KR101800106B1

KR101800106B1 - Core-shell emulsion resin and paint composition containing the same

Info

Publication number: KR101800106B1
Application number: KR1020160008291A
Authority: KR
Inventors: 김경택; 봉재현; 신현민; 안희철; 정강훈; 김창현
Original assignee: 주식회사 케이씨씨
Priority date: 2016-01-22
Filing date: 2016-01-22
Publication date: 2017-11-22
Also published as: KR20170088482A

Abstract

The present invention relates to a core-shell emulsion resin, a method for producing the same, and a coating composition containing the same.

Description

CORE-SHELL EMULSION RESIN AND PAINT COMPOSITION CONTAINING THE SAME [0002]

Since the external coating material of the building is applied to the outside, the coating film formed therefrom is exposed to the outside. Accordingly, the external coating film formed from the paint in which the pigment is dispersed in the acrylate polymer emulsion resin or the acrylate polymer emulsion has problems such as color shift, gloss reduction, and low gloss retention due to various external stimuli such as sunlight and rainwater outside . In order to solve these problems, studies have been made to improve the physical properties of waterborne paints, and as a result, paints having performance similar to that of solventborne paints have been developed with respect to weatherability and water resistance. However, paying attention to the staining property, there is a limit in that even a low-contamination type water-based paint can not reach the level of a solvent-type low-pollution type paint. Since the coating film of the water-based paint is generally less dense than the coating film of the solvent-type coating, it is easy to penetrate the contaminant and the water-soluble monomer is mainly used to improve the water resistance. Therefore, once the contaminant is adhered, It is often difficult.

As a method for solving such a problem, WO 94/06870 discloses a technique of blending a specific organosilicate with a coating material. However, since organosilicate has poor compatibility with common water-based paints, it has disadvantages of generating precipitates and seriously lowering the surface gloss of the gloss paint. In addition, there is a method of applying a polymer surfactant or a metal alkoxide surfactant to the surface of the coating film. However, such a method has a disadvantage in that the initial stain resistance is excellent but the life span is short and the sustainability is limited.

It is an object of the present invention to solve the problems of the prior art as described above, and it is an object of the present invention to provide a water-based coating composition which can dramatically improve stain resistance, particularly stain resistance against organic matter contamination, It is a technical object to provide a low-contamination emulsion resin which can provide excellent weather resistance, water resistance and adhesion.

The present invention relates to a thermoplastic polymer composition comprising 90 to 94.5 parts by weight of an ethylenically unsaturated monomer, 1 to 5.5 parts by weight of an amino group-, sulfur- or phosphorus-containing hydrophilic monomer, an olefin-containing crosslinkable polyfunctional 0.1 to 5 parts by weight of a monomer, and 1 to 5 parts by weight of a carboxylic acid group-containing monomer as polymerized units; And 90 to 94.5 parts by weight of an ethylenically unsaturated monomer, 1 to 5.5 parts by weight of an amino group-, sulfur- or phosphorus-containing hydrophilic monomer, and 0.1 to 10 parts by weight of an olefin-containing crosslinkable polyfunctional monomer 0.1 To 5 parts by weight of a core-shell structure containing a shell containing as a polymerized unit a core-shell emulsion resin.

(1) 90 to 94.5 parts by weight of an ethylenically unsaturated monomer, 1 to 5.5 parts by weight of an amino group-, sulfur- or phosphorus-containing hydrophilic monomer, 100 to 500 parts by weight of an olefin-containing crosslinkable polyfunctional 0.1 to 5 parts by weight of a monomer, and 1 to 5 parts by weight of a carboxylic acid group-containing monomer are copolymerized by emulsion polymerization to prepare a core emulsion polymer; (2) adding 0.5 to 1.2 equivalents of a neutralizing agent to one equivalent of carboxylic acid of the core emulsion polymer prepared in the step (1) to prepare a pseudo water-soluble resin; And (3) 90 to 94.5 parts by weight of an ethylenically unsaturated monomer, 1 to 5.5 parts by weight of an amino group-, sulfur- or phosphorus-containing hydrophilic monomer, and 0.1 to 5 parts by weight of an olefin-containing crosslinkable polyfunctional monomer, 5 parts by weight of a shell composition is added to the resultant mixture of the step (2) and copolymerized to prepare a core-shell emulsion resin.

