KR20160107883A - Method of manufacturing uv curabal micro-gel resin, uv curabal micro-gel resin and paint composition comprising uv curabal micro-gel resin - Google Patents

Method of manufacturing uv curabal micro-gel resin, uv curabal micro-gel resin and paint composition comprising uv curabal micro-gel resin Download PDF

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KR20160107883A
KR20160107883A KR1020150031394A KR20150031394A KR20160107883A KR 20160107883 A KR20160107883 A KR 20160107883A KR 1020150031394 A KR1020150031394 A KR 1020150031394A KR 20150031394 A KR20150031394 A KR 20150031394A KR 20160107883 A KR20160107883 A KR 20160107883A
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acrylate
meth
microgel
reaction
group
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정명혜
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(주)녹색정유
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/26—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Paints Or Removers (AREA)

Abstract

I and the present invention is transparent having a nano-size of a mean particle size of 30nm or less and a functional group participating in the UV curing reaction, when applied to a UV-curable coating composition, the coating film to lower the viscosity of the coating composition To a microgel resin capable of improving processability.
The microgel resin according to the present invention comprises a step of synthesizing an intermediate microgel by synthesizing a stabilizer monomer, an acrylic polyfunctional monomer and an acrylic monofunctional monomer in the presence of an initiator and a solvent, and a step of reacting a urethane reaction, - epoxy reaction, and introducing a functional group capable of participating in the ultraviolet curing reaction into the intermediate microgel.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating composition containing a UV-curable microgel resin, a UV-curable microgel resin, a UV-curable microgel resin and an ultraviolet curable microgel resin. GEL RESIN}

The present invention relates to a method for producing a nano-sized microgel resin capable of ultraviolet curing, a microgel resin prepared by the method, and a coating composition comprising the microgel resin. More specifically, Sized, transparent and capable of participating in the ultraviolet curing reaction When applied to an ultraviolet curable coating composition, the viscosity of the coating composition is lowered, And improving workability.

The ultraviolet curing type coating material includes an oligomer, a monomer, a photoinitiator, and an additive. When the ultraviolet ray is irradiated, the double bond contained in the oligomer or monomer is crosslinked by the radical formed in the photoinitiator. Such ultraviolet curable paints are environmentally friendly because they are curable at low temperatures, are suitable for coating of materials with low heat, have good productivity due to short curing time, and do not require the use of volatile organic compounds (VOC).

However, UV curable paints do not contain volatile organic compounds (VOCs). Therefore, a large amount of low molecular weight oligomers and monomers having low viscosity are used in consideration of workability and the like. The use of oligomers having a low molecular weight, It is possible to obtain a coating film having a high hardness, but the workability of the coating film is deteriorated. When the workability of the coating film is poor, there is a problem that a crack or a peeling phenomenon occurs in the coating film after the formation of the coating film.

On the contrary, when a high-molecular-weight resin is added to improve workability, cracks and peeling phenomena occurring in the coating film can be improved, but the viscosity is increased and the workability is lowered.

Korean Patent Laid-Open Publication No. 2014-0113766 Korean Patent Publication No. 2003-0058457

The object of the present invention is to provide a microgel resin having a size of 30 nm or less and being transparent and applicable to transparent paints and capable of ultraviolet curing, and a method for producing the same.

Another object of the present invention is to provide a coating composition which does not deteriorate workability because the viscosity is not high while cracks and peeling phenomena are reduced in the coating film after the formation of the coating film.

According to a first aspect of the present invention, there is provided a process for preparing an intermediate microgel, which comprises synthesizing an intermediate microgel by synthesizing a stabilizer monomer, an acrylic multi-functional monomer and an acrylic monofunctional monomer in the presence of an initiator and a solvent, And introducing a functional group capable of participating in an ultraviolet curing reaction into the intermediate microgel through at least one of an esterification reaction, an acid reaction, and an acid-epoxy reaction.

A second aspect of the present invention for solving the above problems is to provide an ultraviolet curable microgel resin having a double bond capable of participating in an ultraviolet curing reaction and having an average particle size of 30 nm or less and being transparent.

