CN116554392A - Water-soluble heat-crosslinking multipolymer, negative-working lithographic plate precursor and preparation method - Google Patents
Water-soluble heat-crosslinking multipolymer, negative-working lithographic plate precursor and preparation method Download PDFInfo
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- CN116554392A CN116554392A CN202210111181.XA CN202210111181A CN116554392A CN 116554392 A CN116554392 A CN 116554392A CN 202210111181 A CN202210111181 A CN 202210111181A CN 116554392 A CN116554392 A CN 116554392A
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- Prior art keywords
- water
- copolymer
- crosslinking
- soluble
- weight
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- 238000004132 cross linking Methods 0.000 title claims abstract description 63
- 239000002243 precursor Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000007639 printing Methods 0.000 claims abstract description 99
- -1 n-octyl Chemical group 0.000 claims description 73
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 70
- 229920001577 copolymer Polymers 0.000 claims description 64
- 239000000178 monomer Substances 0.000 claims description 37
- 239000000975 dye Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 30
- 239000003999 initiator Substances 0.000 claims description 24
- 230000005855 radiation Effects 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 238000007334 copolymerization reaction Methods 0.000 claims description 15
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 15
- 229910052783 alkali metal Inorganic materials 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 12
- 229920006322 acrylamide copolymer Polymers 0.000 claims description 11
- 239000006099 infrared radiation absorber Substances 0.000 claims description 10
- 230000009477 glass transition Effects 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
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- 229910052708 sodium Inorganic materials 0.000 claims description 6
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- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 239000000049 pigment Substances 0.000 claims description 5
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 125000005227 alkyl sulfonate group Chemical group 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
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- 229910052700 potassium Chemical group 0.000 claims description 3
- 239000011591 potassium Chemical group 0.000 claims description 3
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- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 150000004714 phosphonium salts Chemical class 0.000 claims description 2
- SPVXKVOXSXTJOY-UHFFFAOYSA-O selenonium Chemical class [SeH3+] SPVXKVOXSXTJOY-UHFFFAOYSA-O 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims 1
- 235000019400 benzoyl peroxide Nutrition 0.000 claims 1
- 239000003505 polymerization initiator Substances 0.000 claims 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 claims 1
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 85
- 239000010410 layer Substances 0.000 description 66
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- 238000006243 chemical reaction Methods 0.000 description 55
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- 150000001875 compounds Chemical class 0.000 description 49
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 34
- 238000000576 coating method Methods 0.000 description 30
- 239000011248 coating agent Substances 0.000 description 28
- 238000010438 heat treatment Methods 0.000 description 26
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- 239000000243 solution Substances 0.000 description 24
- 239000008367 deionised water Substances 0.000 description 23
- 229910021641 deionized water Inorganic materials 0.000 description 23
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- 239000000976 ink Substances 0.000 description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 20
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- 238000010907 mechanical stirring Methods 0.000 description 20
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- 239000000543 intermediate Substances 0.000 description 16
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 239000002245 particle Substances 0.000 description 13
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- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 12
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 229920002635 polyurethane Polymers 0.000 description 11
- 239000004814 polyurethane Substances 0.000 description 11
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 9
- QRHHZFRCJDAUNA-UHFFFAOYSA-N 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=CC(OC)=CC=C1C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 QRHHZFRCJDAUNA-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- 150000004982 aromatic amines Chemical class 0.000 description 9
- 238000003384 imaging method Methods 0.000 description 9
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- NSGDYZCDUPSTQT-UHFFFAOYSA-N N-[5-bromo-1-[(4-fluorophenyl)methyl]-4-methyl-2-oxopyridin-3-yl]cycloheptanecarboxamide Chemical compound Cc1c(Br)cn(Cc2ccc(F)cc2)c(=O)c1NC(=O)C1CCCCCC1 NSGDYZCDUPSTQT-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 7
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- 229920002451 polyvinyl alcohol Polymers 0.000 description 7
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 6
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 6
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- 230000005660 hydrophilic surface Effects 0.000 description 6
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 5
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- 241000196324 Embryophyta Species 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- WORJEOGGNQDSOE-UHFFFAOYSA-N chloroform;methanol Chemical compound OC.ClC(Cl)Cl WORJEOGGNQDSOE-UHFFFAOYSA-N 0.000 description 4
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- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
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- RSJLWBUYLGJOBD-UHFFFAOYSA-M diphenyliodanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[I+]C1=CC=CC=C1 RSJLWBUYLGJOBD-UHFFFAOYSA-M 0.000 description 1
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- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002170 ethers Chemical group 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- OYQYHJRSHHYEIG-UHFFFAOYSA-N ethyl carbamate;urea Chemical compound NC(N)=O.CCOC(N)=O OYQYHJRSHHYEIG-UHFFFAOYSA-N 0.000 description 1
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- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-O hydron;1,3-oxazole Chemical compound C1=COC=[NH+]1 ZCQWOFVYLHDMMC-UHFFFAOYSA-O 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- WNZQDUSMALZDQF-UHFFFAOYSA-N isobenzofuranone Natural products C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical group 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- QSNBIXOLKHEACL-UHFFFAOYSA-N n,n-dimethylacetamide;propan-2-one Chemical compound CC(C)=O.CN(C)C(C)=O QSNBIXOLKHEACL-UHFFFAOYSA-N 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- AZHVQJLDOFKHPZ-UHFFFAOYSA-N oxathiazine Chemical class O1SN=CC=C1 AZHVQJLDOFKHPZ-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 125000005506 phthalide group Chemical group 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
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- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- ZRJTVSMQFMVHCA-UHFFFAOYSA-M potassium 3-chloropropane-1-sulfonate Chemical compound ClCCCS(=O)(=O)[O-].[K+] ZRJTVSMQFMVHCA-UHFFFAOYSA-M 0.000 description 1
- KIDBBTHHMJOMAU-UHFFFAOYSA-N propan-1-ol;hydrate Chemical compound O.CCCO KIDBBTHHMJOMAU-UHFFFAOYSA-N 0.000 description 1
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical compound C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 description 1
- 239000006100 radiation absorber Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
- B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
- B41N1/00—Printing plates or foils; Materials therefor
- B41N1/16—Curved printing plates, especially cylinders
- B41N1/22—Curved printing plates, especially cylinders made of other substances
-
- 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- 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
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
- C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
-
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
Abstract
The invention provides a water-soluble thermal crosslinking multipolymer, a negative-working lithographic printing plate precursor and a preparation method thereof. The negative image plate is a non-processing plate, and after being exposed by infrared laser scanning, the negative image plate can be directly arranged on a printer for printing without any washing processing step, namely, the negative image plate is an on-press development type non-processing plate.
Description
Technical Field
The invention relates to a negative-working lithographic plate, in particular to a water-soluble heat-crosslinking multipolymer, a negative-working lithographic plate precursor and a preparation method. The application belongs to green printing materials in the 3.19 ecological environment material sub-direction under the 3.1 novel functional material industry key direction in the 3 new material industry of the strategic emerging industry catalogue.
Background
The present invention relates to on-press developable negative-working plate precursors that are exposed to light radiation. In particular, the present invention relates to on-press developable printing plate precursors having a radiation-sensitive layer.
Lithographic printing plate precursors generally comprise a radiation sensitive coating coated on a hydrophilic surface of a substrate. The radiation sensitive coating typically includes one or more radiation sensitive components dispersed in an organic polymer binder. After exposing a portion of the coating to radiation (commonly referred to as exposure imaging), the exposed portions of the coating become easier or more difficult to develop in a particular liquid (developer) than the unexposed portions. Such plate precursors are generally considered negative precursors (or negative printing plates, negative printing plates) when the exposed portions or areas become difficult to develop in the developer and the unexposed portions are removed during development. After development in a suitable liquid, the imaged areas (image portions) are printed receptive to ink, while the exposed surface of the hydrophilic surface of the substrate repels ink.
The radiation-sensitive photopolymerizable compositions used in negative-working offset printing plate precursors typically comprise a polymerizable component, a radiation absorber, an initiator composition, and optionally one or more polymeric binders.
In recent years, industry has emphasized simplifying lithographic printing plate manufacturing processes, both in terms of global environmental protection and in terms of adaptive digitization, by omitting the pre-development heating step (pre-heating) and using lithographic inks, fountain solutions or both for on-press Development (DOP) to remove unwanted coating material on the lithographic printing plate precursor. It is a method of using an image recording layer capable of removing a non-image portion of a lithographic printing plate precursor in a normal printing process and removing the non-image portion after exposure on a printing press to obtain a lithographic printing plate. As a specific example of on-press development, for example, a method of removing a soluble image-recording layer of a lithographic printing plate precursor using a dampening solution, an ink, or both a dampening solution and an ink; and a method of mechanically removing the image recording layer by contacting the roller and the blanket after reducing cohesive strength of the image recording layer or adhesive strength of the image recording layer to the support by penetration of a dampening solution and ink.
Because the on-press developing lithographic technology is that the precoated lithographic printing plate material is subjected to scanning and plate making by a CTP plate making machine, the coating of a non-image-text area is removed by the action of fountain water and printing ink on a printing machine, most of the fallen coating is taken away by the passing printing paper, and the coating is less likely to be dissolved in the fountain water to expose a hydrophilic aluminum plate base, the environmental protection purpose of no pollutant emission in the pre-printing process is realized by the mode, but the potential risk of printing machine pollution exists. Lithographic printing plate precursors designed for DOP applications are thus typically either free of an oxygen barrier (protective) layer (which is common among other precursors) or if such an oxygen barrier layer is present, the layer is at low coverage.
