In order to synthesize high-solid coatings, acrylic resins (HSAs) containing 90% solid content were first synthesized, then the synthesized HSAs were cured with a curing agent, isocyanate, at room temperature to obtain high-solid coatings. In the HSAs synthesis, conversion was in a range of 82~87%, and viscosities and number-averaged molecular weight (Mn) of the HSAs were in a range of 4380~8010 cP and 1540~1660, respectively. From the correlation between Tg value, viscosity and Mn, it was found that, with increasing Tg value, viscosity increases rapidly and molecular weight increases slowly. From the visco-elasity measured by the pendulum method, it was found that the curing time decreased with increasing Tg values. From the tests of physical properties of the coatings' film, 60˚ specular gloss, impact resistance and heat resistance were proved to be good and pencil hardness, drying time and pot-life were proved to be poor.

In order to prepare high-solid coatings, acrylic resins, HSCs [poly (EA/EMA/2-HEMA/CLA)] that contain 90% solid, were synthesized by copolymerization of ethyl acrylate (EA), ethyl methacrylate (EMA), 2-hydroxyethyl methacrylate (2-HEMA) and caprolactone acrylate (CLA). The high-solid coatings named as CHSCs (HSCs/HDI-trimer) were prepared by the curing reaction between the acrylic resins containing 90% solid contents and the isocyanates (HDI-trimer) curing agent room temperature. The curing behavior and various properties were examined on the film coated with the both high-solid coatings. The glass transition temperatures (Tg) of CHSCs increased proportionally with increasing the predicted Tg value by Fox equation, and had nothing to do with the solid contents. The prepared film showed good properties for 60˚ specular gloss, impact resistance, cross-hatch adhesion and heat resistance, and bad properties for pencil hardness, drying time, and pot-life. Among the film properties, the heat resistance was very excellent and could be explained by the introduction of functional monomers of CLA.

In order to prepare high-solid coatings, first acrylic resins (HSAs) which contain 80% solid were synthesized, and then the prepared resins were cured with isocyanate at room temperature. In the synthesis of HSAs, viscosity, number average molecular weight (Mn) and conversion were 1372~2700 cps, 1520~1650 and 83~87%, respectively. Among the four kinds of initiators used, tert-amylperoxy-2-ethyl hexanoate was the most proper one in the synthesis of HSAs. With increasing Tg values, viscosity increased rapidly and molecular weight increased slowly. As a result of the examination of coated films, it was found that 60˚ specular gloss, impact resistance, heat resistance and cross-hatch adhesion were good, and pencil hardness, drying time and pot life were poor.

The high-solid coatings were prepared by blending the synthesized acrylic resin in the previous paper, and hexamethylene diisocyanate-trimer and curing it at room temperature. The characterization of the films of the prepared coatings was performed. The 60˚ specular gloss, impact resistance, cross-hatch adhesion, and heat resistance of the films proved to be good, and the pencil hardness, drying time, and pot-life proved to be slightly poor. From a viscoelastic measurement using a rigid-body pendulum, curing was accelerated with the Tg value.

Acrylic resins (HSCs : EA/EMA/2-HEMA/CLA) which contain 80% solid content were synthesized by the copolymerization of monomers (ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate) and functional monomer (caprolactone acrylate : CLA) which improves the crosslinking density and physical properties of films. The physical properties of the prepared acrylic resins (HSCs) containing CLA, are as follows: viscosity 1440~2630 cps ; Mn 1590~1660 ; and conversions, 81~86%, respectively. From the correlation of Tg values, viscosities, and Mn of the HSCs, it was found thst viscosity and Mn increased with Tg value.

In the previous study, three kinds of monomers and the functional monomer, acetoacetoxyethyl methacrylate (AAEM), which could improve the film property and cross-linkage, were polymerzied into acrylic resin copolymers (HSA-98-20, HSA-98-0, HSA-98+20) containing 80% solid content. In this study, the high-solid coatings(HSA-98-20C, HSA-98-0C, HSA-98+20C) were prepared by the curing reaction between acrylic resins containing 80% solid content and isocyanate at room temperature. Various properties were examined for the film coated with the prepared high-solid coatings. The introduction of AAEM in the coatings enhanced the abrasion resistance and solvent resistance of coatings, which indicated the possible use of high-solid coatings for top-coating materials of automobile. The curing times measured by viscoelastic measurement were 350, 264, and 212 min for HSA-98-20C, HSA-98-0C, and HSA-98+20C, respectively. This shows that the curing times become shorter with increasing Tg values.

