CN119505116A - A composition of photopolymerizable controlled distribution block polymer and its preparation method and application - Google Patents
A composition of photopolymerizable controlled distribution block polymer and its preparation method and application Download PDFInfo
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- CN119505116A CN119505116A CN202311076123.9A CN202311076123A CN119505116A CN 119505116 A CN119505116 A CN 119505116A CN 202311076123 A CN202311076123 A CN 202311076123A CN 119505116 A CN119505116 A CN 119505116A
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- China
- Prior art keywords
- block polymer
- composition
- photopolymerizable
- controlled distribution
- polymerization
- Prior art date
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- 229920000642 polymer Polymers 0.000 title claims abstract description 80
- 239000000203 mixture Substances 0.000 title claims abstract description 72
- 238000009826 distribution Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 238000007639 printing Methods 0.000 claims abstract description 41
- -1 acrylic ester compound Chemical class 0.000 claims abstract description 28
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 20
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 15
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 13
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 12
- 229920006216 polyvinyl aromatic Polymers 0.000 claims abstract description 12
- 229920005604 random copolymer Polymers 0.000 claims abstract description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 27
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 25
- 238000006116 polymerization reaction Methods 0.000 claims description 25
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical group CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 24
- 239000000178 monomer Substances 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 17
- 239000007822 coupling agent Substances 0.000 claims description 12
- 229920001971 elastomer Polymers 0.000 claims description 11
- 239000005060 rubber Substances 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004014 plasticizer Substances 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 235000003642 hunger Nutrition 0.000 claims description 4
- 239000012442 inert solvent Substances 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 230000037351 starvation Effects 0.000 claims description 4
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 claims description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000005859 coupling reaction Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- QRWAIZJYJNLOPG-UHFFFAOYSA-N (2-oxo-1,2-diphenylethyl) acetate Chemical compound C=1C=CC=CC=1C(OC(=O)C)C(=O)C1=CC=CC=C1 QRWAIZJYJNLOPG-UHFFFAOYSA-N 0.000 claims description 2
- VPBZZPOGZPKYKX-UHFFFAOYSA-N 1,2-diethoxypropane Chemical compound CCOCC(C)OCC VPBZZPOGZPKYKX-UHFFFAOYSA-N 0.000 claims description 2
- HSKPJQYAHCKJQC-UHFFFAOYSA-N 1-ethylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CC HSKPJQYAHCKJQC-UHFFFAOYSA-N 0.000 claims description 2
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 claims description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 2
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Chemical class 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- INXWLSDYDXPENO-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CO)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C INXWLSDYDXPENO-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000013538 functional additive Substances 0.000 claims 4
- VZMLJEYQUZKERO-UHFFFAOYSA-N 2-hydroxy-1-(2-methylphenyl)-2-phenylethanone Chemical compound CC1=CC=CC=C1C(=O)C(O)C1=CC=CC=C1 VZMLJEYQUZKERO-UHFFFAOYSA-N 0.000 claims 1
- NXQNMWHBACKBIG-UHFFFAOYSA-N OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCCC(O)(O)O Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCCC(O)(O)O NXQNMWHBACKBIG-UHFFFAOYSA-N 0.000 claims 1
- 229940086559 methyl benzoin Drugs 0.000 claims 1
- 235000005985 organic acids Nutrition 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 238000012545 processing Methods 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000006378 damage Effects 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 230000001276 controlling effect Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 14
- 239000010410 layer Substances 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000499 gel Substances 0.000 description 9
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 8
- RSPISYXLHRIGJD-UHFFFAOYSA-N OOOO Chemical compound OOOO RSPISYXLHRIGJD-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 238000002310 reflectometry Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 229920001400 block copolymer Polymers 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 229920006310 Asahi-Kasei Polymers 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000010147 laser engraving Methods 0.000 description 2
