JPH04154879A - Lustering agent composition and its production - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polishing agent composition for protecting flooring materials and maintaining and improving the aesthetic appearance, and a method for producing the same.

More specifically, a polish that has less scratches from walking etc. or black heel marks attached to the film after the polish has been applied, and which can be easily removed with an alkaline remover if necessary. The present invention relates to a drug composition and a method for producing the same.

[Conventional technology]

Polishing agents commonly used for polishing floors, etc. include:
Developing and maintaining a beautiful luster, ■ Hard to get black heel marks, ■ Excellent abrasion resistance, ■
It is required to have good coating workability, and (1) be able to be easily peeled off.

For this purpose, the coated film needs to be strong and have both water resistance and removability.

On the other hand, conventional polishing agent compositions include compositions in which a polyurethane resin emulsion and an acrylic resin emulsion are mixed (Japanese Patent Publication No. 53-22548);
A composition in which a crosslinking agent is added to an acrylic resin containing a carboxyl group (Japanese Patent Publication No. 47-15597) is known.

[Problem to be solved by the invention]

However, in the conventional polishing agent compositions, the film is not strong and satisfies water resistance and removability, and although the polishing agent compositions have sufficient performance required of the polishing agent compositions. do not have.

The present invention solves the above-mentioned problems, and aims to provide a polish composition having excellent film resistance and peelability, and a method for producing the same.

[Means to solve the problem]

The present inventors have conducted intensive research on the types of synthetic resins and manufacturing methods of polishing agent compositions that affect the physical properties of polishing agent films, especially water resistance and peelability. The present invention was completed by discovering that a composition in which aldehydes are added to a mixture of a resin emulsion, a polyurethane resin emulsion, and a wax emulsion exhibits excellent performance that is compatible with both water resistance and peelability.

That is, the polishing agent composition according to the first invention includes (a) a polyurethane resin emulsion containing a carboxyl group and having an acid value of 20 to 80, and (b) an acrylic resin emulsion containing a carboxyl group and having an acid value of 40 to 100. Resin emulsion, (c
) wax emulsion, (d) a zinc crosslinking agent in an amount of 0.5 to 1.0 chemical equivalents to the carboxyl group of the acrylic resin, and (e) aldehydes.

The "polyurethane resin emulsion" can be selected from various aqueous emulsions that have been conventionally used as water-soluble polishing agents, depending on the purpose, use, etc., and used.

That is, diisocyanate compounds [eg, hexamethylene diisocyanate, tolylene diisocyanate, 4.
Examples include aqueous resins having a skeleton structure of 4'-diphenylmethane diisocyanate, xylylylene diisocyanate, 4°4'-methylenebis(cyclohexyl isocyanate), isophorone diisocyanate, and the like.

Moreover, the acid value of this polyurethane resin needs to be in the range of 20 to 80. This is because if this value is less than 20, the releasability decreases, while if it exceeds 80, the water resistance deteriorates.

The "acrylic resin emulsion" can be produced by generally known emulsion polymerization.

Vinyl monomers used in this emulsion pentapolymerization include styrene, vinyltoluene, acrylonitrile, methacrylonitrile, methyl methacrylate, ethyl methacrylate,
Butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, cyclohexyl acrylate, benzyl acrylate, methacrylic acid Examples include hydroxyethyl, hydroxypropyl methacrylate, methacrylic acid, acrylic acid, itaconic acid, crotonic acid, maleic acid, acrylamide, methylolacrylamide, dimethylacrylamide, and monomers copolymerizable with these monomers.

Moreover, the acid value of this acrylic resin needs to be in the range of 40 to 100. If this value is less than 40, the releasability will decrease, while if it exceeds 100, the water resistance will deteriorate and the viscosity of the emulsion will become too high when a zinc crosslinking agent is added, making it unsuitable for practical use as a polishing agent. It is.