Copolymers (HSA-98-20, HSA-98-0, HSA-98+20) which are acrylic resin containing 80% solid content were synthesized by the reaction of monomers, including methyl methacrylate, n-butyl acrylate, and 2-hydroxyethyl acrylate with a functional monomer, such as acetoacetoxyethyl methacrylate (AAEM), which may improve in cross-linking density and physical properties of films. The physical properties of prepared acrylic resins, containing AAEM, are as follows : viscosity, 1420~5760cps ; number average molecular weight, 2080~2300 ; polydispersity index, 2.07~2.19 ; conversions, 88~93%, respectively. To prepare acryl resins, four kinds of initiators including α,α'-azobisisobutyronitirile (AIBN), di-tert-butyl peroxide (DTBP), t-amylperoxy-2-ethyl hexanoate (APEH), benzoyl peroxide (BPO) were used. The viscosity of the acrylic resins prepared with these initiators was increased in the order of DTBP〉APEH〉AIBN〉BPO. APEH was proved as a suitable initiator in this study. Shear rates of acrylic resins were constant in respect to viscosity. From these results, it would appear that the resins have Newtonian flow characteristics and good workability.

Room temperature cure type of acryl-urethane coatings with high solid content were prepared in this study. Acrylic resins with 80% solid content were cured with hexamethylene diisocyanate (Desmodure N-3600). The cure time of prepared coatings BEHCC-84 (BEHC-84 : Tg=0℃) and BEHCC-87 (BEHC-87 : Tg=30℃), measured by rigid-body pendulum method, was recorded 8.3 hours and 3.8 hours, respectively. Dynamic viscoelastic experiment also revealed the glass transition temperature of BEHCC-84 and BEHCC-87 to be Tg=40.3℃ and Tg=43.3℃, respectively. It was found that the adhesion and flexural properties among various propeties of coatings were enhanced by the incorporation of caprolactone acrylate monomer into the acrylic resins.

High-solid coatings were prepared by blending of previosly synthesized acrylic resins and hexamethylene diisocyanate-trimer and curing it at room temperature. The characterization of the films of the prepared coatings was performed. The impact resistance, cross-hatch adhesion, 60˚specular gloss, and heat resistance of the films proved to be good, and the pencil hardness and drying time proved to be slightly poor. Especially, there was a remarkable improvement in the heat resistance. This improvement may stem from the regular arrangement of ethyl groups introduced into the acrylic resin. As a result of Rigid-body pendulum visco-elasticity measurement, dynamic Tg values of cured films increased with dynamic Tg values.

Acrylic resins (HSCs : EA/EMA/2-HEMA/CLA) which contain 70% solid content were synthesized by the copolymerization of monomers (2-hydroxyethyl methacrylate, ethyl acrylate, and ethyl methacrylate) and functional monomer (caprolactone acrylate : CLA) which improves the crosslinking density and physical properties of films. The physical properties of the prepared acrylic resins (HSCs) containing CLA, are as follows : viscosity 245~515 cps ; Mn 2670~2840 ; and conversions, 83~91%, respectively. From the correlation of Tg values, viscosities, and Mn of the HSCs, it was found that viscosity and Mn increased with Tg value.

The high-solid coatings were prepared by blending the synthesized acrylic resin in the previous paper and hexamethylene diisocyanate-trimer and curing it at room temperature. The characterization of the films of the prepared coatings was performed. The impact resistance, 60℃ specular gloss, cross-hatch adhension, and heat resistance of the films proved to be good, and the pencil hardness and drying time proved to be slightly poor. Especially, there was a remarkable improvement in the heat resistance. This improvement may stem from the regular arrangement of ethyl groups introduced into the acrylic resin. From a viscoelastic measurement using a rigid-body pendulum, curing was accelerated with the Tg value. With the increase in Tg, log damp value was lowered and dynamic viscoelasic Tg of a cured film was increased.

