JPH04154878A - Lustering agent composition - Google Patents

Abstract

PURPOSE:To obtain the title composition having high luster and high wear resistance, etc., by blending an emulsified copolymer comprising an ethylenic unsaturated monomer, an ethylenic unsaturated carboxylic acid monomer and a specific oligomer with a specific amount of a wax emulsion CONSTITUTION:(A) 100 pts.wt. emulsified copolymer comprising (i) 94-70 pts.wt. ethylenic unsaturated monomer, (ii) 5-20 pts.wt. ethylenic unsaturated carboxylic acid monomer copolymerizable with the monomer of the component (i), and (iii) 1-10 pts.wt. oligomer obtained by reaction between an urethane prepolymer containing an isocyanate group at one end or both ends and an active hydrogen- containing ethylenic unsaturated monomer, is blended with (B) 10-20 pts.wt., calculated as solid content, of wax emulsion such as olefin-based unsaturated polymer or natural wax to give the objective composition suitable for polishing the surface of interior materials such as floor covering materials and wall covering materials.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention mainly relates to a polishing agent composition used for polishing the surface of interior materials such as flooring and wall materials.

[Background of the invention]

-1= This type of polish requires high gloss, high abrasion resistance, high stain resistance, high black heel mark resistance (resistance to markings caused by shoe soles), ease of peeling, etc. Conventionally, acrylic synthetic resin emulsions have been provided to meet such required performance.

However, the acrylic synthetic resin emulsion does not have sufficient black heel mark resistance, adhesion, and abrasion resistance, and requires frequent reapplication.

[Conventional technology]

In order to improve the drawbacks of the above-mentioned acrylic synthetic resin emulsion, a polishing agent composition in which the acrylic synthetic resin emulsion is mixed with a polyurethane emulsion has been proposed (Japanese Patent Publication No. 53-22548). However, when a polyurethane emulsion is mixed with the acrylic synthetic resin emulsion, although the black heel mark resistance and abrasion resistance are improved, the gloss is poor, and unevenness tends to occur during peeling, making reapplication laborious. Ru.

Therefore, in order to improve the compatibility between acrylic synthetic resin and polyurethane, it has been proposed to emulsion polymerize acrylic synthetic resin in a polyurethane emulsion (JP-A-62-23086, JP-A-63- 305
No. 80).

[Problem to be solved by the invention]

However, even if acrylic synthetic resin is emulsion polymerized in a polyurethane emulsion, the mechanism by which polyurethane and acrylic synthetic resin are functionally linked has not been elucidated, and fundamentally the acrylic synthetic resin and polyurethane are simply microblended. There is no change in compatibility, and no clear significant difference is observed between a simple mixture of an acrylic synthetic resin emulsion and a polyurethane emulsion. When such acrylic synthetic resins are simply mixed or microblended, the resulting coating film has a "sea" or "island" structure, and the individual properties of the acrylic synthetic resin and polyurethane do not overlap, and the mixing ratio Components with a large amount form a "sea" structure, and the properties of the coating film are determined by these components.

[Means to solve the problem]

The present invention, as a means for solving the above-mentioned conventional problems,
94 to 70 parts by weight of ethylenically unsaturated monomer A, 85 to 20 parts by weight of ethylenically unsaturated carboxylic acid monomer copolymerizable with ethylenically unsaturated monomer A, and isocyanate 1 at one or both ends. The solid content of the wax emulsion is based on 100 parts by weight of an emulsion copolymer consisting of 01 to 10 parts by weight of an oligomer obtained by the reaction of a urethane prepolymer having - groups and an ethylenically unsaturated monomer having active hydrogen. The object of the present invention is to provide a polishing agent composition obtained by adding 10 to 20 parts by weight in terms of conversion.

The present invention will be explained in more detail below.

[Ethylenically unsaturated monomer A] As the ethylenically unsaturated monomer A used in the present invention, methyl, ethyl, which is an alkyl group having 1 to 20 carbon atoms,
(Meth)acrylic acid esters such as propyl, butyl, cyclohexyl, lauryl, dodecyl, stearyl, etc., 2-hydroxyethyl, 2-hydroxypropyl,
Hydroxyl group-containing vinyl monomers such as (meth)acrylic acid esters, aromatic vinyl monomers such as styrene, α-methylstyrene, and vinyltoluene, (meth)acrylonitrile, (meth)acrylamide and its derivatives, Examples include vinyl monomers such as vinyl chloride, vinylidene chloride, vinyl acetate, and vinyl propionate. Two or more of the above monomers A may be used in combination in a predetermined ratio in order to obtain a desired coating film hardness.