The above-mentioned "wax emulsion" may be selected from among the waxes that have been traditionally used as polishing agents.
Various types can be selected and used depending on the purpose. That is,
Various natural and synthetic hydrocarbon waxes and modified products thereof can be used. Here, natural waxes include beef tallow, hydrogenated hardened pork fat, animal waxes such as lanolin, beeswax, spermaceti, wax obtained by hydrogenating soybean oil, carnauba wax, candelilla wax,
Examples include vegetable waxes such as wood wax and wax wax, and mineral waxes such as montan wax, sericin wax, paraffin wax, and microcrystalline wax. In addition, as a synthetic wax, the molecular weight is 50
Examples include polyethylene wax of about 0 to 5,000, wax produced by the Fischer-Tropsch method, and oxides and acid-modified products of these synthetic waxes. Note that the wax emulsion can be produced, for example, by adding a known emulsifier to these and emulsifying the mixture using various emulsifiers.

As the "zinc crosslinking agent", for example, zinc ammonium carbonate can be used. This zinc crosslinking agent is added to the acrylic resin emulsion, and the amount added is 0.00000000 with respect to the carboxyl group of the acrylic resin.
5 to 1.0 chemical equivalent. Below 0.5 chemical equivalents,
The water resistance of the film formed by applying the polishing agent will be insufficient, and if the chemical equivalent exceeds 1.0, the resin emulsion will coagulate and precipitate due to the presence of the acrylic resin emulsion and unreacted zinc crosslinking agent, resulting in loss of gloss. This is because it is undesirable because it lowers the temperature.

The acrylic resin emulsion may also be a zinc crosslinked acrylic resin emulsion crosslinked with zinc, as shown in the second invention. This is because when a zinc crosslinking agent is added to a polyurethane resin emulsion, the emulsion may become thickened or gelled, and if this zinc crosslinking type is used, such problems will not occur.

The "aldehydes" have the effect of reducing the degree of dissociation of zinc in the acrylic resin, preventing zinc from migrating to the polyurethane resin, and preventing thickening or gelation of the polyurethane resin emulsion. As this aldehyde, formalin, glyoxal, etc. can be used as shown in the third invention. This is because these are aldehydes with relatively little odor. However, in reality,
Aqueous solutions of these aldehydes can be used. Further, this aqueous solution of aldehydes is usually added to the mixture consisting of the polyurethane resin emulsion and the like.

In addition, as shown in Part 4, Part 13 of this issue, when the zinc crosslinking agent contains ammonia, the amount of the aldehyde added is 0.5 to 1.5 mol per 1 mol of ammonia. Appropriate. If the amount added is less than 0.5 mol, the ability to thicken or prevent gelation of the polyurethane resin emulsion will be insufficient, and if it exceeds 1.5 mol, there will be a large amount of unreacted ammonia sequestering agent, resulting in poor water resistance and odor. This is because it adversely affects film-forming properties and the like.

The method for producing a floor polish composition according to the fifth invention includes:
A zinc crosslinking agent in an amount of 0.5 to 1.0 chemical equivalents relative to the carboxyl group of the acrylic resin is added to the acrylic resin emulsion, and the crosslinking reaction is carried out by heating to a temperature equal to or higher than the glass transition point of the acrylic resin. The method is characterized in that an aqueous solution of aldehydes is added to a mixture of the emulsion obtained by performing the above steps, a polyurethane resin emulsion containing a carboxyl group, and a wax emulsion.

In this production method, this zinc crosslinking agent needs to be added to the acrylic resin emulsion. When this zinc crosslinking agent is added to a polyurethane resin emulsion or a mixture of an acrylic resin emulsion and a polyurethane resin emulsion, the polyurethane resin emulsion thickens or gels, making it unsuitable for practical use as a polishing agent. This is because it may disappear.

Further, as the aldehyde, formalin or glyoxal can be used as shown in the sixth invention.

In addition, the polishing composition of the present invention contains, in addition to the above-mentioned essential ingredients,
Tributoxyethyl phosphate, butyl phthalate,
Plasticizers such as octyl phthalate, coalescent agents such as diethylene glycol monoethyl ether, ethylene glycol, diethylene glycol diethyl ether, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, leveling of styrene-maleic acid resin, etc. It can contain auxiliary ingredients used in conventional polishing agents, such as wettability improvers such as agents, fluorosurfactants, antifoaming agents, and preservatives.

〔Example〕

The present invention will be specifically explained below using Examples.