Development of on-press development type processing-free plate, one of the key technologies is development of plate precursors, namely functional organic matters. EP0980754 describes a technique for realizing hydrophilic-hydrophobic transition by decarboxylation of carboxyl groups, but the phase transition compound has too large molecular weight, and the energy threshold value becomes large, so that the decarboxylation is difficult, and thus the printing plate of the technique has poor printability. W094/23954 describes a microcapsule hot melting technology, wherein laser hot melting damages microcapsules, hydrophilic substance damage is converted into hydrophobicity, but damaged objects easily cause pollution at printing blank positions; US4004924 describes a mixture of thermoplastic hydrophobic particles and a hydrophilic binder, but is not print-resistant; the Aikefa EP 2006-5-2406114475.4 and CN200780018820 describe a semi-continuous emulsion method for preparing styrene and acrylonitrile emulsion thermoplastic particles, which can realize hot melting, but do not contain self-emulsifying hydrophilic groups, and have high technical requirements on particle control, poor emulsion stability and need to add an antimicrobial agent; kodak US 2006-7-27 11/494, 235, CN200780028508 describes a solvent-resistant polymer containing hydrophilic groups and cyano side groups, wherein the allyl ester side chains are formed by condensation reaction of carboxyl side groups and allyl halides under the action of alkali, but side reaction byproducts are more, the post-treatment is troublesome, and the ester groups are not resistant to printing; fuji film JP 2000-7-132000-213142, CN01120259 describes a lithographic printing plate precursor, a polymer comprising a three-dimensional polyisocyanate pre-crosslinked structure and comprising hydrophilic graft chains, the three-dimensional pre-crosslinked structure improving the plate printability but reducing the on-press developability of the plate. In recent years, on-press development of a processing-free plate technology has been greatly progressed and commercialized, but there are still problems of low start-up latitude, poor solvent resistance, low printability under UV ink, and the like.
Disclosure of Invention
In order to solve the problems, the invention provides a water-soluble thermal crosslinking multipolymer, a negative-working lithographic printing plate precursor and a preparation method.
The object of the invention is achieved in the following way: a water-soluble, thermally crosslinked multipolymer comprising the structure:
-A-B-C-D-
a represents a styrene copolymer unit;
b represents an ethyl (meth) acrylate copolymer unit;
c represents a copolymerized unit having a urethanized unsaturated double bond branch:
R 1 is H atom or methyl, R 2 Is CH 2 =C(CH 3 ) COOCH2CH2 NCO-groups;
d represents an acrylamide copolymerized unit containing an alkyl sulfonate group:
wherein n is an integer of 0 to 8, R is an alkyl group or an aryl group having 3 to 18 carbon atoms, and M is an alkali metal element.
For the sulfonic acid alkyl group-containing acrylamide copolymer unit D, wherein n is an integer of 1 to 4, R is any one selected from the group consisting of n-hexyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tetradecyl, p-octylphenyl and p-dodecylphenyl, and M is sodium or potassium.
For the sulfonic acid alkyl group-containing acrylamide copolymer unit D, where n is 1, 2, r is any one selected from the group consisting of n-octyl, n-dodecyl, n-tetradecyl, p-dodecylphenyl and n-hexadecyl, and M is sodium.
The weight average molecular weight of the water-soluble heat-crosslinking multipolymer of the invention is 2000-300000; the glass transition temperature is 30-400 ℃; the weight percentage content of the styrene copolymerized unit A in the water-soluble heat-crosslinking multi-component copolymer is 20% -70%; the weight percentage content of the (methyl) acrylic acid ethyl ester copolymer unit B in the water-soluble heat-crosslinking multi-component copolymer is 1-40%; the weight percentage content of the copolymerized unit C with urethanized unsaturated double bond branched chains in the water-soluble heat-crosslinking multi-component copolymer is 1-40%; the weight percentage content of the acrylamide copolymer unit D containing sulfonic acid alkyl in the water-soluble heat-crosslinking multi-component copolymer is 1-40%.
The weight average molecular weight of the water-soluble heat-crosslinking multipolymer is 10000-200000; the glass transition temperature is 40-300 ℃; the weight percentage content of the styrene copolymerized unit A in the water-soluble heat-crosslinking multi-component copolymer is 30% -60%; the weight percentage content of the (methyl) acrylic acid ethyl ester copolymer unit B in the water-soluble heat-crosslinking multi-component copolymer is 1-30%; the weight percentage content of the copolymerized unit C with urethanized unsaturated double bond branched chains in the water-soluble heat-crosslinking multi-component copolymer is 1-30%; the weight percentage content of the acrylamide copolymer unit D containing sulfonic acid alkyl in the water-soluble heat-crosslinking multi-component copolymer is 1-30%.
The weight average molecular weight of the water-soluble heat-crosslinking multipolymer is 30000-150000; the glass transition temperature is 60-150 ℃; the weight percentage content of the styrene copolymerized unit A in the water-soluble heat-crosslinking multi-component copolymer is 40% -60%; the weight percentage content of the (methyl) acrylic acid ethyl ester copolymer unit B in the water-soluble heat-crosslinking multi-component copolymer is 1-25%; the weight percentage content of the copolymerized unit C with urethanized unsaturated double bond branched chains in the water-soluble heat-crosslinking multi-component copolymer is 5-20%; the weight percentage content of the acrylamide copolymer unit D containing sulfonic acid alkyl in the water-soluble heat-crosslinking multi-component copolymer is 5-25%.
A negative working lithographic printing plate precursor of the present invention comprises an imageable layer comprising a water-soluble thermally crosslinked copolymer comprising the water-soluble thermally crosslinked multipolymer described above, a polymerizable/crosslinkable component, an infrared radiation absorber, and an initiator.
The water-soluble heat-crosslinking copolymer accounts for 10% -60% of the weight of the imageable layer (the weight of the imageable layer refers to the dry weight of the imageable layer), the polymerizable/crosslinkable component accounts for 10% -70% of the weight of the imageable layer, the infrared radiation absorber accounts for 1% -30% of the weight of the imageable layer, and the initiator accounts for 1% -30% of the weight of the imageable layer.
The water-soluble heat-crosslinking copolymer accounts for 20% -40% of the weight of the imageable layer, the polymerizable/crosslinking component accounts for 20% -50% of the weight of the imageable layer, the infrared radiation absorber accounts for 1% -15% of the weight of the imageable layer, and the initiator accounts for 3% -20% of the weight of the imageable layer.
The polymerizable/crosslinkable component is comprised of at least one of an ethylenically unsaturated free radically polymerizable monomer or oligomer or a free radically crosslinkable polymer.
The infrared radiation absorbing dye is a cyanine dye absorbing 750-850 nm.
The initiator is selected from one or more of iodonium salt, sulfonium salt, phosphonium salt and selenonium salt.
The imageable layer further includes at least one of pigments, organic or inorganic particles, sensitized dyes, wetting agents, plasticizers, binders, surfactants, antioxidants, co-coaters, anti-stabilizers, and brighteners.
The preparation method of the negative-working lithographic printing plate precursor comprises the steps of mixing raw materials of an imageable layer to obtain a photosensitive liquid preparation, coating the photosensitive liquid preparation on a hydrophilized substrate by using a rod-shaped coating machine or other equipment and methods, and drying in a proper manner to obtain the negative-working lithographic printing plate precursor.
Compared with the prior art, the water-soluble heat-crosslinking copolymer, the negative-working lithographic printing plate precursor and the preparation method of the negative-working lithographic printing plate are provided, and the water-soluble heat-crosslinking copolymer is applied to the negative-working lithographic printing plate precursor, has better solvent resistance, has excellent printing fastness, has good starting-up latitude and is also suitable for UV ink printing. The negative image plate is a non-processing plate, and after being exposed by infrared laser scanning, the negative image plate can be directly arranged on a printer for printing without any washing processing step, namely, the negative image plate is an on-press development type non-processing plate.
Detailed Description
A water-soluble, thermally crosslinked multipolymer comprising the structure:
-A-B-C-D-
a represents a styrene copolymer unit;
b represents an ethyl (meth) acrylate copolymer unit;
c represents a copolymerized unit having a urethanized unsaturated double bond branch:
R 1 is H atom or methyl, R 2 Is CH 2 =C(CH 3 ) COOCH2CH2 NCO-groups;
d represents an acrylamide copolymerized unit containing an alkyl sulfonate group:
wherein n is an integer of 0 to 8, R is an alkyl group or an aryl group having 3 to 18 carbon atoms, and M is an alkali metal element.
In the water-soluble thermal crosslinking multipolymer, the styrene structural unit A has good thermoplasticity and moderate glass transition temperature, and is used as an adhesive with the characteristic of being heated and melted, so that the graph-text of a visible heat part can be firmly combined with a plate base, and the ink-philic performance of the graph-text part is enhanced. The amount of styrene in the water-soluble, thermally crosslinked, multipolymer directly affects the glass transition temperature and the thermoplasticity of the polymer. In the invention, the weight percentage of the styrene copolymer unit A in the water-soluble heat-crosslinking multipolymer is 20-70%, and the weight percentage is preferably 30-70%, 30-60%, 40-60% and 50-60% in sequence.
In the water-soluble thermal crosslinking multipolymer, the (methyl) ethyl acrylate copolymerization unit B and common polymerization and copolymerization monomers can be used for manufacturing polymers and multipolymers, synthetic resins, adhesives, coatings, fiber treating agents and intermediates of molding materials, and can effectively improve and improve the flexibility and toughness of the multipolymer. The content of the (meth) acrylic acid ethyl ester copolymer unit B in the water-soluble heat-crosslinking multi-polymer is 1% to 40% by weight, preferably 1% to 30% by weight, more preferably 1% to 25% by weight.
In the water-soluble heat-crosslinking multipolymer, the branched chain copolymerization unit C with urethanized unsaturated double bonds, unsaturated group grease thereof is crosslinked with the multi-functionality prepolymer under the action of light or heat to form a three-dimensional crosslinking structure, so that the coating can be converted from hydrophilic to hydrophobic, and plate imaging printing can be realized. In addition, polyurethane elastomers have very high abrasion resistance due to the inclusion of highly polar urethane linkages, known as "abrasion resistant king" resins, and therefore we have incorporated highly polar urethane linkages into water-soluble, thermally crosslinked, multi-component copolymers. The emulsion particles have better elasticity and more wear resistance after the urethane bonds with strong polarity are introduced. Meanwhile, the adhesive containing the strong polar urethane bond has strong adsorption effect on the aluminum plate base, and can improve the printing performance of the plate. In addition, the binder containing the polyurethane structure is better than the polyurethane prepolymer, and the plate is not easy to appear pepper points caused by the solubility difference of film forming components.