The present invention also relates to a coating composition comprising the core-shell emulsion resin and an additive selected from the group consisting of thickeners, pigments, film formers, dispersants, defoamers, cryoprotectants, preservatives, preservatives, surface smoothing agents and combinations thereof .

In order to minimize pollution caused by external environment such as rainwater, the present invention is a technique of hydrophilically designing a coating film and overcoming the deterioration in water resistance by gelation of emulsion particles, - a method for producing a shell emulsion resin, a core-shell emulsion resin produced thereby, and a coating composition comprising the same.

Using the core-shell emulsion resin produced by the method of the present invention, it is possible to produce a water-based glossy coating with remarkably improved stain resistance, and has similar or improved weatherability, water resistance and adhesion as compared to a solvent based coating.

The core-shell emulsion resin produced by the method of the present invention can be usefully used for manufacturing interior and exterior coatings for buildings and coating materials for various building materials that require particularly high water resistance and weather resistance.

Hereinafter, the present invention will be described in more detail.

The present invention relates to a thermoplastic polymer composition comprising 90 to 94.5 parts by weight of an ethylenically unsaturated monomer, 1 to 5.5 parts by weight of an amino group-, sulfur- or phosphorus-containing hydrophilic monomer, an olefin-containing crosslinkable polyfunctional 0.1 to 5 parts by weight of a monomer, and 1 to 5 parts by weight of a carboxylic acid group-containing monomer as polymerized units; And 90 to 94.5 parts by weight of an ethylenically unsaturated monomer, 1 to 5.5 parts by weight of an amino group-, sulfur- or phosphorus-containing hydrophilic monomer, and 0.1 to 10 parts by weight of an olefin-containing crosslinkable polyfunctional monomer 0.1 To 5 parts by weight of the core-shell structure as a polymerization unit.

The ethylenically unsaturated monomer can be used without limitation as long as it is generally used in the emulsion polymerization in the art. Examples thereof include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate Acrylic esters including; Methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, and 2-ethylhexyl methacrylate May contain at least one member selected from the group consisting of methacrylic acid ester, amyl acrylate, lauryl methacrylate, benzyl acrylate, benzyl methacrylate, styrene, methylstyrene, and vinyltoluene , But may not be limited thereto.

If the content of the monomer is less than 90 parts by weight or more than 94.5 parts by weight, the coating film may not be formed properly and the gloss and weatherability of the coating film may be deteriorated.

The amino group- or sulfur- or phosphorus-containing hydrophilic monomer may be selected from the group consisting of methyl acrylamide, N-methyl acrylamide, N, N-dimethyl acrylamide, N-ethylmethylacrylamide, methacrylamidoethylene urea, Dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, But are not limited to, butylaminoethyl methacrylate, dialkyl phosphates, ammonium phosphate esters, ammonium polyoxyethylene sulfates, ammonium polyoxyethylene alkyl aryl sulfates, polyoxyethylene aryl ether phosphates, alkyl phosphates, alkyl ether phosphates, sodium 2-methylpropylene sulfonate , Sodium 1-allyloxy-2-hydroxy-3-sulfonate propane, 2-acrylamino-2-methyl-1-propanesulfonate acid, One selected from the group consisting of vinyl sulfonate, sodium methallylsulfonate, sodium methylsulfonate, sodium p-styrene sulfonate, sodium allyl sulfonate, sodium cumene sulfonate, sodium zyrenesulfonate and sodium toluene sulfonate But may not be limited thereto. In addition to the hydrophilic monomers listed above, hydrophilic monomers having an amino group, sulfur or phosphorus can be used without any particular limitation.

If the content of the amino group-, sulfur-, or phosphorus-containing hydrophilic monomer is less than 1 part by weight, the hydrophilic performance may be deteriorated, and if it exceeds 5.5 parts by weight, the water resistance of the coating film may be deteriorated.

