JP2016121247A - Floor polish aqueous resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a floor polish aqueous resin excellent in alcohol resistance, water resistance and adhesibility to a floor coated with an ultraviolet curable resin and suitable for forming a floor polish coating on a floor of a hospital.SOLUTION: The floor polish aqueous resin is provided which is obtained by polymerizing a polymerizable unsaturated monomer (a) to synthesize an aqueous resin (A) and mixing the aqueous resin (A) with a compound (B) having two or more hydrazide groups in a molecule, and in which: the aqueous resin (A) has a glass transition temperature of 40°C or more; the polymerizable unsaturated monomer (a) contains a monomer having a carbonyl group and an ethylenic double bond, in an amount of 2.0 to 5.0 pts.wt. based on 100 pts.wt. of the total amount of the polymerizable unsaturated monomer (a); and the hydrazide group of the component (B) of 0.5 to 5.0 equivalent is added to 1 equivalent of the carboxy group existing in the component (A).SELECTED DRAWING: None

Description

The present invention relates to a floor polish used for a floor of a building or the like, and an aqueous resin for floor polish contained in the floor polish.

Floor polish (floor polish for flooring) is applied to the surface of the flooring material for the purpose of protecting the flooring material of buildings, condominiums, etc. and maintaining the beauty. The film formed on the flooring material maintains the aesthetics and cleanliness by the glazing effect or the like, and plays the role of preventing the flooring material from wearing, contamination, and slip accidents.

As the floor polish, an aqueous polymer type dominates. Examples of aqueous floor polishes include homopolymers of acrylic acid or methacrylic acid or derivatives thereof, copolymers thereof, and copolymers of these with other vinyl monomers such as styrene (hereinafter referred to as (meth) acrylic) And the like, and those containing a crosslinking agent, polyethylene wax, alkali-soluble resin, plasticizer, film forming aid, and the like.

Unlike general paints or coating agents, floor polish is not heat-treated during film formation, and is formed in a room temperature environment, so it is difficult to improve the strength of the film. Nevertheless, the floor polish film is required not only to have a glossing performance but also to have excellent durability performance such as scuff resistance, black heel mark resistance or water resistance. In the present specification, the scuff resistance is resistance to scratches caused by the sole, and the black heel mark resistance is resistance to black rubber stains of the sole attached by walking.

Convenience stores, mass retailers, etc. have higher walking frequency than ordinary households. Since scratches caused by walking (black heel marks) are easy to hit the floor, it is very important for the floor polish to have excellent black heel mark resistance.

In addition, in offices and homes, water and tea may be spilled on the floor or the floor may be wiped with water. Therefore, the floor polish must have excellent water resistance. If the water resistance is poor, the film coated on the floor may whiten.

In hospitals and the like, when the alcohol for disinfection falls on the floor, the floor polish film may be whitened, so that the floor polish is also required to have alcohol resistance.

Patent Document 1 discloses a floor polish excellent in alcohol resistance in consideration of use in a hospital or the like. The floor polish of Document 1 contains a carbodiimide compound and a polyvalent metal compound ([Claim 1], [Table 1]). The floor polish of Patent Document 1 is said to be hard to be whitened because the carbodiimide compound and the polyvalent metal compound are cross-linked to improve the alcohol resistance of the floor polish.

In recent years, tiles constructed in buildings are sometimes coated with ultraviolet curable resin, and of course, hospital floors are also coated with ultraviolet curable resin. Therefore, in the future, the performance required for floor polish is required to be excellent in water-resistant adhesion with an ultraviolet curable resin.

Furthermore, depending on the maintenance situation, “overpainting” of floor polish may be required.

Unlike general paints or coating agents, floor polish is premised on that the dried film is chemically peeled off the flooring. The floor polish film accumulates dirt and scratches due to human walking and the like. Therefore, the floor is periodically cleaned using a detergent, or if the film is heavily soiled and deeply damaged, the floor is cleaned with a polisher using a release agent (hereinafter, “peeling cleaning”). As described above, “film removal performance (peelability)” that is not required for a general paint film is a very important performance for floor polishing.

However, since the durability of the film and the removal performance of the film are mutually contradictory properties, it is not easy for researchers to develop a floor polish that is excellent in both of these characteristics. In addition, most floor polishes are metal-crosslinked to improve durability and removal performance (see Reference 1), but considering the environmental aspects, using metal cross-links for floor polish It is not preferable.

In recent years, environmental demands are increasing in various fields. Especially in hospitals, it has a good balance of durability (water resistance, black heel mark resistance) and removal performance (peelability), and has excellent resistance to alcohol and water-resistant adhesion to floors coated with UV curable resin. There is a need for a floor polish that does not require crosslinking.

JP 2010-070667 A

  The present invention has been made in view of such circumstances, and is excellent in durability performance (water resistance, black heel mark resistance) and removal performance (peelability), and is further coated with alcohol resistance and ultraviolet curable resin. Another object of the present invention is to provide an aqueous resin for floor polishing which is excellent in water-resistant adhesion to a floor and is suitable for forming a floor polish film on a hospital floor.

In the present invention, (a) a polymerizable unsaturated monomer is polymerized to synthesize (A) an aqueous resin, and (A) the aqueous resin and (B) a compound having two or more hydrazide groups in the molecule are mixed. It is an aqueous resin for floor polish obtained by
(A) The aqueous resin has a glass transition temperature of 40 ° C. or higher,
(A) The polymerizable unsaturated monomer includes a monomer having a carbonyl group and an ethylenic double bond, and the monomer having the carbonyl group and the ethylenic double bond is 100 parts by weight in total. Contains 2.0 to 0.5 parts by weight of the body,
Provided is an aqueous resin for floor polishing in which 0.5 to 5.0 equivalents of the hydrazide group of component (B) are added to 1 equivalent of carbonyl group present in component (A).