The water-soluble heat-crosslinking multipolymer of the invention is designed with a copolymerized unit C of urethanized unsaturated double bond branched chains, and the structure is as follows:
R 1 is H atom or methyl, R 2 Is CH 2 =C(CH 3 )COOCH 2 CH 2 NHCO-group. The monomers used for copolymerization to form the copolymerized units C can be of the formula:
Cl:
C2:
In the water-soluble heat-crosslinked multipolymer of the present invention, the content of the copolymerized unit C having a branched chain of urethanized unsaturated double bonds is 1% to 40% by weight, preferably 1% to 30% by weight, more preferably 5% to 25% by weight, still more preferably 5% to 20% by weight.
The urethanized unsaturated double bond branched chain copolymerization units C1 and C2 in the water-soluble heat-crosslinking multipolymer are sold in industrial products, can be conveniently purchased, and can also be synthesized in batches in a laboratory.
The acrylamide copolymerized unit D containing sulfonic acid alkyl in the water-soluble heat-crosslinking multipolymer is generated by an amphiphilic polymerizable monomer when the water-soluble heat-crosslinking multipolymer is prepared. Wherein n is an integer of 0 to 8, R is an alkyl group or an aryl group having 3 to 18 carbon atoms, and M is an alkali metal element.
The amphiphilic polymerizable monomer has a hydrophilic group and a hydrophobic group on a molecular structure, so that the amphiphilic polymerizable monomer has good amphipathy, has a self-solubilization function when being used for preparing a polymer, can obtain a copolymer with an amphiphilic micro-block structure and good solubility, belongs to a derivative of acrylamide, is easily copolymerized with the acrylamide monomer, and has two hydrogen atoms on the amide N replaced, so that the stability of the copolymer and the stability of the copolymer are enhanced, and the anti-solvent performance of the copolymer is improved.
Preferably, n is an integer of 1 to 4, R is any one selected from n-hexyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tetradecyl, p-octylphenyl and p-dodecylphenyl, and M is sodium or potassium.
More preferably, n is 1,2, R is any one selected from n-octyl, n-dodecyl, n-tetradecyl, p-dodecyl phenyl and n-hexadecyl, and M is sodium, and the monomer obtained in this case has better solubility and higher surface activity.
The sulfonic acid alkyl group-containing acrylamide copolymerized unit D in the water-soluble heat-crosslinked multipolymer of the present invention includes, but is not limited to, the following structures: sodium 2-octylacrylamidoethanesulfonate D1, sodium 2-dodecylacrylamidoethanesulfonate D2, sodium 2-tetradecylacrylamidoethanesulfonate D3, potassium 2-tetradecylacrylamidopropane sulfonate D4, sodium 2-hexadecylacrylamidoethanesulfonate D5.
In the water-soluble heat-crosslinked copolymer of the present invention, the content of the sulfonic acid alkyl group-containing acrylamide copolymer unit D is 1% to 40% by weight, preferably 1% to 30% by weight, more preferably 5% to 25% by weight, still more preferably 10% to 25% by weight.
The preparation method of the amphipathic polymerizable monomer comprises the steps of contacting fatty amine with 3-18 carbon atoms or aromatic amine with 3-18 carbon atoms with halogenoalkylsulfonic acid alkali metal salt shown in the following formula (1) in a mixture of an organic solvent and water under alkylation conditions to obtain an intermediate shown in the following formula (2);
X-CH 2 - (CH 2 ) n- SO 3 M type (1)
R-NH- (CH 2 )n+1-SO 3 M type (2)
In the formula (1) and the formula (2), X represents halogen, n is an integer of 0-8, M is an alkali metal element, and R is an alkyl group having 3-18 carbon atoms or an aryl group having 3-18 carbon atoms.
In a preferred case, the molar ratio of fatty amine or aromatic amine to alkali metal salt of haloalkylsulfonic acid is generally from 0.8 to 3:1, preferably from 0.8 to 1.5:1; the molar ratio of the intermediate to the chloride of the acrylic acid is generally between 0.3 and 1.2:1, preferably between 0.5 and 1.2:1. When the use amount of the fatty amine or the aromatic amine and the halogenated alkyl sulfonic acid alkali metal salt is in the range, the obtained amphiphilic polymerizable monomer has better solubility and higher surface activity.
In the preparation method of the amphiphilic polymerizable monomer, the types of the aliphatic amine, the aromatic amine and the halogenated alkyl sulfonic acid alkali metal salt with 3-18 carbon atoms are detailed above, and are not repeated here.
The amphiphilic polymerizable monomer is sold as an industrial product and can be synthesized in batches in a laboratory.
According to the method for preparing an amphiphilic polymerizable monomer of the present invention, in a preferred case, the volume ratio of the organic solvent to water in the mixture of the organic solvent and water may be 2 to 10:1, preferably 4 to 6:1, and the pH under the alkaline condition may be 8 to 12, preferably 9 to 11, and the alkaline condition may be achieved, for example, by adding an alkaline compound (e.g., naOH, KOH, etc.) to the mixture as long as the desired pH range can be achieved; the molar ratio of the organic solvent to the total amount of fatty or aromatic amine and alkali metal salt of haloalkylsulfonate may be 20-50:1, preferably 30-40:1.
The organic solvent may be at least one selected from the group consisting of ethanol, isopropanol, tetrahydrobarking, diethyl ether, chloroform, ethyl acetate, dimethylformamide, benzene and toluene, preferably one or more of ethanol, isopropanol, tetrahydrobarking.
According to the invention, the intermediate can be obtained by filtration after cooling at room temperature.
Since the intermediate of the present invention is prepared by a dehydrohalogenation reaction between a halogenated hydrocarbon and an organic amine, which is a very well-established reaction well-studied in the field of organic chemistry, the solid product obtained by contacting a fatty amine having 3 to 18 carbon atoms or an aromatic amine having 3 to 18 carbon atoms with an alkali metal salt of haloalkylsulfonate represented by the general formula (1) can be proved to have the structure represented by the formula (2) without a special structural characterization, but can also be characterized, for example, by nuclear magnetic resonance and infrared spectrogram.
The conditions for contacting the fatty amine having 3 to 18 carbon atoms or the aromatic amine having 3 to 18 carbon atoms with the alkali metal salt of haloalkylsulfonic acid and the intermediate with the acrylic acid chloride include the temperature and the time of the contact. The temperature of the contact may be selected within a wide temperature range, for example, the temperature at which the aliphatic amine having 3 to 18 carbon atoms or the aromatic amine having 3 to 18 carbon atoms is contacted with the alkali metal salt of haloalkylsulfonic acid may be 40 to 90 ℃, preferably 60 to 85 ℃, and the increase in the contact time is advantageous for the improvement of the reaction yield, but the increase in the yield is not significant due to the excessively long contact time, so that the contact time may be 10 to 20 hours, preferably 10 to 14 hours, in general; the temperature at which the intermediate is contacted with the acryloyl chloride may be from 1 to 10 ℃, preferably from 2 to 5 ℃.
The preparation method of the amphiphilic polymerizable monomer further comprises the steps of filtering and vacuum drying after the contact is finished to obtain the amphiphilic polymerizable monomer. The filtration, vacuum drying and recrystallization modes or methods can be all adopted by the modes or methods commonly used in the field, and the invention has no special requirements. For example, the solvent for recrystallization may be one or more of ethanol, acetone, isopropanol, ethyl acetate.
The preparation method of the water-soluble heat-crosslinking multipolymer comprises the following steps:
the water-soluble heat-crosslinking multipolymer is synthesized by adopting a copolymerization method, wherein the copolymerization reaction can be random copolymerization or block copolymerization, and random copolymerization is preferred. The initiator for polymerization includes peroxides such as di-t-butyl peroxide, phthalide peroxide, persulfates such as potassium persulfate, amine persulfate, azo compounds such as azobisisobutyronitrile, and the like. The copolymerization mode adopts emulsion polymerization.
The reaction solvent can be selected from water, methanol, ethanol, n-propanol, isopropanol, butanol, acetone, methyl ethyl ketone, cyclohexanone,
Ethyl acetate, butyl acetate, tetrahydrobarking, 1, 4 dioxane, N dimethylformamide, dimethylacetamide acetone, methyl ethyl ketone, cyclohexane, ethylene dichloride, toluene, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol dimethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, acetylacetone, diacetone alcohol, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol isopropyl ether, ethylene glycol butyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, dimethyl sulfoxide, methyl lactate, ethyl lactate, and the like, or a mixture thereof. Preferably, a mixture of alcohol and water is used, preferably n-propanol-water or isopropanol-water. The emulsion copolymerization reaction temperature is preferably 40 to 100℃and most preferably 60 to 90 ℃.
The water-soluble heat-crosslinking multipolymer is synthesized, the feeding mode adopts a mode of partially dripping raw materials, the particle size of multipolymer particles can be controlled by changing the concentration of a reaction system and the dripping time, the diameter of multipolymer particles becomes smaller along with the reduction of the concentration of the reaction system and the increase of the dripping time, and the particle size of multipolymer particles can be controlled to be in the nano-micron level by adjusting the concentration of the reaction system and the dripping time.
The weight average molecular weight of the water-soluble heat-crosslinked copolymer of the present invention is 2000 to 300000, preferably 10000 to 200000, more preferably 20000 to 180000, further preferably 30000 to 150000, still further preferably 40000 to 100000. The glass transition temperature is 30 to 400 ℃, preferably 30 to 300 ℃, more preferably 40 to 220 ℃, still more preferably 60 to 150 ℃.
