KR100328876B1 - Preparation of modified polyester resin of excellent solvent resistance - Google Patents
Preparation of modified polyester resin of excellent solvent resistance Download PDFInfo
- Publication number
- KR100328876B1 KR100328876B1 KR1019990045002A KR19990045002A KR100328876B1 KR 100328876 B1 KR100328876 B1 KR 100328876B1 KR 1019990045002 A KR1019990045002 A KR 1019990045002A KR 19990045002 A KR19990045002 A KR 19990045002A KR 100328876 B1 KR100328876 B1 KR 100328876B1
- Authority
- KR
- South Korea
- Prior art keywords
- acrylic
- weight
- parts
- acid
- modified polyester
- Prior art date
Links
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 41
- 239000004645 polyester resin Substances 0.000 title claims abstract description 41
- 239000002904 solvent Substances 0.000 title abstract description 22
- 238000002360 preparation method Methods 0.000 title description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229920000728 polyester Polymers 0.000 claims abstract description 35
- 239000000178 monomer Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 16
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 16
- 150000007519 polyprotic acids Polymers 0.000 claims abstract description 15
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims abstract description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 8
- 238000007348 radical reaction Methods 0.000 claims abstract description 8
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 239000000543 intermediate Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 11
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 7
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- -1 butyl acryl Chemical group 0.000 claims description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 3
- 239000008199 coating composition Substances 0.000 claims description 2
- 239000000049 pigment Substances 0.000 abstract description 14
- 230000000704 physical effect Effects 0.000 abstract description 13
- 229910000831 Steel Inorganic materials 0.000 abstract description 4
- 239000011230 binding agent Substances 0.000 abstract description 4
- 239000010959 steel Substances 0.000 abstract description 4
- 229920002799 BoPET Polymers 0.000 abstract description 2
- 239000007888 film coating Substances 0.000 abstract description 2
- 238000009501 film coating Methods 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 239000002253 acid Substances 0.000 description 29
- 229920005989 resin Polymers 0.000 description 19
- 239000011347 resin Substances 0.000 description 19
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 16
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229910001873 dinitrogen Inorganic materials 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- 229920000178 Acrylic resin Polymers 0.000 description 9
- 239000004925 Acrylic resin Substances 0.000 description 9
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 8
- 239000001361 adipic acid Substances 0.000 description 8
- 235000011037 adipic acid Nutrition 0.000 description 8
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 7
- 239000011324 bead Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001879 gelation Methods 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229920000877 Melamine resin Polymers 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000002685 polymerization catalyst Substances 0.000 description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 2
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical compound CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical class CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229920003180 amino resin Polymers 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 150000007974 melamines Chemical class 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- JZLWSRCQCPAUDP-UHFFFAOYSA-N 1,3,5-triazine-2,4,6-triamine;urea Chemical class NC(N)=O.NC1=NC(N)=NC(N)=N1 JZLWSRCQCPAUDP-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- QBDAFARLDLCWAT-UHFFFAOYSA-N 2,3-dihydropyran-6-one Chemical compound O=C1OCCC=C1 QBDAFARLDLCWAT-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 235000013345 egg yolk Nutrition 0.000 description 1
- 210000002969 egg yolk Anatomy 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
본 발명은 내후성, 안료분산성 등의 물성이 개선된 아크릴변성 폴리에스테르 수지의 제조방법을 제공한다. 이 방법은 (a) 다가 알콜; 다염기산; 및 메타아크릴산, 아크릴산, N-메틸올 아크릴아마이드 또는 2-하이드록시 에틸메타아크릴레이트로부터 선택된 1종 이상의 제1 아크릴 모노머를 중합시켜 분자 말단에 이중결합을 갖는 폴리에스테르 중간체를 제조하는 단계; 및 (b) 상기 단계 (a)에서 얻은 폴리에스테르 중간체를 75℃∼130℃의 온도에서 라디칼 반응을 할 수 있는 1종 또는 2종 이상의 제2 아크릴 모노머와 중합반응시키는 단계를 포함함을 특징으로 한다. 본 발명의 방법에 의해 얻어진 아크릴변성 폴리에스테르는 내후성, 안료분산성, 내용제성 및 건조성 등이 우수하기 때문에, 칼라강판 인쇄용 잉크바인더 또는 내용제성이 요구되는 PET 필름 코팅용으로 유리하게 사용될 수 있다.The present invention provides a method for producing an acrylic modified polyester resin having improved physical properties such as weather resistance and pigment dispersibility. This method comprises (a) a polyhydric alcohol; Polybasic acids; And polymerizing at least one first acrylic monomer selected from methacrylic acid, acrylic acid, N-methylol acrylamide or 2-hydroxy ethyl methacrylate to prepare a polyester intermediate having a double bond at the terminal of the molecule; And (b) polymerizing the polyester intermediate obtained in step (a) with one or two or more second acrylic monomers capable of radical reaction at a temperature of 75 ° C to 130 ° C. do. Since the acrylic modified polyester obtained by the method of the present invention is excellent in weather resistance, pigment dispersibility, solvent resistance, and dryness, it can be advantageously used for ink binder for color steel printing or PET film coating requiring solvent resistance. .
Description
본 발명은 내후성 등의 제반 물성이 우수한 변성 폴리에스테르 수지 및 그의 제조방법에 관한 것이고, 보다 구체적으로는 분자 말단에 이중결합을 갖는 폴리에스테르 중간체를 제조하고, 이를 아크릴 모노머와 중합반응시켜 얻은 내후성 등의 물성이 우수한 아크릴변성 폴리에스테르 수지 및 그를 제조하는 방법에 관한 것이다.The present invention relates to a modified polyester resin having excellent physical properties such as weather resistance, and a method for producing the same. More specifically, to prepare a polyester intermediate having a double bond at the molecular end, and to obtain a weather resistance obtained by polymerizing and reacting with an acrylic monomer. It relates to an acrylic modified polyester resin having excellent physical properties and a method of producing the same.
다염기산 또는 그의 에스테르(예, 디메틸테레프탈레이트)와 다가 알콜(예, 지방족 글리콜 또는 글리콜 혼합물)로부터 얻어지는 폴리에스테르 수지는 건조성, 내후성, 내용제성, 경도, 부착성 등을 요구하는 필름코팅과 같은 연속라인에 적용하기 힘든 문제점이 있다. 즉, 건조성이 좋지 않기 때문에 롤러에 폴리에스테르 필름을 감으려면 라인 속도를 늦추거나 온도를 올려야 하기 때문에 경제성이 떨어진다.Polyester resins obtained from polybasic acids or their esters (e.g. dimethyl terephthalate) and polyhydric alcohols (e.g. aliphatic glycols or glycol mixtures) are continuous such as film coatings requiring dryness, weather resistance, solvent resistance, hardness, adhesion, and the like. There is a problem that is difficult to apply to the line. That is, because the drying property is not good, in order to wind the polyester film on the roller, the line speed or the temperature must be increased so that the economy is inferior.
한편, 아크릴 수지는 건조성, 내후성, 경도 등은 우수하지만 안료분산성, 내용제성, 유연성, 부착성이 떨어져 적용하는데 결점이 있다.On the other hand, acrylic resins have excellent drying properties, weather resistance, hardness, etc., but have disadvantages in that they are poor in pigment dispersibility, solvent resistance, flexibility, and adhesion.
그리고, 고분자량 폴리에스테르 수지(수평균 분자량 : 8000∼35000)는 긴 반응시간동안 (15시간∼45시간) 고온(220℃∼280℃ )에서 에스테르 반응을 시켜 제조하는데 내후성, 색수, 특히 안료분산성 등이 떨어진다. 그리고 수산기가 적어(수산기가: 5∼10) 경화제를 사용하여 원하는 물성을 얻기가 어렵다.In addition, high molecular weight polyester resins (number average molecular weight: 8000 to 35000) are produced by ester reaction at high temperature (220 ° C to 280 ° C) for a long reaction time (15 hours to 45 hours). Acidic drops. And since there are few hydroxyl groups (hydroxyl value: 5-10), it is difficult to obtain desired physical property using a hardening | curing agent.