  In one certain form, the monomer which has a carbonyl group and an ethylenic double bond contains diacetone acrylamide.

  In one certain form, (B) the compound which has 2 or more of hydrazide groups in a molecule | numerator contains adipic acid dihydrazide.

  In one certain form, the acid value of (A) aqueous resin is 30-110 mgKOH / g.

  In one certain form, (A) aqueous resin has a chemical structure derived from butylmethacrylate.

  Moreover, this invention provides the floor polish containing the aqueous resin for floor polishes in any one of the said.

The water-based resin for floor polish according to the present invention forms a floor polish film excellent in alcohol resistance, water-resistant adhesion, black heel mark resistance, water resistance, and peelability, and can be applied over the floor. Polish can be provided.
When the floor polish of the present invention is applied to the floor, the beauty of the floor is protected, the black heel mark is difficult to be attached, and the peeling work is facilitated.

Even if the floor polish of the present invention is applied to a floor that has been sterilized with alcohol, such as a hospital floor, whitening does not occur. Further, even when the floor polish of the present invention is applied to a floor coated with an ultraviolet curable resin and the floor is wetted with water, the adhesion between the floor polish film and the floor is maintained. Further, the adhesion between the floor and the floor polish film is not lowered by moisture, but the floor polish film peeling operation is not difficult.

Since the floor polish of the present invention can be overcoated, maintenance work can be performed efficiently.

The aqueous resin for floor polish according to the present invention is present in an aqueous medium and constitutes one component of floor polish described later. The aqueous resin for floor polish is obtained by mixing (A) an aqueous resin and (B) a compound containing two or more hydrazide groups in the molecule. The aqueous resin for floor polish accounts for 5% by weight or more, preferably 20% by weight or more, more preferably 50% by weight or more of the total nonvolatile content of the floor polish.

In the present specification, the “aqueous medium” refers to general water such as tap water, distilled water, or ion exchange water. The aqueous medium is an organic solvent that is water-soluble or dispersible in water, and may contain a small amount of an organic solvent that is poorly reactive with the raw materials (for example, monomers) of the emulsion according to the present invention. The small amount here means an amount up to 50% by weight, preferably up to 30% by weight, more preferably up to 10% by weight.

<(A) Aqueous resin>
(A) There are three forms of aqueous resin: water-soluble resin, dispersion, and emulsion. Especially, it is especially preferable that the form of (A) aqueous resin is a dispersion or emulsion which is a water dispersion type resin. In the present specification, the dispersion refers to a form showing an intermediate property between the water-soluble resin and the emulsion. Dispersions differ in appearance, particle size, molecular weight, and the like as compared to emulsions.

The dispersion is translucent in appearance and has a particle size of 10 to 70 nm, and the emulsion is white in appearance and has a particle size larger than 70 nm. Therefore, in the present specification, the dispersion and the emulsion are clearly different.

In the present specification, the particle diameter is measured by dynamic light scattering using a nanotrack particle size analyzer. (A) When the aqueous resin is a dispersion or an emulsion, the particle diameter is preferably 5 to 500 nm, particularly preferably 10 to 300 nm.

In the present invention, (A) the aqueous resin has a glass transition temperature of 40 ° C. or higher. The glass transition temperature is preferably 40 to 85 ° C, and most preferably 50 to 70 ° C. (A) When the aqueous resin is an aqueous emulsion, the glass transition temperature is the glass transition temperature of the solid content of the emulsion. The solid content of the emulsion refers to a solid content obtained by drying the emulsion at 105 ° C. for 3 hours.

(A) Since the glass transition temperature of water-based resin exists in the said range, the water-based resin for floor polishes of this invention can provide the floor polish which is excellent in black heel mark resistance and can be overcoated.

In this specification, the glass transition temperature of (A) aqueous resin is computed from Tg of the monomer used as a raw material of a polymer. The mixing ratio (parts by weight) of each monomer is determined in consideration of the glass transition temperature of the homopolymer obtained when each monomer is homopolymerized (hereinafter also referred to as “homopolymer Tg”). Specifically, (A) Tg of aqueous resin emulsion can be calculated | required by calculating using Formula (1).

[In the calculation formula (1), Tg is the theoretical Tg of the copolymer, Cn is the weight ratio in which the nth monomer n is contained in the monomer mixture, and Tgn is the nth monomer n. Tg, n of the homopolymer is a number of monomers constituting the copolymer, and is a positive integer. ]

  The value described in the literature can be used as the Tg of the monomer homopolymer. An example of such a document is “POLYMER HANDBOOK” (4th edition; published by John Wiley & Sons, Inc.).

  As an example, a monomer homopolymer Tg described in POLYMER HANDBOOK is shown below. For example, the Tg of homopolymers of the following monomers is as follows:

Styrene: 105 ° C
Methacrylic acid: 130 ° C
Acrylic acid: 106 ° C
Methyl methacrylate: 105 ° C
n-butyl methacrylate: 20 ° C
n-butyl acrylate: -54 ° C
Diacetone acrylamide: 65 ° C

  In the present invention, (A) the aqueous resin is obtained by polymerization of (a) a polymerizable unsaturated monomer, and (a) the polymerizable unsaturated monomer is a radical having an ethylenic double bond. It is a polymerizable monomer.

As used herein, “ethylenic double bond” refers to a double bond between carbon atoms that can undergo a polymerization reaction (radical polymerization). Examples of such a functional group having an ethylenic double bond include a vinyl group (CH2 = CH-), a (meth) allyl group (CH2 = CH-CH2- and CH2 = C (CH3) -CH2-), ( (Meth) acryloyloxy groups (CH2 = CH-COO- and CH2 = C (CH3) -COO-), (meth) acryloyloxyalkyl groups (CH2 = CH-COO-R- and CH2 = C (CH3) -COO-) R-) and -COO-CH = CH-COO- can be exemplified.

