KR100538846B1 - Core / shell microgel containing alkylene monoisocyanate / poly (ethylene oxide) monoalcohol monomer and coating composition containing same - Google Patents

Abstract

The present invention relates to a core / shell-type microgel containing an alkylene monoisocyanate / poly (ethylene oxide) monoalcohol adduct and to a coating composition containing the same, and more particularly to alkylene monoisocyanate and poly (ethylene oxide) mono A method of preparing a core / shell-type microgel in which a reactive emulsifier obtained by alcohol-containing urethane bonds in an equivalent ratio of 1: 1 is improved in a shell composition and 5 to 100 weight of the microgel as a binder in paint. It is directed to a waterborne coating composition comprising a blend using% and main resin 0-95% by weight and pigments and other paint additives and having a total solids content of at least 15% when applied.

Sub-based coating composition prepared according to the present invention shows excellent water resistance, fouling resistance and adhesion even at relatively low baking conditions and solid content of 15% or more, and can be blended with other urethane resins or urethane copolymers for automotive use. It can be usefully used for refinish paint, plastic paint, and building paint.

Description

Core / shell microgel containing alkylene monoisocyanate / poly (ethylene oxide) monoalcohol monomer and coating composition containing same

The present invention relates to a core / shell-type microgel containing an alkylene monoisocyanate / poly (ethylene oxide) monoalcohol monomer and a coating composition containing the same, and more particularly to alkylene monoisocyanate and poly (ethylene oxide) monoalcohol. Including a reactive emulsifier obtained by urethane bonds in a 1: 1 equivalent ratio in a shell composition to improve the water resistance, fouling resistance and adhesion, and a method for producing a core / shell-type microgel and the above-mentioned microgel; It is for a waterborne coating composition having a total solids content.

Since the early 1970s, the paint has been aqueousized as an attempt to suppress the release of organic solvents, which are air pollution sources. However, conventional water-based resins are not only inferior in physical properties to the paints currently used in terms of physical properties such as water resistance, rust resistance, acid resistance, solvent resistance, etc., and physical properties such as adhesion, impact resistance, and bendability. In addition, the paintability, spray coating conditions and the appearance of the coating could not satisfy the needs of consumers.

Examples of advanced technologies in this field include US Pat. No. 4,539,363 and US Pat. No. 4,403,003 by Backhouse. In these patents, water-based paints, including cores / shells obtained by synthesizing core / shell-type polymer fine particles using a crosslinked core and then swelling the shell by neutralizing the carboxy group of the shell composition with an amine, are less sensitive to changes in temperature and humidity during coating. It shows better resistance to popping during firing, pseudoplastic viscosity behavior, showing excellent properties in spray workability, sag resistance and paint storage. have. In addition, the core / shell-type microgels used as main resins in the patent have cross-linked molecular interiors, so when used as a base coat for automobiles, it affects the penetration of the solvent during the wet-on-wet coating of the subsequent solvent-type clearcoat. Receive less. However, the aqueous resin and the water-based coating composition described in this patent require baking conditions of 100 ° C. or higher, and therefore are used for poor repellency in automotive refinish paints, plastic coating paints, and building paints which are dried or baked at relatively low temperatures. Can not.

Another example of advanced technology in this field is Prog., Reported by Yagi et al . Org. Coat. , 1992, 21, 25-35. The technique crosslinks the hydrophobic acrylic monomer composition which can be crosslinked by emulsion polymerization to the core, and uses an ionic or nonionic methacrylate having a hydrophilic poly (ethylene oxide) group as a reactive emulsifier. Microgels are described. In the above technique, the architectural paint blending the microgel with a conventional emulsion-type resin is flexible and water resistant, and it is possible to make a breathable coating film which can be moved in the microgel by carbon dioxide and water vapor generated in cement, thereby changing the season. It is described that it can withstand. However, the microgel used in this paper is poor in fusion at the time of forming the coating film because the shell forming the coating film is composed of a copolymer having only hydrophilic polyethylene oxide groups. Therefore, when the microgel contains more than 15% of the total resin blend, the water resistance is sharply lowered.

Accordingly, the coating film is well fused even under low temperature baking conditions, and it is urgent to develop a coating composition having excellent water resistance and adhesion, spray workability, pigment storage property and flow resistance.

In order to solve the above problems, the inventors have conducted extensive research, and the present invention has been completed based on this.

