

Info

Publication number: WO2009122921A1
Application number: PCT/JP2009/055391
Authority: WO
Inventors: 明美纐纈
Original assignee: 東亞合成株式会社
Priority date: 2008-04-03
Filing date: 2009-03-19
Publication date: 2009-10-08
Also published as: JP5170237B2; JPWO2009122921A1

Abstract

Disclosed is an emulsion composition for floor polishing that, even though a film forming assistant is not substantially contained, has excellent film forming properties at a low temperature and, at the same time, can form a film having excellent durability and water resistance. Also disclosed is a floor polishing composition using the emulsion composition for floor polishing. The emulsion composition for floor polishing is characterized in that the emulsion composition comprises an emulsion polymer obtained by subjecting an ethylenically unsaturated monomer to multistage emulsion polymerization and contains a compound containing two or more hydrazide groups, and an ethylenically unsaturated monomer mixture (A) for use in a final stage of the multistage emulsion polymerization and an ethylenically unsaturated monomer mixture (B) for use in stages other than the final stage of the multistage emulsion polymerization satisfy specific conditions.

Description

Emulsion composition for floor polish and floor polish composition using the same

The present invention is, for example, a floor polish capable of forming a film intended to protect the floor surface while maintaining the beauty of the floor material by applying it to the surface of a chemical floor material made of synthetic resin or a wooden floor material. The present invention relates to an emulsion composition and a floor polish composition using the same.

A floor polish composition is used for the purpose of preserving the aesthetics of the flooring and protecting the flooring, such as chemical flooring made of synthetic resin, wooden flooring, and stone floors such as concrete and marble. ing. As described in JISK 3920 (Floor Polish Test Method), there are three types of floor polish compositions: oily floor polish, emulsifiable floor polish, and aqueous floor polish, each of which is a polymer type or wax type. Separated. Recently, polymer-type aqueous floor polishes have become the mainstream of floor polish compositions because they can be applied to various flooring materials, and have excellent durability and stain resistance.

Polymer type aqueous floor polish is disclosed in Patent Documents 1 and 2, etc., and comprises an acrylic emulsion, a polyethylene wax emulsion, an alkali-soluble resin, a plasticizer, a film-forming aid, and others.

In order to obtain a sufficient film-forming property, a film-forming auxiliary which is a kind of a volatile organic compound (hereinafter referred to as VOC) is added to the conventional floor polish composition. In recent years, there has been an active movement to suppress organic solvent emissions due to increased awareness of the environment and health. In particular, in the indoor environment of a building, a sick house by VOC is taken up as a social problem, and reduction of VOC is also desired in a floor polish composition.

In order to meet this demand, it is necessary to ensure film-forming properties while reducing the amount of film-forming aid added. For such a problem, studies have been made in the field of water-based paints for a long time. For example, Patent Documents 3, 4 and 5 disclose multilayer structure type polymer emulsions. These disclose a paint having a good film forming property at a low temperature by providing a layer having a low glass transition temperature as an outermost layer of polymer emulsion particles. However, any of the multilayer structure type polymer emulsions has a low acid value in order to improve water resistance, and there is a problem that alkali peelability and black heel mark resistance are insufficient when it is used as a floor polish composition. It was difficult.

On the other hand, the use of a multilayer structure type polymer emulsion in a floor polish composition is disclosed in Patent Documents 6, 7 and 8, etc. However, in the method disclosed in Patent Document 6, although the film-forming property is improved by providing a layer having a low glass transition temperature as the outermost layer of the polymer emulsion particles, the amount of the film-forming aid can be completely reduced. It has not reached. Furthermore, the low glass transition temperature layer was not crosslinked, had low impact resistance, and was not excellent in durability. Further, in the methods disclosed in Patent Documents 7 and 8, a low glass transition temperature layer that is crosslinked is provided on the inner layer of the particles, and although the durability is excellent, the film forming property is not improved.

Japanese Examined Patent Publication No. 44-24407 Japanese Patent Publication No.49-1458 Japanese Patent Laid-Open No. 7-34027 Japanese Patent Laid-Open No. 2002-3778 Japanese Patent Laid-Open No. 2007-100080 Japanese Patent Laid-Open No. 50-71791 Japanese Examined Patent Publication No. 62-4051 Japanese Patent No. 3157464

The present invention is an emulsion composition for floor polish that provides a film having excellent film-forming properties at a low temperature and having excellent durability and water resistance even when it does not substantially contain a film-forming aid, and uses the same. An object is to provide a floor polish composition.

As a result of intensive studies in view of the above problems, the present inventor has excellent film-forming properties at low temperatures by including a compound having two or more hydrazide groups in a specific emulsion polymer obtained by a multistage emulsion polymerization method. And it discovered that the emulsion composition for floor polishes which was excellent in durability, water resistance, peelability from a flooring material, and storage stability was obtained, and came to complete this invention.