The olefin-containing crosslinkable polyfunctional monomer may be at least one selected from the group consisting of divinylbenzene, 1,4-divinylbenzene, aryl acrylate, aryl methacrylate, 1,6-hexanediol diacrylate, 1,6- Butylene glycol dimethacrylate, butanediol diacrylate, diaryl phthalate, tripropylene glycol dimethacrylate, trimethylolpropane, and trimethylolpropane dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, But is not limited to, at least one selected from the group consisting of trimethacrylate, trimethacrylate, and trimethacrylate. For example, the crosslinkable polyfunctional monomer may contain, but not be limited to, two or more olefins in the molecule to increase the grafting reaction.

If the content of the olefin-containing crosslinkable polyfunctional monomer is less than 0.1 parts by weight, the hydrophilicity may be lowered. If the content of the olefin-containing crosslinkable polyfunctional monomer is more than 5 parts by weight, adhesion performance and gloss of the coating film may be lowered.

The carboxylic acid group-containing monomer is preferably a monomer containing a single carboxylic acid group selected from the group consisting of acrylic acid, methacrylic acid, vinylbenzene acid and isopentylbenzene acid, and a monomer containing a carboxylic acid group selected from the group consisting of crotonic acid, itaconic acid, And at least one monomer selected from the group consisting of monomers containing two carboxylic acid groups selected from the group consisting of the above-mentioned monomers.

If the content of the carboxylic acid group-containing monomer is less than 1 part by weight, foreign substances may be generated during emulsion polymerization, and if it exceeds 5 parts by weight, the water resistance of the coating film may be lowered.

The present invention relates to a thermoplastic resin composition comprising (1) 90 to 94.5 parts by weight of an ethylenically unsaturated monomer, 1 to 5.5 parts by weight of an amino group-, sulfur- or phosphorus-containing hydrophilic monomer, 0.1 to 10 parts by weight of an olefin- To 5 parts by weight of a carboxylic acid group-containing monomer, and 1 to 5 parts by weight of a carboxylic acid group-containing monomer are copolymerized by emulsion polymerization to prepare a core emulsion polymer; (2) adding 0.5 to 1.2 equivalents of a neutralizing agent to one equivalent of carboxylic acid of the core emulsion polymer prepared in the step (1) to prepare a pseudo water-soluble resin; And (3) 90 to 94.5 parts by weight of an ethylenically unsaturated monomer, 1 to 5.5 parts by weight of an amino group-, sulfur- or phosphorus-containing hydrophilic monomer, and 0.1 to 5 parts by weight of an olefin-containing crosslinkable polyfunctional monomer, 5 parts by weight of a shell composition is introduced into the resulting mixture of the step (2) and copolymerized.

For example, the steps (1) and (3) may be carried out by using at least one selected from the group consisting of starch, radical initiator, and emulsifier, but the present invention is not limited thereto.

In the copolymerization process for producing the core emulsion polymer of the core-shell emulsion resin of the present invention, about 0.1 to 5 parts by weight of a chain transfer agent may be used for 100 parts by weight of the core monomer composition, . It is now desirable to choose to provide a controlled molecular weight distribution with high transfer activity and should not adversely affect the polymerization rate. The amount of the superplasticizer can be appropriately selected by those skilled in the art from about 0.1 to 5 parts by weight based on 100 parts by weight of the core monomer composition considering the kind and amount of the polymerization initiator.

When the amount of the chain transfer agent is less than 0.1 parts by weight or exceeds 5 parts by weight, an adjustable molecular weight distribution can not be provided, and the polymerization rate may be adversely affected.

Examples of the chain transfer agent include, but are not limited to, alkyl mercaptans having 2 to 10 carbon atoms, mercaptocarboxylic acids having 2 to 8 carbon atoms and their esters, and carbon tetrachloride, bromodichloromethane and the like.

In the process for producing the core-shell emulsion resin of the present invention, radical initiators can be used in the copolymerization process for producing the core emulsion polymer, water-soluble and oil-soluble initiators in which radicals are formed by thermal dissociation at high temperatures, - Initiators in which a radical is generated by a reduction reaction may be used, but the present invention is not limited thereto.