[Ethylenically unsaturated carboxylic acid monomer B1 Examples of the ethylenically unsaturated carboxylic acid monomer B used in the present invention include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, etc. . Two or more of the above monomers B may be used in combination.

[Oligomer C] Oligomer ○ is obtained by the reaction of urethane prepolymer C□ having an isocyanate group at one or both ends and ethylenically unsaturated monomer C2 having active hydrogen. The urethane prepolymer C□ is obtained by reacting an isocyanate with a polyhydroxy compound. Isocyanates used in the urethane prepolymer C□ include 2.4-tolylene diisocyanate, 2.6-tolylene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (MDI), m-xylylene diisocyanate, and p-xylylene diisocyanate. Diisocyanate (XDI), hexamethylene diisocyanate (HDI)
), isophorone diisocyanate (,IPDI), )-
Limethylhexamethylene diisocyanate (TMHMD)
Diisocyanates such as I) are exemplified, and polyhydroxy compounds include so-called polyether polyols such as polyesters, poly(oxypropylene ether) polyols, and poly(oxyethylene-propylene ether) polyols. The above polyester is generally manufactured from a polybasic acid and a hydroxyl compound,
The polybasic acid usually used is phthalic acid, tetrahydrophthalic anhydride, adipic acid, double sulfuric acid, maleic acid, etc., and the hydroxyl compound usually used is ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, trimethylol. Propane, hexanetriol, glycerin, trimethylolethane, pentaerythritol, etc. are used. Furthermore, as the polyether polyol, polyoxypropylene glycol, poly(oxypropylene) poly(oxyethylene) glycol, poly(oxybutylene) glycol, poly(oxytetramethylene) glycol, etc. are usually used. And the above urethane prepolymer C
In order to arrange an isocyanate group at one end or both ends of 1, 1 mol or more of the above-mentioned isocyanate is reacted with 1 mol of the above-mentioned polyhydroxy compound. The monomer C2 is a hydroxyl group-containing monomer such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, allyl alcohol, or a carboxyl group such as monomer B. Examples include amide group-containing monomers such as acrylamide and methacrylamide, and amino group-containing monomers such as dimethylaminoethyl acrylate and dimethylaminoethyl methacrylate.

In order to produce the above oligomer C, the isocyanate indicated above is reacted with the above polyhydroxy compound in an anhydrous state to produce a urethane prepolymer C□.

Then monomer C2 is reacted. The amounts of the isocyanate, the polyhydroxy compound, and the monomer C2 to be charged are usually in a molar ratio of 215/1.010.8 to 1.0. Further, as a reaction catalyst, a tin-based or amine-based catalyst is usually used.

[Emulsion Copolymer] The above-mentioned monomer A, monomer B, and oligomer C are emulsion copolymerized by a conventional method. That is, the above-mentioned monomer A, monomer B, and oligomer 〇 are mixed, and the above-mentioned monomer mixture is converted into =8- ammonium persulfate by using an anionic emulsifier or an anionic-nonionic mixed emulsifier in an aqueous solvent. , potassium persulfate, perboric acid 1~
Emulsion polymerization is carried out using a radical initiator such as lithium.

In the emulsion polymerization, monomer A is used in an amount of 94 to 70 parts by weight, monomer B is used in an amount of 5 to 20 parts by weight, and oligomer C is used in an amount of 1 to 10 parts by weight.

[Preparation of polish composition] The polish composition of the present invention is prepared by adding 10 to 20 parts by weight of wax emulsion in terms of solid content to 100 parts by weight of the emulsion copolymer. . The wax emulsion used in the present invention is an emulsion of one or a mixture of two or more of natural waxes, synthetic waxes, olefinically unsaturated polymers, slip agents, etc., and typical examples thereof include a molecular weight of 3,000 to 15,000.
Examples include wax emulsions of non-oxidized polyethylene or oxidized polyethylene having a density of 0.92 to 0.99 and a softening point of 100 to 140°C.

[Second component] 19= In the polish composition of the present invention, the third component further includes an alkali-soluble resin, a plasticizer, a coalescing agent, a surfactant,
Antifoaming agents, preservatives, etc. may be added as necessary. The alkali-soluble resin contributes to the leveling of the formed coating film by uniformly dispersing the emulsion copolymer and the wax emulsion, and examples of the alkali-soluble resin include rosin/maleic acid derivatives, styrene/anhydride, etc. Examples include maleic acid copolymers and carboxyl-modified acrylic low molecular weight polymers. The above-mentioned alkali-soluble resin has a solid content of 3 to 1, based on the polishing agent composition of the present invention.
Preferably, it is added in an amount of 5% by weight.