이런 문제점을 개선하기 위하여 우레탄변성 폴리에스테르 수지가 제안되었지만, 이 수지는 건조성, 인장력, 경도 등이 우수한 반면 설계 고형분이 낮아 작업성(점도에 비해 고형분이 낮음)이 떨어져 연속라인에 적용하는데 문제점이 있다. 나아가 우레탄변성 폴리에스테르 수지, 아크릴 수지 등은 분자량 분포가 좁아 특히 안료분산성이 떨어진다.Urethane-modified polyester resins have been proposed to improve these problems, but these resins are excellent in dryness, tensile strength, hardness, etc., but have low design solids, resulting in poor workability (low solids compared to viscosity), and thus are applicable to continuous lines. There is this. Furthermore, urethane-modified polyester resins and acrylic resins have a narrow molecular weight distribution, and are particularly poor in pigment dispersibility.
한편, 박막화가 가능하며 내용제성 및 안료분산성이 우수한 분체도료용 아크릴변성 폴리에스테르 수지가 제안되었다 (한국특허공고 95-7994호 및 한국특허 제139274호). 이들 문헌에 따르면, 산과 알콜의 혼합물로부터 하이드록실 폴리에스테르 프리폴리머를 제조하고, 이와는 별도로 아크릴 모노머와 카르복실기를 갖는 아크릴 모노머를 용액중합하여 아크릴 수지를 제조하고, 이렇게 제조한 폴리에스테르 프리폴리머와 아크릴 수지를 다가산 혼합물과 함께 반응시켜 아크릴변성 폴리에스테르 수지를 제조하는 방법이 개시되어 있다.On the other hand, acrylic modified polyester resins for powder coating that can be thinned and have excellent solvent resistance and pigment dispersibility have been proposed (Korean Patent Publication No. 95-7994 and Korean Patent No. 139274). According to these documents, a hydroxyl polyester prepolymer is prepared from a mixture of an acid and an alcohol, and an acrylic resin is prepared by solution polymerization of an acrylic monomer having an acrylic monomer and a carboxyl group, and the polyester prepolymer and the acrylic resin thus prepared are multiplied. A method of producing an acrylic modified polyester resin by reacting with an acid mixture is disclosed.
미국특허 제 4,355,080호에는, 다염기산과 다가 알콜로부터 얻어진 폴리에스테르 수지에 CH2=CHCO2R (R은 탄소수 1-12의 직쇄 또는 분지쇄 알킬기이다) 또는 CH2=C(CH3)CO2R1(R1은 탄소수 1-12의 직쇄 또는 분지쇄 알킬기이다) 모노머로부터제조된 아크릴 필름을 적층시켜서 내후성을 향상시킨 폴리에스테르-아크릴 복합체 시트가 제안되어 있다.U.S. Patent No. 4,355,080 discloses a polyester resin obtained from a polybasic acid and a polyhydric alcohol, wherein CH 2 = CHCO 2 R (R is a straight or branched chain alkyl group having 1 to 12 carbon atoms) or CH 2 = C (CH 3 ) CO 2 R A polyester-acrylic composite sheet having improved weather resistance by stacking an acrylic film produced from a monomer of 1 (R 1 is a straight or branched chain alkyl group having 1 to 12 carbon atoms) has been proposed.
그러나 이러한 기존의 방법들은 각각의 수지들을 제조하여 이들을 적용시키거나 또는 다시금 반응시키는 여러 단계들로 이루어져 있어서 시간과 비용적인 측면에서 경제적이지 못한 결점이 있고, 사용하는 적용분야가 전혀 다르다.However, these conventional methods are made up of several steps for preparing and applying the respective resins or reacting them again, which is not economically disadvantageous in terms of time and cost, and uses different applications.
한국특허 제149695호에는, 내후성이 우수한 변성 폴리에스테르 수지-함유 도료 조성물을 얻기 위하여, 폴리에스테르 폴리올 수지와 아크릴 폴리올 수지를 각각 제조한 후, 이들을 디이소시아네이트와 반응시켜 우레탄 결합을 갖게 한 변성 폴리에스테르 수지를 제공하고 있다. 이는 도료 응용시 멜라민 열경화용에 관한 것으로서, 도료 응용시 변성 폴리에스테르 수지에 우레탄 경화제를 첨가하여 상온·저온에서 경화시키는 시스템에 관해 후술하게 될 본 발명과는 적용분야가 상이하다.In Korean Patent No. 149695, in order to obtain a modified polyester resin-containing coating composition excellent in weatherability, a polyester polyol resin and an acrylic polyol resin are prepared, respectively, and then modified polyesters having a urethane bond by reacting them with diisocyanates. Resin is provided. This relates to the melamine thermosetting for coating applications, the application field is different from the present invention will be described later with respect to the system for curing at room temperature and low temperature by adding a urethane curing agent to the modified polyester resin during coating applications.
이러한 상황하에서 본 발명자들은 보다 경제적인 방법으로 내용제성, 내후성 및 건조성등이 우수한 변성 폴리에스테르 수지를 제공하고자 광범위한 연구를 행하였고, 그 결과로서 본 발명을 완성하기에 이르렀다.Under these circumstances, the present inventors have conducted extensive research to provide a modified polyester resin having excellent solvent resistance, weather resistance, and dryness in a more economical manner, and as a result, the present invention has been completed.
즉, 본 발명은 내후성, 내용제성, 건조성 및 부착성 등이 우수한 변성 폴리에스테르 수지 및 이를 제조하는 방법을 제공하는 것을 목적으로 한다.That is, an object of the present invention is to provide a modified polyester resin excellent in weather resistance, solvent resistance, dryness and adhesion, and a method of producing the same.
본 발명에 따르면, 다음 단계 :According to the invention, the following steps:
(a) 다가 알콜; 다염기산; 및 하기 (1)~(4)로부터 선택된 1종 이상의 제1 아크릴 모노머를 중합시켜 분자 말단에 이중결합을 갖는 하기 일반식 (Ⅰ)~(Ⅳ)의 폴리에스테르 중간체를 각각 제조하는 단계;(a) polyhydric alcohols; Polybasic acids; And polymerizing one or more first acrylic monomers selected from the following (1) to (4) to prepare polyester intermediates of the following general formulas (I) to (IV) each having a double bond at the terminal of the molecule;
(1) 메타아크릴산(1) methacrylic acid
(2) 아크릴산(2) acrylic acid
(3) N-메틸올 아크릴아마이드(3) N-methylol acrylamide
(4) 2-하이드록시 에틸메타아크릴레이트(4) 2-hydroxy ethyl methacrylate
(상기 식중, R1은 폴리에스테르 폴리머 잔기이다)(Wherein R 1 is a polyester polymer residue)
(b) 상기 단계 (a)에서 얻은 폴리에스테르 중간체를 75℃∼130℃의 온도에서 라디칼 반응을 할 수 있는 1종 또는 2종 이상의 제2 아크릴 모노머와 중합반응시키는 단계(b) polymerizing the polyester intermediate obtained in step (a) with one or two or more second acrylic monomers capable of radical reaction at a temperature of 75 ° C to 130 ° C.
를 포함함을 특징으로 하는 아크릴변성 폴리에스테르 수지의 제조방법이 제공된다.Provided is a method for producing an acrylic modified polyester resin comprising a.
본 발명은 또한 상기 방법에 의해 얻은 아크릴변성 폴리에스테르 수지를 제공한다.The present invention also provides an acrylic modified polyester resin obtained by the above method.
본 발명은 나아가 상기 방법에 의해 얻은 아크릴변성 폴리에스테르 수지를 포함하는 칼라 강판 잉크 바인더를 제공한다.The present invention further provides a color steel sheet ink binder comprising an acrylic modified polyester resin obtained by the above method.
