KR102075677B1 - Pre-emulsion composite and water soluble acrylic emulsion resin prepared by using the same - Google Patents

Abstract

The present invention relates to a preemulsion composition and a water-soluble acrylic emulsion resin prepared using the same, to provide a preemulsion composition comprising an acrylic monomer and a nonionic surfactant and a water-soluble acrylic emulsion resin prepared using the same.

Description

Pre-emulsion composition and water-soluble acrylic emulsion resin prepared using the same {PRE-EMULSION COMPOSITE AND WATER SOLUBLE ACRYLIC EMULSION RESIN PREPARED BY USING THE SAME}

The present invention relates to a preemulsion composition and a water-soluble acrylic emulsion resin prepared using the same.

In general, the painting has a purpose to protect the body as well as the aesthetic function. In particular, many studies have been made to prevent corrosion of metal structures, components, transportation means, etc. As a result of these studies, many kinds of oil paints have been developed and used successfully.

Recently, with increasing interest in environmental protection and energy around the world, there is a growing movement to limit the use of organic solvents (or volatile organic compounds) derived from fossil raw materials. It is being prepared or implemented.

In accordance with these requirements, interest in water-soluble paints is increased, thereby increasing interest in water-soluble resin compositions that are environmentally friendly and have excellent workability. In particular, the coating composition containing a water-soluble acrylic resin emulsion is commonly used to form a coating film having a relatively durable when drying at room temperature. Such conventional water-soluble acrylic resin emulsions are known to be prepared by emulsion polymerization using anionic surfactants as emulsifiers in the synthesis of resins, and are widely used in various industrial fields.

However, when the anionic surfactant is applied, bubbles are generated in the resin synthesis process, and when the coating material to which the resin is applied is coated on the material, water resistance of the coating film is reduced. In order to solve this problem, studies are being conducted to add an antifoaming agent to paint. However, even if the antifoaming agent was applied, it was difficult to reduce the generation of bubbles due to the anionic surfactant, which did not sufficiently solve the problem of decreasing the water resistance of the coating film.

Thereby, development of the composition for water-soluble acrylic resin emulsion production which is excellent in defoaming property and excellent in the water resistance of a coating film using only a nonionic surfactant is calculated | required.

An object of the present invention is to provide a preemulsion composition excellent in synthetic stability and anti-foaming, and a water-soluble acrylic emulsion resin prepared using the same.

In order to achieve the above object, the present invention comprises an acrylic monomer, a nonionic surfactant and a polymerization initiator, the nonionic surfactant is a first nonionic surfactant having a hydrophile-lipophile balance (HLB) of 3 to 8 and It provides a pre-emulsion composition comprising a second nonionic surfactant having a hydrophile-lipophile balance (HLB) of 16 to 20.

The nonionic surfactant may be included in an amount of 1 to 15 parts by weight based on 100 parts by weight of the acrylic monomer.

The first nonionic surfactant and the second nonionic surfactant may be included in a weight ratio of 6: 4 to 2: 8 based on the solids content of the nonionic surfactant included in the preemulsion composition.

The acrylic monomer may include one or more selected from the group consisting of (meth) acrylic acid, (meth) acrylic acid derivatives, and mixtures thereof.

The acrylic monomer may be included in an amount of 30 to 60% by weight based on the total weight of the preemulsion composition.

The present invention also provides a water-soluble acrylic emulsion resin prepared using the preemulsion composition.

The water-soluble acrylic emulsion resin may have a glass transition temperature of -30 to 0 ℃.

Since the water-soluble acrylic emulsion resin prepared by using the preemulsion composition of the present invention has a glass transition temperature of -30 to 0 ° C, physical properties such as synthetic stability and antifoaming properties are improved, and the paint containing such a water-soluble acrylic emulsion resin The water resistance of the coating film formed using the composition can be improved.

Hereinafter, the present invention will be described in detail.

The present invention provides a preemulsion composition.

The preemulsion composition of this invention contains an acryl-type monomer, a nonionic surfactant, and a polymerization initiator.

<Acrylic monomer>

The acrylic monomer may include one or more selected from the group consisting of (meth) acrylic acid, (meth) acrylic acid derivatives, and mixtures thereof as components for improving durability and adhesion of the coating film.

The (meth) acrylic acid derivatives include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl acrylate and t- Butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl acrylate, isooctyl acrylate, octyl methacrylate, 2-ethylhexyl acrylate, isodecyl acrylate, decyl methacrylate, dodecyl methacrylate Rate, isobonyl methacrylate, and the like. For example, the (meth) acrylic acid derivative may be methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, 2-ethylhexyl acrylate, or the like.

