KR102033957B1 - UV Curable Liquid Resin composition for Printing Plate Having Improved Resolution and the Making Method thereof - Google Patents
UV Curable Liquid Resin composition for Printing Plate Having Improved Resolution and the Making Method thereof Download PDFInfo
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- KR102033957B1 KR102033957B1 KR1020180058129A KR20180058129A KR102033957B1 KR 102033957 B1 KR102033957 B1 KR 102033957B1 KR 1020180058129 A KR1020180058129 A KR 1020180058129A KR 20180058129 A KR20180058129 A KR 20180058129A KR 102033957 B1 KR102033957 B1 KR 102033957B1
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- acrylate
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- 239000011342 resin composition Substances 0.000 title claims abstract description 42
- 239000007788 liquid Substances 0.000 title claims abstract description 39
- 238000007639 printing Methods 0.000 title abstract description 25
- 238000000034 method Methods 0.000 title description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 70
- 229920005862 polyol Polymers 0.000 claims abstract description 45
- 150000003077 polyols Chemical class 0.000 claims abstract description 37
- 229920000570 polyether Polymers 0.000 claims abstract description 27
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 26
- 229920002635 polyurethane Polymers 0.000 claims abstract description 24
- 239000004814 polyurethane Substances 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 239000000654 additive Substances 0.000 claims abstract description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 4
- 150000002513 isocyanates Chemical class 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 16
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 abstract description 14
- 230000002194 synthesizing effect Effects 0.000 abstract description 5
- 125000005442 diisocyanate group Chemical group 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract 1
- -1 ether polyol Chemical class 0.000 description 21
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 12
- 239000003085 diluting agent Substances 0.000 description 11
- 238000001723 curing Methods 0.000 description 10
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- KFJJYOKMAAQFHC-UHFFFAOYSA-N (4-methoxy-5,5-dimethylcyclohexa-1,3-dien-1-yl)-phenylmethanone Chemical compound C1C(C)(C)C(OC)=CC=C1C(=O)C1=CC=CC=C1 KFJJYOKMAAQFHC-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- JHGGYGMFCRSWIZ-UHFFFAOYSA-N 2,2-dichloro-1-(4-phenoxyphenyl)ethanone Chemical compound C1=CC(C(=O)C(Cl)Cl)=CC=C1OC1=CC=CC=C1 JHGGYGMFCRSWIZ-UHFFFAOYSA-N 0.000 description 1
- GIMQKKFOOYOQGB-UHFFFAOYSA-N 2,2-diethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)(OCC)C(=O)C1=CC=CC=C1 GIMQKKFOOYOQGB-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- OWPUOLBODXJOKH-UHFFFAOYSA-N 2,3-dihydroxypropyl prop-2-enoate Chemical compound OCC(O)COC(=O)C=C OWPUOLBODXJOKH-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- 239000012957 2-hydroxy-2-methyl-1-phenylpropanone Substances 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- 241000448280 Elates Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- NQSMEZJWJJVYOI-UHFFFAOYSA-N Methyl 2-benzoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 NQSMEZJWJJVYOI-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 229940024874 benzophenone Drugs 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229940117969 neopentyl glycol Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
Abstract
Description
본 발명은 해상도가 향상된 자외선 경화형 액상 수지 조성물 및 이의 제조방법에 관한 것으로서, 폴리우레탄 (메타)아크릴레이트 올리고머 제조시 프리폴리머 합성단계를 생략하고 바로 폴리우레탄 (메타)아크릴레이트 올리고머 제조함으로써 생산성이 향상되고, 폴리우레탄 (메타)아크릴레이트 올리고머 제조시 산화에틸렌이 부가되지 않은 에테르계 폴리올을 사용함으로써 인쇄체의 해상도를 향상시키는 것을 그 특징으로 한다. The present invention relates to a UV-curable liquid resin composition with improved resolution and a method for manufacturing the same, which eliminates the prepolymer synthesis step in preparing a polyurethane (meth) acrylate oligomer and directly improves productivity by preparing a polyurethane (meth) acrylate oligomer. In the production of the polyurethane (meth) acrylate oligomer, an ether-based polyol to which ethylene oxide is not added is used to improve the resolution of a printed matter.
본 발명인 해상도가 향상된 자외선 경화형 액상 수지 조성물은 골판지 등에 인쇄를 하기 위해 잉크 전달 역할을 하는 인쇄판으로 사용된다. 과거에는 인쇄판으로 고무를 많이 사용하였으나 내구성 및 해상도 등의 문제 등으로 자외선 경화형 인쇄판으로 많이 대체되었다. The resolution-enhanced UV-curable liquid resin composition of the present invention is used as a printing plate that plays an ink transfer role for printing on corrugated cardboard or the like. In the past, rubber was used a lot as a printing plate, but it was replaced by a UV-curable printing plate due to problems such as durability and resolution.
자외선 경화형 인쇄판은 크게 고체 형태의 인쇄판과 액상 형태의 수지를 경화시켜 사용하는 인쇄판으로 크게 분류할 수 있다. 고체 형태의 인쇄판은 해상도가 높은 장점이 있는 반면, 자외선으로 경화 후 미경화 부위 세척시 유기 용제를 사용하여 환경 문제를 제기되고 있다. 액상 형태의 수지를 경화시켜 사용하는 인쇄판은 자외선 경화 후 미경화된 액상 수지를 재활용하여 사용할 수 있으며, 세척시 물을 사용하여 환경 문제를 발생시키지 않는 장점이 있으나, 고체 형태의 인쇄판에 비해 해상도가 떨어지는 단점을 가지고 있다.The ultraviolet curable printing plate can be broadly classified into a printing plate in which a solid printing plate and a liquid resin are cured. While the printing plate of the solid form has an advantage of high resolution, environmental problems are raised by using an organic solvent when washing the uncured portion after curing with ultraviolet rays. The printing plate used by curing the resin in the liquid form can be used by recycling the uncured liquid resin after UV curing, and there is an advantage that does not cause environmental problems by using water when washing, but the resolution is higher than the solid printing plate It has a downside.