본 발명의 방법에 의해 얻어진 아크릴변성 폴리에스테르 수지는 일반 폴리에스테르 수지의 장점인 부착성, 내용제성, 광택, 유연성, 내충격성, 안료분산성 등의 물성과 아크릴 수지의 장점인 내후성, 건조성, 내약품성, 경도 등의 물성이 상호 보안된 우수한 물성을 가지며, 폴리에스테르 필름(PET FILM), 칼라 강판 잉크 바인더, 목공용 클리어 바니쉬(clear varnish), 종이 코팅(paper coating), 염화비닐 수지판 (PVC SHEET)등 다양한 분야에 적용할 수 있다.The acrylic modified polyester resin obtained by the method of the present invention has properties such as adhesion, solvent resistance, gloss, flexibility, impact resistance and pigment dispersibility, which are advantages of general polyester resins, and weather resistance, dryness, It has excellent physical properties, such as chemical resistance and hardness, which are mutually secured, and includes polyester film, color steel ink binder, clear varnish for woodwork, paper coating, and vinyl chloride resin plate ( It can be applied to various fields such as PVC sheet.
이상 본 발명을 보다 상세히 설명한다.The present invention is described in more detail above.
본 발명에 따르면, 먼저 분자말단에 이중결합을 갖는 상기 일반식 (Ⅰ) 내지 (Ⅳ)로 나타내지는 폴리에스테르 중간체를 제조하고, 이어서 이 중간체를 75℃∼130℃의 온도에서 라디칼 반응을 할 수 있는 1종 또는 2종 이상의 제2 아크릴 모노머와 중합반응시킴으로써 아크릴변성 폴리에스테르 수지를 얻는다.According to the present invention, first, a polyester intermediate represented by the above general formulas (I) to (IV) having a double bond at the molecular end can be prepared, and the intermediate can then be subjected to a radical reaction at a temperature of 75 ° C to 130 ° C. An acrylic modified polyester resin is obtained by polymerizing with one or two or more kinds of second acrylic monomers.
일반식 (Ⅰ) 내지 (Ⅳ)의 폴리에스테르 중간체는 다가 알콜; 다염기산; 및 하기 (1)~(4)로부터 선택된 1종 이상의 제1 아크릴 모노머를 축합반응시켜 제조한다.Polyester intermediates of the general formulas (I) to (IV) include polyhydric alcohols; Polybasic acids; And at least one first acrylic monomer selected from the following (1) to (4).
(1) 메타아크릴산(1) methacrylic acid
(2) 아크릴산(2) acrylic acid
(3) N-메틸올 아크릴아마이드(3) N-methylol acrylamide
(4) 2-하이드록시 에틸메타아크릴레이트(4) 2-hydroxy ethyl methacrylate
일반식 (Ⅰ) 내지 (Ⅳ)의 폴리에스테르 중간체의 제조에 사용되는 다염기산은 폴리에스테르를 제조하는데 사용되며 당업자에게 주지된 것들로부터 선택할 수 있으며, 예를 들면 아디핀산, 이소프탈산, 무수프탈산, 테레프탈산, 세바시크산, 숙신산, 1,4-사이클로헥산디카르복실산, 아제라인산, 하이믹산, 트리멜리틱산, 디메티올프로피온산, 벤조인산 등에서 선택된 1종 또는 2종 이상을 혼합하여 사용할 수 있다.The polybasic acids used for the preparation of the polyester intermediates of general formulas (I) to (IV) can be selected from those used to prepare the polyester and are well known to those skilled in the art, for example adipic acid, isophthalic acid, phthalic anhydride, terephthalic acid , One or two or more selected from sebacic acid, succinic acid, 1,4-cyclohexanedicarboxylic acid, azeline acid, hymic acid, trimellitic acid, dimetholpropionic acid, benzoic acid and the like can be used.
한편, 다가알콜로는 예를 들면 네오펜틸글리콜, 디에틸렌글리콜, 디프로필렌글리콜, 프로필렌글리콜, 에틸렌글리콜, 1,6-헥산디올, 헥실렌글리콜, 펜탄디올, 1,3-부틸렌글리콜, 1,4-부틸렌글리콜, 글리세린, 트리에틸렌글리콜, 펜타에리트리올, 트리메틸올 프로판, 트리메틸올 에탄 또는 1,4-사이클로헥산디메탄올에서 선택된 1종 또는 2종 이상을 혼합하여 사용할 수 있다.Meanwhile, as the polyhydric alcohol, for example, neopentyl glycol, diethylene glycol, dipropylene glycol, propylene glycol, ethylene glycol, 1,6-hexanediol, hexylene glycol, pentanediol, 1,3-butylene glycol, 1 1 type, or 2 or more types selected from, 4-butylene glycol, glycerin, triethylene glycol, pentaerytriol, trimethylol propane, trimethylol ethane or 1,4-cyclohexanedimethanol can be used in mixture.
다가 알콜과 다염기산의 사용량은 고형분 100중량부 중에서 다염기산류는 아디픽산 10-45중량부, 이소프탈산 20-55중량부, 무수 프탈산 0-10중량부, 1,4-사이클로헥산디카르복실산 약 30중량부를 사용할 수 있고, 다가 알콜로는 네오펜틸 글리콜 20-55중량부, 트리메틸올 프로판 15-30중량부, 1,6-헥산디올 5-20중량부, 트리메틸올 에탄 0-30중량부 등을 사용할 수 있다.The amount of the polyhydric alcohol and the polybasic acid used is 100 parts by weight of the solid, and the polybasic acids are 10-45 parts by weight of adipic acid, 20-55 parts by weight of isophthalic acid, 0-10 parts by weight of phthalic anhydride, and 1,4-cyclohexanedicarboxylic acid. 30 parts by weight may be used, and as polyhydric alcohol, 20-55 parts by weight of neopentyl glycol, 15-30 parts by weight of trimethylol propane, 5-20 parts by weight of 1,6-hexanediol, 0-30 parts by weight of trimethylol ethane, etc. Can be used.
아디픽산을 약 45중량부 이상의 양으로 사용하면 최종 제품의 경도가 떨어지고, 10중량부 미만의 양으로 사용하면 제품의 부착성 및 유연성 등이 떨어진다. 한편 이소프탈산의 경우 약 55중량부 이상의 양으로 사용하면 경도 및 광택은 좋으나 유연성 및 내후성이 떨어지고, 20중량부 미만에서는 경도 및 내약품성이 떨어진다. 무수 프탈산의 경우 10중량부를 초과하는 경우 내후성이 떨어지는 단점이 있다. 1,4-디사이클로헥산디카르복실산을 30중량부 이상의 양으로 사용하면 경도 및 광택이 떨어진다.If the amount of adipic acid is used in an amount of about 45 parts by weight or more, the hardness of the final product is lowered. If it is used in an amount of less than 10 parts by weight, the adhesion and flexibility of the product are inferior. On the other hand, in the case of isophthalic acid, when used in an amount of about 55 parts by weight or more, the hardness and gloss are good, but the flexibility and weather resistance are poor, and the hardness and the chemical resistance are less than 20 parts by weight. Phthalic anhydride has a disadvantage in that weather resistance is lower than 10 parts by weight. When 1,4-dicyclohexanedicarboxylic acid is used in an amount of 30 parts by weight or more, the hardness and gloss are poor.
다가 알콜의 경우, 네오펜틸 글리콜을 55중량부를 초과하는 양으로 사용하면, 제품의 광택이 떨어지고 20중량부 미만의 사용량에서는 내열성이 떨어진다. 트리메틸올 프로판을 30중량부 이상의 양으로 사용하면 수지의 골격에 가지가 많아져서 아크릴 변성시 겔화 위험이 많고 15중량부 미만에서는 수지골격에 가지가 적어져 도막의 경도가 떨어진다. 1,6-헥산디올을 20중량부 이상의 양으로 사용하면 유연성은 좋으나 경도가 떨어지고, 5중량부 미만의 사용량에서는 유연성 및 부착성이 떨어진다. 한편 트리메틸올 에탄의 경우 30중량부를 초과하면 수지의 골격에 가지가 많아져서 아크릴 변성시 겔화 위험이 많다.In the case of polyhydric alcohols, when neopentyl glycol is used in an amount exceeding 55 parts by weight, the gloss of the product is lowered and heat resistance is lowered at an amount of less than 20 parts by weight. When trimethylol propane is used in an amount of 30 parts by weight or more, there are more branches in the skeleton of the resin, which increases the risk of gelation when the acrylic is modified. When 1,6-hexanediol is used in an amount of 20 parts by weight or more, the flexibility is good, but the hardness is low, and when the amount is less than 5 parts by weight, flexibility and adhesion are inferior. On the other hand, in the case of trimethylol ethane, more than 30 parts by weight of the branch of the resin has a lot of gelation at the time of acrylic denaturation risk.