The acrylic monomer may be included in an amount of 30 to 60% by weight, for example 40 to 50% by weight, based on the total weight of the preemulsion composition. If the content of the acrylic monomer is less than 30% by weight may reduce the adhesion and durability of the coating film, if the content of the acrylic monomer exceeds 60% by weight the coating film may be too flexible or peeled off.

The acrylic monomer is polymerized in the presence of a nonionic surfactant and a polymerization initiator to form an acrylic copolymer.

<Nonionic Surfactant>

The nonionic surfactant is a component that allows the acrylic monomers to be polymerized into a stabilized uniform phase. The nonionic surfactants include polyethylene oxide alkyl ethers, polyethylene oxide alkyl phenyl ethers, sorbitan fatty acid esters, polyoxyethylene fatty acid amides, N, N-bis-2-hydroxy alkyl amines, and glycerin fatty acid monos. Ester-based, methyl ester ethoxylate-based, pentathiol fatty acid ester-based, and the like.

The nonionic surfactant may be included in an amount of 1 to 15 parts by weight, for example, 5 to 10 parts by weight, based on 100 parts by weight of the acrylic monomer. If the content of the nonionic surfactant is less than 1 part by weight, the emulsion cannot be synthesized due to the lack of emulsifying power. If the content of the nonionic surfactant exceeds 15 parts by weight, the particles of the emulsion resin are small, so that the viscosity of the resin is high or Particle phase in the ground is not maintained and may gel.

The nonionic surfactant may include two or more nonionic surfactants having different hydrophile-lipophile balances (HLBs) in terms of improving synthetic stability and antifoaming properties of the water-soluble acrylic resin preemulsion composition. For example, two or more nonionic surfactants having different hydrophile-lipophile balances (HLB) may have a hydrophile-lipophile balance (HLB) of 16 to 1 and a first nonionic surfactant having a hydrophile-lipophile balance (HLB) of 3 to 8. 20 may be a second nonionic surfactant.

 The first nonionic surfactant and the second nonionic surfactant have a hydrophile-lipophile balance (HLB) determined according to a ratio of a hydrophilic group portion and a hydrophobic group portion, and for example, an aliphatic alcohol alkylene oxide adduct as a nonionic surfactant. , Alkyl phenol alkylene oxide adducts, fatty acid alkylene oxide adducts, polyhydric alcohol fatty acid ester alkylene oxide adducts, higher alkyl amine alkylene oxide adducts, fatty acid amide alkylene oxide adducts, alkylene oxide adducts of fats and oils , Polypropylene glycol ethylene oxide adducts, fatty acid esters of glycerol, fatty acid esters of pentaerythritol, alkyl esters of polyhydric alcohols, and the like.

The first nonionic surfactant and the second nonionic surfactant may be included in a weight ratio of 6: 4 to 2: 8 based on the solids content of the nonionic surfactant included in the preemulsion composition. If the first nonionic surfactant exceeds the value, the antifoaming property is lowered, and if the first nonionic surfactant is less than the value, the synthetic stability may be inferior.

<Polymerization Initiator>

The polymerization initiator is for initiating the emulsion polymerization, and is not particularly limited as long as it is a substance that decomposes by heat and generates radicals. For example, ammonium persulfate, potassium persulfate, sodium hyposulfite hydrosulfite), sodium persulfate, sodium hydrogen sulfate, or a combination thereof.

The polymerization initiator may be included in an amount of 0.01 to 1 parts by weight, for example, 0.05 to 0.5 parts by weight based on 100 parts by weight of the acrylic monomer. If the content of the polymerization initiator is less than 0.01 parts by weight, the polymerization may not occur properly. If the content of the polymerization initiator exceeds 1 part by weight, problems may occur due to unreacted initiator and low polymerization degree.

The water-soluble acrylic resin preemulsion can be produced by the preemulsion composition of the present invention composed of the above components, and the water-soluble acrylic emulsion resin can be prepared using the water-soluble acrylic resin preemulsion thus prepared.

First, the preemulsion containing an acrylic monomer, a 1st solvent, a 1st emulsifier, and an initiator is manufactured.

Next, a dispersion solution containing a second solvent and a second emulsifier is prepared, and a part of the preemulsion, for example, 1 to 30% by weight, and another example, 1 to 10% by weight, is added to the dispersion solution to preliminarily emulsify. The polymerization may be carried out to prepare a seed emulsion resin. Thereafter, the remaining preemulsion may be added to the seed emulsion resin, followed by emulsion polymerization to prepare a water-soluble acrylic emulsion resin. The pre-emulsion and the water-soluble acrylic emulsion resin may be prepared by further comprising additives such as antifoaming agent, water repellent, wetting agent, thickener, corrosion inhibitor, leveling agent, preservative, pH adjusting agent.

