KR100326231B1 - Environmental acceptable acrylic-styrene copolymer and the polish compositions comprising the copolymer - Google Patents

Abstract

The present invention relates to an environmentally friendly acrylic-styrene copolymer and a brightener composition using the same. More particularly, the present invention has a core-shell multilayer structure and a core portion includes a high concentration of hydrophilic monomer and a shell. The part contains an acryl-styrene-based copolymer containing a relatively high concentration of hydrophobic monomer as a main component of the polishing composition, so that a multivalent cation such as zinc, zirconium or cadmium, which has been added and used for crosslinking in the manufacture of the polishing product The present invention relates to an acrylic-styrene-based copolymer having excellent durability and detergent resistance as well as excellent general properties required for other polishes, and a polisher composition using the same, without including heavy heavy metal ions.

Description

Environment-friendly acrylic-styrene copolymer and polish composition using the same {Environmental acceptable acrylic-styrene copolymer and the polish compositions comprising the copolymer}

The present invention relates to an environmentally friendly acrylic-styrene copolymer and a brightener composition using the same. More particularly, the present invention has a core-shell multilayer structure and a core portion includes a high concentration of hydrophilic monomer and a shell. The part contains an acryl-styrene-based copolymer containing a relatively high concentration of hydrophobic monomer as a main component of the polishing composition, so that a multivalent cation such as zinc, zirconium or cadmium, which has been added and used for crosslinking in the manufacture of the polishing product The present invention relates to an acrylic-styrene-based copolymer having excellent durability and detergent resistance as well as excellent general properties required for other polishes, and a polisher composition using the same, without including heavy heavy metal ions.

Polishing agents are functional chemical compositions widely used for interior and exterior surface treatment or polishing of furniture, automobiles, houses and industrial buildings, as well as a wide range of indoor and outdoor floor finishes such as PVC tiles, wooden floors, stone and cement floors. In addition, the gloss agent is used as an uninterruptible treatment agent for semiconductor equipment or as an invincible treatment agent for agricultural film production.

Gloss agents used for floors inside and outside buildings or building interior and exterior materials are typical surface treatment compositions used for the purpose of surface gloss of a substrate, scratch prevention, and slip prevention.

In general, the brightener composition contains an acrylic polymer as a main component and a polyvalent cationic heavy metal ion such as zinc, zirconium or cadmium as an ion binder. The polyvalent cationic heavy metal ions contained in the ion binder material are coated with a gloss agent by forming ionic bonds with various polar functional groups in the resin to give durability and detergent resistance, and after a period of use, the cationic heavy metal crosslinker is used by using an alkaline remover. By dissolving the ionic bonds, the resin can be removed by washing with water. However, since cationic heavy metal crosslinking agents are practically impossible to be recovered by separate methods during removal, they are dissolved in the wash water used during the removal process and are introduced into rivers or into sewage pipes, causing environmental pollution. In addition, the multivalent cationic heavy metal ions contained in the polisher may remain in the floor or air in a dusty state during use or after use, and may enter the human body and cause harmful damage to the human body. If it penetrates into the basement, the use of drinking water of groundwater contaminated with such heavy metals may also cause problems of inflow into the human body. In addition, when introduced into a river, organic deposits are formed by taking ionic bonds with various organic substances dissolved in water, which means that the cationic heavy metals are accepted to act as precipitants of organic substances. .

As described above, the polyvalent cationic heavy metal ions included in the manufacture of general polishes are also a problem of contamination of the heavy metals themselves, but they promote the deposition of organic matter, causing various pollutants to be continuously deposited and accumulated on the bottom of rivers or lakes. There is a seriousness in being a causative agent.

Therefore, the inventors of the present invention have a technique for producing a water-dispersible polymer without using any polyvalent cationic heavy metal ions which are inevitably used for improving the durability of the polish and increasing the detergent resistance while having a problem of environmental pollution, and the resin as a main component. Efforts have been made to produce environmentally friendly varnish compositions. As a result, a multistage polymerization process is performed in which the composition of the monomer mixture, that is, the mixing ratio of the polyfunctional / monofunctional monomer and the mixing ratio of the hydrophilic / hydrophobic monomer, is varied according to the polymerization progress in preparing the acrylic-styrene copolymer contained in the varnish composition. When the size of the prepared copolymer fine particles has a small particle size of about 0.1 ~ 0.5 ㎛ or less, and exhibited a fine and uniformly dispersed composition difference to realize the unique physical properties by completing the present invention.