Some useful water-soluble, thermally crosslinked copolymers exist in particulate form, such discrete particles may have an average particle size of at least l0nm and up to and including 1500nm, or typically at least 80nm and up to and including 600nm, and are generally uniformly distributed within the imageable layer that is sensitive to infrared radiation.
A lithographic printing plate precursor of the present invention having the structure and composition as described below was prepared.
Imageable layer
The imageable layer includes one or more water-soluble thermally crosslinked copolymers, which can be selected from a number of materials known in the art, and can be composed of vinyl copolymerized units containing branched hydrophilic groups, (meth) acrylonitrile copolymerized units, amphiphilic polymerizable monomer copolymerized units, (meth) acrylate copolymerized units, or branched (meth) acrylate copolymerized units having urethanized unsaturated double bonds, and the like. Some useful multipolymers contain repeat units having side chains that contain sulfonic acid alkyl segments, and the like. Other useful multipolymers comprise two or more types of repeating units having different side chains containing urethane segments of unsaturated double bonds.
The water-soluble, thermally crosslinked copolymer must include the water-soluble, thermally crosslinked, multi-component copolymers described herein.
Some water-soluble, thermally crosslinked copolymers exist in particulate form, such discrete particles may have an average particle size of at least l0nm and up to and including 1500nm, or typically at least 80nm and up to and including 600nm, and are generally uniformly distributed within the imageable layer that is sensitive to infrared radiation.
The water-soluble, thermally crosslinked copolymer may comprise from 10 to 60%, preferably from 20 to 40% of the solids content of the imaging layer of the lithographic printing plate of the present invention.
The imageable layer includes a polymerizable/crosslinkable component that includes one or more free radically polymerizable/crosslinkable compounds that each contain one or more free radically polymerizable groups that can be polymerized using free radicals. In some embodiments, the infrared radiation sensitive imageable layer comprises two or more radically polymerizable components that have different numbers of radically polymerizable groups in each molecule.
Useful free radically polymerizable components can contain one or more free radically polymerizable monomers or oligomers having one or more ethylenically unsaturated polymerizable or crosslinkable groups that can be polymerized or crosslinked by free radical initiation. Thus, suitable polymerizable or cross-linked ethylenically unsaturated compounds include ethylenically unsaturated polymerizable monomers having one or more polymerizable groups, including unsaturated esters of alcohols, such as (meth) acrylates of polyols. Oligomers and/or prepolymers, such as urethane (meth) acrylates, may also be used.
Similarly, crosslinkable polymers having such free radically polymerizable groups may also be used. Oligomers or prepolymers such as urethane acrylates and methacrylates, epoxide acrylates and methacrylates, polyester acrylates and methacrylates, polyether acrylates and methacrylates, and unsaturated polyester resins may be used. In some embodiments, the free radically polymerizable component comprises a carboxyl group.
Particularly useful free radically polymerizable components include free radically polymerizable monomers or oligomers that comprise addition polymerizable ethylenically unsaturated groups, including a plurality of acrylate and methacrylate groups, and combinations thereof, or free radically crosslinkable polymers. More particularly useful free radically polymerizable compounds include those derived from urea urethane (meth) acrylates or urethane (meth) acrylates having multiple polymerizable groups.
The polymerizable/crosslinkable component comprises from 10 to 70%, preferably from 20 to 50% of the solids content of the imaging layer of the lithographic printing plate according to the invention.
The imageable layer includes one or more infrared radiation absorbers which may be a cyanine dye that is sensitive to near infrared radiation or infrared radiation having a wavelength of 750-1200 nm, the cyanine dye containing a variable color group and polymerizable/crosslinkable unsaturated double bonds. The cyanine dye has good imaging contrast due to the special structure, and the dye residue can participate in photopolymerization reaction during imaging due to the polymerizable/crosslinkable double bond contained in the molecule, so that the printing plate printing durability is improved.
The infrared radiation absorber can be a cyanine dye absorbing 750-850 nm.
The initiation system capable of initiating polymerization/crosslinking can contain other proper photothermal conversion dyes besides the cyanine dye-containing infrared photothermal conversion material. Such as methine, polymethine, arylmethine, cyanine, hemicyanine, merocyanine, squarylium, pyrylium, oxonol, naphthoquinone, anthraquinone. Porphyrins, azo, croconium, triarylamines, thiazolium, indolium, oxazolium, indigo tricarbocyanines, oxatricarbocyanines, phthalocyanine, thiocyanines, thiotricarbocyanines, merocyanines, cryptocyanines, naphthalocyanines, polyanilines, polypyrroles, polythiophenes, thiopyrano arylene and bis (thiopyrrolo) polymethines, oxathiazines, pyrazoline azo and the like.
Preferably at least one infrared radiation absorber in the imageable layer of the lithographic printing plates of the present invention is a cyanine dye comprising a tetraarylborate anion.
The cyanine dye structure used in the present invention is exemplified as follows, but is not limited to these structures.
The total amount of infrared radiation absorber in the imaging layer of the lithographic printing plate according to the invention represents a solids content of 1 to 30%, preferably 1 to 15%.
The imageable layer also includes an initiator selected from onium salts, such as sulfonium salts, iodonium salts, and the like that provides free radicals to initiate polymerization of one or more free radically polymerizable components upon exposure of the radiation-sensitive imageable layer to infrared radiation. Suitable onium salts include sulfonium salts, oxomaple onium salts, oxosulfonium salts, sulfoxides, diazonium salts, and halonium salts such as iodonium salts and the like. Specific examples of suitable onium salts are: diphenyliodonium chloride, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate [4- [ (2-hydroxytetradecyl-oxy ] phenyl ] phenyliodonium hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium iodonium octylsulfate, 2-methoxy-4-aminophenyl diazonium hexafluorophosphate, phenoxyphenyl diazonium hexafluoroantimonate, and the like.
The initiator may comprise 1 to 30%, preferably 3 to 20% solids in the imaging layer of the lithographic printing plate of the present invention.
In some embodiments, the secondary multipolymer is more hydrophilic than the primary multipolymer. Examples of such hydrophilic secondary multi-polymers include, but are not limited to, cellulose derivatives, such as hydroxypropyl cellulose, carboxymethyl cellulose; and polyvinyl alcohols having various degrees of saponification.
Additionally, pigments/dyes and color developers may be included in the imageable layer as known in the art. Useful pigments/dyes include, but are not limited to, phthalides and fluoran leuco dyes containing a lactone backbone having acid dissociating properties, and the like.
The imageable layer of the lithographic plates of the present invention can also contain various materials in combination with the necessary components of the present invention. For example, pigments, organic or inorganic particles, sensitized dyes, wetting agents, plasticizers, binders, surfactants, antioxidants, co-coaters, anti-stabilizers, brighteners, etc., can be used in the present invention without affecting its properties, or any other additives commonly used in the lithographic arts in conventional amounts.
Protective layer
In some embodiments, the negative-working lithographic printing plate precursor does not have an outermost layer disposed on the imageable layer, but it is possible that the precursor may be designed with a hydrophilic protective layer (or oxygen barrier layer or overcoat) disposed directly on the imageable layer (no intermediate layer between the two layers). Such precursors may be developed on-press, and off-press using any suitable developer as described below.
The protective layer can prevent and hinder low molecular compounds such as oxygen and alkaline substances in the atmosphere from being mixed into the photosensitive layer, and influence the image forming reaction in the photosensitive layer caused by exposure. Therefore, the protective layer is required to have low penetrability of a low molecular compound such as oxygen, substantially not to block light transmission used for exposure, and good adhesion to a photosensitive layer, and to be easily removable in on-press development of a plate. In addition, other properties may be imparted to the protective layer. For example, by adding a colorant (water-soluble dye or the like) which is excellent in light transmittance at 780 to 850nm and can efficiently absorb light out of the 780 to 850nm range, plate making safety of a lithographic plate under white light can be improved without causing a decrease in sensitivity.
Among materials that can be used for the protective layer, for example, water-soluble polymer compounds having good crystallinity are preferably used, and concretely, water-soluble polymers such as polyvinyl alcohol, polyvinylpyrrolidone, acid celluloses, gelatin, gum arabic, and polyacrylic acid are known, and among these, when polyvinyl alcohol is used as a main component, the best results are obtained with respect to basic properties such as oxygen barrier property and development removability. The polyvinyl alcohol used in the protective layer may contain an unsubstituted vinyl alcohol unit in an amount sufficient to provide the desired oxygen barrier properties and water solubility, and some of them may be substituted with esters, ethers and acetals. In addition, some of them may have other copolymerization components as well. As concrete examples of polyvinyl alcohol, compounds having a molecular weight of 300 to 2400 and having 71 to 100% hydrolysis can be exemplified. Specific examples are: PVA-105, PVA-110, PVA-117H, PVA-120, PVA-124H, PVA-CS, PVA-CST, PVA-HC. PVA-203, PVA-204, PVA-205, PVA-210, etc.
The composition (PVA selection, use of additives), coating amount, and the like of the protective layer are selected in consideration of the fog resistance, adhesion, and scratch resistance in addition to the oxygen blocking property and the development removability. In general, the higher the hydrolysis rate of PVA used (the higher the content of unsubstituted vinyl alcohol units in the protective layer), the thicker the film thickness, and the higher the oxygen barrier property, which is advantageous in terms of photosensitivity. In addition, adhesion to an image portion and scratch resistance are very important in handling of a printing plate. That is, if a hydrophilic layer made of a water-soluble polymer is laminated on a lipophilic polymer layer, film peeling due to insufficient adhesion is likely to occur, and defects such as poor film curing due to polymerization inhibition by oxygen are likely to occur in the peeled portion.
When present, the protective layer generally has a dry coat weight of 0.l-4 g/m 2 Preferably 0.2-2.0g/m 2 . In some embodiments the dry coating weight is 0.l to 0.9g/m 2 So that the hydrophilic protective layer is relatively thin for easy removal during off-line development or on-press development.