A third aspect of the present invention to solve the above-mentioned problems is to provide a coating composition comprising an ultraviolet-curable microgel resin having an average particle size of 30 nm or less and being transparent and capable of participating in an ultraviolet curing reaction .

The microgel resin according to the present invention is obtained by obtaining an intermediate microgel resin having a hydroxyl group, a carboxyl group and an epoxy group formed by polymerization reaction of a stabilizer monomer, an acrylic monofunctional monomer and a polyfunctional monomer, A double bond capable of participating in the ultraviolet curing reaction is formed through a functional group introduction step such as an acid-epoxy reaction or an ester reaction.

The microgel resin formed through the above-mentioned synthesis process has nano-sized particles with an average particle size of 30 nm or less and is transparent and can be applied to a transparent paint. When incorporated into an ultraviolet curing paint, the microgel resin participates in an ultraviolet curing reaction And can improve the workability of the coating film.

The microgel resin prepared according to the present invention is transparent to a size of 30 nm or less and can be applied to transparent paints. It can participate in ultraviolet curing reaction at the same time as low viscosity, which is an advantage of existing microgels, and can improve the workability of the coating film.

In addition, the coating composition comprising the microgel resin according to the present invention is not only poor in workability because the viscosity is not high, and can also reduce the cracking and peeling phenomenon in the coating film after the formation of the coating film.

1 shows FT-IR analysis results for confirming a urethane reaction for introducing an ultraviolet curing functional group in a coating composition according to an embodiment of the present invention.
2 shows the results of comparing the viscosity of the coating composition according to the example of the present invention with that of the coating composition according to the comparative example.

Hereinafter, the present invention will be described in detail with reference to the attached drawings. However, the present invention should not be construed as being limited to the following embodiments.

In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear. Also, when a part is referred to as "including " an element, it does not exclude other elements unless specifically stated otherwise.

The microgel resin according to the present invention is obtained by synthesizing an intermediate microgel resin and then introducing a double bond capable of participating in the ultraviolet curing reaction through a reaction such as urethane reaction, ester reaction or acid-epoxy reaction to the intermediate microgel resin .

The intermediate microgel resin is prepared by solution polymerization in the presence of a stabilizer monomer, an acrylic multifunctional monomer and an acrylic monofunctional monomer in the presence of an initiator and a solvent.

The stabilizer monomer used in the microgel synthesis is a component contributing to the stabilization of the nano-sized microgel resin through the effect of steric repulsion by the long chain.

Examples of the stabilizer monomer include octadecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, methacrylic ester, lauryl (meth) acrylate, hexadecyl (Meth) acrylate, behenyl (meth) acrylate, polyether-modified (meth) acrylate, nonylphenol (meth) acrylate.

The content of the stabilizer monomer in the synthesis is preferably at least 30 mol% and at most 90 mol% with respect to the total monomer content used in the synthesis. If the content of the stabilizer monomer is less than 30 mol% If the content of the stabilizer monomer exceeds 90 mol% of the total monomer content, the acrylic monofunctional monomer content is small and the number of functional groups for introduction of the ultraviolet curing functional group is reduced .

The acrylic multi-functional monomer used in the microgel synthesis is a component that forms a particle through crosslinking.

Examples of the acrylic polyfunctional monomer include diethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,10-dodecane Acrylate, diethylene glycol di (meth) acrylate, diol di (meth) acrylate, bisphenol-A di (meth) acrylate, neopentyl glycol di At least one reactive group selected from the group consisting of (meth) acrylate, glyceryl tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta Can be used.

The content of the acrylic polyfunctional monomer during the synthesis is preferably in the range of 1 to 20 mol% with respect to the total monomer content used in the synthesis. When the content is less than 1 mol%, the crosslinking degree of the non- If it exceeds 20 mol%, the crosslinking degree becomes too high, and gelation may occur.

The acrylic monofunctional monomer used in the synthesis of the microgels is a component that functions to impart functional groups for introducing a double bond.

Examples of the acrylic monofunctional monomer include (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Diallyl methacrylate, and the like.

The content of the acrylic monofunctional monomer at the time of the synthesis is preferably in the range of 10 to 70 mol% with respect to the total monomer content used in the synthesis. When the content is less than 10 mol%, the functional group for introducing a double bond is insufficient, %, The stabilizer monomer content is low and stable microgel synthesis can not be achieved.