Accordingly, an object of the present invention is to provide an alkylene monoisocyanate / poly (ethylene oxide) monoalcohol monomer as a shell composition as a reactive emulsifier that can increase the colloidal stability of the particles, salts and emulsifiers generated during neutralization To provide a core / shell-type microgel showing excellent water resistance, fouling resistance and adhesion that can reduce the use of.

It is another object of the present invention to include a core / shell-type microgel in which the alkylene monoisocyanate / poly (ethylene oxide) monoalcohol monomer is included in a shell composition, and drying is possible at 5 ° C. or higher and a curing temperature of 50 ° C. or higher. The present invention provides a water-based coating composition which can be baked at low temperature and can be used as a refinish paint for automobiles that exhibits excellent water resistance, stain resistance and adhesion even at a content of 15% or more of the resin solids.

The water-based coating composition according to the above object of the present invention may be compatible with other aqueous acrylic resins, that is, urethane resins or acrylic-urethane copolymers, polyester-urethane copolymers and alkyd-urethane copolymers, in particular breathable It has a popping resistance.

Core / shell-type microgel according to the present invention for achieving the above object is n-isocyanatoalkyl methacrylate represented by the following formula (1a) or dialkyl meth- isopropenyl benzyl isocyanate and alkoxide represented by the formula (1b) Reaction of poly (ethylene oxide) monoalcohol represented by the following formula (2) using a catalyst at 50-130 ° C. in a 1: 1 equivalent ratio until the residual isocyanate group disappears without a solvent Alkylene monoisocyanate / poly (ethylene oxide) monoalcohol monomer prepared by the shell composition is included.

Here, n is an integer of 1-6.

Here m is an integer of 0-3.

Here, x is an integer of 0-14, y is an integer of 10-75, the average molecular weight of the whole molecule | numerator is 3000 or less, Preferably it is the range of 1200-2000.

The alkylene monoisocyanate / poly (ethylene oxide) monoalcohol monomer has a urethane bond with a hydrophilic poly (ethylene oxide) group, and acts as a reactive emulsifier and a monomer, thereby allowing the use of a carboxy group of a shell composition used for the stability of the resin. Since it is possible to minimize the use of salts and emulsifiers generated during neutralization, the water-based coating composition including the core / shell-type microgel of the present invention containing it as a shell composition shows excellent water resistance, fouling resistance and adhesion, and other urethanes. It can be blended compatible with resins or urethane copolymers.

Core / shell-type microgel constituting the water-based coating composition of the present invention for achieving the above object is prepared by using an emulsion polymerization method using a three-step conventional emulsifier and initiator of the seed / core / shell, formed in one step Seed latex of 1 to 7% by weight of the total resin composition, 19 to 78% by weight of the total resin composition formed by using a crosslinkable composition on the seed latex polymerized in step 2 and the total resin constituting the finally formed coating film It consists of 15 to 79% by weight of the shell.

Water-based coating composition for achieving another object of the present invention comprises a blend and a pigment and other paint additives using 5 to 100% by weight of the microgel and 0 to 95% by weight of the main resin, and at least 15% of the total Have a solids content.

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

The core / shell-type microgel of the present invention is synthesized by three step polymerization by an emulsion method using an emulsifier and an initiator in an aqueous phase, and the characteristics of the step are as follows.

First, a seed latex is produced in a first step, and a core is formed by using a crosslinkable composition on the seed latex by a two-step polymerization, and in the final step, a part that finally forms a coating film using a hydrophilic composition rather than a core composition is used. To produce polymer particles having a size of 0.01 to 100 microns having a multi-layer structure composed of a shell.

The seed is for uniform distribution of the final particle size produced, consisting of 1 to 7% by weight of the total resin composition, if the seed is less than 1% by weight of the total resin composition in the subsequent core and shell polymerization step Rather than producing particles in a multi-layered structure, new particles are produced, making it difficult to produce microgels with ideal core / shell morphologies, and coagulum occurs during polymerization. The composition of the core and shell is reduced, making it difficult to produce particles with the desired physical properties. The seed is methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, styrene, acrylonitrile, acrylamide, vinyl chloride, vinyl acetate, vinyl pro And one or more monomer mixtures from the group consisting of pinonate and vinyltoluene. In addition, some of the following core compositions may be prepared by polymerizing first.