상기에서 설명된 (1)~(4)에서 선택되는 제1 아크릴 모노머는 반응혼합물 100중량부에 대해 2~30중량부의 비율로 사용된다. 2중량부 미만에서는 후에 이어질 아크릴 중합반응시 상용성의 문제가 있고, 30중량부를 초과하는 경우에는 가교밀도가 높고 고분자량화되어 겔화 가능성이 매우 높기 때문이다.The first acrylic monomer selected from (1) to (4) described above is used in a ratio of 2 to 30 parts by weight based on 100 parts by weight of the reaction mixture. If it is less than 2 parts by weight, there is a compatibility problem in the acrylic polymerization reaction to be carried out later, and if it exceeds 30 parts by weight, the crosslinking density is high and the high molecular weight is very high gelation possibility.
제1 아크릴 모노머는 다가 알콜과 다염기산 반응에 의한 폴리에스테르 중간체의 제조단계 초기부터 이들 출발물질과 함께 반응시킬 수도 있고, 이들 다가 알콜과 다염기산을 먼저 반응시키다가 적정한 점도와 산가에서 제1 아크릴 모노머를 첨가하고 나머지 반응을 진행시켜 폴리에스테르 중간체를 제조할 수 있다.The first acrylic monomer may be reacted with these starting materials from the beginning of the preparation of the polyester intermediate by the polyhydric alcohol and the polybasic acid reaction, and the first acrylic monomer is reacted with the appropriate viscosity and acid value after first reacting the polyhydric alcohol and the polybasic acid. Polyester intermediates can be prepared by addition and by proceeding with the rest of the reaction.
첫번째의 경우, 모든 중합반응 원료들을 사입하고 천천히 반응온도를 올려 최고 약 210~250℃의 온도까지 승온유지 반응시켜 불휘발분 60%(톨루엔), 기포점도 H-P(Gardner 점도계), 산가 10 이하에서 용제 비점(Bp) 이하의 온도로 내리고, 용제를 사입하여 불휘발분 60%(톨루엔), 점도 H-P(Gardner 점도계), 산가 10 이하의 유동성이 좋은 폴리에스테르 중간체를 제조한다.In the first case, all the raw materials of the polymerization reaction are introduced, and the reaction temperature is slowly raised to maintain the temperature of up to about 210 to 250 ° C. The reaction is carried out at 60% nonvolatile matter (toluene), bubble viscosity HP (Gardner viscometer), and solvent at an acid value of 10 The temperature is lowered to the boiling point (Bp) or lower, and a solvent is added to prepare a polyester intermediate having good fluidity of 60% of nonvolatile content (toluene), viscosity HP (Gardner viscometer), and acid value of 10 or less.
두번째의 경우, 먼저 다가 알콜과 다염기산을 반응기에 사입하고 천천히 승온하여 최고 온도가 210℃∼250℃에 이르도록 하여 이 온도를 유지하면서 반응시켜 산가가 10 이하로 되면 온도를 내리고 80℃이하의 온도에서 제1 아크릴 모노머를 사입하여 100℃∼190℃의 온도에서 에스테르 반응을 진행한다. 그리고 불휘발분 60%(톨루엔), 기포점도 H-P(Gardner 점도계), 산가 10 이하에서 용제 비점(Bp) 이하의 온도로 내리고, 용제를 사입하여 불휘발분 60%(톨루엔), 점도 H-P(Gardner 점도계), 수산기가 30-150, 산가 10 이하의 유동성이 좋은 폴리에스테르 중간체를 제조한다.In the second case, first, polyhydric alcohol and polybasic acid are introduced into the reactor, and the temperature is slowly raised to a maximum temperature of 210 ° C. to 250 ° C. and maintained while maintaining this temperature. When the acid value reaches 10 or less, the temperature is lowered and the temperature is 80 ° C. or less. In the first acrylic monomer is injected into the ester reaction at a temperature of 100 ℃ to 190 ℃. Then, 60% non-volatile content (toluene), bubble viscosity HP (Gardner viscometer), acid value is lowered to the temperature below the solvent boiling point (Bp) at 10 or less, and a solvent is added to the non-volatile content 60% (toluene), viscosity HP (Gardner viscometer) A polyester intermediate having good fluidity with a hydroxyl value of 30 to 150 and an acid value of 10 or less is produced.
일반식 (Ⅰ) 내지 (Ⅳ)의 중간체는 분자내 폴리머 말단에 라디칼 반응 인자(-CH=CH2)가 있으므로, 후속하는 제2 아크릴 모노머와의 중합반응시 겔화 가능성이 적다. 그러나, 통상의 폴리에스테를 제조하는데 이용되는 무수말레인산, 후말산 또는 무수 테트라 하이드로 프탈산를 이용하여 폴리에스테르 중간체를 제조한다면, 폴리머 중간에 1개 이상의 라디칼 반응 인자(-CH=CH-)가 있으므로 후속하는 아크릴 모노머와의 중합반응시 고분자량화되어 겔화 가능성이 매우 높다. 그 이유는 라디칼 반응인자가 폴리머 말단에 존재하지 않고 중간에 있기 때문이며, 그 결과 얻어지는 변성 폴리에스테르 수지는 도료의 작업성 등이 나쁜 문제점이 있다.Since the intermediates of the general formulas (I) to (IV) have a radical reaction factor (-CH = CH 2 ) at the end of the intramolecular polymer, there is little possibility of gelation during the polymerization reaction with the second acrylic monomer. However, if polyester intermediates are prepared using maleic anhydride, fumaric acid, or tetrahydrophthalic anhydride, which are used to make conventional polyesters, there is at least one radical reaction factor (-CH = CH-) in the middle of the polymer, The high molecular weight during the polymerization reaction with the acrylic monomer is very high gelation possibility. The reason is that the radical reaction factor is not present at the end of the polymer and is in the middle, and the resulting modified polyester resin has a problem in that the workability of the paint and the like are bad.
이상의 반응에 의해 얻은 폴리에스테르 중간체는 4구 플라스크에 사입하고 온도를 75℃∼130℃로 승온하여 유지하고 온도를 안정화시킨 후, 이어 약 75~130℃에서 라디칼 반응할 수 있는 아크릴 모노머 ('제2 아크릴 모노머')와 중합반응을 시켜 아크릴변성을 수행한다.The polyester intermediate obtained by the above reaction was injected into a four-necked flask, the temperature was maintained at 75 ° C to 130 ° C, and the temperature was stabilized, followed by an acrylic monomer capable of radical reaction at about 75 ° C to 130 ° C. 2 acrylic monomer ') to polymerize the acrylic modification.
제2 아크릴 모노머로는 메틸 메타아크릴레이트, 스티렌 모노머, 2-하이드록시 에틸메타아크릴레이트, 2-하이드록시 에틸아크릴레이트, 메타크릭산, 아크릴산, 부틸아크릴레이트, N-부틸메타아크릴레이트 등이 사용된다.As the second acrylic monomer, methyl methacrylate, styrene monomer, 2-hydroxy ethyl methacrylate, 2-hydroxy ethyl acrylate, methacrylic acid, acrylic acid, butyl acrylate, N-butyl methacrylate and the like are used. do.