In this specification, acrylic acid and methacrylic acid are collectively referred to as “(meth) acrylic acid”, and “acrylic acid ester and methacrylic acid ester” are collectively referred to as “(meth) acrylic acid ester” or “ It is also called “(meth) acrylate”. The same applies to allyl groups and acryloyloxy groups.

In the present invention, (a) the polymerizable unsaturated monomer includes a monomer having a carbonyl group and an ethylenic double bond. In the present invention, (a) the polymerizable unsaturated monomer includes a monomer having a carbonyl group and an ethylenic double bond. The carbonyl group (—CO—) reacts with the hydrazide group (—CO—NH—NH ₂ ) of component (B) to form the formula

Is formed. That is, the carbonyl group referred to in the present invention is a carbonyl group of an aldehyde or a ketone.

Examples of the “monomer having a carbonyl group and an ethylenic double bond” 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 consideration of industrial availability, and diacetone acrylamide is particularly preferable in consideration of crosslinkability with the component (B).

In the present invention, (a) the polymerizable unsaturated monomer includes a monomer having a carbonyl group and an ethylenic double bond, and the carbonyl group and the ethylenic double bond are added to the total weight of 100 parts by weight. 2.0 to 5.0 parts by weight of a monomer having When the monomer having a carbonyl group and an ethylenic double bond is included in the above range, the aqueous resin for floor polish of the present invention has excellent alcohol resistance and water resistance adhesion. Preferably, the content of the monomer having a carbonyl group and an ethylenic double bond with respect to 100 parts by weight of the total component (a) is 2.0 to 3.0 parts by weight.

(A) The polymerizable unsaturated monomer includes not only a monomer having a carbonyl group and an ethylenic double bond, but also a “monomer having an acid group and an ethylenic double bond” or “ester group and ethylene. It is preferable to contain a “monomer having an ionic double bond”.

  The “monomer having an acid group and an ethylenic double bond” refers to a compound capable of imparting an acid group to the aqueous resin (A) obtained by radical polymerization reaction, and (A) according to the present invention. There is no particular limitation as long as an aqueous resin can be obtained and the desired aqueous resin for floor polish can be obtained.

As used herein, the term “acid group” refers to a functional group that can release a hydrogen ion in water to form a corresponding negatively charged functional group (for example, —COOH and —SO ₃ H), and the corresponding negative group. functional group having a charge (e.g., -COO ^- and -SO ₃ ^-, etc.) functional groups (for example, and negative charges are electrically neutralized by a counter cation, -COO ^- Na ⁺ and _-SO ³ - ^{K +} Etc.). These “functional groups capable of releasing a hydrogen ion in water to form a negatively charged functional group”, “functional group having a negative charge” and “functionality in which the negative charge is electrically neutralized by a counter cation. It goes without saying that the “group” can be easily converted into each other by changing the state around each functional group, for example, pH.

Here, as the “functional group capable of releasing a hydrogen ion in water to form a functional group having a negative charge”, for example, a carboxyl group (—COOH), a sulfonic acid group (or sulfo group) (—SO ₃ H) And a phosphate group (—PO ₄ H ₂ ) and the like.

Furthermore, the "functional group having a negative charge,""negative charges are electrically neutralized by a counter cation functional groups" and, for example, carboxylate (-COO ^- and -COOM ^1), sulfonate ( -SO ₃ ^- and _-SO 3 ^M 2), and phosphate groups _{^{(-PO 4 H -, -PO 4}} 2- , and _-PO ^{4 M} 3 ^M 4) or the like can be exemplified ^[where, M ^{1, M} 2, M ³ and M ⁴ are an alkali metal, an alkaline earth metal, or ammonium (note that any one of M ³ and M ⁴ may be hydrogen)].

The “ethylenic double bond” is as described above.

Examples of such “monomer having an acid group and an ethylenic double bond” include the following compounds:

Compounds having a carboxyl group and an ethylenic double bond, such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, maleic acid half ester, and the like, and compounds having a carboxylate group and an ethylenic double bond;

A compound having a sulfonic acid group and an ethylenic double bond, such as styrenesulfonic acid, and a compound having a sulfonate group and an ethylenic double bond;

(Meth) acrylic acid oxyethyl amide phosphate, etc., a compound having a phosphate group and an ethylenic double bond, and a compound having a phosphate group and an ethylenic double bond.
The counter cation of the carboxylate group, the sulfonate group, and the phosphate group is preferably an ammonium ion or an alkali metal ion, and particularly preferably an ammonium ion, a potassium ion, or a sodium ion.

In particular, as the monomer having an acid group and an ethylenic double bond, a compound having a carboxyl group and an ethylenic double bond, and a compound having a carboxylate group and an ethylenic double bond are preferred, and acrylic acid and methacrylic acid are preferred. Is particularly preferred.

These monomers can be used alone or in combination, and can be appropriately used depending on the characteristics of the aqueous resin for floor polish intended by the present invention. The “monomer having an ester group and an ethylenic double bond” in the present invention has an ester group (R—COO—R ′), and “a monomer having an acid group and an ethylenic double bond”. "Refers to a monomer that can be copolymerized (radical polymerization).

The kind of ester group is not particularly limited, and can be appropriately used depending on the properties of the desired (A) aqueous resin. The “ethylenic double bond” is as described above.

The “monomer having an ester group and an ethylenic double bond” is important for controlling the glass transition temperature (hereinafter abbreviated as “Tg”) of the aqueous resin (A) described later. It is considered that by increasing the Tg, the black heel mark resistance of the water-based resin for floor polishing is improved and the water resistance is also improved.

Examples of the “monomer having an ester group and an ethylenic double bond” include (meth) acrylic acid alkyl esters, which are preferred. Examples of (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate octyl (meth) acrylate, octyl ( Examples include (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate and the like.

In the present invention, among these, methyl methacrylate, butyl acrylate, and butyl methacrylate are preferably used, and butyl methacrylate is particularly preferably used.