Therefore, the present invention uses a monomer mixture containing a high concentration of hydrophilic monomers at the beginning of the polymerization reaction, and a emulsion of the core-shell multilayer structure obtained by emulsion polymerization using a monomer mixture containing a relatively high concentration of hydrophobic monomers at the end of the polymerization reaction. An object of the present invention is to provide an acryl-styrene copolymer and an environmentally friendly brightener composition having excellent durability and detergent resistance obtained by containing it as a main component.

The present invention has a core-shell multilayer structure, the core portion contains a relatively high proportion of hydrophilic monomers including polyfunctional hydrophilic monomers, and the shell portion contains a crosslinkable multimer monomer. An acrylic-styrene copolymer for a varnish composition, characterized in that the ratio of the hydrophobic monomer to be included in a relatively high concentration and the use of heavy metal ion crosslinking agent is excluded.

In addition, the present invention is another feature of the varnish composition containing 5 to 50% by weight (based on the solid content) of the acrylic-styrene copolymer of the core-shell multilayer structure as described above.

Referring to the present invention in more detail as follows.

The present invention provides a novel acryl-styrene copolymer having a core-shell multilayer structure composed of a core containing relatively high concentrations of hydrophilic monomers and a shell containing relatively high concentrations of hydrophobic monomers. In addition, the present invention relates to a gloss composition having excellent general properties required as a glossing agent as well as durability and detergent resistance even if no polyvalent cationic heavy metal ions are generally included as a crosslinking agent. That is, in the acrylic-styrene copolymer of the present invention, the shell containing relatively high hydrophobic monomer improves the durability and detergent resistance of the copolymer due to hydrophobicity, and the core containing relatively high hydrophilic monomer is alkaline water. Easily removed by being easily dissolved and removed when washing with. In particular, by controlling the mixing ratio of the polyfunctional / monofunctional monomer in each monomer mixture constituting the core and the shell, the durability and the detergent resistance can be improved more efficiently. The covalently branched structure of the copolymer acts to exert the effect of increasing the detergent resistance and durability by ionic crosslinking, which has been achieved by heavy metal ion crosslinking agents, and intensively contained in the core. The polyfunctional hydrophilic functional group makes the water solubility easier by the action of the ionic bonds by the alkaline detergent, thereby exhibiting the two opposite properties according to the respective operating conditions to produce a high performance water dispersible varnish resin excluding heavy metal crosslinking agents. Would be possible.

As a result, the acryl-styrene copolymer according to the present invention exhibits improved durability and detergent resistance without using a polyvalent cationic heavy metal ion which is inevitably included for improving durability and detergent resistance.

The production process of the acrylic-styrene-based copolymer of the core-shell multilayer structure according to the present invention is performed by a multi-step emulsion polymerization process of varying the composition and content of monomers according to the progress of polymerization. This multistage polymerization process in emulsion polymerization process can be effectively used to have a core-shell multilayer structure in the polymer particles to be polymerized together with the technique using the difference in the reactivity ratio of the polymer monomer. .

The synthesis method of the acrylic-styrene copolymer according to the present invention will be described in more detail as follows.

First, a hydrophilic monomer emulsion is prepared by dissolving a surfactant in deionized water and then adding and mixing a monomer mixture containing a relatively large amount of hydrophilic monomer under stirring. Separately, an initiator solution is prepared by dissolving the initiator in deionized water. Then, deionized water in which the surfactant is dissolved is heated to 50 to 90 ° C. under a nitrogen stream, and the hydrophilic monomer emulsion and initiator solution prepared above are added thereto while stirring. After the addition is continued, stirring is continued to form an additional core by emulsion polymerization.