[Effect]

In the polishing agent composition of the present invention, a wax emulsion is added to 100 parts by weight of the emulsion copolymer consisting of 94 to 70 parts by weight of the monomer A, 85 to 20 parts by weight of the monomer, and 1 to 10 parts by weight of the oligomer C. The above emulsion copolymer has a urethane bond derived from oligomer 〇 in the polymer side chain, so it has high wear resistance, high stain resistance, and high stain resistance. While exhibiting black heel mark resistance, it has much better gloss than conventional mixtures. Furthermore, when the above oligomer C is made by reacting monomer C2 with the isocyanate groups at both ends of a urethane prepolymer C1, the copolymer forms a crosslinked structure with urethane bond chains, greatly improving water resistance. do. In conventional acrylic synthetic resin emulsions, carboxyl groups are introduced into the polymer and a cross-linked structure is formed between the carboxyl groups using divalent or higher metal salts such as zinc or zirconium, metal complexes, or metal chelates to achieve water resistance. However, increasing the amount of carboxyl groups to increase the crosslinking density leads to a decrease in the gloss of the coating film, but as described above, the present invention has a crosslinked structure with urethane bond chains, so the crosslinking density Even if the value is increased, the gloss of the coating film does not decrease.

Since the emulsion copolymer further contains a carboxyl group derived from monomer B, the coating film can be easily peeled off and good recoating workability can be obtained. However, if the monomer B is used in less than 5 parts by weight, the peelability will be insufficient, and if it is more than 20 parts by weight, the water resistance will be adversely affected. As described above, in the emulsion copolymer of the present invention, since the carboxyl group does not participate in the formation of a crosslinked structure, the amount of monomer B can be limited to an amount that does not adversely affect water resistance.

In the polish composition of the present invention, the wax emulsion imparts smoothness to the coating film and improves durability such as gloss retention, stain resistance, abrasion resistance, etc., but if it is less than 10 parts by weight, the above effects will be reduced. The paint film is easily smudged and scratched by friction, resulting in poor gloss retention.If the wax is more than 20 parts by weight, the wax will be released from the paint film, and the released wax will peel off over time. This results in a disadvantage that the glossiness decreases and the function as a polishing agent is lost.

〔Example〕

[Synthesis of oligomer CNo. 1] 1.0 mol of adipic acid and 1.2 mol of 2,2-dimethyl-1,3-propanediol were charged into a 2Q flask.
Heated at 200℃ for 15 hours with stirring to give an acid value of 0.6.
(KOH■/g), the reaction was stopped and the mixture was cooled to obtain a hydroxyl value of 55.6 (KOH■/g). The number average molecular weight of this polyester diol was 1220 (measured using high performance liquid chromatography). Next, 3 moles of 2.4-)-lylene diisocyanate were added to 2 moles of this polyester diol and stirred at a temperature of 60 to 90°C. When the remaining isocyanate group was 1.8% by weight, 2-
2 moles of hydroxyethyl acrylate and MEHQ (
0.04% by weight of monomethyl ether hydroquinone)
was added and stirred at room temperature to 50°C for 8 hours, and the reaction was terminated when 0.2% by weight of isocyanate groups remained. In this way, oligomers No. 1 having the structure of neopentyl adipate tolylene diisocyanate diacrylate having an average molecular weight of 1200 were obtained.

[Synthesis of Oligomer C No. 2] Using the same method as the synthesis method of Oligomer No. 1, 1.5 mol of isophorone diisocyanate was added to 1 mol of poly(propylene oxide) diol having an average molecular weight of 800, and then 1 mol. An oligomer CNo.2 to which 2-hydroxyethyl acrylate was bonded was obtained.

[Synthesis of Oligomer C No. 3 Using a method similar to the synthesis method of Cooligomer C No. 1, 1 mol of poly(propylene oxide) diol with an average molecular weight of 1000 was mixed with 1 mol of hexamethylene diisocyanate.
．． After addition of 5 moles, oligomer C No. 3 was obtained in which 1 mole of 2-hydroxyethyl methacrylate was bound.

Example 1 Polymerization of a homogeneous acrylic copolymer emulsion was carried out in a 2Q flask equipped with a stirrer, a thermometer, a catalyst inlet, a nitrogen inlet, a pre-emulsion dropping inlet, and a reflux condenser, and the flask under a nitrogen atmosphere. In 300 g of deionized water heated to 60°C, oligomer CNo consisting of 108 g of butyl acrylate, 232 g of methyl methacrylate, 52 g of methacrylic acid and the previously synthesized neopentyl adipate tolylene diiso=14-cyanate diacrylate,
], 270 g of deionized water, and 5 g of sodium lauryl sulfate as an emulsifier were made into a pre-emulsion, and 2 g of ammonium persulfate as a catalyst was dissolved in 30 g of deionized water, and both were added dropwise from separate ports over a period of 3 hours. . The polymerization temperature is maintained at 84° C. and the reaction proceeds. After completion of pre-emulsion dropping and maintaining at 85°C for 30 minutes 2
Cool to 5°C.

