PU type flame-retardant coatings (TBAO/L-75, TBAOL ; TBAO/N-100, TBAON) were prepared by blending bromine-containing modified polyester (TBAO) which was synthesized in our earlier work. with two kinds of isocyanate curing agents, Desmodur L-75 and Desmodur N-100. Physical properties of the prepared flame-retardant coatings were tested. TBAOL shows better hardness than TBAON, while TBAON shows better viscosity, accelerated weathering resistance, yellowness index and lightness index difference than TBAOL. There were no remarkable differences in fineness of grind, 60˚ specular gloss, cross-hatch adhesion, and abrasion resistance of TBAOL and TBAON. There was no discernable difference in flame-retardancy between the two flame-retardant coatings, TBAOL and TBAON. When the content of tribromo acetic acid, which is flame-retarding component, was 30wt% the LOI value was in a range of 29~30%, which indicates that the two coatings are good flame-retardant coatings.

It is attempted to develop flame retardant polyurethane coatings, which have received significant attention in recent years. It is the purpose of this study to synthesize new reactive polyurethane coatings containing halogen. Lactone based modified polyester polyols, using trichlorobenzoic acid as chlorine moiety (TBAOs) were synthesized. These polyesters were cured with isophorone diisocyanate (IPDI)-isocyanurate at room temperature (TBAPUs). Physical properties of these flame retardant coatings were similar with those of non-flame retardant coatings. The flammability of coatings was strongly dependent on the chlorine contents. We found that the increasing chlorine contents showed better flame retarding properties and that, however, they also resulted in more smog generation during combustion. The detailed results of flammability test using various methods indicated 24~26% in LOI and 3.7~5.3 cm char length in 45˚ Meckel burner method.

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.

In order to obtain the maximum flame retardancy as well as the minimum deterioration of physical properties of PU flame-retardant coatings, chlorine and phosphorus functional groups were introduced into the pre-polymer of modified polyesters. In the first step, the tetramethylene bis(orthophosphate) (TBOP) and neohexanediol dichloroacetate (DCA-adduct) intermediates were synthesized. In the second step, 1,4-butanediol and adipic acid monomers were polymerized with the two kinds of intermediates to obtain copolymers. The modified polyesters containing chlorine and phosphorus (ATBA-10C, -20C, and -30C) were synthesized by adjusting that the content of phosphorus compound was fixed as 2wt% and the contents of chlorine compound (dichloroacetic acid) were varied as 10, 20, and 30wt%. Average molecular weight and polydispersity index of the preparation of ATBAs were decreased with increasing DCA content because of the increase in hydroxyl group that retards reaction.

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.

Modified polyesters (TTBA-10C, -20C, -30C) that contain phosphorus and chlorine were synthesized by the condensation polymerization of tetramethylene bis(orthophosphate), neohexanediol trichlorobenzoate, 1,4-butanediol and adipic acid, in which tetramethylene bis(orthophosphate) and neohexanediol trichlorobenzoate were prepared previously in our laboratory. In this study, two-component flame-retardant polyurethane coatings (TTBA-10C/HDI-trimer=TTHD-10C, TTBA-20C/ HDI-trimer= TTHD-20C, TTBA-30C/HDI-trimer= TTHD-30C) were obtained by curing at room temperature with the synthesized TTBAs and hexamethylene diisocyanate (HDI)-trimer as a curing agent. The obtained TTHDs were made into coating samples and used as test samples for various physical properties. The physical properties of the flame-retardant coatings containing chlorine and phosphorus groups were generally inferior to those containing only phosphorus group. Flame retardancy was tested by vertical and horizontal combustion method, and 45˚ Meckel burner method. Since the retardancy of flame-retardant coatings containing chlorine and phosphorus groups was better than that containing only phosphorus group, it could be concluded that the retardancy by the synergism effect of chlorine and phosphorus groups exhibited.

Solvent-free low foaming scouring agents (LFSC) were prepared by blending of 2-ethylhexylaminoethyl sulfate (2-EHAS), POE(10) octadecylbenzyl- ammonium chloride (POBAC) and Sedlan FF-200 (FF-200). As the results of several tests, 2-EHAS/POBAC/FF-200/water (8g/12g/20g/60g) mixture (LFSC-5) showed good cleaning power, penetrating ability and stability to alkali, and gave less problem in water pollution. The foaming power of LFSC-5 measured by Ross and Miles method was 8mm foam height immediately after foaming, and that measured by Ross and Clark method was less than 300mm foam height at 30℃, and 18mm at 80℃. As a result, LFSC-5 proved a good low foaming scouring agent for fiber.

The aim of this study is to synthesis basic resins for the preparation of PU flame-retardant coatings that contain phosphorus and chlorine. After synthesizing intermediates of tetramethylene bis(orthophophate) (TMBO) and neohexanediol trichlorobenzoate (TBA-adduct), the condensation polymerization was performed with the intermediates, 1,4-butanediol, and adipic acid to obtain four-component copolymers. In the condensation polymerization, the content of phosphorus was fixed to be 2%, and the content of trichlorobenzoic acid (TBA) that provides chlorine component was varied to be 10, 20, and 30wt%, and we designated the prepared modified polyesters containing chlorine and phosphorus as TTBA-10C, TTBA-20C and TTBA-30C. Average molecular weight and polydispersity index of the prepared TTBAs decreased with increasing TBA content because of the increase in the number of hydroxyl groups that retards reaction. We found that the thermal stability of the prepared TTBAs increased with chlorine content at high temperatures.