The emulsion is cooled and hydrophobic monomer mixture and deionized water containing a relatively large amount of hydrophobic monomer prepared in advance are added thereto. The mixture is heated again to 50-90 ° C. to emulsify to form a shell. After the polymerization is completed, the emulsion polymer is cooled to room temperature, and ammonia water is added to adjust the polymer to weak alkali (pH 8.0 to 8.5).

In the emulsion polymerization process according to the present invention as described above, by using the core-shell multilayer structure forming technology, the copolymerization composition ratio of the monomer forming the core portion in the particle and the copolymer composition ratio of the monomer forming the shell portion of the particle shell Configure differently. In particular, the core portion of the copolymer particles to include a relatively high concentration of the hydrophilic monomer that is essentially included in the polyfunctional hydrophilic monomer, the shell portion of the outer shell of the particle in a relatively high concentration of the polyfunctional hydrophobic monomer Include it.

That is, the composition of the monomer mixture used to form the core at the beginning of the emulsion polymerization is composed of 3 to 30% by weight of the hydrophilic monomer and 70 to 97% by weight of the hydrophobic monomer, wherein the polyfunctional hydrophilic monomer is essentially included in the hydrophilic monomer. Preferably, the polyfunctional hydrophilic monomer is included in the range of 20 to 100% by weight based on the total hydrophilic monomer mixture used at the beginning of the polymerization. In addition, the composition of the monomer mixture to be used to form the shell at the end of the emulsion polymerization is preferably contained at 3% by weight or less, or more preferably at least 3% by weight of the hydrophilic monomer, wherein the hydrophobic monomer is multisynthetic (crosslinkable ) Monomers are essentially included, and the multisynthetic monomer is preferably included in the range of 0.1 to 2.0% by weight based on the monomer mixture used at the end of the polymerization.

As the polyfunctional hydrophilic monomer to be used in the emulsion polymerization process according to the present invention, itaconic acid, fumaric acid, maleic acid, muconic acid, aconic acid One or more carboxylic acid groups are selected from the compound containing two or more, and it is more preferable to use itaconic acid, fumaric acid, maleic acid as the polyfunctional hydrophilic monomer.

The monofunctional hydrophilic monomer is selected from compounds containing one carboxylic acid group such as acrylic acid, methacrylic acid, crotonic acid, and hydroxyethyl methacrylate, and is used in combination with one or more of them. Preferably, acrylic acid and methacrylic acid are used.

As the multisynthetic monomer, one or more selected from divinylbenzene, butadiene, dimethylbutadiene and methylenediphenylene bismaleide is preferably used together.

As the monofunctional hydrophobic monomer, styrene, acrylic, α-olefin, acrylonitrile, allyl and other vinyl monomers may be used, but it is preferable to use styrene monomer and acrylic monomer. Examples of the styrene monomers include styrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, and 3,5-dimethylstyrene. Preference is given to using one or more selected from among pt-butylstyrene, and more preferably using a styrene or p-methylstyrene monomer. The acrylic monomer is preferably used at least one selected from methyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl It is more preferable to select and use among methacrylate, butyl methacrylate, methyl acrylate or butyl acrylate.

In addition, in performing the emulsion polymerization according to the present invention, a commonly used molecular weight regulator, more specifically, mercaptan, which is well known as a molecular weight lowering agent, may be used, which is 0.1 to 3.0 weight based on the total amount of monomers used. It is appropriate to add%, and it is also possible to add a different content in the multistage polymerization process.

In addition, the surfactants used for stabilizing the water dispersion of the resin particles may be a known anionic or nonionic surfactant compound, but nonionic surfactants have a large size of the resulting emulsion particles and stabilize relative water dispersion. Since the effect is low, it is more preferable to use anionic surfactant. Such a surfactant is preferably used 1 to 10% by weight based on the total amount of the monomers. If the surfactant is used below the above range, the stability of the water-dispersed particles in the polymerization system is lowered to form a polymer lump or the particles are excessively enlarged, and the leveling to the subject is poor after the formation of the varnish composition. Problems may arise. On the other hand, when the content of the surfactant exceeds the above range, bubbles are excessively generated in the polymerization process, there is a problem that the wear resistance is reduced and the water resistance is weakened after coating the coating.