The first solvent and the second solvent may be deionized water, and the first solvent and the second solvent are each included in an amount of 15 to 60 parts by weight, for example, 15 to 50 parts by weight, based on 100 parts by weight of the acrylic monomer. It may be.

Specific details of the acrylic monomer are the same as those described above.

The first emulsifier and the second emulsifier may be a nonionic surfactant, and the first emulsifier and the second emulsifier may be two or more nonionic interfaces having different HLBs in order to improve synthetic stability and antifoaming properties of the water-soluble acrylic resin preemulsion. It may include an active agent. Specific matters of the nonionic surfactant are the same as those of the above-mentioned <nonionic surfactant>.

The polymerization temperature in the emulsion polymerization is not particularly limited, but may be 50 to 100 ° C., for example, 70 to 85 ° C.

Solid content of the water-soluble acrylic emulsion resin prepared by the emulsion polymerization may be 60% by weight or less. When the solid content is more than 60% by weight, the viscosity of the water-soluble acrylic resin preemulsion is too high, the stability during the reaction is lowered, the dispersion stability is worsened, the aggregation may occur over time.

PH of the prepared water-soluble acrylic emulsion resin may be in the range of 5 to 10, for example 7 to 9. The pH of the water-soluble acrylic emulsion resin can be adjusted by adding ammonia water, water-soluble amines, aqueous alkali hydroxide solution and the like in the emulsion.

Since the water-soluble acrylic emulsion resin produced as described above has a glass transition temperature of -30 to 0 ° C, physical properties such as synthetic stability and antifoaming properties are improved. And when such a water-soluble acrylic emulsion resin is used as one component of a coating composition, the water resistance of the coating film formed using the said coating composition improves. If the glass transition temperature of the water-soluble acrylic emulsion resin is less than -30 ℃ coating film formed by using the coating composition containing the water-soluble acrylic emulsion resin may not be formed, if it is more than 0 ℃ paint containing the water-soluble acrylic emulsion resin The water resistance and impact resistance of the coating film formed using the composition may be poor.

Hereinafter, the present invention will be described in detail by way of examples.

However, the following examples are intended to specifically illustrate the present invention, the contents of the present invention is not limited by the following examples.

Preemulsion  Produce

[ Example  One]

Deionized water 24.1g, the first nonionic surfactant (C ₁₂ H ₂₅ -O- (CH ₂ CH _{2 O} ) ₃ -H, HLB7.8, solid content 100%) 0.9g, the second nonionic surfactant ( C ₁₂ H ₂₅ -O- (CH ₂ CH _{2 O} ) ₅₀ -H, HLB18.0,100% solids) 0.9 g, acrylic acid 0.6 g, methyl methacrylate 20.0 g, 2-ethylhexyl acrylate 23.2 g and ammonium per 0.1 g of sulfate was added thereto, followed by stirring to prepare a preemulsion.

[ Example  2]

23.6 g of deionized water in the reaction vessel, 0.9 g of a first nonionic surfactant (C ₁₂ H ₂₅ -O- (CH ₂ CH _{2 O} ) ₃ -H, HLB7.8, 100% solids), a second nonionic surfactant ( poly (oxy-1,2-ethanediyl, α- [1- (hydroxymethyl) -2- (2-propenyloxy) ethyl] -ω-hydroxy-, C11-rich C10-14-branched alkyl ethers, HLB 16.5, solids 65 %) 1.4g, acrylic acid 0.6g, methyl methacrylate 20.0g, 2-ethylhexyl acrylate 23.2g and ammonium persulfate 0.1g was added and stirred to prepare a preemulsion.

[ Example  3]

23.6 g of deionized water in the reaction vessel, 0.9 g of a first nonionic surfactant (C ₁₂ H ₂₅ -O- (CH ₂ CH _{2 O} ) ₃ -H, HLB7.8, 100% solids), a second nonionic surfactant ( poly (oxy-1,2-ethanediyl, α- [1- (hydroxymethyl) -2- (2-propenyloxy) ethyl] -ω-hydroxy-, C11-rich C10-14-branched alkyl ethers, HLB 16.5, solids 65 %) 1.4g, acrylic acid 0.6g, methyl methacrylate 17.1g, 2-ethylhexyl acrylate 26.1g and ammonium persulfate 0.1g was added to prepare a preemulsion.

[ Example  4]

23.6 g of deionized water in a separate reaction vessel, 0.9 g of a first nonionic surfactant (C ₁₂ H ₂₅ -O- (CH ₂ CH _{2 O} ) ₃ -H, HLB7.8, 100% solids), a second nonionic interface Activator (poly (oxy-1,2-ethanediyl, α- [1- (hydroxymethyl) -2- (2-propenyloxy) ethyl] -ω-hydroxy-, C11-rich C10-14-branched alkyl ethers), HLB 16.5 , Solid content 65%) 1.4g, acrylic acid 0.6g, methyl methacrylate 22.8g, 2-ethylhexyl acrylate 20.4g and ammonium persulfate 0.1g was added to prepare a preemulsion.

