KR20040107976A - The Method for Manufacturing of Emulsion Polymerization Resin for Antifog coating - Google Patents

Abstract

PURPOSE: Provided is a method for preparing emulsion polymer resin for anti-fog coating used in glasses, glass for cars and greenhouses, mirrors for bathroom or the like, which has excellent transparency, coating surface hardness, weather resistance, heat resistance, coating adhesion and anti-static property. CONSTITUTION: The method for preparing emulsion polymer resin for anti-fog coating comprises the steps of: mixing 20-50 wt% of a hydrophilic monomer, 1-40 wt% of a copolymerizable monomer, 0.1-5 wt% of a crosslinking agent, 0.05-5 wt% of a polymerization initiator and 50-80 wt% of a solvent; and interrupting the polymerization reaction when the reaction is performed to a prepolymerization degree, adding 0.01-2 wt% of an anti-polymerizing agent and 0.05-2 wt% of a polymerization initiator to form a coating agent, and performing coating and heat treatment, followed by polymerization.

Description

The Method for Manufacturing of Emulsion Polymerization Resin for Antifog coating

The present invention relates to a method for producing an emulsion polymerization resin for anti-fog coating, and more particularly, to have transparency, weather resistance, UV protection, heat resistance, and excellent antistatic property depending on the use while having excellent transparency and improved anti-fog property. It can be advantageously used for automobile glass, eyeglass lens, greenhouse glass, bathroom mirror and agricultural vinyl house where these physical properties are required, and it does not generate frost and keeps clear and transparent all day long. It is not only excellent in hardness of coating surface but also thin in coating layer, it can maintain high hydrophilicity and adhesion of coating film over long period of time and can suppress the decrease of hydrophilicity and coating film adhesion even under physical external force or high temperature and humidity conditions. Surface hardness improves adhesion The present invention relates to the antifogging method for producing a resin for coating the emulsion polymerization has the effect.

In general, glass or transparent plastics are divided into mirror glass, automobile glass, glasses glass, window glass, optical glass, and other special glass according to their use. Depending on the cloudy steaming, there is discomfort to block the view.

As the anti-fog method for such glass or plastic products, the following methods have been mainly used.

First, there is a method of coating a surfactant, second, a method of coating a mineral hydrophobic material (water repellent) such as silicone oil, and third, a method of coating a hydrophilic resin.

However, the surfactant method is an extremely temporary effect, and in the case of glasses, it may cause eye irritation and side effects due to skin contact. Also, since the method of coating silicone oil is a method using water repellency, the oil may be volatilized. Its function is extinguished, and there is a problem that the effect is remarkably decreased when there is much contact of moisture. However, some of the hydrophilic resins in the market are UV-curable resins, and the antifogging effect is weak, and in the case of the vinyl house, the physical properties of the surface are not suitable for coating.

SUMMARY OF THE INVENTION The present invention has been made to solve various problems as described above. The object of the present invention is to fully exhibit the value of use and commerciality by maintaining the required physical properties. It is attached to various glass and mirrors such as a cover to prevent fog caused by humidity or temperature difference, or attached to various mirrors such as a side mirror of a car to prevent condensation of water droplets on the mirror surface due to rain. It is to provide a method for producing an emulsion polymerization resin for anti-coat.

In order to achieve the above object, the method for producing an antifogging coating emulsion resin of the present invention includes 20 to 50% by weight of a hydrophilic monomer, 1 to 40% by weight of a monomer for copolymerization, 0.1 to 5% by weight of a crosslinking agent, and polymerization. 0.05-5% by weight of the initiator, 50-80% by weight of the solvent, the reaction was stopped at the degree of prepolymerization in the form of oligomer, and then 0.01-0.2% by weight of the polymerization inhibitor and 0.05-2% by weight of the polymerization initiator were added. After the production of the coating agent, and then characterized in that it comprises a step of polymerization through the actual coating and heat treatment process.