In the present invention, it is preferable that (A) the aqueous resin has a chemical structure derived from butyl methacrylate. The aqueous resin for floor polish of the present invention is excellent in black heel mark resistance because (A) has a chemical structure derived from butyl methacrylate.

Butyl methacrylate is used in an amount of 3 to 50 parts by weight, preferably 5 to 30 parts by weight, more preferably 10 to 20 parts by weight, based on 100 parts by weight of the entire polymerizable unsaturated monomer (a). The By using butyl methacrylate in an amount within the above range, (A) the Tg of the water-based resin is optimized to give the floor polish film excellent water resistance and black heel mark resistance, and performance such as peelability. Can be applied to the floor polish in a well-balanced manner.

These alkyl (meth) acrylates can be used alone or in combination.

The (A) aqueous resin according to the present invention can be obtained by radical polymerization of (a) a polymerizable unsaturated monomer. As long as the desired (A) aqueous resin can be obtained, the polymerization method is not particularly limited, and the (A) aqueous resin can be obtained using a general radical polymerization method. For example, (a) a polymerizable unsaturated monomer can be obtained by polymerizing in an organic solvent and replacing with an aqueous medium, and this method is preferred. (A) The aqueous resin may be neutralized with an alkaline substance as necessary according to characteristics such as water solubility.

(A) Polymerization conditions such as the reaction temperature, reaction time, type of organic solvent, type and concentration of monomer, stirring speed, type and concentration of catalyst, and the like are the objectives. (A) It can be appropriately selected depending on the characteristics of the aqueous resin.

The “catalyst” is a compound that can cause the polymerization of the polymerizable unsaturated monomer (a) by addition of a small amount, and is preferably a compound that can be used in an organic solvent. For example, ammonium persulfate, sodium persulfate, potassium persulfate, t-butyl peroxybenzoate, 2,2-azobisisobutonitrile (AIBN) and 2,2-azobis (2-amidinopropane) dihydrochloride, and 2, Examples include 2-azobis (2,4-dimethylvaleronitrile), and 2,2-azobisisobutyronitrile (AIBN) is particularly preferable.

A chain transfer agent or the like can be suitably used for the polymerization in the present invention. As the “chain transfer agent” for adjusting the molecular weight, compounds well known to those skilled in the art can be used. For example, mercaptans such as n-dodecyl mercaptan and lauryl methyl mercaptan can be exemplified.
After polymerization, the organic solvent is preferably replaced with an aqueous medium. Conventional methods can be used to replace the organic solvent with the aqueous medium. For example, a method of adding an aqueous medium after distilling off the organic solvent by distillation, and a method of distilling off the organic solvent by distillation after adding the aqueous medium can be exemplified.

In the present specification, the “aqueous medium” refers to so-called water such as distilled water, ion-exchanged water, and pure water, and can include water-soluble organic solvents such as acetone and lower alcohols. By replacing the organic medium with an aqueous medium, (A) an aqueous resin can be obtained.

(A) The aqueous resin may be neutralized according to the characteristics of the aqueous resin. Here, “neutralization” can be performed by adding an alkaline substance usually used for neutralization. As a result, (A) the anionic group of the aqueous resin, particularly the carboxyl group, can be neutralized to impart water solubility to the (A) aqueous resin, but (A) the aqueous resin is not completely water soluble. Prepared.

In the present specification, the “alkaline substance” means a substance that exhibits a pH greater than 7 when dissolved in water, and the form of the alkaline substance is not limited to gas, liquid, and solid, but is water-soluble in water. Is preferred because it is easy to handle and the neutralization reaction is easily controlled. Examples of such “alkaline substances” include alkali metals such as ammonia, sodium and potassium, alkali metals such as calcium and magnesium, alkaline earth metals such as calcium and magnesium, and the like. An aqueous solution is preferred.

The acid value of the (A) aqueous resin according to the present invention is 30 to 110 mg KOH / g, particularly preferably 40 to 80 mg KOH / g, and most preferably 50 to 60 mg KOH / g. (A) When the acid value of the aqueous resin is in the above range, the floor polish film is provided with excellent water resistance and black heel mark resistance, and performance such as peelability can be imparted to the floor polish in a balanced manner. it can.

The “acid value” of the (A) aqueous resin according to the present invention is the potassium hydroxide required to neutralize the acid group assuming that the acid group contained in 1 g of the resin is all free. It is expressed as a calculated value of mg. Therefore, even if it exists as a base in the actual system, it is considered as a free acid.

This corresponds to the acid group contained in “a monomer having an acid group and an ethylenic double bond” in the polymerizable unsaturated monomer (a).

The “acid value” according to the present invention can be determined by the following formula (2).

Acid value (mgKOH / g)
= (Weight of monomer having acid group and ethylenic double bond / molecular weight of monomer having acid group and ethylenic double bond) × 1 mol of monomer having acid group and ethylenic double bond Number of moles of acid groups contained in x Formula weight of KOH x 1000 / (A) Weight of aqueous resin (2)

  (A) Polymerization of the polymerizable unsaturated monomer is performed by ordinary radical polymerization such as solution polymerization or emulsion polymerization.

The solution polymerization can be performed, for example, by radical polymerization of the above-described (a) polymerizable unsaturated monomer using a suitable catalyst or the like in an organic solvent. Here, the “organic solvent” means (a) a polymer that can be used to polymerize a polymerizable unsaturated monomer, and does not substantially adversely affect the characteristics as an aqueous resin for floor polish after the polymerization reaction. If it is, it will not specifically limit. Examples of such solvents include lower alcohols such as methanol, ethanol and propanol, esters such as ethyl acetate, and combinations thereof.

Emulsion polymerization includes one-stage polymerization and multi-stage polymerization, and can be performed by a known method such as a polymerization method by adding a polymerization initiator, an aqueous medium or an emulsifier at once, a so-called monomer dropping method or a pre-emulsion method. it can.