제2 아크릴 모노머의 사용량은 상기한 여러 종류의 제2 아크릴 모노머들을 혼합하여 사용하는 경우, 제2 아크릴 모노머의 총량 100중량부를 기준으로 할 때, 메틸 메타아크릴레이트 20-90중량부, 스티렌 모노머 0-20중량부, 2-하이드록시 에틸메타아크릴레이트 또는 2-하이드록시 에틸아크릴레이트 5-30중량부, 메타크릭산 또는 아크릴산 5-30중량부, 부틸아크릴레이트 또는 N-부틸메타아크릴레이트 5-60중량부가 사용될 수 있다.When the amount of the second acrylic monomer is used by mixing the various types of the second acrylic monomers described above, based on 100 parts by weight of the total amount of the second acrylic monomer, 20-90 parts by weight of methyl methacrylate, styrene monomer 0 -20 parts by weight, 5-30 parts by weight of 2-hydroxy ethyl methacrylate or 2-hydroxy ethyl acrylate, 5-30 parts by weight of methacrylic acid or acrylic acid, butyl acrylate or N-butyl methacrylate 5- 60 parts by weight may be used.
메틸 메타아크릴레이트가 90중량부를 초과하는 경우에는 제품의 경도 및 건조성은 좋으나 부착성이 떨어지고, 20중량부 미만의 경우에는 건조성이 떨어진다. 2-하이드록시 에틸메타아크릴레이트 혹은 2-하이드록시 에틸아크릴레이트를 30중량부를 초과하여 사용하면 이소시아네이트 경화제의 사용량이 많아져서 건조성이 떨어지고, 경화제가 고가이므로 경제적인 측면에서도 불리하다. 이들을 5중량부 미만으로 사용하면 가교밀도가 적어져서 내용제성, 내약품성 등의 물성이 떨어진다. 메타크릭산 혹은 아크릴산을 30중량부 이상의 양으로 사용하면 도료의 저장성 및 내수성이 떨어지고, 5중량부 미만의 양으로 사용하면 안료분산성이 떨어진다. 부틸아크릴레이트 또는 N-부틸메타아크릴레이트를 60중량부 이상의 양으로 사용하면 경도 및 건조성이 떨어지고 5중량부 미만의 양으로 사용하면 유연성이 떨어진다.If the methyl methacrylate exceeds 90 parts by weight, the hardness and dryness of the product is good, but the adhesion is inferior, if less than 20 parts by weight, the dryness is inferior. If more than 30 parts by weight of 2-hydroxy ethyl methacrylate or 2-hydroxy ethyl acrylate is used, the amount of isocyanate curing agent is increased, resulting in poor drying properties, and the curing agent is expensive, which is disadvantageous in terms of economics. When these are used in less than 5 parts by weight, the crosslinking density decreases, resulting in poor physical properties such as solvent resistance and chemical resistance. When the amount of methacrylic acid or acrylic acid is used in an amount of 30 parts by weight or more, the storage property and water resistance of the coating are inferior, and when used in an amount of less than 5 parts by weight, the pigment dispersibility is inferior. When butyl acrylate or N-butyl methacrylate is used in an amount of 60 parts by weight or more, hardness and dryness are inferior, and when used in an amount of less than 5 parts by weight, flexibility is inferior.
일반식 (Ⅰ) 내지 (Ⅳ)의 폴리에스테르 중간체와 제2 아크릴 모노머의 중합반응은 라디칼 중합촉매의 존재하에 실시하는데, 예를 들면 제2 아크릴 모노머와 중합촉매의 혼합물을 적하깔대기(FUNNEL)를 이용하여 폴리에스테르 중간체가 들어있는 반응기에 1∼6시간동안 일정한 시간으로 적하하여 중합반응을 실시함으로써 아크릴변성 폴리에스테르수지를 제조한다. 과도한 중합열의 발생 및 폴리머의 겔화방지를 위하여 적하하는 것이 필요하다.The polymerization reaction of the polyester intermediates of the general formulas (I) to (IV) with the second acrylic monomer is carried out in the presence of a radical polymerization catalyst. For example, the mixture of the second acrylic monomer and the polymerization catalyst is added with a funnel. The acrylic modified polyester resin was prepared by dropwise addition to the reactor containing the polyester intermediate at a constant time for 1 to 6 hours to carry out the polymerization reaction. It is necessary to add dropping in order to generate excessive heat of polymerization and to prevent gelation of the polymer.
중합촉매는 통상의 라디칼 중합촉매중에서 선택할 수 있으며, 아조비스이소부티로니트릴, 벤조일퍼옥시드, 디부틸퍼옥시드 또는 쿠멘히드로퍼옥시드 등을 예시할 수 있다. 이들 촉매는 단독으로 또는 혼합하여 사용할 수 있으며, 본 발명에서 사용될 수 있는 촉매가 이들에만 한정되는 것은 아니다.The polymerization catalyst can be selected from ordinary radical polymerization catalysts and examples thereof include azobisisobutyronitrile, benzoyl peroxide, dibutyl peroxide or cumene hydroperoxide. These catalysts can be used alone or in combination, and the catalysts that can be used in the present invention are not limited thereto.
아크릴 변성이 수지의 중합도(분자량)가 낮으면 도막이 약하고 건조성, 내구성, 내약품성, 내후성, 기계적 물성 등이 저하되고, 중합도가 너무 높으면 수지의 점도가 높아서 살오름성, 스프레이시 작업성 등이 나빠진다. 그러므로 제2 아크릴 모노머는 유리전이온도(Tg) 50~90℃의 범위내에서 선택한다. 유리전이온도가 90℃ 이상인 경우에는 유연성, 부착성이 떨어지고, 50℃ 이하에서는 건조성, 내약품성, 내후성 등이 떨어진다.When the acrylic modification is low in the polymerization degree (molecular weight) of the resin, the coating film is weak, and the dryness, durability, chemical resistance, weather resistance, mechanical properties, etc. are lowered, and when the polymerization degree is too high, the viscosity of the resin is high, so that the rise property and workability during spraying Worse Therefore, the 2nd acrylic monomer is selected in the range of 50-90 degreeC of glass transition temperature (Tg). If the glass transition temperature is 90 ° C or higher, flexibility and adhesion are inferior, and at 50 ° C or lower, dryness, chemical resistance, weather resistance, and the like are poor.
폴리에스테르 중간체와 제2 아크릴 모너머의 비는 최종 폴리에스테르 수지의 물성에 많은 영향을 주는데, 내용제성, 부착성, 내충격성, 안료분산성, 유연성 등의 물성을 향상시키기 위해서 아크릴 수지보다 폴리에스테르 중간체의 비율이 많은 것이 요구된다. 예를 들면 폴리에스테르/아크릴수지=50∼80/50∼20의 범위에서 선정할 수 있다. 반면, 건조성, 내구성, 내약품성, 내후성 등의 물성을 보다 더 향상시키고자 하는 경우에는 폴리에스테르 중간체보다 제2 아크릴 모노머의 비를 증가시키는 것, 예를 들어 폴리에스테르/아크릴수지=45∼5/55∼95의 범위에서 선택할 수 있다.The ratio of the polyester intermediate and the second acrylic monomer has a great influence on the physical properties of the final polyester resin, and in order to improve physical properties such as solvent resistance, adhesion, impact resistance, pigment dispersibility, and flexibility, polyesters are better than polyester resins. High proportions of intermediates are required. For example, it can select from the range of polyester / acrylic resin = 50-80 / 50-20. On the other hand, when it is desired to further improve physical properties such as dryness, durability, chemical resistance and weather resistance, increasing the ratio of the second acrylic monomer than the polyester intermediate, for example, polyester / acrylic resin = 45 to 5 It can select from the range of / 55-95.
용제의 선택으로 탄화수소류, 케톤류, 에스테르류 등을 사용하고, 알콜류의 용제는 반드시 배제되어야 한다. 이는 도료화 및 바니쉬를 제조하여 우레탄 경화제를 사용할 때가 있기 때문이다.Hydrocarbons, ketones, esters and the like are used for the selection of the solvent, and solvents of alcohols must be excluded. This is because the paint and varnish are sometimes manufactured to use a urethane curing agent.