Plate base
The substrate present in the precursor typically has a hydrophilic surface, or at least a surface that is more hydrophilic than the infrared radiation sensitive imageable layer applied on the imaging side of the substrate. The substrate comprises a support, which may be composed of any material conventionally used for preparing lithographic printing plate precursors.
A useful substrate consists of an aluminum support, which is a high purity aluminum plate, preferably having an aluminum content of greater than 99%. The aluminum support may be treated using techniques known in the art, including roughening of some type by physical (mechanical), electrochemical or chemical graining, typically followed by anodization. The electrolyte used for electrolytic roughening may be an aqueous solution of an acid, a base or a salt or an aqueous solution containing an organic solvent. Among them, aqueous solutions of hydrochloric acid, nitric acid or salts thereof are preferable as the electrolyte. Anodization is typically performed using phosphoric or sulfuric acid and conventional procedures.
Firstly, the aluminum plate is put into 1 to 30 percent aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate and the like, and chemical corrosion is carried out for 5 to 250 seconds at the temperature of 20 to 80 ℃. However, the method is thatThen neutralizing in 10-30% nitric acid or sulfuric acid at 20-70 deg.c to eliminate ash. The aluminum plate after the cleaning treatment is processed by rectangular wave, table wave or sine wave with alternately changed positive and negative at the temperature of 10-60 ℃ with the speed of 5-100A/dm 2 Is electrolytically treated in an electrolyte of nitric acid or hydrochloric acid for 10 to 300 seconds. Then, the electrolytic aluminum plate is subjected to anodic oxidation treatment. Anodic oxidation is generally carried out by the sulfuric acid method. The concentration of sulfuric acid is 5-30% and the current density is 1-15A/dm 2 The oxidation temperature is 20-60 ℃ and the oxidation time is 5-250 seconds to form 1-10 g/m 2 Is formed on the substrate. The oxide film formed in this way has high oxide film micropores, high adsorption capacity and easy dirt adhesion. It is also generally necessary to carry out a sealing treatment. The sealing treatment may be carried out by various methods, and it is preferable to seal 50 to 80% by volume of the micropores of the oxide film. The anodized aluminum support may be further treated to seal the oxide pores and render its surface hydrophilic using a known post-anodizing treatment (PAT) process, such as treatment in aqueous solutions of poly (vinyl phosphonic acid) (PVPA), vinyl phosphonic acid copolymers, poly (meth) acrylic acid), or acrylic acid copolymers, mixtures of phosphates and fluorides, or sodium silicate.
The solution used for the sealing treatment of the plate base of the lithographic plate of the present invention is preferably an aqueous solution containing fluoride ions and phosphate.
The lithographic plates of the present invention can be prepared by applying an imageable layer to the hydrophilic surface of a lithographic substrate by conventional techniques. The imageable layer can be applied by any suitable method such as coating or lamination.
Typically, the components of the imageable layer are dispersed or dissolved in a suitable coating solvent. Such as water, water and organic solvents. Such as methanol, ethanol, isopropanol, and/or mixtures of acetone. Surfactants, such as fluorinated surfactants or polyethoxylated dimethylpolysiloxane copolymers, or mixtures of surfactants, may be present to aid in the dispersion of the other ingredients in the coating solvent. The resulting mixture is applied to a lithographic substrate by conventional methods such as spin coating, bar coating, gravure coating, extrusion plate coating (die coating), slot coating or roll coating. After coating, the imageable layer is dried to evaporate the solvent. The imageable layer can be air-dried at room temperature or at an elevated temperature, such as in an oven. Alternatively, the imageable layer can be dried by blowing warm air over the imageable element.
After the application of the imageable layer, a protective layer may also be applied over this layer.
After the negative-working lithographic printing plate precursor of the present invention is made, the relief image is given by imagewise exposure of the digital data with a laser, as opposed to the master. As a preferable exposure light source, for example, a solid-state laser and a semiconductor laser which radiate infrared rays of 780 to 850nm, the infrared laser used in the present invention is preferably a laser capable of outputting 100mW or more, and the exposure time per pixel is preferably not longer than 20 microseconds. The radiation energy is preferably 10-300 mj/cm 2 。
After imagewise exposing the lithographic printing plate precursor of the invention, printing is performed by supplying printing ink and dampening solution without receiving a development process. Specifically, a lithographic printing plate precursor is image-wise exposed with a laser beam, then a coating layer of a blank area is removed on a printing machine by supplying a printing ink and a dampening solution, a printing ink-philic portion having an ink-philic surface is formed on an exposed portion of the image recording layer by exposure of the hardened image recording layer, the unhardened image recording layer is made porous by the dampening solution supplied, and then removed by sticking off the printing ink to transfer to a paper, and a hydrophilic surface is exposed at the unexposed portion, to prepare a lithographic printing plate that can be printed. Subsequently, the dampening solution adheres to the exposed hydrophilic surface and the printing ink adheres to the image recording layer of the exposed portion, starting the printing process.
In the on-press development process, the surface of the plate material should be soaked with the fountain solution in advance, the longer the time is, the larger the fountain solution amount is, and the more favorable the removal of the coating in the blank area is. The ink is then transferred to the surface of the lithographic printing plate precursor by means of an ink roller, and the coating of the blank area is stripped off by means of the viscosity of the ink, the ink contact time being 10-30 seconds, the longer the time the more advantageous the blank area coating removal.
In some cases, the aqueous rinse may be used off-line to remove the unexposed areas to develop the imaged precursor, and in turn provide a protective layer or coating over the entire imaged and developed (rinsed) precursor printing surface. After off-line development, printing can be performed by placing the exposed and developed lithographic printing plate on a suitable press.
The present invention will now be described in detail with reference to specific examples, which are given herein for further illustration only and are not to be construed as limiting the scope of the invention, since numerous insubstantial modifications and adaptations thereof will now occur to those skilled in the art in light of the foregoing disclosure.
Starting materials used in the amphiphilic polymerizable monomer examples:
Nanjing chemical reagent plant for fatty amine or aromatic amine
Haloalkylsulfonic acid alkali salt Ala Ding Shiji Co
Acrylamide Ala Ding Shiji Co
Acrylic acid Ala Ding Shiji Co
2-acrylamido-2-methylpropanesulfonic acid Ara Ding Shiji Co
Initiator national medicine group chemical reagent Co
Preparation of amphiphilic polymerizable monomers:
example 1:
adding lmol N-octylamine, lmol chloroethyl sodium sulfonate, 320mL of ethanol and 80mL of water (volume ratio is 4:1), adding 20g of sodium hydroxide into a 1L three-port bottle, reacting for 12 hours at 50 ℃ with the pH value of a solution in a reactor at 10.2, cooling, filtering to obtain a solid, and determining the solid as an N-octyl sodium ethyl sulfonate intermediate by nuclear magnetic resonance analysis; adding 0.4mol of the N-octyl sodium ethyl sulfonate intermediate into a 500mL three-port bottle, adding 120mL of water, adding 10g of sodium hydroxide, dropwise adding 0.5 mol of acryloyl chloride after dissolution, reacting for 12 hours at the temperature of 5 ℃, evaporating solvent water, recrystallizing by using a chloroform-methanol (volume ratio of 7:1) mixed solvent, filtering, and drying to obtain a solid, wherein the prepared solid is confirmed by nuclear magnetic resonance analysis to be the amphiphilic polymerizable monomer 2-octyl acrylamide sodium ethyl sulfonate D1.
Example 2:
adding lmol dodecyl amine, lmol chloroethyl sodium sulfonate, 300mL of ethanol and 60mL of water (volume ratio is 5:1), adding 22g of sodium hydroxide into a 1L three-mouth bottle, reacting for 12 hours at 55 ℃ with the pH value of a solution in a reactor at 10.9, cooling, filtering to obtain a solid, and determining the solid as an N-dodecyl sodium ethyl sulfonate intermediate by nuclear magnetic resonance analysis; adding the N-dodecyl sodium ethyl sulfonate intermediate 0.4mo1 into a 500mL three-mouth bottle, adding 120mL of water, adding 10g of sodium hydroxide, dropwise adding 0.52mol of acryloyl chloride after dissolution, reacting for 12 hours at 8 ℃, evaporating solvent water, recrystallizing by using a chloroform-methanol (volume ratio is 7:1) mixed solvent, filtering, and drying to obtain a solid, wherein the prepared solid is confirmed by nuclear magnetic resonance analysis to be the amphiphilic polymerizable monomer 2-dodecyl sodium acrylamide ethyl sulfonate D2 provided by the invention.
Example 3:
adding lmol tetramine, lmol chloroethyl sodium sulfonate, 240mL ethanol and 40mL water (volume ratio is 6:1), adding 18g sodium hydroxide into a 1L three-port bottle, reacting for 14 hours at 60 ℃ with the pH value of a solution in a reactor, cooling, filtering to obtain a solid, and determining the solid as an N-tetradecyl sodium ethyl sulfonate intermediate by nuclear magnetic resonance analysis; adding 0.4mol of the N-tetradecyl sodium ethyl sulfonate intermediate into a 500mL three-port bottle, adding 120mL of water, adding lOg of sodium hydroxide, dropwise adding 0.55 mol of acryloyl chloride after dissolution, reacting for 16 hours at 8 ℃, evaporating solvent water, recrystallizing by using a chloroform-methanol (volume ratio is 7:1) mixed solvent, filtering, and drying to obtain a solid, wherein the prepared solid is confirmed by nuclear magnetic resonance analysis to be the amphiphilic polymerizable monomer 2-tetradecyl sodium acrylamide ethyl sulfonate D3.
Example 4:
an amphiphilic monomer was prepared by the method for preparing an amphiphilic monomer in example 3, except that sodium chloroethyl sulfonate was replaced by potassium chloropropylsulfonate, and solvent ethanol was replaced by methanol, to prepare potassium 2-tetradecylacrylamide propane sulfonate D4 as an amphiphilic monomer.