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.

To maximize a synergy effect in flame-retardancy of flame-retardant coatings, phosphorus and chlorine were introduced in polymer chains. Two-components PU flame-retardant modified polyesters (ABTTC-10C, -20C, -30C) were prepared by curing, at room temperature, of isocyanate (allophanate-trimer) and prepared modified polyesters which contain phosphorus and chlorine. To examine the film properties of the prepared flame-retardant coatings, film specimens were prepared with the prepared coatings. The film properties of ABTTC, ABTTC-10C and ABTTC-20C, which contain 0, 10 and 20wt%, 2,4-dichlorobenzoic acid (2,4-DCBA), respectively, were proved to be good, whereas the film properties of ABTTC-30C, which contains 30wt% 2,4-DCBA, were proved to be a little bit poor. Two kinds of flame retardancy tests, 45˚Meckel burner method and LOI method, were performed. With the 45˚Meckel burner method, three flame-retardant coatings except ABTTC showed less than 3.4 cm of char length, and showed less than 2 seconds of afterflaming and afterglow. From this result, the prepared flame-retardant coatings were proved to have the 1st grade flame retardancy. With the LOI method, the LOI values of the coatings containing more than 10wt% 2,4-DCBA were higher than 30wt%, which means that the coatings possess good flame-retardancy. From these results, it was found that synergistic effect in flame-retardancy was taken place by the introduced phosphorus and chlorine.

This study was focused on the maximization of flame-retardancy of polyesters by a synergism of simultaneously introduced chlorine and phosphorus into polymer chains of modified polyesters. To prepare modified polyesters, reaction intermediates, TD-adduct (prepared from trimethylolpropane /2,4-dichlorobenzoic acid (2,4-DCBA)) and TMBO (prepared from tetramethlene bis (orthophosphate)), were prepared first, then condensation polymerization of the prepared intermediates, adipic acid, and 1,4-butanediol were carried out. In the condensation polymerization, the content of phosphorus was fixed to be 2wt%, and the content of 2,4-DCBA that provides chlorine component was varied to be 10, 20, and 30wt%, and we designated the prepared modified polyesters containing chlorine and phosphorus as ABTTs. The prepared intermediates and modified polyesters were characterized with FT-IR, NMR, GPC, and TGA analysis. Average molecular weight and polydipersity index of the preparation of ABTTs were decreased with increasing 2,4-DCBA content because of the incease in hydroxyl group that retards reaction. We found that the thermal stability of the prepared ABTTs increased with chlorine content at high temperatures.

Reaction intermediates PCP/BZA (PBI) and tetramethylene bis(orthophosphate)(TBOP) were synthesized from polycaprolactone (PCP) and benzoic acid (BZA) and from pyrophosphoric acid and 1,4-butanediol, respectively. Benzoic acid modified polyesters containing phosphorus (APTB-S, -10, -15) were synthesized by polycondensation of the prepared PBI (containing 5, 10, 15wt% of benzoic acid), TBOP, adipic acid, and 1,4-butanediol. Network structured PU flame-retardant coatings (APHD) were prepared by curing the synthesized benzoic acid modified polyesters containing phosphorus (APT B - 5 , -10, -15) with hexamethylene diisocyanate (HDI)-timer. From the TGA analysis of APTBs, it was found that the afterglow decreased with the amount of BZA content at the high temperatures. With the introduction of BZA, 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, 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.

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.

Na2CO3. Sodium orthosilicate (Na-OSi), Tetronix T-701 (T-701), Na-dioctyl sulfosuccinate (303C), Newpol PE-68 (PE-68), MJU-100A, and tetrasodium pyrophosphate were blended to prepare high performance alkaline cleaning agents (ACASs). The results of cleaning test with steel specimen showed that ACAS-6 (Na2CO3 50g/Na-OSi 35g/T-701 20g/303C 18g/PE-68 17g/MJU-100A 10g/TSPP 20g/ water 180g mixture) had a good cleaning power. The cleaning power for press-rust preventing oil was 98% and 99% degreasing at 4wt%, 70℃ and 90℃, respectively ; for quenching oil, the cleaning power of ACAS-6 was 91% degreasing at 4wt% and 70℃. The foam heights measured immediately after foaming by Ross & Miles method and Ross & Clark method at 6wt%, 60℃ were 18mm and 65mm, respectively. It was concluded that ACAS-6 had a good low foaming cleaning agent.

An acid cleaning agent (AACA) for aluminum was prepared by blending of sorbitol, n-octanoic acid, MJU-100A, Tetronix T-701, PPA-23, C8-83 and phosphoric acid. With the prepared AACA, degreasing, foam height, etching and derusting tests were carried out. As a result, AACA-4 and AACA-7 showed better cleaning ability than commercial acid cleaning agents.

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.