In the copolymerization process for producing the core emulsion polymer of the core-shell emulsion resin of the present invention, about 0.2 parts by weight to about 1.5 parts by weight of the water-soluble thermal deterioration radical initiator may be used per 100 parts by weight of the core monomer composition, But may not be limited thereto. When the thermally dissociative radical initiator is used, polarity can be preferably imparted to the surface of the core.

Examples of the water soluble thermal deterioration initiator include ammonium, potassium, sodium persulfate, ammonium persulfate, sodium persulfate, cyclohexyl hydroperoxide, cumene hydroperoxide, n-octyl hydroperoxide, But are not limited to, those selected from the group consisting of methyl, ethyl, ethyl, isopropyl, n-butyl, isopropyl, n-butyl,

The neutralizing agent used in the method for producing the core-shell emulsion resin of the present invention is an inorganic base such as ammonia, sodium hydroxide (NaOH), potassium hydroxide (KOH), lithium hydroxide (LiOH); And dimethylethanolamine, AMP 95 (manufactured by Angus), which is an organic base; But are not limited to, primary, secondary, tertiary amines such as triethylamine and triethylamine. The neutralizing agent is used in an amount of about 0.5 to 1.2 equivalents based on 1 equivalent of the carboxylic acid of the core emulsion polymer. When the neutralizing agent is used in an amount less than 0.5 equivalent, the degree of water-solubilization during neutralization is low, And if it exceeds 1.2 equivalents, it is completely water-soluble, so that the subsequent shell process can not perform the role of emulsifier as well.

The degree of neutralization is one of the most important factors affecting the swelling / dissolution behavior of the core. When the degree of neutralization is increased, the dissolution behavior is strengthened to accelerate the acceptance of core particles. However, if the degree of neutralization is too high, the stability of shell polymerization may not be secured have. Therefore, in order to ensure the stability of the shell polymerization, an appropriate degree of neutralization is required. In the present invention, the degree of neutralization is preferably about 10 to 105% based on the total number of carboxylic acid groups in the core, to be.

The present invention relates to the above-mentioned core-shell emulsion resin; And an additive selected from the group consisting of a thickener, a pigment, a film forming aid, a dispersant, a defoaming agent, a cryoprotectant, a preservative, a preservative, a surface smoothing agent, and combinations thereof. The thickener, the pigment, the film forming auxiliary, the dispersing agent, the defoaming agent, the cryoprotectant, the preservative, the preservative, and the surface smoothing agent can be used without limitation as long as they are commonly used in the art.

Hereinafter, the present invention will be described more specifically by way of examples. However, these examples are provided only for the understanding of the present invention, and the scope of the present invention is not limited to these examples in any sense.

[Example]

Example: Preparation of core-shell emulsion resin

A thermocouple, a stirrer and a reflux condenser were placed in a 2-L four-necked round flask, and 205.2 g of deionized water and 1.9 g of an emulsifier FES32 (BASF) were charged and heated to 80 ° C.

For the preparation of the core, a mixture of 24.9 g of deionized water and 1.1 g of ammonium persulfate as a radical initiator was prepared at 80 ° C. Subsequently, 100.8 g of deionized water, 2.8 g of the emulsifier FES32, 8 g of sodium methallylsulfonate as the sulfur-containing hydrophilic monomer, 83.7 g of butyl methacrylate as the ethylenically unsaturated monomer and 130.8 g of methyl methacrylate (methyl methacrylate) 10 g of methacrylic acid as a carboxylic acid group-containing monomer and 2.0 g of aryl methacrylate as an olefin-containing crosslinkable polyfunctional monomer were mixed and 5% of the mixture was added dropwise to the reactor. 70% of the subsequently prepared mixture was added dropwise to the reactor. And maintained at 80 [deg.] C for 20 minutes after dropwise addition.

The remaining mixture was then added dropwise for 2 hours and then kept for 1 hour. Then, a mixture of 5 g of neutralizer amp-95 and 12.5 g of deionized water was prepared and then added dropwise to the reactor. After the dropwise addition, the remaining initiator solution was added dropwise to the reactor.