자외선 경화형 액상 수지 조성물은 에폭시 아크릴레이트, 우레탄 아크릴레이트, 폴리에스터 아크릴레이트, 실리콘 아크릴레이트 등의 아크릴레이트계 올리고머에 반응성 모노머 희석제, 광개시제, 산화방지제, 기타 첨가제 등을 첨가하여 구성되어 있다. 상기 언급된 올리고머 중 우레탄 아크릴레이트 올리고머는 생산단가와 인장강도, 신율, 인열강도 등 기계적 강도의 우수성 때문에 인쇄판용에 주로 사용되고 있다.The ultraviolet curable liquid resin composition is formed by adding a reactive monomer diluent, a photoinitiator, an antioxidant, and other additives to acrylate oligomers such as epoxy acrylate, urethane acrylate, polyester acrylate, and silicone acrylate. Among the above-mentioned oligomers, urethane acrylate oligomers are mainly used for printing plates because of their excellent mechanical strength such as production cost, tensile strength, elongation and tear strength.
자외선에 의해 경화되는 메커니즘은 광가교형, 광분해형, 광중합형으로 분류할 수 있다. 우레탄 아크릴레이트를 기본 구조로 하는 본 발명의 자외선 경화형 액상 수지 조성물은 아크릴레이트의 비닐기가 이중 결합을 가지고 있고, 자외선 조사에 의해 라디칼이 발생되고 이 라디칼에 의해 라디칼 중합이 발생된다. 본 발명의 자외선 경화형 액상 수지 조성물은 이러한 메커니즘으로 경화되므로 광중합형 수지 조성물이라 한다. 일반적으로 자외선 경화형 수지 조성물은 올리고머, 반응성 모노머 희석제, 광개시제, 산화방지제, 기타 첨가제 등으로 구성되어 있다.Mechanisms cured by ultraviolet rays can be classified into photocrosslinking type, photolysis type, and photopolymerization type. In the ultraviolet curable liquid resin composition of the present invention having a urethane acrylate as a basic structure, the vinyl group of the acrylate has a double bond, and radicals are generated by ultraviolet irradiation, and radical polymerization is generated by the radicals. Since the ultraviolet curable liquid resin composition of the present invention is cured by such a mechanism, it is called a photopolymerizable resin composition. In general, the ultraviolet curable resin composition is composed of an oligomer, a reactive monomer diluent, a photoinitiator, an antioxidant, and other additives.
일반적으로 우레탄 아크릴레이트계 자외선 경화형 액상 수지 조성물은 첫번째 단계로 프리폴리머를 제조하고, 두번째 단계로 상기 프리폴리머에 아크릴레이트를 합성시켜 올리고머를 제조하고, 세번째 단계로 반응성 모노머 희석제, 광개시제 및 기타 첨가제 혼합의 순서로 제조되어지고 있다. In general, the urethane acrylate UV curable liquid resin composition may be prepared by preparing a prepolymer in a first step, synthesizing an acrylate to the prepolymer in a second step, and preparing an oligomer, and mixing a reactive monomer diluent, a photoinitiator, and other additives in a third step. Is being manufactured.
이러한 인쇄판은 여러 개의 선이나 망점들이 모여 하나의 인쇄체를 형성하게 되는데, 이미지의 정밀도에 의해서 인쇄체의 선명성이 차이가 난다. 인쇄 선명성은 잉크를 피인쇄물에 전이시켜 주는 인쇄판에 의해 좌우된다. 화면 또는 인쇄 등에서 이미지의 정밀도를 나타내는 지표를 해상도라 한다. 인쇄에서 해상도의 측정 척도는 LPI(Line Per Inch)이다. LPI는 인쇄기에서 세로 방향의 문자 간격을 나타내는 단위로 인쇄 매체에서 1인치 안에 그을 수 있는 선의 수를 표시하는 단위이다.In such a printing plate, a plurality of lines or dots are gathered to form a single printed matter, and the sharpness of the printed matter varies depending on the precision of the image. Print clarity is dictated by the printing plate which transfers the ink to the substrate. An index indicating the precision of an image on a screen or printing is called a resolution. The measure of resolution in printing is LPI (Line Per Inch). LPI is a unit for indicating the length of characters in the vertical direction on a printing press and indicating the number of lines that can be drawn within 1 inch of the print media.
본 발명과 관련한 종래 기술을 살펴보면, 액상 자외선 경화형 수지 조성물을 개시하고 있는 종래기술로서는 등록특허 제567121호(발명의 명칭: 액상 자외선 경화형 수지 조성물)은 경도, 강인성 및 수현상성 향상을 목적으로 하며 분자량이 높은 폴리에테르 폴리올과 수분산 극성기를 갖는 폴리에스터 폴리올을 첨가하는 것을 특징으로 하는 것이며, 등록특허 제1204214호(발명의 명칭: 몰드 제조용 액상 자외선 경화형 수지 조성물)는 에폭시 수지를 특정량 추가 혼입하여 몰드 제작시 내열 특성을 나타내기 위한 것을 특징으로 하고, 등록특허 제156694호은 조성물의 점도를 낮추므로써 경화되지 않은 액상 수지 조성물의 회수율을 높이는 기술을 개시하고 있지만, 인쇄에서 해상도 향상시켜 이미지의 정밀도를 높여주는 기술에 대하여는 개시된 바 없다.Looking at the prior art related to the present invention, as a prior art that discloses a liquid UV curable resin composition Patent No. 567121 (name of the invention: liquid UV curable resin composition) is aimed at improving hardness, toughness and water developability and molecular weight The high polyether polyol and a polyester polyol having a water-dispersing polar group are added. Patent No. 1204214 (Invention: Liquid UV Curable Resin Composition for Mold Manufacturing) adds a specific amount of an epoxy resin. It is characterized in that it exhibits heat resistance characteristics during the manufacture of the mold, and Patent No. 156694 discloses a technique for increasing the recovery rate of the uncured liquid resin composition by lowering the viscosity of the composition, but improving the resolution in printing to improve the accuracy of the image. There is no disclosure of a technique for elevating.