[ Example  5]

23.6 g of deionized water in the reaction vessel, 0.9 g of a first nonionic surfactant (C ₁₂ H ₂₅ -O- (CH ₂ CH _{2 O} ) ₃ -H, HLB7.8, 100% solids), a second nonionic surfactant ( poly (oxy-1,2-ethanediyl, α- [1- (hydroxymethyl) -2- (2-propenyloxy) ethyl] -ω-hydroxy-, C11-rich C10-14-branched alkyl ethers, HLB 16.5, solids 65 %) 1.4 g, acrylic acid 0.6 g, methyl methacrylate 25.2 g, 2-ethylhexyl acrylate 18.0 g and ammonium persulfate were added and stirred to prepare a preemulsion.

[ Example  6]

23.5 g of deionized water, 0.4 g of a first nonionic surfactant (C ₁₂ H ₂₅ -O- (CH ₂ CH _{2 O} ) ₃ -H, HLB7.8, 100% solids), a second nonionic surfactant ( poly (oxy-1,2-ethanediyl, α- [1- (hydroxymethyl) -2- (2-propenyloxy) ethyl] -ω-hydroxy-, C11-rich C10-14-branched alkyl ethers, HLB 16.5, solids 65 %) 2.2 g, acrylic acid 0.6 g, methyl methacrylate 19.9 g, 2-ethylhexyl acrylate 23.2 g and ammonium persulfate 0.1 g were added to the mixture to prepare a preemulsion.

[ Example  7]

23.6 g of deionized water, 1 g of nonionic surfactant (C ₁₂ H ₂₅ -O- (CH ₂ CH _{2 O} ) ₃ -H, HLB7.8, 100% solids), 2nd nonionic surfactant ( poly (oxy-1,2-ethanediyl, α- [1- (hydroxymethyl) -2- (2-propenyloxy) ethyl] -ω-hydroxy-, C11-rich C10-14-branched alkyl ethers, HLB 16.5, solids 65 %) 1.1g, acrylic acid 0.6g, methyl methacrylate 20.1g, 2-ethylhexyl acrylate 23.2g and ammonium persulfate 0.1g was added to prepare a preemulsion.

[ Example  8]

23.5 g of deionized water, 0.7 g of a first nonionic surfactant (C ₁₂ H ₂₅ -O- (CH ₂ CH _{2 O} ) ₃ -H, HLB7.8, 100% solids), a second nonionic surfactant ( poly (oxy-1,2-ethanediyl, α- [1- (hydroxymethyl) -2- (2-propenyloxy) ethyl] -ω-hydroxy-, C11-rich C10-14-branched alkyl ethers, HLB 16.5, solids 65 %) 1.7 g, acrylic acid 0.6 g, methyl methacrylate 20.0 g, 2-ethylhexyl acrylate 23.2 g and ammonium persulfate 0.1 g were added and stirred to prepare a preemulsion.

[ Example  9]

23.5 g of deionized water, 0.5 g of a first nonionic surfactant (C ₁₂ H ₂₅ -O- (CH ₂ CH _{2 O} ) ₃ -H, HLB7.8, 100% solids), a second nonionic surfactant ( poly (oxy-1,2-ethanediyl, α- [1- (hydroxymethyl) -2- (2-propenyloxy) ethyl] -ω-hydroxy-, C11-rich C10-14-branched alkyl ethers, HLB 16.5, solids 65 %) 1.9 g, acrylic acid 0.6 g, methyl methacrylate 20.0 g, 2-ethylhexyl acrylate 23.2 g and ammonium persulfate 0.1 g were added and stirred to prepare a preemulsion.

[ Example  10]

23.6 g of deionized water, a first nonionic surfactant (C ₁₂ H ₂₅ -O- (CH ₂ CH _{2 O} ) ₃ -H, HLB7.8, 100% solids) 0.8 g, a second nonionic surfactant ( poly (oxy-1,2-ethanediyl, α- [1- (hydroxymethyl) -2- (2-propenyloxy) ethyl] -ω-hydroxy-, C11-rich C10-14-branched alkyl ethers, HLB 16.5, solids 65 %) 1.3 g, acrylic acid 0.6 g, methyl methacrylate 20.1 g, 2-ethylhexyl acrylate 23.3 g, and ammonium persulfate 0.1 g were added and stirred to prepare a preemulsion.