Then, for the preparation of the shell, 102 g of deionized water, 3.5 g of emulsifier FES32, 8 g of dimethyl acrylamide as amino group-containing hydrophilic monomer, 68.8 g of butyl acrylate as an ethylenically unsaturated monomer and 125 g of methyl methacrylate, A mixture of 2 g of aryl methacrylate as a crosslinkable polyfunctional monomer and 1 g of methyl mercaptopropionate as a twin screw extruder was added dropwise over 90 minutes, and the mixture was allowed to react for 1 hour. After the holding reaction, the water-soluble core-shell emulsion resin of the examples was prepared by cooling to 50 캜 and packing while being filtered using a filter of 150 mesh.

The particle size of the synthesized emulsion particles measured by LLS (light laser scattering) was measured at 145 nm, and the solids content was measured as 45.01%, pH 7, and viscosity 110 cps. The obtained emulsion was used to prepare a coating material, and a stain resistance, a contact angle, an initial gloss value, a gloss retention rate and a water resistance evaluation test were conducted on the coating material.

[Comparative Example]

Comparative Example 1

A thermocouple, a stirrer and a reflux condenser were attached to a 2-L four-necked round flask, and to this were added 190 g of deionized water, 1.68 g of emulsifier SR-10 (ASIA DENKA), 0.52 g of emulsifier FL- And 10.8 g of 3-methacryloxypropyltrimethoxysilane were charged, and the temperature was raised to 80 占 폚. After adding a mixture of 50 g of deionized water and 0.21 g of potassium persulfate at 80 캜, 12.2 g of deionized water, 0.052 g of FL-10, 0.04 g of SR-10, 0.059 g of potassium persulfate, 6.33 g of butyl acrylate, A mixture of 2.49 g of methyl methacrylate, 5.5 g of butyl methacrylate, 9.87 g of cyclohexyl methacrylate and 1.2 g of methacrylic acid was added dropwise over 20 minutes, and the mixture was maintained for 40 minutes.

Then, 109.8 g of deionized water, 0.468 g of FL-10, 0.36 g of SR-10, 0.531 g of potassium persulfate, 56.97 g of butyl acrylate, 22.41 g of methyl methacrylate, 49.5 g of butyl methacrylate, g, 10.8 g of methacrylic acid, 1.8 g of methyltrimethoxysilane and 2.5 g of methyl-3-mercaptopropionate was added dropwise over 180 minutes, and the mixture was maintained for 40 minutes.

Thereafter, 6.7 g of an aqueous ammonia solution (25%) was added dropwise over 10 minutes, and then maintained for 20 minutes. Subsequently, a mixture of 52 g of deionized water and 0.3 g of potassium persulfate and 20.9 g of butyl acrylate, 5 g of methyl methacrylate, 49 g of butyl methacrylate, 28 g of cyclohexyl methacrylate and 1,6-hexane diol diacryl And 2 g of the mixture was simultaneously added dropwise over 90 minutes, and the mixture was allowed to react for 1 hour. After the above holding reaction, the emulsion resin of Comparative Example 1 was prepared by cooling to 50 캜 and packing while being filtered using a filter of 150 mesh. The particle size of the synthesized emulsion particle was measured at 145 nm, the glass transition temperature (Tg) was 31.5 ℃, the solid content was 46.56%, the pH was 8.44, and the viscosity was 194 cps as measured by LLS (Light Laser Scattering).

Comparative Example 2

A thermocouple, a stirrer and a reflux condenser were placed in a 2-L four-necked round flask, and 205.2 g of deionized water and 1.9 g of an emulsifier FES32 (BASF) were charged into the flask and the temperature was raised to 80 ° C. A mixture of 24.9 g deionized water and 1.1 g ammonium persulfate was prepared at 80 ° C. To prepare the core, a mixture of 100.8 g of deionized water, 2.8 g of emulsifier FES32, 83.7 g of butyl methacrylate as the ethylenically unsaturated monomer, 136.8 g of methyl methacrylate, and 10 g of methacrylic acid as the carboxylic acid group- % Was added dropwise to the reactor once per minute. Unlike the examples, amino-, sulfur-, or phosphorus-containing hydrophilic monomers and olefin-containing crosslinkable polyfunctional monomers were not used. 70% of the subsequently prepared mixture was added dropwise to the reactor. And maintained at 80 [deg.] C for 20 minutes after dropwise addition. After the maintenance, the remaining monomer mixture was added dropwise for 2 hours and maintained for 1 hour. A mixture of 5 g of neutralizer amp-95 and 12.5 g of deionized water was prepared and added dropwise to the reactor. After the dropwise addition, the remaining initiator solution was added dropwise to the reactor.