On the other hand, another production method of the emulsion polymerization resin for anti-fog coating of the present invention, 20 to 50% by weight of the hydrophilic monomer, 1 to 40% by weight of the monomer for copolymerization, 0.1 to 5% by weight of the crosslinking agent, 0.05 ~ polymerization initiator 5 weight%, 50-80 weight% of solvents are mixed, and the polymerization is completed, and the polymerization reaction is completely terminated. It is characterized by including the actual coating and drying step.

Preferably, the hydrophilic monomer is 2-hydroxyethyl methacrylate.

It is selected from the group consisting of 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, acrylic acid, methacrylic acid and N-vinylpyrrolidone or in combination. In addition, the copolymerization monomer is composed of vinyl toluene, vinyl acetate, styrene, acrylonitrile, vinyl chloride, methyl methacrylate, butyl methacrylate, ethyl methacrylate, isobornyl acrylate and acrylated epoxy resin It is preferable to select from 1 type or in combination from a group.

On the other hand, crosslinking agents are ethylene glycol dimethacrylate and ethylene glycol diacrylate. Polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, triethylene glycol diacrylate, tripropylene glycol dimethacrylate, tripropylene glycol diacrylate, tetraethylene Glycol Dimethacrylate, Tetramethylene Glycol Diacrylate, Trimethylol Propane Trimethacrylate, Trimethylol Propane Triacrylate, Pantaerythritol Tetraacrylate, Glycerol Propoxytriacrylate, Arylmethacrylate and Glyci It is selected from the group consisting of dimethacrylate and one or a combination thereof. The polymerization initiator also consists of azobisisobutylonitrile, benzoyl peroxide, cumene hydroperoxide, t-butylperoxide, t-butylperbenzoate, methylethylketone peroxide, ammonium persulfate and potassium persulfate. It is preferable to select from 1 type or in combination from a group. In addition, the polymerization inhibitor is selected from the group consisting of hydroquinone, hydroquinone methyl ester, naphthylamine and P-methoxyphenol, or in combination. The solvent is preferably selected from the group consisting of water, methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, toluene, cellosolves, cellosolve acetates, or a combination thereof.

Hereinafter, the configuration and operation of the present invention will be described in more detail.

The hydrophilic resin which concerns on this invention was developed so that the value as a use and a commercial property can fully be exhibited by maintaining the physical property as shown in Table 1.

Hydrophilic resins usually consist of water-soluble or water-swellable polymers. The water-soluble or water-swellable polymer refers to having the following hydrophilic group in the structure of the polymer. That is, -OH, -CONH ₂ , -COOH, -NH ₂ , -COO- and the like. The hydrophilic polymer used in the polyester or polycarbonate film or sheet of the present invention is obtained by polymerizing or copolymerizing one or more monomers having these hydrophilic groups or by mixing one or more polymers having these hydrophilic groups. Is made. Among them, the main raw materials required to prepare the anti-fog coating resin of the present invention are as follows.

As hydrophilic monomers, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, acrylic acid, methacrylic acid and N-vinyl Pyrrolidone is preferred.

As the copolymerization monomer, vinyltoluene, vinyl acetate, styrene, acrylonitrile, vinyl chloride, methyl methacrylate, butyl methacrylate, ethyl methacrylate, isobornyl acrylate and acrylate epoxy resin are preferable. Do.

A crosslinking agent refers to a monomer having two or more functional groups. Ethylene glycol dimethacrylate, ethylene glycol diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacryl Ethylene Polyethylene Glycol Dimethacrylate, Triethylene Glycol Diacrylate, Tripropylene Glycol Dimethacrylate, Tripropylene Glycol Diacrylate, Tetraethylene Glycol Dimethacrylate, Tetramethylene Glycol Diacrylate Preference, trimethylolpropanetrimethacrylate, trimethylolpropanetriacrylate, panthaerythrilet tetraacrylate, glycerol propoxytriacrylate, arylmethacrylate and glycidylmethacrylate are preferred.

Polymerization initiators include azobisisobutylonitrile, benzoyl peroxide, cumene hydroperoxide, t-butylperoxide, t-butylperbenzoate, methylethylketone peroxide, ammonium persulfate and potassium persulfate. Is preferred.

Preferred polymerization inhibitors are hydroquinone, hydroquinone methylester, naphthylamine and P-methoxyphenol.