A copolymer 〈HSAs : EA/EMA/2-HEMA/AAEM) which is an acrylic resin containing 70% solid content was synthesized by the reaction of monomers, including ethyl acrylate, ethyl methacrylate, and 2-hydroxyethyl methacrylate with a functional monomer, such as acetoacetoxyethyl methacrylate, which may give improvements in cross-linking density and physical properties of films. The physical properties of prepared acrylic resins, HSA containing AAEM, are as follows : viscosity, 203~550cps ; Mn, 2590~2850 ; and conversion, 82~89%, respectively. It was found from the plotting of Tg versus viscosity and Tg versus molecular weight that viscosity increased with Tg while number averaged molecular weight decreased with increasing Tg.

Environmental friendly acrylics/urea high-solid paints (BEHCU) were prepared through the curing reaction of acrylics resin(BEHC) containing 70wt% of solids content and butylated urea curing agent. BEHC was synthesized by addition copolymerization of caprolactone acrylate(CLA), 2-hydroxypropyl methacrylate(2-HPMA), ethyl methacrylate, and n-butyl acrylate. The addition polymerization of these monomers, especially including flexible CLA monomer and 2-HPMA monomer with OH funtional group, under appropriate reaction conditions resulted in polymers with controlled glass transition temperature(Tg) and crosslinking density. The molecular weight(Mw) of these polymers(BEHCs) was 2940~3240 and polydispersity (Mw/Mn) was in the range of 1.61~1.72. The viscosity and the molecular weight of these acrylic resins increased with increasing Tg. The coated films were prepared using curing reaction between BEHC resin and butylated urea curing agent at 100℃ for 30 minutes. Our experimental resulted showed that enhancement of the coating properties such as adhesion, flexibility, impact resistance, water resistance, and abrasion resistance could be expected through introducing CLA component in acrylic resin for the high-solid content acrylics/urea coatings.

An ACR/HMMM film was prepared by blending high-solid ACR with curing agent, hexamethoxymethyl melamine (HMMM). An active curing reaction was observed at 170℃. The dynamic viscoelastic Tg of the final film increased with the static viscoelastic Tg of the film. The log damp value, which means a viscoelastic ratio, decreased with the increase in the curing temperature of the film. Physical properties of the films were within a suitable range for films, and by an accelerated weathering resistance test the films were proved weather resistible ones.

Acrylic resin(ACR) was blended with a curing agent, hexamethoxymethylmela-mine(HMMM), in which blending ratio was 70:30. The curing behavior was examined using Rheovibron. Cross-linking reaction started at 170℃ in 2 min of reaction and curing was completed in 10 min. It was found that the extent of cross-linking increased with the content of acetoacetoxyethyl methacrylate monomer in the ACR.

Curing reaction was carried out with the acrylic resin (ACR) [n-butyl acrylate/atyrene/2-hydroxyethyl methacrylate/acetoacetoxyethyl methacrylate (AAEM)] synthesized before and a curing agent, hexamethoxymethylmelamine (HMMM). With rotational rheometer, the effect of catalysts on curing rate of acrylic resin/melamine was examined. Among the four catalysts used, p-toluene sulfonic acid showed the highest reactivity, and the optimum amount of catalyst was 0.5 phr. It was observed that in the ACR/HMMM curing reaction, gelation point was lowered with the increasing the amount of AAEM and HMMM in the ACR.

Acrylic quarternary polymers were synthesized to prepare high-solid coatings. Acrylic resins were synthesized by the radical polymerization of n-butyl acrylate, methyl methacrylate, 2-hydroxyethyl methacrylate and acetoacetoxyethyl methacrylate. From the results of experiment on reaction condition to get high-solid acrylic resins with 70% solid content and viscosity of 1200cps, it was found that di-tert-amyl peroxide among the four types of initiators have lower viscosity and higher degree of conversion. The optinum initiator amount, chain transfer agent, reaction temperature and the dropping time were 5wt%, 4wt%, 150℃ and 5hrs, respectively.

Quater polymer(MBHA) containing two types of acrylic functional group, acetoacetoxyethyl methacrylate(AAM) and 2-hydroxyethyl acrylate was prepared. Then, the MBHA was blended with polyisocyanate type Desmodur IL as a curing agent. Thereafter the mixture was cured at room temperature to get high solid acrylic/polyisocyanate. The MBHA was synthesized at 150℃ for 6 hours typically, and the final conversion reached 87-88%. Lowering Tg and increasing AAM amount in the MBHA resulted in high value of conversion. There was no difference in conversion with the variations of OH values. From the results of physical property tests, MIHS coating was proved to be a good automotive top-coating material.