The core is composed of 19 to 78% by weight of the total resin composition, when the core is less than 19% by weight causes a problem that the structure of the core / shell is reversed when the degree of crosslinking is low, and when the core exceeds 78% by weight Since the ratio is lowered, the fusion performance is lowered when the coating film is formed, which causes a problem of not exhibiting the desired plasticity viscosity behavior. 88.0-99.9% by weight of the core composition consists of one or more monomers having one or more polymerizable reactive groups used in the seed, and 0.2-12.0% by weight of divinylbenzene, aryl methacrylate, 1,6-hexanedioldiacrylic It is characterized in that it consists of monomers having two or more reactive groups polymerized from the group consisting of latex, diethylene glycol diacrylate and butanediol diacrylate. Journal of Coating Technology, 1990, 52, 33-38, reported by Crews et al . And Proc. ACS DIV. According to the description of PMSE , 1985, 52, 326-330, the use of crosslinked microgels increases the tensile strength of the final coating and is insoluble in organic solvents when used as a basecoat for automobiles, so that subsequent oil-soluble clearcoats Wet-on-wet coatings are less susceptible to attack by organic solvents, which can eliminate wrinkles. In addition, since the polyfunctional monomer having two or more reactive groups to be polymerized forms a reactive microgel in which olefins remain on the inside and the surface of the core, the microgel may have a core / shell form if the polymerization process of the shell is added later. J. Appl., Reported by Verbrugge . Polym Sci. , 1970, 14, 897-909, ASE (akali-swellable emulsion) type thickener showed a much higher viscosity in the cross-linked polymer than the non-cross-linked polymer. Therefore, the use of the crosslinked core of the present patent can increase the viscosity when neutralizing with an amine in the use of a monomer containing carboxylic acid in the shell composition than when using a non-crosslinked core, thereby minimizing the use of other thickeners. have.

The shell is composed of 15 to 79% by weight of the total resin composition, if less than 15% by weight has a problem that the fusion performance and the desired plasticity viscosity behavior is not exhibited when forming the coating film, if the content exceeds 79% by weight core / shell blanket The inversion of the lodge occurs or, in addition to the generation of particles of a multi-layer structure during the polymerization, new particles are generated, causing problems of deterioration of the overall physical properties of the final coating film. The shell is from 2 to 100% by weight of alkylene monoisocyanate / poly (ethylene oxide) monoalcohol adduct, 0 to 20% by weight of acrylic acid or methacrylic acid alone or mixture, 0 to 20% by weight. It is characterized by consisting of one or more monomers each having one or more polymerized reactive groups which can be used either alone or in a mixture of 2-hydroxy ethylacrylate or 2-hydroxy propylacrylate and from 0 to 95% by weight of seeds. Here, the mixing of each component is 100%. In this case, when the content of the alkylene monoisocyanate / poly (ethylene oxide) monoalcohol adduct constituting the shell is less than 2% by weight, there is a problem in polymerization stability such as aggregation due to lack of emulsifier.

In the present invention, the adduct of the alkylene monoisocyanate / poly (ethylene oxide) monoalcohol, which is a monomer having a poly (ethylene oxide) group at the terminal, is represented by the alkylene monoisocyanate group represented by the following general formula (1a) or (1b). The hydroxyl groups of the compounds are prepared by reacting to form urethane bonds under suitable conditions. Here, the reaction conditions are generally made to react without solvent using a catalyst of amines or organometallic compounds with an equivalent ratio of isocyanate group / hydroxyl group at 50 to 130 ° C. as 1/1. At this time, if the reaction temperature is less than 50 ℃ polymerization rate is very long, the polymerization time is very long, and if it exceeds 130 ℃ the exothermic reaction temperature is very high causing the problem that the side reaction occurs.

Organometallic compounds (mainly Tin-based compounds) used to promote the urethanization reaction are generally well known triethylenediamine, morpholine, normal-ethyl-morpholine, piperazine, triethanolamine, triethylamine, tributyl 0.001-0.1 weight of total solids as tindilaurate, stanus octoate, dioctyl tin diacetate, dioctate, stanus oleate, stanustalate, dibutyl tin oxide, etc., alone or as a mixture of two or more thereof. It is used in about%, and when it exceeds 0.1% by weight acts as an impurity of the final paint has a problem of lowering the overall physical properties of the coating.