- 238000007645 offset printing Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229920006132 styrene block copolymer Polymers 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- QMYGFTJCQFEDST-UHFFFAOYSA-N 3-methoxybutyl acetate Chemical compound COC(C)CCOC(C)=O QMYGFTJCQFEDST-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- APMOEFCWQRJOPS-UHFFFAOYSA-N 5-ethenyl-1,5-dimethylcyclohexa-1,3-diene Chemical compound CC1=CC=CC(C)(C=C)C1 APMOEFCWQRJOPS-UHFFFAOYSA-N 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
- 229920002633 Kraton (polymer) Polymers 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 241000765083 Ondina Species 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical group CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- RVWADWOERKNWRY-UHFFFAOYSA-N [2-(dimethylamino)phenyl]-phenylmethanone Chemical compound CN(C)C1=CC=CC=C1C(=O)C1=CC=CC=C1 RVWADWOERKNWRY-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012660 binary copolymerization Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
-
- 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
- C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block 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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
- C08F297/046—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes polymerising vinyl aromatic monomers and isoprene, optionally with other conjugated dienes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a composition of a photopolymerisable controlled distribution block polymer, a preparation method and application thereof. The composition comprises a block polymer, an acrylic ester compound and a polymerization initiator, wherein the block polymer comprises a thermoplastic elastomer copolymer S1-C-S2 and/or (S-C) nX, S1, S2 and S are polyvinyl aromatic hydrocarbon blocks with the number average molecular weight of 7000-40000, and C is a vinyl aromatic hydrocarbon-isoprene-butadiene random copolymer block. Based on the synergistic effect of the components, the composition realizes excellent transparency and good processing hardness of the product by regulating and controlling the contents of the block components and vinyl aromatic hydrocarbon in the block polymer, and the preparation process of the composition does not need to add additional production equipment, and has the advantages of simple process, wide raw material sources, low cost and the like. The flexible printing plate prepared based on the composition has the advantages of damage resistance, transparency and fine line reproducibility, and the application scene of the printing plate is greatly widened.
Description
Technical Field
The invention relates to a photopolymerizable composition, in particular to a composition of a photopolymerizable controlled distribution block polymer, a preparation method and application thereof, and belongs to the technical field of flexographic printing plates.
Background
Photopolymerizable printing plates are used to prepare flexographic printing plates. Generally, a printing plate of a desired feature is obtained by exposing an image or text (other portions are opaque or less transparent) to be printed to light radiation for photopolymerization, exposing the areas to light radiation to photopolymerization, resulting in harder and less soluble areas than the unexposed areas, and dissolving and washing the unexposed areas with a suitable solvent to remove the unexposed areas while preserving the exposed areas. Such a patent for obtaining a printing plate by photopolymerization has been known, and a method for producing a flexographic printing plate by photopolymerization by irradiation with laser light is described in detail in, for example, a method for producing a photopolymerizable lithographic printing plate of CN 100537263C, a method for producing a flexographic printing plate precursor for laser engraving of CN104339821a, a flexographic printing plate precursor for laser engraving, a flexographic printing plate-making method, and a flexographic printing plate. Another patent is U.S. Pat. No.4266005, 4320188, no.4126466, no.4460675, no.5213948, etc. which describes a process for preparing such photopolymerizable printing plates. Such printing plates typically include a support layer, an optional adhesive or other underlayer, one or more photopolymerizable layers, an optional elastomeric intermediate layer, and a cover layer.
The preparation of such multilayer photopolymerizable flexographic printing plates is generally accomplished by calendaring the composition between the support layer and the cover layer by means of a calender to form a photopolymerizable layer between the two layers, which is quick and convenient.
Among the layers of flexographic printing plates, the layer that is the most technically demanding, more studied, and critical layer is the photopolymerizable layer. The photopolymerizable compositions are complex and contain binders, photopolymerizable monomers and polymers, photoinitiators and additional auxiliaries such as plasticizers, fillers and stabilizers etc.
The binder in the photopolymerizable layer is typically a thermoplastic elastomeric block polymer. These block polymers generally comprise thermoplastic blocks A and elastomeric blocks B of the general formulA A-B-A or A-B or (A-B) n or (A-B) nX, in particular linear and star block polymers having polyvinylarene ends. As described in CN 1698015.