The initiator used in the microgel synthesis is a component that initiates a polymerization reaction by forming radicals.

Examples of the initiator include, for example, 2,2-azobis 2-methylbutylonitrile, 2,2-azobisisobutyronitrile, dibenzoyl peroxide, tertiary butyl peroxybenzoate, At least one member selected from the group consisting of terephthalic anhydride, terephthalic anhydride, terephthalic anhydride, terephthalic anhydride, terephthalic anhydride, terephthalic anhydride, terephthalic anhydride,

The content of the initiator in the synthesis is preferably in the range of 0.03 to 2.0 wt% with respect to the total monomer content. When the content is less than 0.03 wt%, the reactivity is low. When the content is more than 2.0 wt% This is because a problem that can not be solved occurs.

The solvent used in the microgel synthesis is a component to be added for the purpose of synthesis stability and easy stirring.

Examples of the solvent include aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, ethyl propyl ketone, methyl isobutyl ketone and methyl amyl ketone, Ester solvents such as ethyl acetate, normal propyl acetate, isopropyl acetate, isopropyl acetate, butyl acetate, methyl cellosolve acetate, cellosolve acetate, butyl cellosolve acetate and carbitol acetate, and solvents such as ethanol, butanol, isobutanol , And alcoholic solvents such as normal butanol, isopropanol, n-butanol, tertiary butanol, etc. may be used.

The content of the solvent during the synthesis is preferably in the range of 30 to 80% by weight based on the total weight of the synthetic solution composition. When the content is less than 30% by weight, microgel synthesis can not be stably performed, This is because the synthesis yield of microgels is low.

Intermediate microgel resins synthesized by solution polymerization introduce functional groups capable of participating in the ultraviolet curing reaction through reactions such as urethane reaction, ester reaction or acid-epoxy reaction.

Examples of the material used for the urethane reaction include 2-isocyanatoethyl (meth) acrylate, isocyanatopropyl (meth) acrylate, isocyanato butyl (meth) acrylate and the like .

Examples of the substance used in the ester reaction include (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl Rate and so on.

Examples of the material used for the acid-epoxy reaction include (meth) acrylic acid, glycidyl methacrylate, and the like.

The materials used for the urethane reaction, the ester reaction and the acid-epoxy reaction are preferably used in a range of 5% to 40%, more preferably 10% to 20%, of the molar percent of the total monomers synthesized by solution polymerization, to be.

[Example]

Synthesis of intermediate microgels

Synthesis of an intermediate microgel according to an embodiment of the present invention was carried out by adding MEK (final solid content 50% by weight) and a monomer mixture (manufactured by Mitsubishi Chemical Corporation) to an 1 L four-necked flask equipped with a mechanical stirrer, a condenser, (ODA + HEA + HDDA) and a polymerization initiator (AIBN) were added to the dropping vessel over 1 hour and 30 minutes while the temperature was being raised to 70 ° C with stirring. Followed by dropping at a constant rate. And the temperature was maintained for 6 hours after completion of the dropping.

The composition of the monomers used and the particle size and the synthetic stability of the synthesized intermediate microgels are shown in Table 1 below. The particle size was measured using a Zetasizer nano ZS (Malvern) product.

Monomer
(mol%) Average particle size
(nm) Synthetic stability
ROOM HEA HDDA Example 1 30 65 5 25 Good Example 2 50 45 5 12 Good Example 3 70 25 5 10 Good Example 4 50 40 10 14 Good Example 5 50 35 15 19 Good Comparative Example 1 20 75 5 - Gelling Comparative Example 2 50 50 - - Particle formation Comparative Example 3 50 30 20 - Gelling

ODA: octadecyl acrylate

HEA: 2-hydroxyethyl acrylate

HDDA: 1,6-hexanediol diacrylate

As can be seen from the above Table 1, in the range of Examples 1 to 5 of the present invention, When the composition is controlled, it is understood that a microgel having an average particle size of 30 nm or less is synthesized.