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 ether sulfate, polyvinyl alcohol, polyacrylate, water-soluble (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer salt, styrene- (meth) acrylic copolymer salt, poly Polymeric 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. The desirable amount of the emulsifier is preferably 0.05 to 5 parts by weight with respect to the total weight of the polymerizable unsaturated monomer mixture in consideration of water resistance.

As the polymerization initiator, any of a water-soluble polymerization initiator and an oil-soluble polymerization initiator can be used. For example, organic peroxides such as hydrogen peroxide, benzoyl peroxide, tert-butyl peroxide, 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 weight, particularly preferably 0.1 to 3% by weight, based on the total weight of the polymerizable unsaturated monomer mixture.

<(B) Compound having two or more hydrazide groups in the molecule>
In the present invention, (B) a compound having two or more hydrazide groups in the molecule is mixed with (A) an aqueous resin to produce an aqueous resin for floor polishing. The water-based resin for floor polish is excellent in black heel mark resistance, water resistance, and peelability because the hydrazide group present in component (B) reacts with the carbonyl group present in component (A) to crosslink. It is possible to provide a floor polish that can be overcoated. Component (B) preferably has two hydrazide groups in the molecule.

The blending amount of (A) the aqueous resin and (B) the compound having two or more hydrazide groups in the molecule is such that (A) 100 parts by weight of the aqueous resin has (B) two or more hydrazide groups in the molecule. The compound is preferably 0.2 to 10 parts by weight, particularly preferably 0.3 to 5.0 parts by weight, and most preferably 0.5 to 3.0 parts by weight.

When the blending amount of the component (A) and the component (B) is in the above range, the floor polish aqueous resin of the present invention provides a floor polish film having an excellent balance between black heel mark resistance and peelability. To do.

In the present invention, 0.5 to 5.0 equivalents of the hydrazide group of the component (B) are added to 1 equivalent of the carbonyl group present in the component (A). When the equivalent ratio of the hydrazide group to the carbonyl group is within the above range, the floor polish aqueous resin of the present invention forms a floor polish film excellent in both black heel mark resistance and peelability. The equivalent ratio of hydrazide groups to carbonyl groups is preferably 0.5 to 3.0, more preferably 0.8 to 1.5.

(B) Examples of the compound containing 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 , Isophthalic acid dihydrazide, citric acid dihydrazide, 1,2,4-benzenetridihydrazide, thiocarbodihydrazide, trade names “APA-M950”, “APA-M980”, “APA-P250”, “APA” manufactured by Otsuka Chemical Co., Ltd. And hydrazide polymers such as “-P280”. Among these, carbohydrazide, adipic acid dihydrazide, succinic acid dihydrazide, and hydrazide polymer are preferable from the balance of dispersibility in emulsion and water resistance, and adipic acid dihydrazide is particularly preferable in consideration of crosslinkability with component (A). .

The floor polish according to the present invention is an aqueous dispersion (for example, wax emulsion or urethane dispersion) containing an alkali-soluble resin, a crosslinking agent, a plasticizer, and a film forming aid in the above-described aqueous resin for floor polish, and an antifoaming agent. , Preservatives, fillers, thickeners, dispersants and the like.

Examples of the crosslinking agent include non-metallic or metallic compounds that can act on carboxyl groups. Examples of the nonmetallic crosslinking agent include compounds containing a carbodiimide group, an oxazoline group, and the like. Examples of the metal-based cross-linking agent include polyvalent metals such as zinc and magnesium and compounds thereof, but it is preferable not to use a metal-based cross-linking agent from the viewpoint of reducing environmental burden, and from the viewpoint of improving peelability It is more preferable not to use.

Examples of plasticizers include phosphate esters such as tributoxyethyl phosphate, tributyl phosphate and triphenyl phosphate, phthalate esters such as dibutyl phthalate and di-2-ethylhexyl phthalate, citrate esters such as tributyl acetylcitrate, dimethyl adipic acid, Examples include adipic acid esters such as dibutyl adipic acid, and alkylene oxide adducts to alcohols such as 2-ethylhexanol.
Conventionally, tributoxyethyl phosphate has been widely used as a plasticizer for floor polish. However, in order to reduce the environmental load, the use of such phosphorus compounds is avoided (that is, non-phosphorization). It is preferable that no phosphorus compound is contained. Among such non-phosphorus compounds, it is preferable to use an ethylene oxide adduct of 2-ethylhexanol among the above plasticizers because it can improve the wettability to flooring. Furthermore, it is preferable to use an ethylene oxide 1-8 mol adduct of 2-ethylhexanol.

As wax of the wax emulsion, natural wax, synthetic wax, modified products thereof and the like can be widely used.

Examples of natural waxes include animal waxes such as hydrogenated cured wax such as beef tallow and pork tallow, lanolin and beeswax;
Vegetable waxes such as hydrogenated waxes such as soybean oil and castor oil, carnauba wax, candelilla wax, tree wax, and nuka wax;
Mineral waxes such as montan wax, sericin wax, paraffin wax, microcrystalline wax;
Can be mentioned.

Examples of the synthetic wax include polyethylene wax, polypropylene wax, and Fischer-Tropsch wax having a molecular weight of about 500 to 5,000. These wax emulsions can be produced by a known method such as emulsification by adding an emulsifier to these waxes.

Examples of film forming aids include alcohols such as benzyl alcohol and 3-methoxy-3-methylbutanol, and glycols such as diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol ethyl ether, dipropylene glycol methyl ether, and ethylene glycol phenyl ether. Etc.