Such block polymers include the following block polymers or mixtures of the block polymers.
| S-B-S | Polystyrene-polybutadiene-polystyrene |
| S-I-S | Polystyrene-polyisoprene-polystyrene |
| S-I/B-S | Polystyrene-isoprene-butadiene co-polystyrene |
| (S-B)nSi | N (polystyrene-polybutadiene) silane, n is an integer of 1 to 4 |
| (S-I)nSi | N (polystyrene-polyisoprene) silane, n is an integer of 1 to 4 |
| (S-I/B)nSi | N (polystyrene-isoprene and butadiene copolymerization) silane, n is an integer of 1 to 4 |
It is also known to use block polymers having a certain vinyl content in order to meet specific requirements, for example in EP0525206A for improving the properties of printing plates having specific monomers or for preparing printing plates without addition of monomers.
Until now, linear or star-shaped block polymers of the type S-B-S and S-I-S or mixtures thereof have been used for the production of flexographic printing plates. Because the thermoplastic elastomer materials such as S-B-S and S-I-S are easily available, have proper price and have excellent processability and transparency. However, the polymer has the defects that if S-I-S is used, the obtained offset printing plate has low Shore hardness and is easy to degrade, the surface is sticky to influence the use, and if S-B-S is used for preparing the offset printing plate, the processing stability is unsatisfactory, partial gel is generated in the processing process, and the resolution of the final developing plate is poor.
Still another approach is to mix S-B-S with S-I-S to adjust the properties, and the resulting printing plate has satisfactory flexibility, and effectively overcomes the deficiencies of both being used alone. However, by mixing, the two are not fully compatible with each other, resulting in haze and UV scattering, which reduces resolution.
In view of the above, there are improved photopolymerizable compositions. The photopolymerizable composition comprises as an adhesive a mixture of SIS and SBS block polymer, ethylenically unsaturated monomer, plasticizer and photoinitiator. The SIS block polymer may be conventional block polymers of styrene and isoprene (e.g., YH-1105, YH-1106 and KRATON. RTM. RD1161 and rubber 1250 of Baling, etc.). The improvement is that the vinyl content of the SBS block polymer is selected to be 50-60% (while the vinyl content of the general SBS block polymer is 10-20%), and the selection of such SBS can obtain a crystal transparent photopolymerisable composition, but the selection of the raw material SBS by the person skilled in the art will be severely limited.
A further development is to add a monomer based on binary copolymerization of vinylaromatic hydrocarbon with isoprene or vinylaromatic hydrocarbon with butadiene, such as the terpolymer S-C-S of vinylaromatic hydrocarbon with isoprene and butadiene mentioned in CN1698015, where S is the vinylaromatic polymer block and C is the random copolymer block (I/B) of isoprene and butadiene. This terpolymer overcomes the problem of UV scattering caused by the inability of SIS and SBS to be fully compatible with each other.
However, the foregoing solutions still have some drawbacks, such as degradation of the chain scission or gel formation of the midblock I/B during processing such as light irradiation, and poor surface tackiness or resolution caused by these problems still result in a poor experience during use. The prepared flexible printed board cannot be provided with three characteristics of defect resistance, excellent transparency and sufficient fine line reproducibility.
The invention solves the problem of UV scattering caused by incomplete mutual compatibility of SIS and SBS, has no limitation on raw material selection, and improves the problems of intermediate block degradation, stickiness and gel generation. The prepared flexible printed board has the three characteristics of defect resistance, excellent transparency and sufficient fine line reproducibility.
Disclosure of Invention
A first object of the present invention, which is directed to solving the problems of UV scattering of the product caused by incomplete compatibility of SIS and SBS, is to provide a composition of a photopolymerisable controlled distribution block polymer, which is improved in terms of the general applicability and compatibility of the product by controlling the contents of each block component and vinylaromatic hydrocarbon in the block polymer based on the synergistic effect between the components, while achieving excellent transparency and good processing hardness of the product.
The preparation process provided by the invention is based on the production process of the styrene block copolymer, realizes continuous preparation of the composition by strictly regulating the component parameters and polymerization steps of each block in each composition, does not need to add extra production equipment, and has the advantages of simple process, wide raw material sources, low cost and the like.