That is, the emulsion composition for floor polish according to the present invention is an emulsion polymer obtained by a multistage emulsion polymerization method using an ethylenically unsaturated monomer, and the ethylenically unsaturated monomer used in the final stage of the multistage emulsion polymerization. The saturated monomer mixture (A) and the ethylenically unsaturated monomer mixture (B) used in a stage other than the final stage of the multistage emulsion polymerization satisfy the following conditions and further contain a compound having two or more hydrazide groups. It is an emulsion composition for floor polish characterized by doing.
(1) The ethylenically unsaturated monomer mixture (A) comprises (a) 40 to 94% by mass of an alkyl acrylate or alkyl methacrylate monomer unit having an alkyl group having 4 to 12 carbon atoms, and (b) an ethylenically unsaturated monomer. 5 to 30% by mass of a saturated carboxylic acid monomer unit, (c) 1 to 30% by mass of an ethylenically unsaturated monomer unit having a carbonyl group [where (a) + (b) + (c) = 100 The glass transition temperature Tg (A) of the copolymer is −60 to 5 ° C., and the HLB (A) of the copolymer is 3 to 10.
(2) The ethylenically unsaturated monomer mixture (B) comprises (a) 1 to 65% by mass of an alkyl acrylate or alkyl methacrylate monomer unit having an alkyl group having 4 to 12 carbon atoms, and (b) an ethylenically unsaturated monomer. 5 to 20% by mass of a saturated carboxylic acid monomer unit, (d) 30 to 90% by mass of another monomer unit copolymerizable with the above (a) and (b) [where (a) + (b ) + (D) = 100 mass%], the glass transition temperature Tg (A) of the copolymer is 0 to 100 ° C., and the HLB (B) of the copolymer is 1 to 10.

The ethylenically unsaturated monomer mixture (A) further contains 40% by mass or less of other monomer units (d) copolymerizable with the above (a), (b) and (c) [where, (A) + (b) + (c) + (d) = 100% by mass] is preferably contained.

The floor polish emulsion composition has a difference between the HLB (A) of the ethylenically unsaturated monomer mixture (A) and the HLB (B) of the ethylenically unsaturated monomer mixture (B) of 0.1. The above is preferable.

The floor polish emulsion composition preferably has a mass ratio of the ethylenically unsaturated monomer mixture (A) to the ethylenically unsaturated monomer mixture (B) of 30/70 to 80/20. .

The floor polish composition according to the present invention contains the above emulsion composition for floor polish.

Moreover, it is preferable that the floor polish composition according to the present invention does not substantially contain a film-forming aid.

As described above, the emulsion composition for floor polish according to the present invention contains a specific emulsion polymer obtained by a multistage emulsion polymerization method and a compound having two or more hydrazide groups. Therefore, it has excellent film-forming properties at low temperatures even without substantially containing a film-forming auxiliary, and has a film with excellent durability such as black heel mark resistance and scuff resistance, water resistance and adhesion. The emulsion composition for floor polish to give and the floor polish composition using the same can be provided. Moreover, the floor polish composition using the said emulsion composition for floor polishes has favorable storage stability.

Hereinafter, embodiments of the present invention will be described in detail. In this specification, “(meth) acryl” means “acryl or methacryl”.
The emulsion composition for floor polish of the present invention is obtained by multistage emulsion polymerization of an ethylenically unsaturated monomer.

The multistage emulsion polymerization is carried out in two or more stages. The ethylenically unsaturated monomer mixture (A) used in the final stage and the ethylenically unsaturated monomer used in other than the final stage of the multistage emulsion polymerization. It consists of a monomer mixture (B), and the component (B) may further consist of a plurality of stages having different compositions.

The ethylenically unsaturated monomer mixture (A) used in the final stage includes (a) an alkyl (meth) acrylate monomer unit having an alkyl group having 4 to 12 carbon atoms, and (b) an ethylenically unsaturated carboxylic acid. Other monomer units comprising a monomer unit, (c) an ethylenically unsaturated monomer unit having a carbonyl group, and further copolymerizable with the above (a), (b) and (c) (D) is contained.

Examples of the (a) alkyl (meth) acrylate monomer having an alkyl group having 4 to 12 carbon atoms include n-butyl (meth) acrylate, i-butyl (meth) acrylate, and n-hexyl (meth) acrylate. N-octyl (meth) acrylate, i-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, i-nonyl (meth) acrylate, n-decyl (meth) acrylate, n -Lauryl (meth) acrylate etc. can be mentioned, These 1 type (s) or 2 or more types can be used. Among these, n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable because they are inexpensive and easily available industrially.

Examples of the (b) ethylenically unsaturated carboxylic acid monomer include unsaturated monobasic acids such as (meth) acrylic acid, crotonic acid, vinyl acetic acid, acryloxypropionic acid, maleic acid, fumaric acid, and mesaconic acid. , Unsaturated dibasic acids such as citraconic acid, itaconic acid and cyclohexanedicarboxylic acid, and unsaturated acid anhydrides such as maleic anhydride and tetrahydrophthalic anhydride. Can be used. Among these, (meth) acrylic acid is preferable because it is inexpensive and easily causes a copolymerization reaction with other various monomers.

Examples of the (c) ethylenically unsaturated monomer having a carbonyl group include acrolein, diacetone (meth) acrylamide, formysterol, (meth) acryloxyalkylpropanal, diacetone (meth) biacrylate, acetonyl ( (Meth) acrylate, acetoacetoxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate-acetyl acetate, butanediol-1,4-acrylate-acetyl acrylate, vinyl methyl ketone, vinyl ethyl ketone, vinyl isobutyl ketone, etc. 1 type, or 2 or more types of these can be used. Among these, acrolein and diacetone acrylamide are preferable in view of industrial availability, and diacetone acrylamide is particularly preferable.