본 발명은 상기와 같은 종래의 문제점을 해소하고자 발명된 것으로 다음과 같은 목적을 가진다.The present invention has been invented to solve the conventional problems as described above has the following object.
본 발명은 전술한 과제를 해결하기 위해 인쇄판 해상도를 높이기 위해 산화에틸렌이 부가된 폴리올을 사용하지 않는 자외선 경화형 수지 조성물과 그 제조방법을 제공하는 데 그 목적이 있다.The present invention has been made in an effort to provide an ultraviolet curable resin composition and a method for producing the same, which do not use a polyol to which ethylene oxide is added to increase the printing plate resolution in order to solve the above problems.
또한, 본 발명은 우레탄 아크릴레이트계 자외선 경화형 액상 수지 조성물 일반적인 생산단계를 단순화하여 생산성이 높은 자외선 경화형 수지 조성물과 그 제조방법을 제공하는 데 그 목적이 있다.In addition, an object of the present invention is to provide a highly productive UV curable resin composition and a method of manufacturing the same by simplifying a general production step of the urethane acrylate UV curable liquid resin composition.
상기와 같은 목적을 달성하기 위한 본 발명은 다음과 같은 해결 수단에 의하여 구현된다.The present invention for achieving the above object is implemented by the following solving means.
본 발명은 해상도가 향상된 자외선 경화형 액상 수지 조성물을 제조하는 방법에 관한 것으로서, 폴리에테르계 폴리올, 이소시아네이트, 및 수산기를 포함하는 (메타)아크릴레이트를 동시에 혼합하고 반응시켜 폴리우레탄 (메타)아크릴레이트 올리고머를 합성하는 단계(S1); 상기 폴리우레탄 (메타)아크릴레이트 올리고머에 반응성 모노머와 광개시제 및 기타 첨가제를 투입하는 단계(S2)를 포함하되, 상기 폴리에테르계 폴리올이 함유하는 산화알킬렌은 산화프로필렌만인 것을 특징으로 한다.The present invention relates to a method for producing a UV-curable liquid resin composition with improved resolution, and is a polyurethane (meth) acrylate oligomer by simultaneously mixing and reacting a (meth) acrylate containing a polyether polyol, an isocyanate, and a hydroxyl group. Synthesizing (S1); And a step (S2) of injecting a reactive monomer, a photoinitiator and other additives into the polyurethane (meth) acrylate oligomer, wherein the alkylene oxide contained in the polyether polyol is only propylene oxide.
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본 발명은 앞서 본 구성에 의하여 다음과 같은 효과를 가진다.The present invention has the following effects by the above configuration.
본 발명은 산화에틸렌이 부가된 폴리올을 사용하지 않는 자외선 경화형 수지 조성물을 제조하므로서 인쇄판 해상도를 높이는 효과가 있다. The present invention has the effect of increasing the printing plate resolution by producing an ultraviolet curable resin composition that does not use a polyol added with ethylene oxide.
또한, 본 발명은 우레탄 아크릴레이트계 자외선 경화형 액상 수지 조성물의 일반적인 생산단계를 단순화하여 수지 조성물의 생산성을 높이는 효과가 있다.In addition, the present invention has the effect of simplifying the general production step of the urethane acrylate-based UV-curable liquid resin composition to increase the productivity of the resin composition.
도 1은 본 발명에 따른 인쇄판용 액상 수지 조성물의 생산과정을 나타낸 도면이다.1 is a view showing the production process of the liquid resin composition for a printing plate according to the present invention.
출원인은 이하에서 앞서 본 과제의 해결수단을 상세하게 설명한다 본 발명의 요지를 불필요하게 흐릴 수 있다고 판단되는 공지기술에 대한 상세한 내용은 생략한다.Applicant will now describe the solution of the present invention in detail below. Details of the well-known technology that are determined to unnecessarily obscure the subject matter of the present invention will be omitted.
본 발명은 해상도가 향상된 자외선 경화형 액상 수지 조성물에 관한 것으로서 폴리에테르계 폴리올, 이소시아네이트, 및 수산기를 포함하는 (메타)아크릴레이트로부터 합성된 폴리우레탄 (메타)아크릴레이트 올리고머 60 ∼ 90 중량부; 반응성 모노머 20 ∼ 40 중량부; 광개시제 및 기타 첨가제 1 ∼ 8 중량부를 포함하고 상기 폴리에테르계 폴리올에는 산화알킬렌이 함유되되, 상기 산화알킬렌에는 산화에틸렌이 제외되는 것을 특징으로 한다. 바람직하게는, 상기 산화알킬렌으로 산화프로필렌만을 사용하고, 상기 에테르계 폴리올의 중량 평균 분자량은 2,000 ∼ 6,000이고, 2종 이상의 에테르계 폴리올이 혼합된 것을 특징으로 한다. 그리고, 상기 자외선 경화형 액상 수지 조성물의 점도는 20,000∼30,000 cps인 것을 특징으로 한다.The present invention relates to a UV-curable liquid resin composition with improved resolution, 60 to 90 parts by weight of a polyurethane (meth) acrylate oligomer synthesized from a (meth) acrylate containing a polyether polyol, an isocyanate, and a hydroxyl group; 20 to 40 parts by weight of the reactive monomer; 1 to 8 parts by weight of the photoinitiator and other additives, the polyether-based polyol is characterized in that the alkylene oxide, the alkylene oxide is characterized in that ethylene oxide is excluded. Preferably, only propylene oxide is used as the alkylene oxide, and the weight average molecular weight of the ether polyol is 2,000 to 6,000, characterized in that two or more ether polyols are mixed. The viscosity of the ultraviolet curable liquid resin composition is 20,000 to 30,000 cps.
