JP2005255703A - Floor polish composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a floor polish composition which exhibits sufficient serviceability and is phosphorus-free and substantially free from a multivalent metal compound or styrene in consideration of environmental problems. <P>SOLUTION: The floor polish composition comprises at least one benzoate as a plasticizer (A). The composition may contains further an aqueous resin dispersion for floors (B) constituted of an α,β-unsaturated carboxylic acid monomer (component a), at least one of an acrylate monomer and a methacrylate monomer (component b) and a monomer (component c) copolymerizable with the components (a) and (b), an auxiliary film-forming agent (C), a slipping property-adjusting agent (D), a wettability-enhancing agent (E), a urethane resin emulsion (F) and an alkali-soluble resin (G). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  For floor surfaces such as wooden floors, chemical floors made of synthetic resin, stone floors such as concrete and marble, etc., the floor polish composition is intended to protect the floor surface while maintaining the aesthetics of the flooring. .

  Floor polish compositions are widely used in department stores, supermarkets, mass retailers, retail stores, convenience stores, schools, libraries, hospitals, welfare facilities, airport facilities, railway facilities, office buildings, and the like.

  The floor polish composition is generally from an oily type using a solvent to an aqueous or emulsified state.

  The classification of the floor polish composition is stipulated in “JFPA (Japan Floor Polish Industry Association) Standard-00”, the definition of the general term of the floor polish test method.

  Of the floor polishes in this standard, those that are mainstream as floor polishes are of the aqueous polymer type. This aqueous polymer type is disclosed in Japanese Patent Publication No. 44-24407 (see Patent Document 1), Japanese Patent Publication No. 49-1458 (see Patent Document 2), Soap Cosmetic Chemical Specialties, 61 (9), 86 (1985) ( (See Non-Patent Document 1) and the like, and comprises an acrylic copolymer emulsion, a polyethylene wax emulsion, an alkali-soluble resin, a plasticizer, and the like.

  Conventionally, phosphate esters represented by tributoxyethyl phosphate have been widely used as floor plasticizers and leveling agents in floor polish compositions. In recent years, as a result of active efforts to the environment and pollution, evaluation and examination have been started on the environmental impact and toxicity of phosphorus contained in phosphate esters.

  By using an alkyl citrate ester as a plasticizer instead of a phosphate ester, there is no possibility of causing pollution problems, and a floor polish composition excellent in black heel mark resistance, abrasion resistance and leveling property is obtained. It is disclosed by Unexamined-Japanese-Patent No. 2003-73628 (refer patent document 3).

  In addition, a polishing agent composition for floors that contains an oxyacid ester and / or an unsaturated dicarboxylic acid ester as a plasticizer for improving the flexibility of the film, can improve cracking and peeling of the film, and has excellent blending stability. Is disclosed in Japanese Patent Application Laid-Open No. 11-217543 (see Patent Document 4).

  Japanese Patent Publication No. 47-14019 (refer to Patent Document 5) and Japanese Patent Publication No. 47-15597 (refer to Patent Document 6) include wooden flooring, chemical flooring made of synthetic resin, concrete, marble, etc. A floor polish composition using a polyvalent metal compound on a floor surface such as a stone floor is disclosed. In this case, the polyvalent metal compound includes a heavy metal such as zinc, cobalt, cadmium, nickel, chromium, zirconium, tin, tungsten, and aluminum, and a composition for floor polishing that forms a complex with amine or ammonia is disclosed. Yes.

In addition, a composition for floor polish that does not use these complexes has also been proposed. For example, Japanese Patent Publication No. 60-48542 (see Patent Document 7) proposes a method of dispersing zinc oxide in a polymer emulsion instead of using a metal complex. This method includes a step of dispersing zinc oxide in an emulsion containing an acrylic copolymer by, for example, stirring and mixing, whereby a composition for floor polishing that is stable and does not have an amine odor upon drying can be obtained. It is characterized.
These polyvalent metal compounds have been added to improve the durability, water resistance and peelability of floor polish compositions. However, as interest in environmental issues has increased in recent years, they have been properly managed. For floor polish compositions that are not directly related to problems such as water pollution, it is necessary to use polyvalent metal compounds (heavy metals, etc.) to prevent environmental pollution and negative safety factors. ) Etc. are not desired.

  Furthermore, it has been attempted to use calcium as a metal cross-linking agent because the use of a zinc compound may cause environmental pollution due to heavy metals. For example, Japanese Patent Application Laid-Open No. 8-92529 (see Patent Document 8) discloses the provision of a composition for floor polishing using calcium as a metal crosslinking agent, but the metal crosslinking agent is simply replaced with calcium. In comparison with metal crosslinking using zinc, which is normally used, sufficient durability and wear resistance cannot be added to the film. In the above invention, the aqueous polyurethane resin is crosslinked with a calcium compound. To compensate for the lack of durability and wear resistance.