[ Example  11]

23.5 g of deionized water, 0.2 g of a first nonionic surfactant (C ₁₂ H ₂₅ -O- (CH ₂ CH _{2 O} ) ₃ -H, HLB7.8, 100% solids), a second nonionic surfactant ( poly (oxy-1,2-ethanediyl, α- [1- (hydroxymethyl) -2- (2-propenyloxy) ethyl] -ω-hydroxy-, C11-rich C10-14-branched alkyl ethers, HLB 16.5, solids 65 %) 2.5 g, 0.6 g acrylic acid, 19.9 g methyl methacrylate, 23.1 g 2-ethylhexyl acrylate and 0.1 g ammonium persulfate were added and stirred to prepare a preemulsion.

[ Comparative example  One]

23.5 g of deionized water and a second nonionic surfactant in the reaction vessel (poly (oxy-1,2-ethanediyl, α- [1- (hydroxymethyl) -2- (2-propenyloxy) ethyl] -ω-hydroxy-, C11 -rich C10-14-branched alkyl ethers, HLB 16.5, solids 65%) 2.8g, acrylic acid 0.6g, methyl methacrylate 19.9g, 2-ethylhexyl acrylate 23.1g and ammonium persulfate 0.1g and stirred to free An emulsion was prepared.

[ Comparative example  2]

Deionized water 23.5g, 1st nonionic surfactant (C ₁₂ H ₂₅ -O- (CH ₂ CH _{2 O} ) ₃ -H, HLB7.8, 100% solids) 2.8g, 0.6g acrylic acid, methylmethacryl Pre-emulsion was prepared by adding 19.9 g of rate, 23.1 g of 2-ethylhexyl acrylate and 0.1 g of ammonium persulfate.

Water Soluble Acrylic System Emulsion  Resin manufacturing

[ Production Example  One]

Into a reactor equipped with a stirrer, a thermometer and a condenser, 26.6 g of deionized water and 0.6 g of a second nonionic surfactant (C ₁₂ H ₂₅ -O- (CH ₂ CH _{2 O} ) ₅₀ -H, HLB18.0, 100% solids) were added. After the addition and the temperature was raised to 80 ℃, 5% by weight (3.5 g) of the pre-emulsion prepared in Example 1 was added and then maintained for 20 minutes to prepare a seed emulsion resin. Then, 95% by weight of the preemulsion prepared in Example 1 was added to the reactor for 4 hours continuously and maintained at 80 ° C. for 1 hour to prepare a stabilized uniform emulsion. After the holding time, the mixture was cooled to 40 ° C., 2.8 g of deionized water and 0.2 g of ammonia water were added and maintained for 1 hour to prepare an emulsion resin having excellent synthetic stability and uniform particle shape.

[ Production Example  2]

26.6 g of deionized water and a second nonionic surfactant (poly (oxy-1,2-ethanediyl, α- (1- (hydroxymethyl) -2- (2-propenyloxy) ethyl) ethyl in a reactor equipped with a stirrer, a thermometer and a condenser) ] -ω-hydroxy-, C11-rich C10-14-branched alkyl ethers, HLB 16.5, solids 65%) 0.6g was added and the temperature was raised to 80 ℃, the pre-emulsion prepared in Example 2 Seed emulsion resin was prepared by adding 20% by weight (3.5 g) and then maintaining for 20 minutes, 95% by weight of the pre-emulsion prepared in Example 2 was continuously added to the reactor for 4 hours, and maintained at 80 ° C. for 1 hour. After the holding time, the mixture was cooled to 40 ° C. and 2.8 g of deionized water and 0.2 g of ammonia water were kept for 1 hour to prepare an emulsion resin having excellent synthetic stability and uniform particle shape. Prepared.

[ Production Example  3]

26.6 g of deionized water and a second nonionic surfactant in a reactor equipped with a stirrer, a thermometer and a condenser (poly (oxy-1,2-ethanediyl, α- [1- (hydroxymethyl) -2- (2-propenyloxy) ethyl] -ω-hydroxy-, C11-rich C10-14-branched alkyl ethers, HLB 16.5, solids 65%) 0.6g was added and the temperature was raised to 80 ℃, 5 in the pre-emulsion prepared in Example 3 Seed emulsion resin was prepared by adding 20 wt% (3.5 g) and then holding for 20 min. Then, at 80 ° C., 95 wt% of the preemulsion prepared in Example 3 was continuously added to the reactor for 4 hours. An emulsion of a stabilized homogeneous form was prepared by maintaining for 1 hour, and when the holding time was over, the mixture was cooled to 40 ° C. and 2.8 g of deionized water and 0.2 g of ammonia water were kept for 1 hour to maintain an excellent synthetic stability and uniform particle shape. Resin was prepared.