Alkylene monoisocyanate used as a reactant having an isocyanate group refers to a group of n-isocyanatoalkyl methacrylate (Formula 1a) and dialkylmetho-isopropenylbenzyl isocyanate (Formula 1b), each represented by the following formula: .

Formula 1a

Here, n is an integer of 1-6.

Formula 1b

Here m is an integer of 0-3.

2-Isocyanatoethyl methacrylate (2-IEMA) having n = 2 in Formula 1a is commercialized by Dow Chemical, and dimethylmeth-isopropenylbenzyl isocyanate having m = 0 in Formula 1b is It is known that it is commercialized by Cytec's TMI.

Poly (ethylene oxide) monoalcohol (Formula 2) as a reactant having a hydroxyl group is a substance obtained by ring opening reaction of ethylene oxide by anionic polymerization by an alkoxide.

Formula 2

Here, x is an integer of 0-14, y is an integer of 10-75, the average molecular weight of the whole molecule | numerator is 3000 or less, Preferably it is the range of 1200-2000, and when the said molecular weight exceeds 3000, molecular weight is large. There is a problem that the polymerization reaction proceeds very slowly or the polymerization does not occur. In Formula 2, x = 0 is commonly known as "MPEG's" (methoxy polyethylene glycols), and is commercially available as a product having various molecular weights, for example, by Union Carbide. A commercially available trade name is MPEG XXXX, where XXXX means a mass average molecular weight ranging from 1200 to 3000. Particularly preferred materials of these are MPEG 1450 and MPEG 2000.

The temperature at each stage of polymerization should usually be at least 10 ° C higher than the glass transition temperature of the polymer. The emulsifiers used are anionic emulsifiers selected from the group consisting of potassium laurate, potassium stearate, potassium oleate, sodium decyl sulfate, sodium dodecyl sulfate and sodium rosinate and linear or branched alkyl and alkylaryl polyethylene glycols. Or a group consisting of an alkylphenoxypoly (ethyleneoxy) ethanol or an sulfated form of ammonium salt thereof as an adduct of polypropylene glycol ether and thioether, 1 mole nonylphenol and 5 to 12 moles of ethylene oxide. The nonionic emulsifier selected from the above is used alone or in combination of two or more thereof.

Initiators used in the reaction are commonly used radical initiators such as ammonium persulfate, sodium persulfate, potassium persulfate, bis (2-ethylhexyl) peroxy dicarbonate, di-n-butylperoxy dicarbonate, t- Butyl pulpvalate, t-butyl hydroperoxide, cumene hydroperoxide, dibenzoyl peroxide, dilauroyl peroxide, 2,2'-azobisisobutylonitrile and 2,2'-azobis-2 -A group consisting of methylbutyronitrile or a mixture of redox initiators in the form of a mixture of such initiators with reducing agents such as alkali metal sulfites, hyposulfite and sodium formaldehyde sulfoxylate, alone or in combination of two or more Is used.

When using acrylic acid or methacrylic acid in the shell composition, the neutralizing agent used is a mixture of diethanolamine, diethylethanolamine, phenyl diethanolamine, methyl diethanolamine, dimethylaminoethanol or triethanolamine alone or in combination of two or more thereof. , To partially or fully neutralize core / shell microgels. The core / shell microgel thus prepared accounts for 5 to 50% by weight of the total paint content.

The co-solvent which helps the fusion of the coating film alone or two kinds of n-butanol, n-propanol, ethoxyethanol, methoxyethanol, 2-butoxyethanol, 1-methoxy-2-propanol, hexyl cellosolve or acosolve It is mixed above.

The total solid content of the paint is 15% or more when preparing the paint, wherein the pigment is used in an amount of 0.1 to 60% by weight based on the total water-soluble paint composition, and when the amount of the pigment exceeds 60% by weight, the amount of the binder is relatively reduced. This results in a problem of deterioration of various physical properties.

Other paint additives are hardeners, fillers, plasticizers, rheology modifiers, antioxidants, co-solvents, dispersants, antifoaming agents, leveling agents and the like, and can be used at 0.1 to 12% by weight relative to the total water-soluble coating composition. The water-based coating composition of the present invention thus prepared may be dried at a temperature of 5 ° C or more when coated on the coating.

Although the present invention will be described in more detail with reference to the following examples, the scope of the present invention is not limited to the following examples.