 Furthermore, aqueous coating compositions that do not contain any metal crosslinkers have also been proposed. For example, in Japanese Patent Laid-Open No. 2001-2980 (see Patent Document 9), 0.1 to 100 parts by weight of an amine compound is added to 100 parts by weight (solid content) of an aqueous copolymer dispersion having a glass transition temperature of 80 ° C. or less. The durability is increased by including the above. However, this method has the disadvantages that when the polish is applied repeatedly, the amine does not sufficiently obtain gloss because it corrodes the film of the base polish, and the viscosity becomes high and the coating workability is deteriorated.

  Japanese Unexamined Patent Publication No. 2000-290596 (see Patent Document 10) discloses a floor polish agent composition using a vinyl monomer having an aliphatic cyclic structure. However, the specifically disclosed polymers are rich in styrene and the disclosed compositions require metal crosslinking.

Japanese Patent Publication No. 44-24407 Japanese Patent Publication No.49-1458 Soap Cosmetic Chemical Specialties, 61 (9), 86 (1985) JP 2003-73628 A Japanese Patent Laid-Open No. 11-217543 Japanese Examined Patent Publication No. 47-14019 Japanese Patent Publication No. 47-15597 Japanese Patent Publication No. 60-48542 JP-A-8-92529 JP 2001-2980 A JP 2000-290596 A

  In recent years, due to the spread of convenience stores, mass retailers, etc., when floor polish composition is applied in places with high walking frequency, it is more likely to cause damage and wear of the film due to walking than usual. There is.

  Furthermore, as the interest in environmental issues increases, floor polish compositions that are not directly related to problems such as water pollution if handled under proper management should be free from environmental pollution and negative safety factors. In order to prevent this, a material that does not contain a phosphate ester or the like as a plasticizer has been desired.

  Of the aromatic vinyl monomer units conventionally used in aqueous floor resin dispersions, styrene is an indispensable monomer unit for increasing the gloss of the coating film. Is widely known. In recent years, unreacted styrene monomer slightly contained in the styrene copolymer used in the floor polish composition has been raised in response to problems such as sick houses and thick schools derived from building materials. In the proper use form of the polish composition, it is beginning to be examined how much it can be a problem when compared with the guideline value indicated by the government.

  Accordingly, it is an object of the present invention to provide a floor polish composition that exhibits sufficient practicality in the floor polish composition, is dephosphorized in consideration of environmental problems, and further contains substantially no polyvalent metal compound or styrene. And Another object of the present invention is to provide a floor polish composition having storage stability, film-forming property, leveling property, black heel mark resistance, scuff resistance, water resistance and recoating property.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have completed a floor pollish that can be dephosphorized by using a specific benzoate instead of a phosphate. It was. In addition, it has storage stability, film-forming property, leveling property, black heel mark resistance, scuff resistance, water resistance and recoating property, and exhibits sufficient practicality. In addition, a floor polish composition containing no styrene was also completed.

  That is, the first gist of the present invention is (A) a floor polish containing at least one benzoic acid ester as a plasticizer. In addition, at least one of benzoic acid ester (A) and (B) α, β-unsaturated carboxylic acid monomer (component a), acrylic acid ester monomer, and methacrylic acid ester monomer as the plasticizer (A). On the other hand, the above-mentioned floor polish composition containing (b component) and an aqueous floor resin dispersion composed of a monomer (c component) copolymerizable with the above component (a) and (b) The gist of 2. Among them, in particular, the benzoic acid ester of the component (A) is obtained from a reaction mixture of isodecyl benzoate, isobutyl benzoate, isomethyl benzoate, 2-ethylhexyl benzoate, dipropylene glycol benzoate, and benzoic acid and polyethylene glycol. The above-mentioned floor polish composition which is at least one or more selected is a third gist.

In addition, in the floor polish composition according to the fourth aspect, the ratio of each monomer in the aqueous floor resin dispersion as the component (B) is set to the following ratio based on the total amount of all monomers. The gist of
(A) 2 to 40% by mass of an α, β-unsaturated carboxylic acid monomer.
(B) 20 to 90% by mass of at least one of an acrylate monomer and a methacrylic acid ester monomer.
(C) 0 to 78% by mass of a monomer copolymerizable with the monomers (a) and (b).

  Especially, the floor polish composition which does not substantially contain a styrene monomer as the monomer of the component (c) in the aqueous resin dispersion for an aqueous floor which is the component (B) is the fifth gist. And

  And the said floor polish composition containing (C) film formation adjuvant, (D) slip adjustment agent, and (E) wettability improvement agent with respect to said (A) and (B) component is 6th summary. And

  Furthermore, (F) the floor polish composition containing a urethane resin emulsion is the seventh gist, and (G) the floor polish composition containing an alkali-soluble resin is the eighth gist.

  Further, the ninth aspect of the present invention is the above floor polish composition containing substantially no polyvalent metal compound as a crosslinking agent.

  The floor polish composition of the present invention can be suitably used for coated objects such as plastic floors such as vinyl-based and synthetic resin-coated floors, stone floors, cement-based floors, and flooring (wood floors).

  And by using a specific benzoate ester as a plasticizer and a specific aqueous resin dispersion for flooring, excellent storage stability, film-forming property, leveling property, black heel mark resistance, scuff resistance, water resistance and By using at least one benzoic acid ester as a plasticizer, it is possible to provide a floor polish composition excellent in environmental safety due to non-phosphorusization. Furthermore, it is also possible to provide a floor polish composition that substantially does not contain a polyvalent metal compound or styrene as a monomer.