It is a third object of the present invention to provide the use of a composition of photopolymerisable controlled distribution block polymers for the preparation of photopolymerisable flexographic printing plates. The flexible printing plate prepared based on the composition provided by the invention has excellent transparency and good processing hardness, and the problems of stickiness and gel generation caused by degradation of the block polymer are solved, so that the printing plate has both damage resistance, transparency and fine line reproducibility, and the application scene of the printing plate is greatly widened.
The invention provides a composition of a photo-polymerizable controlled distribution block polymer, which comprises a block polymer, an acrylic ester compound and a polymerization initiator, wherein the mass ratio of the block polymer to the acrylic ester compound is 0.3-98:1, and the addition amount of the polymerization initiator is 0.5-10wt% of the mass of the composition;
The block polymer comprises a thermoplastic elastomer copolymer, wherein the thermoplastic elastomer copolymer is S1-C-S2 and/or (S-C) nX, S1, S2 and S are polyvinyl aromatic hydrocarbon blocks with number average molecular weight of 7000-40000, C is a vinyl aromatic hydrocarbon-isoprene-butadiene random copolymer block, n is an integer greater than or equal to 2, X is a coupling agent residue, and the content of the polyvinyl aromatic hydrocarbon blocks in the thermoplastic elastomer copolymer is 10-45 wt%.
As a preferred scheme, the composition further comprises a functional auxiliary agent, and the addition amount of the functional auxiliary agent is not more than 40% of the total mass of the composition.
As a preferred embodiment, the functional auxiliary agent is at least one of a plasticizer, an antioxidant, an anti-polymerization inhibitor, a pigment and a rubber compatible with the composition.
As a preferable scheme, the content of the polyvinyl aromatic hydrocarbon in the thermoplastic elastomer copolymer is 15-35 wt%. Further preferably, the polyvinyl aromatic hydrocarbon in the thermoplastic elastomer copolymer is 18 to 30wt%.
As a preferable scheme, the polyvinyl aromatic hydrocarbon is obtained by polymerizing at least one of styrene, C1-C4 alkylstyrene and C1-C4 dialkylstyrene. Further preferably, the polyvinylarene monomer is ethylene, alpha-methylstyrene, ortho-methylstyrene, para-methylstyrene, 1, 3-dimethylstyrene, para-t-butylstyrene, vinylnaphthalene, or a mixture thereof.
As a preferable scheme, the number average molecular weight of S1, S2 and S is 10000-25000. The number average molecular weight of S1, S2 and S is strictly executed according to the requirements, the polyvinyl aromatic hydrocarbon block in the block copolymer is an aggregation phase, the aggregation phase is too large, light rays in certain wave bands can be scattered, transparency and resolution are affected, the aggregation phase is too small, phase separation is incomplete or cannot be carried out, and the block copolymer is used for flexible printing plates, has poor flexibility, insufficient definition of printed images and poor printing resistance.
As a preferable scheme, the number of the polymerized units contained in the C is less than or equal to 50, wherein the content of the vinyl aromatic hydrocarbon units is 2-20wt%, and the mass ratio of the isoprene units to the butadiene units is 0.25-4:1. Further preferably, the number of monomer units contained in the C is less than or equal to 20, and the content of vinyl aromatic hydrocarbon monomer in the C is 3-10wt%. The number of the monomers directly influences the chain length of C, and if the number of the monomers is too large, the chain length is too long, light scattering is caused, and the transparency of the product is seriously influenced.
As a preferred embodiment, the block polymer further comprises at least one of linear SBS, SIS and SI/BS and/or at least one of star SBS, SIS and SI/BS.
As a preferred embodiment, the mass ratio of S1-C-S2 and/or (S-C) nX in the block polymer is not less than 30%.
The block copolymers provided by the present invention may be linear or branched star-block copolymers. It may also be triblock, tetrablock or multiblock, but contains at least two polyvinylarene blocks and one ternary random copolymer block C.