Examples of other monomers copolymerizable with (d) (a), (b) and (c) include methyl (meth) acrylate, ethyl (meth) acrylate, and n-propyl (meth) acrylate. Cyano group-containing vinyl monomers such as alkyl (meth) acrylates having 1 to 3 carbon atoms such as i-propyl (meth) acrylate, (meth) acrylonitrile, α-chloroacrylonitrile, 2-hydroxyethyl ( (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene Glycol-poly Hydroxyl group-containing vinyl monomers such as mono (meth) acrylate of propylene glycol copolymer, styrene, vinyl toluene, divinyl toluene, α-methyl styrene, paramethyl styrene, chlorostyrene, vinyl dibenzyl chloride, benzyl (meth) acrylate Aromatic vinyl monomers such as cyclohexyl (meth) acrylate, alicyclic vinyl monomers such as isobornyl (meth) acrylate, itaconic acid monoethyl ester, fumaric acid monobutyl ester, maleic acid monobutyl ester, etc. Unsaturated dicarboxylic acid monoalkyl esters, acrylamides, methacrylamides, N-methylol acrylamides, N-methoxymethyl acrylamides, N-methoxybutyl acrylamides and the like, and N-substituted compounds thereof Unsaturated alcohols such as allyl alcohol, vinyl acetate, glycidyl (meth) acrylate, vinyl chloride, there may be mentioned vinylidene chloride, can be used alone or in combination of two or more thereof. Among these, methyl (meth) acrylate, ethyl (meth) acrylate, styrene, and cyclohexyl (meth) acrylate are preferable because they are inexpensive and easily available industrially.

The constituent ratios of the constituent monomer units in the copolymer are as follows.
(A) 40 to 94% by mass of an alkyl (meth) acrylate monomer unit having an alkyl group having 4 to 12 carbon atoms, (b) 5 to 30% by mass of an ethylenically unsaturated carboxylic acid monomer unit, (c) The ethylenically unsaturated monomer unit having a carbonyl group is required to be 1 to 30% by mass [where (a) + (b) + (c) = 100% by mass]. It is preferable that the amount is from 90 to 90% by mass, (b) from 7 to 25% by mass, and (c) from 3 to 15% by mass. The monomer mixture preferably contains 40% by mass or less of other monomer units (d) copolymerizable with the above (a), (b) and (c).

(A) When the alkyl (meth) acrylate monomer unit having an alkyl group having 4 to 12 carbon atoms is less than 40% by mass, the resulting floor polish composition has insufficient film-forming properties, and exceeds 94% by mass. And durability such as black heel mark resistance and scuff mark resistance may be insufficient.

(B) When the ethylenically unsaturated carboxylic acid monomer unit is less than 5% by mass, the resulting floor polish composition may have insufficient alkali peelability and durability. Sexuality may be insufficient.

(C) When the amount of the ethylenically unsaturated monomer unit having a carbonyl group is less than 1% by mass, crosslinking is not sufficiently performed, and the durability and water resistance of the resulting floor polish composition are insufficient, and 30% by mass is obtained. When it exceeds, adhesiveness and water resistance may be insufficient.

(D) Durability and gloss of the resulting floor polish composition are improved by containing 40% by mass or less of other monomer units copolymerizable with (a), (b) and (c). Therefore, it is preferable. However, if it exceeds 40% by mass, the film forming property may be insufficient.

The glass transition temperature (hereinafter referred to as “Tg”) of the copolymer composed of the component (A) needs to be −60 to 5 ° C., more preferably −55 to 0 ° C., More preferred is a temperature of 50 to -5 ° C.
When the Tg is lower than −60 ° C., the durability of the resulting composition for floor polishing is insufficient, and the coating tends to block, and when it exceeds 5 ° C., the film forming property at low temperatures may be insufficient.

Accordingly, in designing the emulsion composition for floor polish, it is desirable to select the monomer units (a) to (d) so that the Tg of the resulting copolymer is set within the above range. Note that Tg used in the present invention is calculated by the Fox equation shown below.
1 / Tg = W1 / Tg1 + W2 / Tg2 + W3 / Tg3 ...
Here, W1, W2, W3... Indicate the mass fraction of monomer units 1, 2, 3,... In the polymer, and Tg1, Tg2, Tg3. The Tg (in the above formula, absolute temperature is used) of the homopolymer (homopolymer) is shown.

In the above formula, for Tg of a homopolymer (homopolymer), a value described in “PolymerHand Book (Third Edition, J. Brandup and EH Immergut)” or the like can be used. For example, poly n-butyl acrylate: −54 ° C., poly 2-ethylhexyl acrylate: −70 ° C., polyacrylic acid: 106 ° C., polymethacrylic acid: 185 ° C., polydiacetone acrylamide: 65 ° C., polystyrene: 100 ° C., polymethyl Methacrylate: 105 ° C., polycyclohexyl acrylate 16 ° C. and the like.

Further, the HLB of the copolymer composed of the component (A) needs to be 3 to 10, more preferably 4 to 8. If the HLB is lower than 3, the resulting floor polish composition will be more lipophilic and more compatible with rubber, so the black heel mark resistance will be insufficient, and if it exceeds 10, the hydrophilicity will increase and absorb water. Since it becomes easy, water resistance may be insufficient.

Therefore, in designing the emulsion composition for floor polish, it is desirable to select the monomer units (a) to (d) so that the HLB of the resulting copolymer is set within the above range. In addition, HLB (Hydrophile-Lipophile Balance, hydrophilic / lipophilic balance) used in the present invention is calculated from the HLB of each monomer by the following formula, and from the weighted average of monomer units constituting the component (A). It means what is calculated.
HLB = Σinorganic / Σorganic × 10
Here, for inorganicity and organicity, for example, the values in the inorganic base table shown in Kaoru Fujita, Masami Akatsuka, “Systematic Organic Qualitative Analysis (mixture)”, Kazama Shobo (1974) can be adopted. Good.