<Example>

The abbreviations shown below are used in the examples below.

2-IEMA: 2-isocyanatoethyl methacrylate

TMI: Dimethyl meta-isopropenylbenzyl isocyanate

MPEG 1450: methoxypolyethylene glycol (mass average molecular weight = 1450)

MPEG 2000: methoxypolyethylene glycol (mass average molecular weight = 2000)

CO-436: Ammonium salt in sulfated form of alkylphenoxypoly (ethyleneoxy 5 mol) ethanol

AIBN: 2,2'-azobis isobutylonitrile

DMEA: Dimethylethanolamine

Preparation Example 1

Preparation of Alkylene Monoisocyanate / Poly (ethylene Oxide) Monoalcohol Adduct I (2-IEMA / MPEG1450)

matter Volume (g)  MPEG 1450 449.50  2-IEMA  50.50  Dibutyl tindiolate   0.05

Into a 1000 ml flask equipped with a stirrer, a thermometer, a dropping tank, a nitrogen injection tube and a reflux condenser, 449.5 g of the above MPEG 1450 was inserted and heated to 70 ° C., followed by adding 0.05 g of dibutyltin dioleate. Subsequently, when 50.5 g of 2-IEMA is added, exotherm occurs at about 90 to 100 ° C., and the reaction is continued for 2 hours while maintaining this temperature. If the isocyanate band disappears in the infrared spectrum during the reaction, the reaction is terminated and cooled to room temperature.

Preparation Example 2

Preparation of Alkylene Monoisocyanate / Poly (ethylene Oxide) Monoalcohol Adduct II (2-IEMA / MPEG2000)

matter Volume (g)  MPEG 2000 462.30  2-IEMA  37.70  Dibutyl tindiolate   0.05

In the same manner as in Preparation Example 1, MPEG 2000 was first heated to 80 ° C, dibutyltindiolate and 2-IEMA were added thereto, maintained at 100 ° C or lower, and reacted for 2 hours. If there is no isocyanate content during the reaction, the reaction is terminated and cooled to room temperature.

Preparation Example 3

Preparation of alkylene monoisocyanate / poly (ethylene oxide) monoalcohol adduct III (TMI / MPEG1450)

matter Volume (g) MPEG 1450 436.40 TMI 63.60 Dibutyl tindiolate 0.05

In the same manner as in Preparation Example 1, the temperature of MPEG 1450 was first raised to 90 ° C., and then dibutyltin dioleate and TMI were added and maintained at 110 ° C. or lower for 2 hours. If there is no isocyanate content during the reaction, the reaction is terminated and cooled to room temperature.

Preparation Example 4

Preparation of Alkylene Monoisocyanate / Poly (ethylene Oxide) Monoalcohol Adduct IV (TMI / MPEG2000)

matter Volume (g) MPEG 2000 452.20 TMI 47.80 Dibutyl tindiolate 0.05

In the same manner as in Preparation Example 1, first, the temperature of MPEG 2000 was increased to 100 ° C., and then dibutyltin dioleate and TMI were added and maintained at 120 ° C. or lower for 2 hours. If there is no isocyanate content during the reaction, the reaction is terminated and cooled to room temperature.

Examples 1-4 and Comparative Example 1

Preparation of Core / Shell Type Microgels Comprising Alkylene Monoisocyanate / Poly (ethylene Oxide) Monoalcohol Adduct

A core / shell-type microgel was prepared with or without the alkylene monoisocyanate / poly (ethylene oxide) monoalcohol adduct as the following component.

 additive Volume (g) Example 1 Example 2 Example 3 Example 4 Comparative Example 1  Additive I Deionized Water CO-436 Monomer Mixture I 2-ethylhexylacrylate Styrene AIBN 445.01.95.15.50.4 445.01.95.15.50.4 445.01.95.15.50.4 445.01.95.15.50.4 445.01.95.15.50.4  Additive II Deionized Water CO-436 Monomer Mixture II Styrene Methyl Methacrylate 2-ethylhexylacrylate 1,6-hexanedioldiacrylate AIBN 134.21.545.065.661.41.70.9 134.21.545.065.661.41.70.9 134.21.545.065.661.41.70.9  134.21.545.065.661.41.70.9  134.21.545.065.661.41.70.9  Additive III Deionized Water 2-IEMA / MPEG1450 2-IEMA / MPEG2000 TMI / MPEG1450 TMI / MPEG2000 CO-436 Monomer Mixture III Methacrylic Acid 2-ethylhexylacrylate Ethylacrylate Methacrylate AIBN 66.22.5 ---- 3.75.028.518.60.3 66.2-2.5 --- 3.75.028.518.60.3 66.2--2.5--3.75.028.518.60.3 66.2 --- 2.5-3.75.028.518.60.3 66.2- --- 1.03.75.028.518.60.3