Example 5
Adding lmol hexadecylamine, lmol sodium chloroethyl sulfonate, 280mL ethanol and 40mL water (volume ratio is 7:1), adding 22g sodium hydroxide into a 1L three-port bottle, reacting for 14 hours at 65 ℃ with the pH value of a solution in a reactor, cooling, filtering to obtain a solid, and determining the solid as an N-hexadecyl sodium ethyl sulfonate intermediate by nuclear magnetic resonance analysis; adding the N-hexadecyl sodium ethyl sulfonate intermediate 0.4mo 1 into a 500mL three-mouth bottle, adding 120mL of water, adding lOg of sodium hydroxide, dropwise adding 0.58mol of acryloyl chloride after dissolution, reacting for 12 hours at the temperature of 5 ℃, evaporating solvent water, recrystallizing by using a chloroform-methanol (volume ratio is 8:1) mixed solvent, filtering, and drying to obtain a solid, wherein the prepared solid is confirmed by nuclear magnetic resonance analysis to be the amphiphilic polymerizable monomer 2-hexadecyl sodium acrylamide sodium ethyl sulfonate D5.
The starting materials used in the preparation examples of the water-soluble, thermally crosslinked, multipolymer:
styrene Nanjing chemical reagent plant
Ethyl acrylate/methacrylate Aca Ding Shiji Co
Exemplary Compounds C1/C2 Baoding Lekeka chemical Co., ltd
Exemplary Compounds D1/D2/D3/D4/D5 Baoding Lekeka chemical Co., ltd
Azodiisobutyronitrile Nanjing chemical reagent plant
Potassium persulfate Nanjing chemical reagent plant
Preparation of a Water-soluble thermally crosslinked multipolymer:
example 1 (multipolymer P01)
500g of isopropanol, 150g of deionized water and 30g of ethyl methacrylate are added into a four-neck flask which is 1000 ml provided with a temperature-controlled heating device, a mechanical stirring device, a condensation reflux device and a nitrogen protection device, 30g of an example compound C1 are heated and stirred uniformly, 20g of styrene, 20g of an example compound D1 and 0.7g of AIBN (azodiisobutyronitrile) are added dropwise at 60 ℃ for 2.5 hours, after 7.5 hours of reaction, 0.3g of AIBN (azodiisobutyronitrile) is added, and the reaction is continued for 12 hours.
Example 2 (multipolymer P02)
500g of isopropanol, 150g of deionized water and 1g of ethyl methacrylate are added into a four-neck flask which is 1000 ml provided with a temperature-controlled heating device, a mechanical stirring device, a condensation reflux device and a nitrogen protection device, 19g of the example compound C1 are heated and stirred uniformly, 70g of styrene, 10g of the example compound D1 and 0.7g of AIBN (azodiisobutyronitrile) are added dropwise at 60 ℃ for 2.5 hours, after the reaction is carried out for 7.5 hours again, 0.3g of AIBN (azodiisobutyronitrile) is added, and the reaction is continued for 12 hours again, and then the reaction is finished.
Example 3 (multipolymer P03)
500g of isopropanol, 150g of deionized water and 40g of ethyl methacrylate are added into a four-neck flask which is 1000 ml provided with a temperature-controlled heating device, a mechanical stirring device, a condensation reflux device and a nitrogen protection device, 25g of an example compound C1 is heated and stirred uniformly, 25g of styrene, 10g of an example compound D1 and 0.7g of AIBN (azodiisobutyronitrile) are dropwise added at 60 ℃ for 2.5 hours, after 7.5 hours of reaction, 0.3g of AIBN (azodiisobutyronitrile) is additionally added, and the reaction is continued for 12 hours.
Example 4 (multipolymer P04)
500g of isopropanol, 150g of deionized water and 29g of ethyl methacrylate are added into a four-neck flask which is 1000 ml provided with a temperature-controlled heating device, a mechanical stirring device, a condensation reflux device and a nitrogen protection device, 1g of the example compound C1 is heated and stirred uniformly, 30g of styrene, 40g of the example compound D1 and 0.7g of potassium persulfate are added dropwise at 60 ℃ for 2.5 hours, 0.3g of AIBN (azodiisobutyronitrile) is added after the reaction is carried out for 7.5 hours again, and the reaction is continued for 12 hours again.
Example 5 (multipolymer P05)
500g of isopropanol, 150g of deionized water and 20g of ethyl methacrylate are added into a four-neck flask which is 1000 ml provided with a temperature-controlled heating device, a mechanical stirring device, a condensation reflux device and a nitrogen protection device, 40g of an example compound C1 are heated and stirred uniformly, 39g of styrene and 1g of an example compound D1 are added dropwise at 60 ℃ for 2.5 hours, 0.3g of AIBN (azodiisobutyronitrile) is added after the reaction is carried out for 7.5 hours again, and the reaction is continued for 12 hours again.
Example 6 (multipolymer P06)
500g of isopropanol, 150g of deionized water and 30g of ethyl acrylate are added into a four-neck flask which is 1000 ml provided with a temperature-controlled heating device, a mechanical stirring device, a condensation reflux device and a nitrogen protection device, 30g of an example compound C1 are heated and stirred uniformly, 20g of styrene, 20g of an example compound D1 and 0.7g of AIBN (azodiisobutyronitrile) are dropwise added at 60 ℃ for 2.5 hours, 0.3g of AIBN (azodiisobutyronitrile) is added after the reaction is carried out for 7.5 hours again, and the reaction is continued for 12 hours again, and then the reaction is finished.
Example 7 (multipolymer P07)
500g of isopropanol, 150g of deionized water and 19g of ethyl acrylate are added into a four-neck flask which is 1000 ml provided with a temperature-controlled heating device, a mechanical stirring device, a condensation reflux device and a nitrogen protection device, 1g of an example compound C1 is heated and stirred uniformly, 40g of styrene, 40g of an example compound D1 and 0.7g of potassium persulfate are dropwise added at 60 ℃ for 2.5 hours, after 7.5 hours of reaction, 0.3g of AIBN (azobisisobutyronitrile) is added, and the reaction is continued for 12 hours.
Example 8 (multipolymer P08)
500g of isopropanol, 150g of deionized water and 1g of ethyl acrylate are added into a four-neck flask which is 1000 ml provided with a temperature-controlled heating device, a mechanical stirring device, a condensation reflux device and a nitrogen protection device, 19g of an example compound C1 are heated and stirred uniformly, 70g of styrene, 10g of an example compound D1 and 0.7g of AIBN (azodiisobutyronitrile) are dropwise added at 60 ℃ for 2.5 hours, 0.3g of AIBN (azodiisobutyronitrile) is added after the reaction is carried out for 7.5 hours again, and the reaction is continued for 12 hours again, and then the reaction is finished.
Example 9 (multipolymer P09)
500g of isopropanol, 150g of deionized water and 30g of ethyl methacrylate are added into a four-neck flask which is 1000 ml provided with a temperature-controlled heating device, a mechanical stirring device, a condensation reflux device and a nitrogen protection device, 40g of an example compound C2 are heated and stirred uniformly, 20g of styrene, 10g of an example compound D1 and 0.7g of AIBN (azodiisobutyronitrile) are dropwise added at 60 ℃ for 2.5 hours, after 7.5 hours of reaction, 0.3g of AIBN (azodiisobutyronitrile) is additionally added, and the reaction is continued for 12 hours.
Example 10 (multipolymer P10)
500g of isopropanol, 150g of deionized water, 20g of ethyl methacrylate and 10g of example compound C2 are added into a four-neck flask which is 1000 and ml is provided with a temperature control heating device, a mechanical stirring device, a condensation reflux device and a nitrogen protection device, the mixture is heated and stirred uniformly, 69g of styrene, 1g of example compound D1 and 0.7g of potassium persulfate are added dropwise at 60 ℃ for 2.5 hours, 0.3g of AIBN (azodiisobutyronitrile) is added after the mixture is reacted for 7.5 hours again, and the reaction is continued for 12 hours.
Example 11 (multipolymer P11)
500g of isopropanol, 150g of deionized water and 1g of ethyl acrylate are added into a four-neck flask which is 1000 ml provided with a temperature-controlled heating device, a mechanical stirring device, a condensation reflux device and a nitrogen protection device, 19g of an example compound C1 are heated and stirred uniformly, 70g of styrene, 10g of an example compound D2 and 0.7g of AIBN (azodiisobutyronitrile) are dropwise added at 60 ℃ for 2.5 hours, 0.3g of AIBN (azodiisobutyronitrile) is added after the reaction is carried out for 7.5 hours again, and the reaction is continued for 12 hours again, and then the reaction is finished.
Example 12 (multipolymer P12)
500g of isopropanol, 150g of deionized water and 30g of ethyl methacrylate are added into a four-neck flask which is 1000 ml provided with a temperature-controlled heating device, a mechanical stirring device, a condensation reflux device and a nitrogen protection device, 40g of an example compound C2 are heated and stirred uniformly, 20g of styrene, 10g of an example compound D2 and 0.7g of AIBN (azodiisobutyronitrile) are added dropwise at 60 ℃ for 2.5 hours, after 7.5 hours of reaction, 0.3g of AIBN (azodiisobutyronitrile) is added, and the reaction is continued for 12 hours.
Example 13 (multipolymer P13)
500g of isopropanol, 150g of deionized water and 20g of ethyl methacrylate are added into a four-neck flask which is 1000 ml provided with a temperature-controlled heating device, a mechanical stirring device, a condensation reflux device and a nitrogen protection device, 10g of an example compound C1 are heated and stirred uniformly, 50g of styrene, 20g of an example compound D2 and 0.7g of potassium persulfate are added dropwise at 60 ℃ for 2.5 hours, 0.3g of AIBN (azodiisobutyronitrile) is added after the reaction is carried out for 7.5 hours again, and the reaction is continued for 12 hours again.