  The antifoaming agent is not particularly limited as long as it is usually an antifoaming agent. Examples include hydrophobic silica, metal soap, amide, modified silicone, silicone compound, polyether, emulsion, and powder. For example, as the hydrophobic silica, Nopco SN Deformer 777 (trade name) (manufactured by San Nopco), SN Deformer VL (trade name) (manufactured by San Nopco), and Nopco NXZ (trade name) (San Nopco for metal soaps) Nopco 267-A (trade name) (manufactured by San Nopco Co., Ltd.) as modified amide antifoaming agent, silicone KM80 (trade name) (manufactured by Shin-Etsu Chemical), silicone SN Deformer 121N (trade name) (manufactured by San Nopco Co., Ltd.) as a compound type anti-foaming agent, SN Deformer PC (trade name) (manufactured by San Nopco Co., Ltd.), an emulsion type anti-foaming agent as a polyether type anti-foaming agent Nopco KF-99 (trade name) (manufactured by San Nopco Co., Ltd.), SN-deformer 14-HP (trade name) ( N'nopuko Ltd. Co.) and the like can be exemplified.

  Examples of the preservative include ACTICIDE LG (trade name) (manufactured by So Japan Co., Ltd.), ACTICIDE MBS (trade name) (manufactured by So Japan Co., Ltd.), and the like.

  The film forming aid is not particularly limited as long as it is generally used as a film forming aid. For example, CS-12 (trade name) (manufactured by Chisso Corporation), benzyl alcohol, butyl glycol, 2-ethylhexyl glycol, phenylpropylene glycol, dibutyl diglycol, dipropylene glycol mono n-butyl ether, tripropylene mono Organic esters of polyhydric alcohol monoalkyl ethers such as glycol n-butyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether, diethylene glycol mono n-butyl ether, 3-ethoxypropionic acid esters, 3-methoxy-3 acetate -Methyl-butyl etc. can be illustrated.

The filler refers to a substance added for the purpose of improving performance, reducing costs, and the like, and is not particularly limited as long as it is normally used as a filler. Specific examples include calcium carbonate, magnesium carbonate, silica, talc, clay, and alumina.

The thickener is not particularly limited as long as it is usually a thickener. For example, a modified acrylic polymer can be exemplified as an alkali thickening type thickener, and a urethane-modified polyether and polyether can be exemplified as an association type thickening agent. As an alkali thickening type thickener, for example, hydroxyethyl cellulose (SP600 (trade name) manufactured by Daicel Chemical Industries), SN thickener 615 (trade name) (manufactured by San Nopco), ASE 60 (trade name) (R & H (stock) )), KA10K (trade name) (manufactured by Henkel Japan Ltd.), and the like. Moreover, as an association type thickener, for example, SN812 (trade name) (manufactured by San Nopco), RM8W (trade name) (manufactured by R & H), UH752 (trade name) (manufactured by ADEKA), etc. Can be illustrated.

The dispersant is not particularly limited as long as it is normally a dispersant. For example, potassium tripolyphosphate (manufactured by Taihei Chemical Industry Co., Ltd.), Primal 850 (trade name) (manufactured by Rohm & Haas), Demol EP (trade name) (manufactured by Kao Corp.) DISCOAT N-14 (commodity) Name) (Daiichi Kogyo Seiyaku Co., Ltd.), Orotan 165A (trade name) (R & H), SN Dispersant 5020 (trade name) (San Nopco).

The floor polish of the present invention can be applied to all general floor materials such as various base materials known as general floor materials, such as wood materials, plastics, and inorganic building materials. The floor polish of the present invention is applied by first applying to a flooring material and drying to form a film. The floor polish is applied and dried in an environment of normal temperature and pressure. Thereafter, if the floor polish film is contaminated or damaged, the film is removed. The removal of the floor polish film is performed by bringing the floor polish remover into contact with the film to be removed and rubbing the film on which the floor polish remover has acted. Then, the floor polish of the present invention is applied again to the surface of the floor material from which the floor polish film has been removed.

The floor polish of the present invention does not whiten even when applied to an alcohol-sterilized floor, and peels off even if the floor is wiped with water after being applied to a floor coated with an ultraviolet curable resin. There is nothing.

The floor coated with the floor polish of the present invention is difficult to be marked with a black heel mark, the film can be easily removed by a peeling operation, and repeated coating on the floor is possible, so that periodic maintenance is facilitated.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely and in detail, these Examples are only one aspect | mode of this invention, and this invention is not limited at all by these examples. In the examples, parts means parts by weight.

(A) Manufacture of aqueous resin Hereinafter, (A) monomer (a) used for manufacture of aqueous resin is shown.

Methyl methacrylate (MMA, glass transition temperature 105 ° C, manufactured by Wako Pure Chemical Industries, Ltd.)
Butyl methacrylate (BMA, glass transition temperature (Tg) 20 ° C, manufactured by Wako Pure Chemical Industries, Ltd.)
n-butyl acrylate (BA, manufactured by Wako Pure Chemical Industries, Ltd., glass transition temperature (Tg) -54 ° C.)
Acrylic acid (AA, manufactured by Wako Pure Chemical Industries, Ltd., glass transition temperature (Tg) 106 ° C)
Diacetone acrylic amide (DAAM, manufactured by KH Neochem Co., Ltd., glass transition temperature (Tg) 65 ° C)

<Synthesis of (A1) aqueous resin>
A four-necked flask equipped with a stirring blade, a thermometer, and a reflux condenser was charged with 95 parts by weight of water and 6 parts by weight of a surfactant “AQUALON KH1025” (trade name) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. The charged solution was heated to 80 ° C. An emulsion was prepared by adding 2 parts by weight of “AQUALON KH1025” (trade name) and 38 parts by weight of water to the monomer mixture in the amounts shown in Table 1.

The obtained emulsion and 14 parts by weight of a 2% aqueous solution of sodium persulfate were added dropwise to the charged solution in the four-necked flask continuously over 3 hours using separate dropping funnels, and emulsion polymerization was performed. Two hours after the dropping, the mixture was cooled to complete the polymerization, thereby obtaining (A) an aqueous resin.