[ Production Example  4]

26.6 g of deionized water and a second nonionic surfactant in a reactor equipped with a stirrer, a thermometer and a condenser (poly (oxy-1,2-ethanediyl, α- [1- (hydroxymethyl) -2- (2-propenyloxy) ethyl] -ω-hydroxy-, C11-rich C10-14-branched alkyl ethers, HLB 16.5, solids 65%) 0.6g was added and the temperature was raised to 80 ℃, 5 in the pre-emulsion prepared in Example 4 Seed emulsion resin was prepared by adding 20 wt% (3.5 g) and then maintaining for 20 min. 95 wt% of the preemulsion prepared in Example 4 was continuously added to the reactor for 4 hours, and maintained at 80 ° C. for 1 hour. After the holding time, the mixture was cooled to 40 ° C. and 2.8 g of deionized water and 0.2 g of ammonia water were kept for 1 hour to prepare an emulsion resin having excellent synthetic stability and uniform particle shape. Prepared.

[ Production Example  5]

26.6 g of deionized water and a second nonionic surfactant in a reactor equipped with a stirrer, a thermometer and a condenser (poly (oxy-1,2-ethanediyl, α- [1- (hydroxymethyl) -2- (2-propenyloxy) ethyl] -ω-hydroxy-, C11-rich C10-14-branched alkyl ethers, HLB 16.5, solids 65%) 0.6g was added and the temperature was raised to 80 ℃, 5 in the pre-emulsion prepared in Example 5 The seed emulsion resin was prepared by adding the weight% (3.5 g) and then holding for 20 minutes, and then, at 80 ° C., 95% by weight of the preemulsion prepared in Example 5 was continuously added to the reactor for 4 hours. After maintaining for 1 hour, a stabilized emulsion was prepared, and when the holding time was over, the mixture was cooled to 40 ° C. and 2.8 g of deionized water and 0.2 g of ammonia water were kept there for 1 hour to maintain excellent synthetic stability and uniform particle shape. An emulsion resin was prepared.

[ Production Example  6]

26.5 g of deionized water and a second nonionic surfactant in a reactor equipped with a stirrer, a thermometer and a condenser (poly (oxy-1,2-ethanediyl, α- [1- (hydroxymethyl) -2- (2-propenyloxy) ethyl] -ω-hydroxy-, C11-rich C10-14-branched alkyl ethers, HLB 16.5, solids 65%) 0.6g was added and the temperature was raised to 80 ℃, 5 weight of the pre-emulsion prepared in Example 10 Seed emulsion resin was prepared by adding% (3.5 g) and then holding for 20 min. Then, 95 wt% of the preemulsion prepared in Example 10 was added to the reactor for 1 hour at 80 DEG C. for 1 hour. Emulsion of stabilized homogeneous form was prepared by keeping it for a while After the holding time, the mixture was cooled to 40 ° C. and added with 2.8 g of deionized water and 0.2 g of ammonia water and maintained for 1 hour to provide an emulsion resin having excellent synthetic stability and uniform particle shape. Was prepared.

[ Production Example  7]

Deionized water 26.6 g Second nonionic surfactant in a reactor equipped with a stirrer, a thermometer and a condenser (poly (oxy-1,2-ethanediyl, α- [1- (hydroxymethyl) -2- (2-propenyloxy) ethyl]- ω-hydroxy-, C11-rich C10-14-branched alkyl ethers, HLB 16.5, solids 65%) 0.6g was added and the temperature was raised to 80 ℃, 5 in the pre-emulsion prepared in Example 7 Seed emulsion resin was prepared by adding 20 wt% (3.5 g) and then maintaining for 20 min. Then, at 95 ° C., 95 wt% of the preemulsion prepared in Example 7 was continuously added to the reactor for 4 hours. After maintaining for 1 hour, a stabilized emulsion was prepared, and when the holding time was over, the mixture was cooled to 40 ° C. and 2.8 g of deionized water and 0.2 g of ammonia water were kept there for 1 hour to maintain excellent synthetic stability and uniform particle shape. An emulsion resin was prepared.

[ Production Example  8]

26.6 g of deionized water and a second nonionic surfactant in a reactor equipped with a stirrer, a thermometer and a condenser (poly (oxy-1,2-ethanediyl, α- [1- (hydroxymethyl) -2- (2-propenyloxy) ethyl] -ω-hydroxy-, C11-rich C10-14-branched alkyl ethers, HLB 16.5, solids 65%) 0.6g was added and the temperature was raised to 80 ℃, 5 weight in the pre-emulsion prepared in Example 8 Seed emulsion resin was prepared by adding% (3.5 g) and then holding for 20 minutes, and then, 95 wt% of the preemulsion prepared in Example 8 was added to the reactor for 4 hours continuously at 1 ° C. at 80 ° C. Emulsion of stabilized homogeneous form was prepared by maintaining for a while After the holding time, the mixture was cooled to 40 ° C. and added with 2.8 g of deionized water and 0.2 g of ammonia to maintain for 1 hour. Resin was prepared.

