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.

Chlorine-containing modified polyester polyols were synthesized by two-step condensation reactions. Intermediate was synthesized by the esterification of monochloroacetic acid with trimethylolpropane in the first step. Polycondensation of the intermediate (MCAOs), 1,4-butanediol, and trimethylolpropane with adipic acid was carried out. Two-component polyurethane (PU) coatings were prepared by blending MCAOs and IPDI-isocyanurate. There new flame-retardant coatings showed various properties comparable to other non-flame-retardant coatings. They were superior to flammable coatings from the experimental results showing rapid and 10 to 13 hours of pot-life. Coatings with 30wt% monochloroacetic acid was not flammable by the vertical flame retardancy test.

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.

Film properties of monodispersed model composite latexes with particle size of 190 nm, which consist of n-butyl acrylate as a soft phase monomer and methyl methacrylate as a hard phase monomer with different morphology was examined. Five different types of model latexes were used in this study such as random copolymer particle, soft-core/hard-shell particle, hard-core/soft-shell particle, gradient type particle, and mixed type particle. Tensile strength and tensile elongation at break of final films were evaluated. Those properties can be interpreted in terms of PBA/PMMA phase ratio and their morphology. The interfacial adhesion strength was also evaluated using 180˚ peel strength measurement and cross hatch cutting test.

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.

Film forming behavior of monodispersed model composite latexes with particle size of 190 nm, which consist of n-butyl acrylate as a soft phase monomer and methyl methacrylate as a hard phase monomer with different morphology was examined. Five different types of model latexes were used in this study such as random copolymer particle, soft-core/hard-shell particle, hard-core/soft-shell particle, gradient type particle, and mixed type particle. The film forming behavior was evaluated using pseudo on-line measurements of the cumulative weight loss, the UV transmittance, and the tensile fracture energy. Each stages of film formation I, II were not sensitive to the morphology of model latexes, but stage-ill was largely dependent on the morphology of model latexes. The chain mobility of polymer which composed the shell component was found to dominantly determine the behavior of film forming stage-III.

In this study, various model composite latexes were synthesized using n-butyl acrylate and methyl methacrylate as comonomers by seeded multi-staged emulsion polymerization. Monodispersed model composite latex particles with size of 190 nm and polydispersity index of 1.05, which have various morphology including random copolymer particle, soft-core/hard-shell particle, hard-core/soft shell particle, and gradient-type copolymer particle, homopolymers particles were prepared. The designed morphology of model composite particles were confirmed.

PU flame-retardant coatings (APHD) containing phosphorous were prepared by blending of hexamethylene diisocyanate-trimer, white pigment, dispersing agent, flowing agent, and previously prepared benzoic acid modified polyester (APTB) that contains phosphorous. Physical properties of the prepared APHD were examined. With the introduction of BZA (contained in APTB), the film viscosity and film hardness of APHD decreased. With the introduction of caprolactone group, the flexibility, impact resistance, accelerated weathering resistance of APTBs increased. Flame retardancy of the coatings was tested. In a vertical burning method, APHD shows 210~313 seconds, and in a 45˚ Meckel burner method, shows 1.3~4.0cm2 of char length, which indicates that the coatings are good flame-retardant coatings. Moreover, the amount of afterglow and flame retardancy of the coatings are decreased with increasing BZA content.

Reaction intermediates PCP/BZA (PBI) and tetramethylene bis(orthophosphate) (TBOP) wer synthesized from polycaprolactone (PCP) and benzoic acid (BZA) and from pyrophosphoric acid and 1,4-butanediol, respectively. Benzoic acid modified polyesters containing phosphorus (APTB-5, -10, -15) were synthesized by polycondensation of the prepared PBI (containing 5, 10, 15wt% of benzoic acid), TBOP, adipic acid, and 1,4-butanediol. The structure and characteristics of APTBs were examined using FT-IR, NMR, GPC, and TGA analysis. The increase of the amount of BZA in the synthesis of APTBs resulted in decrease in average molecular weight and kinematic viscosity. From the TGA analysis of APTBs, it was found that the afterglow decreased with the amount of BZA content at the high temperatures.

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.

Pyrophosphoric modified polyesters (TATBs) were synthesized by polycondensation of adipic acid, trimethylolpropane, 1,4-butanediol, and tetramethylene bis(orthophosphate). Two-component PU flame-retardant coatings (TATBCs) were prepared by blending TATBs with HDI-Biuret. Most of the physical properties of the flame-retardant coatings were comparable to those of non-flame-retardant coatings. Coatings containing 10 and 15wt% 1,4-butanediol, TATBC-10C and TATBC-15C were not flammable in the vertical flame-retardancy test.

Two-component polyurethane flame retardant coatings (ATTBC) were prepared by blending polyisocyanate (TDI-adduct) with ATTBs mentioned at the previous paper. Most of the physical properties of the flame retardant coatings were comparable to those of non-flame retardant coatings. Especially, the hardness, impact resistance, and accelerated weathering resistance were remarkably improved with the increase of the content of 1,4-butanediol. Coatings containing 10 and 15 wt% 1,4-butanediol, ATTBC-10C and ATTBC-15C, were not flammable in vertical flame-retardancy test. Their char area recorded 1.1~11.6 cm2 in 45˚ eckel burner method.

An intermediate, tetramethylene bis (orthophosphate), was prepared by the esterification of pyrophosphoric acid and l,4-butanediol. Then pyrophosphoric-containing modified polyesters (ATTBs) were synthesized by polycondensation of tetramethylene bis(orthophosphate), trimethylolpropane, adipic acid, and l,4-butanediol. The content of l,4-butanediol was varied from 10 to 20wt% for the reaction. The increase of the amount of l,4-butanediol in the synthesis of ATTBs resulted in increase in average molecular weight and decrease in kinematic viscosity owing to the excellent flowability and reactivity of l,4-butanediol.

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.

Environmental friendly acrylic/urea high-solid paint(MUHC) were prepared through the curing reaction of acrylics resin(EBHC) containing 70wt% of solids content and butylated urea curing agent. The synthesis of EBHC Was done at 150℃ for 6 hours, and the results were obtained as follows : Mn=1830~2190, Mw 3290~4000, Mw/Mn=1.80~1.83 viscosity=110~352 cps, and conversion=82~92%. After the film was coated with MUHC, the various physical properties were measured. They showed that enhancement of the coating properties such as adhesion, flexibility, abrasion resistance, impact resistance, and water resistance could be expected through introdl1cing caprolactone acrylate component in acrylics resin for the high-solids content acrylics/urea coatings.

Two PU flame-retardant coatings, 2,3-DBPO/N-l00 (DBPON) and 2,3-DBPO/IL (DBPOI), were prepared by curing 2,3-dibromo modified polyester (2,3-DBPO) with isocyanate curing agent Desmodur N-l00 (or Desmodur IL) at room temperature. The physical properties and flame-retardancy of the two coatings were tested and compared. As a result, the pot-life, yellowness index, lightness index difference, 60˚ specular gloss, cross-hatch adhesion, viscosity, and accelerated weathering resistance of DBPON were better than those of DBPOI; the fineness of grind of the two coatings were the same; and the drying time, hardness, and abrasion resistance of DBPOI were better than those of DBPON. The flame retardancy of the flame-retardant coatings increased with the content of the flame retarding component, 2,3-dibromopropanoic acid (2,3-DBP); and the LOI values of the two coatings were in a range of 27~29% when the content of 2,3-DBP was 30wt%.