그리고 폴리머중의 수산기가에 따라 우레탄 반응시 물성 차이가 많다. 아크릴변성 폴리에스테르 수지의 수산기가는 10-90(불휘발분 50%)의 범위에 있다. 수산기가가 너무 낮으면(10이하) 우레탄 반응시 가교밀도가 적어 내용제성, 경도, 스크래치성, 내화학성, 내수성 등이 나빠지게 되고, 수산기가가 90이상으로 너무 높으면 기계적 물성, 부착성, 유연성 등이 나빠져 필름코팅시 도막이 떨어지는 현상이 발생하고 우레탄 경화제 (가격고가)의 양이 많아져 경제성 면에서 불리하다.And there are many differences in physical properties during the urethane reaction depending on the hydroxyl value in the polymer. The hydroxyl value of acrylic modified polyester resin exists in the range of 10-90 (50% of non volatile matter). If the hydroxyl value is too low (less than 10), the crosslinking density is low during the urethane reaction, resulting in poor solvent resistance, hardness, scratch resistance, chemical resistance, water resistance, etc., and when the hydroxyl value is too high (90 or more), mechanical properties, adhesion and flexibility It is disadvantageous in terms of economic efficiency because the back is worsened and the coating film falls when the film is coated, and the amount of urethane curing agent (price price) is increased.
이러한 방법으로 합성된 아크릴변성 폴리에스테르수지는 안료분산성이 우수하기 때문에 단독으로 또는 2액형으로 사용한다. 2액형의 경화제로는 우레탄 경화제, 아미노 수지가 이용된다. 예를들면 우레탄 경화제는 황 변경화제, 난황변경화제, 무황변경화제 등이 있으며 단독 또는 2개 이상 혼합하여 사용한다.The acrylic modified polyester resin synthesized in this way is used alone or in two-component type because of its excellent pigment dispersibility. A urethane hardener and an amino resin are used as a two-component hardener. For example, the urethane curing agent may be a sulfur change agent, an egg yolk change agent, a sulfur-free change agent, etc., and may be used alone or in combination of two or more thereof.
본 발명에서는 디부틸틴 디라우레이트(DBTDL), 징크 아세테이트 등의 촉매를 경화촉진제로 사용할 수 있다. 이 목적으로 사용되는 경화 촉매의 사용량은 폴리에스테르 수지를 기준으로 0.01%중량부 미만이다. 그리고 아미노 수지는 부틸화 요소수지, 부틸화 요소 멜라민 수지, 부틸화 멜라민 수지, 메틸화 멜라민 수지 등이 있으며 단독 또는 2개 이상 혼합하여 사용할 수 있다.In the present invention, a catalyst such as dibutyltin dilaurate (DBTDL) and zinc acetate may be used as a curing accelerator. The amount of the curing catalyst used for this purpose is less than 0.01% by weight based on the polyester resin. The amino resins include butylated urea resins, butylated urea melamine resins, butylated melamine resins, methylated melamine resins, and the like.
P-톨루엔 술폰산, 디노닐 나프탈렌디술폰산 등의 산촉매를 경화촉진제로 사용할 수 있다. 이 목적을 위해 사용되는 산촉매의 사용량은 폴리에스테르수지를 기준으로 1%중량부 미만이다. 사용목적에 따라서 기타 안료 및 첨가제를 사용할 수 있다.Acid catalysts, such as P-toluene sulfonic acid and dinonyl naphthalene disulfonic acid, can be used as a hardening accelerator. The amount of the acid catalyst used for this purpose is less than 1% by weight based on the polyester resin. Other pigments and additives may be used depending on the intended use.
이하 각종 실시예를 들어 본 발명을 보다 상세히 설명하지만, 본 발명이 이들 실시예로만 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to various examples, but the present invention is not limited to these examples.
[실시예 1]Example 1
질소가스 도입관, 교반장치, 온도계, 냉각콘덴서및 비드데칸터,적하깔대기가 장착된 4∼5리터의4구 플라스크에 네오펜틸글리콜 268중량부, 트리메틸올프로판 175중량부, 1,6헥산디올 80중량부, 아디핀산 268.3중량부, 이소프탈산 340중량부, 메타아크릭산 10중량부를 넣고 질소가스 분위기 하에서 천천히 230℃로 승온 유지반응 시킨 후 4시간에서 6시간동안 에스테르 반응시켰다. 산가가 8이하가 되면 냉각시켰다. 100℃이하가 되면 톨루엔 666.6중량부를 넣어 희석시켜 고형분 60.3%, 기포점도 M, 산가 4.1이하의 폴리에스테르 중간체 수지를 합성하였다.268 parts by weight of neopentyl glycol, 175 parts by weight of trimethylolpropane, 1,6 hexanediol in a 4-5 liter four-necked flask equipped with a nitrogen gas introduction tube, a stirrer, a thermometer, a cooling capacitor and a bead decanter, and a dropping funnel. 80 parts by weight, 268.3 parts by weight of adipic acid, 340 parts by weight of isophthalic acid, and 10 parts by weight of metaacrylic acid were added and then slowly heated and maintained at 230 ° C. under a nitrogen gas atmosphere, and then esterified for 4 hours to 6 hours. The acid was cooled to 8 or less. When it became 100 degrees C or less, 666.6 weight part of toluene was put and diluted, and the polyester intermediate resin of 60.3% of solid content, bubble viscosity M, and an acid value of 4.1 or less was synthesize | combined.
위의 플라스크에서 비드데칸터를 제거하고 적하깔대기를 장착하였다. 그리고 톨루엔 390중량부를 사입하고 90℃로 승온하여 안정화시켰다. 미리 준비된 메틸 메타아크릴레이트 567.4중량부, 2-하이드록시 에틸 메타아크릴레이트 44.4중량부, 메타아크릴산 5.1중량부, 부틸 아크릴레이트 36.5중량부, 디부틸퍼옥시드(BPO) 13.2중량부를 1∼3리터 비이커에 혼합하고 균일하게 저어주었다. 그리고 적하깔대기에 사입한 후 2시간동안 일정한 시간으로 적하하면서 중합열을 제어하고 6시간에서 10시간 동안 반응시켰다. 불휘발분과 점도 변화가 없을 때 냉각하고 88℃ 이하에서 메틸에틸케톤 487.5중량부를 넣어 희석하고, 불휘발분 50.2%, 기포점도 W-X, 수산기가 52.1, 산가 4.4의 아크릴 변성 폴리에스테르 수지를 합성한다.Bead decanter was removed from the flask and a dropping funnel was mounted. Then, 390 parts by weight of toluene was purchased and stabilized by raising the temperature to 90 ° C. 567.4 parts by weight of methyl methacrylate prepared in advance, 44.4 parts by weight of 2-hydroxyethyl methacrylate, 5.1 parts by weight of methacrylic acid, 36.5 parts by weight of butyl acrylate, 13.2 parts by weight of dibutyl peroxide (BPO) 1 to 3 liter beaker Mix in and stir evenly. Then, the mixture was added to the dropping funnel, and then added dropwise at a constant time for 2 hours to control the heat of polymerization and reacted for 6 to 10 hours. When there is no non volatile matter and a viscosity change, it cools and dilutes 487.5 weight part of methyl ethyl ketones at 88 degrees C or less, and synthesize | combines acrylic modified polyester resin of 50.2% of non volatile matters, bubble viscosity W-X, a hydroxyl value of 52.1, and an acid value of 4.4.