또한, 본 발명은 해상도가 향상된 자외선 경화형 액상 수지 조성물을 제조하는 방법에 관한 것으로서, 폴리에테르계 폴리올, 이소시아네이트, 및 수산기를 포함하는 (메타)아크릴레이트를 동시에 혼합하고 반응시켜 폴리우레탄 (메타)아크릴레이트 올리고머를 합성하는 단계(S1); 상기 폴리우레탄 (메타)아크릴레이트 올리고머에 반응성 모노머와 광개시제 및 기타 첨가제를 투입하는 단계(S2)를 포함하되, 상기 폴리에테르계 폴리올이 함유하는 산화알킬렌은 산화프로필렌만인 것을 특징으로 한다.In addition, the present invention relates to a method for producing a UV-curable liquid resin composition with improved resolution, a poly (ether) polyol, isocyanate, and (meth) acrylate containing a hydroxyl group at the same time by mixing and reacting polyurethane (meth) acrylic Synthesizing the rate oligomer (S1); And a step (S2) of injecting a reactive monomer, a photoinitiator and other additives into the polyurethane (meth) acrylate oligomer, wherein the alkylene oxide contained in the polyether polyol is only propylene oxide.
일반적으로 우레탄 아크릴레이트계 자외선 경화형 액상 수지 조성물은 첫번째 단계로 프리폴리머를 제조하고, 두번째 단계로 상기 프리폴리머에 아크릴레이트를 합성시켜 올리고머를 제조하고, 세번째 단계로 반응성 모노머 희석제, 광개시제 및 기타 첨가제 혼합의 순서로 제조되고 있다. In general, the urethane acrylate UV curable liquid resin composition may be prepared by preparing a prepolymer in a first step, synthesizing an acrylate to the prepolymer in a second step, and preparing an oligomer, and mixing a reactive monomer diluent, a photoinitiator, and other additives in a third step. It is manufactured.
그러나, 본 발명의 자외선 경화형 액상 수지 조성물은 폴리에테르계 폴리올, 디이소시아네이트, 수산기를 함유하고 있는 (메타)아크릴레이트 화합물을 사용하여 폴리우레탄 프리폴리머 단계를 거치지 않고 폴리우레탄 (메타)아크릴레이트 올리고머를 제조하고, 이와 같이 제조된 폴리우레탄 (메타)아크릴레이트 올리고머에 자외선 조사에 의해 라디칼 반응기를 생성시켜 경화 메커니즘을 나타내는 반응성 모노머 희석제, 반응성 모노머 희석제의 라디칼 반응기 생성을 도와주는 광개시제, 산화방지제 및 기타 첨가제가 혼합되어 제조되는 것을 특징으로 한다. 이와 같이, 본 발명은 우레탄 아크릴레이트계 자외선 경화형 액상 수지 조성물의 일반적인 생산단계를 단순화하여 수지 조성물의 생산성을 높이는 효과를 얻을 수 있다.However, the ultraviolet curable liquid resin composition of the present invention uses a (meth) acrylate compound containing a polyether polyol, a diisocyanate, and a hydroxyl group to prepare a polyurethane (meth) acrylate oligomer without undergoing a polyurethane prepolymer step. In addition, the reactive monomer diluent exhibiting a curing mechanism by generating a radical reactor by ultraviolet irradiation to the polyurethane (meth) acrylate oligomer thus prepared, photoinitiators, antioxidants and other additives to help generate the radical reactor of the reactive monomer diluent It is characterized by being manufactured by mixing. As such, the present invention can obtain the effect of increasing the productivity of the resin composition by simplifying a general production step of the urethane acrylate-based UV-curable liquid resin composition.
폴리올은 폴리에스테르 폴리올과 폴리에테르 폴리올이 있으며 본 발명에서는 폴리에테르계 폴리올을 사용한다. 폴리에테르계 폴리올은 일반적으로 프로필렌 글리콜, 산화 알킬렌인 산화에틸렌과 글리세린 등의 반응 개시제와 반응하여 얻어진다. 산화에틸렌이 함유된 에테르계 폴리올을 사용함으로 인해 인장강도, 신율, 인열강도 등이 향상되므로, 에테르계 폴리올에 산화에틸렌 함유는 필수적이다. Polyols include polyester polyols and polyether polyols, and polyether-based polyols are used in the present invention. The polyether polyol is generally obtained by reacting with a reaction initiator such as propylene glycol, alkylene oxide ethylene oxide and glycerin. Since tensile strength, elongation, tear strength, etc. are improved by using the ether polyol containing ethylene oxide, it is essential to contain ethylene oxide in the ether polyol.
그러나, 산화에틸렌이 포함된 에테르계 폴리올은 흐림점(CLOUD POINT)이 낮아 저온에서는 점도가 급격히 상승하여 겨울철에는 취급하기가 어려우며, 수분 흡습을 쉽게 하여 합성시 과점도가 나오는 경향이 있어 보관 관리를 철저하게 진행하여야 하는 어려움이 있다. 무엇보다도, 본 발명자의 연구 결과에 의하면, 폴리에테르계 폴리올에서 산화에틸렌의 함량을 0%로 하면 즉, 폴리우레탄 (메타)아크릴레이트 올리고머 제조시 산화에틸렌이 부가되지 않은 에테르계 폴리올을 사용함으로써 인쇄체의 해상도가 향상됨을 확인하였다.However, ether-based polyols containing ethylene oxide have a low cloud point, so the viscosity rises sharply at low temperatures, making it difficult to handle in winter. There is a difficulty to proceed thoroughly. Above all, according to the research results of the present inventors, when the content of ethylene oxide in the polyether polyol is 0%, that is, by using an ether polyol which is not added ethylene oxide when preparing a polyurethane (meth) acrylate oligomer, It is confirmed that the resolution is improved.
폴리우레탄은 에테르계 폴리올의 분자량에 의해 기계적 강도를 영향을 받게 된다. 분자량이 증가하면 인장강도 및 인열강도는 낮아지는 경향을 보이며 신율을 증가하는 경향을 보이는데, 2종 이상의 에테르계 폴리올을 적정 비율로 사용하면 기계적 강도가 보완됨을 확인하였다. 이러한 기계적 강도 보완을 위해서는 에테르계 폴리올의 중량 평균 분자량은 2,000∼6,000임이 제일 바람직하며, 반드시 2종 이상의 에테르계 폴리올을 사용하여야 한다.Polyurethane is affected by mechanical strength by the molecular weight of the ether polyol. As molecular weight increases, tensile and tear strengths tend to be lowered and elongation tends to increase. When two or more ether-based polyols are used in an appropriate ratio, it is confirmed that mechanical strength is complemented. In order to supplement the mechanical strength, the weight average molecular weight of the ether polyol is most preferably 2,000 to 6,000, and two or more ether polyols must be used.