As solvents, water, methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, toluene, cellosolves, and cellosolve acetates are preferable.

These raw materials are mixed so as to be in a range of about 10 to 50% of solids, and polymerized by a conventional method to produce and produce an anti-fog coating.

First, 20-50 weight% of hydrophilic monomers, 1-40 weight% of copolymerization monomers, 0.1-5 weight% of crosslinking agents, 0.05-5 weight% of polymerization initiators, and 50-80 weight% of solvents mix and polymerize. At this time, the preparation of the coating hydrophilic resin can be prepared by polymerization in two ways depending on the degree of polymerization.

First, after the reaction is stopped at the degree of prepolymerization in the form of oligomer, 0.01 to 0.2% by weight of the polymerization inhibitor and 0.05 to 2% by weight of the polymerization initiator are added to prepare a coating agent, and then the polymerization is carried out through actual coating and heat treatment. It can be carried out by two steps of the two-step polymerization method to complete 100%, and secondly, to produce a product that has completely terminated the polymerization reaction to complete the actual coating and drying.

Referring to the manufacturing process of the anti-fogging coating emulsion resin of the present invention in more detail.

A reactor equipped with a stirrer, a dropping funnel, a reflux cooler, and a thermostat was prepared, and a hydrophilic monomer, a polymerization initiator, a crosslinking agent, and a solvent were mixed and dissolved in a dropping funnel. It is injected into the reactor and the remaining 90% is left in the dropping funnel. Thereafter, 10% of the mixed solution is subjected to a prepolymerization reaction (seed polymerization) at about 70 ~ 80 ℃ in the reactor. When the viscosity of the prepolymer rises and the reaction starts, the mixed solution of the dropping funnel is slowly dropped over about 3 hours to perform a polymerization reaction. After the dropping and polymerization is completed, the mixture is cooled to room temperature to prepare a polymer having a solid content of about 30%. Anti-fog coating resin is prepared and produced by mixing and dissolving a polymerization inhibitor in the resin solution after polymerization.

The resin solution prepared above was roller coated with a thickness of about 25 to 35 μm on the surface of the corona discharge-treated polyester or polycarbonate film, and then dried in a drying furnace at a temperature of about 120 ° C. to 140 ° C. for about 5 to 15 minutes. Hardening process produces anti-fog tinting film.

The film thus produced exhibits the most effective function when used after aging at room temperature for at least one month.

The following examples are intended to illustrate the present invention in more detail, and various modifications may be made without limiting the scope of the present invention.

Example 1

The blending ratio of the raw materials for the production of emulsion polymerization resin for anti-fog coating is as follows.

A group: 170.0 kg 2-hydroxyethyl methacrylate, 27.0 kg methacrylate, 64.0 kg acrylate epoxy resin, 19.0 kg triethylene glycol dimethacrylate, 21.0 kg potassium dialkylsulfosinate, benzoyl peroxide 3.0 kg, potassium persulfate 3.0 kg, ethylene glycol monomethyl ether 500.0 kg, purified water 200.0 kg, total 1,007.0 kg

B Group: Hydroquinone 0.2kg, Cumene Hydroperoxide 5.0kg, Total 5.2kg

Prepare a reactor equipped with a stirrer, a dropping funnel, a reflux cooler, and a thermostat, mix and dissolve the raw materials of A group in a dropping tank, inject 10% of them into the reactor, and drop the remaining 90%. Left in the tank.

The raw materials of the A group are, for example, 2-hydroxyethyl methacrylate and methacrylic acid as hydrophilic monomers, benzoyl peroxide and potassium persulfate as polymerization initiators, triethylene glycol dimethacrylate and acrylate epoxy resins as crosslinking agents, and solvents. 10% of a mixed solution of phosphorus ethylene glycol monomethyl ether and purified water and the like was subjected to a prepolymerization reaction at about 75 ° C in a reactor.

When the viscosity of the prepolymer rises and the reaction starts, the mixed solution of the dropping tank is slowly dropped over about 3 hours to perform a polymerization reaction.