The ethylenically unsaturated monomer mixture (B) used in other than the final stage of the multi-stage emulsion polymerization is (a) an alkyl (meth) acrylate monomer unit having an alkyl group having 4 to 12 carbon atoms, and (b) ethylene. A unsaturated unsaturated carboxylic acid monomer unit, (d) comprising other monomer units copolymerizable with the above (a) and (b), and the constitution of the constituent monomer units in the copolymer The ratio is (a) 1 to 65% by mass of an alkyl (meth) acrylate monomer unit having an alkyl group having 4 to 12 carbon atoms, (b) 5 to 20% by mass of an ethylenically unsaturated carboxylic acid monomer unit, (D) The other monomer units should be 30 to 90% by mass [where (a) + (b) + (d) = 100% by mass], and (a) 5 to 60% by mass described above. %, (B) 7 to 15% by mass, (d) 40 to 85% by mass In which it is more preferable.

The monomer units (a), (b) and (d) may be the same as the monomer units of the ethylenically unsaturated monomer mixture (A) used in the final stage of the multistage emulsion polymerization. it can. Moreover, although the ethylenically unsaturated monomer mixture (B) having different compositions may be dropped in a plurality of stages, it is necessary that the total composition ratio falls within the above range.

(A) When the alkyl (meth) acrylate monomer unit having an alkyl group having 4 to 12 carbon atoms exceeds 65 mass%, the durability of the resulting floor polish composition may be insufficient.

(B) If the ethylenically unsaturated carboxylic acid monomer unit is less than 5% by mass, the resulting floor polish composition may have insufficient alkali peelability and durability, and if it exceeds 20% by mass, water resistance will be insufficient. There is a case.

The Tg of the copolymer composed of the component (B) needs to be 0 to 100 ° C., more preferably 15 to 100 ° C., and still more preferably 30 to 100 ° C.
When the Tg is lower than 0 ° C., the durability of the resulting floor polish composition may be insufficient. When Tg exceeds 100 ° C., the film forming property may be deteriorated.

Further, the HLB of the copolymer composed of the component (B) needs to be 1 to 10, and more preferably 3 to 8. When the HLB is lower than 1, the stability of the resulting emulsion for floor polish is reduced, and the black heel mark resistance of the resulting floor polish composition is insufficient, and when it exceeds 10, the water resistance may be insufficient.

The emulsion polymer obtained by the multistage emulsion polymerization method further contains a compound having two or more hydrazide groups to form an emulsion composition for floor polishing. A compound having two or more hydrazide groups reacts with a carbonyl group in the emulsion and functions to improve the durability, water resistance, and film-forming property of the floor polish composition.

Examples of the compound having two or more hydrazide groups in the molecule include carbohydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, and isophthalic acid. Dihydrazide, citric acid dihydrazide, 1,2,4-benzenetridihydrazide, thiocarbodihydrazide, trade names “APA-M950”, “APA-M980”, “APA-P250”, “APA-P280” manufactured by Otsuka Chemical Co., Ltd. And hydrazide polymers. Among these, carbohydrazide, adipic acid hydrazide, succinic acid dihydrazide, and hydrazide polymer are preferable from the balance of dispersibility in emulsion and water resistance.

The compounding amount of the compound containing two or more hydrazide groups in the molecule is not particularly limited, but is 0.1 to 2 equivalents of hydrazide group to 1 equivalent of carbonyl group in component (A). Such an amount is appropriate. When the hydrazide group is less than 0.1 equivalent with respect to 1 equivalent of the carbonyl group, crosslinking is insufficient, and the resulting floor polish composition may have insufficient blocking resistance and durability. May remain and water resistance and detergent resistance may be insufficient.

The HLB (A) of the ethylenic monomer mixture (A) used in the final stage of the multistage emulsion polymerization and the HLB (B) of the ethylenic monomer mixture (B) used in other than the final stage of the multistage emulsion polymerization. ) Is preferably 0.1 or more (usually 10 or less), more preferably 0.3 or more. If it is less than 0.1, the (A) layer and the (B) layer may be uniformly mixed in the resulting polymer particles.

The mass ratio of the ethylenic monomer mixture (A) used in the final stage of the multistage emulsion polymerization and the ethylenic monomer mixture (B) used in other than the final stage of the multistage emulsion polymerization was 30/70. It is preferably 80/20. When the (A) is less than 30, the film-forming property of the obtained floor polish composition is deteriorated, and when the (A) exceeds 80, the obtained floor polish composition has insufficient blocking resistance and durability. There is a case.

The multi-stage emulsion polymerization method for obtaining the emulsion composition for floor polish of the present invention is a known method such as a polymerization method in which a polymerization initiator, an aqueous medium or an emulsifier is added all at once, a so-called monomer dropping method or a pre-emulsion method. Can be done by the method.

Examples of the emulsifier include anionic surfactants such as sodium alkylbenzenesulfonate, sodium alkylsulfate, sodium polyoxyethylene alkylphenyl ether sulfate, sodium polyoxyethylenealkylsulfate, sodium dialkylsulfosuccinate, and formalin condensate of naphthalenesulfonic acid. Nonionic surfactants such as polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, polyethylene glycol fatty acid ester, sorbitan fatty acid ester, sodium styrenesulfonate, sodium allylalkylsulfonate, sodium alkylallylsulfosuccinate, polyoxyethylene Alkyl allyl glycerin ether sulfate, polyoxyethylene alkylphenol allyl glyce Reactive emulsifiers such as phosphorus ether sulfate, polyvinyl alcohol, polyacrylate, water-soluble (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer salt, styrene- (meth) acrylic copolymer salt, poly Polymer surfactants such as (meth) acrylamide and poly (meth) acrylamide copolymers can be used, and these can be used alone or in combination of two or more. A desirable amount of the emulsifier is preferably 0.05 to 5 parts by mass with respect to the total mass of the ethylenically unsaturated monomer mixture used. When it exceeds 5 mass parts, it may be inferior to water resistance.