In the Examples and Comparative Examples below, "parts" are parts by weight unless otherwise specified.

(1) Preparation of each component ■ Polyurethane resin emulsion A polyester polyol is synthesized using adipic acid, neopentyl glycol, l,6-hexanediol and dimethylolpropionic acid, and this polyester polyol and hydrogenated MDI (4,4 A hydrogenated product of °-diphenylmethane diisocyanate) was reacted to form a polyurethane. Next, triethylamine is added to neutralize the carboxyl groups and dispersed in water until the solid concentration is 3.
A polyurethane resin emulsion containing 3% by weight (hereinafter simply referred to as 1%) and an acid value of solid content of 15.30.60.90 (respectively referred to as A, B, C, and D).

) was obtained.

■Zinc cross-linked acrylic resin emulsion deionized water 59
．． Ammonium persulfate 0.0 as a polymerization initiator to 97 parts
After adding 8 parts of sodium lauryl sulfate and 2 parts of 30 mole adduct of nonylphenol E as an emulsifier and heating to 75°C, a monomer consisting of ethyl acrylate, methyl methacrylate, styrene and methacrylic acid was added. The polymer mixture was added dropwise over a period of 3 hours to obtain an acrylic resin emulsion. Next, 7 parts of zinc oxide and ammonia water (concentration 25%) were added to 100 parts of this acrylic resin emulsion.
), a zinc crosslinking agent consisting of 12 parts of ammonium hydrogen carbonate and 67 parts of water was added, and a crosslinking reaction was carried out at 70 to 75°C for 1 hour.

In this way, a zinc crosslinked acrylic resin emulsion having a glass transition point of 70°C was obtained. Here, Table 1 shows the obtained zinc crosslinked acrylic resin emulsion.

In Table 1, "amount of zinc crosslinking agent added" refers to the amount of zinc crosslinking agent added to 100 parts of the acrylic resin emulsion, and "chemical equivalent of zinc" refers to the amount of zinc crosslinking agent added to 100 parts of the acrylic resin emulsion. Chemical equivalents are shown.

(2) Preparation of each polishing agent composition Each composition related to the present example and comparative example was prepared by blending each component shown in Tables 2 and 3 in a predetermined ratio. In addition, in the same table, "the amount of aldehydes added" refers to the amount of aldehydes (added) per 1 mole of ammonia contained in the zinc crosslinking agent.
Indicates the amount (moles) added of (pure amount). The table also lists the acid value and zinc chemical equivalent of each resin.

In addition, "wax emulsion" (manufactured by Allied Chemical Co., Ltd.) in the same table is oxidized polyethylene wax AC392.
This is an emulsion prepared by neutralizing this with KOH and emulsifying it in water using a 10 mole adduct of nonylphenol E0.

In addition, the numerical values outside the range of the preferred invention in Table 3 *
Marked.

(3) Performance test In order to clarify the performance of the polishing agent composition of the present invention,
Performance tests were conducted on each of the compositions in Tables 2 and 3. The test items and test methods are listed below, and the test results are shown in Table 4. Note that the * mark in the same table indicates that the performance test could not be performed because the sample could not be applied well.

■Storage stability The state of the liquid was observed and evaluated after it was left at room temperature for 7 days.

The display of this evaluation is as follows.

○: No abnormality, △: thickening, X: gelation of liquid.

■Glossiness Japan Floor - Polish Industry Association Standards (JFPA Standards-1)
0), the following tests were conducted.

That is, using non-asbestos floor tiles as the flooring material, the sample emulsion was applied three times thereto, and after drying for 30 minutes or more, the degree of gloss (%) was measured according to JIS Z8741 (specular gloss measurement method).

■Heel mark resistance Japan Floor Borish Industry Association standard (JFPA standard-1
According to 1), the following tests were conducted.

That is, when non-asbestos floor tiles were used as the flooring material, a sample solution was applied thereto, dried, and then tested using a heel mark tester. was visually evaluated. The display of this evaluation is as follows.

○: Good, △: Slightly poor, ×: Poor.

■Water resistant Japanese Floor - Polish Industry Association Standards (JFPA Standards-1)
3), the following tests were conducted.