[ Production Example  9]

26.6 g of deionized water and a second nonionic surfactant in a reactor equipped with a stirrer, a thermometer and a condenser (poly (oxy-1,2-ethanediyl, α- [1- (hydroxymethyl) -2- (2-propenyloxy) ethyl] -ω-hydroxy-, C11-rich C10-14-branched alkyl ethers, HLB 16.5, solids 65%) 0.6g was added and the temperature was raised to 80 ℃, 5 weight of the pre-emulsion prepared in Example 9 Seed emulsion resin was prepared by adding% (3.5 g) and then holding for 20 minutes, and then, 95 wt% of the preemulsion prepared in Example 9 was added to the reactor for 4 hours continuously at 1 ° C. at 80 ° C. Emulsion of stabilized homogeneous form was prepared by keeping it for a while After the holding time, the mixture was cooled to 40 ° C. and added with 2.8 g of deionized water and 0.2 g of ammonia water and maintained for 1 hour to provide an emulsion resin having excellent synthetic stability and uniform particle shape. Was prepared.

[ Production Example  10]

 26.6 g of deionized water and a second nonionic surfactant in a reactor equipped with a stirrer, a thermometer and a condenser (poly (oxy-1,2-ethanediyl, α- [1- (hydroxymethyl) -2- (2-propenyloxy) ethyl] 0.6 g of -ω-hydroxy-, C11-rich C10-14-branched alkyl ethers, HLB 16.5, solids 65%) and the temperature was raised to 80 ° C., and then 5 of the pre-emulsion prepared in Example 6 Seed emulsion resin was prepared by adding 20% by weight (3.5 g) and then holding it for 20 min. Then, 95% by weight of the preemulsion prepared in Example 6 was continuously fed to the reactor at 80 ° C. for 4 hours. After maintaining for 1 hour, a stabilized emulsion was prepared.Then, after the holding time was completed, the mixture was cooled to 40 ° C. and 2.8 g of deionized water and 0.2 g of ammonia water were kept for 1 hour. One emulsion resin was prepared.

[ Production Example  11]

26.5 g of deionized water and a second nonionic surfactant in a reactor equipped with a stirrer, a thermometer and a condenser (poly (oxy-1,2-ethanediyl, α- [1- (hydroxymethyl) -2- (2-propenyloxy) ethyl] -ω-hydroxy-, C11-rich C10-14-branched alkyl ethers, HLB 16.5, solids 65%) 0.6g was added and the temperature was raised to 80 ℃, 5 weight of the pre-emulsion prepared in Example 11 Seed emulsion resin was prepared by adding% (3.5 g) and then maintaining for 20 minutes, 95 wt% of the preemulsion prepared in Example 11 was maintained at 80 ° C. for 1 hour while continuously feeding the reactor for 4 hours. After the retention time, the emulsion was cooled to 40 ° C. and 2.8 g of deionized water and 0.2 g of ammonia were added for 1 hour, thereby preparing an emulsion resin having excellent synthetic stability and uniform particle shape. It was.

[ Comparative Production Example  One]

26.4 g of deionized water and a second nonionic surfactant (poly (oxy-1,2-ethanediyl, α- [1- (hydroxymethyl) -2- (2-propenyloxy) ethyl]) in a reactor equipped with a stirrer, a thermometer and a condenser -ω-hydroxy-, C11-rich C10-14-branched alkyl ethers, HLB 16.5, solids 65%) 0.6g was added and the temperature was raised to 80 ℃, 5 weight in the pre-emulsion prepared in Comparative Example 1 Seed emulsion resin was prepared by adding% (3.5 g) and then maintaining for 20 min. Then, 95 wt% of the preemulsion prepared in Comparative Example 1 was introduced into the reactor for 4 hours continuously at 1 ° C at 80 ° C. Emulsion of the stabilized homogeneous form was prepared by maintaining for a period of time After the holding time was completed, the mixture was cooled to 40 ° C. and 2.8 g of deionized water and 0.2 g of ammonia were added for 1 hour to maintain the synthetic stability. Was prepared.

[ Comparative Production Example  2]

In a reactor equipped with a stirrer, a thermometer and a condenser, 26.4 g of deionized water and 0.6 g of a first nonionic surfactant (C ₁₂ H ₂₅ -O- (CH ₂ CH _{2 O} ) ₃ -H, HLB7.8, 100% solids) were added. After the addition and the temperature was raised to 80 ℃, 5% by weight (3.5 g) of the pre-emulsion prepared in Comparative Example 2 was added and then maintained for 20 minutes to prepare a seed emulsion resin. Then, 95% by weight of the preemulsion prepared in Comparative Example 2 was added to the reactor for 4 hours continuously, the synthetic stability was poor, it was not able to prepare an emulsion resin with uniform particle shape.