In this way, a homogeneous acrylic copolymer emulsion containing oligomers No. 1 and No. 1 having urethane bonding chains and having a solid content of 40% was produced.

Examples 2 to 6 and Comparative Examples 1 and 2 In Examples 2 to 6, emulsions were prepared in the same manner as in Example 1 according to the monomer and oligomer C blending ratios shown in Table 1. In Comparative Examples 1 and 2, samples were also prepared using a known method.

MMA=Methyl Methacrylate ST-Styrene MAA-Methacrylic Acid [Physical Properties Testco These emulsions were tested for physical properties testing according to the floor polish formulations shown below.

(Left below) 1G - Floor polish formulation *1: Polyethylene wax emulsion Toho Chemical) 1
ytecE-4B! 2=Rosin-maleic acid copolymer Z
ecolac 802 (Zigler Chemical & Mineral Co., Ltd.) 15% alkaline aqueous solution *3 Nitributoxyethyl phosphate *4 = diethylene glycol 1,000 ethyl ether, *5: Fluorine thread surfactant FC-129 Sumitomo 3M *: 5WS-121 (Stauffer-ua
*7: The results of the formalin 37% aqueous solution physical property test are shown in Table 2.

Physical property test method The tests were conducted in accordance with the Japan Floor Polish Industry Association JFPA standards.

Items not specified in the above standards were determined using the following method.

■, Storage stability: JFPA standard-03◎: Excellent, ○:
Good, Δ: Average, X: Bad 2, Glossiness:, IFPA
Standard-04 (Gloss measuring device conforms to JTS-Z874)
◎: Excellent, O: Good, Δ: Average, X: Bad 3, Water resistance
: JFPA Standard-06 ◎: Excellent, 0: Good, △: Fair, ×: Bad 4, Removability: JFPA Standard-07 ◎: Excellent, ○: Good, △: Average, X: Bad 5, Detergent resistance: JFPA Standard-08 ◎: Excellent, ○: Good, △: Average, ×: Bad -18 = 6, Leveling property: Visually evaluate the leveling state of the coated test panel according to the gloss measurement method.

◎: , 0: Good, Δ: Fair, ×: Bad 7. Reapplyability: Reapplyability is visually evaluated to see if the base is re-emulsified during the second application.

@: Excellent, O: Good, Δ: Average, ×: Bad 8, Black heel mark resistance: JFPA standard test panel, coated on standard white tile according to gloss measurement method, is attached to Snell capsule type device. Get 6 heels (black). After spinning for 10 minutes, the tile is removed and the state of adhesion of the black heel mark is visually evaluated.

◎: Excellent, O: Good, Δ: Average, X: Bad 9, Durability
: A test panel coated according to the gloss measurement method is laid out on the laboratory floor and walked repeatedly. Visually evaluate the surface condition after one month.

◎: Excellent, ○: Good, Δ: Fair, ×: Bad Looking at Table 2, Comparative Example 1, which contains only an acrylic copolymer emulsion that does not contain oligomer 〇, has better gloss, water resistance, and
It is recognized that the black heel mark resistance is poor and the durability is extremely poor. Comparative Example 2, in which a polyurethane emulsion was mixed with an acrylic copolymer emulsion containing no oligomer C, showed some improvement in water resistance and black heel mark resistance, but did not have sufficient gloss and durability.

〔Effect of the invention〕

Therefore, the polish composition of the present invention provides a coating film having high gloss, high abrasion resistance, high stain resistance, high black heel mark resistance, and easy peelability.

The polishing agent composition of the present invention is useful for imparting luster to metal surfaces such as bronze and stainless steel, wood, polished stone, linoleum containing natural stones such as marble, artificial stones, plastic tiles such as vinyl tiles, etc. Particularly useful.

Patent applicant: Japan Acrylic Chemical Co., Ltd. r?・　－・

Claims (1)

[Claims] 94 to 70 parts by weight of an ethylenically unsaturated monomer A, 5 to 20 parts by weight of an ethylenically unsaturated carboxylic acid monomer B copolymerizable with the ethylenically unsaturated monomer A, and an isocyanate group at one or both ends. A wax emulsion is added in terms of solid content to 100 parts by weight of an emulsion copolymer consisting of 1 to 10 parts by weight of oligomer C obtained by the reaction of a urethane prepolymer having Polishing agent composition obtained by adding 10 to 20 parts by weight