Example 14 (multipolymer P14)
500g of isopropanol, 150g of deionized water and 40g of ethyl acrylate are added into a four-neck flask which is 1000 ml provided with a temperature-controlled heating device, a mechanical stirring device, a condensation reflux device and a nitrogen protection device, 20g of an example compound C2 are heated and stirred uniformly, 30g of styrene, 10g of an example compound D3 and 0.7g of AIBN (azodiisobutyronitrile) are dropwise added at 60 ℃ for 2.5 hours, 0.3g of AIBN (azodiisobutyronitrile) is added after the reaction is carried out for 7.5 hours again, and the reaction is continued for 12 hours again, and then the reaction is finished.
Example 15 (multipolymer P15)
500g of isopropanol, 150g of deionized water and 19g of ethyl acrylate are added into a four-neck flask which is 1000 ml provided with a temperature-controlled heating device, a mechanical stirring device, a condensation reflux device and a nitrogen protection device, 1g of an example compound C1 is heated and stirred uniformly, 40g of styrene, 40g of an example compound D3 and 0.7g of potassium persulfate are dropwise added at 60 ℃ for 2.5 hours, after 7.5 hours of reaction, 0.3g of AIBN (azobisisobutyronitrile) is added, and the reaction is continued for 12 hours.
Example 16 (multipolymer P16)
500g of isopropanol, 150g of deionized water and 30g of ethyl methacrylate are added into a four-neck flask which is 1000 ml provided with a temperature-controlled heating device, a mechanical stirring device, a condensation reflux device and a nitrogen protection device, 30g of an example compound C2 are heated and stirred uniformly, 20g of styrene, 20g of an example compound D4 and 0.7g of AIBN (azodiisobutyronitrile) are added dropwise at 60 ℃ for 2.5 hours, after 7.5 hours of reaction, 0.3g of AIBN (azodiisobutyronitrile) is added, and the reaction is continued for 12 hours.
Example 17 (multipolymer P17)
500g of isopropanol, 150g of deionized water, 20g of ethyl acrylate, 20g of example compound C1 and uniformly stirring by heating are added into a four-neck flask which is 1000 ml and is provided with a temperature control heating device, a mechanical stirring device, a condensation reflux device and a nitrogen protection device, 50g of styrene, 10g of example compound D4 and 0.7g of potassium persulfate are dropwise added at 60 ℃ for 2.5 hours, 0.3g of AIBN (azodiisobutyronitrile) is added after the reaction is carried out for 7.5 hours again, and the reaction is continued for 12 hours again.
Example 18 (multipolymer P18)
500g of isopropanol, 150g of deionized water and 1g of ethyl acrylate are added into a four-neck flask which is 1000 ml provided with a temperature-controlled heating device, a mechanical stirring device, a condensation reflux device and a nitrogen protection device, 19g of an example compound C2 are heated and stirred uniformly, 70g of styrene, 10g of an example compound D5 and 0.7g of AIBN (azobisisobutyronitrile) are dropwise added at 60 ℃ for 2.5 hours, 0.3g of AIBN (azobisisobutyronitrile) is added after the reaction is carried out for 7.5 hours again, and the reaction is continued for 12 hours again, and then the reaction is finished.
Example 19 (multipolymer P03)
500g of isopropanol, 150g of deionized water, 10g of ethyl acrylate, 40g of example compound C1, uniformly heating and stirring, dropwise adding 30g of styrene, 20g of example compound D5,0.7g of AIBN (azobisisobutyronitrile) at 60 ℃ for 2.5 hours, reacting for 7.5 hours, adding 0.3g of AIBN (azobisisobutyronitrile), and reacting for 12 hours.
Example 20 (multipolymer P20)
500g of isopropanol, 150g of deionized water, 15g of ethyl methacrylate and 15g of example compound C1 are added into a four-neck flask which is 1000 and ml is provided with a temperature control heating device, a mechanical stirring device, a condensation reflux device and a nitrogen protection device, the mixture is heated and stirred uniformly, 30g of styrene, 40g of example compound D5 and 0.7g of potassium persulfate are added dropwise at 60 ℃ for 2.5 hours, after 7.5 hours of further reaction, 0.3g of AIBN (azobisisobutyronitrile) is added, and the further reaction is continued for 12 hours, and then the reaction is finished.
Comparative example 21 (multipolymer P21)
500g of isopropanol, 150g of deionized water, 15g of ethyl acrylate, 15g of example compound C2, uniformly heating and stirring, dropwise adding 10g of styrene, 60g of example compound D2,0.7g of AIBN (azobisisobutyronitrile) at 60 ℃ for 2.5 hours, reacting for 7.5 hours, adding 0.3g of AIBN (azobisisobutyronitrile), and reacting for 12 hours.
Comparative example 22 (multipolymer P22)
500g of isopropanol, 150g of deionized water and 10g of ethyl methacrylate are added into a four-neck flask which is 1000 ml provided with a temperature-controlled heating device, a mechanical stirring device, a condensation reflux device and a nitrogen protection device, 5g of an example compound C1 are heated and stirred uniformly, 80g of styrene, 5g of an example compound D1 and 0.7g of potassium persulfate are added dropwise at 60 ℃ for 2.5 hours, 0.3g of AIBN (azodiisobutyronitrile) is added after the reaction is carried out for 7.5 hours again, and the reaction is continued for 12 hours again.
Comparative example 23 (multipolymer P23)
500g of isopropanol, 150g of deionized water, 10g of ethyl methacrylate, 55g of example compound C2, uniformly heating and stirring, dropwise adding 20g of styrene, 15g of example compound D1 and 0.7g of potassium persulfate at 60 ℃ for 2.5 hours, reacting for 7.5 hours, adding 0.3g of AIBN (azobisisobutyronitrile) and reacting for 12 hours.
Raw materials used in formulation examples in the formulation of imageable layers:
multipolymer of structure P, lekehua optical printing technology Co.Ltd
Polyurethane acrylic prepolymer Baoding LekeKai chemical Co., ltd
Sartomer 399 Sartomer Co.，Inc.
Iodonium salt initiator Lekai institute
Infrared absorbing dye IR Lekai institute
BYK-330 BYK Co
1-methoxy-2-propanol Nanjing Tokyo Zhu Gong Mao Co., ltd
The multipolymer of structure P was a 25.0% solution in DMF (weight percent), a common solvent in organic synthesis. The structure P is the water-soluble heat-crosslinked multipolymer P1-P23 obtained in the above examples and comparative examples.
The prepolymer was a 50% solution in MEK (weight percent), a common solvent in organic synthesis.
The iodonium salt initiator has the following structure:
the IR structure of the IR absorbing dye is as follows:
description of the terminology:
starting-up latitude: the adaptability of the machine development type printing plate to the state of the printing machine, the water quantity of the fountain solution, the water leaning time, the printing ink and the like in the developing process of the machine development type printing plate on the printing machine is high, and the large starting-up latitude of the printing plate indicates that the adaptability of the machine development type printing plate to the printing machine, the fountain solution and the printing ink is good, and the long operation space of the printing machine is large.
Number of paper passes: refers to the number of sheets lost from the start of feeding to blank cleaning and ink balance.
Solvent resistance: after coating, drying and balancing on the substrate and plate making and exposure, the coating loss is measured by soaking in a solvent such as isopropanol for a certain time. If the coating loss is large, it means that the plate material has poor solvent resistance and low UV ink durability during printing.
Preparation of a plate base: a1050 rolled aluminum plate having a diameter purity of 99.5% and a thickness of 0.3mm was prepared by dissolving 70% by mass of a 5% aqueous sodium hydroxide solution O C for 20 seconds, and immediately after rinsing with running water, the solution was neutralized with 1% by mass of aqueous nitric acid. Then in 1% hydrochloric acid aqueous solution, 40 O C AC power of 40A/dm was applied with sine wave 2 Is electrocoarsened for 16 seconds. Then 40 O And C, neutralizing with 5% sodium hydroxide aqueous solution for 10 seconds. And (5) washing with water. Finally at 30 O C, using a sulfuric acid aqueous solution with a mass fraction of 20% at 15A/dm 2 Is anodized for 20 seconds. And (5) washing with water. 200ppm sodium fluoride and at 60 DEG CAnd carrying out hole sealing treatment on the sodium dihydrogen phosphate aqueous solution with the mass fraction of 6 percent for 20 seconds. And (5) washing with water. And (5) drying. The average thickness of the center line of the thus obtained plate was 0.40. Mu.m, and the oxide film weight was 3.0g/m 2 。
Coating a photosensitive layer: the following photosensitive liquid formulation was coated on the above hydrophilized plate using a bar coater, and then dried at 100 ℃ for 60 seconds. Yield 1.0g/m 2 Form a negative-working lithographic printing plate precursor that is sensitive to infrared radiation. The photosensitive layer is herein the imageable layer. The following components (each component in parts by weight) were used and mixed to obtain a photosensitive liquid formulation.