As the polymerization initiator, either a water-soluble polymerization initiator or an oil-soluble polymerization initiator can be used. For example, hydrogen peroxide, benzoyl peroxide, tert-butyl peroxide, organic peroxides such as dicumyl peroxide, azo such as azobisisobutyronitrile, azobis (2-methylbutyronitrile), azobiscyanovaleric acid, etc. Compounds, inorganic peroxides such as sodium persulfate, potassium persulfate and ammonium persulfate, and redox polymerization initiators composed of these peroxides and reducing agents such as sulfites, ascorbic acid and erythorbate It is done. The amount of the polymerization initiator used is preferably 0.01 to 5% by mass, particularly preferably 0.1 to 3% by mass, based on the total mass of the ethylenically unsaturated monomer mixture used.

The temperature of the polymerization reaction is preferably 20 to 100 ° C., particularly preferably 40 to 95 ° C. The polymerization time is preferably 1 to 10 hours.

As the aqueous medium, water is usually used. A hydrophilic solvent such as a lower alcohol or a ketone can be used as necessary, but it is preferable that no organic solvent is contained. The usage-amount of the said aqueous medium is not specifically limited, What is necessary is just to set suitably so that solid content of the emulsion polymer for floor polish obtained may become predetermined amount.

In the multistage emulsion polymerization, a chain transfer agent can be used for adjusting the molecular weight of the resulting emulsion polymer. Examples of the chain transfer agent include lauryl mercaptan, tert-dodecyl mercaptan, octyl mercaptan, 2-ethylhexyl thioglycolate, 2-methyl-5-tert-butylthiophenol, and 3-mercaptopropionic acid. The amount of the chain transfer agent used is not particularly limited, and may be appropriately set according to the type of ethylenically unsaturated monomer mixture to be used, reaction conditions, and the like.

Further, a neutralizing agent may be used to adjust the pH of the obtained emulsion composition for floor polish. As the neutralizing agent, amines such as ammonia, triethylamine, N, N-dimethylaminoethanol, 2-amino-2-methyl-1-propanol, and hydroxides such as sodium hydroxide and potassium hydroxide are used. . The pH can be adjusted at any time during and before and after the polymerization.

The emulsion polymer obtained by the multi-stage emulsion polymerization is obtained as an emulsion having a solid content of 10 to 70% by mass, and is added to the floor polish composition of the present invention in a range of 10 to 60% by mass as the solid content. .

The floor polish composition of the present invention is a known polyvalent metal compound, plasticizer, film-forming aid, alkali-soluble resin, slip adjuster, wettability improver as a component other than the above-mentioned emulsion component for floor polish. It is comprised using components, such as.

Examples of the polyvalent metal compound include polyvalent metal ions, ammonia of polyvalent metal ions, and amine complexes (and particularly NH3 coordinated). The multivalent ions can be added to the composition in the form of oxides, hydroxides or basic salts, acidic salts or neutral salts having a remarkable solubility of at least about 1% by weight in water. Examples include beryllium, cadmium, copper, calcium, magnesium, zinc, zirconium, barium, strontium, aluminum, bismuth, antimony, lead, cobalt, nickel, iron, and many polyvalent metal ions. Examples of amines capable of forming complexes of ammonia and amine complexes of the above polyvalent metal ions include morpholine, monoethanolamine, diethylaminoethanol, and ethylenediamine. Moreover, the polyvalent metal complex (salt) of the organic acid which can be solubilized in alkaline pH range can also be used. In addition, anions such as acetate ion, glutamate ion, formate ion, carbonate ion, salicylate ion, glycolate ion, octoate ion, benzoate ion, gluconate ion, oxalate ion and lactate ion are also used. In addition, polyvalent metal chelates whose ligands are bidentate amino acids such as glycine and alanine are also used.

Examples of plasticizers include citrate esters such as acetyl tributyl citrate, phosphate esters such as tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, tributoxyethyl phosphate, and adipic acid. Aliphatic dibasic esters such as dibutyl, di-2-ethylhexyl adipate, di-n-alkyl adipate 610, di-2-ethylhexyl azelate, dibutyl sebacate, di-2-ethylhexyl sebacate, isobutyl pentadiol An ester derivative, chlorinated paraffin, or the like can be used.

As film-forming aids, alcohols such as ethanol and isopropyl alcohol, polyhydric alcohols such as ethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, ethylene glycol mono -Glycol ethers such as 2-methylhexyl ether and diethylene glycol mono-2-methylhexyl ether, α-amino alcohol, β-amino alcohol, diethanolamine, triethanolamine, 2-aminoisohexyl alcohol, N, N-dimethylethanol Amine, N, N-diethylethanolamine, aminoethylethanolamine, N-methyl-N, N-diethanolamine, N, Amine compounds such as N-butylethanolamine, N-methylethanolamine, and 3-amino-1-propanol can be used. However, it is preferable that the film-forming aid is blended in a small amount or not substantially blended in order to obtain environmental safety. In addition, the floor polish composition of the present invention can obtain a film-forming property at a low temperature without substantially adding a film-forming aid.

Examples of the alkali-soluble resin include diisobutylene-maleic anhydride copolymer, rosin-modified maleic acid resin, styrene maleic acid resin, (meth) acrylic acid ester- (meth) acrylic acid copolymer, and shellac. . In addition, in the floor polish composition of this invention, these are used arbitrarily.