As a preferable scheme, the acrylic ester compound at least comprises one unsaturated olefinic bond, and the mass ratio of the block polymer to the acrylic ester compound is 1.8-19:1.
As a preferable scheme, the acrylic ester compound is at least one of butyl acrylate, isodecyl acrylate, 1, 6-hexanediol dimethacrylate, 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate and dipentaerythritol monohydroxypentaacrylate.
As a preferable scheme, the polymerization initiator is an organic matter containing a photoinitiator or a photoinitiation system, and the addition amount of the polymerization initiator is 0.5-5wt% of the mass of the composition.
As a preferred embodiment, the polymerization initiator is at least one of methylbenzin, benzoin acetate, benzophenone, benzildimethylketal and ethylanthraquinone/4, 4-bis (dimethylamino) benzophenone.
The invention also provides a preparation method of the composition of the photo-polymerizable controlled distribution block polymer, which comprises the steps of uniformly mixing an inert solvent, a vinyl aromatic monomer, a regulator and an initiator to initiate vinyl aromatic polymerization, adding isoprene and butadiene after polymerization is completed, uniformly mixing, adopting a starvation method to polymerize, adding the vinyl aromatic monomer again to perform polymerization reaction after polymerization by the starvation method is completed or adding a coupling agent to perform coupling reaction, adding a terminator after reaction is completed to obtain the block polymer, or mixing the inert solvent, the vinyl aromatic monomer, the mixture of isoprene and butadiene, the regulator and the initiator to perform polymerization reaction, adding the vinyl aromatic monomer to perform polymerization reaction when reaction is completed to obtain the block polymer, uniformly mixing the block polymer and the functional auxiliary agent, adding the block polymer into a preheated mixer, sequentially adding an acrylic ester compound and the polymerization initiator, uniformly mixing, and cooling to room temperature to obtain the block polymer.
As a preferable scheme, the solvent is at least one of cyclopentane, cyclohexane and n-hexane, and the terminator is one of methanol, ethanol, water, phenols and organic acid.
As a preferred embodiment, the regulator is at least one of N, N, N ', N' -tetramethyl ethylenediamine, tetrahydrofuran, monoglyme, diglyme, diethoxyethane, 1, 2-diethoxypropane and 1-ethoxy-2, 2-t-butoxyethane.
As a preferred embodiment, the coupling agent is a silicon coupling agent, an alkoxysilane, a tin coupling agent, a divinylaromatic compound, a halogenated alkane and an epoxy compound.
As a preferable scheme, the temperature of the preheated reactor is 120-150 ℃, the mixing mode of the mixer is stirring and mixing, the rotating speed is 30-60 rpm, and the stirring time is 4-5 min.
The invention also provides the use of a composition of photopolymerisable controlled distribution block polymers, characterized in that it is used for the preparation of photopolymerisable flexographic printing plates.
Compared with the prior art, the invention has the beneficial technical effects that:
1) The composition provided by the invention is based on the synergistic effect of the components, and realizes excellent transparency and good processing hardness of the product by regulating and controlling the contents of the block components and vinyl aromatic hydrocarbon in the block polymer, solves the problem of UV scattering of the product caused by incomplete compatibility of SIS and SBS, and improves the problems of stickiness and gel generation caused by degradation of the block polymer, thereby improving the universality and compatibility of the product.
2) The preparation process provided by the invention is based on the production process of the styrene block copolymer, realizes continuous preparation of the composition by strictly regulating the component parameters and polymerization steps of each block in each composition, does not need additional production equipment, and has the advantages of simple process, wide raw material sources, low cost and the like.
3) According to the technical scheme provided by the invention, the flexible printing plate prepared based on the composition provided by the invention has excellent transparency and good processing hardness, and the problems of stickiness and gel generation caused by degradation of the block polymer are solved, so that the printing plate has damage resistance, transparency and fine line reproducibility at the same time, and the application scene of the printing plate is greatly widened.
Detailed Description
The present invention is specifically described by the following examples, but the scope of the present invention is not limited to these examples.