  Next, the best mode for carrying out the present invention will be described in detail.

As the benzoic acid ester of the component (A) used as a plasticizer in the present invention, benzoic acid represented by isodecyl benzoate, isobutyl benzoate, N-butyl benzoate, isomethyl benzoate, 2-ethylhexyl benzoate and the like Benzoic acid ester obtained from the reaction of C 6-14 with alcohol, dipropylene glycol benzoate, reaction mixture of benzoic acid and polyethylene glycol, 2,2,4-trimethyl-1,3-pentanediol benzoate Isobutyl, 2,2,4-pentanediol dibenzoate, hexyloxyethoxyethyl p-hydroxybenzoate, hexyloxypropoxypropyl p-hydroxybenzoate, hexyloxybutoxybutyl p-hydroxybenzoate, octyl p-hydroxybenzoate Oxyethoxyethyl, p Octyloxypropoxypropyl hydroxybenzoate, octyloxybutoxybutyl p-hydroxybenzoate, 2'-ethylhexyloxyethoxyethyl p-hydroxybenzoate, 2'-ethylhexyloxypropoxypropyl p-hydroxybenzoate, p-oxybenzoic acid 2 Examples include '-ethylhexyloxybutoxybutyl, decyloxyethoxyethyl p-hydroxybenzoate, decyloxypropoxypropyl p-hydroxybenzoate, and decyloxybutoxybutyl p-hydroxybenzoate. More than one species may be used in combination.
Of these, isodecyl benzoate, isobutyl benzoate, isomethyl benzoate, 2-ethylhexyl benzoate, dipropylene glycol benzoate, and a reaction mixture of benzoic acid and polyethylene glycol can be preferably used.

In the present invention, at least one kind of the benzoic acid ester is contained in the floor polish composition in a proportion of 0.1 to 5% by mass (hereinafter abbreviated as “%”).
If it is less than 0.1%, the leveling property is poor, and if it exceeds 5%, it is not preferable in terms of balance with other components. Especially, it is preferable to mix | blend in 1 to 3% of range.

  In the present invention, as the plasticizer, in addition to at least one benzoic acid ester of component (A), other plasticizers such as aliphatic oxyacid esters, aliphatic unsaturated dicarboxylic acid esters, phosphate esters, etc. The conventional plasticizer can also be used in combination.

Specifically, citrate esters such as lactic acid ester, tartaric acid ester and tributyl acetyl citrate, phosphate esters such as ricinoleic acid ester, fumarate ester, maleic acid ester, tributoxyethyl phosphate, tributyl phosphate and triphenyl phosphate, dibutyl phthalate Phthalic acid esters such as dihexyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, diisooctyl phthalate, didecyl phthalate, dinolyl phthalate, diisononyl phthalate, diisodecyl phthalate, butyl benzyl phthalate octyl benzyl phthalate 2-ethylhexyl adipate, dimethyl adipate, dibutyl adipate, etc. Shin acid esters, aliphatic dibasic acid esters such as di-2-ethylhexyl sebacate ester, isobutyl ester derivatives of pentanediol, can be used in combination of two or more such as chlorinated paraffin. At this time, the blending ratio by mass of the benzoic acid ester and the other plasticizer is particularly preferably in the range of 1: 1 to 99: 1. In addition, from the further consideration to environmental safety, it is preferable to combine with other plasticizers as other plasticizers.

  The aqueous floor resin dispersion used in the present invention comprises an α, β-unsaturated carboxylic acid monomer (component a), at least one of an acrylate monomer and a methacrylate ester monomer (component b), It is comprised by the monomer (c component) copolymerizable with the said (a) component and (b) component.

  Examples of the α, β-unsaturated carboxylic acid monomer as component (a) include acrylic acid, methacrylic acid, fumaric acid, itaconic acid, maleic acid, crotonic acid, and the like, preferably acrylic acid, methacrylic acid, An acid is used. These α, β-unsaturated carboxylic acid monomers may be used alone or in combination of two or more.

  Moreover, it is preferable that the said (a) component is mix | blended in the ratio of 2-40 mass% in the resin dispersion for aqueous floors. That is, if it is less than 2% by mass, the durability is poor. On the other hand, if it exceeds 40% by mass, the leveling property is inferior. Especially, it is preferable to copolymerize in the ratio of 5-25 mass% from the point of storage stability.

  And as at least one of the acrylate monomer and the methacrylic acid ester monomer as the component (b), for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, acrylic N-butyl acid, i-butyl acrylate, n-amyl acrylate, i-amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, i-nonyl acrylate, decyl acrylate, hydroxymethyl Acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyamyl acrylate, hydroxyhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, methacrylic acid -Propyl, n-butyl methacrylate, i-butyl methacrylate, n-amyl methacrylate, i-amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, i-nonyl methacrylate, methacrylic acid Examples include decyl, hydroxymethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxyamyl methacrylate, and hydroxyhexyl methacrylate. Of these, n-butyl acrylate, 2-ethylhexyl acrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl acrylate, and cyclohexyl methacrylate are preferably used. These acrylic acid ester monomers and methacrylic acid ester monomers may be used alone or in combination of two or more.