As slip regulators, plant waxes such as candelilla wax, carnauba wax, rice wax, tree wax, jojoba oil, animal waxes such as beeswax, lanolin, whale wax, petroleum oils such as paraffin wax, microcrystalline wax, petrolatum, etc. Synthetic hydrocarbon waxes such as waxes and Fischer-Tropsch waxes, synthetic waxes such as (oxidized) polyethylene waxes and (oxidized) polypropylene waxes, and the like can be used.

Examples of wettability improvers include fluorine surfactants, silicone surfactants, higher alcohol sodium sulfate esters, sodium alkylbenzene sulfonates, sodium dialkyl ester succinates, sodium alkyl diphenyl ether disulfonates, polyoxyethylene alkyl sulfates. Anionic surfactants such as sodium, sodium polyoxyethylene alkylphenyl ether sulfate, sodium alkane sulfonate, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene copolymer, sucrose fatty acid Esters, sorbitan fatty acid esters, polyethylene glycol fatty acid esters, polyglycerin fatty acid esters, etc. Fatty acid esters, coconut oil fatty acid diethanolamide, lauric acid diethanolamide, lauric acid myristic acid diethanolamide, myristic acid diethanolamide, oleic acid diethanolamide, fatty acid alkanolamides such as palm kernel oil fatty acid diethanolamide, alkyl glucoside, etc. Nonionic surfactants, alkylbetaine-type zwitterionic surfactants such as laurylbetaine, imidazoline-type zwitterions such as 2-alkyl-N-carboxymethylimidazolinium betaine and 2-alkyl-N-carboxyethylimidazolinium betaine Surfactants, alkylsulfobetaine type amphoteric surfactants, amide sulfobetaine type amphoteric surfactants such as coconut oil fatty acid amide dimethylhydroxypropyl sulfobetaine, N- Alkyl -β- aminopropionates, N- alkyl -β- iminodipropionates, it is possible to use an amphoteric surfactant such as β- alanine-type ampholytic surface active agent.

In addition, pH adjusting agents such as ammonia, preservatives, antifoaming agents, antibacterial agents, fragrances, dyes, urethane resins, colloidal silica, fluorescent whitening agents, ultraviolet absorbers and the like can also be used as optional components.

In the floor polish composition of the present invention, the non-volatile content including the above optional components is preferably set to about 12 to 40% by mass.

A preferred method for producing a floor polish composition is to add a plasticizer, a film-forming aid, an alkali-soluble resin and a fluorosurfactant to water, then add a polymer of an ethylenically unsaturated compound, and then synthesize It can be produced by mixing wax or the like. In addition, optional components such as ammonia, preservatives, antifoaming agents, antibacterial agents, fragrances, dyes, urethane resins, colloidal silica, fluorescent whitening agents, ultraviolet absorbers, etc., may be added in appropriate steps as necessary. Added.

The floor polish composition of the present invention is effective for objects to be coated such as plastic floor materials such as vinyl-based and synthetic resin-coated floors, stone materials, cement-based floor materials, and wood-based floor materials. Further, the floor polish composition of the present invention can be applied to an object to be coated by a usual method such as spray coating, roller coating, brush coating or brush coating.
The floor polish composition can be used after being diluted with a solvent such as water or a water-miscible solvent according to the apparatus and application conditions. Adjustment of temperature, humidity, etc. as other application conditions can be appropriately performed by a dryer, a blower, an air conditioner, or the like.

The above-mentioned article coated with the floor polish composition of the present invention forms a peelable protective film by drying at room temperature (5-35 ° C. ± 5 ° C.), more preferably around 20-25 ° C. Is done. In order to promote the evaporation of moisture in the process of forming the protective film, moisture removing means such as air blowing, heating, or a combination of both may be used as appropriate. This makes it easy to adjust the formation time of the protective film, but the heating means is only for evaporation of water, and heating is not an essential component for forming the protective film.

Hereinafter, the features of the emulsion composition for floor polish of the present invention and the floor polish composition using the same will be described with reference to examples and comparative examples of the present invention. In the following description, “part” means part by mass, and “%” means mass%. However, the present invention is not limited to these examples.

(Examples 1 to 14, Comparative Example 1)
In a reaction vessel equipped with a stirrer, a reflux condenser, two dropping funnels, a thermometer, and a nitrogen introduction tube, 80 parts of water and 0.7 parts of sodium lauryl sulfate were charged and heated to 80 ° C.
To the monomer mixture of the first stage composition shown in Tables 1 and 2, sodium lauryl sulfate and water were added and emulsified. The obtained monomer emulsion and 6 parts of 5% aqueous ammonium persulfate solution were continuously dropped into the reaction vessel over 2 hours by separate dropping funnels, and emulsion polymerization was performed. After completion of the dropping, the inside of the reaction vessel was kept at 80 ° C. for 30 minutes.
Subsequently, sodium lauryl sulfate and water were added to the monomer mixture having the second stage composition shown in Tables 1 and 2 and emulsified. The obtained second-stage monomer emulsion and 6 parts of 5% ammonium persulfate aqueous solution were continuously dropped into a reaction vessel from a separate dropping funnel over a period of 2 hours for emulsion polymerization. One hour after the completion of the dropping, the system was cooled to complete the polymerization.
Further, zinc oxide solubilized using ammonium bicarbonate and aqueous ammonia so that the molar ion equivalent of zinc is 20% with respect to the carboxyl group in the polymer is mixed, and hydrazide is added to the carbonyl group in the polymer. Adipic acid hydrazide was mixed so that the equivalent was 100% to obtain an emulsion composition for floor polish having a solid content concentration of 38%.
Furthermore, various additives were added to the emulsion composition for floor polish at a ratio as shown in Table 3 and mixed by stirring to obtain a floor polish composition. In addition, the symbol of the ethylenically unsaturated monomer shown in Table 1, 2, 4, 5 and 6 shows the following meaning. The numbers in parentheses in the table indicate the ratio (% by mass) to the total amount of the ethylenically unsaturated monomer.