The preparation processes of the examples and the comparative examples provided by the invention are prepared according to the following steps:
A5L stainless steel polymerizer equipped with a jacket and a stirrer was sufficiently replaced with N 2, 3000ml of cyclohexane, 0.4g of tetrahydrofuran, 1.6g of N, N' -tetramethyl ethylenediamine and 37.5g of styrene were charged into the jacket, warm water was introduced into the jacket, the temperature of the material in the polymerizer was raised to about 55℃while stirring, and an N-butyllithium cyclohexane solution (0.17 g of pure butyllithium) was added to start the polymerization of the first-stage styrene. After the styrene is completely polymerized, the polymerization of the second random section is started, namely 21g of styrene, 102g of isoprene and 102g of butadiene are uniformly mixed in a metering tank, the temperature in a polymerization kettle is kept above 70 ℃, the mixture is continuously and uniformly added into the polymerization kettle, the charging time is kept above 60 minutes, after the charging of the mixture is finished, 2 minutes is needed, 37.5g of styrene is added for the third section polymerization, and after the reaction of the styrene is finished, 0.1g of methanol is added for termination, so that the block polymer is obtained. The obtained block polymer was dehydrated and dried by a hot roll by adding 1g of the primary antioxidant 1076 and 1g of the secondary antioxidant 168, and removing the solvent by condensing with steam, thereby obtaining a sample of the linear block polymer SSIBS.
The polymerization process of the first section of styrene is the same as that of the second section of random section, but the material proportion of the first section is different in that the addition amount of styrene and n-butyllithium is different, the amount of the first section of styrene is 75g, the amount of pure butyllithium is 0.33g, the material proportion of the second section is the same, and the material proportion of the third section of styrene tetrachloride cyclohexane solution is the coupling agent (converted into pure silicon tetrachloride is 0.17 g). And (3) coupling reaction is carried out for 20min, so as to obtain the star-shaped block polymer (SSIB) nSi.
In addition, those skilled in the art will appreciate that by varying the amount of each block and the monomer of the midblock or the ratio of each monomer and the amount of initiator, or adding a suitable coupling agent in the third stage, thermoplastic elastomer samples of different molecular weights and different structures as shown in Table 2 below can be obtained.
The components in the examples are shown in tables 2 and 3 below. The substances in each table are given as examples, but are not limited to the following.
TABLE 2 thermoplastic elastomers of various types
* Represents the sum of the vinyl aromatic hydrocarbon contents in the two-terminal polyvinyl aromatic hydrocarbon blocks in wt%/the vinyl aromatic hydrocarbon content in the middle ternary random copolymer block in wt%.
I/B represents a random copolymer block of isoprene and butadiene. Also S/I/B represents a random copolymer block of vinylarene with isoprene and butadiene.
TABLE 3 auxiliary additive ingredients
| Mineral plasticizer | ONDINA TM N68 perhydrogenated naphthenic mineral oils |
| Photoinitiator | 2, 2-Dimethoxy-1, 2-diphenylethan-1-one |
| Antioxidant | Beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester |
Mixing process
The proportion of each component in the mixing process is weight ratio, plasticizer and solid rubber are mixed at room temperature, plasticizer: solid rubber=1:5 weight ratio, the mixture is poured into a mixer which rotates at 50rpm and is preheated at 140 ℃, then acrylic ester compound is added into the mixer, acrylic ester compound: solid rubber=1:10, after all the previous components are added, reaction monomer is added, mixing is carried out for 4-5min, then photoinitiator is added, the addition amount of the photoinitiator is 2% of the sum of the weights of the solid rubber and acrylic ester compound, and rapid mixing is carried out. After mixing, the mixture was taken out and cooled to room temperature for use.
Plate making process
The mixture obtained above was sandwiched between a polyester film support coated with a thermoplastic elastomer-containing adhesive and having a thickness of mainly 125 μm and a 100 μm polyester cover sheet having a thickness of 4. Mu.m, and the mixture was pressed with a press at 130℃for 4 minutes at 200kg/cm 2 using a 2.5 mm spacer to prepare a photosensitive structure for a flexible printed board.