In the present invention, the polymerization initiator uses a water-soluble radical initiator in the emulsion polymerization process, it is more preferable to use a persulfate compound or a peroxide compound, the half-life at the polymerization temperature is selected from 0.3 to 30 hours to select one or more Particular preference is given to using. In particular, by using different kinds of polymerization initiators according to the progress of polymerization in the multi-stage polymerization process, it is possible to optimize the effect of the coarse polymerization conditions. It is preferable to use 0.2-3.0 weight% of such initiators with respect to the total amount of monomers used.

It is preferable to superpose | polymerize in the temperature range of normal temperature-120 degreeC, and, as for superposition | polymerization temperature, in the characteristic of the superposition | polymerization process which uses water as a dispersion solvent, it is more preferable to superpose | polymerize in 50-90 degreeC temperature range.

The copolymer of the present invention produced by such emulsion polymerization has a multi-layer structure of core-shell, and the size of the particles is usually made of fine particles having a diameter of about 0.2 to 0.5 μm or less and fine and uniform. It is possible to produce varnishes that exhibit unique physical properties through dispersed compositional differences.

On the other hand, the brightener composition according to the present invention contains the acrylic-styrene copolymer, polyolefin wax, alkali-soluble resin, and film forming aid or plasticizer. In addition, antifoaming agents, wetting agents, preservatives, coloring agents, pH buffers, viscosity regulators, antioxidants UV stabilizers, dispersion stabilizers, antistatic agents, anti-slip agents, fluorescent agents and the like can be added to the varnish composition.

The acrylic-styrene copolymer contained in the varnish composition according to the present invention is preferably contained in the range of 5 to 50% by weight (based on solids content). If the content is less than 5% by weight, the durability of the varnish is weak. In addition, if the content exceeds 50% by weight, the spreading (leveling) at the time of applying the varnish worsens and may cause problems such as clouding (powdering) may occur is not preferable.

The varnish composition may contain polyolefin waxes as known to impart buffering to the gloss surface, and such extreme hydrophobic polymer waxes often introduce polar groups by thermal oxidation to achieve water dispersion stability effects. Emulsified products of oxidized polyolefin waxes are used. The polyolefin wax is added to the varnish composition to suppress the surface damage of the varnish film due to frequent mechanical shock and friction, especially in the floor varnish, by the buffer effect, and consequently to increase the durability by increasing the friction and abrasion resistance against shoe marks and surface drag. In addition, it gives glossiness. The polyolefin wax may be contained in an amount of 80 wt% or less (based on solids content) in the total gloss composition, and the composition content of the wax may vary greatly depending on the material and the expected effect of the floor and the gloss base.

Typically, the non-buffering varnish composition contains less than 15% by weight of wax (based on solids content), and the high-buffering varnish composition contains more than 65% by weight of wax (based on solids).

Alkali-soluble resins used to increase the surface uniformity and peelability of the varnish composition are not essential to the varnish composition of the present invention, but may be used in the range of 5 wt% or less (based on solids content), depending on the application. .

In addition, film forming aids and plasticizers widely used in the manufacturing of the varnish composition may also be used in the range of 1 to 10% by weight (based on solids content) when preparing the varnish composition of the present invention. The oligomer type ethylene glycol compound which has, diethylene glycol ethyl ether, dipropylene glycol ethyl ether, etc. are used, and tributoxy ethyl phosphate is mainly used as a plasticizer.

In addition, a foam inhibitor for suppressing the foaming of the varnish composition and the generation of foam marks formed on the varnish film after drying can be used, and is representative as a wetting agent for increasing the application flowability of the varnish solution to the base when applying the varnish. Organic fluorine compounds can be used. In addition, the addition of preservatives to suppress the growth of microorganisms, flavoring fragrances at work or after work or colorants to obtain a suitable coloring effect, pH buffers to adjust pH, viscosity regulators, antioxidants, UV stabilizers, dispersion stabilizers, Static generating inhibitors, anti-slipsing agents, fluorescent agents and the like are included in the compositions as functional additives to produce certain effects.