HA: 2-ethylhexyl acrylate BA: n-butyl acrylate St: styrene MMA: methyl methacrylate AA: acrylic acid MAA: methacrylic acid DAAM: diacetone acrylamide CHA: cyclohexyl acrylate

(Examples 15 to 20, Comparative Examples 2 to 5)
Using the same apparatus as in Example 1, 80 parts of water and 0.7 part of sodium lauryl sulfate were charged and the temperature was raised to 80 ° C.
To the monomer mixture of the first stage composition shown in Tables 4, 5 and 6, sodium lauryl sulfate and water were added and emulsified. The obtained monomer emulsion and 4 parts of a 5% ammonium persulfate aqueous solution were continuously dropped into the reaction vessel over 1 hour using separate dropping funnels, and emulsion polymerization was performed. After completion of the dropping, the inside of the reaction vessel was kept at 80 ° C. for 30 minutes.
Subsequently, sodium lauryl sulfate and water were added to the monomer mixture having the second stage composition shown in Tables 4, 5 and 6 and emulsified. The obtained second-stage monomer emulsion and 4 parts of a 5% aqueous ammonium persulfate solution were continuously dropped into a reaction vessel from another dropping funnel over 1 hour to effect emulsion polymerization. After completion of the dropping, the inside of the reaction vessel was kept at 80 ° C. for 30 minutes.
Subsequently, sodium lauryl sulfate and water were added to the monomer mixture having the third stage composition shown in Tables 4, 5 and 6 and emulsified. The obtained third-stage monomer emulsion and 4 parts of a 5% aqueous ammonium persulfate solution were continuously dropped into a reaction vessel from each separate dropping funnel over 1 hour for emulsion polymerization. One hour after the completion of the dropping, the system was cooled to complete the polymerization.
Furthermore, operation similar to Example 1 was performed and the floor polish composition was obtained through the emulsion composition for floor polishes.

(Comparative Example 6)
Except not using adipic acid dihydrazide, operation similar to Example 1 was performed and the floor polish composition was obtained through the emulsion composition for floor polishes.

In the above examples and comparative examples, the pH of the emulsion composition for floor polish was 6-8.

For the various floor polish compositions obtained, the following low-temperature film-forming properties, glossiness, leveling properties, black heel mark (BHM) resistance, scuff resistance, water resistance, peelability, adhesion, and storage stability are as follows. Evaluation was made according to the test method and criteria, and the results are shown in Tables 7-9.

(1) Low temperature film-forming property [Test method]
Apply the test floor polish composition to a thickness of 50 μm on a glass plate in an environment of 5 ° C., and leave it to stand overnight in an environment of 5 ° C., and visually check the film forming state according to the following criteria. Was judged.
[Criteria]
◎: A uniform film was formed. ○: A coating film was formed, but cracks occurred only on the outer periphery. △: A coating film was formed, but cracks occurred overall. ×: A coating film could not be formed. ,Shattered

(2) Glossiness [Test method]
In accordance with JIS K 3920 (floor polish test method), the test floor polish composition was applied three times (thickness 15 μm) to a homogeneous vinyl tile (manufactured by Toli Co., Ltd., trade name “Machico S-Plane No. 5626”), The glossiness of the product dried for 1 hour at room temperature (10 to 30 ° C.) was measured with a specular gloss meter (manufactured by Nippon Denshoku Industries Co., Ltd., model: PG-1M).

(3) Leveling [Test method]
In accordance with JIS K 3920 (floor polish test method), the test floor polish composition was applied three times (thickness 15 μm) to a homogeneous vinyl tile (manufactured by Toli Co., Ltd., trade name “Machico S-Plane No. 5626”), Immediately after that, an X-shaped mark (hereinafter referred to as “X mark”) was applied along the diagonal line of the substrate, and the substrate was dried at room temperature (10 to 30 ° C.) for 1 hour. The extent to which the X mark disappeared was visually determined according to the following criteria.
[Criteria]
A: X mark is not seen.
○: The outline of the X mark is seen as a difference in gloss.
Δ: Part of the X mark is seen as a ridge.
X: The X mark has an overall ridge shape and is uneven.

(4) Black heel mark (BHM) resistance [test method]
In accordance with JIS K 3920 (floor polish test method), the test floor polish composition was applied three times (thickness 15 μm) to a homogeneous vinyl tile (manufactured by Toli Co., Ltd., trade name “Machico S Plane No. 5626”), What was dried at room temperature (10 to 30 ° C.) for a whole day and night was tested with a heel mark tester and visually judged in 10 stages.
[Criteria]
10: Extremely high BHM resistance.
6 to 9: Appropriate BHM resistance and practicality.
2 to 5: Lack of BHM resistance and practicability.
1: Extremely poor in BHM resistance.

(5) Scuff resistance [test method]
In accordance with JIS K 3920 (floor polish test method), the test floor polish composition was applied three times (thickness 15 μm) to a homogeneous vinyl tile (manufactured by Toli Co., Ltd., trade name “Machico S Plane No. 5626”), What was dried at room temperature (10 to 30 ° C.) for a whole day and night was tested with a heel mark tester and visually judged in 10 stages.
[Criteria]
10: Extremely high scuff resistance.
6 to 9: Appropriate scuff resistance and practicality.
2-5: Lack of scuff resistance and lack of practicality.
1: Very poor scuff resistance.