상기 디이소시아네이트의 화합물은 80-톨루엔 디이소시아네이트(2, 4-톨루엔디이소시아 : 2,6-톨루엔 디이소시아네이트 = 8 : 2), m-페닐렌 디이소시아네이트, 아이소포론 디이소시아네이트, 헥사메틸렌 디이소시아네트, p-페닐렌 디이소시아네이트 등을 단독 또는 2종 이상 병행하여도 된다.Compounds of the diisocyanates include 80-toluene diisocyanate (2, 4-toluene diisocyanate: 2,6-toluene diisocyanate = 8: 2), m-phenylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and p-phenylene diisocyanate may be used alone or in combination of two or more thereof.
상기 수산기를 함유한 (메타)아크릴레이트 화합물은 2-하이드록시에틸(메타)아크릴레이트, 2-하이드록시 프로필(메타)아크릴레이트, 4-하이드록시 부틸(메타)아크릴레이트, 글리세롤아크릴레이트메타크릴레이트, 2-하이드록시-3-아크릴로일프로필메타크릴레이트, 4-하이드록시싸이클로헥실(메타)아크릴레이트, 네오펜틸글리콜모노(메타)아크릴레이트, 폴리프로필렌 글리콜 하이드록시프로필 (메타)아크릴레이트, 프로필렌글리콜(메타)아크릴레이트, 수산기 함유 폴리올폴리아크릴레이트 등을 단독 또는 2종 병행하여도 된다. The (meth) acrylate compound containing the hydroxyl group is 2-hydroxyethyl (meth) acrylate, 2-hydroxy propyl (meth) acrylate, 4-hydroxy butyl (meth) acrylate, glycerol acrylate methacryl 2-hydroxy-3-acryloylpropyl methacrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentylglycol mono (meth) acrylate, polypropylene glycol hydroxypropyl (meth) acrylate , Propylene glycol (meth) acrylate, hydroxyl group-containing polyol polyacrylate, and the like may be used alone or in combination.
본 발명에서 상기와 같이 제조된 우레탄 (메타)아크릴레이트 올리고머는 60∼90중량부 사용하고, 반응성 모노머 20 ∼ 40 중량부; 광개시제 및 기타 첨가제 1 ∼ 8 중량부는 것이 바람직하다. 우레탄 (메타)아크릴레이트 올리고머를 60 중량부 미만 사용시에는 우레탄 고유의 특성인 유연성과 소프트함이 감소하여 강도가 약해져 부스러지는 경향을 보이고, 90중량부 이상 사용시에는 점도가 너무 높아 작업성에 문제를 발생할 수 있다.In the present invention, the urethane (meth) acrylate oligomer prepared as described above is used 60 to 90 parts by weight, 20 to 40 parts by weight of a reactive monomer; It is preferable that 1-8 weight part of photoinitiators and other additives are included. When the urethane (meth) acrylate oligomer is used in less than 60 parts by weight, flexibility and softness, which are inherent in urethane, are reduced, resulting in a weakening of the strength. Can be.
상기와 같이 제조된 우레탄 아크릴레이트 올리고머는 높은 점도에 기인하여 작업성이 어려움을 갖기 때문에 점도를 낮출 목적으로 희석제를 사용한다. 일반적으로 사용되는 희석제로는 유기 용제, 반응성 모노머 희석제가 있다. 본 발명에서는 친환경 제품을 지향하므로 희석제로서 반응성 모노머를 사용하였다.The urethane acrylate oligomer prepared as described above uses a diluent for the purpose of lowering the viscosity because of difficulty in workability due to high viscosity. Commonly used diluents include organic solvents and reactive monomer diluents. In the present invention, since the environmentally friendly product is directed, a reactive monomer was used as the diluent.
상기 반응성 모노머로서는 부틸 (메타)아크릴레이트, 2-에틸헥실 메타)아크릴레이트, 이소데실(메타)아크릴레이트, 라우릴(메타)아크릴레이트, 페노오톡시(메타)아크릴레이트, 에틸렌 글리콜 디(메타)아크릴레이트, 2-하이드록시 에틸(메타)아크릴레이트, 헥산-1,6-디올 디(메타)아크릴레이트, 1,1,1-트리메틸올프로판 트리(메타)아크릴레이트, 테트라에틸렌 글리콜 디(메타)아크릴레이트, 프로필렌글리콜 (메타)아크릴레이트, 트리프로필렌 글리콜 (메타)아크릴레이트, 펜타에리쓰리톨 테트라(메타)아크릴레이트 등이 있다. 이들 중 이소데실(메타)아크릴레이트, 라우릴(메타)아크릴레이트, 1,1,1-트리메틸올프로판 트리(메타)아크릴레이트, 테트라에틸렌 글리콜 디(메타)아크릴레이트, 프로필렌글리콜 (메타)아크릴레이트, 트리프로필렌 글리콜 (메타)아크릴레이트 등이 가장 바람직하며, 이들 중 단독 또는 2종 이상 혼합하여 사용할 수 있다.As said reactive monomer, butyl (meth) acrylate, 2-ethylhexyl methacrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, phenoethoxy (meth) acrylate, ethylene glycol di (meth) ) Acrylate, 2-hydroxy ethyl (meth) acrylate, hexane-1,6-diol di (meth) acrylate, 1,1,1-trimethylolpropane tri (meth) acrylate, tetraethylene glycol di ( Meta) acrylate, propylene glycol (meth) acrylate, tripropylene glycol (meth) acrylate, pentaerythritol tetra (meth) acrylate, and the like. Among them, isodecyl (meth) acrylate, lauryl (meth) acrylate, 1,1,1-trimethylolpropane tri (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol (meth) acrylic Elate, tripropylene glycol (meth) acrylate, etc. are the most preferable, These can be used individually or in mixture of 2 or more types.