The cover sheet of the photosensitive structure was peeled off to adhere the negative film to the polyamide protective layer on the photopolymerizable composition layer for a flexible printed board, and the entire surface of 240mJ/cm 2 was exposed from the support side using an ultraviolet fluorescent lamp having a center wavelength of 370nm on an AFT-1500 exposure machine (ASAHI KASEI E-materials Corp.). Then, an image exposure of 8000mJ/cm 2 was performed through the negative film.
The plates were glued to the rotating barrel of an AFP-1500 developer (Asahi-Kasei chemicalsCorpprtion.) and developed in 3-methoxybutyl acetate developer at 25℃for 5min and dried at 60℃for 2 hours.
UV dose for the following curing process was measured using a UV mini-radiator (e.g., UV Process Supply inc.).
And (3) using a sterilizing lamp with the center wavelength of 254nm to perform post-exposure of 1000mJ/cm 2 on the whole surface of the plate, and then performing post-exposure of 1000mJ/cm 2 by using an ultraviolet fluorescent lamp to obtain the required flexible printing plate.
Related testing
The determination of the vinyl aromatic hydrocarbon content in the vinyl aromatic hydrocarbon block, the ternary random copolymer block can be carried out by means of (1H-NMR) nuclear magnetic resonance.
Haze was measured according to ASTM D1003 on ColorquestII. The table shows the scattering% (Tr%).
Reflectance using "THE color request", THE reflectance was measured in THE reflectance 45/0 optical 2 0 mode (incidence angle=45 0, reflectance viewed normal to THE panel). The standard black panel reflectance was 0%.
UV transmittance the ratio of UV intensity in the presence and absence of a plate, the transmittance, is the plate on a UV miniature radiator passing under a UV lamp. The plate thickness was 2mm.
Gel content the plates to be measured were weighed and immersed in a large amount of toluene for one night, the undissolved fraction was filtered off and dried in vacuo at 70 ℃ until the weight had not decreased further. Gel content (%) =w drying /W Initiation ×100, where W drying is the weight of the undissolved fraction after one night of immersion in toluene after drying, and W Initiation is the weight of the plate measured before immersion in toluene.
Defect resistance A flexible printed board was prepared using a negative film having characters of 8 to 12 points, and the degree of character destruction was observed by a microscope with a NP-type pillbox brushing force tester (contact body: cloth, size: 8cmX cm, load: 1 kg) after about 300 times of rubbing.
Regarding the light transmittance, expressed as reflectance at 400nm, the lower the reflectance, the higher the light transmittance, the test data thereof are as shown in table 4 below.
TABLE 4 Table 4
| SIS/SBS weight ratio (wt%) | Reflectance at 400nm (%) |
| 100/0 | 2.9 |
| 90/10 | 3.9 |
| 80/20 | 3.7 |
| 70/30 | 4.5 |
| 60/40 | 7.3 |
| 40/60 | 6.6 |
| 30/70 | 5.7 |
| 20/80 | 3.8 |
| 10/90 | 2.7 |
| 0/100 | 1.6 |
| British agent (blanco) | 0.0 |
From the data in table 4, the reflectivity of both pure SIS or SBS at 400nm was 2.9% and 1.6%, respectively, indicating that the transparency of the both pure component offset printed boards was quite excellent.
However, the mixture of the two has the defects that the mixture prepared by the mixture of SIS/SBS=10/90 has low average transmittance and high reflectivity (higher than 3%), especially in the range of 20/80-80/20, more obviously in the range of 30/70-70/30, and has higher reflectivity, and the reflectivity shows the maximum value in the ratio of about 50/50, and has the reflectivity in the range of 20/80-80/20, which is equivalent to white 'milky' turbidity in a sample. Thus, users can only use almost pure SIS or SBS-like polymers to prepare low scattering high transparency adhesives or flexographic printing plates, and cannot formulate acceptable high light transmittance/low reflectance intermediate formulations with such SIS and SBS. However, intermediate formulations may provide much more flexibility to the formulator to tailor the characteristics of SIS and SBS, and thus intermediate formulations are necessary and necessary.