Next, for the preparation of the shell, 102 g of deionized water, 3.5 g of emulsifier FES32, 8 g of dimethyl acrylamide as amino group-containing hydrophilic monomer, 68.8 g of butyl acrylate as an ethylenically unsaturated monomer and 135 g of methyl methacrylate, And 1 g of methyl mercaptopropionate was added dropwise over 90 minutes, and the mixture was allowed to react for 1 hour. Unlike the examples, the olefin-containing crosslinkable polyfunctional monomer was not used. After the above holding reaction, the emulsion resin of Comparative Example 2 was prepared by cooling to 50 캜 and packaging while being filtered using a filter of 150 mesh.

The particle size of the synthesized emulsion particles measured by LLS (Light Laser Scattering) was measured at 145 nm and the solids content was measured as 45.01%, pH 7, and viscosity 134 cps. The obtained emulsion was used to prepare a coating material, and a stain resistance, a contact angle, an initial gloss value, a gloss retention rate and a water resistance evaluation test were conducted on the coating material.

Preparation of Coating Composition

Using the emulsion resins prepared in the above Examples and Comparative Examples 1 and 2, a water-soluble paint composition having the composition shown in the following Table 1 was prepared.

The prepared clear paint was mixed with a TiO ₂ slurry at a ratio of 7: 3 to prepare a white paint

Evaluation of Physical Properties of Coating Composition

The properties of the water-soluble paint compositions containing the emulsion resins of the above Examples and Comparative Examples 1 and 2 were evaluated. The water-soluble coating composition was a one-part type room temperature drying type, and physical properties thereof were evaluated and shown in Table 2. The criteria for physical property evaluation are as follows:

* Adhesion: Brush paint was applied to the night light specimen twice, dried for 1 day and then measured with Cross Cut (100 * 100).

* Water resistance: The night light was applied to the specimen twice, and the specimen was immersed in fresh water for one day, and the film change was observed.

* Contact Angle: A white paint was applied to glass specimens with WET 10MIL and dried at room temperature for 1 week and measured with a contact angle meter.

* Gloss: The white paint was applied to the glass specimen with WET 10MIL and dried at room temperature for one week. Then, the gloss was measured using a gloss meter.

* Weatherability: The test pieces were exposed to the accelerated weathering test equipment (ATLAS Ci5 / DMC Weather-O-Meter) for 250 hours according to Test Method 3231 of KS M 5000,

* Stain resistance: It was left on the outer wall next to the carbon adsorption tower with a high pollution level for 2 months after painting for more than 3 months.

According to the results of the physical property evaluation, the water-soluble paint composition containing the core-shell emulsion resin according to the embodiment of the present invention is a paint composition containing the resin of Comparative Example 1 prepared using a very low-boiling monomer and an olefin- Water resistance and adherence as compared with the coating composition containing the resin of Comparative Example 2 which was prepared without using a monomer and showed excellent stain resistance compared with Comparative Examples.

Claims

90 to 94.5 parts by weight of an ethylenically unsaturated monomer, 1 to 5.5 parts by weight of an amino group-, sulfur- or phosphorus-containing hydrophilic monomer, 0.1 to 50 parts by weight of an olefin-containing crosslinkable polyfunctional monomer, 5 to 5 parts by weight of a carboxylic acid group-containing monomer, and 1 to 5 parts by weight of a carboxylic acid group-containing monomer as polymerized units; And
90 to 94.5 parts by weight of an ethylenically unsaturated monomer, 1 to 5.5 parts by weight of an amino group-, sulfur- or phosphorus-containing hydrophilic monomer, and 0.1 to 50 parts by weight of an olefin-containing crosslinkable polyfunctional monomer, based on 100 parts by weight of the polymer constituting the shell, Core-shell structure comprising a shell containing 5 parts by weight as polymerized units
Of the core-shell emulsion resin.