  In particular, among the following components (c), in the case of using an aqueous floor resin dispersion that does not contain a styrene monomer that is specified by the Ministry of Health, Labor and Welfare, and that the indoor concentration guideline value is indicated for chemical sensitivity. It is preferable to use at least one of cyclohexyl acrylate and cyclohexyl methacrylate as an essential monomer.

  It is preferable that the said (b) component is mix | blended in the ratio of 20-90 mass% in the resin dispersion for aqueous floors. That is, when it is less than 20% by mass, the water resistance and weather resistance are poor, and when it exceeds 90% by mass, the glossiness is inferior, which is not preferable. Especially, it is especially preferable that it copolymerizes in the ratio of 40-80 mass% from the point of storage stability.

  Examples of the component (c), that is, a monomer copolymerizable with the monomers (a) and (b), include styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3 -Methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene, 4-ethylstyrene, 4-ethoxystyrene, 3,4-dimethylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chloro-3-methylstyrene, Styrene monomers such as 4-t-butylstyrene, 2,4-dichlorostyrene, 2,6-dichlorostyrene, aromatic vinyl monomers such as 1-vinylnaphthalene and divinylbenzene, benzyl acrylate, phenoxyethyl acrylate , Alkylphenoxyethyl acrylate, phenoxydiethylene glycol acrylate Polyester acrylates such as phenoxy polyethylene glycol acrylate, alkylphenol ethylene oxide acrylate, alkylphenol propylene oxide acrylate, 2-hydroxy-3-phenoxypropyl acrylate, ethylene glycol acrylate monophthalate, ethylene glycol acrylate hydroxyethyl phthalate, benzyl methacrylate, phenoxyethyl methacrylate, alkyl Phenoxyethyl methacrylate, phenoxydiethylene glycol methacrylate, phenoxypolyethylene glycol methacrylate, alkylphenol ethylene oxide methacrylate, alkylphenol propylene oxide methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate Relate, polyester methacrylates such as ethylene glycol methacrylate monophthalate, ethylene glycol methacrylate hydroxyethyl phthalate, epoxy compounds such as allyl glycidyl ether, glycidyl acrylate, methyl glycidyl acrylate, glycidyl methacrylate, methyl glycidyl methacrylate, divinylbenzene, ethylene glycol diacrylate, Diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, butanediol diacrylate, hexane All diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, propylene glycol dimethacrylate, dipropylene glycol di Polyfunctional monomers such as methacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, butanediol dimethacrylate, hexanediol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, acrylamide, N-methylol acrylamide, N-methoxymethyl acrylic Amide, N-butoxymethyl acrylamide, methacrylamide, N-methylol methacrylamide, N-methoxymethyl methacrylamide, N-butoxymethyl methacrylamide, N, N'-methylenebisacrylamide, diacetone acrylamide, maleic amide, maleimide, etc. Amide compounds, vinyl compounds such as vinyl chloride, vinylidene chloride, vinyl acetate, fatty acid vinyl esters, etc., fluorine atom-containing single quantities such as trifluoroethyl acrylate, pentadecafluorooctyl acrylate, trifluoroethyl methacrylate, pentadecafluorooctyl methacrylate , Γ-methacryloylpropanetrimethoxysilane, silicone compounds such as reactive silicone such as Silaplane FMO711 manufactured by Chisso Corporation, aminoethyl Aminoalkyl esters of ethylenically unsaturated carboxylic acids such as acrylate, dimethylaminoethyl acrylate and butylaminoethyl acrylate, aminoalkyl esters of ethylenically unsaturated carboxylic acids such as aminoethylacrylamide, dimethylaminomethylmethacrylamide and methylaminopropylmethacrylamide Examples include vinyl cyanide monomers such as amide, acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile. Among them, styrenic monomers are used in terms of gloss and durability of the floor polish composition. .

  The monomer of component (c) may be used alone or in combination of two or more. And it is preferable to mix | blend in the ratio of 0-78 mass% in the resin dispersion for aqueous floors. That is, when it exceeds 78 mass%, durability is inferior and is not preferable. Especially, it is preferable to copolymerize in the ratio of 0-50 mass% from the point of powdering resistance and the difficulty of a slip.

  And the resin dispersion for aqueous floors which comprised the said (a)-(c) component as a monomer unit is an aqueous dispersion with a solid content of 10-70 mass% concentration in the said floor polish composition, for example. And is added in the range of 10 to 60% by mass as a solid content in the floor polish composition of the present invention.

  The aqueous floor resin dispersion used in the present invention preferably employs a widely known emulsion polymerization method using an emulsifier and a polymerization initiator as described below.