상기 반응성 모노머 희석제의 사용량은 전술한 바와 같이 20 ∼ 40 중량부가 바람직하다. 20중량부 미만일 경우 엑상 수지의 점도를 희석하는 효과가 미미하여 제판 작업성이 불량하며, 40중량부 이상일 경우에는 액상 수지의 점도를 너무 희석시켜 제판 구현이 제대로 되지 않는 단점과 생산단가가 상승하는 단점이 있다. As for the usage-amount of the said reactive monomer diluent, 20-40 weight part is preferable as mentioned above. If it is less than 20 parts by weight, the effect of diluting the viscosity of the liquefied resin is insignificant, and the plate making workability is poor. If it is more than 40 parts by weight, the viscosity of the liquid resin is too diluted so that the plate making is not realized and the production cost is increased. There is this.
본 발명의 자외선 경화형 액상 수지 조성물은 자외선 조사시 (메타)아크릴레이트의 비닐기를 라디칼화시켜 자외선 경화를 시켜야 하므로 광개시제를 사용한다. 여기에서 사용되는 광개제시는 광중합형 광개시제이다. 광중합형 광개시제로서는 벤질디메틸 케탈, 2,2-디에톡시-1,2-디페닐에타논, 1-하이드록시-사이클로헥실-페닐 케톤, 2-하이드록시-2-메틸-1-페닐-프로파논, 2,2-디에톡시-1-페닐에타논, 2,4,6-트리메틸벤조일-디페닐-포스핀 옥사이드, 2,2-디클로로-1-(4-페녹시페닐)-에타논, 벤조페논, 3,3-디메틸-4-메톡시 벤조페논, 메틸 2-벤조일벤조에이트, 4-페닐-벤조페논, 벤질 등을 사용할 수 있으며, 이들 중 1종 또는 2종 이상을 혼합하여 사용할 수 있다. 상기 광개시제의 사용량은 전술한 바와 같이 0.1∼ 1중량부가 바람직하다.The ultraviolet curable liquid resin composition of the present invention uses a photoinitiator because it has to undergo ultraviolet curing by radicalizing a vinyl group of (meth) acrylate during ultraviolet irradiation. The photoinitiator used herein is a photopolymerization type photoinitiator. Examples of the photopolymerization photoinitiator include benzyldimethyl ketal, 2,2-diethoxy-1,2-diphenylethanone, 1-hydroxycyclohexyl-phenyl ketone, and 2-hydroxy-2-methyl-1-phenyl-propanone , 2,2-diethoxy-1-phenylethanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2,2-dichloro-1- (4-phenoxyphenyl) -ethanone, benzo Phenone, 3,3-dimethyl-4-methoxy benzophenone, methyl 2-benzoylbenzoate, 4-phenyl-benzophenone, benzyl and the like can be used, and one or two or more thereof can be mixed and used. . As for the usage-amount of the said photoinitiator, 0.1-1 weight part is preferable as mentioned above.
기타 첨가제로서는 경화 후 인쇄판의 끈적거림을 없애기 위한 지방산, 수지 조성물의 안정성을 위한 산화방지제, 열안정제 및 중합금지제, 광개시제의 활성을 도와주기 위한 보조제 역할을 하는 광증감제 등이 첨가될 수 있다.Other additives may include fatty acids to eliminate stickiness of the printing plate after curing, antioxidants for stability of the resin composition, thermal stabilizers and polymerization inhibitors, and photosensitizers that serve as an aid to assist the photoinitiator. .
아래에서는 본 발명을 구체적인 실시예 및 비교예를 통하여 상세하게 설명한다 다음의 실시예는 본 발명을 좀 더 상세히 설명하는 것이지만, 본 발명의 범위를 한정하는 것은 아니다.Hereinafter, the present invention will be described in detail through specific examples and comparative examples. The following examples illustrate the present invention in more detail, but do not limit the scope of the present invention.
질소개스 도입관, 교반기가 장치되어 있는 1L 용량의 반응기에 중량 평균 분자량이 3000인 폴리에테르 폴리올(금호석유화학 PPG 3000D) 400중량부, 중량 평균분자량이 4000(금호석유화학 PPG 4000)인 폴리에테르 폴리올 240중량부, 80-톨루엔디이소시아네이트 40중량부, 하이드록시프로필 (메타)아크릴레이트 100중량부, 0.2중량부의 디부틸틴라우릴레이트를 넣고, 75℃로 유지하면서 4시간 반응시키면서 폴리우레탄 (메타)아크릴레이트 올리고머를 합성하였다.400 parts by weight of a polyether polyol (Kumho Petrochemical PPG 3000D) having a weight average molecular weight of 3000 and a polyether having a weight average molecular weight of 4000 (Kumho Petrochemical PPG 4000) in a 1 L reactor equipped with a nitrogen gas introduction tube and a stirrer. 240 parts by weight of polyol, 40 parts by weight of 80-toluene diisocyanate, 100 parts by weight of hydroxypropyl (meth) acrylate and 0.2 parts by weight of dibutyl tin laurate were added, and the reaction was carried out for 4 hours while maintaining at 75 ° C. Meta) acrylate oligomers were synthesized.
제조된 폴리우레탄 (메타)아크릴레이트 올리고머 65중량부에 라우릴(메타)아크릴레이트 8중량부, 하이드록시 프로필 (메타)아크릴레이트 20중량부, 트리프로필렌 글리콜(메타)아크릴레이트 5중량부, 광개시제, 산화방지제, 지방산, 중합금지제 2중량부를 투입하여 65℃로 유지하면서 1시간 교반하여 자외선 경화형 액상 수지 조성물을 제조하였다. 제조된 자외선 경화형 액상 수지 조성물은 자외선으로 경화시켜 그 물성을 측정하였다.8 parts by weight of lauryl (meth) acrylate, 20 parts by weight of hydroxypropyl (meth) acrylate, 5 parts by weight of tripropylene glycol (meth) acrylate, and photoinitiator to 65 parts by weight of the prepared polyurethane (meth) acrylate oligomer , 2 parts by weight of an antioxidant, a fatty acid, a polymerization inhibitor, and stirred for 1 hour while maintaining at 65 ℃ to prepare an ultraviolet curable liquid resin composition. The ultraviolet curable liquid resin composition thus prepared was cured with ultraviolet rays to measure its physical properties.