After the dropping and polymerization was completed, the mixture was cooled to room temperature, thereby preparing a polymer having a solid content of about 30%.

Hydroquinone and cumene hydroperoxide, a polymerization initiator, were mixed and dissolved in the resin solution after polymerization to produce and produce an anti-fog coating resin. Appearance physical properties of the anti-fog coating resin prepared therefrom are as follows.

Appearance: translucent milky viscous liquid with slight solvent odor

Viscosity: 550 ± 10 cps

Solids content: 30 ± 2 wt.%

Thereafter, the prepared resin solution was rollercoated to a surface of about 30 μm on the surface of the corona discharge-treated polyester or polycarbonate film, and then dried in a drying furnace and heated at 120 ° C. to 140 ° C. for about 5 to 15 minutes, followed by curing. Treatment to produce anti-fog tinting film. The produced film showed the most effective function when aged after at least 1 month at room temperature.

Table 1 shows physical properties of the anti-fogging tint film prepared according to Example 1.

Properties of anti-fog tinting film Properties / Items SL-30AF SL-30AFU Remarks solution Solid content (%) 30 ± 2 30 ± 2 2Hrs / 120 ℃ Appearance / appearance Translucent solution Translucent solution Specific gravity / sp. gr. (25 ℃) 1.02 1.02 Viscosity / viscosity (cps / 25 ℃) 50 ± 30 50 ± 10 Curing conditions 5mins / 125 ℃ 5mins / 125 ℃ Thinner / solvent / diluents purified water methyl cellosolve pH (25 ℃) 7-8 7-8 surface properties Coating thickness / coating thickness 10 10 (dry condition / μm) Water contact angle 10.23 ° 11.20 ° Visible transmittance (%) visible transmittance 90% 10% UV transmittance (%) UV transmittance - - Blur / haze <0.96 <0.98 ref./1.17 Surface resistance (Ω / cm ² ) 3.5 × 10 ¹⁰ 3.3 × 10 ¹⁰ ref./7.3 × 10 ¹⁰ PET Film adhesion / cross hatch test 100% 100% JIS K-5400 Surface pencil hardness 2H 2H Abrasion resistant steel wool # 0000 pass pass 500g-load10 strokes Remarks For general colored materials UV-blocking, colorless and transparent

As described above, the emulsion polymer product prepared according to the manufacturing method of the present invention has excellent transparency and improved anti-fog property and at the same time have transparency, weather resistance, UV protection, heat resistance and excellent antistatic property according to its use. It can be used for automobile glass, spectacle lens, greenhouse glass, bathroom mirror and agricultural vinyl house where these physical properties are required, and it does not generate frost and keeps the clear and transparent state all day long. It is not only excellent in hardness of coating surface, but also able to maintain high hydrophilicity and adhesion of coating film even for thin coating layer over long periods of time. Excellent surface hardness improves the material adhesion during coating It is one excellent invention.

Claims (15)