Although this invention is demonstrated in detail based on a manufacture example and an Example, this invention is not limited by an Example.

Preparation Examples 1-3: Copolymer Preparation of Core-shell Multi-layer Structure

First, prepare a 2-liter three-necked flask with motor agitation for one-stage polymerization, dissolve 7.5 g of surfactant (Steol CA-460, manufactured by Stefan) in 150 ml of deionized water and stir itaconic acid, methacrylic acid, styrene, methyl Methacrylate and butyl acrylate were added in the amounts as listed in Table 1 to prepare a monomer emulsion.

Separately, a 1 L three-necked flask was prepared and 30 g of surfactant (Steol CA-460) and 1.5 g of ammonium sulfate initiator were dissolved in 250 ml of deionized water to prepare an initiator solution.

Then, prepare a 5 L reactor equipped with a cooling tube, a motor stirrer, a thermometer, and a funnel connected with a nitrogen injector, and add 450 ml of deionized water in which 1.5 g of surfactant (Steol CA-460) was dissolved. The monomer emulsion and initiator solution prepared beforehand were dripped little by little under motor stirring over about 2 hours, heating to 85 degreeC under airflow, and maintaining temperature. After the addition was completed, the reaction was further advanced by stirring for 40 minutes.

The reactor temperature was then cooled to 50 ° C. and a two stage monomer mixture and 25 mL of deionized water were administered. In the monomer mixture of the second step, 300 ml of deionized water and 15 g of a surfactant (Steol CA-460) were added, and divinylbenzene, styrene, and methyl methacrylate were added to the contents shown in Table 1. When the two-stage monomer mixture was administered, a solution of 2 g of t-butylhydroperoxide dissolved in deionized water was administered together.

After maintaining the temperature of the polymerization reactor at 85 ° C. for one hour, cooling to room temperature, and adjusting the pH to a weak alkali (pH 8.0 to 8.5) using 10 to 20 ml of ammonia water for an environmentally friendly brightener composition. The main component resin was prepared.

Preparation Comparative Examples 1-2: Preparation of Homogeneous Copolymer Without Polyfunctional Monomer

A one-step emulsion polymerization process using the same monomer composition as Preparation Examples 1 to 3 was carried out, but a homogeneous acrylic-styrene copolymer was prepared without using a multifunctional copolymer monomer (including a polypolymer monomer).

To this end, first, prepare a 4-liter three-necked flask capable of motor stirring, dissolve 23 g of surfactant (Steol CA-460) in 800 ml of deionized water, and stir with methacrylic acid, styrene, and methyl methacrylate to the contents shown in Table 1. Rate and butyl acrylate were added to prepare a monomer emulsion.

Separately, a 1 L three-necked flask was prepared by dissolving 54 g of surfactant (Steol CA-460) and 5 g of ammonium persulfate initiator in 450 ml of deionized water to prepare an initiator solution. Thereafter, 450 ml of deionized water in which 1.5 g of surfactant (Steol CA-460) was dissolved was added to the 5 L reactor of Preparation Examples 1 to 3, followed by heating to 85 ° C. under nitrogen stream for about 4 hours. The monomer emulsion and initiator solution prepared in advance were added dropwise in small portions under motor agitation, and stirred for 1 hour after completion of the dropwise to further proceed with the reaction.

After the temperature of the polymerization reactor was adjusted to 85 ° C. and maintained for 1 hour, the temperature of the solution was cooled to room temperature and the pH was adjusted to a weak alkali (pH 8.0 to 8.5) using 10 to 20 ml of ammonia water. A principal component resin was prepared for the brightener composition.

Examples 1-3, Comparative Examples 1-2: Preparation of a varnish composition

Copolymer resins prepared in the above Preparation Examples and Comparative Examples, and various additives such as polyolefin wax buffers, alkali-soluble resins, plasticizers, film forming aids, foam inhibitors, wetting agents, preservatives, viscosity regulators, dispersion stabilizers, slippers, etc. Next, as shown in Table 2, by mixing in a content ratio to prepare a brightener composition.