중량 평균 분자량이 2000인 폴리에테르 폴리올(금호석유화학 PPG 2000D) 520중량부와 중량 평균 분자량이 6000인 폴리에테르 폴리올(금호석유화학 PPG 6000) 100중량부를 사용한 것 외에는 실시예 1과 동일하게 제조하였다. 실시예 1과 동일하게 자외선으로 경화시켜 물성을 측정하였다.The preparation was carried out in the same manner as in Example 1, except that 520 parts by weight of a polyether polyol having a weight average molecular weight of 2000 (Kumho Petrochemical PPG 2000D) and 100 parts by weight of a polyether polyol having a weight average molecular weight of 6000 were used. . The physical properties were measured by curing with ultraviolet rays in the same manner as in Example 1.
중량 평균 분자량이 2000인 폴리에테르 폴리올(금호석유화학 PPG-2000D) 470중량부와 중량 평균 분자량이 4000인 폴리에테르 폴리올(금호석유화학 PPG 4000) 160중량부를 사용한 것 외에는 실시예 1과 동일하게 제조하였다. 실시예 1과 동일하게 자외선으로 경화시켜 물성을 측정하였다.Manufactured in the same manner as in Example 1, except that 470 parts by weight of a polyether polyol having a weight average molecular weight of 2000 (Kumho Petrochemical PPG-2000D) and 160 parts by weight of a polyether polyol having a weight average molecular weight of 4000 were used. It was. The physical properties were measured by curing with ultraviolet rays in the same manner as in Example 1.
(비교예 1)(Comparative Example 1)
질소개스 도입관, 교반기가 장치되어 있는 1L 용량의 반응기에 중량 평균 분자량이 3000(금호석유화학 PPG-3000D)인 폴리에테르 폴리올 400중량부, 중량 평균분자량이 4000(금호석유화학 PPG-4020D, 산화에틸렌 함량 20%)인 폴리에테르 폴리올 240중량부, 80-톨루엔디이소시아네이트 40중량부, 하이드록시프로필 (메타)아크릴레이트 100중량부, 0.2중량부의 디부틸틴라우릴레이트를 넣고, 75℃로 유지하면서 4시간 반응시키면서 폴리우레탄 (메타)아크릴레이트 올리고머를 합성하였다.400 parts by weight of a polyether polyol having a weight average molecular weight of 3000 (Kumho Petrochemical PPG-3000D) and a weight average molecular weight of 4000 (Kumho Petrochemical PPG-4020D, oxidation) in a 1 L reactor equipped with a nitrogen gas introduction tube and a stirrer. 240 parts by weight of a polyether polyol having a ethylene content of 20%), 40 parts by weight of 80-toluene diisocyanate, 100 parts by weight of hydroxypropyl (meth) acrylate, and 0.2 parts by weight of dibutyltinlaurylate were added thereto and maintained at 75 ° C. Polyurethane (meth) acrylate oligomer was synthesized while reacting for 4 hours.
폴리우레탄 (메타)아크릴레이트 올리고머 65중량부에 라우릴(메타)아크릴레이트 8중량부, 하이드록시 프로필 (메타)아크릴레이트 20중량부, 트리프로필렌 글리콜(메타)아크릴레이트 5중량부, 광개시제, 산화방지제, 지방산, 중합금지제 2중량부 투입하여 65℃로 유지하면서 1시간 교반하여 자외선 경화형 액상 수지 조성물을 제조하였다. 제조된 자외선 경화형 액상 수지 조성물은 자외선으로 경화시켜 그 물성을 측정하였다.8 parts by weight of lauryl (meth) acrylate, 20 parts by weight of hydroxy propyl (meth) acrylate, 5 parts by weight of tripropylene glycol (meth) acrylate, photoinitiator, oxidation of 65 parts by weight of polyurethane (meth) acrylate oligomer 2 weight part of an inhibitor, a fatty acid, and a polymerization inhibitor were added, and it stirred for 1 hour, maintaining at 65 degreeC, and manufactured the ultraviolet curable liquid resin composition. The ultraviolet curable liquid resin composition thus prepared was cured with ultraviolet rays to measure its physical properties.
(비교예 2)(Comparative Example 2)
중량 평균 분자량이 1000인 폴리에테르 폴리올(금호석유화학 PPG-2000D) 520중량부와 중량 평균 분자량이 4000인 폴리에테르 폴리올(금호석유화학 PPG 4000) 160중량부를 사용한 것 외에는 실시예 1과 동일하게 제조하였다. 실시예 1과 동일하게 자외선으로 경화시켜 물성을 측정하였다.Manufactured in the same manner as in Example 1 except that 520 parts by weight of a polyether polyol having a weight average molecular weight of 1000 (Kumho Petrochemical PPG-2000D) and 160 parts by weight of a polyether polyol having a weight average molecular weight of 4000 were used. It was. The physical properties were measured by curing with ultraviolet rays in the same manner as in Example 1.