  First, as an emulsifier, anionic surface activity such as sodium alkylbenzenesulfonate, sodium alkylsulfate, sodium polyoxyethylene alkylphenyl ether sulfate, sodium polyoxyethylene alkylsulfate, sodium dialkylsulfosuccinate, formalin condensate of naphthalenesulfonic acid, etc. Agent, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, nonionic surfactant such as polyethylene glycol fatty acid ester, sorbitan fatty acid ester, sodium styrene sulfonate, sodium alkyl allyl sulfonate, sodium alkyl allyl sulfo succinate, polyoxy Ethylene alkyl allyl glycerin ether sulfate, polyoxyethylene alkylphenol alkyl glycerin Reactive emulsifiers such as ether sulfate, polyvinyl alcohol, polyacrylic acid, water-soluble acrylate copolymer, water-soluble methacrylic acid ester copolymer, styrene-maleic acid copolymer and their salts, styrene-acrylic acid copolymer Polymer surfactants such as polymers, styrene-methacrylic acid copolymers and their salts, polyacrylamide copolymers, polymethacrylamide copolymers, etc. can be used, and these can be used alone or in combination of two or more. Can be used. A desirable use amount of the emulsifier is usually 0.05 to 5 parts by mass per 100 parts by mass of the monomer. When the amount of the emulsifier used is less than 0.05 parts by mass, the emulsifiability is poor, while when it exceeds 5 parts by mass, the water resistance may be poor.

  As the polymerization initiator, persulfates such as potassium persulfate, ammonium persulfate and sodium persulfate, peroxides such as hydrogen peroxide, benzoyl peroxide and t-butylhydroxyperoxide can be used. These may be used as a redox system in combination with a reducing agent such as sodium bisulfite, sodium pyrobisulfite, ascorbic acid, sodium formaldehyde sulfoxylate.

  The temperature of the polymerization reaction is preferably 20 to 95 ° C, particularly preferably 40 to 90 ° C. The polymerization time is preferably 1 to 10 hours.

  In the aqueous floor resin dispersion used in the present invention, the glass transition temperature of the copolymer is preferably 5 to 115 ° C, more preferably 5 to 80 ° C. When the glass transition temperature of the copolymer is less than 5 ° C., the coating tends to be blocked, whereas when it exceeds 115 ° C., the film formability at room temperature becomes poor.

Therefore, in designing a resin dispersion for aqueous floors, the (a) monomer unit, (b) monomer unit, and (c) monomer unit can be obtained in one or more types. It is desirable to select such that the glass transition temperature (Tg) of the polymer is set within the above range. The glass transition temperature (hereinafter referred to as Tg) used in the present invention is determined by the following Fox equation (Equation 1).
(Equation 1)

1 / Tg = W1 / Tg1 + W2 / Tg2 + W3 / Tg3.
Here, W1, W2, W3,... Indicate the weight fraction of the monomer units 1, 2, 3 in the polymer, and Tg1, Tg2, Tg3,. 2, 3... Shows the glass transition temperature of the homopolymer (homopolymer) (absolute temperature is used in the formula).

In the above formula, for the glass transition temperature (Tg) of the homopolymer (homopolymer), the values described in the polymer handbook and the like can be used.
For example, polymethyl methacrylate: 105 ° C, polybutyl acrylate: -54 ° C, 2-ethylhexyl acrylate: -50 ° C, polycyclohexyl acrylate: 19 ° C, polymethacrylic acid: 228 ° C, polymethacrylic acid Cyclohexyl: 66 ° C, polyacrylic acid: 106 ° C, polystyrene: 100 ° C, and the like.

  The resin dispersion for aqueous floors used in the present invention is obtained, for example, as an aqueous dispersion having a solid content of 10 to 70% by mass. In the floor polish composition of the present invention, 10 to 60% by mass of solids is obtained. Add in range.

  The floor polish composition of this invention is comprised using components, such as a film formation adjuvant, an alkali-soluble resin, a slip regulator, and a wettability improvement agent other than the said plasticizer and aqueous resin dispersion.

(C) As a film-forming aid as component, 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 Glycol ethers such as ether, ethylene glycol mono-2-methylhexyl ether, diethylene glycol mono-2-ethylhexyl ether, α-amino alcohol, β-amino alcohol, diethanolamine, triethanolamine, 2-aminoisohexyl alcohol, N, N, -diethylethanolamine, N, N, -dimethylethanolamine, aminoethylethanolamine, N-methyl-N, N-die An amine compound such as tanolamine, N, N-butylethanolamine, N-methylethanolamine, and 3-amino-1-propanol can be used.
However, in seeking higher environmental safety, it is preferable that the amine compound is blended in a small amount or not substantially blended.

  (D) Component slip modifiers include candelilla wax, carnauba wax, rice wax, tree wax, jojoba oil and other animal waxes, beeswax, lanolin, whale wax and other animal waxes, montan wax, ozokerite, Mineral wax such as ceresin, paraffin wax, microcrystalline wax, petroleum wax such as petrolatum, synthetic hydrocarbon wax such as Fischer-Tropsch wax, synthetic wax such as polyethylene wax, polypropylene wax, oxidized polyethylene wax, oxidized polypropylene wax, etc. Can be used.