Introduction of ultraviolet curing functional groups

A functional group capable of participating in ultraviolet curing was introduced through a urethane reaction between a hydroxyl group contained in the microgel intermediate synthesized according to Example 2 and isocyanatoethyl methacrylate.

Isocyanatoethyl methacrylate was added to the microgel intermediates so as to be 10%, 20%, and 40% of the monomer composition contents as shown in Table 2 below, and reacted at room temperature. At this time, dibutyl tin dilaurate of 0.1 wt% of the solid content of the microgel intermediate charged as the catalyst was used.

Monomer composition
(mol%) Average particle size
(nm) Synthetic stability
ROOM HEA HDDA IEM Example 6 50 45 5 10 13 Good Example 7 50 45 5 20 17 Good Example 8 50 45 5 40 16 Good

IEM: 2-isocyanatoethyl methacrylate

The degree of urethane reaction between the hydroxyl group and the isocyanate in the functional group introduction step according to the example of the present invention was confirmed by FT-IR analysis.

As shown in FIG. 1, it can be seen that the NH peak of 1530 cm -1 and 3330-3360 cm -1 is increased by the urethane reaction with the increase of isocyanatoethyl methacrylate content, and that of 3500 cm -1 It was confirmed that the hydroxyl peak was decreased. At this time, the remaining organic solvent in the microgel solution after synthesis was removed by using a vacuum.

Manufacture of transparent paint and evaluation of physical properties

The microgels prepared according to the present invention were added to the ultraviolet curable clear coating composition to evaluate the viscosity and physical properties of the coating, and the evaluation results are shown in Table 3 below.

Comparative Example 4 Example 9 Example 10 Example 11 Epoxy acrylate
(AgiSyn 占 1010) 60 40 40 40 Butyl acrylate 28 28 28 28 Trimethylolpropane triacrylate 10 10 10 10 Photoinitiator 2 2 2 2 Microgel (Example 6) 20 Micro gel (Example 7) 20 Microgel (Example 8) 20

The comparative example 4 is for comparison with the addition of the microgel according to the embodiment of the present invention. In Example 9, a microgel containing a functional group according to Example 6 was included. Example 10 included a microgel in which a functional group was introduced according to Example 7, and Example 11 was a microgel containing a functional group according to Example 8 And a microgel having a functional group introduced therein.

Change in Viscosity of Transparent Coatings by Microgel Application

The viscosity of the clearcoat was measured using a rheometer (Haake Mars rheometer, Thermo Scientific, Germany) at a shear rate of 0.001 to 50 1 / s.

As a result of the measurement, it was confirmed that the coating compositions of Examples 9 to 11 of the present invention had significantly decreased viscosity as compared with the coating compositions of Comparative Example 4 containing no microgel, as shown in Fig.

Evaluation of Physical Properties of Coating Film

In order to evaluate the coating properties of the coating compositions according to Comparative Examples 4 and 9 to 11, each of the paints was applied to a galvanized steel sheet using a bar coater (# 3), and then exposed to ultraviolet rays And irradiated with a light amount of 1200 mJ / cm < 2 > to form a coating film.

In order to evaluate the workability of the coating film cured with ultraviolet rays, a T-bend test was conducted, and after the bending, whether or not cracks or peeling occurred in the coating film was visually observed, and the maximum bending state, And the results are shown in Table 4 below.

Comparative Example 4 Example 9 Example 10 Example 11 Processability test (T-bend) 6T 2T 2T 3T

If there is no peeling, the grade is applied to the specimen (0T: 180 ° bending of specimen itself, nT: 180 ° bending after inserting n pieces of specimen)

As can be seen from Table 4, the coated film obtained by curing the coating composition to which the microgel was added had a higher resistance to cracking and peeling at the time of bending than in Comparative Example 4, and the workability of the coating film was remarkably improved.