The method according to claim 1,
Wherein said ethylenically unsaturated monomer is selected from the group consisting of acrylic acid esters comprising methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate; Methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, and 2-ethylhexyl methacrylate And at least one selected from the group consisting of methacrylic acid ester, amyl acrylate, lauryl methacrylate, benzyl acrylate, benzyl methacrylate, styrene, methylstyrene, and vinyltoluene. , Core-shell emulsion resin.

The method according to claim 1,
The amino group-, sulfur-, or phosphorus-containing hydrophilic monomer may be at least one selected from the group consisting of methyl acrylamide, N-methylacrylamide, N, N-dimethyl acrylamide, N-ethylmethylacrylamide, methacrylamidoethyleneurea, Dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, But are not limited to, butylaminoethyl methacrylate, dialkyl phosphates, ammonium phosphate esters, ammonium polyoxyethylene sulfates, ammonium polyoxyethylene alkyl aryl sulfates, polyoxyethylene aryl ether phosphates, alkyl phosphates, alkyl ether phosphates, sodium 2-methylpropylene sulfonate , Sodium 1-allyloxy-2-hydroxy-3-sulfonate propane, 2-acrylamino-2-methyl-1-propanesulfonate acid, One selected from the group consisting of sulfonates such as sodium methallyl sulfonate, sodium methallyl sulfonate, sodium methyl sulfonate, sodium p-styrene sulfonate, sodium allyl sulfonate, sodium cumene sulfonate, sodium zyrenesulfonate and sodium toluene sulfonate By weight of the core-shell emulsion resin.

The method according to claim 1,
The olefin-containing crosslinkable polyfunctional monomer may be at least one selected from the group consisting of divinylbenzene, 1,4-divinylbenzene, aryl acrylate, aryl methacrylate, 1,6-hexanediol diacrylate, 1,6- Butylene glycol dimethacrylate, butanediol diacrylate, diaryl phthalate, tripropylene glycol dimethacrylate, trimethylolpropane, trimethylolpropane dimethacrylate, ethylene glycol diacrylate, Wherein the core-shell emulsion resin contains at least one selected from the group consisting of trimethylolpropane triacrylate, trimethacrylate, and triacrylate.

The method according to claim 1,
The carboxylic acid group-containing monomer is preferably a monomer containing a single carboxylic acid group selected from the group consisting of acrylic acid, methacrylic acid, vinylbenzene acid and isopentylbenzene acid, and a monomer containing a carboxylic acid group selected from the group consisting of crotonic acid, itaconic acid, Wherein the core-shell emulsion resin comprises at least one monomer selected from monomers containing two carboxylic acid groups selected from the group consisting of acrylic acid,

(1) 90 to 94.5 parts by weight of an ethylenically unsaturated monomer, 1 to 5.5 parts by weight of an amino group-, sulfur- or phosphorus-containing hydrophilic monomer, 0.1 to 5 parts by weight of an olefin-containing crosslinkable polyfunctional monomer And 1 to 5 parts by weight of a carboxylic acid group-containing monomer are copolymerized by emulsion polymerization to prepare a core emulsion polymer;
(2) adding 0.5 to 1.2 equivalents of a neutralizing agent to one equivalent of carboxylic acid of the core emulsion polymer prepared in the step (1) to prepare a pseudo water-soluble resin; And
(3) 90 to 94.5 parts by weight of an ethylenically unsaturated monomer, 1 to 5.5 parts by weight of an amino group-, sulfur- or phosphorus-containing hydrophilic monomer, and 0.1 to 5 parts by weight of an olefin-containing crosslinkable polyfunctional monomer, By weight of the shell composition is introduced into the resulting mixture of step (2) and copolymerized
Of the core-shell emulsion resin.

The method according to claim 6,
Wherein the steps (1) and (3) are carried out by using at least one selected from the group consisting of starch, radical initiator, and emulsifier, respectively.

The core-shell emulsion resin of any one of claims 1 to 5; And
Additives selected from the group consisting of thickeners, pigments, film formers, dispersants, defoamers, cryoprotectants, preservatives, preservatives, surface smoothing agents and combinations thereof
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