  As the wettability improver which is component (E), fluorine-based surfactant, silicone-based surfactant, sodium higher alcohol sulfate ester, sodium alkylbenzenesulfonate, sodium dialkylester sulfonate succinate, sodium alkyldiphenylether disulfonate, Anionic surfactants such as sodium polyoxyethylene alkyl sulfate sodium, polyoxyethylene alkyl phenyl ether sodium sulfate, sodium alkane sulfonate, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene Copolymer, sucrose fatty acid ester, sorbitan fatty acid ester, polyethylene glycol fatty acid ester, polyglycerin fat Fatty acid esters such as esters, coconut oil fatty acid diethanolamide, lauric acid diethanolamide, lauric acid myristic acid diethanolamide, myristic acid diethanolamide, oleic acid diethanolamide, and fatty acid alkanolamides such as palm kernel oil fatty acid diethanolamide, alkyl glucoside Nonionic surfactants such as, alkylbetaine-type amphoteric surfactants such as laurylbetaine, amidebetaine-type zwitterionic surfactants such as lauroylamidopropylbetaine, 2-alkyl-N-carboxymethylimidazolinium betaine, and 2 -Imazoline-type zwitterionic surfactants such as alkyl-N-carboxyethylimidazolinium betaine, alkylsulfobetaine-type zwitterionic surfactants, coconut fatty acid amide dimethe Amphoteric surfactants such as amidosulfobetaine-type amphoteric surfactants such as luhydroxypropylsulfobetaine, N-alkyl-β-aminopropionate, N-alkyl-β-iminodipropionate, β-alanine-type amphoteric surfactants A surfactant can be used.

  Examples of the urethane resin emulsion as the component (F) include those described in JP-A-62-230863, JP-A-63-23972, and JP-A-6-234912. In addition, as a carboxy group-free urethane resin emulsion, commercially available product name: Superflex 410 (Daiichi Kogyo Seiyaku Co., Ltd.), trade name: Hydran HW-950 (Dainippon Ink Chemical Co., Ltd.), product Name: Takelac W-635 (manufactured by Takeda Pharmaceutical Company Limited) This non-carboxy group-containing urethane resin emulsion is characterized by excellent water resistance and abrasion resistance. Examples of the urethane resin emulsion that is excellent in solvent resistance and does not cause coloration with time include those described in JP-A No. 2003-252948.

  Examples of the alkali-soluble resin (G) include diisobutylene-maleic anhydride copolymer, rosin-modified maleic acid, acrylic acid ester-acrylic acid polymer, acrylic acid ester-methacrylic acid polymer, and methacrylic acid ester-acrylic. An acid polymer, a methacrylic acid ester-methacrylic acid polymer, shellac, or the like can be used.

  In addition, pH adjusting agents such as ammonia, preservatives, antifoaming agents, antibacterial agents, fragrances, dyes, colloidal silica, fluorescent whitening agents, ultraviolet absorbers and the like can also be used as optional components. The pH adjuster is added in an appropriate amount to neutralize the pH of the floor polish composition.

  More preferably, the floor polish composition of the present invention contains, for example, zinc oxide, calcium oxide, calcium hydroxide, aluminum hydroxide, zinc carbonate ammonia, calcium carbonate ethylenediamine-ammonia, zinc acetate ammonia, zinc acrylate ammonia, malic acid. It does not substantially contain polyvalent metal compounds (such as heavy metals) for forming metal bridges such as zinc ammonia and alanine calcium ammonia. The polyvalent metal here is a metal having a valence of 2 or more. Specifically, beryllium, magnesium, calcium, strontium, iron, cobalt, nickel, zinc, manganese, copper, cadmium, lead, bismuth, barium, Antimony, zirconium and the like can be mentioned, and the polyvalent metal compound is a compound containing these polyvalent metals.

  Conventionally, these polyvalent metal compounds are contained in a floor polish composition, applied as a floor polish, and then included in the metal and polymer (polymer of ethylenically unsaturated compounds) in the drying process. Although it has been used to provide durability, water resistance and improved peelability by the mechanism of metal cross-linking with acid components (methacrylic acid, acrylic acid, etc.), environmental safety due to increased interest in environmental issues From the viewpoint of properties, those which do not substantially contain a polyvalent metal compound (such as heavy metal) are preferred.

  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 the aqueous floor resin dispersion of the present invention, 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 articles to be coated such as plastic floors such as vinyl-based and synthetic resin-coated floors, stone floors, cement-based floors, and flooring (wood floors). 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, brush coating, or mop coating. The floor polish composition can be used after being diluted with a solvent such as water or a water-miscible solvent depending on 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 is formed at a room temperature (5-35 ° C. ± 5 ° C.), more preferably at about 20-25 ° C., thereby forming a peelable protective film. Is done. In order to promote evaporation of moisture in the process of forming the protective film, moisture removing means such as 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 the evaporation of moisture, and heating is not an essential component for forming the protective film. .

  Next, examples will be described together with comparative examples. Note that the present invention is not limited to these.

  Using the aqueous floor resin dispersions shown in Tables 1 to 3 below, floor polish compositions having the compositions shown in Examples 1 to 76 and Comparative Examples 1 to 28 in Tables 4 to 22 were prepared, storage stability, Seven items of film property, leveling property, black heel mark resistance, scuff resistance, water resistance and recoating property were evaluated, and the results are shown in Tables 4-22. In the following description, “part” means part by mass, and “%” means mass%.