Addition I was added to a 2000 ml flask equipped with a stirrer, thermometer, dropping tank, nitrogen injection tube and reflux condenser and heated to 80 ° C. while stirring at 180 rpm. When the temperature is kept constant, the monomer mixture I is added dropwise for 10 minutes and held for 30 minutes to prepare the seed mixture. Additive II and monomer mixture II were added dropwise to the prepared seed mixture simultaneously at a constant rate for 3 hours and maintained for 1 hour, then additive III and monomer mixture III were simultaneously dropped at a constant rate for 1 hour and maintained for 1 hour, Prepare core / shell microgels. After the reaction was completed, the mixture was cooled to room temperature, the core / shell microgel emulsion solution was filtered through a 400 mesh nylon filter, and the pH was adjusted to 8.0 by dropping 10% aqueous DMEA solution (final solid content, 22 to 24). %) And leave for 1 day or more.

Examples 5-8 and Comparative Example 2

Preparation of Waterborne Metallic Basecoat Paints

Water-based metallic basecoat paints were prepared using the emulsion solution of the core / shell microgels of Examples 1 to 4 and Comparative Example 1.

additive Volume (g) Example 5 Example 6 Example 7 Example 8 Comparative Example 2 Aluminum paste ¹ 31.2 31.2 31.2 31.2 31.2 2-butoxyethanol 40.4 40.4 40.4 40.4 40.4 2% Laponite Paste ² 58.0 58.0 58.0 58.0 58.0 Core / Shell Microgel Emulsion (Example 1) 250.0 - - - - Core / Shell Microgel Emulsion (Example 2) - 250.0 - - - Core / Shell Microgel Emulsion (Example 3) - - 250.0 - - Core / Shell Microgel Emulsion (Example 4) - - - 250.0 - Core / Shell Microgel Emulsion (Comparative Example 1) - - - - 250.0 10% DMEA aqueous solution 6.1 6.1 6.1 6.1 6.1 Deionized water 17.2 17.2 17.2 17.2 17.2

¹ is WH-R607 purchased from Eckert Berkesa.

² was purchased from Lafort.

The coating composition for the water-based metallic basecoat was prepared using the above components, and the coating conditions were prepared such that the viscosity was 30 seconds (# 4 pod cup) as deionized water, and the pH at this time was 7.5 to 8.0. Thermal stability of the coating composition was evaluated as viscosity gradient after heat storage (50 ° C./7 days).

The physical properties necessary for use as the composition to apply the colored coating composition on a cold rolled steel plate electrodeposited with cations were evaluated. Spraying was carried out at a relative humidity of 60% and a temperature of 26 ° C and dried for 30 minutes. Next, the solvent-type clear coat paint was spray-coated and baked at 60 degreeC for 30 minutes. The coating thickness of the basecoat was 20 microns and the clearcoat was 35 microns. The gloss, DOI, and CROSS-HATCH adhesion of the cured initial air-conducting film and the coating film after 16 hours at 60 ° C. condensed humidity were evaluated. Gloss was measured at a 20 ^° angle using a gloss meter commercially available from SHEEN. DOI was measured by a method according to ASTM 4449-85, and cross-deodorant adhesion was measured using the ASTM3559 test method.

 Properties Example 5 Example 6 Example 7 Example 8 Comparative Example 2 Gloss (20 ^o ), initial / after aging 98/87 100/82 97/94 99/93 98/75  DOI, early / after aging 68/62 70/59 68/66 69/62 69/55  Cross-deodorant adhesive, early / after aging 0/3 0/5 0/0 0/1 2/8  Viscosity (Second, Pod Cup # 4), Initial / After Aging 30/35 30/38 30/34 30/36 30/34

As described in Table 7, the water-based coating composition of the present invention containing a core / shell-type microgel containing an alkylene monoisocyanate / poly (ethylene oxide) monoalcohol monomer includes the monomer having a urethane bond in a shell composition. Since the use of salts and emulsifiers generated during neutralization can be reduced, it shows excellent water resistance, stain resistance and adhesion, and can be blended with other urethane resins or urethane copolymers.