20 to 50% by weight of a hydrophilic monomer, 1 to 40% by weight of a copolymerization monomer, 0.1 to 5% by weight of a crosslinking agent, 0.05 to 5% by weight of a polymerization initiator, and 50 to 80% by weight of a solvent; After stopping the reaction at the degree of prepolymerization in the form of oligomer, adding 0.01 to 0.2% by weight of the polymerization inhibitor and 0.05 to 2% by weight of the polymerization initiator to prepare a coating, and then performing a polymerization process through the actual coating and heat treatment process. Method for producing an emulsion polymerization resin for anti-fog coating. The method of claim 1, wherein the hydrophilic monomer is 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, acrylic acid, methacrylic acid and N -Method for producing emulsion polymerization resin for anti-fog coating, characterized in that selected from the group consisting of vinylpyrrolidone or one or a combination thereof. The method of claim 1, wherein the copolymerization monomer is vinyl toluene, vinyl acetate, styrene, acrylonitrile, vinyl chloride, methyl methacrylate, butyl methacrylate, ethyl methacrylate, isobornyl acrylate and acrylate epoxy Method for producing an emulsion polymerization resin for anti-fog coating, characterized in that selected from the group consisting of resins or in combination. The method of claim 1, wherein the crosslinking agent is ethylene glycol dimethacrylate, ethylene glycol diacrylate. Polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, triethylene glycol diacrylate, tripropylene glycol dimethacrylate, tripropylene glycol diacrylate, tetraethylene Glycol Dimethacrylate, Tetramethylene Glycol Diacrylate, Trimethylol Propane Trimethacrylate, Trimethylol Propane Triacrylate, Pantaerythrite Tetraacrylate, Glycerol Propoxytriacrylate, Arylmethacrylate and Gly Method for producing an emulsion polymerization resin for anti-fog coating, characterized in that selected from the group consisting of cyl methacrylate or in combination. The method of claim 1, wherein the polymerization initiator is azobisisobutylonitrile, benzoyl peroxide, cumene hydroperoxide, t- butyl peroxide, t- butyl per benzoate, methyl ethyl ketone peroxide, ammonium persulfate and Method for producing an emulsion polymerization resin for anti-fog coating, characterized in that selected from the group consisting of potassium persulfate or in combination. The method of claim 1, wherein the polymerization inhibitor is prepared of the emulsion coating resin for anti-fog coating, characterized in that selected from the group consisting of hydroquinone, hydroquinone methyl ester, naphthylamine and P- methoxyphenol. Way. The method of claim 1, wherein the solvent is selected from the group consisting of water, methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, toluene, acetates, cellosolves, cellosolve acetates, or a combination thereof. Method for producing emulsion polymerization resin for anti-fog coating. The method of claim 1, wherein the coating is carried out for 5 minutes to 15 minutes by increasing the temperature from 120 ℃ to 140 ℃ manufacturing method of the emulsion coating resin for anti-fog coating. 20 to 50% by weight of a hydrophilic monomer, 1 to 40% by weight of a copolymerization monomer, 0.1 to 5% by weight of a crosslinking agent, 0.05 to 5% by weight of a polymerization initiator, and 50 to 80% by weight of a solvent; And Method of producing an emulsion polymerization resin for anti-fog coating comprising the step of the actual coating and drying after the completion of the polymerization reaction. The method of claim 9, wherein the hydrophilic monomer is 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, acrylic acid, methacrylic acid and N -Method for producing emulsion polymerization resin for anti-fog coating, characterized in that selected from the group consisting of vinylpyrrolidone or one or a combination thereof. The method of claim 9, wherein the copolymerization monomer is vinyl toluene, vinyl acetate, styrene, acrylonitrile, vinyl chloride, methyl methacrylate, butyl methacrylate, ethyl methacrylate, isobornyl acrylate and acrylate epoxy Method for producing an emulsion polymerization resin for anti-fog coating, characterized in that selected from the group consisting of resins or in combination. The method of claim 9, wherein the crosslinking agent is ethylene glycol dimethacrylate, ethylene glycol diacrylate. Polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, triethylene glycol diacrylate, tripropylene glycol dimethacrylate, tripropylene glycol diacrylate, tetraethylene Glycol Dimethacrylate, Tetramethylene Glycol Diacrylate, Trimethylol Propane Trimethacrylate, Trimethylol Propane Triacrylate, Pantaerythrite Tetraacrylate, Glycerol Propoxytriacrylate, Arylmethacrylate and Gly Method for producing an emulsion polymerization resin for anti-fog coating, characterized in that selected from the group consisting of cyl methacrylate or in combination. The method of claim 9, wherein the polymerization initiator is azobisisobutylonitrile, benzoyl peroxide, cumene hydroperoxide, t- butyl peroxide, t- butyl per benzoate, methyl ethyl ketone peroxide, ammonium persulfate and Method for producing an emulsion polymerization resin for anti-fog coating, characterized in that selected from the group consisting of potassium persulfate or in combination. The method of claim 9, wherein the solvent is selected from the group consisting of water, methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, toluene, acetates, cellosolves, cellosolve acetates, or a combination thereof. Method for producing emulsion polymerization resin for anti-fog coating. 10. The method of claim 9, wherein the coating is performed by increasing the temperature from 120 ° C to 140 ° C for 5 minutes to 15 minutes.