[ Experimental Example ]

The physical properties of the following items were evaluated for the emulsion resins prepared in Preparation Examples and Comparative Preparation Examples, and the results are shown in Tables 1 and 2 below.

-Synthetic stability : After preparing the emulsion resin, it was confirmed that the wire passes through 400 mesh. At this time, evaluation criteria are as follows.

<Evaluation Criteria>

○: all passed without residue

(Triangle | delta): Some thing which remains but resin passed through

X: The resin failed to pass through the filter due to gelation or residues during synthesis.

Water resistance : The coating composition including the emulsion resin was applied to a glass plate having a size of 15 cm * 30 cm in a thickness of 10 μm and then cured at 40 ° C. for 20 minutes. It was then immersed in water for 24 hours. Then, the glass plate was taken out to check the degree of discoloration of the coating film. At this time, evaluation criteria are as follows.

<Evaluation Criteria>

○: no discoloration of the coating film

(Triangle | delta): Some thing which arose by slight discoloration and water resistance lacking

X: The lifting is severe and the coating film is peeled off

- vesicular: To determine the basis of a resin emulsion was prepared by stirring for 5 minutes at 2000rpm arbitrary time after bubbling air bubbles disappear. At this time, evaluation criteria are as follows.

<Evaluation Criteria>

○: bubble removed within 30 minutes

△: bubble removed within 2 hours

X: Bubbles are not removed after 24 hours

-Solids

1) Test conditions: 1.0g sampling of the prepared emulsion resin, 150 ℃ x 30 minutes

2) Solids content (%): (Weight after heating / Weight before heating) x 100

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Low HLB 0.5 0.5 0.5 0.5 0.5 0.6 0.4 0.3 0.2 0.7 0.1 High HLB 0.5 0.5 0.5 0.5 0.5 0.4 0.6 0.7 0.8 0.3 0.9 Tg (℃) -20 -20 -30 -10 0 -20 -20 -20 -20 -20 -20 synthesis
stability O O O O O O O O O △ △ Water resistance O O O O O O O O O - - Antifoam O O O O O O O △ △ - - Solid content (%) 45.8 45.8 45.7 45.9 45.8 45.9 45.9 45.8 45.7 45.5 45.4 particle
Size (nm) 172 168 159 170 175 155 162 164 173 142 188

Comparative Example 1 Comparative Example 2 Tg (℃) -20 -20 Synthetic stability X X Water resistance - - Antifoam - - Solid content (%) 40.2 - Particle size (nm) 192 -

In Table 1, the low HLB (first nonionic surfactant) and the high HLB (second nonionic surfactant) are weight ratios (based on solids) of the nonionic surfactant included in the composition for preparing a water-soluble acrylic resin preemulsion of the present invention. . Referring to Table 1, the glass transition temperature of the emulsion resin is -30 to 0 ℃ by including a low HLB (first nonionic surfactant) and a high HLB (second nonionic surfactant) as in the present invention By using the low HLB (first nonionic surfactant) and the high HLB (second nonionic surfactant) in a predetermined ratio, it can be confirmed that the synthetic stability, the antifoaming property and the water resistance are excellent.

Claims (7)

An acrylic monomer, a nonionic surfactant, and a polymerization initiator,
The nonionic surfactant is a pre-emulsion composition for paints comprising a first nonionic surfactant having a HLB of 3 to 7.8 and a second nonionic surfactant having a HLB of 16 to 20. The method according to claim 1,
The nonionic surfactant is a pre-emulsion composition for paints contained in an amount of 1 to 15 parts by weight based on 100 parts by weight of the acrylic monomer. The method according to claim 1,
The first nonionic surfactant and the second nonionic surfactant are included in a weight ratio of 6: 4 to 2: 8 based on the solids content of the nonionic surfactant included in the preemulsion composition. . The method according to claim 1,
The acrylic monomer is a pre-emulsion composition for paint comprising at least one selected from the group consisting of (meth) acrylic acid, (meth) acrylic acid derivatives and mixtures thereof. The method according to claim 1,
The acrylic monomer is a pre-emulsion composition for a paint is contained in an amount of 30 to 60% by weight based on the total weight of the preemulsion composition. Water-soluble acrylic emulsion resin for paints manufactured using the preemulsion composition of any one of Claims 1-5. The method according to claim 6,
The water-soluble acrylic emulsion resin is a water-soluble acrylic emulsion resin for paints having a glass transition temperature of -30 to 0 ℃.