The data in Table 5 shows that by combining the properties of SIS and SBS based polymers, the skilled artisan can ameliorate some of the deficiencies of SIS or SBS based polymers alone, such as improving the problem of degradation of SIS (MFR increase) and SBS crosslinking to produce gels during processing (processing temperatures typically 140 ℃ to 180 ℃) while maintaining good clarity.
In Table 5, MFR (4 min) and MFR (16 min) are the melt flow indices measured after heating at 160℃for 4min and 16min, respectively.
TABLE 5
The rubber plate compositions of the printing plates in the examples and comparative examples obtained from the above-mentioned different thermoplastic elastomers are shown in Table 6, and provide transparency of the resulting printing plates.
Table 6 transparency of printing plates obtained in examples 1 to 10 and comparative examples 1 to 6
* The data represent the vinyl content of each of the several rubber components corresponding to the second column of the table.
Example 1 Linear S (S/I/B) S was prepared according to the preparation method of the block polymer described above, and flexible printed boards were obtained using the mixing process and the plate manufacturing process described above, and then each test was performed.
The block polymers of the other examples and comparative examples were prepared in substantially the same manner as the block polymers described above, with the linear structure being the same as linear S (S/I/B) S, and the star being the same as star (S (S/I/B)) nSi, except for the material ratios and the types of monomers in the second stage.
The mixing process and the plate making process adopted by the other examples and the comparative examples are identical. The difference is that the types and the proportions of the solid rubber are different. The specific types and proportions are shown in Table 6.
From the data in Table 6, the mixture of SBS+SIS has high scattering and low transmittance, indicating that it has too poor transparency to be used in printing plates.
By comparing the three sample data with the band, it can be directly observed that S (S/I/B) S and (S/I/B)) nX have very significant compatibilization effects on SIS and SBS. While UV transmittance is marginally acceptable, approaching the boundary value, such data suggests that at least 30% S (S/I/B) S or (S/I/B)) nX is required in the mixture to be useful for printing plates with lower definition requirements. If the sharpness requirement is high, the amount of the block polymer of the present invention must be increased.
Examples 9 and 10 demonstrate that compounding of a liquid SI with PB with the block polymer of the invention gives a mixed system with good transparency.
The test results of the chipping resistance are shown in Table 7. The word is represented by "O" if it is not destroyed, and by "X" if it is destroyed.
Table 7 results of test for chipping resistance of printing plates obtained in examples 1 to 10 and comparative examples 1 to 6
| Rubber plate assembly | Defective 5-time test results | |
| Comparative example 1 | SIS | O OOO X |
| Comparative example 2 | SBS | O OXXX |
| Comparative example 3 | SIBS | O OOO X |
| Comparative example 4 | SIBS | O OOO X |
| Comparative example 5 | SIS+SBS;50/50 | O OOXX |
| Comparative example 6 | (SI)nX | O OOO X |
| Comparative example 7 | (SB)nX | O OXXX |
| Comparative example 8 | (SIB)nX | O OOXX |
| Example 1 | S(S/I/B)S | O OOOO |
| Example 2 | S(S/I/B)S | O OOOO |
| Example 3 | (S(S/I/B))nX | O OOOO |
| Example 4 | (S(S/I/B))nX | O OOOO |
| Example 5 | S(S/I/B)S+SIS;50/50 | O OOOO |
| Example 6 | S(S/I/B)S+SBS;50/50 | O OOO X |
| Example 7 | S(S/I/B)S+SIS+SBS;33/33/33 | O OOO X |
| Example 8 | (S(S/I/B))nX+SIS+SBS;33/33/33 | O OOO X |
| Example 9 | (S (S/I/B)) nX+liquid SI, 85/15 | O OOOO |
| Example 10 | (S (S/I/B)) nX+liquid PB 85/15 | O OOOO |
From the test cases of Table 7, it is seen that the use of photopolymerizable compositions comprising the controlled distribution block polymers of the invention shows great advantages in terms of the defect resistance of the resulting flexographic printing plates.
Claims (13)
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