<Synthesis of aqueous resins (A2) to (A12) and synthesis of (A'13) to (A'16)>
Each polymerizable unsaturated monomer is blended in the parts by weight shown in Table 1, and (A1) the synthesis of (A2) to (A12) and (A'13) to (A) by the same method as the synthesis of the aqueous resin. '16) was synthesized. (A) The aqueous resin was dried in an oven at 105 ° C. for 3 hours, the weight before and after drying was measured, and the concentration of the aqueous resin was calculated. The concentration of each aqueous resin was 40% by weight. The concentration of the aqueous resin is calculated by the following formula.

Concentration (mass%) = mass of residual part after drying × 100 / weight before drying

<Manufacture of aqueous resin for floor polish ((A) aqueous resin and (B) mixture of compound having two or more hydrazide groups in molecule)>
Hereinafter, the crosslinking agent used for manufacture of the aqueous resin for floor polishes is shown.

(B) Compound having two or more hydrazide groups in the molecule Adipic acid dihydrazide (Nippon Finechem)

Zinc carbonate ammonia solution 10 parts by weight of zinc oxide was added to 54.49 parts by weight of distilled water to prepare a dispersion. To the obtained dispersion, 17.97 parts by weight of 28% aqueous ammonia and 17.54 parts by weight of ammonia carbonate were added to obtain a zinc carbonate ammonia solution.

Carbodiimide compound Polycarbodiimide "Carbodilite SV-02" (trade name) manufactured by Nisshinbo Chemical Co., Ltd.

Each aqueous resin (A1) to (A12) and (A′13) to (A′16) and a crosslinking agent (component (B) or carbodiimide compound) were mixed at a ratio shown in Table 2, specifically, The mixture was stirred for 1 hour at room temperature using a stirrer to synthesize an aqueous resin for floor polishing. (Examples 1-15 and Comparative Examples 1-10).

The following describes the production of floor polish and the evaluation of its properties.

<Preparation of floor polish>
The floor polish was adjusted by adding an additive to the aqueous resin for floor polish. The compounding ratio of the additives is as described below for each floor polish aqueous resin.

7 parts by weight of Hitech E-9015 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) as wax and SMA-2625-P (trade name, river crude oil) as alkali-soluble resin for 40 parts by weight of aqueous resin for floor polish 3 parts by weight (solid content 15%)), 8 parts by weight of diethylene glycol monoethyl ether as a film-forming aid, 2 parts by weight of TBEP (tributoxyethyl phosphate) as a plasticizer, and Surflon S-211 (leveling agent) 1 part by weight of a trade name, manufactured by AGC Seimi Chemical Co., Ltd. (solid content 1%), and 45 parts by weight of distilled water were added. In addition, the above-mentioned compounding ratio is a value containing both solid content and a solution.

<Evaluation test>
Each floor polish was subjected to the following evaluation test. The results are shown in Tables 1-6.

1. Alcohol-resistant composition vinyl tile (Machico V (product name) manufactured by Toli Co., Ltd., size 300mm x 300mm) is coated with floor polish three times using gauze and then dried for one day. A test piece was obtained.

0.05 g of alcohol-containing gel-like disinfectant was dropped on the test piece. As the alcohol, a gel-like disinfectant (Gojo IHS-N (product name) manufactured by Gojo Japan) containing 76.9 to 81.4% by volume of ethanol was used.

One hour after the dropping, the gel-like disinfectant was wiped off, washed with water, and the state of the test piece after drying was visually evaluated. The evaluation criteria are shown below.

◎: Little whitening and dissolution ○: Slight whitening and dissolution Δ: Whitening and dissolution ×: Whitening and dissolution are quite noticeable

2. Floor using multi-layer vinyl floor sheet (non-wax rumeum NW (product name) manufactured by Toli Co., Ltd., dimensions 300 mm x 300 mm), surface-treated with a water-resistant, highly durable antibacterial UV resin coating layer, using gauze The polish was applied three times. Thereafter, the overcoated tile was dried for 7 days in a constant temperature oven maintained at 50 ° C., and this was used as a test piece.

0.5 mL of water was dropped onto the test piece with a measuring pipette, and after 5 minutes, the water droplet was wiped off. Immediately after wiping, the cellophane adhesive tape was affixed onto the water wetted part. Immediately after applying the cellophane adhesive tape, the end of the tape was kept at a right angle to the surface of the test piece, and was peeled off instantaneously, and the state of the test piece was visually evaluated. The evaluation criteria are shown below.

◎: No peeling of the film ○: The peeling area of the film is less than 1/3 of the cellophane adhesive tape application area Δ: The peeling area of the film is 1/3 or more and less than 2/3 of the cellophane adhesive tape application area X: The peeled area of the film is 2/3 or more of the cellophane adhesive tape application area

3. Evaluation of resistance to black heel mark Evaluation was made with a heel mark tester and method according to JFPA standard-11. The specific method is as follows.

A floor polish was applied three times with gauze to a composition vinyl tile (manufactured by Toli Co., Ltd., Machiko V, dimensions 300 mm × 300 mm), and then dried for one day to obtain a test piece.

The black heel mark resistance tester used a device called a snell capsule. The snell capsule has a hexagonal column shape, and an axis is passed through the center of the hexagon, and the snell capsule can rotate around the axis.

The test piece was cut to a size of 225 mm × 225 mm, mounted on the inner wall surface of a snell capsule (tester), and six standard rubber blocks (JIS S 5050) 50 mm × 50 mm × 50 mm cubes (about 175 g) were put into the tester. The tester was rotated at 50 rpm for 5 minutes and then rotated in the reverse direction for 5 minutes. Since the standard rubber block collided with the test piece by rotation for 10 minutes, the heel mark resistance was evaluated by the contamination of the test piece due to the collision.

In the evaluation, the amount of black heel mark (stains like black rubbing) adhering to the test piece was judged visually. The evaluation criteria are shown below.