Since the water-based coating composition of the present invention is dried at 5 ° C. or higher and hardened at 50 ° C. or lower, baking can be performed at a relatively low temperature, such as automotive refinish paints, plastic coating paints, and building paints. It can be usefully used.

Claims (8)

In the core / shell-type microgel prepared by the three-step emulsion polymerization method of water-based coating seed / core / shell, n-isocyanatoalkyl methacrylate represented by the following general formula (1a) or dialkyl meta represented by the general formula (1b) -The poly (ethylene oxide) monoalcohol represented by the following general formula (2) obtained by ring opening reaction of isopropenyl benzyl isocyanate with an alkoxide by using an catalyst at 50-130 ° C. in a 1: 1 equivalent ratio without solvent A core / shell-type microgel, comprising an alkylene monoisocyanate / poly (ethylene oxide) monoalcohol monomer prepared to have a urethane bond by reaction until the residual isocyanate group disappears. Formula 1a

Here, n is an integer of 1-6. Formula 1b

Here m is an integer of 0-3. Formula 2

Here, x is an integer of 0-14, y is an integer of 10-75, and the average molecular weight of the whole molecule | numerator is 3000 or less. According to claim 1, wherein the core / shell-type microgel synthesized by the three-step emulsion polymerization method of the seed / core / shell is a seed latex (Seed latex), 2 formed in one step by the emulsion polymerization method using an emulsifier and an initiator 0.01 to 100 micron sized particles having a multi-layered structure consisting of a core formed using a crosslinkable composition on the seed latex by a step polymerization, and a shell finally forming a coating film using a hydrophilic composition in the final step. Core / shell microgel to be used. The method of claim 2, wherein the seed is composed of 1 to 7% by weight of the total resin composition, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, 2-ethylhexyl acryl Selected from the group consisting of latex, styrene, acrylonitrile, acrylamide, vinyl chloride, vinyl acetate, vinyl propionate and vinyl toluene or mixed monomers or prepared by first polymerizing a portion of the core composition of claim 4 A core / shell type microgel. The method of claim 2, wherein the core is composed of 19 to 78% by weight of the total resin composition, 88.0 to 99.9% by weight of the core composition is methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, It consists of a monomer mixed with one or more selected from the group consisting of ethyl acrylate, 2-ethylhexyl acrylate, styrene, acrylonitrile, acrylamide, vinyl chloride, vinyl acetate, vinyl propionate and vinyl toluene, 0.2 to 12.0% by weight is composed of monomers having two or more reactive groups polymerized from the group consisting of divinylbenzene, aryl methacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate and butanediol diacrylate Core / shell type microgels characterized in that. The method of claim 2, wherein the shell is composed of 80 to 15% by weight of the total resin composition, 2 to 100% by weight of 100% of the total shell composition is an alkylene monoisocyanate / poly (ethylene oxide) monoalcohol monomer, 0 -20 weight% is the thing which mixed acrylic acid or methacrylic acid individually or mixed, 0-20 weight% is the thing which mixed or mixed 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate alone, 0-95 weight% Is methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, styrene, acrylonitrile, acrylamide, vinyl chloride, vinyl acetate, vinyl propionate And one or more monomers selected from the group consisting of vinyltoluene and mixed. (i) 5-100% by weight of the core / shell type microgel according to claim 1, and (ii) acrylic emulsion resin, acrylic water dispersion resin, urethane water dispersion resin, acrylic urethane water dispersion resin, polyester-urethane water dispersion resin And 0 to 95% by weight of a main resin selected from the group consisting of epoxyurethane water dispersion resins; (Iii) pigments; And (Iii) a single or two or more paint additives selected from the group consisting of curing agents, fillers, plasticizers, rheology modifiers, antioxidants, co-solvents, dispersants, antifoams and leveling agents, A waterborne coating composition having a total solids content of at least 15% when applied. The water-based coating composition according to claim 6, wherein the paint additive is 0.1 to 12% by weight based on the total water-soluble paint composition. The water-based coating composition according to claim 6, wherein the pigment is 0.1 to 60% by weight based on the total water-soluble coating composition.