(실시예 3)(Example 3)
중량 평균 분자량이 3000(금호석유화학 PPG-3000D)인 폴리에테르 폴리올 400중량부, 중량 평균분자량이 4000(금호석유화학 PPG-4000)인 폴리에테르 폴리올 240중량부, 80-톨루엔디이소시아네이트 40중량부, 0.2중량부의 디부틸틴라우릴레이트를 넣고 75℃로 유지하면서 3시간 반응시키면서 우레탄 프리폴리머를 합성한 후, 하이드록시프로필 (메타)아크릴레이트 100중량부, 0.2중량부의 디부틸틴라우릴레이트를 넣고, 75℃로 유지하면서 2시간 반응시키면서 폴리우레탄 (메타)아크릴레이트 올리고머를 합성한 것 외에는 실시예 1과 동일하게 제조하였다. 실시예1과 동일하게 자외선으로 경화시켜 물성을 측정하였다.400 parts by weight of polyether polyol having a weight average molecular weight of 3000 (Kumho Petrochemical PPG-3000D), 240 parts by weight of polyether polyol having a weight average molecular weight of 4000 (Kumho Petrochemical PPG-4000), 40 parts by weight of 80-toluene diisocyanate After adding 0.2 parts by weight of dibutyltin laurate and reacting for 3 hours while maintaining the temperature at 75 ° C., 100 parts by weight of hydroxypropyl (meth) acrylate and 0.2 parts by weight of dibutyltin laurate were added. It prepared and carried out similarly to Example 1 except having synthesize | combined the polyurethane (meth) acrylate oligomer, carrying out reaction for 2 hours, keeping at 75 degreeC. The physical properties were measured by curing with ultraviolet rays in the same manner as in Example 1.
제조된 자외선 경화 액상 수지 조성물의 물성 평가 방법은 다음과 같이 실시하였다.The physical property evaluation method of the manufactured ultraviolet curing liquid resin composition was performed as follows.
<점도 측정><Viscosity measurement>
자외선 경화 액상 수지 조성물을 항온수조에서 방치하여 온도가 25℃가 되도록 한 후 브룩필드 점도계(스핀들 번호 7번, 스핀들 회전속도 20rpm)로 점도를 측정하였다.The ultraviolet curable liquid resin composition was left in a constant temperature water bath so that the temperature was 25 ° C., and the viscosity was measured using a Brookfield viscometer (spindle number 7, spindle rotation speed 20 rpm).
<기계적 강도(인장강도, 인열강도, 신율)><Mechanical strength (tensile strength, tear strength, elongation)>
자외선 경화형 액상 수지 조성물을 365nm의 자외선 A 파장대에서 경화시킨다. 경화된 액상 수지를 KS M 6882에 따라 인장강도 측정용 시편을 3개 이상 준비하였다. 또한 인열강도 측정용 시편울 다이(Die) C를 사용하여 3개 이상 준비하였다. 만능재료 시험기로 인장강도, 인열강도를 측정하였다.The ultraviolet curable liquid resin composition is cured in an ultraviolet A wavelength band of 365 nm. Three or more specimens for tensile strength measurement were prepared according to the cured liquid resin according to KS M 6882. In addition, three or more specimens were prepared using a die C for tear strength measurement. Tensile strength and tear strength were measured by a universal testing machine.
<해상도 측정><Resolution measurement>
해상도를 측정할 수 있는 다양한 인쇄선수의 네거티브 필름을 준비한다. 네거티브 필름 위에 자외선 경화형 액상 수지 조성물을 부은 후 자외선으로 경화시켜 인쇄체 구현이 되는 최대 인쇄선수를 확인하여 해상도를 측정한다.Prepare negative film from various printers that can measure the resolution. The UV curable liquid resin composition is poured onto the negative film, and then cured with ultraviolet rays to determine the maximum printing player that can be printed.
(kgf/cm)The tensile strength
(kgf / cm)
위 표에서 확인할 수 있는 바와 같이 실시예 1 ∼ 3의 경우 산화에틸렌이 함유되지 않고, 산화에틸렌이 함유된 경우(비교예 1)과 마찬가지로 인장강도 및 인열강도가 저하되지 않음을 확인할 수 있었다. As can be seen from the above table, in Examples 1 to 3, ethylene oxide was not contained, and as in the case of containing ethylene oxide (Comparative Example 1), it was confirmed that the tensile strength and the tear strength did not decrease.
올리고머 제조단계를 1단계(폴리우레탄 (메타)아크릴레이트 올리고머 제조시 프리폴리머 합성단계를 생략하고 바로 폴리우레탄 (메타)아크릴레이트 올리고머 제조하는 단계)로만 하여도 2단계로 한 경우와 마찬가지로 해상도가 향상되고, 인장강도 및 인열강도는 저하되지 않음을 확인할 수 있었다. The resolution is improved in the same manner as in the case where the oligomer manufacturing step 1 is a step 2 (step of preparing a polyurethane (meth) acrylate oligomer without omitting the prepolymer synthesis step in preparing the polyurethane (meth) acrylate oligomer). , Tensile strength and tearing strength were confirmed not to decrease.
Claims (5)
상기 폴리우레탄 (메타)아크릴레이트 올리고머에 반응성 모노머와 광개시제 및 기타 첨가제를 투입하는 단계(S2)를 포함하되,
상기 폴리에테르계 폴리올에 함유되는 산화알킬렌은 산화프로필렌만인 것을 특징으로 하여 해상도가 향상된 자외선 경화형 액상 수지 조성물을 제조하는 방법.
Simultaneously mixing and reacting a (meth) acrylate comprising a polyether polyol, an isocyanate, and a hydroxyl group to synthesize a polyurethane (meth) acrylate oligomer (S1);
Including the reactive monomer and photoinitiator and other additives to the polyurethane (meth) acrylate oligomer (S2),
The alkylene oxide contained in the polyether polyol is a propylene oxide, characterized in that the method for producing a UV-curable liquid resin composition with improved resolution.
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| KR20050053188A (en) * | 2003-12-02 | 2005-06-08 | 에스케이케미칼주식회사 | Uv curable liquid resin composition |
| JP2010084147A (en) * | 2008-10-01 | 2010-04-15 | Bayer Materialscience Ag | Polyether-based polyurethane composition for producing holographic medium |
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| KR101566941B1 (en) * | 2015-04-09 | 2015-11-06 | (주)베이스코리아 | UV Curable Liquid Resin composition for Printing Plate Having Improved Recovery Rate for Reuse |
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| KR20050053188A (en) * | 2003-12-02 | 2005-06-08 | 에스케이케미칼주식회사 | Uv curable liquid resin composition |
| JP5271548B2 (en) * | 2008-01-16 | 2013-08-21 | 株式会社イノアックコーポレーション | Hardly discolorable soft polyurethane foam |
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