[실시예 2]Example 2
질소가스 도입관, 교반장치, 온도계, 냉각콘덴서 및 비드데칸터, 적하깔대기가 장착된 4∼5리터의 4구 플라스크에 네오펜틸글리콜 209중량부, 트리메틸올프로판 175중량부, 1,6 헥산디올 140중량부, 아디핀산 196.8중량부, 이소프탈산 409.1중량부, 아크릴산 10중량부를 넣고 질소가스 분위기 하에서 천천히 230℃로 승온 유지반응 시킨 후 4시간에서 6시간동안 에스테르 반응을 행하였다. 산가가 10이하가 되면 반응혼합물을 냉각시켰다. 100℃이하가 되면 톨루엔 666.6중량부를 넣어 희석시켜 고형분 60.6%, 기포점도 N-O, 산가 4.9이하의 폴리에스테르 중간체 수지를 합성하였다.209 parts by weight of neopentyl glycol, 175 parts by weight of trimethylolpropane, 1,6 hexanediol in a 4-5 liter four-necked flask equipped with a nitrogen gas introduction tube, a stirring device, a thermometer, a cooling capacitor and a bead decanter, and a dropping funnel. 140 parts by weight, adipic acid 196.8 parts by weight, isophthalic acid 409.1 parts by weight, and acrylic acid 10 parts by weight were slowly reacted at a temperature of 230 ° C. under a nitrogen gas atmosphere, and then an ester reaction was carried out for 4 to 6 hours. When the acid value was less than 10, the reaction mixture was cooled. When the temperature was 100 ° C. or lower, 666.6 parts by weight of toluene was added and diluted to synthesize a polyester intermediate resin having a solid content of 60.6%, bubble viscosity N-O, and an acid value of 4.9 or less.
이어 실시예 1과 동일한 방법으로 아크릴 변성을 하여 불휘발분 50%, 기포점도 X-Y, 수산기가 51.3, 산가 4.1의 아크릴 변성 폴리에스테르 수지를 합성하였다.Subsequently, acrylic modification was carried out in the same manner as in Example 1 to synthesize an acrylic modified polyester resin having a nonvolatile content of 50%, bubble viscosity X-Y, a hydroxyl value of 51.3, and an acid value of 4.1.
[실시예 3]Example 3
질소가스 도입관, 교반장치, 온도계, 냉각콘덴서 및 비드데칸터, 적하깔대기가 장착된 4∼5리터의 4구 플라스크에 네오펜틸글리콜 180중량부, 트리메틸올프로판 200중량부, 1,6 헥산디올 140중량부, 아디핀산 214.9중량부, 이소프탈산 390중량부, 2-하이드록시 에틸 메타아크릴레이트 15중량부를 넣고 질소가스 분위기 하에서 천천히 230℃로 승온유지 반응시킨 후 4시간에서 6시간동안 에스테르 반응을 행하였다. 산가가 8이하가 되면 냉각시키고, 110℃이하가 되면 톨루엔 666.6중량부를 넣어 희석시켜 고형분 60.5%, 기포점도 N-O, 산가 5.3의 폴리에스테르 중간체 수지를 합성하였다.180 parts by weight of neopentyl glycol, 200 parts by weight of trimethylolpropane, 1,6 hexanediol in a 4 to 5 liter four-necked flask equipped with a nitrogen gas introduction tube, a stirring device, a thermometer, a cooling capacitor and a bead decanter, and a dropping funnel. 140 parts by weight, 214.9 parts by weight of adipic acid, 390 parts by weight of isophthalic acid, and 15 parts by weight of 2-hydroxyethyl methacrylate were slowly reacted at 230 ° C. under a nitrogen gas atmosphere, followed by ester reaction for 4 to 6 hours. It was done. When the acid value was 8 or less, the mixture was cooled. When it was 110 ° C. or less, 666.6 parts by weight of toluene was added and diluted to synthesize a polyester intermediate resin having a solid content of 60.5%, bubble viscosity N-O, and an acid value of 5.3.
실시예 1과 동일한 방법으로 아크릴 변성을 하여 불휘발분 50.3%, 기포점도 X-Y, 수산기가 52.7, 산가 3.8의 아크릴 변성 폴리에스테르 수지를 합성하였다.Acrylic modification was carried out in the same manner as in Example 1 to synthesize an acrylic modified polyester resin having a nonvolatile content of 50.3%, bubble viscosity X-Y, a hydroxyl value of 52.7, and an acid value of 3.8.
[실시예 4]Example 4
실시예 3과 동일하게 실시하되, 2-하이드록시 에틸아크릴레이트 15중량부 대신 2-하이드록시 에틸메타아크릴레이트 15중량부를 이용하여 불휘발분 50.6%, 기포점도 X-Y, 수산기가 49.8, 산가 4.1의 아크릴 변성 폴리에스테르 수지를 합성하였다.In the same manner as in Example 3, using 15 parts by weight of 2-hydroxy ethyl methacrylate instead of 15 parts by weight of 2-hydroxy ethyl acrylate, non-volatile content of 50.6%, bubble viscosity XY, hydroxyl value of 49.8, acid value of 4.1 acrylic A modified polyester resin was synthesized.
[비교예 1]Comparative Example 1
질소가스 도입관, 교반장치, 온도계, 냉각콘덴서 및 비드데칸터, 적하깔대기가 장착된 4∼5리터의 4구 플라스크에 네오펜틸글리콜 264중량부, 트리메틸올프로판 250중량부, 아디핀산 250중량부, 이소프탈산 380중량부를 넣고 질소가스 분위기 하에서 천천히 230℃로 승온 유지반응 시킨 후 4시간에서 6시간동안 에스테르 반응을 행하였다. 산가가 8이하가 되면 냉각시키고, 110℃이하가 되면 톨루엔 666.6중량부를 넣어 희석시켜 고형분 60.5%, 기포점도 O, 산가 7.3의 폴리에스테르 중간체 수지를 합성하였다.264 parts of neopentyl glycol, 250 parts by weight of trimethylolpropane, 250 parts by weight of adipic acid in a 4-5 liter four-necked flask equipped with a nitrogen gas introduction tube, a stirring device, a thermometer, a cooling capacitor and a bead decanter, and a dropping funnel. After adding 380 parts by weight of isophthalic acid, the reaction was slowly maintained at 230 ° C. under a nitrogen gas atmosphere, and then esterified for 4 to 6 hours. When the acid value was 8 or less, the mixture was cooled, and when it was 110 ° C. or less, 666.6 parts by weight of toluene was added and diluted to synthesize a polyester intermediate resin having a solid content of 60.5%, bubble viscosity O, and an acid value of 7.3.
그리고 실시예 1의 아크릴 변성과 동일한 방법을 수행하여 불휘발분 50.8%, 기포점도는 측정불가(백탁 현상), 수산기가 53.1, 산가 5.7의 아크릴 변성 폴리에스테르 수지를 합성하였다.The acrylic modified polyester resin having a nonvolatile content of 50.8%, bubble viscosity was not measured (cloudy development), a hydroxyl value of 53.1, and an acid value of 5.7 was synthesized by the same method as the acrylic modification of Example 1.
[비교예 2]Comparative Example 2
질소가스 도입관, 교반장치, 온도계, 냉각콘덴서 및 비드데칸터가 장착된 4∼5리터의 4구 플라스크에 네오펜틸글리콜 250중량부, 트리메틸올프로판 200중량부, 1,6헥산디올 50중량부, 아디핀산 279중량부, 이소프탈산 370중량부를 넣고 질소가스 분위기 하에서 천천히 220℃로 승온 유지반응 시킨 후 5시간에서 10시간동안 에스테르 반응을 수행하였다. 산가가 10이하가 되면 냉각시키고, 110℃이하가되면 톨루엔 1000중량부를 넣어 희석시켜 고형분 50.8%, 기포점도 X-Y, 수산기가 49.8, 산가 4.7이하의 폴리에스테르 수지를 합성하였다.250 parts by weight of neopentyl glycol, 200 parts by weight of trimethylolpropane, 50 parts by weight of 1,6 hexanediol in a 4-5 liter four-necked flask equipped with a nitrogen gas introduction tube, a stirring device, a thermometer, a cooling capacitor and a bead decanter. , 279 parts by weight of adipic acid and 370 parts by weight of isophthalic acid were added and then slowly heated and maintained at 220 ° C. under a nitrogen gas atmosphere, and then ester reaction was performed for 5 to 10 hours. When the acid value was 10 or less, the mixture was cooled, and when it was 110 ° C. or less, 1000 parts by weight of toluene was added and diluted to synthesize a polyester resin having a solid content of 50.8%, bubble viscosity X-Y, a hydroxyl value of 49.8, and an acid value of 4.7 or less.