(6) Water resistance [Test method]
In accordance with JIS K 3920 (floor polish test method), the test floor polish composition was applied three times (thickness 15 μm) to a composition vinyl tile (trade name “P-60” manufactured by Tajima Co., Ltd.) at room temperature ( (10-30 ° C.) and dried for 24 hours, and then 0.2 ml of distilled water was added dropwise. After holding the water droplet for 1 hour, it was wiped off, and the whitening state of the coating film surface after 30 minutes was visually judged according to the following criteria.
[Criteria]
A: No whitening is observed. ○: Whitening is thinly observed. Δ: Partial whitening is observed. X: Whitening is recognized entirely.

(7) Peelability [Test method]
In accordance with JIS K 3920 (Floor Polish Test Method), the test floor polish composition was applied three times to a composition vinyl tile (trade name “P-60” manufactured by Tajima Co., Ltd.) (thickness 15 μm) at 50 ° C. The standard stripping solution described in JIS K 3920 (Floor Polish Test Method) was poured into the coating film so that the coating film covered it. Two-way rubbing test was performed using a white pad loaded with 500 g after 2 minutes. After rubbing, the peeled state of the coating film was visually determined according to the following criteria.
[Criteria]
◎: Completely peelable ○: Almost peelable △: Some film remains ×: Almost peelable

(8) Adhesiveness [Test method]
In accordance with JIS K 3920 (Floor Polish Test Method), the test floor polish composition was applied three times to a homogeneous vinyl tile (manufactured by Toli Co., Ltd., trade name “Machico S Plane No. 5626”) (thickness 15 μm), A cellotape (registered trademark) adhesion test was carried out on what was dried overnight at room temperature (10-30 ° C.). The average remaining film area ratio (%) measured three times is shown.

(9) Storage stability [Test method]
In accordance with JIS K 3920 (floor polish test method), the floor polish composition is put in a container, sealed, and stored in a constant temperature drier kept at 50 ° C. for 14 days. The state of the subsequent sample was visually determined according to the following criteria for the presence or absence of gelation, phase separation, solid content precipitation, and the like.
[Criteria]
Pass: No problem is found Fail: There is a problem

From the evaluation results of Examples 1 to 20 above, the floor polish composition of the present invention was found to have low-temperature film-forming properties, glossiness, leveling properties, black heel mark (BHM) resistance, scuff resistance, water resistance, peelability, It turns out that it is a favorable result also in any test item of adhesiveness and storage stability.
Further, in the floor polish composition of the present invention, as shown in Examples 1 to 20, good results were exhibited in each test item, particularly in low-temperature film-forming properties, without using a film-forming auxiliary. You can see that

On the other hand, Comparative Examples 1 to 6 are tests for any of low-temperature film-forming properties, glossiness, leveling properties, black heel mark (BHM) resistance, scuff resistance, water resistance, peelability, adhesion, and storage stability. It turns out that it is inferior to an item.

The emulsion composition for floor polish obtained according to the present invention and the floor polish composition using the same are excellent in film formability and also in durability and water resistance, and thus substantially contain a film-forming aid. Even if it is not necessary, it can be suitably used as a floor polish which gives good low-temperature film-forming properties and is excellent in various physical properties.

Claims

An emulsion polymer obtained by a multistage emulsion polymerization method of an ethylenically unsaturated monomer, the ethylenically unsaturated monomer mixture (A) used in the final stage of the multistage emulsion polymerization, and the multistage emulsion polymerization An emulsion composition for floor polish, characterized in that the ethylenically unsaturated monomer mixture (B) used in other than the final stage contains a compound satisfying the following conditions and further having two or more hydrazide groups.
(1) The ethylenically unsaturated monomer mixture (A) comprises (a) 40 to 94% by mass of an alkyl acrylate or alkyl methacrylate monomer unit having an alkyl group having 4 to 12 carbon atoms, and (b) an ethylenically unsaturated monomer. 5 to 30% by mass of a saturated carboxylic acid monomer unit, (c) 1 to 30% by mass of an ethylenically unsaturated monomer unit having a carbonyl group [where (a) + (b) + (c) = 100 The glass transition temperature Tg (A) of the copolymer is −60 to 5 ° C., and the HLB (A) of the copolymer is 3 to 10.
(2) The ethylenically unsaturated monomer mixture (B) comprises (a) 1 to 65% by mass of an alkyl acrylate or alkyl methacrylate monomer unit having an alkyl group having 4 to 12 carbon atoms, and (b) an ethylenically unsaturated monomer. 5 to 20% by mass of a saturated carboxylic acid monomer unit, (d) 30 to 90% by mass of another monomer unit copolymerizable with the above (a) and (b) [where (a) + (b ) + (D) = 100 mass%], the glass transition temperature Tg (A) of the copolymer is 0 to 100 ° C., and the HLB (B) of the copolymer is 1 to 10.
The ethylenically unsaturated monomer mixture (A) further contains 40% by mass or less of other monomer units (d) copolymerizable with the above (a), (b) and (c) [where, (A) + (b) + (c) + (d) = 100% by mass] The emulsion composition for floor polish according to claim 1, comprising:
The difference between the HLB (A) of the ethylenically unsaturated monomer mixture (A) and the HLB (B) of the ethylenically unsaturated monomer mixture (B) is 0.1 or more. The emulsion composition for floor polishes according to claim 1 or 2.
The mass ratio of the ethylenically unsaturated monomer mixture (A) to the ethylenically unsaturated monomer mixture (B) is 30/70 to 80/20, The emulsion composition for floor polishes of any one of Claims 1.
A floor polish composition containing the emulsion composition for floor polish according to any one of claims 1 to 4.
The floor polish composition according to claim 5, which contains substantially no film-forming aid.