  In addition, the components used in Tables 4 to 22 and their pure components (%) are as follows, and the numerical values in the table are shown as they are.

[Component A] Plasticizer * Benzoic acid ester 1: Reaction mixture of benzoic acid and polyethylene glycol (trade name: Hyester B-203M / Toho Rika Co., Ltd., 100% active ingredient)
* Benzoic acid ester 2: 2-ethylhexyl benzoate (trade name: Hyester B-508 / manufactured by Toho Rika Co., Ltd., 100% active ingredient)
* Benzoic acid ester 3: Isodecyl benzoate (trade name: Hyester B-510 / manufactured by Toho Rika Co., Ltd., 100% active ingredient)
* Citrate ester: Acetyltributyl citrate (trade name: ATBC / Kyowa Hakko, 100% active ingredient)
* Adipic acid ester: Dibutyl adipate (Brand name: DBA / manufactured by Daihachi Chemical Industry Co., Ltd., 100% active ingredient)
* Phosphate ester 1: Tributoxyethyl phosphate (trade name: TBXP / manufactured by Daihachi Chemical Industry Co., Ltd., 100% active ingredient)
* Phosphate ester 3: Dibutyl phthalate (Brand name: DBP / Daihachi Chemical Industry Co., Ltd., 100% active ingredient)

[Component B] Resin dispersion for aqueous bed (1) Preparation of resin dispersion for aqueous bed 60 parts of water in a reaction vessel equipped with a stirrer, reflux condenser, two dropping funnels, thermometer, and nitrogen introduction tube 0.5 part of sodium lauryl sulfate was charged and the temperature was raised to 85 ° C.
To the monomer mixtures shown in Tables 1 to 3, 0.5 parts of sodium lauryl sulfate and 35 parts of water were added and emulsified. The obtained monomer emulsion and 10 parts of a 5% aqueous ammonium persulfate aqueous solution were continuously dropped into the reaction vessel over 3 hours by separate dropping funnels, and emulsion polymerization was performed. One hour after the completion of the dropping, the system was cooled to complete the polymerization to obtain an aqueous floor resin dispersion.

In addition, the monomer composition, mass part, glass transition temperature (° C.), acid value, and nonvolatile component amount (%) of each polymer are also shown.
In Table 1, nBA is n-butyl acrylate, 2EHA is 2-ethylhexyl acrylate, AA is acrylic acid, MAA is methacrylic acid, MMA is methyl methacrylate, ST is styrene, CHA is cyclohexyl acrylate, and CHMA is Cyclohexyl methacrylate, Tg indicates the glass transition temperature, and the amount of non-volatile components indicates the amount (%) of the active component of the polymer in the aqueous resin dispersion.

[Component C] Film formation aid * Film formation aid 1: Diethylene glycol monoethyl ether * Film formation aid 2: Dipropylene glycol monomethyl ether

[Component D] Slip adjuster * Slip adjuster 1: Hitech E-4400 (manufactured by Toho Chemical Co., Ltd., polyethylene wax emulsion, pure content 40%)
* Slip adjusting agent 2: Hitech P-5060S (Toho Chemical Industries, polypropylene wax emulsion, 40% pure)

[E component] wettability improver * Wettability improver 1: Zonyl FSJ (DuPont, 25% pure)

[F component] Urethane resin emulsion * Urethane 1: Neoletz R960 (Avisia, 32% aqueous solution)

[Component G] Alkali-soluble resin * Alkali-soluble resin: Topco LR400 resin solution (manufactured by Toyo Petrolite Co., Ltd., 30% pure)

[Optional ingredients]
* Polyvalent metal compound (crosslinking agent): Zinc ammonium carbonate complex aqueous solution (Zinc content 9.6%)
* Calcium carbonate (crosslinking agent): Calcium carbonate * pH adjuster: 25% by mass ammonia solution * Antifoaming agent: SE-21 (manufactured by WSC, 17% pure)
* Antiseptic: Suraoff WB (manufactured by Takeda Pharmaceutical Company Limited)

The test method and evaluation method for each item are as shown below.
(1) [Storage stability test]
・ Test method In accordance with JIS K 3920 (floor polish test method), the test floor polish composition was put in a container, sealed, and kept at 50 ° C. (manufactured by Isuzu Manufacturing Co., Ltd., model: KAX-730). Hold for 14 days. The state of the subsequent samples was visually determined according to the following evaluation criteria for the presence or absence of gelation, phase separation, solid content precipitation, and the like.
-Evaluation criteria ○: No gelation, phase separation, precipitation of solids, etc. are observed.
Δ: There is no phase separation, but a slight precipitation of solids is observed (withstands actual use).
X: Gelation, phase separation, precipitation of solids, etc. are observed.