[비교예 3]Comparative Example 3
불휘발분 50%, 기포점도 V, 수산기가 41, 산가 3.0의 아크릴 폴리올 수지 (애경화학 제품 AA-951-50).An acrylic polyol resin having a nonvolatile content of 50%, a bubble viscosity V, a hydroxyl value of 41, and an acid value of 3.0 (Aekyung Chemicals AA-951-50).
[실험예 1] 도막 성능 시험Experimental Example 1 Coating Film Performance Test
실시예 1 ~ 4 또는 비교예 1 ~ 3의 수지 130중량부, 이산화티탄 35중량부, 크실렌 15중량부, N-부틸 아세테이트 8.8중량부를 넣고 페인트 쉐이커로 1∼2시간 분산시켜 도료를 제조한 다음, 이들 도료 11.7중량부에 무황변 경화제 DN-980S (NCO% 20.6-21.0 애경화학 제품)를 첨가하였다. 인산아연염으로 전처리한 시편(SPC강판)에 위 도료를 에어스프레이 하여 건조한 후 도막두께 25∼35미크론이 되게 시편을 제작하였다. 그리고 상온에서 1주일 동안 방치한 다음, 아래 표 1에 열거한 물성들을 측정하고 그 결과를 표 1에 정리하였다.130 parts by weight of the resin of Examples 1 to 4 or Comparative Examples 1 to 3, 35 parts by weight of titanium dioxide, 15 parts by weight of xylene, 8.8 parts by weight of N-butyl acetate were added and dispersed in a paint shaker for 1 to 2 hours to prepare a paint. And yellowing-hardening agent DN-980S (NCO% 20.6-21.0 Aekyung Chemical Co., Ltd.) was added to 11.7 weight part of these coating materials. After pre-treatment with zinc phosphate (SPC steel), the above paint was air-sprayed to dry, and the specimen was prepared to have a film thickness of 25 to 35 microns. After leaving for one week at room temperature, the physical properties listed in Table 1 below were measured and the results are summarized in Table 1.
한편 각 시험항목은 다음과 같은 기준에 따라 측정하였다.Meanwhile, each test item was measured according to the following criteria.
1-1. 연필경도 : 연필('UNI', 미쓰비시 펜슬)을 사용하여 측정.1-1. Pencil Hardness: Measured using a pencil ('UNI', Mitsubishi Pencil).
1-2. 내충격성 : 듀퐁파입 충격시험기기를 이용하여 1/2' × 1kg × 50cm에서 측정.1-2. Impact resistance: Measured at 1/2 '× 1kg × 50cm using a DuPont impact tester.
1-3. 광택 : Gloss meter를 사용하여 측정(60°).1-3. Gloss: Measured with a Gloss meter (60 °).
1-4. 내용제성 : MEK RUBBING TESTER를 사용하여 측정(하중 1kg).1-4. Solvent resistance: Measured using MEK RUBBING TESTER (load 1kg).
1-5. 촉진내후성 : JIS K-5400 시험법에 따라 측정1-5. Accelerated weather resistance: measured according to JIS K-5400 test method
QUV : 63℃±3℃, WET 2100±100ml/min: 120분간 조사 중에 18분간.QUV: 63 ° C. ± 3 ° C., WET 2100 ± 100 ml / min: 18 minutes during 120 minutes irradiation.
1-6. 안료분산성 : ASTM-D1210 분산도의 측정법에 따라 측정.1-6. Pigment Dispersibility: Measured according to ASTM-D1210 Measurement of Dispersion.
1-7. 내비등수성 : JIS K-5400 100℃±2℃에서 2시간동안 침적하여 측정.1-7. Boiling resistance: Measured by immersing in JIS K-5400 100 ℃ ± 2 ℃ for 2 hours.
1-8. 내염수분무성 : JIS K-5400 시험법에 따라 측정.1-8. Salt water spray resistance: measured according to JIS K-5400 test method.
35℃±1℃, 5% NaCl, 1-2㎖/H35 ° C ± 1 ° C, 5% NaCl, 1-2mL / H
1-9. 에릭슨 : JIS K-5400의 시험방법에 따라 측정.1-9. Ericsson: Measured according to the test method of JIS K-5400.
표 1에서, 각 기호는 다음의 의미를 갖는다:In Table 1, each symbol has the following meaning:
◎ : 우수 ○ : 양호◎: Excellent ○: Good
○-△ : 보통 △ : 불량○-△: Normal △: Bad
표 1에서, 비교예 1의 수지는 상용성 불량 및 층분리 현상으로 테스트할 수 없었다. 즉, 비교예 1의 수지는 그라프트 반응이 일어나지 않아 상용성 불량으로불투명한 외관과 폴리에스테르 수지와 아크릴 수지가 분리되는 현상 때문에 도막 물성 테스트를 할 수 없었다. 그리고 실시예 1~4에서 제조한 수지는 아크릴 수지와 라디칼 반응하여 투명한 외관과 아크릴 수지와의 상용성이 좋아 우수한 도막 물성을 보여주고 있다.In Table 1, the resin of Comparative Example 1 could not be tested due to poor compatibility and delamination. That is, the resin of Comparative Example 1 could not be tested for coating properties due to the graft reaction did not occur due to poor compatibility and the opaque appearance and the phenomenon that the polyester resin and the acrylic resin are separated. In addition, the resins prepared in Examples 1 to 4 radically react with the acrylic resins, and thus exhibit excellent coating physical properties due to good compatibility with the transparent appearance and the acrylic resins.
표 1의 결과에서 알 수 있듯이, 본 발명의 방법에 따라 제조된 아크릴변성 폴리에스테르 수지로부터 만들어진 도료는 내후성, 내충격성, 내용제성, 안료분산성 등의 물성에 있어서 매우 우수하다.As can be seen from the results of Table 1, the paint made from the acrylic modified polyester resin produced according to the method of the present invention is very excellent in physical properties such as weather resistance, impact resistance, solvent resistance, pigment dispersion properties and the like.
이상 설명한 바와 같이, 본 발명에서 제공되는 아크릴변성 폴리에스테르 수지는 내용제성, 안료분산성, 건조성이 우수한 표면 코팅을 가능하게 하고, 분자량 분포를 넓게 함으로서 안료분산성이 우수하다. 따라서 칼라강판 인쇄용 잉크바인더 또는 내용제성이 요구되는 PET 필름 코팅용으로 유리하게 사용될 수 있다.As described above, the acrylic modified polyester resin provided in the present invention enables surface coating excellent in solvent resistance, pigment dispersibility, and drying property, and is excellent in pigment dispersibility by widening the molecular weight distribution. Therefore, it can be advantageously used for coating the color film printing ink binder or PET film requiring solvent resistance.
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KR100832562B1 (en) * | 2006-12-28 | 2008-05-26 | (주)디피아이 홀딩스 | Acrylic modified polyester resin, method of preparing the same and paint composition including the acrylic modified polyester resin |
KR100918939B1 (en) * | 2007-12-28 | 2009-09-28 | (주)디피아이 홀딩스 | Acrylic modified polyester resin contained phosphate having high moisture resistance and resin composition for color steel sheet using thereof |
KR101343534B1 (en) * | 2012-01-30 | 2013-12-19 | 주식회사 노루홀딩스 | Method of preparing acryl-modified polyester resin composition and top clear paint composition including the resin |
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KR101527065B1 (en) * | 2013-10-31 | 2015-06-09 | 주식회사 제이씨씨 | Polyester modified acrylic resin, method of preparing the same and paint composition including the polyester modified acrylic resin |
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KR100832562B1 (en) * | 2006-12-28 | 2008-05-26 | (주)디피아이 홀딩스 | Acrylic modified polyester resin, method of preparing the same and paint composition including the acrylic modified polyester resin |
KR100918939B1 (en) * | 2007-12-28 | 2009-09-28 | (주)디피아이 홀딩스 | Acrylic modified polyester resin contained phosphate having high moisture resistance and resin composition for color steel sheet using thereof |
KR101343534B1 (en) * | 2012-01-30 | 2013-12-19 | 주식회사 노루홀딩스 | Method of preparing acryl-modified polyester resin composition and top clear paint composition including the resin |
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