A: There is almost no dirt. ○: There is a little dirt.
Δ: Dirt ×: Dirt is noticeable

4). Water polish evaluation Composition vinyl tile (Machico V (product name) manufactured by Toli Co., Ltd., dimensions 300 mm × 300 mm) was overcoated with floor polish three times using gauze. Then, it was set as the test piece by making it dry for 1 day.

0.1 mL of water was dropped on the test piece with a measuring pipette, and after 1 hour, the water drop was wiped off, and the whitening state of the test piece was visually evaluated. The evaluation criteria are as follows.

◎: No whitening phenomenon ○: Whitening outline is slightly seen
Δ: Partially whitened
X: Fully whitened

5. Evaluation of peelability First, a standard stripping solution was prepared. The preparation of the stripping solution is as follows.
After 2 g of sodium lauryl sulfate and 500 ml of ion-exchanged water at 25 ± 5 ° C. are put into a total volume flask and stirred well until it becomes clear, 20 g of benzyl alcohol and 40 g of monoethanolamine are sequentially added and dispersed well. Further, 25 mL ± 5 ° C. ion-exchanged water was added to make the total amount 1 L, which was used as a standard stripping solution.

Next, a test piece for a peel evaluation test was prepared. Details are shown below.
Each floor polish was overlaid three times using gauze on a composition vinyl tile (Machico V (product name) manufactured by Toli Co., Ltd., dimensions 300 mm × 300 mm). Thereafter, the overcoated tile was dried for 7 days in a constant temperature oven maintained at 50 ° C., and this was used as a test piece.

The test piece was cut to a size of 50 mm × 150 mm and immersed in a standard stripping solution for 2 minutes. Thereafter, the specimen was reciprocally polished with a red polishing scourer (manufactured by Sumitomo 3M Co., Ltd., red pad) containing a standard stripping solution, and the number of reciprocating drives required for complete removal of the floor polish film was measured. The evaluation criteria are as follows.

◎: Can be removed in 25 to 50 times ○: Can be removed in 51 to 100 Δ: Can be removed in 101 to 200 times ×: It takes 201 or more times to remove

6). Three coatable composition vinyl tiles (Machico V (product name) manufactured by Toli Co., Ltd., dimensions 300 mm × 300 mm) were prepared, and each floor polish was spread once using gauze. After applying the floor polish, it was allowed to stand and dried for 30 minutes, and then applied to two of the three tiles. Then, after leaving still and drying for 30 minutes, it was set as the test piece by apply | coating floor polish again on two tiles with which floor polish was apply | coated.

Regarding the coatability, the appearance of the test piece was visually evaluated. The evaluation criteria are as follows.

◎: Appearance of multi-layer coating is remarkably superior to the appearance of one-layer coating ○: Appearance of multi-layer coating is not much different from the appearance of one-layer coating Δ: Multi-layer coating than the appearance of one-layer coating Appearance is partially inferior ×: Appearance of multilayer coating is significantly inferior to that of single-layer coating

7. Comprehensive evaluation The overall performance of the floor polish was evaluated by an evaluation test above. The evaluation criteria are as follows.

○: Any performance is ◎ or ○ △: Any performance includes △ and other performance does not include x ×: Any performance includes x

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

As shown in Tables 1-6, the floor polish of the examples is (A) a water-based resin added with (B) adipic acid dihydrazide, and cross-linking of component (A) and component (B) results in durability ( Black heel mark resistance and water resistance) are improved. The floor polishes of the examples are not only durable, but also excellent in alcohol resistance and water-resistant adhesion, and in addition, because they are excellent in peelability and coatability, maintenance is easy.

On the other hand, the floor polish of the comparative example does not contain either (A) an aqueous resin or (B) a compound having two or more hydrazide groups in the molecule, so that it has alcohol resistance, water adhesion resistance, and black resistance. Any of heel mark property, water resistance, peelability, and overcoatability is x.

From these results, when (A) a water-based resin is blended with (B) a compound having two or more hydrazide groups, the floor is excellent in durability, excellent in alcohol resistance, water-resistant adhesion, peelability, and overcoatability. It has been demonstrated that an aqueous resin for polishing can be obtained.

The water-based resin for floor polish according to the present invention can improve the film removal performance (peelability) while maintaining the film durability performance (heel mark resistance, water resistance) of the floor polish, and is further resistant to alcohol. It also has excellent water-resistant adhesion.

Therefore, the floor polish containing the aqueous resin for floor polish and other additives of the present invention is suitable for repeated coating and peeling, and is used very effectively in the building maintenance industry.

Furthermore, since the floor polish is also excellent in alcohol resistance and water resistance adhesion, it is suitable for use on floors that have been sterilized with alcohol, such as hospital floors, or floors that are coated with an ultraviolet curable resin.

Claims (4)

(A) It is obtained by polymerizing a polymerizable unsaturated monomer to synthesize (A) an aqueous resin, and (A) an aqueous resin and (B) a compound having two or more hydrazide groups in the molecule. An aqueous resin for floor polish,
(A) The aqueous resin has a glass transition temperature of 40 ° C. or higher,
(A) The polymerizable unsaturated monomer includes a monomer having a carbonyl group and an ethylenic double bond, and the monomer having the carbonyl group and the ethylenic double bond is 100 parts by weight in total. Contains 2.0 to 5.0 parts by weight of body,
An aqueous resin for floor polishing, wherein 0.5 to 5.0 equivalents of the hydrazide group of the component (B) are added to 1 equivalent of the carbonyl group present in the component (A). (A) The aqueous resin for floor polishes according to claim 1, wherein the acid value of the aqueous resin is 30 to 110 mgKOH / g.   (A) The aqueous resin for floor polishes according to claim 1 or 2, wherein the aqueous resin has a chemical structure derived from butyl methacrylate. The floor polish containing the aqueous resin for floor polishes in any one of Claims 1-3.