(2) [Film-forming property test]
Test Method After 0.5 mL of the test floor polish composition was applied to a slide glass (dimension: 76 × 26 mm, manufactured by MATSU NAMIGLASS), it was placed in a refrigerator (model: KAX-734, manufactured by Hoshizaki) adjusted to 5 ° C. After time placement, the film-forming state of the film was visually observed and evaluated according to the following evaluation criteria.
-Evaluation criteria ○: The film was formed normally.
Δ: A film was formed, but the film was partially cracked.
X: The film could not be formed and was pulverized.

(3) [Leveling test]
・ Test method In accordance with JIS K 3920 (floor polish test method), the test floor polish composition is uniformly spread on a homogeneous vinyl tile (manufactured by Toli Co., Ltd., Machiko S-Plane No. 5626), and immediately after application, the coated surface Write the letter “X” along the diagonal of the base material with the coating tool used for the coating, and after the film dries, visually observe how much the letter “X” disappears, and the following evaluation criteria Was evaluated along.
Evaluation criteria 5: The letter “X” is not recognized.
4: A slight outline of the letter “X” is recognized with some gloss change, but no bulge is observed on the film.
3: The letter “X” is slightly recognized, but almost no bulge is observed on the film.
2: The letter “X” is clearly recognized, but the film has a bump.
1: The letter “X” is clearly recognized and the film is clearly raised.

(4) [Black heel mark resistance test]
・ 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 Tori Co., Ltd., Machico S-Plane No. 5626) and dried at room temperature overnight. The test piece was tested with a heel mark tester and visually evaluated according to the following evaluation criteria.
Evaluation criteria 10: Shows extremely high BHM resistance.
6-9: It has moderate BHM resistance and has practicality.
2 to 5: Lack of BHM resistance and practicability.
1: Extremely poor in BHM resistance.

(5) [Scuff mark resistance test]
・ 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 Tori Co., Ltd., Machico S-Plane No. 5626) and dried at room temperature overnight. The test piece was tested with a heel mark tester and visually evaluated in 10 stages according to the following evaluation criteria.
-Evaluation criteria 10: Shows extremely high scuff resistance.
6-9: It has moderate scuff resistance and has practicality.
2 to 5: Lack of scuff resistance and lack of practicality.
1: Very poor scuff resistance.

(6) [Water resistance test]
・ 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 (manufactured by Tori Co., Ltd., New Machico V No. 33), in an atmosphere of 38 ° C. Then, 0.1 mL of water droplets were dropped. Further, the whitening state of the surface of the composition vinyl tile when allowed to stand for 1 hour was visually evaluated.
・ Evaluation criteria ○: Whitening is not allowed.
X: Whitening is recognized.

(7) [Coating property test]
・ Test method In accordance with JIS K 3920 (floor polish test method), once a test floor polish composition is applied to a homogeneous vinyl tile (manufactured by Tori Co., Machiko S-Plane No. 5626) once. The degree of appearance of the coating and the multilayer coating was visually determined according to the following evaluation criteria.
Evaluation criteria ○: The multilayer coating is clearly superior to the single coating.
(Triangle | delta): Multi-layer coating does not have much difference from 1-time coating.
X: The multilayer coating is clearly inferior to the single coating.

From the evaluation results of Examples 1 to 76, good results were obtained in any of the items of storage stability, film-forming property, leveling property, black heel mark resistance, scuff resistance, water resistance and recoating property. You can see that

Claims (9)

(A) A floor polish composition comprising at least one benzoic acid ester as a plasticizer. (A) at least one benzoic acid ester as a plasticizer and (B) at least one of an α, β-unsaturated carboxylic acid monomer (component a), an acrylic acid ester monomer and a methacrylic acid ester monomer ( 2. A resin dispersion for an aqueous floor comprising a component (b), a monomer copolymerizable with the component (a) and the component (b) (component c). Floor polish composition. The benzoic acid ester of the component (A) is at least one selected from isodecyl benzoate, isobutyl benzoate, isomethyl benzoate, 2-ethylhexyl benzoate, dipropylene glycol benzoate, and a reaction mixture of benzoic acid and polyethylene glycol. It is the above, The floor polish composition of Claim 1 or 2 characterized by the above-mentioned. The ratio of each monomer in the resin dispersion for aqueous floors as the component (B) is set to the following ratio based on the total amount of all monomers. The floor polish composition described in 1.
(A) 2 to 40% by mass of an α, β-unsaturated carboxylic acid monomer.
(B) 20 to 90% by mass of at least one of an acrylate monomer and a methacrylic acid ester monomer.
(C) 0 to 78% by mass of a monomer copolymerizable with the monomers (a) and (b). The styrene monomer is not substantially contained as a monomer of the component (c) in the aqueous resin dispersion for an aqueous floor which is the component (B). The floor polish composition described in 1. The floor polish composition according to any one of claims 1 to 5, further comprising (C) a film-forming aid, (D) a slip modifier, and (E) a wettability improver. Furthermore, (F) urethane resin emulsion is contained, The floor polish composition as described in any one of Claims 1-6 characterized by the above-mentioned. The floor polish composition according to any one of claims 1 to 7, further comprising (G) an alkali-soluble resin. The floor polish composition as described in any one of Claims 1-8 which does not contain a polyvalent metal compound substantially as a crosslinking agent.