Example 1 (printing plate A1)
Water-soluble, thermally crosslinked, multipolymer P01.79
Polyurethane acrylic oligomer 4.62
Multifunctional acrylic monomer (Sartomer 399) 0.90
Iodonium salt initiator 0.70
2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine 0.09
Infrared absorbing dye IR 0.71
BYK-330 0.28
1-methoxy-2-propanol 92.40
Example 2 (printing plate A2)
Water-soluble, thermally crosslinked, multipolymer P02 4.72
Polyurethane acrylic oligomer 0.69
Multifunctional acrylic monomer (Sartomer 399) 0.10
Iodonium salt initiator 1.50
2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine 0.27
Infrared absorbing dye IR 0.39
BYK-330 0.20
1-methoxy-2-propanol 92.40
Example 3 (printing plate A3)
Water-soluble, thermally crosslinked, multipolymer P03.3.15
Polyurethane acrylic oligomer 1.17
Multifunctional acrylic monomer (Sartomer 399) 0.80
Iodonium salt initiator 1.90
2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine 0.46
Infrared absorbing dye IR 0.12
BYK-330 0.28
1-methoxy-2-propanol 92.40
Example 4 (printing plate A4)
Water-soluble, thermally crosslinked, multipolymer P04 1.97
Polyurethane acrylic oligomer 1.95
Polyfunctional acrylic monomer (Sartomer 399) 1.20
Iodonium salt initiator 0.10
2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine 0.02
Infrared absorbing dye IR 2.36
BYK-330 0.28
1-methoxy-2-propanol 92.40
Example 5 (printing plate A5)
Water-soluble, thermally crosslinked, multipolymer P05.3.15
Polyurethane acrylic oligomer 1.80
Multifunctional acrylic monomer (Sartomer 399) 0.95
Iodonium salt initiator 0.90
2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine 0.32
Infrared absorbing dye IR 0.48
BYK-330 0.28
1-methoxy-2-propanol 92.40
Example 6 (printing plate A6)
Water-soluble, thermally crosslinked, multipolymer P06.75
Polyurethane acrylic oligomer 2.05
Polyfunctional acrylic monomer (Sartomer 399) 1.10
Iodonium salt initiator 0.80
2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine 0.42
Infrared absorbing dye IR 0.48
BYK-330 0.28
1-methoxy-2-propanol 92.40
Example 7 (printing plate A7)
Water-soluble, thermally crosslinked, multipolymer P07 3.15
Polyurethane acrylic oligomer 1.17
Multifunctional acrylic monomer (Sartomer 399) 0.80
Iodonium salt initiator 2.06
2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine 0.30
Infrared absorbing dye IR 0.12
BYK-330 0.28
1-methoxy-2-propanol 92.40
Example 8 (printing plate A8)
Water-soluble, thermally crosslinked, multipolymer P08.1.97
Polyurethane acrylic oligomer 1.95
Polyfunctional acrylic monomer (Sartomer 399) 1.20
Iodonium salt initiator 0.10
2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine 0.02
Infrared absorbing dye IR 2.36
BYK-330 0.28
1-methoxy-2-propanol 92.40
In the following examples, the water-soluble heat-crosslinking multipolymer was used in the same amount as the other components in the respective photoreceptor formulations, and when the water-soluble heat-crosslinking multipolymer was P9 to P20, printing plate examples A9 to A20 were obtained in the order of the respective water-soluble heat-crosslinking multipolymer, and when the water-soluble heat-crosslinking multipolymer was P21 to P23, printing plate comparative examples A21 to A23 were obtained.
Water-soluble, thermally crosslinked, multipolymer P3.05
Polyurethane acrylic oligomer 2.25
Multifunctional acrylic monomer (Sartomer 399) 0.85
Iodonium salt initiator 0.81
2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine 0.18
Infrared absorbing dye IR 0.48
BYK-330 0.28
1-methoxy-2-propanol 92.40
The plate thus obtained was exposed on a Kodak full-face thermosensitive CTP plate making machine, and appropriate exposure energy was determined. And then the exposed plate is directly arranged on a Heidelberg SpeedMaster74 printer according to the corresponding exposure energy, the printer is started, 50% of the water content of the fountain solution wets the whole plate for 10 seconds, and then the printing is started by paper feeding. The properties are shown in Table 1 below and the number of passes is shown in Table 1 below.
The plate obtained by the method is exposed on a Kodak full-winning thermosensitive CTP plate making machine, and proper exposure energy is determined. And then the exposed plate is directly installed on a Manland 700 printing machine according to the corresponding exposure energy, the printing machine is started, the water content of the fountain solution is 35%, the whole plate is wetted for 90 seconds, and then the printing is started by paper feeding. The number of the printing paper passing through is listed in the following table-starting method (2).
List one
While only the preferred embodiments of the present invention have been described above, the scope of the present invention is not limited thereto, and it should be noted that equivalents and modifications, variations and improvements made according to the technical solution of the present invention and the inventive concept thereof, as well as those skilled in the art, should be considered as the scope of the present invention, without departing from the general inventive concept thereof.
Claims (10)
1. A water-soluble, thermally crosslinked, multipolymer characterized in that: the water-soluble heat-crosslinking copolymer at least contains the following copolymerization units: -a-B-C-D-;
a represents a styrene copolymer unit; b represents an ethyl (meth) acrylate copolymer unit; c represents a copolymerized unit having a urethanized unsaturated double bond branch:
R 1 Is H atom or methyl, R 2 Is CH 2 =C(CH 3 ) COOCH2CH2 NHCO-group;
d represents an acrylamide copolymerized unit containing an alkyl sulfonate group:
wherein n is an integer of 0 to 8, R is an alkyl group or an aryl group having 3 to 18 carbon atoms, and M is an alkali metal element.
2. The water-soluble, thermally crosslinked, multipolymer of claim 1, characterized in that: for an acrylamide copolymer unit D containing sulfonic acid alkyl, wherein n is an integer of 1-4, R is any one selected from n-hexyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tetradecyl, p-octylphenyl and p-dodecylphenyl, and M is sodium or potassium;
the weight average molecular weight of the water-soluble heat-crosslinking copolymer is 2000-300000; the glass transition temperature is 30-400 ℃;
the weight percentage content of the styrene copolymerized unit A in the water-soluble heat-crosslinking multi-component copolymer is 20% -70%; the weight percentage content of the (methyl) acrylic acid ethyl ester copolymer unit B in the water-soluble heat-crosslinking multi-component copolymer is 1-40%; the weight percentage content of the copolymerized unit C with urethanized unsaturated double bond branched chains in the water-soluble heat-crosslinking multi-component copolymer is 1-40%; the weight percentage content of the acrylamide copolymer unit D containing sulfonic acid alkyl in the water-soluble heat-crosslinking multi-component copolymer is 1-40%.
3. The water-soluble, thermally crosslinked, multipolymer of claim 1, characterized in that: for an acrylamide copolymer unit D containing sulfonic acid alkyl groups, wherein n is 1 or 2, R is any one selected from n-octyl, n-dodecyl, n-tetradecyl, p-dodecylphenyl and n-hexadecyl, and M is sodium;
the weight average molecular weight of the water-soluble heat-crosslinking copolymer is 10000-200000; the glass transition temperature is 40-300 ℃;
the weight percentage content of the styrene copolymerized unit A in the water-soluble heat-crosslinking multi-component copolymer is 30% -60%; the weight percentage content of the (methyl) acrylic acid ethyl ester copolymer unit B in the water-soluble heat-crosslinking multi-component copolymer is 1-30%; the weight percentage content of the copolymerized unit C with urethanized unsaturated double bond branched chains in the water-soluble heat-crosslinking multi-component copolymer is 1-30%; the weight percentage content of the acrylamide copolymer unit D containing sulfonic acid alkyl in the water-soluble heat-crosslinking multi-component copolymer is 1-30%.
4. A process for the preparation of a water-soluble, thermally crosslinked, multipolymer according to any of claims 1-3, characterized in that: the polymerization initiator at least contains one of benzoyl peroxide, persulfate or azo compound by adopting a random copolymerization method, and emulsion polymerization is adopted in the copolymerization mode.
5. A negative-working lithographic printing plate precursor characterized by: comprising an imageable layer comprising a water-soluble, thermally crosslinked copolymer comprising the water-soluble, thermally crosslinked copolymer of any one of claims 1-4, a polymerizable/crosslinkable component, an infrared radiation absorber, and an initiator.
6. The negative-working lithographic printing plate precursor of claim 5, wherein: the water-soluble heat-crosslinking copolymer accounts for 10% -60% of the weight of the imageable layer, the polymerizable/crosslinking component accounts for 10% -70% of the weight of the imageable layer, the infrared radiation absorber accounts for 1% -30% of the weight of the imageable layer, and the initiator accounts for 1% -30% of the weight of the imageable layer.
7. The negative-working lithographic printing plate precursor of claim 6, wherein: the water-soluble heat-crosslinking copolymer accounts for 20% -40% of the weight of the imageable layer, the polymerizable/crosslinking component accounts for 20% -50% of the weight of the imageable layer, the infrared radiation absorber accounts for 1% -15% of the weight of the imageable layer, and the initiator accounts for 3% -20% of the weight of the imageable layer.
8. The negative working lithographic printing plate precursor according to any of claims 5-7, wherein: the weight average molecular weight of the water-soluble heat-crosslinking multipolymer is 30000-150000; the glass transition temperature is 60-150 ℃;
The weight percentage content of the styrene copolymerized unit A in the water-soluble heat-crosslinking multi-component copolymer is 40% -60%; the weight percentage content of the (methyl) acrylic acid ethyl ester copolymer unit B in the water-soluble heat-crosslinking multi-component copolymer is 1-25%; the weight percentage content of the copolymerized unit C with urethanized unsaturated double bond branched chains in the water-soluble heat-crosslinking multi-component copolymer is 5-20%; the weight percentage content of the acrylamide copolymer unit D containing sulfonic acid alkyl in the water-soluble heat-crosslinking multi-component copolymer is 5-25%;
the polymerizable/crosslinkable component is comprised of at least one of an ethylenically unsaturated free radically polymerizable monomer or oligomer or a free radically crosslinkable polymer; the infrared radiation absorbing dye is a cyanine dye absorbing 750-850 nm; the initiator is selected from one or more of iodonium salt, sulfonium salt, phosphonium salt and selenonium salt.
9. The negative-working lithographic printing plate precursor of claim 5, wherein: the imageable layer further includes at least one of pigments, organic or inorganic particles, sensitized dyes, wetting agents, plasticizers, binders, surfactants, antioxidants, co-coaters, anti-stabilizers, and brighteners.
10. A method of preparing a negative working lithographic printing plate precursor according to any of claims 5 to 9, wherein: the raw materials of the imageable layer are mixed to obtain a photosensitive liquid preparation, and then the photosensitive liquid preparation is coated on a hydrophilized plate base by using a rod coater or other equipment and methods, and then dried in a proper way to obtain the negative-working lithographic printing plate precursor.
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