Claims (13)

Synthesizing an intermediate microgel by synthesizing a stabilizer monomer, an acrylic polyfunctional monomer and an acrylic monofunctional monomer in the presence of an initiator and a solvent;
Introducing a functional group capable of participating in an ultraviolet curing reaction into the intermediate microgel through at least one of urethane reaction, ester reaction, and acid-epoxy reaction. The method according to claim 1,
The stabilizer monomer may be selected from the group consisting of octadecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, methacrylic ester, lauryl (meth) acrylate, hexadecyl (Meth) acrylate, behenyl (meth) acrylate, polyether-modified (meth) acrylate, nonylphenol (meth) acrylate. The method according to claim 1,
The acrylic polyfunctional monomer may be at least one selected from the group consisting of diethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, Acrylate, trimethylolpropane tri (meth) acrylate, diethylene glycol di (meth) acrylate, bisphenol-A di (meth) acrylate, neopentyl glycol di (Meth) acrylate having at least two reactive groups selected from the group consisting of glyceryl tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta A method for producing a curable microgel resin. The method according to claim 1,
The acrylic monofunctional monomer may be at least one selected from the group consisting of (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and glycidyl methacrylate Wherein the ultraviolet curing type microgel resin comprises at least one selected from the group consisting of the following. The method according to claim 1,
The initiator may be selected from the group consisting of 2,2-azobis 2-methylbutylonitrile, 2,2-azobisisobutylonitrile, dibenzoyl peroxide, tertiary butyl peroxybenzoate, ditertiary butyl peroxide, tertiary butyl An ultraviolet curable microgel resin containing at least one member selected from the group consisting of peroxy-2-ethylhexanoate, tertiary butyl peroxyacetate, cumyl hydroperoxide, dicumyl peroxide and tertiary butyl hydroperoxide Gt; The method according to claim 1,
Examples of the solvent include aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, ethyl propyl ketone, methyl isobutyl ketone and methyl amyl ketone, methyl acetate, ethyl acetate, Butanol, isobutanol, n-butanol, isobutanol, n-butanol, isobutanol, isobutanol, isobutanol, isobutanol, propyl acetate, isopropyl acetate, isopropyl acetate, butyl acetate, methyl cellosolve acetate, cellosolve acetate, butyl cellosolve acetate or carbitol acetate, Wherein the solvent comprises at least one member selected from the group consisting of isopropanol, n-butanol, and alcohol-based solvents including tertiary butanol. The method according to claim 1,
The substance causing the reaction of at least one of the urethane reaction, the ester reaction and the acid-epoxy reaction is at least one selected from the group consisting of 2-isocyanatoethyl (meth) acrylate, isocyanatopropyl (meth) acrylate, (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl And at least one member selected from the group consisting of acrylic acid, maleic acid, maleic acid, maleic acid, maleic acid, maleic acid, maleic acid, maleic acid, maleic acid and maleic acid. 3. The method of claim 2,
Wherein the stabilizer monomer is contained in an amount of 30 mol% to 90 mol% with respect to the total monomer content in the synthesis step. The method of claim 3,
Wherein the acryl-based polyfunctional monomer is contained in an amount of 1 to 20 mol% based on the total monomer content in the synthesis step. 5. The method of claim 4,
Wherein the acrylic monofunctional monomer is contained in an amount of 10 mol% to 70 mol% with respect to the total monomer content in the synthesis step. An ultraviolet curable microgel resin having a mean particle size of 30 nm or less, a transparent, double bond capable of participating in an ultraviolet curing reaction. 12. The method of claim 11,
The microgel resin is the ultraviolet curable microgel resin produced by any one of claims 1 to 11. A coating composition comprising the ultraviolet-curing microgel resin according to claim 12.
KR1020150031394A 2015-03-06 2015-03-06 Method of manufacturing uv curabal micro-gel resin, uv curabal micro-gel resin and paint composition comprising uv curabal micro-gel resin KR20160107883A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20030058457A (en) 2001-12-31 2003-07-07 주식회사 디피아이 Non Aqueous Dispersion Copolymer Composition And Method for Preparing the Same
KR20140113766A (en) 2013-03-13 2014-09-25 포항공과대학교 산학협력단 Non-aqueous dispersion resin composition and paint composition comprising the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20030058457A (en) 2001-12-31 2003-07-07 주식회사 디피아이 Non Aqueous Dispersion Copolymer Composition And Method for Preparing the Same
KR20140113766A (en) 2013-03-13 2014-09-25 포항공과대학교 산학협력단 Non-aqueous dispersion resin composition and paint composition comprising the same

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