The varnish composition thus prepared was applied to a corridor with a PVC tile floor. Based on the PVC tile floor surface of 1 m in width and 2 m in length, a coating using a general rotary pad was applied once, followed by drying for 2 hours, followed by one additional coating with the same polish composition, followed by drying to prepare a test evaluation specimen. .

In order to test the black heel resistance by the fabricated specimens, the test was carried out for one week in the area where the daily traffic volume was 500 people or more, and then the number of black heel marks and the trace clarity were evaluated. For other evaluation items, the relevant test methods specified in ASTM and KS were used. Each test method is as follows.

-Test evaluation method

(1) Glossiness: Method using the glossmeter of ASTM D1455 and KS 2743 (visible light source,

60 ° angle).

(2) Detergent resistance: It evaluated by the method according to ASTM D3207.

(3) Removal characteristics: evaluated in accordance with ASTM D1792.

(4) Water stain resistance: It evaluated by the method according to KS 2743.

As described above, the present invention provides a resin having excellent properties in all the required physical properties without the use of heavy metal ion crosslinking agent in the production of a polymer resin for a brightener, as well as the safety of manufacturers and handlers of a brightener composition, It is an environmentally friendly product that prevents indoor air pollution and groundwater contamination after removal of polish, and organic matter accumulation in rivers and lakes.It can be used for furniture polishes and automobile polishes by various changes in composition additives. have.

Claims (8)

It has a core-shell multilayer structure, the core portion contains a relatively high proportion of hydrophilic monomers including polyfunctional hydrophilic monomers, and the shell portion includes hydrophobic polymers containing crosslinkable multimer monomers. Acrylic-styrene copolymer for a varnish composition, characterized in that the proportion of the monomer is contained in a relatively high concentration. According to claim 1, wherein the hydrophilic monomer is one or two or more monofunctional hydrophilic monomers selected from acrylic acid, methacrylic acid, crotonic acid and hydroxy ethyl methacrylate and itaconic acid, fumaric acid, maleic acid, yukon acid and aconic acid Acrylic-styrene-based copolymer for a varnish composition, characterized in that a mixture of one or two or more polyfunctional hydrophilic monomers selected from. The method according to claim 1, wherein the hydrophobic monomer is styrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3, One or two or more styrene monomers selected from 5-dimethylstyrene and pt-butylstyrene; One or two or more acrylic monomers selected from methyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and decyl acrylate; And a mixture of one or two or more crosslinkable multimer monomers selected from divinylbenzene, butadiene, dimethylbutadiene and methylenediphenylenebismaleimide. delete Glossy composition, characterized in that 5 to 50% by weight (based on the solid content) of the acrylic-styrene-based copolymer of the core-shell multilayer structure of claim 1. Iii) The solution in which the surfactant is dissolved is kept at 50 to 90 DEG C, and the solution is composed of 3 to 30% by weight of hydrophilic monomer and 70 to 97% by weight of hydrophobic monomer as a one-stage monomer mixture. Forming a core by emulsion-polymerizing the hydrophilic monomer mixture containing 20 to 100% by weight of the total hydrophilic monomer and the initiator solution while stirring and adding the hydrophilic monomer; Ii) after the polymerization of the polymer, a two-stage monomer mixture comprising 2% by weight or less of hydrophilic monomers and 98% by weight of hydrophobic monomers, including a hydrophobic monomer mixture containing 0.1 to 2.0% by weight of a crosslinkable multipolymer monomer; Adding deionized water, followed by emulsion polymerization at a polymerization temperature of 50 to 90 ° C. to form a shell; And, Iii) A method of producing an acrylic-styrene copolymer for a varnish composition, characterized in that the emulsion polymer is cooled to room temperature and adjusted to weak alkali (pH 8.0 to 8.5) using ammonia water. The method of claim 6, wherein the surfactant is used in combination with anionic surfactants alone or in combination with nonionic surfactants. The method according to claim 6, wherein the initiator is at least two selected from persulfate compounds and peroxide compounds using an initiator prepared as a separate type for each polymerization step, and using 0.2 to 3.0% by weight relative to the total amount of the monomer mixture A method for producing an acrylic-styrene copolymer for a varnish composition.