That is, 0 sample liquid was applied to the test piece (non-asbestos floor tile).
．． 1- is dropped onto the test piece, covered with a cover glass, and left to stand for 1 hour, after which the cover glass is removed and water droplets remaining on the test piece are sucked up. Then, the whitening state of the test piece after being left for 1 hour was visually evaluated. The display of this evaluation is as follows.

○: No change in the film, △: Slight change in the film, ×: Whitening of the film.

■Removability (peelability) Japan Floor Polish Industry Association Standards (JFPA Standards-1)
5), the following tests were conducted.

That is, non-asbestos floor tiles were used as flooring material, a sample solution was applied thereto, and after drying at room temperature for 30 minutes or more,
It was left at ℃ for 6 hours. Next, place one test piece in water at room temperature.
After soaking for an hour, the sample was taken out and left at 38° C. for 18 hours. Next, the film was immersed in a standard removal solution at 20° C. for 20 minutes, rinsed with running water, and air-dried to evaluate the state of film removal.

The display of this evaluation is as follows.

○: When the film is completely removed, X: When the film is not completely removed.

(4) Effects of Examples The composition of Comparative Example 1 had poor storage stability and could not be coated well as a sample, making it impossible to perform a performance test.

Furthermore, Comparative Examples 2.3 and 9 had poor removability, Comparative Examples 4 to 6 had poor water resistance, and Comparative Example 8 had poor heel mark resistance.

On the other hand, the compositions of Examples 1 to 5 have excellent water resistance, removability, heel mark resistance, gloss, and storage stability, and are very well-balanced. still,
In Example 6, except for slightly inferior water resistance and gloss, other performances were excellent.

From the above, the amount of aldehydes added is 0.52 to 1.49
In the range (Examples 1 to 5), particularly excellent performance is shown.

It should be noted that the present invention is not limited to those shown in the above-mentioned specific embodiments, and may be modified in various ways within the scope of the present invention depending on the purpose and use.

〔Effect of the invention〕

The polish composition of the present invention provides a tough film when applied to, for example, a floor, and at the same time can be easily peeled off (removed). That is, according to the present composition, a well-balanced polishing agent having excellent water resistance, removability (peelability), heel mark resistance, glossiness, and storage stability can be obtained.

Patent applicant: Yushiro Chemical Industry Co., Ltd. Agent
Patent attorney Kiyoji Kojima-22=

Claims (6)

[Claims] (1) (a) Acid value 20-80 containing carboxyl group
polyurethane resin emulsion, (b) acrylic resin emulsion containing carboxyl groups and having an acid value of 40 to 100, (c) wax emulsion, (d) 0.5 to 1.0 to the carboxyl group of the acrylic resin. A polish composition comprising a chemical equivalent of a zinc crosslinking agent and (e) an aldehyde. (2) (a) Acid value 20-80 containing carboxyl group
polyurethane resin emulsion, (f) a zinc crosslinked acrylic resin emulsion crosslinked with 0.5 to 1.0 chemical equivalents of zinc to the carboxyl group of the acrylic resin, (c) a wax emulsion, (d) A polishing composition comprising a zinc crosslinking agent and (e) an aldehyde in an amount of 0.5 to 1.0 chemical equivalents to the carboxyl group of an acrylic resin. (3) The polish composition according to claim 1 or 2, wherein the aldehyde is formalin or glyoxal. (4) The zinc crosslinking agent is a compound containing ammonia, and the amount of the aldehyde added is 0.5 to 1.5 mol per 1 mol of the ammonia contained in the zinc crosslinking agent. Items 1 to 3. The polishing agent composition according to items 1 to 3. (5) Add a zinc crosslinking agent of 0.5 to 1.0 chemical equivalents to the carboxyl group of the acrylic resin to the acrylic resin emulsion, and heat to a temperature equal to or higher than the glass transition point of the acrylic resin. A method for producing a polishing agent composition, which comprises adding an aqueous solution of aldehydes to a mixture of an emulsion obtained by crosslinking reaction, a polyurethane resin emulsion containing a carboxyl group, and a wax emulsion. (6) The method for producing a polish composition according to claim 5, wherein the aldehyde is formalin or glyoxal.